difluoromethylnicotinic indanyl carboxamides

专利摘要:
Difluoromethylnicotinic indanyl carboxamides The present invention relates to novel difluoromethylnicotinic indanyl carboxamides, processes for preparing these compounds, compositions comprising these compounds and their use as biologically active compounds, especially for controlling harmful microorganisms in the field of crop protection and protection. of materials.
公开号:BR112015014191B1
申请号:R112015014191
申请日:2013-12-16
公开日:2019-08-27
发明作者:Sudau Alexander；Dubost Christophe；Bernier David；Lachaise Hélène；Vors Jean-Pierre；Carles Lionel；Wasnaire Pierre；Coqueron Pierre-Yves；Maechling Simon；Brunet Stéphane；Wachendorff-Neumann Ulrike
申请人:Bayer Cropscience Ag；
IPC主号:

专利说明:

[001] The present invention relates to new difluoromethylnicotinic indanyl carboxamides, to processes for the preparation of these compounds, to compositions comprising these compounds and to their use as biologically active compounds, especially for controlling harmful microorganisms in the field of crop protection and protection of materials.
[002] It is already known that certain pyrazole indanyl carboxamides have fungicidal properties (for example, WO 1992/12970, WO 2012/065947, J. Org. Chem. 1995, 60, 1626-1631 eWO 2012/084812).
[003] It is also known that certain pyridine indanyl carboxamides or benzofuran carboxamides have fungicidal properties (for example EP-A 0 256 503, JP-A, 1117864, JP-A1211568, EP-A 315502, J. Pesticides Sei. 18,1993 , 4957, J. Pesticide Sci. 18, 1993, 245-251).
[004] It is also known that certain benzoyl indanyl amides have fungicidal properties (WO 2010/109301).
[005] Since the current active ingredients, namely fungicides, are constantly undergoing new requirements from the point of view of costs and ecology, for example, with regard to the spectrum of activity, toxicity, selectivity, application rates , formation of residues and favorable manufacturing, and which, in addition, may present problems such as, for example, the development of resistance, there is a permanent need for new fungicidal compositions that have advantages over known compositions, at least in some areas.
[006] The present invention now provides new indanyl carboxamides
2/116
(D [007] in which [008] X ¹ represents halogen; cyano; C1-C6 alkyl, C1-C6 haloalkyl having 1 to 9 equal or different halogen atoms; C3-C7 cycloalkyl, C3-C7 halocycloalkyl with 1 to 9 equal or different halogen atoms; [009] n represents 0, 1,2 or 3;
[010] T represents an oxygen or sulfur atom;
[011] Q represents hydrogen, optionally substituted C 1 -C 6 alkylsulfonyl; optionally substituted C1-4 alkoxy-C1-4 alkyl, optionally substituted haloalkyl-C1-4 sulfonyl;
[012] R ^a represents hydrogen, halogen, nitro, cyano, C1 -C2 alkyl; halo-C 1 -C 6 alkyl with 1 to 9 equal or different halogen atoms; C3-C7-cycloalkyl, C3-C7-halocycloalkyl with 1 to 9 equal or different halogen atoms; C1-6 alkoxy; halo-C 1 -C 6 -alkoxy with 1 to 9 equal or different halogen atoms; C1-6 alkylsulfanyl; halo-C 1 -C 6 -sulfanyl with 1 to 9 equal or different halogen atoms; C1-6 alkylsulfonyl; halo-C 1-6 alkylsulfonyl with 1 to 9 equal or different halogen atoms; C2 -C12 alkenyl; C2 -C12 alkynyl; (C 1 -C 8) trialkyl silyl;
[013] Y represents O, S, CR ³ R ⁴ ;
[014] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of each other represent hydrogen; halogen; cyan; C 1-6 alkyl; halo-C1-6 alkyl with 1 to 9 equal or different halogen atoms; cycloalkyl-Cs-Cs; (C3-C8-cycloalkyl) C1-Ce alkyl; (C3-C8-cycloalkyl) C3-C8-cycloalkyl; C2-C8-alkenyl; C2-C8-alkynyl; C2-C1- alkenyl-C1-6-alkyl; C2-C8-alkynyl-C1-C6-alkyl; C1-6 alkoxy; cycloalkyloxy-C3Ce; (C3-C8-cycloalkyl) C1-8-alkyloxy; alkyl-C 1 -C-sulfanyl; cycloalkyl-C3-C8sulfanyl; (C3-C8-cycloalkyl) C1-6-alkylsulfanyl; alkenyloxy-C2-C8; alkynyloxy-Cs-Cs;
3/116 arylalkyloxy-Ci-Ce optionally substituted with up to 6 same or different R ^b groups; arylalkyl-C 1 -C-sulfanyl optionally substituted with up to 6 same or different R ^b groups; aryloxy optionally substituted with up to 6 same or different R ^b groups; arylsulfanyl optionally substituted with up to 6 same or different R ^b groups; (C3-C8-cycloalkyl) C2-Ce alkenyl; (C3-C8-cycloalkyl) C2-Ce alkynyl; optionally substituted trialkyl (C1 -Cs) silyl; trialkyl (C1-C8) silylalkyl-C1C; arylalkyl-C 1 -C optionally substituted with up to 6 same or different R ^b groups; arylalkenyl-C2-C8 optionally substituted with up to 6 same or different R ^b groups; arylalkynyl-C2-C8 optionally substituted with up to 6 same or different R ^b groups; alkyl-C1-Ce-amino; dialkyl-Ci-Ce-amino; arylamino optionally substituted with up to 6 same or different R ^b groups; alkyl-C 1 -Cecarbonyl, alkyl-C 1 -C-carbonyloxy; alkyl-C 1 -C-carbonylamino; alkoxycarbonyl-CiCe; alkyloxy-C1-Ce-carbonyloxy; alkyl-C1-Ce-carbamoyl; dialkyl-Ci-Ce-carbamoyl; alkyl-C 1 -C-aminocarbonyloxy; dialkyl-C1-Cs-aminocarbonyloxy; N- (C1-6 alkyl-hydroxycarbamoyl; C1-6 alkoxy-C-carbamoyl; N- (C1-8 alkyl) C1-8 alkoxycarbamoyl; arylalkyl-C1-Cs-amino optionally substituted with up to 6 equal or different R ^b groups; ( alkoxy-C-C8-imino) alkyl-C1-Ce; (cycloalkoxy-C2-Cimino) alkyl-C1-C8; alkyl-C1-Ce-iminoxy; alkyl-C1-Ce-iminoxyalkyl-C1-Ce; each of which are optionally substituted, or [015] R ¹ and R ² together with the carbon atom to which they are attached may form a Cs-Ce cycloalkyl; C3-Ce cycloalkenyl, or a 5, 6 or 7 saturated heterocycle ring atoms; each of which is optionally substituted; or may represent a group ^ (Y ^ Y ² or a group = NOR ^c ; or [016] R ³ and R ⁴ together with the carbon atom to which they are attached they may form a Cs-Cs cycloalkyl; Cs-Cs cycloalkenyl, or a saturated heterocycle of 5, 6 or 7 ring atoms; each of which is optionally substituted; or they may represent a group = C (Y ¹ ) Y ² or a group = NOR ^C , or [0 17] R ⁵ and R ⁶ together with the carbon atom to which they are attached can form a Cs-Cs-cycloalkyl; C3-C8-cycloalkenyl, or a saturated heterocycle of 5, 6 or 7 ring atoms; each of which is optionally
4/116 replaced; or they can represent a group = C (Y ¹ ) Y ² or a group = NOR ^C ; [018] Y ¹ and Y ² independently of each other represent hydrogen, halogen, C 1 -C 2 alkyl; halo-C 1 -C 6 alkyl with 1 to 9 equal or different halogen atoms; alkylsulfanyl-C1-Ce; phenyl; each of which is optionally substituted; or Y ¹ and Y ² together with the carbon atom to which they are attached may form a C3-C8 cycloalkyl or a C3-C8 cycloalkenyl or a saturated heterocycle with 5, 6 or 7 ring atoms; each of which is optionally substituted;
[019] R ^b represents halogen; nitro, cyano, C 1 -C 2 alkyl; halo-C 1 -C 6 alkyl with 1 to 9 equal or different halogen atoms; C 1 -C 6 alkoxy; haloalkoxy-C1-6 with 1 to 9 equal or different halogen atoms; C 1 -C 6 alkylsulfanyl; halo-C 1 -C 6 -sulfanyl with 1 to 9 equal or different halogen atoms; C1-6 alkylsulfonyl; halo-C 1 -C 6 -sulfonyl having 1 to 9 equal or different halogen atoms; C2 -C12 alkenyl; C2 -C12 alkynyl; C3-C7-cycloalkyl; trialkyl (CiCejsililo;
[020] R ^c represents C 1 -C 6 alkyl; halo-C 1 -C 6 alkyl with 1 to 9 equal or different halogen atoms; C3-Ce cycloalkyl; (C3-C8-cycloalkyl) C1-6 alkyl; (C3-C8-cycloalkyl) C3-C8-cycloalkyl; alkenyl-C2-C8-alkyl-C1-C6; alkynyl-C2 Ce-alkyl-C1-C6; arylalkyl-C 1 -C optionally substituted with up to 6 same or different R ^b groups; each of which is optionally replaced.
[021] Formula (I) represents a general definition of the 1-methylpyrazole (thio) indanyl carboxamides according to the invention. Definitions of preferred radicals for the formulas presented above and below are given below. These definitions apply equally to the final products of formula (I) and to all intermediaries.
[022] X ¹ preferably represents halogen; C1-6 alkyl, C1-6 haloalkyl of 1 to 9 equal or different halogen atoms;
[023] X ¹ particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl;
[024] X ¹ most particularly preferably represents fluorine, chlorine, methyl;
5/116 [025] n preferably represents 0, 1 or 2;
[026] n particularly preferably represents 0;
[02η T preferably represents an oxygen atom;
[028] Q preferably represents hydrogen, C 1 -C 4 -sulphonyl, C 1 -C 3 -alkyl-C 1 -alkoxy, halo-C 1 -C 4 -sulphonyl, haloalkyl-C 1 -C 3 -C 3 -alkyl-C 1 -alkyl from 1 to 9 fluorine, chlorine and / or bromine atoms;
[029] Q particularly preferably represents hydrogen, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, trifluoromethylsulfonyl, trifluoromethoxy;
[030] Q very particularly preferably represents hydrogen;
[031] R ^a preferably represents hydrogen, fluorine, chlorine, methyl trifluoromethyl and cyclopropyl or [032] R ^a preferably represents hydrogen, fluorine, chlorine, methyl or trifluoromethyl, cyclopropyl and bromine;
[033] R ^a particularly preferably represents hydrogen;
[034] R ^a also particularly preferably represents fluorine, the fluorine being particularly preferably located at positions 4, 5 or 6, very particularly preferably at positions 4 or 6, in particular at the position of the indanyl radical;
[035] R ^a also particularly preferably represents chlorine, the chlorine being particularly preferably located at positions 4 or 5, in particular at position 4 of the indanyl radical;
[036] R ^a also particularly preferably represents methyl, the methyl being particularly preferably located at positions 4 or 5 of the indanyl radical;
[03η R ^a also particularly preferably represents trifluoromethyl, the trifluoromethyl being particularly preferably located at positions 4 or of the indanyl radical;
[038] Y preferably represents O, CR ³ R ⁴ ;
6/116 [039] Y particularly preferably represents CR ³ R ⁴ ;
[040] Y particularly preferably represents O;
[041] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of each other preferably represent hydrogen, halogen; cyan; C1-6 alkyl-C1-6 haloalkyl-C1- with 1 to 9 equal or different halogen atoms; C3-Cs-cycloalkyl; (C3-Ce cycloalkyl) C1-C8 alkyl; (C3-C8-cycloalkyl) C3-C8-cycloalkyl; C ₂ -C ₈ alkenyl; C2-Ce alkynyl; alkenyl-C2-C8-alkyl-C1-C6; C ₂ -C 8 alkynyl-C ₁ -C ₆ alkyl; C1-6 alkoxy; cycloalkyloxy-Cs-Ce; (C3-C8-cycloalkyl) C1-8-alkyloxy; alkyl-C 1 -C-sulfanyl; cyclo-C3-C8-sulfanyl; (C3-Ce-cycloalkyl) C1-C8-sulfanyl alkyl; alkenyloxy-C ₂ Ce; alkynyloxy-C3-C8; arylalkyloxy-Ci-Ce optionally substituted with up to 6 same or different R ^b groups; arylalkyl-C 1 -Cs-sulfanyl optionally substituted with up to 6 same or different R ^b groups; aryloxy optionally substituted with up to 6 same or different R ^b groups; arylsulfanyl optionally substituted with up to 6 same or different R ^b groups; (C3-C8-cycloalkyl) C2-C8-alkenyl; (C3C8-cycloalkyl) C2-C8-alkynyl; (C 1 -C 8) trialkyl silyl; (C 1 -C 8) trialkyl (C 1 -C 8) silyl; arylalkylCi-Ce optionally substituted with up to 6 same or different R ^b groups; arylalkenyl-C2-C8 optionally substituted with up to 6 same or different R ^b groups; arylalkynyl-C ₂ -Cs optionally substituted with up to 6 same or different R ^b groups; each of which is optionally substituted;
[042] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of each other represent in particular hydrogen, fluorine, chlorine, bromine, iodine; C 1 -C ₁ alkyl; halo-C 1 -C 6 alkyl with 1 to 9 equal or different halogen atoms; C3-C6-cycloalkyl; (C3-C6-cycloalkyl) C1-3-alkyl; (C3-C6-cycloalkyl) C3-C6-cycloalkyl; alkoxy-Ci _2; C3-C6-cycloalkyloxy; (C3-C6-cycloalkyl) C1-6-alkyloxy;
[043] R ¹ , R ² , R ³ , R- ⁴ , R ⁵ and R ⁶ independently of each other very particularly preferably they represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec- butyl, tert-butyl, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy, tert-butyloxy, difluoromethyl, trifluoromethyl or [044] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of each other very
7/116 particularly preferably represent hydrogen, methyl, ethyl, propyl, isopropyl, 2,2-dimethylpropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy , iso-butyloxy, sec-butyloxy, tert-butyloxy, difluoromethyl, trifluoromethyl or [045] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of each other very particularly preferably they represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, difluoromethyl;
[046] R ¹ and R ² can preferably form, together with the carbon atom to which they are attached, a C3-Ce cycloalkyl; or they can form the group = C (Y ¹ ) Y ² or a group = NOR ^C ;
[θ4η R ¹ and R ² can particularly preferably form, together with the carbon atom to which they are attached, a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; or they can form the group = C (Y ¹ ) Y ² or a group = N-OR ^c ;
[048] R ³ and R ⁴ can preferably form, together with the carbon atom to which they are attached, a Cs-Cs-cycloalkyl; or they can form the group = C (Y ¹ ) Y ² or a group = NOR ^C ;
[049] R ³ and R ⁴ can particularly preferably form, together with the carbon atom to which they are attached, a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; or they can form the group = C (Y ¹ ) Y ² or a group = NOR ^C ;
[050] R ⁵ and R ⁶ can preferably form, together with the carbon atom to which they are attached, a cycloalkyl-Cs-Ce; or they can form the group = C (Y ¹ ) Y ² or a group = NOR ^C ;
[051] R ⁵ and R ⁶ can particularly preferably form, together with the carbon atom to which they are attached, a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; or they can form the group = C (Y ¹ ) Y ² or a group = NOR ^C ;
[052] R ^b preferably represents halogen; nitro, cyano, C1-6 alkyl; halo-C 1 -C 4 -alkyl With 1 to 9 equal or different halogen atoms; alkoxyCic; haloalkoxy-C-C4 with 1 to 9 equal or different halogen atoms; C1-6 alkylsulfanyl; haloalkyl-C1-C4-sulfanyl with 1 to 9 halogen atoms
8/116 the same or different; C1-6 alkylsulfonyl; halo-C1- C4-sulfonyl with 1 to 9 equal or different halogen atoms; C2-Ce alkenyl; C2-Cs alkynyl; C3-C6-cycloalkyl; trialkyl (C-C6) silyl;
[053] R ^b particularly preferably represents fluorine, chlorine, bromine; C 1 -C 6 alkyl; halo-C 1 -C 4 alkyl with 1 to 9 equal or different halogen atoms; C1-4 alkoxy; halo-C 1 -C 4 -alkoxy with 1 to 9 equal or different halogen atoms; C 1-4 alkylsulfanyl; halo-C1- C4-sulfanyl with 1 to 9 equal or different halogen atoms; C 1-4 alkylsulfonyl; halo-C 1 -C 4 sulfonyl with 1 to 9 equal or different halogen atoms; C2-C6-alkenyl; C2-C6-alkynyl; cycloalkyl-Cs-Ce; (C 1 -C 4) trialkyl silyl;
[054] R ^b most particularly preferably represents fluorine, chlorine, bromine; methyl, ethyl, n-propyl, isopropyl, n-, i-, s-, t-butyl, trifluoromethyl, trichloromethyl, difluoromethyl, methoxy, trifluoromethoxy, methylsulfanyl, trifluoromethylsulfanyl, vinyl, allyl, ethinyl, propylgyl, cyclopropyl;
[055] R ^c preferably represents C 1 -C 2 alkyl; halo-C 1 -C 6 alkyl with 1 to 9 equal or different halogen atoms; C3-C6-cycloalkyl; (C3-C6-cycloalkyl) C1-C6-alkyl; (C3-C6-cycloalkyl) C3-C6-cycloalkyl; C2-C6-alkenyl-C-C12-alkyl; C2-C6-alkynyl-C1-C12 alkyl; aryl-C 1 -C 6 alkyl optionally substituted with up to 6 same or different R ^b groups; each of which is optionally substituted;
[056] R ^c most particularly preferably represents methyl, ethyl, npropyl, isopropyl, n-, i-, s-, t-butyl, trifluoromethyl, trichloromethyl, difluoromethyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzyl;
[057] R ^c particularly preferably represents C1-6 alkyl; haloC1- C4alkyl having 1 to 9 equal or different atoms of fluorine, chlorine or bromine; C3-C6 cycloalkyl (C3-C6 cycloalkyl) C1-C4 alkyl; alkenyl-C2-C6-alkyl-C1-C8; alkynyl-C2-C6alkyl-C1-Ce; aryl-C 1 -C 4 alkyl optionally substituted with up to 5 same or different R ^b groups; each of which is optionally substituted;
[058] R ^c most particularly preferably represents methyl, ethyl, npropyl, isopropyl, n-, i-, s-, t-butyl, trifluoromethyl, trichloromethyl, difluoromethyl,
9/116 cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
[059] Y ¹ and Y ² preferably independently of each other represent hydrogen, halogen, C 1 -C 2 alkyl, C 1 -C 6 haloalkyl having the same or different halogen atoms or, together with the carbon atom at to which they are attached, they can form an optionally substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;
[060] Y ¹ and Y ² particularly preferably, independently of each other, represent hydrogen, fluorine, chlorine, bromine, methyl; ethyl, propyl, isopropyl. [061] Most preferred are compounds according to formula (I), where [062] n represents 0;
[063] T represents oxygen or sulfur;
[064] Q represents hydrogen;
[065] R ^a represents hydrogen, fluorine, chlorine, methyl or trifluoromethyl, cyclopropyl.
[066] R ¹ , R ² , R- ³ , R ⁴ , R ⁵ and R ⁶ independently of each other represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, secbutyl, tert-butyl, difluoromethyl; or [067] R ⁵ and R ⁶ can form the group = NOR ^c ;
[068] Y represents O, CR ³ R ⁴ ;
[069] R ^c represents methyl, ethyl, n-propyl, isopropyl, n-, i-, s-, t-butyl.
[070] Unless otherwise specified, a group or a substituted substituent according to the invention is replaced with one or more groups selected from the group of halogens; nitro, cyano, C1-6 alkyl; halo-C 1 -C 6 alkyl with 1 to 9 equal or different halogen atoms; C 1 -C 6 alkoxy; halo-C 1 -C 6 -alkoxy with 1 to 9 equal or different halogen atoms; C1-6 alkylsulfanyl; haloC1-6 alkylsulfanyl with 1 to 9 equal or different halogen atoms; C 1-6 alkylsulfonyl; halo-C 1 -C 6 -sulfonyl having 1 to 9 equal or different halogen atoms; C2 -C12 alkenyl; C2 -C12 alkynyl; C3-C7-cycloalkyl; phenyl; trialkyl (CiCe) silyl; trialkyl (C1-C8) silyl-C1-C8 alkyl.
10/116 [071] Finally, it was found that the new (uncle) carboxamides of formula (I) have very good microbicidal properties and can be used to control undesirable microorganisms in the field of crop protection and material protection.
[072] The definition of C1-6 -alkyl comprises the largest range defined herein for an alkyl radical. Specifically, this definition comprises the meanings methyl, ethyl, n-isopropyl, n-, iso-, sec-, tert-butyl and also, in each case, all pentyl and hexyl isomers. A preferred range is C2C12-alkyl, such as an ethyl and, straight or branched-chain, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, particularly straight-chain or branched C3-alkyl Cio, such as propyl, 1-methylethyl, butyl, 1methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, nhexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1- dimethylbutyl, 2,2-dimethylbutyl, 3,3dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-3-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, 1-methylheptyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1-propylpentyl, 2propylpentyl, nonyl, 1-methyloctyl, 2-methyloctyl, 2-methylocyl, 1 2-ethylheptyl, 1propylhexyl , 2-propylhexyl, decyl, 1-methylnonyl, 2-methylnonyl, 1-ethyloctyl, 2-ethyloctyl, 1-propylheptyl and 2-propylheptyl, in particular propyl, 1-methylethyl, butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , 1,1-dimethylethyl, 1,2-dimethylbutyl, 1,3dimethylbutyl, pentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, 3-methylpentyl, heptyl, 1methylhexyl, 1-ethyl-3-methylbutyl, 1-methylheptyl, 1 , 2-dimethylhexyl, 1,3-dimethyloctyl, 4methyloctyl, 1,2,2,3-tetramethylbutyl, 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, 1,3dimethylpentyl, 1,3-dimethylhexyl, 5 -methyl-3-hexyl, 2-methyl-4-heptyl, 2,6-dimethyl-4heptyl and 1-methyl-2-cyclopropylethyl.
[073] Alkyl-substituted alkyl is, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2 fluoroethyl, 2,2-fluoroethyl, 2,2-fluoroethyl, 2,2-fluoroethyl , 2-chloro-2-fluoroethyl, 2-chloro-2,2difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 3-chloro-1methylbutyl, 2-chloro-1-methylbutyl , 1-chlorobutyl, 3,3-dichloro-1-methylbutyl, 3-chloro-1methylbutyl, 1-methyl-3-trifluoromethylbutyl, 3-methyl-1-trifluoromethylbutyl.
[074] The definition of triaqluil (Ci-Ce) silyl represents the following radicals: SiMe3, SiMe2Et, SiMe2CHMe2, SiMe2CH2CHMe2, SiMe2CH2CMe3, SiMe2CMe3, SiMe2CMe3, SiMe ₂ CH2CH ₂ Me.
[075] The definition of C2-C12 alkenyl comprises the largest range defined herein for an alkenyl radical. Specifically, this definition includes the meanings ethenyl, n-isopropenyl, n-, iso-, sec-, tert-butenyl, and also, in each case, all isomers of pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl , dodecenyl, 1-methyl-1-propenyl, 1-ethyl-1-butyl, 2,4-dimethyl1-pentenyl, 2,4-dimethyl-2-pentenyl.
[076] The C2-C12 alkynyl definition comprises the largest range defined here for an alkynyl radical. Specifically, this definition includes the meanings ethynyl, n-, iso-propynyl, n-, iso-, sec-, tert-butynyl, and also in each case all isomers of pentynyl, hexynyl, heptinyl, octinyl, noninyl, decynyl, undecynyl, dodecynyl.
[077] The cycloalkyl definition comprises univalent monocyclic hydrocarbon radicals saturated with 3 to 8 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
[078] The definition of aryl comprises unsubstituted or substituted aromatic mono-, bi- or tricyclic rings, for example, phenyl, naphthyl, anthracenyl (anthryl), phenanthracenyl (phenanthryl).
[079] The definition of heterocycle comprises unsaturated heterocyclic rings of 5 to 7 ring atoms, substituted or unsubstituted, with up to 4 heteroatoms selected from N, O and S, namely: 2-furyl, 3-furyl, 2-thienyl, 3- thienyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5 pyrazolyl, 1-pyrazolyl, 1 H-imidazol-2-yl, 1H-imidazol-4-yl, 1H-imidazol-5 -yl, 1Himidazol-1-yl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl,
11/12
3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1H-1,2,3-triazol-1-yl, 1H-1,2,3-triazol-4- yl, 1H-1,2,3-triazol-5-yl, 2H-1,2,3-triazol2-yl, 2H-1 _l 2,3-triazol-4-yl, 1 H-1,2,4 -triazol-3-yl, 1 H-1,2,4-triazol-5-yl, 1 H-1,2,4triazol-1-yl, 4H-1,2,4-triazol-3-yl, 4H -1,2,4-triazol-4-yl, 1H-tetrazol-1-yl, 1Htetrazol-5-yl, 2H-tetrazol-2-yl, 2H-tetrazol-5-yl, 1,2,4-oxadiazole -3-yl, 1,2,4oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-oxadiazol-2-yl ,
1.3.4- thiadiazol-2-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,3-thiadiazol-4yl, 1,2,3- thiadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,2,5-thiadiazol-3-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2- pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl,
1.2.4- triazin-6-yl.
[080] The optionally substituted radicals can be mono- or polysubstituted, and in the case of polysubstitution the substituents can be the same or different. Thus, the definition of dialkylamino also encompasses an amino group asymmetrically substituted with alkyl, such as, for example, methyl ethylamino. [081] Halogen-substituted radicals, such as, for example, halogenoalkyl, are mono- or polyhalogenated. In the case of polyhalogenation, the halogen atoms can be the same or different. Here, halogen is fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
[082] However, definitions or illustrations given behind radicals in general or preferred radicals can also be combined together as desired, namely combinations between the respective ranges and the preferred ranges. They apply to final products and, correspondingly, to precursors and intermediates.
[083] The definitions and explanations of radicals given above in general terms or according to the preferred ranges can also be combined together as desired, namely, between the specific ranges and the preferred ranges. They apply to both final products and the corresponding precursors and intermediates. In addition, individual definitions may not apply.
13/116 [084] Preference is given to the compounds of formula (I), in which each of the radicals has the preferred definitions mentioned above.
[085] Particular preference is given to the compounds of formula (I), in which each of the radicals has the most preferred definitions mentioned above.
[086] Particular preference is given to the compounds of formula (I), in which each of the radicals has the most preferred definitions of all of the above.
[087] The compounds according to the invention may possibly be present as mixtures of different possible isomeric forms, in particular stereoisomers, such as, for example E and Z, threus and erythro, and also of optical isomers and, if applicable case of tautomers. Both E and Z isomers, as well as threus and erythro isomers and optical isomers, any mixtures of these isomers and possible tautomeric forms are claimed.
[088] If applicable, the compounds of the present invention can exist in one or more forms of optical or chiral isomers, depending on the number of asymmetric centers of the compound. The invention, therefore, relates equally to all optical isomers and their racemic or scalemic mixtures (the term "scalemic" denotes a mixture of enantiomers in different proportions) and mixtures of all possible stereoisomers, in all proportions. Diastereoisomers and / or optical isomers can be separated according to methods known to a person skilled in the art.
[089] The compounds of the present invention may also eventually exist in one or more forms of geometric isomers depending on the number of double bonds in the compound. The invention, therefore, relates equally to all geometric isomers and to all possible mixtures, in all proportions. Geometric isomers can be separated according to general methods known to a person skilled in the art.
[090] If applicable, the compounds of the present invention may also exist in one or more forms of geometric isomers, depending on the relative position (sin / anti or cis / trans) of the substituents on the B ring. The invention,
14/116 therefore, refers equally to all sin / anti (or cis / trans) isomers and to all possible sin / anti (or cis / trans) mixtures, in all proportions. The sin / anti (or cis / trans) isomers can be separated according to general methods known to a person skilled in the art.
[091] The invention also provides compounds of the formula (ll-a)
[092] in which [093] the radicals, Q, R ^a , R ¹ , R ² , Y, R ⁵ , R ⁶ are as defined in formula (I).
[094] The preferred, particularly preferred and very particularly preferred radicals R ^a , R ¹ , R ² , Y, R ⁵ , R ⁶ are defined by formula (l).
[095] Illustration of intermediate processes and products [096] The carboxamides of formula (la), that is, carboxamides of formula (I) in which T represents oxygen, are obtained when carbonyl halides or acids of formula (II) are made react with amines of the formula (ll-a), if necessary in the presence of a coupling agent, optionally in the presence of an acid binder, and optionally in the presence of a diluent [Process (a)]:
(Π) (lll-a) (l-a) [097] Formula (II) provides a general definition of the carbonyl halides or acids needed as starting materials to carry out the process (a) according to the invention.
[098] In this formula (II), X ¹ has in general and preferably the meanings
15/116 previously given to these radicals when describing the compounds of formula (I). X ² represents halogen, hydroxyl or an activated hydroxyl group. X ² preferably represents fluorine, chlorine or hydroxyl, particularly preferably chlorine or hydroxyl.
[099] By activated hydroxyl group it is understood that the hydroxyl forms together with the adjacent carbonyl an ester that reacts spontaneously with an amino group. Common activated esters include esters of p-nitrophenyl, pentafluorophenyl, succinimide or phosphorus anhydrides.
[100] The formula (ll-a) provides a general definition of the amines needed as starting materials to carry out Process (a) according to the invention. In this formula (lll-a), Q, R ^a , R ¹ , R ² , Y, R ⁵ and R ⁶ generally have, preferably, particularly preferably, very particularly preferably, the meanings mentioned above for these radicals when description of the compounds of formula (I).
[101] The carbonyl halides or acids of formula (II) can be prepared by procedures similar to those described in Chem. Commun., 2008, 4207-4209 [102] The thiocarboxamides of the formula (lb), that is, carboxamides of the formula (I) in which T represents sulfur, are obtained when carboxamides of the formula (la) react with a thioning agent, optionally in the presence of a diluent and optionally in the presence of a catalytic, stoichiometric or higher amount of a base [Process (b)]:
(l * a) (Ib) [103] The compounds of the formula (lll-a) used as raw materials are prepared by known methods (Fragrance chemistry: the science of the sense of smell / published by Emst T. Theimer - Synthetic Benzenoid Musks by
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T. W. Wood; Chemistry-A European Journal, 8 (4), 853-858; 2002; Tetrahedron, 59 (37), 7389-7395; 2003; Journal of Medicinal Chemistry, 48 (1), 71-90; 2005; Bioorganic & Medicinal Chemistry Letters, 18 (6), 1830-1834; 2008; US 5 21 317, WO 2010/109301, EP315502A1) and can be obtained commercially or can be prepared by reacting bromides of the formula (lll-b) with compounds of the formula (IV) in the presence of a catalyst, optionally in the presence of a acid binder, in the presence of a diluent, followed by treatment with an appropriate acid [Process (c) J:
[104]
general definition of the bromides needed as starting materials to carry out Process (c) according to the invention. In this formula (lll-b), Q, R ^a , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ generally have, particularly preferably, very particularly preferably the meanings mentioned above for these radicals when describing the compounds of formula (I).
[105] In formula (IV), M represents hydrogen, C1-6 alkyl, C1-6 alkyloxy.
phenoxy, benzyloxy.
[106] The compounds of the formula (lll-b) used as raw materials are prepared by known methods (Fragrance chemistry: the science of the sense of smell / published by Emst T. Theimer - Synthetic Benzenoid Musks by TW Wood; Chemistry- -A European Journal, 8 (4), 853-858; 2002; Tetrahedron, 59 (37), 7389-7395; 2003; Journal of Medicinal Chemistry, 48 (1), 71-90; 2005; Bioorganic & Medicinal Chemistry Letters , 18 (6), 1830-1834; 2008; US 5,521,317, WO 2010/109301) or are commercially available.
[107] The diluents suitable for carrying out processes (a), (b) and (c) according to the invention are all inert organic solvents. Preferably,
17/116 include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decaline; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as ethyl ether, diisopropyl ether, methyl-t-butyl ether, methyl-t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisol; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide.N-methylpyrrolidone or hexamethylphosphoric triamide; mixtures with water or pure water.
[108] Process (a) according to the invention can possibly be carried out in the presence of a suitable acid acceptor when X ³ is halogen. Suitable acid acceptors are all common inorganic or organic bases. These preferably include alkali earth or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, lithium diisopropylamide, sodium methoxide, ethoxide sodium, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, Ν, Ν-dimethylbenzylamine, pyridine, Nmethylpiperidine, N-methylmorpholine, Ν, Ν-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonene (DBN) or diazabicyclone.
[109] Process (a) according to the invention is, if necessary, carried out in the presence of an appropriate coupling agent when X ³ is a hydroxyl. Suitable coupling agents are all the usual carbonyl activators. Preferably, they include N- [3- (dimethylamino) propyl] -N'-ethylcarbodiimide hydrochloride, N, N'-di-sec-butylcarbodiimide, Ν, Ν'-dicyclohexylcarbodiimide, N, N'diisopropylcarbodiimide, 1- metiodide (3- (dimethylamino) propyl) -3-
18/116 ethylcarbodiimide, 2-bromo-3-ethyl-4-methylthiazolium tetrafluoroborate, N, Nbis [2-oxo-3-oxazolidinyl] phosphorodiamide, chlorotripyrrolidinofosphonium hexafluorophosphate hexafluorophosphate hexafluorophosphate hexafluorophosphate hexafluorophosphate (1 H-benzotriazol-1-yloxy) tris (dimethylamino) phosphonium, O- (1 H-benzotriazol-1-yl) -N, N, Ν ', N'-tetramethyluronium,
O- (1 H-benzotriazol-1-yl) -N, N, Ν ', N'-bis (tetramethylene) uronium,
O- (1 H-benzotriazol-1-yl) -N, N, Ν ', N'-bis (tetramethylene) uronium, N tetrafluoroborate, N, N', N'-bis (tetramethylene) chloride, O hexafluorophosphate - (7-azabenzotriazol-1-yl) -N, N, N, N-tetramethyluronium and hydroxybenzotriazol-1. These reagent tetrafluoroborate can be used separately or in combination.
[110] In Process (a) according to the invention, reaction temperatures can be made to vary a relatively wide range. In general, the process is carried out at temperatures of 0 ° C to 150 ° C, preferably at temperatures of 20 ° C to 110 ° C.
[111] In Process (a) according to the invention, in order to prepare the compounds of the formula (la), in general 0.2 to 5 mol, preferably 0.5 to 2 mol of amine of formula (III) per mole of carbonyl halide or acid of formula (II). The process is carried out by the usual methods.
[112] For carrying out Process (b) according to the invention, in order to prepare the compounds of formula (lf), starting amide derivatives of formula (le) can be prepared according to Process (a) .
[113] Suitable thioning agents for carrying out Process (b) according to the invention may include sulfur (S), sulfuric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfide (NaHS), trisulfide boron (B2S3), bis (diethylaluminum) sulfide ((AIEt2) 2S), ammonium sulfide ((NH ^ S), phosphorus pentasulfide (P2S5), Lawesson's reagent (2,4-bis disulfide ( 4-methoxyphenyl) -1,2,3,4-dithiadiphosphethane) or a thionation reagent supported on a polymer as described in J. Chem. Soc. Perkin 1 2001, 358.
[114] The acids suitable for carrying out the treatment of process (c) can be chosen from the usual Bronsted acids, such as HCI,
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HzSCU, H3PO4, KHSO4, AcOH, TFA, PTSA, CSA, TEA · HCI, Pyridine · HCI.
[115] The catalysts suitable for carrying out the process (c) according to the invention can be chosen from salts and metal complexes. Metal derivatives suitable for this purpose are based on palladium or copper. Suitable metal salts or complexes for this purpose are palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride or 1,1'-bis (diphenylphosphino) ferrocenopalladium (ll) chloride, iodide copper, copper bromide, copper thiophenocarboxylate, copper trifluoromethanesulfonate, copper (I) oxide [116] It is also possible to generate a palladium complex in the reaction mixture by separately adding to the reaction a palladium salt and a binder or salt , such as a phosphine, for example, triethylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, 2 (dicyclohexylphosphine) biphenyl, 2- (di-tert-butylphosphine) biphenyl, 2- (dicyclohexylphosphine) -2 '(N, ) biphenyl, triphenylphosphine, tris- (o-tolyl) phosphine, 3 (diphenylphosphino) sodium benzolsulfonate, tris-2- (methoxyphenyl) phosphine, 2,2'-bis- (diphenylphosphine) -1,1 '-binaftyl, 1 , 4-bis- (diphenylphosphine) butane, 1,2-bis- (diphenylphosphine) ethane, 1,4-bis- (dicyclohexylphosphine) butane, 1,2-bi s- (dicyclohexylphosphine) ethane, 2 (dicyclohexylphosphine) -2 '- (N, N-dimethylamino) biphenyl, bis (diphenylphosphino) ferrocene, tris (2,4-tert-butylphenyl) phosphite, (R) - (-) - 1 - [(S) -2- (diphenylphosphino) ferrocenyl] etildi-tertbutylphosphine, (S) - (+) - 1 - [(R) -2- (diphenylphosphino) ferrocenyl] ethyldicyclohexylphosphine, (R) - (-) 1 - [(S) -2- (diphenylphosphino) ferrocenyl] ethyldicyclohexylphosphine, (S) - (+) - 1 - [(R) -2 (diphenylphosphino) ferrocenyljetildi-t-butylphosphine or 1,3-bis (2, 4,6-trimethylphenyl) imidazolium.
[117] It is also possible to generate a copper complex in the reaction mixture by separately adding to the reaction a copper salt and a binder or salt, such as a diamine, for example cyclohexyl-1,2-diamine, N, N ' -dimethylethylenediamine, cyclohexyl-NN-dimethylamine.
[118] It is also advantageous to choose the appropriate catalyst and / or binder from commercial catalogs such as “Metal Catalysts for Organic Synthesis by Strem Chemicals or“ Phosphorous Ligands and Compounds by Strem
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Chemicals.
[119] Suitable bases for carrying out the process (c) according to the invention are the usual inorganic and organic bases in such reactions. Preference is given to the use of alkaline earth metals, alkali metal hydrides, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxides, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, alkali metal acetates or alkaline earth metals, such as sodium acetate, acetate potassium, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, A /./ V-dimethylaniline, pyridine, / V-methylpiperidine, A /, / V-dimethylaminopyridine, 1,4-diazabicycles [ 2.2.2] octane (DABCO), 1,5-diazabicycles [4.3.0] non-5-ene (DBN) or 1,8-diazabicycles [5.4.0] undec-7-ene (DBU).
[120] Processes (a), (b) and (c) are generally carried out under atmospheric pressure. However, it is also possible to operate at high or low pressure - generally between 0.1 bare 100 bar.
[121] Composition / Formulation [122] The present invention also relates to a phytopharmaceutical composition for controlling unwanted microorganisms, especially unwanted fungi and bacteria, which composition comprises an effective and non-phytotoxic amount of the inventive active ingredients. These are preferably fungicidal compositions consisting of agriculturally suitable auxiliaries, solvents, carriers, surfactants or extenders [123] In the context of the present invention, "control of harmful microorganisms" means a reduction in infestation by harmful microorganisms compared to the untreated plant, measured as fungicidal efficacy, preferably a 25-50% reduction compared to the untreated plant
21/116 (100%), more preferably a 40-79% reduction compared to the untreated plant (100%); even more preferably, the infection by harmful microorganisms is completely suppressed (in 70-100%). The control can be curative, that is, to treat already infected plants, or protective, to protect plants that have not yet been infected.
[124] "An effective, but non-phytotoxic amount" means an amount of the composition of the invention that is sufficient to satisfactorily control fungal disease from the plant or to eradicate fungal disease completely, while simultaneously causing no significant symptoms of phytotoxicity . In general, this application rate can vary over a relatively wide range. It depends on several factors, for example the fungus to be controlled, the plant, the climatic conditions and the components of the inventive compositions.
[125] Appropriate organic solvents include all polar and support organic solvents normally used for formulation purposes. Preferably, the solvents are selected from ketones, for example methylisobutyl ketone and cyclohexanone, amides, for example dimethylformamide and alkanocarboxylic acid amides, for example Ν, Ν-dimethyldecanoamide and N, N-dimethyloctanamide, cyclic solvents, for example N-methylpyrrolidone, -dodecylpyrrolidone, N-octylcaprolactam, N-dodecylcaprolactam and butyrolactone, strongly polar solvents, for example dimethylsulfoxide and aromatic hydrocarbons, for example xylol, Solvesso ™, mineral oils, for example mineral turpentine, petroleum, aquilbenzenes and machine oil, are also esters. for example propylene glycol monomethyl ether acetate, adipic acid dibutyl ester, acetic acid hexyl ester, acetic acid heptyl ester, citric acid tri-n-butyl ester and di-n-butyl ester of phthalic acid, and also alcohols , for example benzyl alcohol and 1-methoxy-2-propanol.
[126] According to the invention, a carrier is a natural or synthetic substance, organic or inorganic, with which the active ingredients are mixed or combined for better applicability, especially for application
22/116 on plants or parts of plants or seeds. The carrier, which can be solid or liquid, is generally inert and must be suitable for agricultural use.
[127] Useful solid or liquid carriers include, for example, ammonium salts and natural rock powders, such as kaolin, clay, talc, chalk, quartz, atapulgite, montmorillonite or diatomaceous earth, and synthetic rock powders, such as such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils and their derivatives. Likewise, mixtures of these carriers can be used.
[128] Suitable solid extenders and carriers include inorganic particles, for example, carbonates, silicates, sulphates and oxides, with an average particle size of 0.005 to 20 pm, preferably 0.02 to 10 pm, for example ammonium sulphate , ammonium phosphate, urea, calcium carbonate, calcium sulfate, magnesium sulfate, magnesium oxide, aluminum oxide, silicon dioxide, the so-called fine particle silica, silica gels, natural or synthetic silicates, and aluminosilicates and vegetable products such as bran, wood / sawdust powder and cellulose powder.
[129] Solid carriers useful as granules include, for example, crushed and fractionated natural rocks, such as calcite, marble, pedrapomes, sepiolite, dolomite and synthetic granules of inorganic and organic bran, and also granules of organic materials such as sawdust, bark coconut, corn cobs and tobacco stalks.
[130] Useful liquefied gas extenders or carriers are those liquids that are gaseous under normal conditions of temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, but also butane, propane, nitrogen and carbon dioxide.
[131] In the formulations, it is possible to use adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powder, granules or latex, such as arabic gum, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins , and synthetic phospholipids.
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Other additives can be mineral and vegetable oils.
[132] If the extender used is water, one can also use, for example, organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatics like xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, like chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons like cyclohexane or paraffins, for example, mineral oil fractions, mineral and vegetable oils, alcohols like butanol or glycol and its ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and also water.
[133] Suitable surfactants (adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and adhesives) include all common ionic and nonionic substances, for example ethoxylated nonylphenols, linear or branched polyalkylene glycol ether, products of the reaction of alkyl phenols with ethylene oxide and / or propylene oxide, fatty acid amine reaction products with ethylene oxide and / or propylene oxide, in addition, fatty acid esters, alkylsulfonates, alkylsulfates, alkylsulfates, alkylethers phosphates, arylsulfates, ethoxylated arylalkylphenols, for example tristyrylphenol ethoxylates, in addition, ethoxylated and propoxylated arylalkylphenols such as sulfated or phosphated arylalkylphenols and ethoxy- and propoxylates. Other examples of natural and synthetic water-soluble polymers are lignosulfonates, gelatin, gum arabic, phospholipids, starch, hydrophobic modified starch and cellulose derivatives, in particular cellulose ester and cellulose ether, in addition, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid and (meth) acrylic acid co-polymerisers and (meth) acrylic acid esters, in addition, methacrylic acid co-polymerisers and methacrylic acid esters neutralized with alkali metal hydroxides, and also products condensation of naphthalenesulfonic acid salts optionally substituted with formaldehyde. The presence of a surfactant is necessary if one of the active ingredients and / or one of the
24/116 inert conveyors are insoluble in water and when the application is carried out in water. The proportion of surfactants is 5 to 40% by weight of the composition of the invention.
[134] It is possible to use dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, organic dyes such as alizarin dyes, azo dyes and metallophthalocyanine dyes, and oligonutrients such as iron, manganese, boron salts, copper, cobalt, molybdenum and zinc.
[135] Anti-foam agents that may be present in formulations include, for example, silicone emulsions, long-chain alcohols, fatty acids and their salts, as well as fluororganic substances and mixtures thereof.
[136] Examples of thickeners include polysaccharides, such as xanthan gum or Veegum, silicates, for example atapulgite, bentonite, as well as finely divided silica.
[137] If necessary, other components may also be present, for example, protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestrants and complexing agents. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
[138] The active ingredients or compositions of the invention can be used as such or, depending on their specific physical and / or chemical properties, in the form of formulations or forms of use prepared therefrom, such as aerosols, capsule suspensions , cold fogging concentrates, hot fogging concentrates, encapsulated granules, fine granules, loose concentrates for seed treatment, ready-to-use solutions, dustable powders, emulsion concentrates, oil-in-water emulsions, water-in-oil emulsions , macrogranules, microgranules, oil-dispersible powders, loose oil-miscible concentrates, oil-miscible liquids, gas (under pressure), gas-generating products, foams, pastes, pesticide-coated seeds, suspension concentrates,
25/116 concentrates for suspoemulsion, soluble concentrates, suspensions, wettable powders, soluble powders, powders and granules, water-soluble and water-dispersible granules or tablets, water-soluble and water-dispersible powders for the treatment of seeds, wettable powders, natural products and synthetic substances impregnated with the active ingredient, as well as microencapsulations in polymeric substances and in seed coating materials, as well as formulations of hot mist and cold mist of ultra low volume (UBV).
[139] The compositions of the invention include not only ready-to-use formulations that can be applied to the plant or seeds by means of a suitable device, but also commercial concentrates that must be diluted with water before use. Common applications are, for example, dilution in water and subsequent spraying of the resulting spray syrup, application after dilution in oil, direct application without dilution, seed treatment or application of granules to the soil.
[140] The compositions and formulations of the present invention generally contain from 0.05 to 99% by weight, from 0.01 to 98% by weight, preferably from 0.1 to 95% by weight, more preferably from 0 , 5 to 90% by weight, more preferably 10 to 70% by weight of the active ingredient. For special applications, for example in the protection of wood and wood products, inventive compositions and formulations generally contain from 0.0001% to 95% by weight, preferably from 0.001 to 60% by weight of the active ingredient.
[141] The active ingredient content in the application forms prepared from the formulations can vary over a wide range. The concentration of the active ingredients in the application forms is generally from 0.000001 to 95% by weight, preferably from 0.0001 to 2% by weight.
[142] The above formulations can be prepared in a known manner, for example, by mixing the active ingredients with at least one extender, solvent or diluent, adjuvant, emulsifier, dispersant, and / or binder or fixative,
26/116 humectant, water repellent, if necessary desiccants and UV stabilizers and, if necessary, dyes and pigments, antifoaming agents, preservatives, organic and inorganic thickeners, adhesives, gibberellins, other processing aids and also water. Depending on the type of formulation, additional processing steps may be necessary, for example wet milling, dry milling and granulation.
[143] The active ingredients of the invention can be present by themselves or in their (commercial) formulations and in the forms of use prepared from these formulations, in the form of a mixture with other (known) active ingredients, such as insecticides, attractive , sterilizers, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, phytotoxicity and / or semi-chemical protectors.
[144] The inventive treatment of plants and plant parts with the active ingredients or compositions is carried out directly or by action in their proximity, habitat or storage space, by the usual methods of treatment, for example immersion, spraying, atomization, irrigation, evaporation, dusting, misting, broadcasting, foam, painting, spreading, watering (drenching), drip irrigation and, in the case of propagating material, especially in the case of seeds, also by dry treatment of seeds, wet treatment of seeds, treatment of suspensions, inlay, coating with one or more layers, etc. It is also possible to apply the active ingredients by the ultra low volume method or by injection into the soil of a preparation of the active ingredient or the active ingredient itself.
[145] Plant / Crop Protection [146] The active ingredients or compositions of the invention have a potent microbicidal activity and can be used to control unwanted microorganisms, such as fungi and bacteria, in the field of crop and material protection.
[147] The invention also relates to a method for controlling unwanted microorganisms, characterized by the inventive active ingredients
27/116 be applied to phytopathogenic fungi, phytopathogenic bacteria and / or in their habitat.
[148] To control phytopathogenic fungi and protect crops, fungicides can be used. These are characterized by an excellent efficacy against a wide spectrum of phytopathogenic fungi, including soil pathogens, in particular elements of the classes Plasmodiophoromycetes, Peronosporomycetes (syn .: Oomycetes),
Chytrídiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (sin .: Fungi imperfecti). Some fungicides are systemically active and can be used to protect plants as foliar fungicides, seed treatment or soil. In addition, they are suitable for combating infesting fungi of, in particular, wood or plant roots.
[149] Bactericides can be used to protect crops, to control Pseudomonadaceae, Rhizobiaceae, Enterobacteríaceae, Corynebacteríaceae and Streptomycetaceae.
[150] Non-limiting examples of pathogens for fungal diseases that can be treated according to the invention include:
[151] diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumería graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; species of Uncinula, for example Uncinula necator, [152] diseases caused by pathogens of rust disease, for example species of Gymnosporangium, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatríx; Phacospsora species, for example Phacopsora pachyrhizi and Phacopsora meibomiae; Puccinia species, for example Puccinia recondite, P. triticina, P. graminis or P. striiformis; Uromyces species, for example Uromyces appendiculatus;
[153] diseases caused by pathogens in the Oomycetes group, for example Albugo species, for example Albugo candida; Bremia species, for example Bremia latucae; Peronospora species, for example
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Peronospora pisi or P. brassicae; Phytophtora species, for example Phytophtora infestans ', Plasmopara species, for example Plasmopara viticola-, Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis', Pythium species, for example Pythium ultimum;
[154] leaf spot diseases and leaf wilt diseases caused, for example, by Alternaria species, such as Alternaria solani; species of Cercospora, for example Cercospora beticola ', species of Cladiosporium, for example Cladiosporium cucumerinum; species of Cochliobolus, for example Cochliobolus sativus (conidia form; Drechslera, sin .; Helminthosporium), Cochliobolus miiabeanus; Colletotrichum species, for example Colletotrichum lindemuthianum ·, Cycloconium species, for example Cycloconium oleaginunr, Diaporthe species, for example Diaporthe citri; species of Elsinoe, for example Elsinoe fawcettir, species of Gloeosporium, for example Gloeosporium laeticolor, species of Glomerella, for * example Glomerella cingulata-, species of Guignardia, for example Guignardia bidwellir, species of Leptosphaeria, for example Leptosphaería maculans and Leptha; Magnaporthe species, for example Magnaporthe grisea; Microdochium species, for example Microdochium nivale; Mycosphaerella species, for example Mycosphaerella gramnicola, M. arachidicola and M. fijiensis ', Phaeosphaeria species, for example Phaeosphaeria nodorum, Pyrenophora species, for example Pyrenophora teres, Pyrenophora tritici repentis', Ramularia collo- cygni, Ramularia areola ', Rhynchosporium species, for example Rhynchosporium secalis; Septoria species, for example Septoria apii, Septoria lycopersii; Typhula species, for example Typhula incamata; Venturia species, for example Venturia inaequalis', [155] root and stem diseases caused, for example, by Corticium species, for example Corticium graminaarunr, Fusarium species, for example Fusarium oxysporunr, Gaeumannomyces species, for example
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Gaeumannomyces graminis; Rhizoctonia species, for example Rhizoctonia solani; Sarocladium diseases caused, for example, by Sarocladium oryzae; Sclerotium diseases caused, for example, by Sclerotium oryzae; Tapesia species, for example Tapesia acuformis; Thielaviopsis species, for example Thielaviopsis basicola;
[156] diseases of the ear and panicle (including ears of corn) caused, for example by Alternaria species, for example Alternaria spp .; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladiosporíum cladosporioides; species of Claviceps, for example Claviceps purpurea; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Monographella species, for example Monographella nivalis; Septoria species, for example Septoria nodorum;
[157] diseases caused by coal fungus, for example Sphacelotheca species, for example Sphacelotheca reiliana; Tilletia species, for example Tilletia caries, T. controversa; Urocystis species, for example Urocystis occulta; Ustilago species, for example Ustilago nuda, U. nuda tritici;
[158] fruit rot diseases caused, for example, by Aspergillus species, for example Aspergillus flavus; Botrytis species, for example Botrytis cinerea; Penicillium species, for example Penicillium expansum and Penicillium purpurogenum; Sclerotinia species, for example Sclerotinia sclerotiorum; Verticillium species, for example Verticillium alboatrum;
[159] diseases of decomposition, mold, wilting, rotting and seedling rot originating from seeds and soil caused, for example, by species of Alternaria, for example Alternaria brassicicola; Aphanomyces species, for example Aphanomyces euteiches; Ascochyta species, for example Ascochyta lentis; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium herbarum; Cochliobolus species, for example Cochliobolus sativus; (form of conidia: Drechslera,
11/30
Bipolaris sin .: Helminthosporium); Colletotrichum species, for example Colletotrichum coccodes; Fusarium species, for example Fusarium culmorurrr, Gibberella species, for example Gibberella zeae ', Macrophomina species, for example Macrophomina phaseolina', Monographella species, for example Monographella nivalis', Penicillium species, for example Penicillium expansunr, species of Phoma, for example Phoma lingarrr, Phomopsis species, for example Phomopsisoyae; Phitofthora species, for example Phitofthora cactorurrr, Pyrenophora species, for example Pyrenophora graminea; Pyricularia species, for example Pyrícularía oryzae; Pythium species, for example Pythium ultimum; Rhizoctonia species, for example Rhizoctonia solani; Rhizopus species, for example Rhizopus oryzae ', Sclerotium species, for example Sclerotium rolfsii; Septoría species, for example Septoría nodorum; Typhula species, for example Typhula incamata; Verticillium species, for example Verticillium dahliae;
[160] diseases of cancer, galls and witches' broom caused, for example, by species of Nectria, for example Nectría galligena;
[161] wilting diseases caused, for example, by species of Monilinia, for example Monilinia laxa;
[162] leaf blistering or rolling diseases caused, for example, by Exobasidium species, for example Exobasidium vexans; Taphrina species, for example Taphrina deformans;
[163] woody plant decline diseases caused, for example, by esca, for example Phaeomoniella clamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterrânea ', eutypiosis caused by, for example, Eutypa lata', Ganoderma diseases caused, for example, by Ganoderma boninense ; Rigidoporus diseases caused, for example, by Rigidoporus lignosus [164] diseases of flowers and seeds caused, for example, by Botrytis species, for example Botrytis cinerea;
[165] tuber diseases caused, for example, by Rhizoctonia species, for example Rhizoctonia solanr, Helminthosporium species, by
11/31 example Helminthosporíum solani;
[166] cabbage colt diseases caused, for example, by species of Plasmodiophora, for example Plamodiophora brassicae.
[167] diseases caused by bacterial pathogens, for example, by Xanthomonas species, for example Xanthomonas campestrís pv. oryzae Pseudomonas species, for example Pseudomonas syríngae pv. Iachrymans species of Erwinia, for example Erwinia amylovora.
[168] Preferably, the following soy diseases are controlled:
[169] Fungal diseases of leaves, stems, pods and seeds, for example, leaf spot by alternariosis (Alternaria spec. Atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. Truncatum), brown spot (Septoría glycines), spot and burned leaf spot by cercosporosis (Cercospora kikuchii), leaf burn by Choanephora (Choanephora infundibulifera trispora (sin.)), leaf spot by Dactuliophora (Dactuliophora gyicines), downy mildew (Peronospora manshurica), burnt by Drechslera (eye-leaf), Drechslera (leaf) frog (Cercospora sojina), leaf spot by Leptosphaerulina (Leptosphaerulina trifoli), leaf spot by Phyllosticta (Phyillostictaoyaecola), burnt pod and stem (Phomopsis soye), powdery mildew (Microsphaera diffusa), leaf spot by Pyrenochaeta (Pyrenochaeta), Pyrenochaeta (Pyrenochaeta), Pyrenochaeta (Pyrenochaeta), Pyrenochaeta (Pyrenochaeta), Pyrenochaeta (Pyrenochaeta), Pyrenochaeta (Pyrenochaeta), burning of aerial parts, foliage and mycelia web by rhizoctonia (Rhizoctonia solani), rust (Phacospora pachyrhizi, Phacopsora meibomiae), stoned (Sphacel oma gyicines), leaf burning by Stemphylium (Stemphylium botryosum), manchaalvo (Corynespora cassiicola).
[170] Fungal diseases of the root and base of the stem, for example, black root rot (Calonactría crotalariae), coal rot (Macrophomina phaseolina), burned or withered, root rot and pod and colon rot by Fusarium (Fusarium oxysporum, Fusarium Orthoceras Fusaríum semitectum, Fusarium equiseti), root rot by Mycoleptodiscus (Mycoleptodiscus terrestrís), Neocosmospora (Neocosmopspora vasinfeta), burnt pod and stem (Diaporthe phaseolorum), stem cancer (Diaporthe
32/116 phaseolorum var. caulivora), phytophora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pitium rot (Phythium aphanidermatum, Pythium irregulare, Phythium debaryanum, Phythium myríotylum, root disease, Phythium ultimurri seedlings by rhizoctonia (Rhizoctonia solani), decomposition of the stem by sclerotin (Sclerotinia sclerotiorum), burned (Southem blighf) by sclerotin (Sclerotinia rolfsii), root rot by Tielaviopsis (Tielaviopsis basicola).
[171] The fungicidal compositions of the invention can be used as curative or protective / preventive control of phytopathogenic fungi. The invention, therefore, also relates to curative and protective methods to control phytopathogenic fungi through the use of the active ingredients or compositions of the invention, which are applied to the seed, plant or parts of the plant, and to the fruit or soil in which the plants grow.
[172] The fact that the active ingredients are well tolerated by plants at the concentrations necessary to control their diseases allows treatment of plant parts above ground, propagating material and seeds, and soil.
[173] According to the invention, all plants and parts of plants can be treated. By plants, we mean all plants and plant populations, such as desirable and undesirable wild plants, cultivars and plant varieties (subject to protection of the plant variety or breeder's right). Plant cultivars and varieties can be obtained by conventional propagation and assisted reproduction methods or complemented by one or more biotechnological methods, such as doublehaploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers, or bioengineering and bioengineering methods. genetic engineering. Plant parts are understood to mean all parts above ground and below ground, as well as plant organs, such as shoots, leaves, flowers and roots, examples of which are leaves, needles, stems, branches, flowers, fruit bodies ,
33/116 fruits and seeds, as well as roots, tubers and rhizomes. Plant parts also include crops and material for vegetative and generative propagation, for example, seedlings, tubers, rhizomes, cuttings and seeds.
[174] When the active ingredients of the invention are well tolerated by plants and, in addition, have a toxicity favorable to homeothermia and good tolerance to the environment, then they are appropriate to protect plants and plant organs, as well as to improve crop yields and the quality of the material collected. Preferably, they are used as phytopharmaceutical compositions. They are active against normally sensitive and resistant species in all or some stages of development.
[175] Plants that can be treated according to the invention include plants from the following main crops: corn, soy, alfalfa, cotton, sunflower, Brassica oil seeds like Brassica napus (for example canola, rapeseed), Brassica rapa, B. juncea (for example, brown mustard) and Brassica carinata, Arecaceae sp. (eg palm oil, coconut), rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet and sorghum, triticale, flax, nuts, grapes and vines, various fruits and vegetables of various botanical taxa, for example Rosaceae sp. (for example fruits of pome trees, such as apples and pears, but also stone fruits such as apricots, cherries, almonds, plums and peaches and berries such as strawberries, raspberries, red and black currants and gooseberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp. (e.g. olive), Actinidaceae sp., Lauraceae sp. (for example avocado, cinnamon, camphor), Musaceae sp. (for example, banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp. (for example tea), Sterculiceae sp., Rutaceae sp. (for example, lemons, oranges, tangerines and grapefruits), Solanaceae sp. (for example, tomatoes, potatoes, peppers, capsicum, eggplants, tobacco), Liliaceae sp., Compositae sp. (for example, lettuce, artichoke and chicory - including chicory root, endive or common chicory), Umbelliferae sp. (for example, carrots, parsley, celery and celeriac), Cucurbitaceae sp. (for example,
34/116 cucumbers - including itches, pumpkins, watermelons, gourds and melons), Alliaceae sp. (for example leek and onion), Cruciferae sp. (for example, white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, couverábano, radishes, horseradish, watercress and Chinese cabbage), Leguminosae sp. (for example, peanuts, peas, lentils and beans - for example common beans and broad beans), Chenopodiaceae sp. (for example, chard, fodder beet, spinach, beet), Linaceae sp. (for example, hemp), Cannabeacea sp. (for example, cannabis), Malvaceae sp. (for example, okra, cocoa), Papaveraceae (for example, poppy), Asparagaceae (for example, asparagus); useful plants and ornamental plants from the garden and forest, including grass, lawn, grass and Stevia rebaudiana; and, in each case, the genetically modified types of these plants.
[176] Resistance / Phytosanitary induction and other effects [177] The active compounds according to the invention also have a potent plant strengthening effect. Therefore, they can be used to mobilize the plant's defenses against attack by unwanted microorganisms.
[178] Plant-strengthening substances (resistance induction) should be understood in the present context as those substances capable of stimulating the plant's defense system in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants exhibit a high degree of resistance to these microorganisms.
[179] The active compounds according to the invention are also suitable for increasing crop yields. In addition, they have reduced toxicity and are well tolerated by plants.
[180] Furthermore, in the context of the present invention, the effects on plant physiology are as follows:
[181] tolerance to abiotic stress, including temperature tolerance, drought tolerance and recovery after drought exposure, water use efficiency (corresponding to a reduction in water consumption), flood tolerance, ozone tolerance and UV rays, tolerance to chemicals such
35/116 as heavy metals, salts, pesticides (phytotoxicity protector), etc .;
[182] tolerance to biotic stress, including increased resistance to fungi, nematodes, viruses and bacteria. In the context of the present invention, tolerance to biotic stress preferably comprises increased resistance to fungi and increased resistance to nematodes.
[183] increased plant vigor, namely plant health / quality and seed vigor, reduced planting risk, improved appearance, improved recovery, improved greening effect and improved photosynthetic efficiency;
[184] effects on plant hormones and / or functional enzymes;
[185] effects on growth regulators (promoters), including early germination, better emergence, more developed root system and / or improved root growth, increased tillering capacity, more productive tillers, early flowering, height increase and / or plant biomass, shortening of the stems, improvement in shoot growth, number of grains / ear, number of ears / m ² , number of stolons and / or number of flowers, higher harvest rate, larger leaves, less dead leaves in the base, improved phyllotaxis, early ripening / early finishing of the fruit, homogeneous ripening, prolonged grain filling, better finishing of the fruit, larger fruit / vegetable size, resistance to germination and reduced litter;
[186] higher yield, based on total biomass per hectare, yield per hectare, grain / fruit weight, seed size and / or weight per hectolitre, as well as better product quality, comprising:
[187] better processability due to size distribution (grain, fruit, etc.), homogeneous ripening, grain moisture, better grinding, better vinification, better brewing, greater juice yield, ease of harvest, digestibility, index of sedimentation, fall time, pod stability, storage stability, improvement in fiber length / strength / uniformity, improvement in milk quality and / or
36/116 of the meat of animals fed with silage, suitability for cooking and frying;
[188] including easier marketing due to improved fruit / grain quality, size distribution (grains, fruit, etc.), longer shelf life / shelf life, firmness / softness, flavor (aroma, texture, etc. ), class (size, shape, number of berries, etc.), number of berries / fruits per bunch, crunchy texture, freshness, covering with wax, frequency of physiological disorders, color, etc .;
[189] further comprising the increase in desired components such as, for example, protein content, fatty acids, oil content, oil quality, amino acid composition, sugar content, acidity (pH) content, sugar / sugar ratio acid (Brix), polyphenols, starch content, nutritional quality, gluten content / index, energy content, flavor, etc .;
[190] and further comprising the reduction of unwanted components such as, for example, less mycotoxins, less aflatoxins, geosmin level, phenolic flavors, lactase, polyphenol oxidases and peroxidases, nitrate content, etc.
[191] sustainable agriculture, including nutrient utilization efficiency, especially nitrogen utilization efficiency (N), phosphorus utilization efficiency (P), water utilization efficiency, better transpiration, better breathing and / or better assimilation rate CO2, better nodulation, improved Ca metabolism, etc .;
[192] delayed senescence, comprising improvement in plant physiology, which is manifested, for example, by a phase of filling the grain of longer duration leading to a higher yield, longer coloration of the green leaves of the plant and, as such, comprising color (greening), water content, dryness, etc. In this sense, in the context of the present invention, it was found that the specific inventive application of the combination of active compounds makes it possible to prolong the duration of the green leaf area, delaying the maturation (senescence) of the plant. The main advantage for the farmer is a prolonged grain filling phase, leading to greater yield. There are also
37/116 for the farmer the advantage of greater flexibility in harvest time.
[193] Here, "sedimentation index" is a measure of protein quality and describes, according to Zeleny (Zeleny value), the degree of sedimentation of flour suspended in a lactic acid solution during a standard time interval. This is taken as a measure of the quality of cooking. The expansion of the gluten fraction of the flour in the lactic acid solution affects the settling speed of a flour suspension. Both a higher content and a better quality of gluten result in slower sedimentation and higher Zeleny test values. The sedimentation index of the flour depends on the composition of the wheat protein and is correlated mainly with the protein content, the wheat hardness and the volume of artisan breads. A strong correlation between bread volume and Zeleny's sedimentation volume compared to the SDS sedimentation volume may be due to the protein content, which influences Zeleny's volume and value (Czech J. Food Sei. Vol. 21 , no. 3: 91-96, 2000).
[194] Furthermore, the "fall time" as referred to here is a measure of the cooking quality of cereals, especially wheat. The drop time test indicates that damage to the shoots may have occurred. This means that changes have already occurred in the physical properties of the starch in the wheat seed. Here, the drop time instrument analyzes viscosity by measuring the resistance of a dough and water to a falling plunger. The time (in seconds) for this to happen is known as the down time. The fall time results are recorded as an index of the enzymatic activity of a sample of wheat or flour and are expressed in seconds. A high fall time (for example, greater than 300 seconds) indicates minimal enzymatic activity and good quality of wheat or flour. A low fall time (for example, less than 250 seconds) indicates substantial enzymatic activity and wheat or flour from damaged sprouts.
[195] The term "more developed root system" / "improved root growth" refers to a longer root system, more growth
38/116 deep root, faster root growth, higher dry root / fresh root weight ratio, greater root volume, greater root surface area, greater root diameter, greater root stability, more root branching, greater number of root hairs, and / or more root ends, and can be measured by analyzing the root architecture using appropriate methodologies and image analysis programs (for example, WinRhizo).
[196] The term "water use efficiency by culture" refers, from a technical point of view, to the mass of agricultural product per unit of water consumed and, from an economic point of view, to the value of the product (s ) produced per unit volume of water consumed, and can be expressed, for example, in terms of yield per ha, plant biomass, mass of a thousand seeds and the number of ears per m ² .
[197] The term 'nitrogen utilization efficiency' from a technical point of view refers to the mass of agricultural product produced per unit of nitrogen consumed and, economically speaking, to the value of the product (s) produced by nitrogen unit consumed, reflecting absorption and utilization efficiency.
[198] Improvements in greening / color and photosynthetic efficiency, as well as delay in senescence, can be assessed by well-known techniques, such as a HandyPea (Hansatech) system. Fv / Fm is a widely used parameter, which indicates the maximum quantum efficiency of photosystem II (FSII). This parameter is considered a selective indication of the photosynthetic performance of the plants, with healthy samples normally reaching a maximum Fv / Fm value of approximately 0.85. Lower values are observed if the sample has been exposed to some type of biotic or abiotic stress factor, which has reduced its photochemical energy absorption capacity in the FSII. Fv / Fm is presented as the ratio between the variable fluorescence (Fv) and the maximum fluorescence value (Fm). The performance index is essentially an indicator of the sample's vitality. (See, for example Advanced Techniques in Soíl Microbiology, 2007, 11, 319-341; Applied Soíl Ecology, 2000, 15, 169-182.) [199] Improvements in greening / color and photosynthetic efficiency, as well
39/116, such as senescence delay, can also be assessed by measuring the liquid photosynthetic rate (Pn), measuring the chlorophyll content, for example, by using the Ziegler and Ehle pigment extraction method, measuring the photochemical efficiency (Fv ratio / Fm), determination of shoot growth and final root and / or crown biomass, determination of tiller density, as well as root mortality.
[200] Within the scope of the present invention, preference is given to improving the effects on the physiology of plants selected from the group of: improved root growth / more developed root system, improvement in greening, greater water use efficiency (corresponding to water consumption reduced water), greater efficiency in the use of nutrients, especially comprising greater efficiency in the use of nitrogen (N), delayed senescence and greater yield.
[201] With regard to the increase in yield, preference is given to an improvement in the sedimentation index and fall time, as well as an improvement in the protein and sugar content - especially in plants selected from the cereal group (preferably , wheat).
[202] Preferably, the new use of the fungicidal compositions of the present invention refers to a combined use for a) preventive and / or curative control of fungi and / or pathogenic nematodes, with or without resistance management and b) at least one between improved root growth, improved greening, greater water use efficiency, delayed senescence and increased yield. In group b), improvement of the root system, efficiency of water use and use of N are particularly preferred [203] Seed treatment [204] The invention further comprises a method of seed treatment.
[205] The invention also relates to seeds that have been treated by one of the methods previously described. The seeds of the invention are used in methods of protecting seeds against unwanted microorganisms. In these methods, seeds treated with at least one active ingredient of
40/116 invention.
[206] The active ingredients or compositions of the invention are also suitable for seed treatment. A large part of the damage caused to crops by harmful organisms is triggered by infection of the seeds during storage or after sowing, and also during and after the germination of the plant. This stage is particularly important, since the roots and shoots of the growing plant are especially sensitive, and even minor damage can result in the death of the plant. As such, there is a great interest in protecting the seed and the germinating plant with suitable compositions.
[207] The control of phytopathogenic fungi through seed treatment has been known for a long time and has been the subject of constant improvements. However, seed treatment involves a number of problems that cannot always be satisfactorily solved. For example, it is desirable to develop methods of protecting seeds and germinating plants that dispense with, or at least significantly reduce, the additional use of plant protection compositions after planting or after plant emergence. It is also desirable to optimize the amount of active ingredient used, in order to offer the best possible protection to the seed and the germinating plant against attack by phytopathogenic fungi, without damaging the plant itself with the active ingredient used. In particular, seed treatment methods must also take into account the intrinsic fungicidal properties of transgenic plants, in order to ensure optimum protection of the seed and the germinating plant with a minimum of cost in plant protection compositions.
[208] The present invention, therefore, also relates to a method of protecting seeds and germinating plants against attack by phytopathogenic fungi, by treating the seeds with an inventive composition. Likewise, the invention relates to the use of inventive compositions in the treatment of seeds to protect the seed and the germinating plant against phytopathogenic fungi. The invention also relates to seeds that have been
41/116 treated with an inventive composition to protect against phytopathogenic fungi.
[209] The control of phytopathogenic fungi that damage postemergence plants is mainly carried out by treating the soil and plant parts at / above ground with plant protection compositions. Bearing in mind the concern with a possible impact of plant protection compositions on the environment and on the health of humans and animals, efforts have been made to reduce the amount of active ingredients applied.
[210] One of the advantages of the present invention is due to the fact that, due to the specific systemic properties of the active ingredients and compositions of the invention, the treatment of seeds with these active principles and compositions not only protects the seed itself against phytopathogenic fungi , but also post-emergence plants. In this way, immediate treatment of the crop at the moment of sowing, or immediately afterwards, can be dispensed with.
[211] It is also considered advantageous that the active ingredients or compositions of the invention can be used especially with transgenic seeds, in which the plant that grows from this seed expresses a protein that acts against infestations. When treating seeds with the active ingredients or compositions of the invention, certain infestations can be controlled by the simple expression of a protein, for example, an insecticidal protein. Surprisingly, an additional synergistic effect can be seen here, which further increases the effectiveness of protection against infestation attack.
[212] The compositions according to the invention are suitable for protecting the seeds of any plant variety used in agriculture, in greenhouses, in forests or in horticulture or viticulture. These are, in particular, cereal seeds (such as wheat, barley, rye, triticale, sorghum / millet and oats), corn, cotton, soybeans, rice, potatoes, sunflower, beans, coffee, beets (for example, sugar beet and fodder beet), peanut, rapeseed, poppy, olive,
42/116 coconut, cocoa, sugar cane, tobacco, vegetables (such as tomatoes, cucumbers, onions and lettuce), grass and ornamental plants (see also below). The treatment of cereal seeds (such as wheat, barley, rye, triticale and oats), corn and rice is of special importance.
[213] As also described below, the treatment of transgenic seeds with the mixtures or compositions of the invention is of special importance. This concerns plant seeds that carry at least one heterologous gene. The definition and examples of suitable heterologous genes are given below.
[214] In the context of the present invention, the composition of the invention is applied by itself to the seed or in a suitable formulation. Preferably, the seed to be treated is in a sufficiently stable state to not be damaged during treatment. In general, the seed can be treated at any time between harvest and sowing. Usually, the seed used is separated from the plant and released from the cores, shells, stems, coverings, coat or pulp of the fruits. Thus, it is possible to use, for example, seeds that have been harvested, cleaned and dried to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seeds that, after drying, have been treated, for example, with water, and dried again.
[215] When treating seeds, care should generally be taken to ensure that the amount of inventive composition applied to the seed, and / or the amount of other additives, is chosen so as not to affect seed germination or not to damage the plant that will result. This must be taken into account especially in the case of active ingredients that may have phytotoxic effects at certain rates of application.
[216] The compositions of the invention can be applied directly, that is, without including other components and without prior dilution. In general, it is preferable to apply the compositions to the seeds in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in
43/116 following documents: US 4,272,417, US 4,245,432, US 4,808,430, US 5,876,739, US 2003/0176428 A1, WO 2002/080675 and WO 2002/028186.
[217] The active ingredients used according to the invention can be converted into the usual seed treatment formulations, such as solutions, emulsions, suspensions, powders, foams, pastes or other seed treatment compositions, as well as ultra volume formulations low.
[218] These formulations are prepared in a known manner, by mixing the active ingredients with the usual additives, such as, for example, extenders, solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoaming agents, preservatives, secondary thickeners, adherents , gibberellins and also water.
[219] Suitable dyes that may be present in seed treatment formulations used according to the invention include all the usual dyes for such purposes. Both water-soluble pigments and water-soluble dyes can be used. Examples that can be mentioned include the dyes known under the designations of Rhodamine B, C.l. Red Pigment 112eC.I. Red Solvent 1.
[220] Useful wetting agents that may be present in seed treatment formulations used in accordance with the invention include all substances that promote wetting, which are conventionally used in the formulation of active agrochemicals. Preference is given to the use of alkyl naphthalenesulfonates, such as diisopropyl or diisobutyl naphthalenesulfonates.
[221] Useful dispersants and / or emulsifiers that may be present in seed treatment formulations used according to the invention include all nonionic, anionic and cationic dispersants used conventionally in the formulation of active agrochemicals. Preferably, nonionic or anionic dispersants, or mixtures of nonionic or anionic dispersants are used. Suitable non-ionic dispersants are block polymers of ethylene oxide-propylene oxide, ethers
44/116 alkylphenol polyglycolic and tristyrylphenol polyglycolic ethers and their phosphated or sulfated derivatives. Especially suitable anionic dispersants are lignosulfonates, polyacrylic acid salts and arylsulfonatoformaldehyde condensates.
[222] The antifoam agents that may be present in the seed treatment formulations used according to the invention include all foam-inhibiting substances that are common in the formulation of active agrochemicals. Preference is given to the use of silicone defoaming agents and magnesium stearate.
[223] The preservatives that may be present in the seed treatment formulations used in accordance with the invention are all substances used for the same purposes in agrochemical compositions. For example, dichlorophene and benziform hemiformal may be mentioned.
[224] The secondary thickeners that may be present in the seed treatment formulations used according to the invention are all substances that can be used for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clays and finely divided silica.
[225] Adhesive agents that may be present in seed treatment formulations used according to the invention include all of the usual binders used in seed treatment products. Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose can be mentioned as preferred examples.
[226] The gibberellins which may be present in the seed treatment formulations used according to the invention are preferably the gibberellins Α1, A3 (= gibberellic acid), A4 and A7; special preference is given to gibberellic acid. Gibberellins are well known (see R. Wegler “Chemie der Pflanzenschutz- und Schãdlingsbekâmpfungsmittef '[The Chemistry of Plant Protection and Pesticide Compositions], Vol. 2, Springer Verlag, 1970, pp. 401-412).
45/116 [227] Seed treatment formulations that can be used according to the invention can be used directly or after previous dilution with water, for the treatment of a wide range of different seeds, including the seeds of transgenic plants. In this case, synergistic effects may also occur in the interaction with the substances formed by expression.
[228] To treat seeds with the seed treatment formulations used according to the invention, or with the preparations obtained therefrom by adding water, all mixing units normally used for seed treatment purposes are useful. Concretely, the procedure adopted during the treatment consists of introducing the seeds in a mixer, adding the specific amount of seed treatment formulation required alone or previously diluted with water, and mixing until the formulation is evenly distributed over the seed. Optionally, it is followed by a drying operation.
[229] Mycotoxins [230] Furthermore, the treatment according to the invention can reduce the content of mycotoxins in the material collected and in the food prepared from it. Especially, but not exclusively, mycotoxins include: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, toxins T2 and HT2, fumonisins, zearalenone, moniliformine, fusarin, diaceotoxiscirpenol (DAS), beauvericin, eniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins caused, for example, by the following fungi: Fusarium species such as F. acuminatum, F. asiaticum, F. avenaceum,
F. crookwellense, F. culmorum, F. graminearum (Gibberella zeae), F. equiseti, F. fujicoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotríchoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides etc., and also Aspergillus species such as A. flavus, A. parasiticus, A. nomius , A. ochraceus, A. clavatus, A. terreus, A. versicolor, species of
46/116
Penicillium, such as P. verrucosum, P. virídicatum, P. citrínum, P. expansum, P. claviforme, P. roqueforti, Claviceps species, such as C. purpurea, C. fusiformis, C. paspali, C. africana, species of Stachybotrys, and others.
[231] Protection of Materials [232] The active ingredients or compositions of the invention can also be used in the protection of materials, to protect industrial materials from attack and destruction by harmful microorganisms, for example fungi and insects.
[233] In addition, the active ingredients or compositions of the invention can be used as anti-fouling compositions, either alone or in combinations with other active ingredients.
[234] Industrial materials in the current context are inanimate materials that have been prepared for use in industry. Industrial materials that need to be protected by the active principles of the invention against alteration or destruction by microbes are, for example, adhesives, glues, paper, wallpaper and cardboard / cardboard, textiles, carpets, leather, wood, fibers and fabrics , paints and plastic articles, cooling lubricants and other materials that can be infected or destroyed by microorganisms. Parts of factories and buildings, for example, water cooling circuits, cooling and heating systems, and ventilation and air conditioning units, which can be harmed by the proliferation of microorganisms, are also part of the materials that need protection. Industrial materials within the scope of the present invention preferably include adhesives, sealants, paper and board, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.
The. The active ingredients or compositions of the invention can prevent adverse effects, such as rotting, decomposition, discoloration, or mold formation.
[235] In the case of wood treatment, the compounds / compositions according to the invention can also be used against fungal diseases susceptible to growing on the surface or inside the wood. The term «wood»
47/116 means all types of wood species and all types of wood products intended for construction, for example, solid wood, high density wood, laminated and plywood. The method for treating the wood according to the invention consists mainly of contacting it with one or more compounds according to the invention, or a composition according to the invention; this includes, for example, direct application, spraying, dipping, injection or any other suitable means.
[236] In addition, the compounds of the invention can be used to protect objects that come into contact with salt or brackish water, especially hulls, screens, nets, buildings, anchorages and signaling systems, against vegetative growth.
[237] The method according to the invention can also be used to protect stored goods. Stored goods are understood to mean natural substances, of vegetable or animal origin, or their processed products of natural origin, for which long-term protection is desired. Stored goods of plant origin, such as plants or parts of plants, for example, stems, leaves, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or after processing by (pre) drying, wetting, fragmentation, grinding, pressing or roasting. Stored goods also include wood, either in unprocessed form, such as construction wood, electricity poles and barriers, or in the form of finished items, such as furniture. Stored goods of animal origin consist of, for example, furs, leather, fur with fur, and fur. The active ingredients of the invention can prevent adverse effects, such as rotting, decomposition, discoloration or mold formation.
[238] Microorganisms capable of degrading or altering industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms. The active ingredients of the invention preferably act against fungi, especially molds, wood decolorizing fungi and wood destroying fungi (Ascomycetes, Basidiomycetes, Deuteromycetes and
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Zygomycetes), and against slime and algae organisms. Examples include organisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosurrr, Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucurrr, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans ', Sclerophoma, such as Sclerophoma pityophila-, Trichoderma, such as Trichoderma viride', Ophiostoma spp., Spat., Spat. Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Cladosporium spp., Paecilomyces spp., Mucor spp., Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus, such as Staphylococcus aureus, Candida spp. and Saccharomyces spp., such as Saccharomyces cerevisae.
[239] Antimycotic activity [240] In addition, the active ingredients of the invention also have excellent antimycotic activity, namely a very broad spectrum of antimycotic activity, especially against dermatophytes and yeasts, molds and diphasic fungi (for example, against Candida species like C. albicans, C. glabrata), and Epidermophyton floccosum, Aspergillus species, like A. niger and A. fumigatus, Trichophyton species, like T. mentagrophytes, Microsporon species, like M. canis and M. audouinii. The present list of fungi is for illustrative purposes only and does not restrict the covered mycotic spectrum in any way.
[241] The active ingredients of the invention can therefore be used in medical and non-medical applications.
[242] GMOs [243] As mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, species of wild plants and cultivars are treated, or plants obtained by conventional methods of biological reproduction, such as crossing or fusion of
49/116 protoplasts, and their parts. In a preferred embodiment, transgenic plants and cultivars obtained by genetic engineering methods are treated, possibly in combination with conventional methods (Genetically Modified Organisms), and their parts. The terms "parts" or "parts of plants", or "parts of the plant" have been explained above. More preferably, plants of cultivars that are commercially available or currently in use are treated according to the invention. Cultivars are plants that have new characteristics ("traits") and that have been obtained by conventional breeding, mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, biotypes or genotypes.
[244] The treatment method according to the invention can be used in the treatment of genetically modified organisms (GMOs), for example, plants or seeds. Genetically modified plants (or transgenic plants) are plants with a heterologous gene integrated stably into the genome. The expression "heterologous gene" essentially means a gene that has been obtained or "assembled" outside the plant and which, after being introduced into the nuclear, chloroplastic or mitochondrial genome, gives rise to a new transformed plant, with agronomic or other properties, improved either by the expression of a protein or polypeptide of interest, or by the downregulation or silencing of other gene (s) present in the plant (using, for example, antisense technology, cosuppression technology, RNA interference (RNAi) technology, or technology micro-RNA (miRNA) A heterologous gene located in the genome is also called a transgene A transgene, which is defined by its specific location in the plant's genome, is called a transformation or transgenic event.
[245] Depending on the species of plant or cultivar, the location and growing conditions (soil, climate, growing season, nutrition), the treatment according to the invention can also give rise to superadditive ("synergistic") effects. Thus, it is possible to achieve, for example, reduced application rates, and / or broadening the spectrum of activity, and / or an increase in the activity of
50/116 compositions and active compounds that can be used according to the invention, better plant growth, greater tolerance to high or low temperatures, greater tolerance to drought or salt content in water or soil, more intense flowering, easier harvesting, accelerated ripening, higher yield of crops, larger fruits, greater plant height, greener leaf, early flowering, better quality and / or greater nutritional value of harvested products, higher concentration of sugar in fruits, better stability storage and / or processing capacity of harvested products, which exceed the expected effects.
[246] At certain application rates, combinations of active compounds according to the invention can also exert a plant-strengthening effect. Therefore, they are also suitable for mobilizing the plant's defense system against attack by unwanted microorganisms. This may possibly be one of the reasons for the increased activity of the combinations according to the invention, for example, against fungi. Plant strengthening substances (resistance induction) should be understood, in the present context, those substances or combinations of substances capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants exhibit a high degree of resistance to these microorganisms. In the present case, unwanted microorganisms include fungi, bacteria and phytopathogenic viruses. Thus, the substances according to the invention can be used to protect plants against attack by the aforementioned pathogens, for a certain period of time after treatment. The period of protective effects generally extends from 1 to 10 days, preferably from 1 to 7 days, after treatment of the plants with the active compounds. [24η The plants and cultivars preferably treated according to the invention include all plants with genetic material that gives them especially advantageous and useful characteristics (whether obtained by reproduction and / or by biotechnological means).
51/116 [248] The plants and cultivars preferably treated according to the invention are resistant against one or more biotic stresses, that is, these plants exhibit good defense against animal and microbial pests, such as nematodes, insects, mites, and fungi , bacteria, viruses and phytopathogenic viroids.
[249] Examples of plants resistant to nematodes or insects are described in US Patent Applications 11/765 491.11 / 765 494, 10 / 926819,10 / 782 020, 12/032 479, 10/783 417, 10/782 096, 11/657 964, 12/192 904, 11/396 808, 12/166 253, 12/166 239, 12/166 124, 12/166 209, 11/762 886, 12/364 335, 11/763 947, 12/252 453, 12/209 354, 12/491 396, 12/497 221, 12/644 632, 12/646 004, 12/701 058, 12/718 059, 12/721 595, 12/638 591.
[250] The plants and cultivars that can also be treated according to the invention are those resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, exposure to cold, exposure to heat, osmotic stress, flooding, increased soil salinity, increased exposure to minerals, exposure to ozone, too much exposure to light, limited availability of nutrients nitrogen, limited availability of phosphorous nutrients, avoidance of shade.
[251] Plants and cultivars that can also be treated according to the invention are characterized by a higher yield. Higher yield of said plants may be the result of, for example, improvements in plant physiology, growth and development, such as water use efficiency, water retention efficiency, better nitrogen utilization, greater carbon assimilation, better photosynthesis, greater germination efficiency and accelerated maturation. Yield can also be affected by improved plant architecture (under stress and non-stress conditions), including, but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, number of pods or ears, number of seeds per pod or ear, seed mass, seed filling
52/116 improved, reduced seed dispersion, reduced pod dehiscence and resistance to bedding. Other yield characteristics include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction to anti-nutritional compounds, improved processability and better storage stability.
[252] The plants that can be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor that generally results in an increase in yield, vigor, health and resistance to biotic and abiotic stress factors. These plants are usually prepared by crossing a pure andro-sterile parental line (the female parent) with another pure androfferable parental line (the male parent). Hybrid seed is usually harvested from androestile plants and sold to producers. Sometimes (for example, in the case of corn), andro-sterile plants are obtained by removing the tassel, that is, by the mechanical removal of the male reproductive organs (or male flowers), but normally male sterility is the result of genetic determinants of the genome of the plant. In this case, and especially when the seed is the desired product, the harvest path of hybrid plants is generally useful to ensure that male fertility in hybrid plants is fully restored. This can be achieved by ensuring that male parents have adequate fertility restoring genes, capable of restoring male fertility in hybrid plants carrying the genetic determinants responsible for male sterility. The genetic determinants of male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) have been described, for example, for the species Brassica (WO 92/05251, WO 95/09910, WO 98/27806, WO 05/002324, WO 06/021972 and US 6 229 072). However, genetic determinants of male sterility can also be found in the nuclear genome. Sterile male plants can also be obtained by methods of plant biotechnology, such as genetic engineering. An especially useful way of obtaining androestile plants is described in
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WO 89/10396, in which a ribonuclease such as barnase is selectively expressed in tapetum stem cells. Fertility can be restored by expression, in tapetum cells, of a ribonuclease inhibitor, such as the barstar gene (for example, WO 91/02069).
[253] Plants or cultivars (obtained by methods of plant biotechnology, such as genetic engineering) that can be treated according to the invention are tolerant to herbicides, that is, made tolerant to one or more certain herbicides. These plants can be obtained either by genetic transformation or by selecting plants with a mutation that gives them such tolerance to herbicides.
[254] Herbicide-resistant plants are, for example, tolerant to glyphosate, that is, made tolerant to the herbicide glyphosate or its salts. Plants can be made tolerant to glyphosate in several ways. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5enolpyruvylchiquimate-3-phosphate synthase (EPSPS). Examples of EPSPS genes are the AroA gene (CT7 mutant) from the bacterium Salmonalla tiphyimuríum (Science 1983, 221, 370-371), the CP4 gene from the bacterium Agrobacterium sp. (Curr. Topics Plant Physiol. 1992, 7, 139-145), the genes encoding a petunia EPSPS (Science 1986, 233, 478-481), a tomato EPSPS (J. Biol. Chem. 1988, 263, 4280-4289), or an EPSPS of Eleusina (WO 01/66704). It can also be a mutant EPSPS as described in, for example, EP 0837944, WO 00/66746, WO 00/66747 or WO 02/26995. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding the glyphosphateeductase oxide enzyme, as described in US 5,776,760 and US 5,463,175. Glyphosate tolerant plants can also be obtained by expressing an enzyme encoding gene glyphosate-acetyltransferase as described in, for example, WO 02/036782, WO 03/092360, WO 2005/012515 and WO 2007/024782. Glyphosate tolerant plants can also be obtained by selecting plants carrying natural mutations of the aforementioned genes, as described in, for example,
54/116 example, WO 01/024615 or WO 03/013226. Plants that express EPSPS genes that confer glyphosate tolerance are described, for example, in U.S. Patent Applications 11/517 991, 10/739 610, 12/139 408, 12/352 532,
11/312 866, 11/315 678, 12/421 292, 11/400 598, 11/651 752, 11/681 285,
11/605 824, 12/468 205, 11/760 570, 11/762 526, 11/769 327, 11/769 255,
11/943 801 or 12/362 774. Plants carrying other genes that confer glyphosate tolerance, such as the decarboxylase genes, are described, for example, in US Patent Applications 11/588 811, 11/185 342, 12 // 364 724, 11/185 560 or 12/423 926.
[255] Other herbicide-resistant plants are, for example, plants that have been made tolerant to herbicides that inhibit the glutamine synthase enzyme, such as bialaphos, phosphinothricin or glufosinate. These plants can be obtained by expressing an herbicide detoxifying enzyme or an inhibiting resistant glutamine synthase mutant enzyme as, for example, described in US Patent Application 11/760 602. An efficient detoxifying enzyme is an enzyme encoding a phosphinothricin-acetyltransferase (such as the BAR or PAT protein of Streptomyces species). Plants that express an exogenous phosphinothricin-acetyltransferase are described in U.S. Patents 5,561,236; 5,648,477; 5 646 024; 5,273,894; 5 637 489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.
[256] Other herbicide tolerant plants also include plants made tolerant to herbicides that inhibit the hydroxyphenylpyruvatodioxigenase (HPPD) enzyme. HPPD is an enzyme that catalyzes the reaction by which parahydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme, or with a gene encoding a mutant or chimeric HPPD enzyme as described in WO 96/38567, WO 99/24585, WO 99 / 24586, WO 09/144079, WO 02/046387, or US 6 768 044. Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes encoding certain enzymes that
55/116 allow the formation of the homogentisate despite the inhibition of the native enzyme HPPD by the HPPD inhibitor. These plants and genes are described in WO 99/34008 and WO 02/36787. Plant tolerance to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme with prefenate dehydrogenase (PDH) activity, and with a gene encoding an HPPD-tolerant enzyme, as described in WO 04/024928 . In addition, plants can become more tolerant of HPPD-inhibiting herbicides by adding to their genome a gene encoding an enzyme capable of metabolizing or degrading HPPD-inhibitors, such as the CYP450 enzymes disclosed in WO 2007/103567 and WO 2008/150473.
[257] Still other herbicide-resistant plants are plants made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitors include, for example, sulfonylurea herbicides, imidazolinone, triazolopyrimidines, pyrimidinioxy (thio) benzoates and / or sulfonylaminocarbonyltriazolinone. Different mutations in the ALS enzyme (also known as acetohydroxy acid synthase, AHAS) are known to confer tolerance to different herbicides and groups of herbicides as described, for example, in Tranel and Wright (Weed Science 2002, 50, 700-712), and also in US Patents 5,605,011, 5,378,824, 5,141,870 and 5,013,659. The preparation of sulfonylurea tolerant plants and imidazolinone tolerant plants is described in US Patents 5,605,011; 5,013,659; 5,141,870; 5,767,361; 5,731,180; 5,304,732; 4,761,373; 5,331,107; 5 928 937; and 5,378,824; and WO 96/33270. Other imidazolinone tolerant plants are described in, for example, WO 2004/040012, WO 2004/106529, WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351, and WO 2006 / 060634. Other sulfonylurea and imidazolinone tolerant plants are also described in, for example, WO 2007/024782 and in U.S. Patent Application 61/288958. Still other plants tolerant to imidazolinone and / or sulfonylurea can be obtained by induced mutagenesis, by selection in cell cultures in the presence of the herbicide, or by random mutagenesis as described, for example, for
56/116 soy in US 5,084,082, for rice in WO 97/41218, for sugar beet in US 5,773,702 and WO 99/057965, for lettuce in US 5,198,599, or for sunflower in WO 01/065922.
[258] Plants or cultivars (obtained by methods of plant biotechnology, such as genetic engineering) that can also be treated according to the invention are transgenic plants resistant to insects, that is, plants made resistant to attack by certain target insects. These plants can be obtained by genetic transformation, or by selecting plants with a mutation that gives them such resistance to insects.
[259] The term "insect resistant transgenic plant" as used herein includes any plant that contains at least one transgene with a coding sequence of:
1) an insecticidal crystallized protein from Bacillus thuringiensis or an insecticidal portion thereof, such as the insecticidal crystallized proteins listed in Crickmore et al. (1998, Microbiology and Molecular Biology Reviews, 62: 807-813), updated by Crickmore et al. (2005) in the nomenclature of the Bacillus thuringiensis toxin at http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/) or its insecticidal portions, for example, proteins in the Cry protein classes, namely CrylAb, CrylAc, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab, Cry3Aa, or Cry3Bb, or their insecticidal moieties (for example, EP-A 1 999 141 and WO 2007/107302), or proteins encoded by synthetic genes as, for example, described in US Patent Application 12/249,016; or
2) a crystallized protein from Bacillus thuringiensis or a portion thereof that is insecticidal in the presence of another second crystallized protein from Bacillus thuringiensis or a portion thereof, such as the binary toxin composed of the crystalline proteins Cry34 and Cry35 (Nat. Biotechnol. 2001 , 19, 668-72; Applied Environm. Microbiol. 2006, 71,1765-1774), or the binary toxin consisting of the Cry1A or Cry1F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (US Patent Application 12/214 022 and EP -A 2 300 618); or
3) a hybrid insecticidal protein composed of parts from different
57/116 Bacillus thuringiensis insecticidal crystalline proteins, such as a hybrid of the proteins in 1) behind or a hybrid of the proteins in 2) behind, for example, the Cry1A.1O5 protein produced by the MON98034 corn event (WO 2007/027777) ; or
4) a protein from any of the groups from 1) to 3) above, in which some, particularly from 1 to 10, amino acids have been replaced by other amino acids to obtain greater insecticidal activity against a target insect species, and / or in order to expand the range of affected target insect species, and / or due to changes introduced in the coding DNA during cloning or transformation, such as the Cry3Bb1 protein in the MON863 or MON88017 corn events, or the Cry3A protein in corn event MIR604; or
5) an insecticidal protein secreted by Bacillus thuringiensis or Bacillus cereus, or an insecticidal portion thereof, such as the vegetative insecticidal proteins (VIP) listed in:
http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html, for example, proteins of the VIP3Aa class; or
6) a protein secreted by Bacillus thuringiensis or Bacillus cereus, which is insecticidal in the presence of a second protein secreted by Bacillus thuringiensis or B. cereus, such as the binary toxin composed of the VIP1A and VIP2A proteins (WO 94/21795); or
7) a hybrid insecticidal protein composed of parts of different proteins secreted by Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins in 1) behind or a hybrid of the proteins in 2) behind; or
8) a protein from any of the groups from 5) to 7) above, in which some, particularly from 1 to 10, amino acids have been replaced by other amino acids in order to achieve greater insecticidal activity against a target insect species, and / or in order to expand the range of affected target insect species, and / or due to changes introduced in the coding DNA during cloning or transformation (simultaneously encoding an insecticidal protein), such as the VIP3Aa protein in the COT102 cotton event ; or
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9) a protein secreted by Bacillus thuringiensis or Bacillus cereus, which is an insecticide in the presence of a crystallized protein from Bacillus thuringiensis, such as the binary toxin composed of VIP3 eCrylAou Cry1F (US Patent Application 61/126083 and 61/195019), or binary toxin composed of the VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (US Patent Application 12/214 022 and EP-A 2 300 618); or
10) a protein from 9) above, in which some, particularly from 1 to 10, amino acids have been replaced by another amino acid in order to achieve greater insecticidal activity against a target insect species, and / or in order to expand the range of target insect species affected, and / or because of changes introduced in the coding DNA during cloning or transformation (still encoding an insecticidal protein) [260] Of course, a transgenic insect resistant plant in the current context also includes any plant carrier of a combination of genes encoding proteins from any of the classes 1 to 10 above. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any of the previous classes 1 to 10, in order to expand the range of target insect species affected by the use of different proteins targeting different species of target insects, or in order to delay the development of insect resistance to plants by using different insecticidal proteins for the same target insect species, but with a different mode of action, such as binding to different binding sites of the receptors in the insect.
[261] A «insect resistant transgenic plant» as used herein further includes any plant carrying at least one transgene with a sequence that, after expression, produces a double-stranded RNA, which, after ingestion by an agricultural insect pest , inhibits the growth of that insect pest, as described, for example, in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO 2007/080127 and WO 2007/035650.
[262] Plants or cultivars (obtained by methods of plant biotechnology,
59/116 as genetic engineering) that can also be treated according to the invention are tolerant to abiotic stresses. These plants can be obtained by genetic transformation, or by selecting plants that carry a mutation that confers such resistance to stress. Especially useful stress-tolerant plants include:
1) plants carrying a transgene capable of reducing the expression and / or activity of the poly (ADP-ribose) polymerase (PARP) gene in plant cells or plants as described in WO 00/04173, WO 2006/045633 , EPA 1 807 519, or EP-A 2,018,431.
2) plants carrying a transgene that increases tolerance to stress, being able to reduce the expression and / or activity of PARG coding genes in plants or plant cells as described, for example, in WO 2004/090140.
3) plants carrying a transgene that increases tolerance to stress, which codes for a functional enzyme in the plant from the salvage synthesis pathway of the nicotinamide and adenine dinucleotide, such as nicotinamidase, nicotinate-phosphoribosyltransferase, mononucleotide of nicotinic acid-adenyltransferase, nicotinamide and adenine synthase dinucleotide or nicotinamide-phosphoribosyltransferase, as described, for example, in EPA 1 794 306, WO 2006/133827, WO 2007/107326, EP-A 1 999 263, or WO 2007/107326.
[263] Plants or cultivars (obtained by methods of plant biotechnology, such as genetic engineering) that can also be treated according to the invention show changes in quantity, quality and / or storage stability of the harvested product and / or changes in properties specific components of the harvested product, such as:
1) transgenic plants that synthesize a modified starch, whose physico-chemical characteristics, in particular the amylose content or the amylose / amylopectin ratio, the degree of branching, the average chain length, the distribution of side chains, the behavior of viscosity , consistency
60/116 of the gel, the size of starch grains and / or the morphology of starch grains are different from those of starch synthesized in plant cells or wild type plants, the former being more suitable for special applications. Said transgenic plants that synthesize modified starch are described in, for example, EP-A 0 571 427, WO 95/04826, EP-A 0 719 338, WO 96/15248, WO
WO
WO
WO
WO
WO
WO
WO
WO
WO
WO
WO
WO
WO
96/27674,
97/44472,
99/58690,
00/28052,
WO
WO
WO
WO
WO
WO
WO
97/11188,
97/45545,
99/58654,
00/77229,
07/031860,
2005/095632,
2005/123927,
WO 2007/009823, WO 00/22140,
WO
WO
WO
WO
WO
WO
WO
97/26362,
98/27212,
08/08184,
12/01782,
WO
04/056999,
2005/095617,
2006/018319,
WO
WO
WO
WO
WO
WO
WO
96/19581,
97/42328,
99/58688,
08/08175,
10/02/10,
2005/030941,
2005/095618,
2006/108702,
2006/072603, WO 02/034923, WO 2008/017518,
2008/080631, WO 2008/090008, WO 01/14569, WO
WO
97/32985, ’98/40503,
08/08185,
12/01826,
05/030942,
2005/095619,
2006/103107,
2006/063862, 2008/080630, 02/79410,
WO 03/33540, WO 2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145, WO 99/12950, WO 99/66050, WO 99/53072, US 6,734,341, WO 00 / 11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/98509, WO 2005/002359, US 5,824,790, US 6,013,861, WO 94/04693, WO 94/09144, WO 94/11520, WO 95/35026, WO 97/20936, WO 2010/012796, WO 2010/003701,
2) transgenic plants that synthesize polymers of carbohydrates other than starch, or that synthesize polymers of carbohydrates other than starch with altered properties compared to wild type plants without any genetic modification. Examples are plants that produce polyfructose, especially of the inulin and levan type, as disclosed in EP-A 0 663 956, WO 96/01904, WO 96/21023, WO 98/39460 and WO 99/24593, plants that produce alpha-1 , 4-glucans, as disclosed in WO 95/31553, US 2002031826, US 6 284 479, US 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808 and
WO 00/14249, plants that produce alpha-1,4-branched alpha-1,6-glucans,
61/116 as disclosed in WO 00/73422, alternate producing plants, as disclosed in, for example, WO 00/47727, WO 00/73422, US 5 908 975 and EP-A 0 728 213;
3) transgenic plants that produce hyaluronic acid, as disclosed in, for example, WO 2006/032538, WO 2007/039314, WO 2007/039315, WO 2007/039316, JP-A 2006-304779 and WO 2005/012529;
4) transgenic or hybrid plants, such as onions with characteristics such as a "high soluble solids content", "low pungency" (LP) and / or "long storage" (LS), as described in US Patent Application 12 / 020 360.
[264] Plants or cultivars (which can be obtained by methods of plant biotechnology, such as genetic engineering) that can also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. These plants can be obtained by genetic transformation or by selecting plants with a mutation that gives them such altered fiber characteristics and include:
a) Plants, such as cotton plants, that contain an altered form of cellulose synthase genes, as described in WO 98/00549.
b) Plants, such as cotton plants, that contain an altered form of homologous nucleic acids rsw2 or rsw3, as described in WO 2004/053219.
c) Plants, such as cotton plants, with an increase in sucrose synthase phosphate expression, as described in WO 01/17333.
d) Plants, such as cotton plants, with an increase in sucrose synthase expression, as described in WO 02/45485.
e) Plants, such as cotton plants, in which the moment of opening and closing of fibrous cell plasmodesms is altered, for example, by infrarregulation of fiber-selective P-1,3-glucanase, as described in WO 2005/017157 or WO 2009/143995.
f) Plants, such as cotton plants, where the fibers present
62/116 an altered reactivity, for example, by the expression of the Nateylglucosamine transferase gene, including the nodC and chitin synthase genes, as described in WO 2006/136351.
[265] Plants or cultivars (which can be obtained by methods of plant biotechnology, such as genetic engineering) that can also be treated according to the invention are plants, such as rapeseed or brassica, with altered oil characteristics. These plants can be obtained by genetic transformation or by selecting plants with a mutation that gives them these altered oil characteristics and include:
a) Plants, such as rapeseed plants, which produce oil with a high oleic acid content, as described, for example, in US 5 969 169, US 5 840 946, US 6 323 392 or US 6 063 947.
b) Plants, such as rapeseed plants, which produce oil with a low content of linolenic acid, as described in US 6,270,828, US 6,169,190, or US 5,965,755.
c) Plants, such as rapeseed plants, which produce oil with a low content of saturated fatty acids, as described, for example, in US 5,434,283 or in Patent Application 12/668303.
[266] The plants or cultivars (which can be obtained by methods of plant biotechnology, such as genetic engineering) that can also be treated according to the invention are plants, such as rapeseed or brassica plants, with altered natural threshing characteristics. These plants can be obtained by genetic transformation or by selecting plants that carry a mutation that gives them these altered natural threshing characteristics, and include plants such as rapeseed plants with delayed or reduced natural threshing, as described in US Patent Application 61 / 135 230, WO 2009/0683131 and WO 2010/006732.
[26η Plants or cultivars (which can be obtained by methods of plant biotechnology, such as genetic engineering) that can also be treated according to the invention are plants like the tobacco plant, with
63/116 altered patterns of post-translational protein modifications, for example, as described in WO 2010/121818 and WO 2010/145846.
[268] Particularly useful transgenic plants that can be treated according to the invention are plants that carry transformation events, or a combination of transformation events, which are being the subject of applications for "unregulated" status in the States United States of America, addressed to the Plant Healt Inspection Service (APHIS) of the United States Department of Agriculture (USDA), whether these applications have been approved or remain pending. This information can be readily obtained, at any time, from APHIS (4700 River Road, Riverdale, MD 20737, USA), for example through its website (URL http://www.aphis.usda.gov/brs/not_reg. html). At the date of filing the present application for invention, applications for non-regulated status that were still pending or had been approved by APHIS were those that contained the following information:
[269] Order: order identification number. The technical descriptions of the transformation events are found in the individual order documents obtained from APHIS, for example on the APHIS website, by reference to that order number. These descriptions are incorporated into this document by reference.
[270] Extension of request: reference to a previous request for which an extension is requested.
[271] Institution: name of the entity submitting the request.
[272] Regulated article: the species of plant concerned.
[273] Transgenic phenotype: the characteristic conferred to the plant by the transformation event.
[274] Event or transformation line: the name of the event or events (sometimes also referred to as line or lines) for which non-regulated status is requested.
[275] APHIS documents: several documents published by APHIS in relation to the Order and which can be requested from APHIS.
64/116 [276] Other particularly useful plants carrying unique transformation events or combinations of transformation events are listed, for example, in the databases of various national or regional regulatory agencies (see, for example, http: // gmoinfo .jrc.it / gmp_browse.aspx and http://www.agbios.com/dbase.fp).
[277] Particularly useful transgenic plants that can be treated according to the invention are plants that contain transformation events, or a combination of transformation events, and which are listed, for example, in the databases of various national regulatory agencies or regional, including Event 1143-14A (cotton, insect control, not deposited, described in WO 2006/128569); Event 1143-51B (cotton, insect control, not deposited, described in WO 2006/128570); Event 1445 (cotton, herbicide tolerance, not deposited, described in US-A 2002-120964 or WO 02/034946); Event 17053 (rice, herbicide tolerance, deposited as PTA-9843, described in WO 2010/117737); Event 17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO 2010/117735); Event 281-24-236 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in WO 2005/103266 or US-A 2005-216969); Event 3006-210-23 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in US-A 2007-143876 or WO 2005/103266); Event 3272 (corn, quality characteristic, deposited as PTA-9972, described in WO 2006/098952 or USA 2006-230473); Event 40416 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-11508, described in WO 2011/075593); Event 43A47 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-11509, described in WO 2011/075595); Event 5307 (corn, insect control, deposited as ATCC PTA-9561, described in WO 2010/077816); Event ASR-368 (agrostid grass, herbicide tolerance, deposited as ATCC PTA-4816, described in US-A 2006-162007 or WO 2004/053062); Event B16 (maize, herbicide tolerance, not deposited, described in US-A 2003-126634); Event BPS-CV127-9 (soybean, herbicide tolerance, deposited
65/116 as NCIMB No. 41603, described in WO 2010/080829); Event CE43-67B (cotton, insect control, deposited as DSM ACC2724, described in USA 2009-217423 or WO 2006/128573); Event CE44 - 69D (cotton, insect control, not deposited, described in US-A 2010-0024077); Event CE44 - 69D (cotton, insect control, not deposited, described in WO 2006/128571); Event CE46-02A (cotton, insect control, not deposited, described in WO 2006/128572); Event COT102 (cotton, insect control, not deposited, described in US-A 2006-130175 or WO 2004/039986); Event COT202 (cotton, insect control, not deposited, described in US-A 2007067868 or WO 2005/054479); Event COT203 (cotton, insect control, not deposited, described in WO 2005/054480); DAS40278 event (corn, herbicide tolerance, deposited as ATCC PTA-10244, described in WO 2011/022469); Event DAS-59122-7 (corn, insect control - herbicide tolerance, deposited as ATCC PTA 11384, described in US-A 2006-070139); Event DAS-59132 (corn, insect control - herbicide tolerance, not deposited, described in WO 2009/100188); Event DAS-68416 (soybean, herbicide tolerance, deposited as ATCC PTA-10442, described in WO 2011/066384 or WO 2011/066360); Event DP-098140-6 (corn, herbicide tolerance, deposited as ATCC PTA-8296, described in US-A 2009-137395 or WO 2008/112019); Event DP-305423-1 (soybean, quality characteristic, not deposited, described in US-A-2008 312082 or WO 2008/054747); Event DP-32138-1 (corn, hybridization system, deposited as ATCC PTA-9158, described in US-A 20090210970 or WO 2009/103049); Event DP-356043-5 (soybean, herbicide tolerance, deposited as ATCC PTA-8287, described in US-A 2010-0184079 or WO 2008/002872); Event EE-1 (eggplant, insect control, not deposited, described in WO 2007/091277); Event FI117 (corn, herbicide tolerance, deposited as ATCC 209031, described in US-A 2006-059581 or WO 98/044140); Event GA21 (corn, herbicide tolerance, deposited as ATCC 209033, described in US-A 2005-086719 or WO 98/044140); Event GG25 (maize, herbicide tolerance, deposited as ATCC 209032, described in US-A
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2005-188434 or WO 98/044140); Event GHB119 (cotton, herbicide tolerance insect control, deposited as ATCC PTA-8398, described in WO 2008/151780); Event GHB614 (cotton, herbicide tolerance, deposited as ATCC PTA-6878, described in US-A 2010-050282 or WO 2007/017186); Event GJ11 (corn, herbicide tolerance, deposited as ATCC 209030, described in US-A 2005-188434 or WO 98/044140); GM RZ13 event (sugar beet, virus resistance, deposited as NCIMB-41601, described in WO 2010/076212); Event H7-1 (sugar beet, herbicide tolerance, deposited as NCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO 2004/074492); Event J0PLIN1 (wheat, disease tolerance, not deposited, described in US-A 2008-064032); Event LL27 (soybean, herbicide tolerance, deposited as NCIMB41658, described in WO 2006/108674 or USA 2008-320616); Event LL55 (soybean, herbicide tolerance, deposited as NCIMB 41660, described in WO 2006/108675 or US-A 2008-196127); Event LLcotton25 (cotton, herbicide tolerance, deposited as ATCC PTA-3343, described in WO 03/013224 or US-A 2003-097687); Event LLRICE06 (rice, herbicide tolerance, deposited as ATCC-23352, described in US 6 468 747 or WO 00/026345); Event LLRICE601 (rice, herbicide tolerance, deposited as ATCC PTA-2600, described in US-A 2008-2289060 or WO 00/026356/00); Event LY038 (corn, quality characteristic, deposited as ATCC PTA5623, described in US-A 2007-028322 or WO 2005/061720); Event MIR162 (corn, insect control, deposited as PTA-8166, described in US-A 2009300784 or WO 2007/142840); Event MIR604 (corn, insect control, not deposited, described in US-A 2008-167456 or WO 2005/103301); Event MON15985 (cotton, insect control, deposited as ATCC PTA-2516, described in US-A 2004-250317 or WO 02/100163); MON810 event (corn, insect control, not deposited, described in US-A 2002-102582); MON863 event (corn, insect control, deposited as ATCC PTA-2605, described in WO 2004/011601 or US-A 2006-095986); Event MON87427 (corn, pollination control, deposited as ATCC PTA-7899, described in
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WO 2011/062904); Event MON87460 (corn, tolerance to stress, deposited as ATCC PTA-8910, described in WO 2009/111263 or US-A 2011-0138504); MON87701 event (soybean, insect control, deposited as ATCC PTA-8194, described in US-A 2009-130071 or WO 2009/064652); Event MON87705 (soybean, quality characteristic - herbicide tolerance, deposited as ATCC PTA9241, described in US-A 2010-0080887 or WO 2010/037016); Event MON87708 (soybean, herbicide tolerance, deposited as ATCC PTA9670, described in WO 2011/034704); Event MON87754 (soybean, quality characteristic, deposited as ATCC PTA-9385, described in WO 2010/024976); Event MON87769 (soybean, quality characteristic, deposited as ATCC ΡΤΑ-8911, described in US-A 2011-0067141 or WO 2009/102873); Event MON88017 (maize, insect control - herbicide tolerance, deposited as ATCC PTA5582, described in US-A 2008-028482 or WO 2005/059103); Event MON88913 (cotton, herbicide tolerance, deposited as ATCC PTA-4854, described in WO 2004/072235 or US-A 2006-059590); Event MON89034 (corn, insect control, deposited as ATCC PTA-7455, described in WO 2007/140256 or USA 2008-260932); Event MON89788 (soybean, herbicide tolerance, deposited as ATCC PTA-6708, described in US-A 2006-282915 or WO 2006/130436); Event MS11 (rapeseed, pollination control - herbicide tolerance, deposited as ATCC PTA-850 or PTA-2485, described in WO 01/031042); Event MS8 (rapeseed, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in WO 01/041558 or US-A 2003-188347); Event NK603 (corn, herbicide tolerance, deposited as ATCC PTA-2478, described in USA 2007-292854); Event PE-7 (rice, insect control, not deposited, described in WO 2008/114282); Event RF3 (rapeseed, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in WO 01/041558 or US-A 2003-188347); Event RT73 (rapeseed, herbicide tolerance, not deposited, described in WO 02/036831 or US-A2008-070260); Event T227-1 (sugar beet, herbicide tolerance, not deposited, described in WO 02/44407 or USA 2009-265817); Event T25 (maize, herbicide tolerance, not deposited,
68/116 described in US-A 2001-029014 or WO 01/051654); Event T304-40 (cotton, insect control - herbicide tolerance, deposited as ATCC PTA-8171, described in US-A 2010-077501 or WO 2008/122406); Event T342-142 (cotton, insect control, not deposited, described in 2006/128568); Event TC1507 (corn, insect control - herbicide tolerance, not deposited, described in US-A 2005-039226 or WO 2004/099447); Event VIP1034 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-3925., Described in WO 03/052073), Event 32316 (corn, insect control-herbicide tolerance, deposited as PTA-11507, described in WO 2011/084632), Event 4114 (corn, insect control-tolerance to herbicide, deposited as PTA-11506, described in WO 2011/084621).
[278] Application periods and rates [279] When using the active ingredients of the invention as fungicides, application rates can vary over a relatively wide range, depending on the type of application. The application rate of the active ingredient of the invention is:
• in the case of treatment of plant parts, for example, leaves: from 0.1 to 10,000 g / ha, preferably from 10 to 1000 g / ha, more preferably from 10 to 800 g / ha, up to more than preferably from 50 to 300 g / ha (in the case of irrigation or drip application, it is possible to further reduce the application rate, especially when inert substrates such as rock wool or perlite);
• in the case of seed treatment: from 2 to 200 g / 100 kg of seeds, preferably from 3 to 150 g per 100 kg of seeds, more preferably from 2.5 to 25 g per 100 kg of seeds, still greater preference of 2.5 to 12.5 g per 100 kg of seeds;
• in the case of soil treatment: from 0.1 to 10,000 g / ha, preferably from 1 to 5000 g / ha.
[280] These application rates are for illustration only and are not limiting for the purposes of the invention.
[281] The active ingredients or compositions of the invention can thus be used to protect plants against attack by said agents
69/116 pathogenic, for some time after treatment. The protection period should extend, in general, from 1 to 28 days, preferably from 1 to 14 days, more preferably from 1 to 10 days, even more preferably from 1 to 7 days after the treatment of the plants with the active ingredients , or up to 200 days after seed treatment.
[282] The treatment method according to the invention also provides for the use or application of compounds (A) and (B) and / or (C) simultaneously, separately or sequentially. If the individual active ingredients are applied sequentially, that is, at different times, then they are applied one after the other in a reasonably short period, of a few hours or days. Preferably, the order of application of compounds (A) and (B) and / or (C) is not essential for the operation of the present invention.
[283] In a particularly advantageous manner, the said plants can be treated according to the invention with the compounds of the general formula (I) and with the inventive compositions. The preferred ranges indicated above for the active ingredients or compositions also apply to the treatment of these plants. Special emphasis is placed on the treatment of plants with the compounds or compositions referred to specifically in this text.
[284] The invention is illustrated by the following examples. However, the invention is not restricted by these examples.
[285] Preparation examples [286] In analogy with the previous examples and according to the general description of the processes for preparing the compounds according to the invention, the compounds according to formula (I) of the following Table can be obtained 1.
(I)
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Table 1
Ex. n X ¹ T Q R ^a R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ logP[The]1 0 - 0 H H Me H H H Me Me 3.29 (°)2 0 - 0 H 4-F Me H H H Me Me 3.35 ( ^to J3 0 - O H H Me H H H / Pr H 3,651 ^a ) R ¹ and R ⁵ configur. Cis mainly 4 0 - 0 H H Me H H H H H 2.63 ( ³ )5 0 - 0 H H H H H H = N-O-Me 2.151 ^a )6 0 - 0 H H H H H H = N-O-Bu 3,441 ^a )7 0 - 0 H H H H H H = N-O-Pr 3.001 ^a )8 0 - 0 H H H H H H = N-O-Et 2.541 ^a )9 0 - s H H Me H H H Me Me 3.741 ^a )10 0 - 0 H 4-cPr Me H H H Me Me 3.79 ( ³ )11 0 - 0 H 4-Me Me H H H Me Me 3,411 ^a )12 0 - O H H Me H 0 Me Me 2.11 ( ³ )13 0 - 0 H H Me H H H Me Me 3.251 ^a ) Enantiomer(R) 14 0 - 0 H H H H Me H Me Me 3,331 ^a )15 0 - 0 H 4-Br Me H 0 Me Me 2,891 ^a )16 0 - 0 H 4-CI Me H H H Me Me 3.731 ^a )17 0 - 0 H H H H 0 Me Me 2.01 W18 1 6-CI 0 H H Me H H H Me Me 3.991 ^a )19 1 6-CI 0 H 4-F Me H H H Me Me 4.091 ^a )20 0 - 0 H H H H H H -CH2-CH2- 2,781 ^a )21 1 5-Me 0 H H Me H H H Me Me 3.55 ( ³ )22 1 5-Me 0 H H Me H 0 Me Me 2,371 ^a )23 1 5-Me 0 H 4-F Me H H H Me Me 3,641 ^a )24 1 6-CI 0 H H Me H 0 Me Me 2.77 ( ^a )25 0 - 0 H H Me H 0 Et Et 2,861 ^a )26 1 5-Me O H H Me H 0 Et Et 3.151 ^a )27 0 - 0 H H H H Me H / Pr H 3.781 ^a ) R ³ and R ⁵ configur. Cis mainly
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Ex. η X ¹ T Q R ^a R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ logPsuch28 1 4-CHFz O H H Me H H H Me Me 3.791 ^a '29 1 5-Me 0 H H Me H H H = N-O-Me 2,611 ^a '30 0 - 0 H H Me H H H = N-O-Me 2.32 ' ^a '31 1 6-CI 0 H H H H Me Me = N-O-Me 3.50 + 3.63f ^a l32 1 5-Me 0 H H H H Me Me = N-O-Me 3.08 + 3,231 ^a '33 0 - 0 H H Me H Me H Me Me 3,481 ^a ' R ¹ and R ³ config. Trans mainly 34 0 - 0 H H H H Me Me = N-O-Me 2.78 + 2.92 ' ^a '35 1 5-Me 0 H H Me H Me H Me Me 3.79 ^ 1 R ¹ and R ³ config. Trans mainly 36 0 - 0 H H H H Me H Me H 3.06 ' ^a ' R ³ and R ⁵ configur. Cis mainly 37 0 - 0 H H H H Et H Me Me 3.78 ' ^a '38 1 5-Me 0 H H H H Et H Me Me 4,061 ^a '39 0 - 0 H H H H H H tBu H 3.78 ' ^a '40 1 4- CHF ₂ 0 H H Me H 0 Me Me 2.66 ' ^a '41 0 - 0 H H H H H H / Bu H 3.94 ' ^a '42 0 - 0 H H Me H H H -CH2-CH 2- 3.00 ' ^a '43 0 - 0 H H H H / Pr H Me Me 4.11 ( ^a ]44 1 5-Me 0 H H H H iPr H Me Me 4.41 (8)45 1 6-CI 0 H H H H / Pr H Me Me 4.77 ' ^a '
72/116
Ex. η X ¹ T Q R ^a R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ logP[The]46 0 - 0 H H Me H H H -CH ₂ tBu H 4,391 ^a · R ¹ and R ⁵ configur. Cis mainly 47 1 6-CI 0 H H H H Me Me H H 3.761 ^a ·48 1 5-Me 0 H H H H Me Me H H 3.351 ^a )49 0 - 0 H H H H Me Me H H 3.061 ^a )50 1 5-Me 0 H H Me H H H = N-O-Et 2,991 ^a )51 0 - O H H Me H H H = N-O-Bu 3.181 ^a )52 0 - 0 H H Me H H H = N-O-Et 2.71 W53 1 5-Me 0 H H Me H H H = N-O-Bu 3,461 ^a ·54 1 5-Me 0 H H Me H H H -CH2-CH2- 3,311 ^a )55 1 5-CI 0 H H Me H H H Me Me 4.061 ^a )56 0 - 0 H H / Pr H 0 Et Et 3,641 ^a )57 0 - 0 H H Me H H H / Bu H 4.151 ^a ) R ¹ and R ^s configur. Cis mainly 58 1 6-CI 0 H H Me H H H -CH2-CH 2- 3.731 ^a )59 0 - s H H Me H H H -CH2tBu H 4,871 ^a ) R ¹ and R ⁵ configur. Cis mainly 60 0 - 0 H H H H Et Et Me H 4,111 ^a )61 1 5-Me 0 H H H H Et Et Me H 4.391 ^a )62 0 - 0 H H H H Me Me Me H 3.351 ^a )63 1 5-Me 0 H H H H Me Me Me H 3,651 ^a )64 1 6-CI 0 H H H H Me Me Me H 4.041 ^a )65 0 - s H H H H / Pr H Me Me 4,461 ^a )66 1 6-CI s H H H H / Pr H Me Me 5.11 «67 1 5-Me s H H H H / Pr H Me Me 4,741 ^a )68 1 5-Me s H H Me H H H -CH ₂ -CH 2- 3,681 ^a )69 0 - s H H H H Et H Me Me 4.161 ^a )70 1 5-Me s H H H H Et H Me Me 4.411 ^a )71 0 - O H H Et H 0 Et Et 3,231 ^a )72 1 5-Me 0 H H Et H O Et Et 3.521 ^a )
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Εχ. η X ¹ T Q R ^a R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ logPM73 1 5-Me 0 H H Et H 0 Me Me 2,641 ^a )74 1 6-CI 0 H H Et H 0 Me Me 3.091 ^a )75 1 5-Me O H H / Pr H 0 Me Me 3.001 ^a )76 0 - 0 H H / Pr H 0 Me Me 2.731 ^a )77 0 - 0 H H Et H 0 Me Me 2.391 ^a )78 0 - 0 H H Me H H H Et Et 4.011a)79 1 5-Me 0 H H Me H H H Et Et 4.31 I ^a )80 1 6-CI O H H Me H H H Et Et 4.721®]81 0 - 0 H H Me H H H Et Me 3,641 ^a ) mixed cis / trans 82 1 5-Me O H H Me H H H Me Et 3,941 ^a ) mixed cis / trans 83 1 6-CI O H H Me H H H Me Et 4.361 ^a ) mixed cis / trans 84 0 - 0 H H / Bu H H H H H 3,621 ^a )85 0 - 0 H H Me H Me Me H H 3.291 ^a )86 1 5-Me 0 H H Me H Me Me H H 3.591 ^a )87 1 6-CI O H H Me H Me Me H H 3,961 ^a )88 0 - 0 H H Me H H H Et H 3,371 ^a ) R ¹ and R ^s configur. Cis mainly 89 0 - 0 H H Me H H H nPr H 3.791 ^a ) R ¹ and R ⁵ configur. Cis mainly 90 0 - 0 H H -CH ₂ tBu H H H H H 3,921 ^a )91 0 - 0 H H H H Me H Et Et 3.991 ^a )92 0 - 0 H H H H H H Me Me 3.081a)93 0 - 0 H H Me H H H t-Bu H 3.941a) R ¹ and R ⁵ configur. Cis mainly 94 0 - 0 H H chf ₂ H H H Me Me 3.151 ^a )95 0 - 0 H H -ch ₂ - fBu H H H Me Me 4,541 ^a )96 0 - 0 H H -CHCI ₂ H H H Me Me 3,971 ^a )97 0 - 0 H H = CCI ₂ H H H H 2.961 ^a )
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Ex. n X ¹ T Q R ^a R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ logPia]98 0 - 0 H H Me H H H = CHCI 3.71 ^to l99 0 - 0 H H Me H H H = CCI ₂ 3.13l ^to l100 0 - 0 H 6-F Me H H H Me Me 3.26l ^to l
Me = methyl, Et = ethyl, Pr = propyl, / Pr = isopropyl, cPr = cyclopropyl, Bu = butyl, / Bu = isobutyl, tBu = tertbutyl [287] In analogy with the previous examples and according to the general description of processes for preparing the compounds according to the invention, the compounds according to the formula (II-a) of the following Table 2 can be obtained.
Ex. Q R ^a R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ logPW GCMS (min)lll-a-1 H H Me H H H Et H4.97 R ¹ and R ⁵ configur. Cis mainly lll-a-2 H H Me H H H tBu H5.74 R ¹ and R ⁵ configur. Cis mainly lll-a-3 H H = CCI ₂ H H H H 3.42l ^to lHCI salt lll-a-4 H H Me H H H = CCI ₂ 3.60 ^Ial HCI salt lll-a-5 H H Me H Me Me H H HCI salt lll-a-6 H H -CH ₂ tBu H H H Me Me 4.98 ^(at w lll-a-7 H H -CHCIz H H H Me Me 4.39í ^to > lll-a-8 H H -CHztBu H H H H H 4.04 ^to 1HCI salt
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lll-a-9 H H chf ₂ H H H Me Me 2,751 ^a ) lll-a-10 H 6-F Me H H H Me Me 3.711 ^a » Me = methyl, Et = eti o, íBu = tertbutyl
[288] The determination of logP values was carried out in accordance with EEC Directive 79/831, Annex V.A8, by HPLC (high performance liquid chromatography) on reverse phase columns using the following methods:
[289] ^[a] LC-MS measurement made at pH 2.7 with 0.1% formic acid in water and with acetonitrile (containing 0.1% formic acid) as the eluent, with a 10% linear gradient up to 95% acetonitrile.
The. Calibration was performed with unbranched alkan-2-ones (with 3 to 16 carbon atoms) with known logP values (logP values were determined using retention times with linear interpolation between successive alkanones). The maximum lambda values were determined by UV spectra between 200 nm to 400 nm and the peak values of the chromatographic signals.
B. The GC-MS retention times were determined on a DB17ms column (15 mx 0.25 pm x 0.25 pm), with a gradient of 30 ° C / min, from 40 ° C to 310 ° C and a flow rate of He gas of 1.5 ml / min.
[290] NMR peak lists [291] The 1H NMR results of some examples are presented in the form of 1H NMR peak lists. For each signal peak, the values of δ in ppm and the signal strength in curved brackets are listed. Between the pairs of value of δ - signal strength the semicolon sign appears as a delimiter.
[292] The list of peaks in an example therefore takes the following form:
[293] δι (i-intensity); Ó2 (intensity2); ...; õi (intensityi); ...; ón (intensity) [294] A printed example of an NMR spectrum in cm shows that the intensity of the sharp signals is correlated with their height, and it also shows the actual relationships between signal strengths. You can see from several
76/116 wide signal peaks, or the medium of the signal and its strength relative to the strongest signal in the spectrum.
[295] To calibrate the chemical shift of the 1H spectra, tetramethylsilane and / or the chemical shift of the solvent used were used, especially in the case of spectra determined with DMSO. Therefore, in the NMR peak lists, the tetramethylsilane peak may or may not occur.
[296] The 1H NMR peak lists are similar to the classic 1H NMR images and, as such, contain all of the peaks generally listed in the classical NMR interpretation. In addition, they can show, as in the classic 1H NMR images, signs of solvents, of the stereoisomers of the target compounds and which are also the subject of the invention, and / or peak impurities.
[29η To show signs of compounds in the solvent and / or water delta range, the usual solvent peaks, for example the DMSO peaks in DMSO-D6 and the water peak, appear in the 1H and NMR peak lists generally have a high intensity on average.
[298] The peaks of stereoisomers of the target compounds and / or peaks of impurities are generally on average less than the peaks of the target compounds (for example, with a degree of purity> 90%).
[299] These stereoisomers and / or impurities may be typical of the specific preparation process. Therefore, its peaks can help to recognize the reproducibility of the preparation process through the “fingerprints of the by-products”.
[300] An expert who estimates the peaks of the target compounds by known methods (MestreC, ACD simulation, but also by empirical evaluations of the expected values) can isolate the peaks of the target compounds as needed, using optionally additional intensity filters. This isolation would be similar to choosing the relevant peak in a classic 1H NMR interpretation.
[301] More information on the NMR data described with peak lists can be found in the publication “Citation of NMR Peaklist Data within Patent
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Applications from Research Disclosure database number 564025.
[302] NMR Peak Lists from Table 1
Example T ¹ H-NMR (400.1 MHz, DMSO):
δ = 10,295 (3.8); 8,850 (2.3); 8,847 (2.4); 8,838 (2.4); 8.162 (2.0); 8.142 (2.2); 7,771 (1.6); 7.759 (1.7); 7,752 (1.6); 7,740 (1.4); 7.362 (1.6); 7.303 (1.8); 7.285 (3.4); 7.253 (2.0); 7.234 (3.4); 7.227 (3.9);
7.215 (1.5); 7.098 (3.1); 7.092 (2.4); 7.081 (2.3); 3,484 (0.7); 3,467 (1.3); 3.448 (1.3); 3,431 (0.7);
3.399 (0.3); 3,349 (26.0); 2.561 (0.4); 2,515 (21.4); 2,511 (26.9); 2.507 (20.2); 2,190 (1.4); 2.169 (1.6);
2.158 (1.7); 2.138 (1.5); 1,576 (1.7); 1.560 (1.7); 1.544 (1.6); 1.529 (1.5); 1.329 (15.9); 1.292 (0.4);
1.279 (0.3); 1.268 (0.3); 1,244 (0.7); 1,218 (9.1); 1,200 (12.5); 1,195 (16.0)
Example 2i ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.238 (3.5); 8,837 (2.3); 8,833 (2.5); 8,825 (2.4); 8,821 (2,3); 8.146 (2.0); 8.127 (2.2); 7,756 (1.7); 7,744 (1.7); 7,736 (1.6); 7,724 (1.4); 7.341 (2.5); 7.338 (2.3); 7.326 (1.9); 7.316 (2.0); 7.305 (2.0);
7.205 (4.5); 7.070 (2.3); 7.035 (1.8); 7.011 (2.4); 6,989 (1.6); 3,510 (0.6); 3.492 (0.9); 3.475 (1.0);
3.458 (0.7); 3.312 (15.8); 2.50 (1.6); 2.50 (3.4); 2,500 (4.6); 2,496 (3.3); 2,491 (1.5); 2,221 (1.6);
2,200 (1.8); 2.189 (2.0); 2,180 (0.3); 2.167 (1.8); 1.988 (0.9); 1.909 (0.5); 1.633 (2.0); 1.620 (2.0);
1.601 (1.9); 1,587 (1.9); 1.428 (16.0); 1.355 (0.6); 1.316 (15.8); 1.267 (0.4); 1,248 (0.7); 1,218 (10.6); 1.201 (10.4); 1.193 (0.9); 1,175 (0.6); 1.157 (0.4); 0.858 (0.9); 0.840 (0.3); 0.000 (4.3)
Example 3: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.278 (5.5); 8,848 (3.4); 8,844 (3.7); 8,836 (4.0); 8,832 (3.9); 8.162 (3.1); 8.143 (3.5); 7,767 (2.4); 7,755 (2.8); 7,748 (2.5); 7,736 (2.4); 7.372 (0.5); 7.357 (3.0); 7.337 (0.4); 7,271 (2.1); 7.252 (5.2);
7.236 (3.5); 7.221 (8.3); 7.199 (2.4); 7.179 (0.5); 7.106 (4.1); 7.086 (5.7); 7.066 (0.6); 4.046 (0.6);
4.028 (0.6); 3.911 (0.7); 3.380 (1.0); 3,361 (1.9); 3,343 (2.0); 3.318 (38.3); 3.086 (0.8); 3.072 (1.0);
3.065 (1.8); 3.053 (1.9); 3.044 (1.2); 3.032 (1.0); 2,677 (0.4); 2,672 (0.3); 2,530 (1.1); 2,516 (25.1);
2,512 (51.1); 2.507 (69.1); 2.503 (48.9); 2,499 (22.8); 2,463 (0.4); 2.458 (0.4); 2.339 (0.4); 2.334 (0.5); 2.325 (1.3); 2.303 (2.2); 2.292 (1.6); 2.281 (1.4); 2,271 (2.4); 2.257 (0.6); 2.249 (1.4); 2,240 (1.2);
2,224 (1.8); 2.211 (1.7); 2.194 (1.4); 2.177 (0.6); 1.995 (2.6); 1,400 (1.4); 1.381 (2.2); 1.368 (1.5);
1.362 (1.5); 1.349 (2.0); 1,329 (1.3); 1.306 (0.4); 1.253 (0.4); 1.243 (0.7); 1.218 (14.5); 1.201 (14.7); 1.182 (1.7); 1,171 (0.4); 1.164 (0.9); 1.127 (1.2); 1,114 (1.1); 1.110 (1.3); 1.097 (0.8); 1.034 (14.5);
1.017 (14.2); 0.997 (1.0); 0.980 (1.3); 0.964 (0.9); 0.770 (16.0); 0.754 (15.7); 0.726 (0.6); 0.715 (0.9); 0.698 (0.8)
Example 4: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.208 (5.7); 8,839 (3.5); 8,836 (3.9); 8,827 (4.1); 8,824 (4.1); 8.153 (3.3); 8.133 (3.7); 7,761 (2.5); 7,749 (2.8); 7,742 (2.8); 7,730 (2.5); 7.370 (3.6); 7.351 (4.6); 7.339 (4.1); 7.203 (8.3); 7.199 (3.6);
7.180 (5.5); 7.161 (3.6); 7.119 (4.9); 7.101 (3.1); 7.068 (4.0); 3.50 (1.2); 3.477 (1.5); 3,486 (1.9);
3,479 (2.0); 3,468 (1.6); 3,460 (1.4); 3.451 (0.6); 3,441 (0.5); 3,391 (0.4); 3,340 (134.1); 3.291 (0.5);
78/116
3.041 (0.8); 3.020 (1.7); 3,000 (1.9); 2.980 (2.5); 2.959 (1.3); 2,852 (1.2); 2.842 (1.5); 2.830 (1.6);
2.820 (1.7); 2.812 (1.2); 2.802 (1.1); 2,790 (1.1); 2,780 (1.1); 2.682 (0.5); 2,677 (0.7); 2,673 (0.5);
2.531 (1.5); 2.526 (2.3); 2,517 (35.5); 2,513 (76.7); 2.50 (108.5); 2.50 (84.9); 2,499 (48.7); 2.459 (1.0); 2.340 (0.5); 2.335 (0.7); 2,331 (0.6); 2,244 (0.7); 2,222 (1.8); 2.213 (1.1); 2.201 (2.0); 2.191 (2.3);
2,180 (1.0); 2,170 (2.0); 2.149 (0.7); 1.709 (0.8); 1,700 (1.6); 1.690 (1.6); 1,679 (2.2); 1,669 (2.2);
1.659 (1.6); 1,649 (1.5); 1.639 (0.9); 1.124 (15.6); 1.106 (16.0)
Example 5: ¹ H-NMR (300.2 MHl CDCl3):
δ = 8.806 (1.0); 8.801 (1.0); 8,790 (1.1); 8.157 (0.8); 8.131 (0.9); 8.095 (1.0); 8.069 (1.0); 7.639 (0.7); 7,600 (0.8); 7.589 (1.7); 7.564 (1.9); 7.382 (0.7); 7.356 (1.2); 7.329 (0.6); 7.262 (19.6); 7.136 (1.1); 6,953 (2,3); 6,771 (1.1); 3.999 (16.0); 2.981 (0.4); 2,957 (6.7); 2.950 (2.4); 2.936 (0.7); 2.925 (0.7); 1.570 (15.5); 1.263 (0.4); 0.000 (6.7)
Example is ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.802 (0.9); 8,798 (0.9); 8.786 (0.9); 8,782 (0.9); 8.147 (0.7); 8.121 (0.8); 8.077 (0.9); 8.051 (0.9); 7.633 (0.7); 7.594 (1.7); 7.569 (2.0); 7.551 (0.6); 7.367 (0.6); 7.341 (1.1); 7.315 (0.5); 7.262 (11.4); 7.140 (1.1); 6,957 (2.2); 6,775 (1.1); 4.482 (0.4); 4,461 (1.0); 4,441 (1.4); 4.420 (1.0); 4,399 (0.4); 2.947 (10.2); 2.928 (0.4); 2.921 (0.4); 1.580 (10.7); 1.314 (16.0); 1.293 (15.9); 0.000 (5.6)
Example 7: 'H-NMR (300.2 MHz, CDCl3);
δ = 8.794 (1.4); 8,790 (1.5); 8,778 (1.5); 8,774 (1.5); 8.133 (1.1); 8.108 (1.3); 8.059 (1.4); 8.032 (1.5); 7.670 (1.1); 7.584 (2.6); 7.560 (3.1); 7.540 (0.9); 7.363 (1.0); 7.337 (1.7); 7.311 (0.8); 7.263 (7.8);
7.136 (1.7); 6,954 (3.5); 6,771 (1.7); 4.209 (3.3); 4,187 (6.9); 4.165 (3.4); 2.949 (16.0); 2.930 (0.7);
2.913 (0.3); 1.753 (0.6); 1.730 (1.9); 1.722 (0.7); 1.708 (2.4); 1.681 (2.1); 1.659 (0.9); 1.617 (6.0);
1.496 (0.5); 1,472 (1.5); 1.446 (2.2); 1.428 (1.1); 1.421 (2.3); 1.404 (0.5); 1.397 (1.4); 1.373 (0.5);
0.985 (5.6); 0.961 (11.3); 0.936 (4.5); 0.000 (4.4)
Example ¹ H-NMR (300.2 MHz ^ CDCl3):
δ = 8.799 (1.3); 8,795 (1.4); 8,783 (1.4); 8,779 (1.4); 8.143 (1.0); 8.117 (1.2); 8.073 (1.3); 8.047 (1.4); 7.653 (1.0); 7.590 (2.6); 7.565 (3.0); 7.548 (0.9); 7.370 (1.0); 7.344 (1.6); 7.317 (0.8); 7.263 (10.8); 7.138 (1.6); 6,955 (3.3); 6,773 (1.6); 4,273 (1.7); 4.250 (5.5); 4.238 (0.4); 4.246 (5.6); 4.215 (0.4); 4.203 (1.8); 2.955 (16.0); 1,597 (12.4); 1.356 (5.8); 1,333 (12.2); 1.309 (5.7); 0.000 (4.9)
Example 9: ¹ H-NMR (300.2 MHz ^ CDCI3):
δ = 8.856 (0.8); 8,736 (1.4); 8,731 (1.4); 8,720 (1.5); 8,716 (1.5); 8.067 (1.4); 8.041 (1.5); 7.645 (1.8); 7.618 (2.1); 7.607 (0.9); 7.531 (1.2); 7.515 (1.2); 7.505 (1.2); 7.488 (1.0); 7.358 (1.2); 7.332 (2.5);
7.305 (1.5); 7.261 (131.2); 7.194 (0.5); 7.181 (2.3); 7.152 (2.4); 6,969 (3.5); 6,936 (0.6); 6,910 (0.8); 6,787 (1.6); 5.301 (3.6); 3.878 (0.6); 3,871 (1.9); 3,455 (0.6); 3,431 (1.0); 3.406 (1.0); 3.384 (0.6);
2,268 (1.6); 2.241 (1.6); 2.226 (1.8); 2,199 (1.7); 2.046 (1.3); 2.009 (1.1); 1.682 (2.1); 1,661 (2.5);
1.640 (3.1); 1.618 (5.5); 1,598 (8.0); 1.507 (1.6); 1,484 (1.5); 1.455 (0.4); 1.378 (16.0); 1.325 (2.0); 1.291 (9.7); 1.268 (10.2); 1,260 (1.9); 1.237 (15.4); 1.125 (1.9); 0.882 (0.5); 0.067 (0.4); 0.011 (3.2);
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0.000 (85.4); -0.011 (3.7); -0.051 (0.4); -0.067 (0.5)
Example 1Õ: ¹ H-NMR (400.0 MHz, DMSO):
δ = 10,120 (1.7); 8,827 (1.0); 8,823 (1.1); 8,815 (1.0); 8,811 (1.0); 8.124 (0.9); 8.104 (0.9); 7,746 (0.7); 7,735 (0.7); 7,727 (0.7); 7,715 (0.6); 7.329 (0.8); 7.199 (1.6); 7.194 (2.0); 7.178 (1.7); 7.058 (0.9);
6,790 (1.4); 6.769 (1.3); 3,382 (0.4); 3.365 (0.4); 3.347 (0.3); 3.323 (23.5); 2.523 (0.8); 2,519 (1.2);
2,510 (14.1); 2.50 (28.1); 2,501 (36.7); 2,497 (26.2); 2.492 (12.3); 2,170 (0.7); 2.149 (0.8); 2,139 (1.1); 2.129 (0.4); 2.121 (0.9); 2,117 (1.0); 2.108 (0.4); 2,100 (0.4); 1.613 (0.8); 1,600 (0.8); 1,581 (0.8);
1.568 (0.8); 1.522 (8.5); 1.397 (16.0); 1.394 (9.4); 1.320 (0.5); 1.208 (0.5); 1.198 (4.4); 1,181 (4.4);
0.941 (1.5); 0.924 (1.2); 0.920 (1.5); 0.721 (0.4); 0.713 (0.9); 0.707 (1.1); 0.700 (1.2); 0.695 (1.0);
0.690 (0.7); 0.682 (0.3); 0.008 (0.5); 0.000 (15.3); -0.009 (0.5)
Example ΪΤ ¹ H-NMR (400.0 MHz, DMSO);
δ = 10,134 (3.5); 8,828 (2.4); 8,816 (2.3); 8.132 (2.1); 8.113 (2.2); 7,748 (1.6); 7,736 (1.7); 7.729 (1.5); 7,717 (1.3); 7.339 (1.5); 7.203 (4.0); 7.198 (3.1); 7.178 (3.2); 7.068 (1.6); 6,981 (2.9); 6,961 (2.3); 5.757 (0.4); 4.037 (0.5); 4.020 (0.5); 3,398 (0.8); 3,381 (1.2); 3.364 (1.3); 3,346 (1.1); 3,323 (14.8); 2.50 (39.9); 2,501 (43.8); 2,497 (31.1); 2,351 (14.8); 2.149 (1.4); 2.127 (1.6); 2,117 (1.7); 2.095 (1.4); 1,988 (2.0); 1,584 (1.7); 1.570 (1.7); 1.552 (1.5); 1.539 (1.4); 1.406 (16.0); 1.281 (15.2); 1.258 (0.6); 1.234 (0.5); 1.196 (9.0); 1.178 (8.6); 1.156 (0.7); 0.002 (7.1); 0.000 (14.8); -0.008 (0.6)
Example 12: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.480 (3.4); 8,854 (2.0); 8,850 (2.2); 8,842 (2.2); 8,838 (2.1); 8.170 (1.7); 8.151 (1.9); 7,771 (1.4); 7.759 (1.4); 7,751 (1.4); 7,739 (1.3); 7.385 (0.8); 7.381 (1.2); 7.365 (3.7); 7.361 (3.5); 7.357 (3.1);
7.350 (2.2); 7.339 (2.7); 7.320 (1.1); 7.215 (4.0); 7.157 (2.3); 7.153 (2.3); 7.139 (2.0); 7.136 (1.9);
7.080 (2.1); 5.409 (0.7); 5.394 (2.3); 5.378 (2.3); 5.362 (0.6); 4.043 (0.5); 4.026 (0.5); 3,395 (0.6);
3,394 (0.7); 3.390 (0.7); 3.352 (96.4); 3.313 (0.6); 3.310 (0.6); 2.530 (0.4); 2.526 (0.6); 2,517 (6.4);
2,513 (13.1); 2.508 (17.7); 2.503 (12.4); 2,499 (5.7); 1.995 (2.2); 1,495 (16.0); 1,478 (0.5); 1.455 (0.4); 1.416 (0.3); 1.393 (14.4); 1.360 (0.4); 1,336 (9.2); 1.321 (9.0); 1.252 (0.4); 1.198 (0.6); 1,180 (1.2);
1,162 (0.6); 0.863 (0.6)
Example 13: ¹ H-NMR (499.9 MHz ^ CDCl3):
δ = 8.770 (1.2); 8,762 (1.2); 8.035 (0.9); 8.020 (0.9); 7,753 (1.0); 7,737 (1.0); 7.691 (1.0); 7.517 (0.7); 7.507 (0.8); 7.493 (0.6); 7.274 (0.6); 7.258 (2.7); 7.243 (0.6); 7.127 (1.4); 7.035 (1.7); 7.018 (3.9);
6.908 (1.5); 4,113 (0.8); 4.098 (0.8); 3.374 (0.4); 3.360 (0.7); 3.348 (0.7); 3.334 (0.4); 2.251 (1.3);
2,234 (1.4); 2,225 (1.5); 2.208 (1.4); 2.025 (3.4); 1,666 (2.5); 1.656 (1.8); 1.640 (1.5); 1.630 (1.5);
1.345 (16.0); 1.291 (4.8); 1,277 (4.8); 1,268 (1.7); 1.262 (2.0); 1,248 (2.8); 1.238 (8.5); 1.218 (0.3);
0.895 (0.7); 0.881 (1.9); 0.867 (0.9); 0.000 (1.1)
Example 14: ¹ H-NMR (400.0 MHz ^ DMSO):
δ = 10,180 (3.3); 8,830 (2.1); 8,826 (2.2); 8,818 (2.2); 8,815 (2.1); 8.185 (1.9); 8.166 (2.1); 7,959 (1.2); 7,739 (1.5); 7,727 (1.6); 7,720 (1.5); 7.708 (1.3); 7,400 (2.4); 7.381 (2.9); 7.334 (1.6); 7.216 (1.5);
80/116
7.198 (5.9); 7.178 (1.5); 7.063 (4.5); 7.044 (2.3); 3.332 (30.9); 2.996 (1.2); 2.978 (1.4); 2.956 (1.5);
2.938 (1.5); 2,897 (8.4); 2.738 (7.0); 2,517 (15.8); 2,512 (29.7); 2.50 (37.8); 2.503 (27.5); 2,499 (13.6);
2,465 (1.4); 2,451 (1.1); 2.425 (1.2); 2.082 (0.7); 2.074 (0.4); 2.064 (1.1); 2.057 (0.9); 2.046 (0.9);
2.039 (1.1); 2.029 (0.4); 2.021 (0.6); 1,260 (16.0); 1.043 (9.1); 1.026 (8.7); 0.942 (14.1)
Example 15: 'H-NMR (400.0 MHz ^ DMSO):
δ = 10.467 (3.1); 8,847 (1.8); 8,844 (1.9); 8,835 (1.9); 8,832 (1.9); 8.164 (1.6); 8.145 (1.7); 7,765 (1.2); 7,753 (1.3); 7,746 (1.2); 7,734 (1.1); 7.567 (2.3); 7.545 (3.1); 7.424 (3.1); 7.403 (2.4); 7.327 (1.6);
7.191 (3.4); 7.056 (1.7); 5.757 (1.1); 5.420 (0.6); 5.404 (2.1); 5.388 (2.1); 5.373 (0.6); 4.038 (0.5);
4.020 (0.5); 3,323 (19.1); 2,671 (0.4); 2.524 (1.1); 2,510 (22.4); 2.50 (45.0); 2.502 (59.2); 2,497 (43.8); 2.493 (21.8); 2.328 (0.4); 1,989 (2.0); 1.624 (16.0); 1.511 (15.0); 1.349 (8.0); 1,333 (7.9); 1.235 (0.3); 1.193 (0.6); 1,175 (1.1); 1.157 (0.6); 0.008 (1.3); 0.000 (38.1); -0.009 (1.5)
Example 16: ¹ H-NMR (400.0 MHz ^ DMSO):
δ = 10.266 (3.2); 8,837 (1.9); 8,834 (1.9); 8,826 (2.0); 8,822 (1.8); 8.145 (1.6); 8.125 (1.7); 7,758 (1.3); 7,746 (1.3); 7,739 (1.2); 7,727 (1.1); 7.415 (2.6); 7.394 (3.3); 7.330 (1.5); 7.257 (3.0); 7.236 (2.4);
7.195 (3.5); 7.059 (1.8); 5.757 (3.0); 4.038 (0.6); 4.020 (0.6); 3.494 (0.5); 3,481 (0.7); 3,476 (0.8);
3.473 (0.8); 3.460 (0.8); 3,455 (0.7); 3,442 (0.6); 3,323 (16.1); 2.670 (0.4); 2,510 (22.7); 2.50 (43.4); 2,501 (55.3); 2,497 (39.9); 2.492 (19.2); 2.328 (0.4); 2,224 (1.3); 2.201 (1.4); 2.191 (1.6); 2.169 (1.4); 1,989 (2.5); 1.659 (1.6); 1.648 (1.6); 1.627 (1.5); 1.615 (1.5); 1.475 (16.0); 1.374 (13.7); 1.320 (1.2); 1.207 (8.0); 1,190 (8.2); 1,175 (1.6); 1.157 (0.7); 0.008 (1.6); 0.000 (35.8); -0.009 (1.4)
Example Vl ·. ¹ H-NMR (300.2 MHz, CDCI3):
δ = 8.791 (2.6); 8,779 (2.6); 8,775 (2.6); 8.127 (2.0); 8.102 (2.2); 7.698 (2.3); 7.672 (2.9); 7.651 (0.4); 7.615 (0.4); 7.608 (0.4); 7.588 (1.8); 7.571 (2.2); 7.561 (2.5); 7.546 (3.1); 7.498 (0.4); 7.434 (0.6);
7.371 (1.5); 7.346 (3.0); 7.329 (0.7); 7.320 (1.6); 7.262 (37.1); 7.194 (0.3); 7.126 (3.0); 7.027 (4.1);
7,002 (3.5); 6,943 (6.2); 6,930 (0.4); 6,911 (0.3); 6,760 (3.1); 6.748 (0.5); 5.083 (16.0); 5.022 (0.6);
4.455 (0.8); 4.431 (0.8); 4.107 (0.4); 3.702 (3.3); 3.157 (0.4); 3.134 (0.5); 2.181 (0.5); 2.043 (1.5);
1,592 (0.9); 1,571 (13.9); 1.525 (67.3); 1,496 (2.7); 1.453 (1.0); 1.429 (1.8); 1.405 (0.8); 1.283 (0.9); 1.259 (1.9); 1.235 (0.8); 1.093 (0.5); 1.069 (1.0); 1.045 (0.5); 0.070 (0.4); 0.011 (0.9), 0.000 (23.8), 0.011 (0.9)
Example 18: ¹ H-NMR (400.1 MHzj DMSO):
δ = 10.275 (3.9); 8.230 (2.6); 8,210 (3.0); 7,914 (3.0); 7.893 (2.7); 7.354 (2.9); 7.344 (1.9); 7.334 (2.0); 7.322 (1.9); 7.219 (4.6); 7.085 (2.2); 7.039 (1.8); 7.015 (2.4); 6,992 (1.6); 3,491 (0.6); 3,473 (0.9); 3.456 (1.0); 3.439 (0.6); 3,310 (8.1); 2.523 (0.4); 2.518 (0.7); 2,510 (9.6); 2.50 (19.7); 2,501 (26.7); 2,496 (18.7); 2.492 (8.5); 2,221 (1.6); 2,199 (1.8); 2.189 (2.0); 2.167 (1.7); 2.073 (0.3); 1.632 (2.0); 1.618 (1.9); 1.599 (1.8); 1,586 (1.8); 1.425 (16.0); 1.314 (15.4); 1.204 (10.2); 1.186 (10.1)
Example 19: ¹ H-NMR (400.1 MHz, DMSO);
δ = 10.293 (3.1); 8.230 (1.8); 8.209 (2.1); 7,912 (2.2); 7.891 (19); 7.358 (1.7); 7.310 (1.6); 7.292 (2.6);
81/116
7.244 (1.6); 7.224 (5.8); 7.206 (1.2); 7.089 (4.4); 7.072 (2.0); 3.457 (0.5); 3.439 (0.9); 3,421 (0.9);
3.404 (0.6); 3.309 (6.6); 2.522 (0.5); 2.50 (11.4); 2.50 (23.3); 2,500 (31.6); 2,495 (22.2); 2,491 (10.2);
2.182 (1.4); 2.161 (1.5); 2,150 (1.7); 2,130 (1.4); 2.072 (0.7); 1.568 (1.6); 1,553 (1.6); 1.536 (1.5);
1.521 (1.4); 1.317 (16.0); 1.196 (8.5); 1,184 (14.6); 1,179 (10.7)
Example 2Õ: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10,191 (9.6); 8,833 (5.8); 8,830 (6.2); 8,822 (6.0); 8,818 (5.8); 8.199 (5.2); 8.180 (5.6); 7,746 (4.1); 7,734 (4.3); 7,727 (4.0); 7,715 (3.6); 7.366 (6.6); 7.346 (8.3); 7.339 (6.0); 7.219 (0.4); 7.203 (11.4); 7.167 (4.1); 7.148 (7.3); 7.129 (3.6); 7.068 (5.6); 6.621 (7.7); 6.602 (7.2); 5,761 (6.5); 3.377 (0.4); 3,382 (0.4); 3.369 (0.4); 3.319 (137.0); 3,269 (0.4); 3.005 (6.8); 2.987 (12.2); 2.967 (7.5); 2.682 (0.6); 2,677 (0.7); 2,672 (0.6); 2.558 (0.6); 2.547 (0.5); 2,530 (2.1); 2.517 (43.5); 2,512 (88.0); 2.50 (118.4); 2.503 (83.6); 2,499 (39.0); 2.467 (0.4); 2,463 (0.5); 2.459 (0.5); 2.339 (0.5); 2.335 (0.7); 2.330 (0.6); 2,111 (8.8); 2.092 (13.8); 2,073 (8.0); 1.268 (0.6); 1.249 (1.3); 1,244 (0.9); 1,230 (0.6); 0.971 (4.3); 0.967 (3.5); 0.958 (10.9); 0.953 (16.0); 0.945 (8.5); 0.938 (3.7); 0.911 (3.9); 0.904 (9.1); 0.896 (16.0); 0.891 (11.4); 0.882 (3.6); 0.878 (4.4)
Example 2Ϊ: ¹ H-NMR (400.1 MHz ^ DMSO):
δ = 10.227 (2.4); 8.678 (2.1); 8.675 (2.1); 7,963 (2.0); 7.308 (1.2); 7.281 (0.8); 7.278 (0.9); 7.261 (2.2); 7.258 (2.1); 7.244 (1.5); 7.225 (1.9); 7.206 (0.8); 7.172 (2.5); 7.092 (1.7); 7.089 (1.7); 7.074 (1.4); 7.071 (1.4); 7.037 (1.3); 3.484 (0.4); 3,467 (0.7); 3.448 (0.7); 3,431 (0.4); 3.318 (18.9); 2.530 (0.4); 2,517 (7.9); 2,512 (16.1); 2.50 (21.8); 2.503 (15.3); 2,499 (7.1); 2.457 (7.5); 2.189 (1.0); 2,168 (1.1); 2.157 (1.3); 2.136 (1.1); 1.996 (0.6); 1,573 (1.2); 1.558 (1.2); 1,541 (1.1); 1.526 (1.1); 1.347 (0.6); 1,328 (12.1); 1.256 (1.0); 1.210 (6.5); 1.193 (16.0); 1.183 (1.2); 1.165 (0.4); 0.883 (0.4); 0.867 (1.5); 0.849 (0.6)
Example 22: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.428 (3.3); 8.684 (2.9); 8.681 (2.9); 7,975 (2.8); 7.358 (0.6); 7.346 (6.6); 7.339 (3.5); 7.332 (3.1); 7.312 (0.6); 7.297 (1.6); 7.161 (3.8); 7.151 (2.2); 7.144 (1.6); 7.137 (1.8); 7.130 (1.7); 7.026 (1.8); 5.410 (0.6); 5.394 (2.3); 5.379 (2.3); 5.363 (0.6); 4.046 (0.5); 4.028 (0.5); 3.318 (37.4); 2.530 (0.6); 2,517 (13.6); 2,512 (27.8); 2.50 (37.6); 2.503 (26.4); 2,499 (12.2); 2.458 (10.4); 1.995 (2.1); 1,496 (16.0); 1.394 (14.5); 1,333 (9.0); 1.317 (9.0); 1.287 (0.5); 1.266 (0.8); 1.255 (2.1); 1,200 (0.6); 1.182 (1.2); 1,165 (0.6); 0.883 (1.0); 0.866 (3.3); 0.848 (1.2)
Example 23: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.207 (3.8); 8.677 (3.3); 8.674 (3.6); 7,960 (3.5); 7.320 (1.9); 7.309 (2.2); 7.299 (3.7); 7.288 (2.5); 7.164 (3.9); 7.038 (1.9); 7.029 (2.3); 7.015 (2.7); 6,992 (1.7); 3.517 (0.6); 3,500 (1.1); 3,483 (1.1); 3.465 (0.8); 3.319 (37.7); 2.531 (0.5); 2.527 (0.8); 2,518 (12.6); 2,513 (27.7); 2.50 (39.9); 2.50 (31.5); 2,500 (18.6); 2.454 (12.9); 2,227 (1.6); 2.206 (1.8); 2.195 (2.2); 2.173 (2.0); 1.639 (2.0); 1.625 (2.1); 1.606 (1.9); 1.593 (2.0); 1.436 (16.0); 1.362 (0.6); 1.323 (15.9); 1.218 (10.4); 1.201 (10.9)
Example 24: ¹ H-NMR (400.1 MHz, DMSO):
82/116 δ = 10,491 (3.6); 8.258 (2.2); 8.237 (2.5); 7,924 (2.6); 7.903 (2.3); 7.394 (1.3); 7.377 (3.1); 7.375 (3.1); 7.362 (2.9); 7.342 (2.7); 7.323 (1.2); 7.229 (4.2); 7.160 (2.4); 7.158 (2.6); 7.143 (2.2); 7.140 (2.2); 7.095 (2.1); 5.396 (0.7); 5.380 (2.2); 5.364 (2.3); 5.349 (0.7); 3.318 (17.8); 2.531 (0.4); 2.526 (0.7); 2,517 (8.4); 2,513 (17.6); 2.50 (24.5); 2.50 (17.9); 2,499 (9.0); 1,495 (16.0); 1.392 (14.5); 1,328 (8.8); 1.312 (9.0); 1.287 (1.8); 1.274 (2.0); 1.265 (2.7); 1.255 (7.1); 0.883 (3.2); 0.866 (11.6); 0.848 (4.3) Example 25: ’H-NMR (400.1 MHz, CDCl3):
δ = 8,814 (1.9); 8.804 (1.9); 8.091 (1.5); 8.072 (1.6); 7,700 (1.7); 7.681 (1.9); 7.583 (1.1); 7.571 (1.3); 7.565 (1.4); 7.553 (1.2); 7.519 (2.0); 7.512 (1.2); 7.372 (1.2); 7.353 (2.1); 7.334 (1.1); 7.260 (43.7);
7.144 (2.3); 7,007 (4.6); 6,996 (0.4); 6,936 (3.1); 6,918 (2.8); 6,870 (2.3); 5.493 (0.6); 5.477 (1.7);
5.461 (1.7); 5.446 (0.6); 5.298 (1.8); 4.129 (0.7); 4,111 (0.7); 2.042 (3.0); 1.890 (0.7); 1.885 (0.5);
1.872 (1.4); 1.867 (1.4); 1.855 (3.8); 1.848 (2.0); 1.836 (5.4); 1.832 (3.0); 1.818 (3.8); 1.813 (2.6);
1.801 (1.6); 1,795 (0.9); 1,783 (0.7); 1.760 (0.6); 1.742 (1.5); 1.724 (1.7); 1.706 (1.3); 1,688 (1.0);
1.670 (0.5); 1,491 (8.1); 1.475 (8.0); 1.304 (0.4); 1,276 (1.5); 1,265 (1.8); 1.258 (2.8); 1.243 (0.6);
1,240 (1.0); 0.899 (0.9); 0.882 (2.6); 0.864 (1.1); 0.818 (7.4); 0.800 (16.0); 0.781 (7.7); 0.774 (3.9);
0.756 (6.9); 0.737 (3.4); 0.008 (1.0); 0.000 (30.8); -0.009 (1.0)
Example 26: ’H-NMR (400.1 MHz, CDCI3):
δ = 8.711 (0.4); 8.612 (3.4); 8.209 (0.3); 7.874 (3.0); 7.692 (2.1); 7.672 (2.3); 7.532 (2.1); 7.480 (0.3); 7.366 (1.3); 7.347 (2.5); 7.328 (1.3); 7.260 (33.9); 7.098 (2.3); 6,961 (4.8); 6,930 (3.6); 6,911 (3.3);
6,824 (2.4); 5.493 (0.7); 5.477 (2.0); 5.461 (2.1); 5.446 (0.7); 2,476 (11.1); 1.889 (0.8); 1.885 (0.6); 1.871 (1.7); 1.866 (1.7); 1,854 (4.2); 1.848 (2.4); 1.836 (5.9); 1.831 (3.6); 1.818 (4.2); 1.813 (3.0);
1,800 (1.7); 1,794 (1.1); 1,782 (0.8); 1.760 (0.7); 1.741 (1.7); 1.723 (2.0); 1.706 (1.5); 1,688 (1.1);
1,669 (0.5); 1,485 (9.1); 1.470 (9.0); 1.264 (0.8); 1.258 (0.7); 0.899 (0.3); 0.882 (0.9); 0.864 (0.4);
0.817 (7.6); 0.799 (16.0); 0.780 (8.2); 0.774 (4.8); 0.755 (8.2); 0.737 (4.0); 0.008 (0.8); 0.000 (22.0); 0.008 (0.9)
Example 27: ¹ H-NMR (400.1 MHz, CDCl3):
δ = 8.754 (3.6); 8.744 (3.7); 8.059 (3.1); 8.040 (3.3); 7.867 (3.4); 7.847 (3.6); 7.685 (3.1); 7.514 (2.2); 7.502 (2.7); 7.496 (2.6); 7.483 (2.1); 7.261 (2.8); 7.217 (1.7); 7.198 (3.6); 7.179 (2.5); 7.124 (6.8);
7.108 (3.5); 6,987 (6.6); 6,850 (3.3); 4.109 (0.4); 4.091 (0.4); 2.988 (2.2); 2.978 (2.6); 2.969 (2.9);
2.960 (2.7); 2.844 (1.8); 2.824 (2.4); 2.807 (2.2); 2,787 (3.1); 2.726 (0.8); 2.707 (1.6); 2,686 (2.1);
2,667 (1.8); 2.648 (0.9); 2.545 (2.3); 2,521 (1.9); 2.50 (2.0); 2,484 (1.4); 2.143 (0.5); 2.126 (1.4);
2,115 (2.1); 2,110 (2.2); 2.099 (2.0); 2.093 (1.7); 2.083 (1.5); 2.066 (0.7); 2.023 (1.8); 1.720 (1.3);
1.304 (0.4); 1,265 (2.4); 1.247 (1.3); 1.229 (0.7); 1,176 (15.8); 1.159 (16.0); 1.076 (13.3); 1.058 (13.5); 0.898 (0.9); 0.881 (2.1); 0.863 (1.0); 0.681 (11.7); 0.665 (11.9); 0.638 (0.8); 0.000 (1.3)
Example 28: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.897 (1.2); 8,880 (1.3); 7.881 (1.1); 7.855 (1.3); 7.801 (1.0); 7,784 (1.0); 7.506 (0.6); 7.327 (0.8); 7.301 (1.5); 7.275 (0.9); 7.259 (3.4); 7.232 (0.8); 7.065 (1.3); 7.063 (1.3); 7.052 (2.0); 7.040 (1.2);
83/116
6,871 (2.4); 6.690 (1.1); 3.319 (0.4); 3.310 (0.4); 2.285 (0.8); 2.257 (0.8); 2.242 (1.0); 2.213 (0.9); 1,700 (1.1); 1.687 (1.1); 1.657 (1.0); 1.644 (1.0); 1,571 (1.7); 1.346 (9.4); 1.289 (5.9); 1,266 (16.0); 0.904 (0.6); 0.882 (2.0); 0.859 (0.7); 0.000 (2.0)
Example 29: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.607 (1.7); 8.031 (0.9); 8,005 (1.0); 7.898 (1.4); 7.644 (0.8); 7.582 (1.3); 7.558 (1.7); 7.376 (0.8); 7.350 (1.3); 7.324 (0.6); 7.261 (17.7); 7.125 (1.1); 6,942 (2.1); 6.759 (1.1); 5,300 (1.2); 3.995 (16.0); 3,495 (0.5); 3,473 (0.7); 3.451 (0.5); 3.121 (1.0); 3.093 (0.9); 3.058 (1.3); 3.031 (1.1); 2,642 (1.4); 2.635 (1.4); 2,580 (1.1); 2,573 (1.1); 2,479 (5.7); 1,561 (12.5); 1.255 (4.9); 1,231 (4.8); 0.011 (0.4); 0.000 (10.3); -0.011 (0.5)
Example 3Õ: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.815 (0.8); 8.811 (0.8); 8,799 (0.9); 8.113 (0.6); 8.087 (0.7); 8.019 (0.7); 7.993 (0.8); 7.653 (0.6); 7.590 (1.4); 7.577 (0.7); 7.565 (1.7); 7.553 (0.5); 7.378 (0.6); 7.352 (0.9); 7.326 (0.5); 7.262 (10.5);
7.172 (0.9); 6,989 (1.7); 6.807 (0.9); 3,996 (16.0); 3,984 (0.5); 3.502 (0.3); 3,496 (0.4); 3,474 (0.6);
3.452 (0.5); 3,446 (0.4); 3.122 (0.9); 3.094 (0.9); 3.059 (1.3); 3.032 (1.1); 2,642 (1.3); 2.634 (1.3);
2.579 (1.0); 2.572 (1.0); 2.043 (0.6); 1.575 (7.9); 1.282 (0.7); 1.259 (5.0); 1.236 (3.8); 0.904 (0.5);
0.882 (1.8); 0.859 (0.6); 0.000 (6.1)
Example 31: ¹ H-NMR (400.1 ΜΗ! DMSO):
δ = 10,320 (0.8); 8.321 (0.5); 8.301 (0.6); 8.090 (0.5); 8.071 (0.6); 7.908 (0.6); 7.888 (0.5); 7.761 (0.5); 7,741 (0.5); 7.389 (0.3); 7.369 (0.6); 7.363 (0.5); 7.350 (0.3); 7.229 (0.8); 7.095 (0.4); 3,921 (5.0);
3.870 (1.7); 3.316 (0.9); 2.930 (2.1); 2.516 (1.3); 2.512 (2.5); 2.507 (3.3); 2.503 (2.4); 2,499 (1.1);
1.426 (2.6); 1.303 (0.9); 1.286 (2.0); 1.254 (16.0); 0.881 (4.3); 0.865 (13.0); 0.847 (5.2)
Example 32: ¹ H-NMR (400.1 MH DMSO):
δ = 10.268 (1.4); 10.222 (0.4); 8.671 (1.9); 8.086 (1.1); 8.067 (1.2); 8.043 (1.4); 8.026 (0.6); 7,711 (1.0); 7.692 (1.2); 7.666 (0.4); 7.647 (0.4); 7.386 (0.7); 7.366 (1.3); 7.346 (0.6); 7.336 (0.4); 7.316 (0.4); 7.297 (0.9); 7.161 (1.5); 7.151 (0.6); 7.026 (0.8); 3,921 (11.4); 3,871 (4.1); 3.318 (3.2); 2.932 (4.8); 2,517 (4.7); 2,512 (9.8); 2.50 (13.6); 2.503 (10.1); 2,499 (5.2); 2,453 (6.0); 1.427 (6.0); 1.254 (16.0)
Example 33: ’H-NMR (300.2 MHz, DMSO):
δ = 7.263 (0.4); 7.174 (0.4); 3.348 (16.0); 3,324 (1.1); 2.537 (15); 2.531 (3.3); 2.525 (4.7); 2,519 (3.4); 2,513 (1.7); 1.379 (0.4); 1.305 (1.6); 1.234 (1.0); 1.212 (1.0); 1.068 (0.9); 1.045 (0.8); 0.926 (1.4)
Example 3 * ¹ H-NMR (400.1 Mhíl DMSO):
δ = 10.289 (1.3); 10.241 (0.6); 8,839 (1.3); 8,831 (1.1); 8,827 (1.3); 8.227 (0.8); 8.208 (1.2); 8.190 (0.5); 8.086 (1.1); 8.067 (1.1); 7,743 (1.5); 7,731 (1.0); 7,724 (1.5); 7.699 (0.5); 7.681 (0.5); 7.390 (1.0);
7.371 (1.8); 7.351 (0.6); 7.344 (0.9); 7.335 (0.5); 7.321 (0.6); 7.209 (1.7); 7.199 (1.0); 7.074 (0.8);
7.064 (0.5); 3,921 (11.3); 3,871 (6.4); 3.316 (5.9); 2.935 (4.8); 2.530 (0.4); 2,516 (8.9); 2,512 (18.2); 2.507 (24.5); 2.503 (17.2); 2,498 (7.9); 1.995 (0.7); 1.424 (9.2); 1.252 (16.0); 1.182 (0.4); 0.866 (0.5)
Example 35: ¹ H-NMR (300.2 MHz, DMSO):
84/116 δ = 10.384 (0.7); 8.707 (0.8); 8.702 (0.8); 8,008 (0.7); 7.401 (0.4); 7.228 (0.7); 7.220 (0.9); 7.203 (0.7); 7.159 (0.8); 7.136 (0.5); 7.132 (0.4); 7.123 (0.8); 7.119 (0.6); 7.099 (0.5); 7.095 (0.4); 7.039 (0.4); 5,782 (1.6); 3,349 (16.0); 3.325 (1.0); 2.537 (1.4); 2.531 (3.2); 2.525 (4.4); 2,519 (3.2); 2.513 (1.6); 2,477 (2.8); 1.379 (1.1); 1.304 (3.6); 1.227 (2.2); 1.205 (2.1); 1.068 (2.0); 1.045 (1.9); 0.925 (3.1) Example 36: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10,169 (5.8); 8,820 (3.5); 8,817 (3.9); 8.809 (3.9); 8.805 (3.7); 8.179 (3.3); 8.160 (3.6); 7.729 (2.6); 7,717 (2.7); 7,710 (2.7); 7.698 (2.4); 7.392 (3.9); 7.373 (4.8); 7.321 (2.9); 7.193 (2.9); 7.186 (6.9);
7.174 (5.1); 7.155 (2.9); 7.070 (5.1); 7.051 (6.5); 3.306 (66.8); 3.184 (0.5); 3.166 (1.8); 3.148 (2.7);
3.131 (2.0); 3,114 (0.6); 2.975 (1.1); 2,952 (2.6); 2.930 (2.9); 2.907 (1.7); 2,674 (1.3); 2,669 (1.7);
2,664 (1.3); 2,550 (1.6); 2,526 (6.7); 2,522 (7.6); 2.50 (102.1); 2.50 (207.1); 2,500 (286.3);
2,495 (212.5); 2,491 (110.5); 2,331 (1.4); 2,327 (1.9); 2.322 (1.4); 2.072 (0.4); 1.098 (15.7); 1.080 (16.0); 0.933 (13.7); 0.916 (14.0); 0.008 (1.0); 0.000 (26.5); -0.008 (1.4)
Example 37: ¹ H-NMR (300.2 MHz, DMSO):
δ = 10,158 (1,2); 8,826 (0.8); 8,821 (0.8); 8,810 (0.8); 8.805 (0.8); 8.189 (0.7); 8.163 (0.7); 7,742 (0.5); 7.726 (0.6); 7,716 (0.5); 7,700 (0.5); 7.428 (0.8); 7.402 (1.0); 7.371 (0.7); 7.215 (0.6); 7.190 (2.4);
7.165 (0.6); 7.051 (1.0); 7.028 (0.8); 7.010 (0.7); 4.041 (0.4); 4.017 (0.4); 3.323 (16.0); 3.082 (0.4); 3.057 (0.5); 3.029 (0.5); 3.004 (0.5); 2.513 (2.3); 2.507 (5.0); 2,501 (7.1); 2,495 (5.2); 2.489 (2.6);
2.450 (0.5); 2.413 (0.4); 2.397 (0.4); 2,361 (0.4); 1,989 (1.7); 1.849 (0.3); 1.813 (0.4); 1.355 (1.4);
1.319 (0.4); 1.287 (5.8); 1.241 (0.4); 1.198 (0.6); 1.174 (1.0); 1.151 (0.6); 1.005 (1.7); 0.981 (3.5);
0.956 (1.5); 0.932 (4.5); 0.000 (4.6)
Example 38: ¹ H-NMR (300.2 MHz, DMSO):
δ = 10.135 (2.6); 8.655 (2.5); 8.651 (2.6); 8,002 (2.4); 7.393 (1.6); 7.368 (2.2); 7.324 (1.3); 7.210 (1.1); 7.185 (2.2); 7.159 (1.3); 7.143 (2.9); 7.048 (2.2); 7.024 (1.7); 6,962 (1.4); 4.065 (1.2); 4,041 (3.6);
4,017 (3.6); 3.993 (1.2); 3.326 (13.4); 3.073 (0.8); 3.048 (1.0); 3.020 (1.1); 2.995 (1.0); 2.512 (1.0);
2.50 (2.2); 2,500 (3.0); 2.494 (2.2); 2,488 (1.2); 2,441 (9.0); 2.416 (1.3); 2.397 (0.9); 2,362 (0.8);
2.184 (0.4); 2.085 (0.6); 1,988 (16.0); 1.846 (0.7); 1.834 (0.6); 1.821 (0.6); 1.810 (0.8); 1,800 (0.4);
1,786 (0.3); 1,772 (0.4); 1.645 (0.4); 1.632 (0.5); 1.620 (0.5); 1.607 (0.6); 1.601 (0.7); 1,589 (0.6);
1,576 (0.6); 1.564 (0.5); 1.357 (3.3); 1.322 (0.9); 1.287 (12.6); 1.242 (0.7); 1.198 (4.5); 1.174 (8.8); 1,150 (4.3); 1.028 (0.4); 1.006 (3.7); 0.982 (7.2); 0.957 (3.2); 0.933 (9.5); 0.875 (0.4); 0.000 (0.9) Example 39: ¹ H-NMR (300.2 MHz] CDCI3):
δ = 8.793 (0.5); 8,781 (0.6); 8.113 (0.5); 8.088 (0.5); 7.954 (0.5); 7,931 (0.5); 7.571 (0.5); 7.554 (0.7); 7.546 (0.8); 7.530 (0.5); 7.261 (3.5); 7.224 (0.6); 7.198 (1.3); 7.168 (1.0); 6,986 (1.5); 6.804 (0.7);
3.040 (0.4); 3.028 (0.4); 3.012 (0.4); 2.999 (0.4); 2.812 (0.5); 2.738 (0.3); 2.721 (0.3); 2.708 (0.4);
2.182 (0.6); 2.153 (0.7); 2.199 (0.5); 2.125 (0.6); 2.111 (0.5); 1,572 (2.9); 1.267 (0.7); 0.954 (16.0); 0.904 (0.4); 0.882 (0.8); 0.859 (0.3); 0.000 (2.8)
Example 4Q: ¹ H-NMR (300.2 MHz, CDCl3):
85/116 δ = 8.905 (0.5); 8,888 (0.5); 7.813 (0.4); 7,799 (0.8); 7,774 (0.6); 7.408 (0.4); 7.383 (0.8); 7.357 (0.3); 7.261 (14.3); 7.247 (0.4); 7.065 (0.6); 7.055 (0.5); 7.049 (0.6); 7.024 (0.5); 6.883 (0.3); 6,874 (0.9); 6.692 (0.4); 5.442 (0.4); 5.421 (0.4); 4,133 (0.4); 4.109 (0.4); 2.045 (1.8); 1,574 (3.8); 1,552 (0.5);
1.539 (0.4); 1.530 (0.4); 1,500 (2.4); 1,488 (3.6); 1,479 (2.5); 1.330 (0.9); 1.307 (2.0); 1.283 (3.8);
1.267 (12.9); 1,260 (11.3); 1.236 (1.7); 0.904 (4.7); 0.882 (16.0); 0.859 (5.7); 0.011 (0.3); 0.000 (11.7); 0.011 (0.5)
Example 4Ϊ ¹ H-NMR (400.1 MHz, DMSO):
δ = 10,181 (5.1); 8,829 (2.7); 8,825 (2.8); 8,817 (2.9); 8,814 (2.7); 8.186 (2.5); 8.166 (2.7); 7,740 (1.9); 7,728 (2.0); 7,720 (1.9); 7.708 (1.7); 7.414 (2.9); 7.395 (3.5); 7.330 (2.2); 7.205 (1.9); 7.195 (5.2); 7.186 (3.6); 7.167 (2.0); 7.078 (3.7); 7.059 (5.1); 3.317 (10.6); 3.206 (0.4); 3.188 (0.9); 3.175 (1.1); 3.163 (1.1); 3.152 (1.0); 3.133 (0.4); 2.937 (0.6); 2.926 (0.7); 2.915 (0.8); 2.904 (0.8); 2,897 (1.2);
2.885 (1.3); 2.875 (1.3); 2.864 (1.1); 2.807 (0.9); 2,787 (2.1); 2.767 (1.7); 2.746 (1.2); 2.726 (0.6);
2.530 (0.8); 2,516 (17.2); 2,512 (34.5); 2.50 (46.2); 2.503 (32.4); 2.499 (15.0); 2.301 (0.5); 2.290 (0.6); 2.281 (1.0); 2.270 (1.5); 2.261 (1.0); 2,250 (1.6); 2,240 (1.0); 2,231 (0.6); 2.220 (0.5); 1.766 (0.5);
1.760 (0.4); 1.749 (0.8); 1.744 (0.8); 1.728 (1.1); 1.715 (1.1); 1.699 (0.8); 1,685 (1.6); 1,673 (1.4);
1,663 (0.7); 1.653 (1.7); 1,641 (1.4); 1.632 (1.3); 1.618 (1.2); 1.613 (1.5); 1.602 (0.8); 1.593 (1.4);
1,582 (1.4); 1.574 (0.7); 1.563 (1.2); 1.543 (0.5); 1.324 (0.9); 1.313 (1.1); 1,300 (1.1); 1.292 (1.3);
1,288 (1.4); 1.281 (1.0); 1,268 (1.0); 1.255 (0.9); 0.983 (14.4); 0.973 (16.0); 0.967 (15.5); 0.957 (14.7)
Example 42: ¹ H-NMR (400.1 MHz ^ DMSO):
δ = 10.213 (7.2); 8,838 (5.2); 8,828 (5.1); 8.157 (4.3); 8.138 (4.5); 7,760 (3.6); 7,747 (4.1); 7,731 (2.9); 7.341 (4.0); 7.330 (4.9); 7.310 (5.4); 7.206 (5.8); 7.180 (3.5); 7.160 (5.2); 7.141 (2.8); 7.071 (2.8);
7.040 (0.5); 6.623 (5.3); 6.605 (4.9); 3.557 (3.3); 3.541 (2.5); 3.317 (8.8); 2.978 (0.4); 2.969 (0.4);
2.928 (1.2); 2.675 (0.5); 2,507 (73.8); 2,463 (5.1); 2,440 (4.5); 2.431 (4.4); 2,410 (3.4); 2.335 (0.8);
1.604 (3.9); 1.599 (3.9); 1,573 (3.8); 1.343 (0.9); 1,244 (3.7); 1.206 (16.0); 1,190 (15.8); 1.127 (1.2); 1.102 (0.8); 0.997 (5.4); 0.984 (9.0); 0.972 (6.2); 0.907 (2.4); 0.876 (5.5); 0.855 (5.5); 0.847 (5.9);
0.828 (4.9)
Example 43: ¹ H-NMR (300.2 MHzj DMSO):
δ = 10.138 (2.3); 8,825 (1.6); 8,820 (1.7); 8.809 (1.8); 8.804 (1.7); 8.185 (1.4); 8.159 (1.5); 7,742 (1.2); 7,726 (1.2); 7,716 (1.2); 7,700 (1.0); 7.432 (1.7); 7.408 (2.2); 7.369 (1.4); 7.212 (1.2); 7.188 (4.8);
7.160 (1.2); 7.038 (2.2); 7.012 (1.9); 7,008 (2.0); 3.325 (16.0); 3.025 (0.8); 3,000 (0.9); 2.971 (1.0); 2.946 (1.0); 2.553 (0.8); 2,513 (2.1); 2.507 (4.0); 2.501 (5.8); 2,495 (4.3); 2,489 (2.0); 2.465 (0.8);
1,989 (0.6); 1.835 (0.3); 1.813 (0.5); 1.805 (0.6); 1,784 (0.8); 1.763 (0.7); 1.749 (0.9); 1.724 (1.0);
1.717 (1.1); 1,691 (0.8); 1,661 (0.4); 1.380 (12.8); 1.356 (1.7); 1.306 (0.5); 1.207 (0.6); 1.174 (0.4);
1.063 (7.0); 1.048 (11.9); 1.014 (0.7); 1.002 (0.6); 0.984 (0.4); 0.961 (0.3); 0.933 (6.7); 0.912 (6.7); 0.000 (3.7)
Example 44: ¹ H-NMR (300.2 MHz ^ DMSO):
86/116 δ = 10,111 (1.6); 8.654 (1.6); 7,998 (1.4); 7.395 (1.0); 7.369 (1.4); 7.318 (0.8); 7.206 (0.7); 7.181 (1.3); 7.154 (0.8); 7.137 (1.7); 7.036 (1.3); 7.012 (1.0); 6.956 (0.8); 3.322 (16.0); 3.013 (0.5); 2.987 (0.6);
2.959 (0.6); 2.934 (0.6); 2.550 (0.5); 2,513 (3.0); 2.507 (5.7); 2,501 (7.7); 2,495 (5.9); 2,489 (2.8);
2,462 (0.7); 2,441 (5.5); 1,989 (1.2); 1.813 (0.3); 1.806 (0.4); 1,784 (0.5); 1.762 (0.4); 1.744 (0.6);
1.719 (0.6); 1.712 (0.6); 1.686 (0.5); 1,380 (7.6); 1.355 (1.6); 1,300 (0.3); 1.206 (0.4); 1.198 (0.4);
1.174 (0.7); 1,150 (0.4); 1.063 (4.1); 1.047 (7.6); 1.013 (0.5); 0.933 (4.0); 0.912 (3.9); 0.000 (4.6) Example 45: ¹ H-NMR (300.2 MHz ^ DMSO):
δ = 10,160 (2.9); 8.279 (2.2); 8.252 (2.5); 7.897 (2.5); 7.870 (2.2); 7.453 (2.0); 7.428 (2.5); 7.382 (1.6); 7.214 (1.4); 7.203 (3.8); 7.188 (2.7); 7.162 (1.5); 7.040 (2.7); 7.024 (2.1); 7.017 (2.2); 4.041 (0.9);
4.017 (0.9); 3.325 (12.5); 3.019 (0.8); 2.993 (1.0); 2.964 (1.1); 2.939 (1.1); 2.541 (0.9); 2.507 (4.1);
2.501 (4.8); 2,495 (3.6); 2,489 (2.2); 2.453 (0.9); 2.184 (0.3); 1,989 (4.0); 1.834 (0.4); 1.827 (0.3);
1.812 (0.6); 1.804 (0.7); 1,782 (1.0); 1.761 (0.9); 1.747 (1.1); 1.723 (1.1); 1.715 (1.2); 1.690 (1.0);
1.659 (0.4); 1.378 (14.4); 1.356 (3.1); 1.302 (0.6); 1.283 (0.4); 1.266 (0.3); 1.203 (0.9); 1.198 (1.4);
1,175 (2,3); 1.151 (1.2); 1.062 (7.8); 1.043 (16.0); 1,000 (0.7); 0.981 (0.5); 0.958 (0.5); 0.933 (7.4);
0.912 (7.3); 0.898 (1.5); 0.000 (2.6)
Example 46: ¹ H-NMR (400.1 MHz ^ DMSO):
δ = 10.306 (0.9); 8,847 (0.6); 8,844 (0.6); 8,835 (0.6); 8,832 (0.6); 8.164 (0.5); 8.145 (0.6); 7,765 (0.4); 7.753 (0.4); 7,746 (0.4); 7.734 (0.4); 7.355 (0.5); 7.248 (0.9); 7.238 (0.7); 7.220 (1.8); 7.092 (0.7);
7.084 (0.7); 7.074 (0.5); 3.358 (0.4); 3.340 (0.4); 3.316 (2.8); 2.633 (0.4); 2.601 (0.4); 2.516 (4.3);
2,512 (8.9); 2.50 (12.0); 2.503 (8.6); 2,499 (4.1); 1.929 (0.4); 1.924 (0.4); 1.894 (0.5); 1.890 (0.5);
1.404 (0.4); 1.380 (0.4); 1.369 (0.4); 1.345 (0.4); 1.320 (0.4); 1.289 (0.4); 1,219 (2,3); 1.202 (2.3);
1.010 (16.0); 0.986 (0.3); 0.957 (0.6); 0.953 (0.4)
Example 47: ¹ H-NMR (400.1 ΜΗ! DMSO):
δ = 10,188 (1.5); 8.278 (1.2); 8.257 (1.3); 7.888 (1.3); 7.867 (1.2); 7.412 (1.0); 7.392 (1.2); 7.339 (0.8); 7.205 (1.7); 7.174 (0.6); 7.155 (1.3); 7.136 (0.8); 7.071 (2.0); 7.054 (0.9); 5,760 (0.5); 3.317 (3.6); 2.734 (4.1); 2,699 (4.5); 2,516 (4.8); 2,512 (9.7); 2.50 (13.0); 2.503 (9.2); 2,499 (4.3); 1.121 (16.0) Example 48: ¹ I-NMR (400.1 MHz, DMSO):
δ = 10,134 (1.4); 8.658 (1.3); 8.655 (1.3); 8,001 (1.3); 7.360 (0.9); 7.341 (1.1); 7.278 (0.7); 7.166 (0.6); 7.147 (1.3); 7.143 (1.7); 7.128 (0.7); 7.067 (1.1); 7.049 (0.8); 7,007 (0.7); 3.317 (2.9); 2.734 (3.7); 2.704 (4.3); 2,517 (4.1); 2,512 (8.2); 2.50 (11.0); 2.503 (7.7); 2,499 (3.5); 2.447 (4.8); 1.124 (16.0) Example 49: ¹ H-NMR (400.1 ΜΗ! DMSO):
δ = 10,160 (1.5); 8.827 (0.9); 8,824 (1.0); 8,816 (1.0); 8,812 (1.0); 8.185 (0.8); 8.166 (0.9); 7,733 (0.7); 7.722 (0.7); 7,714 (0.7); 7.702 (0.6); 7.394 (1.0); 7.374 (1.1); 7.327 (0.8); 7.191 (1.7); 7.172 (0.6);
7.153 (1.2); 7.134 (0.8); 7,070 (1.2); 7.056 (1.3); 3.318 (2.6); 2.736 (4.0); 2.708 (4.5); 2.530 (0.3);
2,517 (3.9); 2,512 (7.8); 2.50 (10.4); 2.503 (7.5); 2,499 (3.8); 1.123 (16.0)
Example 5Õ: ’H-NMR (300.2 MHz ^ CDCI3):
87/116 δ = 8.614 (1.3); 8.029 (0.7); 8,003 (0.7); 7.902 (1.0); 7.632 (0.6); 7.607 (0.3); 7.585 (1.0); 7.562 (1.2); 7.373 (0.6); 7.346 (1.0); 7.320 (0.5); 7.261 (40.6); 7.128 (0.8); 6,945 (1.7); 6.762 (0.9); 5.301 (3.6);
4.270 (1.0); 4.247 (3.3); 4.235 (0.5); 4.223 (3.4); 4.212 (0.4); 4,200 (1.1); 3.746 (0.7); 3.492 (0.4);
3,472 (0.5); 3.448 (0.4); 3.136 (0.9); 3.108 (0.8); 3.073 (1.1); 3.046 (0.9); 2,652 (1.2); 2.645 (1.1);
2.589 (0.9); 2.582 (0.9); 2.482 (4.2); 2.415 (0.5); 2.219 (0.4); 1,853 (0.8); 1.548 (16.0); 1.356 (3.6); 1.349 (0.6); 1.333 (7.5); 1.326 (1.1); 1.309 (3.5); 1.302 (0.7); 1.283 (0.7); 1.259 (4.6); 1.236 (3.8);
0.011 (1.3); 0.000 (36.9); -0.011 (1.4)
Example 51: ’H-NMR (300.2 MHz, CDCI3):
δ = 8.812 (2.3); 8,799 (2.2); 8.113 (1.6); 8.087 (1.8); 8.010 (1.8); 7,984 (2.0); 7.646 (1.8); 7.589 (3.8); 7.575 (2.2); 7.564 (4.5); 7.371 (1.4); 7.345 (2.4); 7.319 (1.1); 7.262 (16.3); 7.175 (1.9); 6,992 (3.9);
6,810 (2.0); 4,162 (4.9); 4.139 (10.3); 4,117 (5.2); 3,492 (1.0); 3,471 (1.5); 3,448 (1.1); 3.425 (0.4);
3.142 (2.1); 3,115 (1.9); 3.080 (2.8); 3.052 (2.3); 2,650 (3.0); 2,643 (2.8); 2,588 (2.4); 2,580 (2.2);
2.043 (0.5); 1.803 (0.5); 1,778 (2.3); 1,755 (4.7); 1.731 (4.9); 1.708 (2.6); 1,684 (0.7); 1.570 (8.6);
1.264 (11.8); 1,241 (8.9); 1.004 (8.1); 0.979 (16.0); 0.954 (7.2); 0.904 (1.2); 0.882 (3.4); 0.859 (1.3); 0.010 (1.5); 0.000 (14.9); -0.011 (0.6)
Example 52: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.813 (1.8); 8.801 (1.9); 8.113 (1.3); 8.088 (1.5); 8.016 (1.6); 7,989 (1.7); 7.642 (1.4); 7.593 (3.3); 7.568 (3.9); 7.554 (1.2); 7.374 (1.2); 7.348 (2.0); 7.322 (1.0); 7.262 (17.7); 7.175 (1.8); 6,992 (3.5);
6,810 (1.8); 4,271 (2,3); 4.247 (7.2); 4.224 (7.4); 4,200 (2.5); 3.493 (0.8); 3,471 (1.3); 3,449 (0.9);
3,443 (0.8); 3.136 (2.0); 3.108 (1.8); 3.073 (2.6); 3.046 (2.2); 2,651 (2.6); 2.644 (2.6); 2,589 (2.1);
2,581 (2.0); 1.567 (9.2); 1.356 (7.7); 1,333 (16.0); 1.309 (7.6); 1.264 (7.7); 1.241 (7.5); 0.011 (0.5);
0.000 (15.9); -0.011 (0.6)
Example 53: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.609 (1.6); 8.023 (0.9); 7,997 (0.9); 7.899 (1.3); 7.636 (0.8); 7.581 (1.3); 7.558 (1.6); 7.369 (0.7); 7.343 (1.3); 7.318 (0.6); 7.261 (27.2); 7.128 (1.2); 6,945 (2.2); 6,762 (1.2); 4.161 (2.5); 4,139 (5.4);
4.128 (0.6); 4,117 (2.7); 3.492 (0.5); 3,471 (0.7); 3.448 (0.5); 3,441 (0.5); 3.142 (1.1); 3,114 (1.0);
3.079 (1.4); 3.052 (1.2); 2,651 (1.4); 2,644 (1.4); 2,588 (1.2); 2,581 (1.1); 2,481 (5.3); 2.415 (0.4);
2.218 (0.4); 1,778 (1.1); 1.755 (2.3); 1.731 (2.4); 1.708 (1.3); 1,684 (0.4); 1,553 (16.0); 1.282 (0.6);
1,260 (5.2); 1.236 (4.6); 1.004 (4.2); 0.979 (8.4); 0.954 (3.7); 0.011 (0.9); 0.000 (23.8); -0.011 (0.9)
Example 54: ¹ H-NMR (300.2 MHz ^ DMSO):
δ = 10,181 (5.4); 8.663 (4.9); 7,961 (4.7); 7.334 (2.6); 7,300 (3.1); 7.275 (4.5); 7.174 (2.8); 7.153 (7.4); 7.123 (2.2); 6,972 (2.9); 6.615 (4.1); 6.592 (3.9); 5.758 (0.7); 3.579 (1.0); 3.569 (1.2); 3.546 (1.6);
3.528 (1.3); 3.519 (1.0); 3.325 (16.0); 2.50 (5.3); 2,500 (7.1); 2.494 (5.4); 2,449 (17.1); 2.433 (3.8);
2.418 (3.0); 2.390 (2.3); 1.602 (2.6); 1,592 (2.6); 1.560 (2.4); 1.550 (2.4); 1.259 (0.3); 1.235 (0.8);
1.194 (12.6); 1,171 (12.6); 0.993 (2.9); 0.980 (3.5); 0.971 (3.7); 0.963 (4.3); 0.952 (3.0); 0.943 (1.6); 0.922 (0.8); 0.908 (1.2); 0.878 (2.4); 0.867 (2.8); 0.847 (3.5); 0.838 (3.6); 0.817 (2.6); 0.798 (0.9);
88/116
0.781 (0.5); 0.000 (2.3)
Example 55: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10,298 (3.5); 8,926 (3.6); 8,922 (2.9); 8.325 (3.7); 7.351 (1.7); 7.343 (2.1); 7.324 (3.0); 7.254 (1.5); 7.236 (2.7); 7.218 (4.0); 7.098 (2.8); 7.082 (3.4); 3,474 (0.7); 3.457 (1.3); 3,440 (1.3); 3.422 (0.8); 3.315 (7.0); 2.507 (37.9); 2.192 (1.2); 2,171 (1.3); 2,160 (1.5); 2.139 (1.3); 1,579 (1.4); 1.565 (1.4); 1.548 (1.4); 1.533 (1.3); 1.325 (14.1); 1,253 (1.7); 1,195 (16.0); 0.881 (0.5); 0.865 (1.2); 0.848 (0.6) Example 56: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.814 (2.0); 8.801 (2.1); 8.056 (1.6); 8.029 (1.8); 7.671 (1.9); 7.645 (2.3); 7.607 (0.4); 7.589 (1.4); 7.562 (2.2); 7.547 (2.8); 7.361 (1.3); 7.336 (2.4); 7.310 (1.3); 7.262 (21.9); 7.189 (2.3); 7,007 (4.7); 6,963 (3.3); 6,939 (2.9); 6,824 (2.4); 5.324 (2.8); 5.317 (2.9); 4.154 (0.6); 4,130 (1.7); 4.106 (1.8);
4.083 (0.6); 2,130 (0.4); 2,110 (0.8); 2.105 (0.8); 2.089 (1.0); 2.082 (1.0); 2.066 (0.9); 2.060 (0.8);
2.042 (8.5); 1,970 (0.4); 1.962 (0.3); 1,945 (1.4); 1.936 (0.9); 1,920 (2.0); 1.912 (1.5); 1,898 (2.5);
1.889 (2.6); 1.874 (2.9); 1.864 (2.6); 1.848 (3.0); 1.823 (2.7); 1,800 (1.4); 1,776 (0.9); 1.752 (0.3);
1.712 (0.4); 1,688 (1.2); 1,664 (1.5); 1,641 (1.3); 1.617 (1.0); 1,592 (0.4); 1.565 (8.4); 1.306 (0.6);
1.282 (3.3); 1.266 (4.0); 1.258 (7.3); 1.234 (2.6); 1,163 (11.6); 1,140 (11.1); 1.048 (0.4); 1.025 (7.3); 1.001 (16.0); 0.976 (6.7); 0.904 (1.5); 0.882 (4.6); 0.859 (1.7); 0.747 (3.7); 0.723 (7.3); 0.698 (4.1); 0.686 (14.3); 0.663 (13.5); 0.011 (0.6); 0.000 (20.2); -0.011 (1.0)
Example 57: ’H-NMR (300.2 MHz, DMSO):
δ = 10.301 (2.5); 8,843 (1.9); 8,838 (2.0); 8,827 (2.1); 8,822 (2.0); 8.159 (1.6); 8.133 (1.9); 7,765 (1.3); 7,749 (1.4); 7,739 (1.4); 7,723 (1.2); 7.394 (1.7); 7.272 (1.2); 7.247 (2.9); 7.224 (2.1); 7.213 (4.2);
7,200 (2.8); 7.174 (1.3); 7.094 (2.4); 7.070 (1.7); 7.033 (2.0); 3,382 (0.6); 3.358 (1.1); 3.323 (16.0); 3.076 (0.8); 3.054 (0.8); 2.535 (0.7); 2.507 (7.1); 2,501 (8.7); 2,495 (6.9); 2.489 (3.5); 2,466 (1.5);
2.439 (0.7); 1,773 (0.6); 1.741 (1.7); 1.732 (1.6); 1.715 (1.6); 1.701 (1.2); 1,685 (0.6); 1.670 (0.5);
1.350 (0.9); 1.322 (1.1); 1.316 (1.1); 1.289 (1.4); 1,266 (1.5); 1,247 (1.1); 1.242 (1.1); 1,214 (8.0);
1,191 (7.9); 1.109 (0.4); 1.085 (0.4); 0.974 (11.3); 0.957 (11.1); 0.954 (10.7); 0.000 (6.1)
Example 58: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.068 (3.8); 8.040 (4.3); 7.828 (3.8); 7.802 (4.1); 7.761 (0.4), 7.733 (0.3); 7.617 (3.0); 7.578 (4.5); 7.551 (4.1); 7.260 (16.4); 7.234 (2.7); 7.208 (4.5); 7.182 (2.5); 7.127 (0.5); 7.095 (3.3); 6,914 (6.6); 6,733 (3.3); 6.641 (0.4); 6.616 (0.4); 6.559 (5.7); 6.534 (5.3); 5.298 (5.2); 3.412 (0.6); 3,388 (1.9);
3.366 (2.8); 3,344 (2.0); 3.320 (0.6); 2.626 (3.3); 2,598 (3.3); 2,584 (3.8); 2.556 (3.4); 1.633 (0.4);
1.602 (4.9); 1,596 (5.5); 1.560 (4.0); 1.554 (3.9); 1.330 (0.6); 1.319 (1.3); 1.307 (0.9); 1.296 (1.6);
1,271 (16.0); 1,248 (15.9); 1.054 (1.3); 1.043 (1.7); 1.022 (7.3); 1.006 (12.0); 0.991 (3.6); 0.980 (3.1); 0.942 (0.6); 0.923 (0.9); 0.896 (2.4); 0.891 (3.1); 0.869 (6.9); 0.859 (6.9); 0.854 (6.6); 0.838 (5.6);
0.816 (1.7); 0.811 (1.4); 0.011 (0.4); 0.000 (13.2); -0.011 (0.6)
Example 59: ’H-NMR (300.2 MHz, CDCI3):
δ = 8.967 (0.4); 8.699 (0.5); 8.694 (0.5); 8.683 (0.6); 8.679 (0.5); 8.048 (0.5); 8.022 (0.5); 7.521 (0.5);
89/116
7.507 (0.5); 7.494 (0.9); 7.481 (0.4); 7.465 (0.4); 7.338 (0.4); 7.312 (0.8); 7.287 (0.5); 7.258 (1.0);
7.218 (0.7); 7.192 (0.5); 7.147 (0.5); 6,965 (1.1); 6.783 (0.5); 3.344 (0.3); 3.320 (0.4); 2,681 (0.4);
2.639 (0.4); 1,958 (0.4); 1,951 (0.4); 1.911 (0.5); 1.904 (0.5); 1.498 (0.3); 1,477 (0.5); 1.445 (0.5);
1.435 (0.6); 1.431 (0.5); 1.409 (0.3); 1.397 (0.5); 1.394 (0.5); 1.291 (2.8); 1,268 (2.9); 1.018 (16.0);
0.994 (2.2); 0.979 (0.4); 0.000 (0.7)
Example 6Õ: ¹ H-NMR (300.2 MHz, DMSO):
δ = 10,141 (1.0); 8.823 (0.7); 8,819 (0.7); 8.807 (0.7); 8.803 (0.7); 8.180 (0.6); 8.154 (0.7); 7,740 (0.5); 7,724 (0.5); 7,714 (0.5); 7.698 (0.4); 7.398 (0.7); 7.372 (0.9); 7.363 (0.7); 7.182 (1.5); 7.153 (0.9);
7.127 (0.5); 7.033 (0.9); 7,008 (0.7); 7,002 (0.8); 5.759 (1.9); 3.325 (16.0); 2.945 (0.5); 2.920 (0.6);
2.656 (2.3); 2.513 (2.3); 2.507 (4.9); 2,501 (6.8); 2,495 (5.0); 2,489 (2.4); 1.426 (0.5); 1.412 (0.7);
1.404 (0.8); 1.387 (0.8); 1.379 (0.9); 1.354 (0.5); 1.333 (0.5); 1.309 (0.5); 1.287 (0.4); 1.127 (2.5);
1.103 (2.5); 0.853 (1.4); 0.829 (2.9); 0.804 (1.2); 0.773 (1.4); 0.748 (2.9); 0.724 (1.2); 0.000 (5.4)
Example 61: ¹ H-NMR (300.2 MHz, DMSO):
δ = 10,116 (0.8); 8.652 (0.7); 7,991 (0.7); 7.360 (0.5); 7.333 (0.6); 7.311 (0.4); 7.172 (0.3); 7.147 (0.7); 7.130 (0.9); 7,121 (0.4); 7.030 (0.7); 7,005 (0.5); 6,949 (0.4); 5.759 (0.6); 3.324 (16.0); 2.942 (0.4); 2.920 (0.4); 2,651 (1.6); 2,513 (2.8); 2.507 (6.1); 2.501 (8.5); 2,495 (6.2); 2,489 (2.9); 2,442 (2.6);
1.426 (0.3); 1.411 (0.5); 1.404 (0.6); 1.379 (0.6); 1.356 (0.3); 1.309 (0.4); 1.127 (1.7); 1.103 (1.7);
0.853 (0.9); 0.828 (2.0); 0.804 (0.8); 0.772 (0.9); 0.748 (2.0); 0.723 (0.8); 0.000 (8.0)
Example 62: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.168 (3.2); 8,820 (1.9); 8,817 (2.0); 8.808 (2.0); 8.805 (1.9); 8.179 (1.8); 8.160 (1.9); 7,725 (1.3); 7,713 (1.4); 7.706 (1.4); 7.694 (1.2); 7.383 (2.1); 7.363 (2.5); 7.321 (1.5); 7.195 (1.5); 7.185 (3.5);
7.177 (2.7); 7.157 (1.4); 7.050 (1.6); 7.024 (2.5); 7,006 (2.0); 3,310 (2.9); 2.834 (0.5); 2.817 (1.5);
2.799 (1.5); 2,782 (0.6); 2.707 (0.4); 2,667 (5.9); 2.623 (0.3); 2.50 (6.8); 2.50 (13.3); 2,499 (17.7); 2,495 (12.7); 2,491 (6.1); 1,987 (0.5); 1,247 (0.6); 1.174 (0.5); 1,148 (16.0); 1.134 (8.4); 1,116 (7.9);
0.858 (0.8); 0.840 (0.4); 0.801 (13.6); 0.771 (0.5); 0.000 (0.4)
Example 63: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10,141 (3.2); 8.650 (3.0); 8.647 (3.0); 7,995 (3.0); 7.348 (2.1); 7.329 (2.6); 7.272 (1.4); 7.189 (1.4); 7.170 (2.5); 7.151 (1.4); 7.136 (3.1); 7.021 (2.5); 7,001 (3.2); 3.308 (3.8); 2.832 (0.5); 2.814 (1.5); 2,797 (1.6); 2.779 (0.5); 2,661 (6.9); 2.508 (8.1); 2.50 (15.7); 2,499 (20.6); 2,495 (14.7); 2,491 (7.2); 2,439 (10.8); 1,987 (0.7); 1.279 (0.4); 1,247 (2.0); 1.192 (0.4); 1.174 (0.6); 1.149 (16.0); 1.134 (8.3); 1,116 (7.9); 0.875 (0.9); 0.858 (2.6); 0.841 (1.1); 0.801 (14.2); 0.781 (0.5)
Example 64: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10,196 (3.1); 8.272 (2.4); 8.252 (2.6); 7.880 (2.6); 7.860 (2.4); 7,400 (2.2); 7.380 (2.6); 7.333 (1.6); 7.198 (4.8); 7.179 (2.6); 7.159 (1.4); 7.064 (1.7); 7.027 (2.6); 7,009 (2.1); 3.308 (5.3); 2.832 (0.5);
2.814 (1.5); 2,797 (1.6); 2.779 (0.5); 2.699 (0.5); 2,659 (5.4); 2,653 (4.3); 2.612 (0.4); 2.522 (0.7);
2.50 (11.8); 2.50 (23.6); 2,500 (31.5); 2,496 (22.1); 2,491 (10.3); 1.279 (0.4); 1.247 (1.5); 1.147 (16.0);
90/116
1,131 (8.6); 1,114 (8.1); 0.875 (0.7); 0.858 (2.2); 0.841 (0.9); 0.799 (13.7); 0.000 (3.1)
Example 65: ¹ H-NMR (300.2 MHz DMSO):
δ = 11,999 (0.4); 8,740 (0.3); 8,730 (0.3); 7.947 (0.3); 7.329 (0.5); 7.258 (0.4); 7.176 (0.4); 7.165 (0.6); 3.567 (16.0); 3.332 (0.7); 2.512 (0.5); 2,507 (1.1); 2,500 (1.5); 2.494 (1.1), 2.489 (0.5), 1.398 (2.3), 1.061 (2.3); 1.047 (1.2); 0.931 (1.0); 0.910 (1.1); 0.000 (0.6)
Example 66: ¹ H-NMR (300.2 MHz DMSO):
õ = 12.035 (0.3); 8.075 (0.3); 8.048 (0.4); 7.825 (0.4); 7,798 (0.3); 7.372 (0.4); 7.261 (0.4); 7.180 (0.4); 7.162 (0.6); 3.568 (16.0); 3.384 (0.4); 2.513 (0.5); 2.507 (0.8); 2,501 (1.1); 2,495 (0.8); 2.489 (0.4); 1.396 (2.0); 1.355 (0.4); 1.058 (1.9); 1.045 (1.1); 0.927 (0.9); 0.907 (0.9); 0.000 (0.5)
Example 67: ¹ H-NMR (300.2 MHz DMSO):
õ = 11,970 (0.4); 8.575 (0.5); 8.570 (0.5); 7,788 (0.5); 7.299 (0.6); 7.295 (0.7); 7.253 (0.4); 7.176 (0.4); 7.172 (0.4); 7.116 (0.5); 3.567 (16.0); 3.325 (4.3); 2.513 (0.6); 2.507 (1.2); 2.501 (1.7); 2,495 (1.3); 2.489 (0.6); 2.423 (1.6); 1.397 (2.2); 1.355 (0.4); 1.060 (2.1); 1.047 (1.2); 0.931 (1.0); 0.911 (1.0); 0.000 (0.9)
Example 68: ¹ H-NMR (300.2 MHz CDCI3):
δ = 8.863 (1.7); 8.518 (4.0); 8.513 (4.0); 8.425 (0.4); 7.843 (4.0); 7.648 (3.4); 7.621 (4.0); 7.282 (2.6); 7.259 (9.1); 7.230 (2.5); 7.102 (2.6); 6,920 (5.4); 6.822 (0.4); 6,737 (2.7); 6.685 (3.8); 6.660 (3.6);
6.453 (0.3); 5.296 (0.5); 4.123 (0.9); 4.099 (0.9); 3,495 (0.4); 3.481 (0.9); 3,472 (1.0); 3.454 (1.3);
3,449 (1.3); 3,431 (1.1); 3.422 (1.0); 3.408 (0.4); 2,599 (2.2); 2,571 (2.2); 2.557 (2.7); 2.543 (0.4);
2.529 (2.4); 2.448 (15.9); 2.287 (1.1); 2.035 (4.1); 1.649 (2.6); 1.640 (2.7); 1.607 (2.5); 1,598 (2.6); 1,586 (3.6); 1.457 (1.1); 1.434 (1.1); 1.293 (14.9); 1.277 (3.7); 1.269 (16.0); 1.254 (4.3); 1,230 (1.5);
1.053 (0.5); 1.045 (1.1); 1.034 (3.1); 1.028 (3.0); 1.012 (5.5); 1.007 (4.4); 0.994 (1.5); 0.976 (1.0);
0.962 (0.6); 0.955 (1.0); 0.940 (0.5); 0.930 (1.4); 0.915 (4.6); 0.907 (4.8); 0.895 (3.1); 0.882 (4.6);
0.863 (1.2); 0.859 (1.2); 0.846 (0.5); 0.000 (5.7)
Example 69: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.875 (0.9); 8,715 (1.5); 8,711 (1.6); 8.699 (1.6); 8.695 (1.7); 8.087 (1.4); 8.060 (1.6); 7.844 (2.0); 7.817 (2.2); 7.521 (1.2); 7.505 (1.2); 7.495 (1.2); 7.479 (1.1); 7.324 (1.1); 7.298 (2.3); 7.272 (1.4);
7.259 (4.8); 7.160 (2.4); 7.135 (1.8); 7.115 (1.6); 6,933 (3.2); 6,919 (0.5); 6,751 (1.6); 3.035 (0.9);
3.009 (1.0); 2,983 (1.2); 2.957 (1.2); 2.522 (1.0); 2,487 (1.1); 2.470 (0.8); 2.435 (1.0); 2.023 (0.4);
2.011 (0.4); 1.998 (1.5); 1,988 (0.8); 1.975 (0.7); 1,963 (0.9); 1.953 (0.5); 1,940 (0.4); 1.927 (0.4);
1.685 (0.5); 1,672 (0.5); 1.660 (0.6); 1.647 (0.7); 1.641 (0.8); 1.628 (0.7); 1.616 (0.7); 1.603 (0.6);
1.408 (0.6); 1.384 (0.8); 1.372 (0.6); 1.363 (0.7); 1.341 (16.0); 1.303 (0.6); 1,271 (1.7); 1.085 (0.5);
1.061 (0.9); 1.038 (4.5); 1.014 (8.3); 0.993 (15.8); 0.903 (1.0); 0.000 (3.9)
Example 7Õ: ’H-NMR (300.2 MHz CDCI3):
δ = 8.845 (0.9); 8.523 (2.2); 8.518 (2.2); 7.883 (2.1); 7.879 (2.2); 7.846 (1.9); 7.819 (2.1); 7.322 (1.0); 7.296 (2.1); 7.270 (1.3); 7.260 (9.4); 7.156 (2.2); 7.132 (1.7); 7.075 (1.6); 6,893 (3.3); 6,710 (1.6);
91/116
3.033 (0.9); 3.008 (1.0); 2,981 (1.1); 2,956 (1.1); 2.518 (0.9); 2.483 (1.0); 2,451 (9.0); 2.431 (1.3);
2,310 (0.8); 2.022 (0.3); 2.009 (0.3); 1.998 (0.8); 1,986 (0.7); 1,973 (0.7); 1,961 (0.8); 1,951 (0.5);
1,938 (0.4); 1.925 (0.4); 1.684 (0.5); 1,671 (0.5); 1.659 (0.7); 1.645 (0.8); 1.640 (0.9); 1.627 (0.9);
1.615 (0.9); 1.602 (0.8); 1.590 (0.4); 1.407 (0.6); 1.383 (0.7); 1.371 (0.6); 1.363 (0.6); 1.340 (15.9); 1.303 (0.6); 1,273 (1.4); 1.088 (0.4); 1.064 (0.8); 1.039 (4.3); 1.014 (8.3); 0.992 (16.0); 0.909 (1.0);
0.000 (7.7); -0.011 (0.4)
Example 71: ¹ H-NMR (300.2 MHz DMSO):
õ = 10,470 (0.6); 8,845 (0.4); 8,834 (0.4); 8.144 (0.3); 7.344 (1.1); 7.334 (0.7); 7.327 (0.6); 7.208 (0.7); 7.028 (0.4); 4.041 (0.4); 4.017 (0.4); 3.322 (16.0); 2,513 (5.4); 2.507 (12.0); 2.501 (16.9); 2,495 (12.5); 2,489 (6.2); 1,989 (1.8); 1.790 (0.6); 1.765 (0.7); 1.744 (0.4); 1.355 (0.4); 1.198 (0.5); 1.174 (1.0);
1.151 (0.5); 0.920 (0.6); 0.896 (1.3); 0.872 (0.6); 0.797 (0.7); 0.772 (1.5); 0.748 (0.7); 0.685 (0.6);
0.660 (1.3); 0.636 (0.6); 0.011 (0.5); 0.000 (16.0); -0.011 (0.8)
Example 72: ¹ H-NMR (300.2 MHz DMSO):
δ = 10.428 (3.9); 8.680 (3.7); 8.676 (3.7); 7,958 (3.4); 7.335 (4.7); 7.319 (7.4); 7.160 (4.1); 7.058 (0.5); 7.043 (2.1); 7.030 (2.5); 7.015 (1.8); 6,979 (2.1); 5.273 (1.6); 5.266 (1.7); 5.246 (1.7); 4.041 (0.5);
4.017 (0.5); 3.326 (16.0); 2,513 (11.4); 2.507 (24.6); 2,501 (33.9); 2,495 (24.9); 2,489 (12.2); 2,451 (12.2);
2,389 (1.6); 1,989 (2.4); 1.908 (0.9); 1,900 (0.7); 1.875 (0.9); 1.861 (1.0); 1.852 (0.9); 1.836 (1.0);
1.829 (0.9); 1.813 (1.5); 1,789 (4.1); 1.764 (4.9); 1.742 (2.8); 1.718 (1.9); 1,686 (1.7); 1,661 (1.8);
1.639 (1.1); 1.615 (0.8); 1.468 (0.3); 1.444 (0.8); 1.419 (1.0); 1.395 (1.0); 1.369 (1.0); 1.355 (2.0);
1.345 (0.8); 1.234 (0.4); 1.198 (0.8); 1.174 (1.4); 1.151 (0.8); 1,120 (0.3); 0.918 (4.3); 0.894 (8.8);
0.869 (3.8); 0.797 (4.4); 0.773 (10.0); 0.748 (4.2); 0.684 (4.2); 0.660 (9.0); 0.635 (4.0); 0.608 (0.7); 0.584 (0.4); 0.011 (1.1); 0.000 (35.2); -0.011 (1.6)
Example 73: ¹ H-NMR (400.1 MHz DMSO):
δ = 10.435 (3.1); 8.686 (2.8); 8.636 (0.4); 8.110 (0.5); 7,948 (2.8); 7.355 (0.5); 7.335 (2.7); 7.328 (3.2); 7.321 (6.5); 7.308 (0.6); 7.292 (1.5); 7.156 (3.5); 7.149 (2.1); 7.142 (1.8); 7.135 (1.4); 7.128 (1.5);
7.021 (1.7); 5.311 (1.3); 5.305 (1.4); 5.294 (1.4); 5.287 (1.2); 4.063 (1.2); 4.046 (3.7); 4.028 (3.6);
4,010 (1.2); 3.316 (38.4); 2,681 (0.9); 2,677 (1.2); 2,672 (0.8); 2.556 (0.6); 2,530 (3.3); 2,516 (72.1); 2,512 (145.3); 2.50 (195.1); 2.503 (139.0); 2,499 (66.0); 2.459 (10.9); 2,399 (2.8); 2.339 (0.9); 2,334 (1.2); 2.330 (0.9); 2,190 (0.3); 1.995 (16.0); 1.838 (0.5); 1.831 (0.5); 1.819 (0.6); 1.812 (0.7); 1.803 (0.7); 1,796 (0.7); 1,784 (0.7); 1.777 (0.6); 1.767 (0.4); 1.561 (0.7); 1.543 (1.5); 1.539 (2.0); 1.525 (1.3); 1.507 (1.5); 1,495 (15.0); 1.396 (13.1); 1.363 (2.6); 1.243 (0.3); 1,200 (4.4); 1.182 (8.7); 1,164 (4.3); 0.822 (3.7); 0.804 (7.8); 0.785 (3.4)
Example TÃ-. ¹ H-NMR (400.1 MHz DMSO):
δ = 10.512 (2.3); 8.339 (0.4); 8.226 (1.0); 8.205 (1.1); 7,933 (1.2); 7,913 (1.1); 7.805 (0.3); 7.784 (0.3); 7.350 (4.2); 7.343 (2.6); 7.336 (2.3); 7.317 (0.5); 7.221 (2.6); 7.159 (1.5); 7.153 (1.3); 7.146 (1.3);
7.139 (1.3); 7.087 (1.3); 5.293 (1.0); 5.286 (1.1); 5.275 (1.2); 5.269 (1.0); 4.063 (1.2); 4.045 (3.6);
92/116
4.027 (3.6); 4,010 (1.2); 3.317 (3.8); 2,681 (0.4); 2,676 (0.6); 2,672 (0.4); 2.529 (1.1); 2,512 (89.0); 2.507 (120.4); 2.503 (88.9); 2,462 (1.0); 2.457 (1.0); 2.409 (0.3); 2.339 (0.6); 2.334 (0.8); 2.330 (0.6); 1.995 (16.0); 1.915 (1.3); 1.830 (0.4); 1.822 (0.4); 1.811 (0.5); 1.804 (0.6); 1,794 (0.6); 1,786 (0.6); 1.775 (0.6); 1.767 (0.7); 1.553 (0.7); 1.539 (1.7); 1.517 (1.2); 1.493 (13.0); 1.432 (0.5); 1.394 (10.9); 1.363 (1.7); 1.304 (0.3); 1.245 (0.4); 1,199 (4.3); 1.182 (8.5); 1,164 (4.2); 0.949 (0.8); 0.931 (0.5); 0.816 (2.8); 0.798 (5.8); 0.780 (2.6)
Example 75: ¹ H-NMR (400.1 MHz, DMSO):
5 = 10.463 (3.5); 8,682 (3.3); 8.680 (3.3); 7,936 (3.2); 7.343 (0.9); 7.324 (2.6); 7.306 (2.5); 7.286 (4.1); 7.266 (1.6); 7.151 (3.5); 7.132 (2.7); 7.115 (2.3); 7.016 (1.8); 5.753 (0.8); 5.270 (3.2); 5.266 (3.2); 4.056 (0.4); 4.038 (1.1); 4.021 (1.1); 4.003 (0.4); 3.309 (14.0); 2.50 (34.0); 2,500 (44.4); 2,496 (32.3); 2.455 (11.6); 2.388 (0.4); 2.173 (0.4); 2.161 (0.8); 2.156 (0.8); 2.144 (1.1); 2.199 (1.0); 2.127 (0.8); 2.122 (0.8); 2,110 (0.4); 1,988 (4.6); 1.494 (16.0); 1.369 (13.7); 1.334 (0.3); 1.296 (0.4); 1.279 (0.7); 1.247 (3.2); 1.192 (1.3); 1,175 (2.5); 1.157 (1.2); 0.994 (8.4); 0.977 (8.1); 0.875 (1.4); 0.858 (3.9); 0.841 (1.6); 0.529 (8.7); 0.512 (8.5); 0.008 (0.5); 0.000 (8.2)
Example 76: ¹ H-NMR (400.1 MHz, DMSO):
δ = 10.507 (3.6); 8,846 (2,3); 8,838 (2,3); 8,835 (2.2); 8.120 (1.9); 8,100 (2.1); 7,775 (1.5); 7,763 (1.6); 7.756 (1.5); 7,744 (1.3); 7.348 (0.9); 7.330 (2.9); 7.311 (2.8); 7.298 (3.6); 7.281 (1.3); 7.198 (3.5);
7.136 (2.6); 7.120 (2.2); 7.063 (1.8); 5.266 (3.3); 5.262 (3.3); 4.039 (0.9); 4.021 (0.9); 3.311 (7.5);
2.50 (23.6); 2,501 (30.8); 2,496 (23.0); 2.189 (0.3); 2.177 (0.8); 2.172 (0.8); 2,160 (1.1); 2.155 (1.1); 2.143 (0.8); 2.138 (0.8); 2.126 (0.4); 1,988 (3.8); 1,496 (16.0); 1.370 (13.8); 1.279 (0.3); 1.246 (1.4);
1,193 (1.1); 1,175 (2.0); 1.157 (1.0); 0.999 (8.4); 0.981 (8.2); 0.875 (0.6); 0.858 (1.6); 0.841 (0.7);
0.537 (8.7); 0.520 (8.6); 0.000 (4.4)
Example 77: ¹ H-NMR (400.1 MHz ^ DMSO):
δ = 10,471 (3.3); 8,854 (2.0); 8,850 (2.1); 8,842 (2.1); 8,839 (2.0); 8.137 (1.7); 8.118 (1.9); 7,778 (1.4); 7,766 (1.4); 7,758 (1.3); 7,746 (1.2); 7.355 (0.6); 7.344 (6.5); 7.336 (4.1); 7.332 (3.7); 7.312 (0.4);
7.205 (3.8); 7.165 (0.3); 7.154 (2.0); 7.142 (2.1); 7.133 (1.6); 7.069 (1.9); 5.309 (1.3); 5.302 (1.5);
5.291 (1.6); 5.285 (1.3); 3.316 (46.7); 2,681 (0.4); 2,677 (0.5); 2,672 (0.4); 2.558 (0.5); 2,530 (1.4);
2,516 (33.4); 2,512 (67.7); 2.50 (90.9); 2.503 (64.6); 2,499 (30.6); 2.339 (0.4); 2,334 (0.6); 2.330 (0.4); 1.995 (0.7); 1.846 (0.5); 1.839 (0.5); 1.828 (0.6); 1.820 (0.7); 1.811 (0.8); 1.803 (0.7); 1,792 (0.7);
1.785 (0.6); 1.572 (0.7); 1.554 (1.3); 1.537 (1.3); 1.519 (1.2); 1,496 (16.0); 1.397 (13.9); 1.254 (0.9); 1.182 (0.4); 0.882 (0.4); 0.866 (1.2); 0.848 (0.5); 0.825 (3.8); 0.807 (8.2); 0.788 (3.5)
Example 78: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.819 (1.7); 8.806 (1.8); 8.079 (1.6); 8.052 (1.7); 7.810 (1.8); 7,784 (2.1); 7.607 (0.5); 7.578 (1.7); 7.562 (2.6); 7.537 (1.5); 7.295 (1.1); 7.283 (0.5); 7.261 (61.0); 7.250 (1.5); 7.249 (1.5); 7.247 (1.5); 7.243 (1.8); 7.228 (2.3); 7.046 (3.9); 6,963 (2.5); 6,938 (2.2); 6,910 (0.4); 6,864 (1.9); 3,381 (0.5); 3.360 (0.9); 3.335 (1.0); 3.310 (0.6); 2.265 (1.4); 2.236 (1.5); 2,221 (1.8); 2.192 (1.6); 2.008 (14.6);
93/116
1.754 (0.6); 1.733 (0.9); 1.708 (2.8); 1.683 (4.1); 1.658 (3.0); 1,631 (3.5); 1.612 (3.3); 1.604 (1.7);
1,587 (2.8); 1,579 (1.7); 1.567 (2.7); 1.547 (16.0); 1.515 (1.6); 1.494 (1.0); 1.470 (0.7); 1,300 (7.8);
1.277 (7.6); 1.253 (0.8); 0.873 (5.6); 0.849 (11.6); 0.824 (5.0); 0.742 (3.6); 0.717 (7.1); 0.692 (3.3);
0.011 (1.7); 0.009 (1.0); 0.000 (48.9); -0.008 (1.4); -0.011 (1.9)
Example 79: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.613 (3.5); 8,001 (0.6); 7.856 (3.5); 7,800 (2.5); 7,774 (2.7); 7.608 (0.5); 7.569 (1.9); 7.288 (1.5); 7.280 (0.8); 7.278 (0.8); 7.277 (0.9); 7.274 (1.2); 7.272 (1.4); 7.262 (76.1); 7.247 (1.1); 7.245 (1.1); 7.236 (1.9); 7.176 (2.4); 6,994 (4.8); 6,957 (3.3); 6,932 (2.9); 6,911 (0.6); 6,811 (2.5); 3,381 (0.7);
3.356 (1.1); 3.330 (1.2); 3.308 (0.8); 2,474 (12.5); 2.263 (1.9); 2,234 (1.9); 2.219 (2.3); 2,190 (2.0);
1.753 (0.7); 1.728 (1.1); 1.707 (3.5); 1.682 (5.4); 1.657 (4.0); 1.628 (4.6); 1.608 (4.9); 1,583 (7.8);
1.568 (16.0); 1.539 (3.5); 1.514 (2.6); 1,491 (1.5); 1.468 (1.1); 1.445 (0.5); 1.314 (0.8); 1.292 (10.1); 1.269 (10.0); 1,195 (0.9); 0.938 (0.4); 0.914 (0.8); 0.873 (6.7); 0.848 (13.9); 0.824 (6.1); 0.740 (4.5);
0.716 (9.0); 0.691 (4.3); 0.011 (1.8); 0.000 (58.4); -0.009 (1.7); -0.011 (2.3); -0.023 (0.4)
Example 8Õ: ¹ H-NMR (300.2 Mhil CDCI3):
δ = 8,007 (1.1); 7,980 (1.3); 7,737 (0.9); 7.690 (1.1); 7.664 (1.2); 7.540 (1.2); 7.513 (1.1); 7.264 (2.4); 7.236 (1.3); 7.211 (0.7); 7.130 (1.0); 6,965 (1.5); 6,949 (2.3); 6,941 (1.5); 6,768 (1.0); 3.339 (0.5);
3.312 (0.5); 3,290 (0.3); 2.245 (0.8); 2.216 (0.9); 2.201 (1.0); 2.172 (0.9); 1,990 (16.0); 1,751 (0.3); 1.726 (0.5); 1.704 (1.3); 1,679 (1.6); 1.675 (1.5); 1.650 (1.5); 1.635 (0.6); 1.626 (0.8); 1.618 (1.7);
1,598 (1.5); 1.590 (0.9); 1,574 (1.4); 1.565 (0.9); 1.554 (1.5); 1.540 (0.4); 1.528 (0.8); 1.503 (0.8);
1.481 (0.5); 1.458 (0.4); 1.267 (4.1); 1,244 (4.0); 0.868 (2.8); 0.843 (5.9); 0.819 (2.5); 0.731 (2.0);
0.707 (3.9); 0.682 (1.8); 0.000 (1.3)
Example 81: ¹ H-NMR (499.9 MHz, CDCl3):
δ = 8.804 (2.7); 8,796 (2.6); 8.068 (1.8); 8.053 (2.0); 8.029 (0.4); 8,006 (0.9); 7.811 (1.7); 7.803 (1.6); 7,796 (1.5); 7,788 (1.5); 7.589 (1.1); 7.574 (2.3); 7.558 (2.1); 7.547 (2.1); 7.533 (1.8); 7.518 (0.5);
7.316 (0.4); 7.309 (0.3); 7.287 (1.2); 7.271 (2.4); 7.258 (30.4); 7.136 (1.9); 7.027 (3.8); 6,994 (2.4);
6,980 (2.2); 6,917 (1.9); 3.727 (1.5); 3,386 (0.4); 3,371 (0.8); 3.357 (1.1); 3.344 (1.0); 3.330 (0.7);
3.315 (0.4); 2.948 (6.2); 2.875 (6.0); 2.802 (1.7); 2,362 (1.1); 2.345 (1.1); 2,336 (1.2); 2.319 (1.1);
2.123 (1.4); 2.106 (1.4); 2.097 (1.7); 2.080 (1.5); 1.745 (1.6); 1.734 (1.8); 1.719 (2.1); 1.708 (1.9);
1,691 (1.9); 1,676 (2.1); 1,661 (2.0); 1.645 (1.8); 1.632 (1.2); 1.618 (1.0); 1.609 (1.1); 1.593 (1.0);
1,578 (1.1); 1.548 (10.7); 1.537 (4.4); 1.526 (3.0); 1.511 (2.1); 1,500 (1.9); 1.319 (0.9); 1.309 (16.0); 1.297 (9.1); 1.283 (8.8); 1.189 (9.7); 0.924 (4.8); 0.909 (9.7); 0.894 (4.5); 0.815 (1.9); 0.800 (3.7);
0.785 (1.9); 0.006 (0.8); 0.000 (19.6); -0.007 (1.3)
Example 82: ¹ H-NMR (400.1 MHz, CDCl3):
δ = 8.608 (4.0); 8.011 (0.4); 7.854 (3.6); 7.805 (2.0); 7,793 (1.3); 7,785 (2.1); 7.576 (2.0); 7.289 (1.5); 7.269 (3.0); 7.260 (32.1); 7.250 (1.8); 7.116 (2.7); 6,993 (3.2); 6,979 (6.6); 6,842 (2.8); 3.390 (0.6); 3,373 (1.0); 3.356 (1.2); 3.339 (0.9); 3.323 (0.5); 2,469 (13.4); 2.364 (0.8); 2.343 (0.8); 2.332 (0.9);
94/116
2,310 (0.8); 2.126 (2.0); 2.104 (2.1); 2.093 (2.5); 2.072 (2.3); 2.002 (12.6); 1.747 (2.5); 1.734 (2.4); 1.724 (1.0); 1.715 (2.2); 1.709 (1.3); 1.706 (1.5); 1.701 (2.2); 1,690 (2.8); 1.680 (1.0); 1,671 (2.9);
1,662 (2.7); 1.653 (1.2); 1.643 (2.9); 1.627 (1.5); 1.609 (1.4); 1.593 (1.0); 1.575 (1.0); 1.562 (0.7);
1.557 (0.7); 1.544 (1.0); 1.539 (1.5); 1.526 (1.8); 1.507 (1.4); 1.494 (1.3); 1.308 (11.3); 1.292 (11.2); 1.274 (11.0); 1.189 (16.0); 0.928 (6.9); 0.909 (14.5); 0.890 (6.3); 0.818 (1.5); 0.800 (2.8); 0.781 (1.3); 0.000 (7.7)
Example 83: ¹ H-NMR (400.1 MHz, CDCl3):
δ = 8.051 (1.8); 8.030 (1.8); 7,798 (1.1); 7,790 (1.0); 7,778 (1.3); 7,771 (1.1); 7.582 (2.6); 7.563 (2.5); 7.291 (1.0); 7.272 (2.1); 7.259 (32.8); 7.069 (1.2); 6,999 (1.9); 6,981 (1.7); 6,933 (2.4); 6,797 (1.2); 3.358 (0.5); 3.343 (0.7); 3.325 (0.7); 3.312 (0.6); 3.294 (0.3); 2,366 (1.1); 2,344 (1.1); 2,333 (1.2);
2,311 (1.1); 2.127 (0.9); 2.105 (1.0); 2.094 (1.2); 2,073 (1.1); 2.003 (0.6); 1,750 (1.1); 1.736 (1.0);
1.723 (0.5); 1.717 (0.9); 1.704 (1.3); 1,688 (1.3); 1,678 (0.4); 1.670 (1.3); 1.659 (1.1); 1.651 (0.5);
1,641 (1.2); 1.625 (0.7); 1.607 (0.8); 1,592 (0.8); 1.574 (0.7); 1,541 (9.1); 1.529 (2.1); 1.509 (1.9);
1,496 (1.5); 1.307 (16.0); 1,284 (6.9); 1.267 (6.8); 1,187 (6.6); 0.925 (3.2); 0.907 (6.8); 0.888 (2.9); 0.816 (1.9); 0.798 (3.7); 0.779 (1.8); 0.000 (8.1)
Example 84: ¹ H-NMR (400.1 MHz, CDCl3):
δ = 8.815 (3.1); 8.805 (3.1); 8.066 (2.3); 8.046 (2.5); 7.898 (2.5); 7.879 (2.9); 7,852 (1.0); 7.681 (0.6);
7.566 (1.7); 7.554 (2.0); 7.545 (2.8); 7.535 (1.7); 7.518 (1.4); 7,477 (2.1); 7.407 (0.7); 7.309 (0.5); 7.259 (206.3); 7.248 (2.6 ; 7.228 (3.4); 7.208 (2.4); 7.172 (5.3) 7.153 (2.3); 7,133 (1.5); 7.118 (0.8); 7,100 (4.0); 7.080 (3.1); 7.036 (8.6); 7,008 (1.2); 6,995 (1.3); 6,969 (0.8); 6,951 (0.7); 6,899 (4.4); 6.047 (0.5); 4.148 (0.6); 4,130 (1.8); 4,112 (1.8); 4.095 (0.6); 3,361 (0.6); 3.336 (0.6); 3.321 (0.8); 3.309 (0.7); 3.252 (1.6); 3,232 (2.7); 3,210 (1.9); 3.085 (0.8); 3.059 (1.1); 3.044 (1.8); 3,020 (2.1); 2,999 (1.9); 2.985 (0.9); 2.959 (0.7); 2.919 (0.5); 2.888 (2.2); 2.865 (2.6); 2.848 (3.1); 2.829 (2.3); 2.810 (0.8); 2.788 (0.8); 2.470 (0.8); 2.455 (0.5); 2.282 (0.4); 2.250 (0.8); 2,224 (0.9); 2.204 (1.5); 2.192 (1.1); 2.178 (1.5); 2.169 (1.8); 2.149 (1.9); 2,126 (1.4); 2.103 (1.1); 2.097 (1.2); 2.082 (0.8); 2.043 (9.4); 2.021 (1.2); 2.005 (1.0); 1,984 (1.2); 1,969 (3.7); 1,954 (3.0); 1,949 (3.6); 1,945 (2.8); 1,937 (3.1); 1.922 (2.0); 1,917 (2.5); 1,913 (1.8); 1.882 (1.0); 1.868 (1.0); 1.830 (1.1); 1.819 (1.2); 1,804 (1.2); 1,786 (1.3); 1,762 (1.2); 1.753 (1.2); 1,744 (1.2); 1,737 (1.3); 1.720 (1.6); 1.704 (2.0); 1,695 (2.1); 1.687 (1.9); 1,679 (2.0); 1,669 (1.8); 1.653 (1.2); 1,637 (0.7); 1,594 (0.4); 1.574 (0.4); 1,521 (0.3); 1.433 (1.5); 1.422 (1.8); 1,405 (1.6); 1,397 (2.6); 1.388 (2.4); 1.370 (2.4); 1.360 (2.4); 1.346 (0.7); 1,337 (1.1); 1.325 (1.0); 1,308 (0.7); 1,284 (1.2); 1,276 (3.1); 1,271 (1.3); 1.259 (7.6); 1,241 (3.5); 1,232 (2.0); 1,222 (2,3); 1,198 (1.2); 1,190 (1.0); 1.109 (0.5); 1,010 (3.8); 0.994 (3.6); 0.973 (7.9); 0.956 (8.2); 0.948 (4.7); 0.936 (5.8); 0.932 (8.3); 0.920 (5.4); 0.916 (5.0); 0.873 (15.1);
0.857 (16.0); 0.849 (12.7); 0.832 (11.2); 0.753 (0.3); 0.716 (0.3); 0.146 (0.5); 0.008 (4.7); 0.000 (154.8); 0.009 (5.6); -0.051 (0.5); -0.150 (0.7)
Example 85: ¹ H-NMR (400.1 MHz, CDCl3):
95/116 δ = 8.805 (1.2); 8,795 (1.1); 8.098 (1.0); 8.078 (1.0); 7,926 (1.1); 7,906 (1.1); 7.576 (0.8); 7.564 (0.9); 7.557 (1.0); 7.545 (1.2); 7.518 (0.5); 7.259 (38.0); 7.234 (0.7); 7.214 (1.3); 7.195 (0.8); 7.142 (1.1); 7.053 (1.5); 7.034 (1.3); 7,005 (2,3); 6,869 (1.1); 5.298 (0.4); 2.903 (1.3); 2.864 (1.7); 2.775 (0.5); 2.757 (1.6); 2.739 (1.6); 2.722 (0.5); 2,597 (2.1); 2.558 (1.7); 1.538 (25.2); 1,119 (16.0); 1.078 (5.3); 1.060 (5.2); 1.027 (8.7); 0.000 (3.1)
Example 86: ¹ H-NMR (400.1 MHz, CDCl3):
δ = 8,600 (1.9); 7,920 (1.2); 7,900 (1.3); 7.879 (1.8); 7.549 (0.9); 7.260 (15.7); 7.227 (0.7); 7.208 (1.4); 7.188 (0.8); 7.089 (1.5); 7.045 (1.7); 7.027 (1.4); 6,952 (3.2); 6,815 (1.6); 5.298 (0.5); 2,900 (1.5);
2,861 (1.9); 2.772 (0.5); 2.754 (1.6); 2.737 (1.6); 2.719 (0.5); 2.592 (2.3); 2,553 (1.8); 2,472 (6.5);
1.551 (5.4); 1,118 (16.0); 1.070 (5.9); 1.052 (5.8); 1,024 (10.2); 0.000 (1.3)
Example 87: ¹ H-NMR (400.1 MHz, CDCl3):
δ = 8.079 (1.3); 8.059 (1.3); 7.905 (1.1); 7.885 (1.2); 7.591 (1.3); 7.570 (1.3); 7.543 (0.8); 7.518 (0.5); 7.309 (0.5); 7.259 (64.2); 7.229 (0.7); 7.208 (1.2); 7.190 (0.8); 7.056 (1.7); 7.038 (1.5); 6.995 (0.4); 6.907 (1.8); 6,771 (0.9); 5.299 (1.5); 2.901 (1.3); 2.862 (1.7); 2.757 (0.5); 2.740 (1.5); 2.722 (1.6); 2.704 (0.5); 2.594 (2.3); 2,555 (1.8); 1.534 (42.9); 1,120 (16.0); 1.064 (5.0); 1.046 (5.0); 1.022 (8.6); 0.000 (5.4)
Example 88: ¹ H-NMR (300.2 MHz] CDCI3):
δ = 8.814 (0.7); 8,799 (0.8); 8.085 (0.6); 8.060 (0.7); 7,790 (0.6); 7,764 (0.7); 7.607 (0.3); 7.581 (0.9); 7.564 (0.7); 7.539 (0.5); 7.291 (0.5); 7.261 (28.0); 7.249 (0.7); 7.247 (0.6); 7.246 (0.6); 7.240 (0.8);
7.212 (0.8); 7.111 (0.9); 7.086 (0.7); 7.030 (1.5); 6.848 (0.7); 3,321 (0.5); 3.298 (0.5); 3,276 (0.4);
2.998 (0.4); 2,600 (0.5); 2.571 (0.8); 2.557 (0.5); 2.543 (0.4); 2.528 (0.9); 2,500 (0.4); 2.008 (0.6);
1.937 (0.3); 1.929 (0.4); 1.909 (0.5); 1,893 (0.4); 1.884 (0.4); 1.868 (0.4); 1,552 (16.0); 1.522 (0.5); 1.516 (0.5); 1.502 (0.4); 1,491 (0.4); 1,473 (0.7); 1.453 (0.9); 1.434 (0.7); 1.410 (0.9); 1.391 (0.5);
1.307 (2.9); 1,284 (2.9); 1.186 (0.5); 1,162 (0.4); 1.057 (2.5); 1.032 (5.2); 1.017 (0.6); 1.008 (2.2);
0.993 (0.7); 0.908 (0.7); 0.885 (1.3); 0.863 (0.6); 0.011 (0.6); 0.008 (0.4); 0.000 (19.5); -0.009 (0.7); 0.011 (0.9)
Example 89: ¹ H-NMR (300.2 MHz] CDCI3):
δ = 8.814 (0.7); 8.801 (0.7); 8.083 (0.6); 8.059 (0.7); 7,781 (0.7); 7.755 (0.8); 7.607 (0.5); 7.595 (0.6); 7.580 (0.7); 7.563 (0.6); 7.554 (0.6); 7.536 (0.5); 7.288 (0.5); 7.272 (0.4); 7.262 (24.2); 7.253 (0.7); 7.251 (0.6); 7.250 (0.5); 7.248 (0.4); 7.247 (0.4); 7,245 (0.4); 7.238 (0.7); 7.213 (1.0); 7.109 (1.0);
7.084 (0.8); 7.031 (1.7); 6.848 (0.8); 3.317 (0.5); 3.293 (0.5); 3.069 (0.4); 2.599 (0.5); 2.570 (0.9);
2.556 (0.7); 2.542 (0.5); 2.527 (1.0); 2.499 (0.5); 2.008 (0.6); 1.856 (0.3); 1.846 (0.4); 1.840 (0.6);
1.829 (0.5); 1.569 (16.0); 1.527 (0.6); 1.513 (0.4); 1.503 (0.7); 1,495 (0.6); 1.485 (0.8); 1,472 (1.5); 1,463 (1.2); 1.448 (1.6); 1.444 (1.6); 1,424 (1.1); 1.421 (1.0); 1,400 (1.0); 1.381 (0.6); 1.307 (3.2);
1,284 (3.2); 1.256 (0.6); 1,000 (1.8); 0.977 (3.6); 0.952 (1.8); 0.011 (0.4); 0.000 (13.7); -0.009 (0.4); 0.011 (0.6)
96/116
Example 90: ¹ H-NMR (300.2 MHz, DMSO):
õ = 10,121 (0.7); 8,844 (0.4); 8,839 (0.5); 8.828 (0.5); 8.823 (0.5); 8.233 (0.4); 8.207 (0.4); 7,751 (0.3); 7.461 (0.3); 7.280 (0.7); 7,201 (0.7); 7.194 (1.1); 7.171 (0.8); 7.145 (0.4); 7.129 (0.5); 7,100 (0.6); 3.324 (16.0); 2,513 (2.7); 2.507 (5.6); 2,501 (7.7); 2,495 (5.6); 2.489 (2.7); 1.314 (0.9); 1.286 (0.4); 0.847 (10.2); 0.011 (0.4); 0.000 (9.6); -0.011 (0.4)
Example 91: ¹ H-NMR (300.2 MHz, CDCI3): δ = 8.759 (4.3); 8,744 (4.4); 8.639 (0.4); 8.631 (0.4); 8.622 (0.4) 8.044 (3.1); 8.019 (3.5); 7.848 (1.0); 7,821 (1.2); 7,717 (3.1); 7.691 (3.8); 7,615 (3.1); 7.518 (2.7); 7,501 (3.1); 7.495 (3.1); 7.477 (2.5); 7.326 (0.3); 7.261 (7.2); 7.254 (0.6); 7,241 (1.3); 7.217 (2.9); 7,190 (7.1); 7.174 (2.6); 7.107 (0.6); 7.098 (0.6); 7.082 (3.2); 7.055 (2.7); 7.041 (1.1); 7,008 (8.1); 7,003 (3.8); 6,992 (2.5); 6,927 (1.4); 6.903 (1.2); 6,872 (0.4); 6.837 (0.6); 6.825 (4.0); 6,821 (1.9); 6,810 (1.2); 4,112 (1.0); 4.088 (1.0); 4.064 (0.3); 3.043 (0.5); 3.028 (0.6); 3.019 (0.7); 3.005 (0.6); 2.997 (0.5); 2.979 (0.6); 2.971 (0.6); 2.955 (1.3); 2.947 (1.4); 2.931 (1.5); 2.923 (1.6); 2.901 (0.7); 2.883 (0.9); 2.858 (0.9); 2.819 (0.5); 2,771 (0.5); 2.752 (0.5); 2.715 (0.6); 2,697 (0.6); 2,672 (0.4); 2.614 (0.4); 2.594 (0.5); 2.550 (1.5); 2.513 (1.6); 2,478 (0.8); 2.458 (1.2); 2.445 (0.8); 2.439 (0.8); 2.425 (1.4); 2,395 (0.4); 2.386 (0.3); 2,364 (0.7); 2,344 (0.7); 2.284 (0.4); 2.268 (0.4); 2.246 (0.9); 2,222 (3.3); 2.212 (3.1); 2.204 (2.0); 2,181 (2.5); 2.154 (0.9); 2,145 (1.0); 2,120 (0.9); 2,100 (0.4); 2.025 (4.7); 1.889 (0.3); 1,875 (0.4); 1.868 (0.4); 1,854 (0.5); 1.837 (0.7); 1.813 (0.8); 1.790 (0.8); 1,765 (0.8); 1,737 (2.4); 1,691 (0.3); 1,676 (0.5); 1.666 (0.4); 1.650 (0.6); 1,626 (0.8); 1,604 (1.3); 1,580 (1.3); 1.567 (0.5); 1,556 (0.8); 1.532 (0.6); 1,520 (0.5); 1.507 (0.4); 1,495 (0.6); 1,474 (1.1); 1.450 (1.5); 1.434 (1.2); 1,428 (1.7); 1,422 (1.9); 1,415 (1.5); 1.403 (2.6); 1,389 (3.4); 1,365 (3.7); 1.351 (2.1); 1,336 (3.0); 1.327 (2.9); 1.307 (16.0); 1.283 (15.4); 1,271 (7.6) ; 1.267 (7.8) 1,247 (4.7); 1,232 (1.5); 1,223 (2.8); 1.205 (1.0); 1,198 (1.6); 1,185 (0.8); 1,175 (0.6); 1,160 (0.7); 1,154 (0.5); 1,133 (0.6); 1,105 (5.4); 1.081 (6.1); 1.071 (5.7); 1,049 (8.1); 1.026 (14.2); 1.011 (8.3); 1.006 (11.4); 0.994 (3.2); 0.992 (3.3); 0.980 (3.7); 0.966 (4.8); 0.955 (6.0); 0.931 (12.4); 0.925 (8.8); 0.914 (9.5); 0.903 (4.6); 0.895 (4.8); 0.881 (9.2); 0.858 (3.4); 0.846 (1.7); 0.835 (1.3); 0.816 (0.5); 0.808 (0.7); 0.795 (2.6); 0.770 (5.0); 0.757 (2.5); 0.745 (2.6); 0.732 (4.3); 0.708 (2.0); 0.691 (0.5); 0.667 (0.3); 0.615 (0.3); 0.592 (0.7); 0.570 (0.4); 0.000 (4.0)
Example 92: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.736 (0.7); 8,732 (0.8); 8.721 (0.8); 8.716 (0.8); 8.039 (0.6); 8.013 (0.7); 7.878 (0.6); 7.786 (0.8); 7.759 (0.9); 7.493 (0.5); 7.477 (0.5); 7.468 (0.5); 7.452 (0.4); 7.270 (0.6); 7.254 (0.4); 7.228 (0.8);
7.202 (0.5); 7.168 (0.8); 7.026 (1.1); 7,001 (0.9); 6,986 (1.8); 6.804 (0.9); 4.128 (0.4); 4.104 (1.1);
4.080 (1.1); 4.057 (0.4); 2.827 (1.0); 2.803 (2.0); 2,779 (1.2); 2.018 (4.9); 1,972 (1.6); 1,961 (0.4);
1,948 (2.8); 1.924 (1.5); 1.262 (16.0); 1.243 (3.2); 1,219 (1.7); 1.193 (0.4); 1.046 (0.6)
Example 93: ¹ H-NMR (300.2 ΜΗ! CDCl3):
δ = 8.817 (0.4); 8.805 (0.4); 8.076 (0.3); 8.051 (0.4); 7.786 (0.3); 7,760 (0.4); 7.578 (0.3); 7.562 (0.5);
97/116
7.296 (0.6); 7.261 (15.1); 7.232 (0.5); 7.218 (0.5); 7.035 (0.8); 6.853 (0.4); 3.036 (0.3); 2,495 (0.4); 2.450 (0.4); 1,556 (12.3); 1.520 (0.5); 1.499 (0.3); 1.324 (1.5); 1.301 (1.5); 1.038 (16.0); 0.011 (0.3); 0.000 (10.5); -0.011 (0.5)
Example 94: ¹ H-NMR (300.2 MHz, DMSO):
δ = 10,395 (3.2); 8,836 (2.1); 8,825 (2.1); 8,820 (2.0); 8.187 (1.7); 8.161 (1.9); 7,771 (1.4); 7,755 (1.5); 7,745 (1.3); 7.729 (1.2); 7.420 (1.4); 7.397 (3.1); 7.375 (1.9); 7.367 (2.1); 7.341 (2.7); 7.315 (1.1);
7.194 (3.5); 7.167 (2.4); 7.145 (1.9); 7.014 (1.8); 6.472 (0.7); 6.462 (0.6); 6.286 (1.0); 6.273 (1.0);
6.095 (0.6); 6.083 (0.6); 5.759 (0.3); 4.088 (0.5); 4.057 (0.5); 4.040 (1.0); 4.017 (1.0); 3.993 (0.6);
3,977 (0.5); 3.326 (141.7); 3.258 (0.6); 2.541 (0.4); 2,513 (11.0); 2.507 (23.7); 2.501 (32.5); 2,495 (23.8);
2,489 (11.3); 2.147 (0.6); 2.117 (0.5); 2.102 (2.1); 2.071 (4.0); 2.054 (2.4); 2.025 (0.7); 2.008 (0.5); 1,989 (3.2); 1.317 (15.6); 1.263 (16.0); 1,247 (9.9); 1.198 (1.3); 1.174 (2.0); 1,150 (1.0); 0.880 (2.6); 0.858 (8.7); 0.835 (3.1); 0.011 (0.8); 0.000 (25.7); -0.011 (1.1)
Example 95: ¹ H-NMR (300.2 MHz, DMSO):
5 = 10.144 (1.2); 8,851 (0.7); 8,846 (0.8); 8.835 (0.8); 8,830 (0.8); 8.227 (0.6); 8.202 (0.7); 7,780 (0.5); 7.765 (0.5); 7.755 (0.5); 7,739 (0.4); 7.471 (0.6); 7.290 (1.1); 7.234 (0.9); 7.209 (1.0); 7.188 (1.0);
7.184 (1.2); 7.162 (0.5); 7.158 (0.4); 7.109 (1.4); 7.089 (0.7); 7.084 (0.7); 6.928 (0.3); 5.759 (0.9);
3.393 (0.4); 3.326 (19.6); 2.513 (1.6); 2.507 (3.6); 2.501 (5.1); 2,495 (3.8); 2,489 (1.9); 2,199 (0.4); 2,170 (0.4); 2.156 (0.5); 2.127 (0.4); 1,989 (0.3); 1,787 (0.5); 1,774 (0.6); 1.760 (0.6); 1.743 (0.5);
1.731 (0.5); 1.716 (0.7); 1.316 (5.0); 1.293 (0.7); 1.254 (2.1); 1,247 (3.1); 1,232 (1.9); 1,217 (5.2);
1.174 (0.6); 1,150 (0.5); 0.902 (0.4); 0.880 (1.1); 0.858 (2.7); 0.828 (16.0); 0.000 (5.5)
Example 96: ’H-NMR (300.2 MHz ^ DMSO):
δ = 10.353 (3.8); 8,814 (2.2); 8,810 (2.4); 8,799 (2.4); 8,794 (2.3); 8.089 (1.9); 8.062 (2.2); 7,741 (1.6); 7,726 (1.7); 7,716 (1.5); 7.699 (1.3); 7.394 (1.8); 7.272 (1.2); 7.247 (3.1); 7.221 (2.6); 7.214 (4.1);
7.117 (3.4); 7.090 (4.7); 7.064 (2.5); 7.034 (2.0); 6.107 (4.2); 6.076 (4.3); 5.706 (3.5); 4.228 (0.6);
4,199 (2.0); 4,171 (1.9); 4.142 (0.7); 3,273 (38.3); 2,460 (6.8); 2.455 (14.9); 2,449 (20.9); 2,443 (15.6); 2.437 (7.8); 2,225 (1.5); 2.198 (1.6); 2.183 (1.9); 2.156 (1.6); 1.936 (0.8); 1.693 (1.5); 1,664 (1.6);
1.652 (1.5); 1.622 (1.3); 1.297 (16.0); 1.254 (0.9); 1.229 (1.7); 1.194 (11.5); 1.142 (15.0); 1,122 (1.4);
1.098 (0.6); 0.827 (3.3); 0.806 (10.7); 0.782 (4.0); -0.042 (0.7); -0.053 (23.1); -0.064 (1.2)
Example 97I ¹ H-NMR (300.2 MHz ^ CDCl3):
δ = 8.828 (6.2); 8,816 (6.5); 8.093 (4.6); 8.065 (7.1); 7,947 (3.9); 7,921 (4.1); 7.608 (0.6); 7.573 (3.4); 7.558 (4.0); 7.550 (3.8); 7.533 (3.1); 7.426 (3.3); 7,400 (6.2); 7.375 (3.7); 7.330 (0.5); 7.313 (0.3);
7.262 (72.3); 7.238 (7.8); 7.196 (0.7); 7.172 (8.4); 7.148 (7.0); 7.056 (14.6); 6,911 (0.5); 6,875 (7.3);
4.157 (0.5); 4,133 (1.4); 4.109 (1.4); 4.085 (0.5); 3.075 (2.1); 3.060 (3.8); 3.047 (7.8); 3.042 (7.8);
3.029 (16.0); 3.011 (16.0); 2.998 (8.9); 2.978 (4.3); 2.045 (6.7); 1.639 (0.4); 1,571 (95.8); 1.506 (0.5); 1.333 (0.4); 1.306 (1.0); 1.283 (3.2); 1.259 (8.0); 1,235 (2.4); 0.904 (1.9); 0.882 (5.9); 0.859 (2.3);
0.011 (1.5); 0.000 (48.7); -0.011 (2.4); -0.066 (0.3)
98/116
Example 98: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 7,282 (1.4); 7.259 (11.7); 7.242 (1.2); 7.234 (3.8); 7.186 (5.3); 7.162 (3.3); 7.133 (0.6); 2.356 (16.0); 1.577 (11.8); 1.242 (0.5); 1.218 (0.4); 0.000 (4.1)
Example 99] ¹ H-NMR (300.2 MHz, CDCl3):
δ = 8.817 (4.3); 8.803 (4.3); 8.123 (3.3); 8.097 (3.7); 8.011 (3.6); 7,977 (6.7); 7,950 (5.9); 7.689 (0.4); 7.656 (0.4); 7.604 (5.4); 7.590 (5.3); 7.564 (2.6); 7.536 (0.6); 7.453 (0.4); 7.397 (2.7); 7.370 (4.4);
7.342 (2.3); 7.261 (102.2); 7.188 (2.3); 7.167 (4.2); 7.090 (0.4); 6,985 (5.9); 6,911 (0.5); 6.803 (3.0); 3.419 (2.0); 3,395 (3.2); 3,373 (2,3); 3.209 (3.1); 3.181 (2.5); 3.152 (4.1); 3.124 (3.4); 2,667 (4.9);
2,610 (4.0); 2.357 (5.6); 2.009 (0.4); 1.620 (0.6); 1,558 (130.0); 1.481 (0.5); 1.431 (0.4); 1.414 (0.4); 1.406 (0.4); 1.243 (16.0); 1,220 (15.2); 0.902 (1.5); 0.882 (3.0); 0.859 (1.4); 0.000 (63.5); -0.196 (0.4) Example 1ÕÕ] ¹ H-NMR (300.2 MHz, CDCI3):
δ = 8.786 (1.4); 8,774 (1.5); 8.081 (1.1); 8.055 (1.2); 7.704 (1.3); 7.524 (0.8); 7.508 (0.9); 7.499 (0.9); 7.483 (0.8); 7.277 (1.6); 7.265 (2.6); 7.095 (3.2); 7.055 (0.6); 7.037 (0.9); 7.027 (2.0); 7.010 (3.1);
6,977 (1.5); 6,949 (0.6); 6,913 (1.6); 5.295 (1.2); 4,113 (0.5); 4.089 (0.6); 3.507 (0.4); 3.483 (0.8);
3.459 (0.8); 3.436 (0.4); 2.273 (1.2); 2.246 (1.2); 2.221 (1.5); 2.204 (1.3); 2.027 (2.5); 1,689 (1.9);
1.651 (1.6); 1.629 (1.6); 1.609 (1.5); 1,586 (1.4); 1.363 (0.3); 1,337 (16.0); 1.304 (0.6); 1.285 (0.8); 1,271 (2.2); 1.258 (6.8); 1,248 (3.0); 1,235 (6.2); 1,223 (3.1); 1,213 (9.7); 1,162 (0.4); 0.903 (0.4);
0.881 (1.2); 0.858 (0.4); 0.000 (1.4) [303] NMR Peak Lists from Table 2
Example lll-a-1: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 7.606 (0.4); 7.277 (0.3); 7.275 (0.4); 7.274 (0.4); 7.272 (0.5); 7.271 (0.7); 7.260 (67.3); 7.250 (1.0); 7.248 (0.8); 7.247 (0.7); 7.244 (0.5); 7.236 (0.4); 7.038 (1.7); 7.013 (3.7); 6,987 (2.2); 6.909 (0.4);
6.672 (3.1); 6.647 (2.8); 6.514 (3.4); 6.489 (3.1); 3,666 (0.4); 3.603 (1.0); 3.493 (0.6); 3,212 (0.9);
3.188 (1.2); 3.167 (1.2); 3.144 (0.9); 3.122 (0.3); 2.949 (0.5); 2.932 (0.6); 2.918 (0.9); 2.902 (1.3);
2.884 (0.9); 2.871 (0.8); 2.854 (0.5); 2.558 (1.2); 2.529 (2.2); 2.514 (1.4); 2,500 (1.1); 2,486 (2.4);
2.457 (1.1); 1,930 (0.4); 1.905 (0.8); 1.888 (0.9); 1.880 (1.0); 1.861 (1.3); 1.843 (1.1); 1.835 (1.2);
1.819 (1.1); 1.811 (0.6); 1,794 (0.5); 1,553 (4.0); 1.518 (1.5); 1.494 (1.3); 1.487 (1.2); 1,473 (1.0);
1,463 (1.1); 1.448 (1.0); 1,442 (2.1); 1.423 (2.6); 1.405 (1.4); 1.398 (1.5); 1,380 (2.1); 1.361 (1.6);
1.352 (16.0); 1,329 (15.7); 1,220 (1.8); 1.205 (1.0); 1,197 (1.8); 1.182 (1.0); 1.041 (6.9); 1.017 (13.8); 1.002 (1.1); 0.992 (6.0); 0.978 (1.1); 0.964 (0.3); 0.953 (0.5); 0.928 (1.0); 0.908 (0.5); 0.011 (1.0);
0.009 (0.5); 0.000 (38.5); -0.010 (1.6); -0.011 (1.9)
Example lll-a-6: ¹ H-NMR (300.2 MHz, DMSO):
Õ = 7.312 (0.9); 7.191 (0.4); 7.167 (0.5); 7.141 (1.9); 6,971 (1.3); 6.929 (0.4); 3.975 (0.3); 3.891 (0.4); 3.842 (0.3); 3.309 (0.4); 2.501 (15.4); 2.188 (0.4); 2,119 (0.4); 2.103 (0.5); 2.074 (0.5); 1.849 (0.6);
1.804 (0.5); 1,780 (0.7); 1.733 (0.8); 1.339 (0.5); 1.303 (1.4); 1,276 (5.3); 1.255 (2.4); 1.234 (1.8);
1.204 (5.2); 1.178 (1.9); 1.151 (0.7); 1.121 (0.8); 0.998 (16.0); 0.902 (0.5); 0.881 (1.0); 0.858 (1.2);
99/116
0.835 (0.6); 0.000 (10.6)
Example lll-a-8: ¹ H-NMR (300.2 MHz, DMSO):
δ = 7.215 (0.4); 7.197 (2.7); 7.176 (0.5); 5,761 (1.3); 3.473 (0.3); 2.515 (0.5); 2.50 (1.2); 2.503 (1.6); 2,497 (1.2); 2,491 (0.6); 1.997 (0.4); 1,971 (0.3); 1,478 (0.4); 1.431 (0.7); 1.327 (0.5); 1.292 (0.5); 1.280 (0.3); 1,000 (16.0); 0.000 (1.2)
Example lll-a-10: ¹ H-NMR (300.2 MHz, CDCl3):
δ = 7.249 (1.4); 6,877 (1.1); 6,850 (1.3); 6,840 (1.2); 6,813 (1.2); 6.486 (1.5); 6.472 (1.6); 6.459 (1.4); 6.444 (1.4); 3,484 (0.6); 3,273 (0.4); 3,249 (0.6); 3,230 (0.6); 3.206 (0.5); 2.257 (1.4); 2,229 (1.4); 2.215 (1.7); 2.186 (1.6); 2.043 (1.1); 1,671 (1.6); 1,655 (1.6); 1.629 (1.4); 1.613 (1.4); 1.355 (10.1); 1.331 (10.0); 1.308 (0.4); 1.293 (16.0); 1.257 (0.8); 1,233 (0.4); 1.184 (16.0); 0.000 (0.9) [304] Experimental examples [305] Process (a)
[306] 2- (difluoromethyl) -N- (2-ethyl-1,1-dimethyl-2,3-dihydro-1 H-inden-4-yl) -5methylnicotinamide (example 38) [307] In a tube sealable microwave, propanophosphonic anhydride (50% in AcOEt, 0.94 ml, 1.58 mmol, 3 eq.) was added to a solution of 2 (difluoromethyl) -5-methylnicotinic acid (118 mg, 0.63 mmol) , 1.2 eq.) And 2-ethyl-1,1dimethylindan-4-amine (100 mg, 0.528 mmol, 1 eq.) In 10 ml of THF. The tube was sealed and microwaved for 10 min at 150 ° C. The resulting solution was cooled with saturated aqueous K2CO3, extracted with AcOEt, washed with saturated aqueous NH4CI and filtered through alumina. The solvent was evaporated to obtain pure material (80%) [308] Process (b)
100/116
[309] 2- (difluoromethyl) -N- (2-ethyl-1,1-dimethyl-2,3-dihydro-1 H-inden-4-yl) -5methylpyridine-3-carbothioamide (example 70) [310] In a sealable microwave tube, P2S5 (29 mg, 0.132 mmol, 0.5 eq.) Was added to a solution of 2- (difluoromethyl) -N- (2-ethyl-1,1-dimethyl-2,3- dihydro1H-inden-4-yl) -5-methylnicotinamide (95 mg, 0.264 mmol, 1 eq.) in 2 ml of dioxane. The tube was sealed and microwaved for 20 min at 130 ° C. The resulting solution was filtered through alumina and washed with dioxane. The solvent was evaporated and the residue was purified by silica gel chromatography to obtain pure material (67%) [311] Process (c)
2,2,3-trimethylindan-4-amine (example lll-a-5) [312] In a sealable reactor, 7-bromo-1,2,2-trimethylindane (1 eq.) Was dissolved in 1.4 -dioxane (15 ml for 250 mg of SM), tBu-carbamate (1.5 eq.) was added followed by XPHOS (0.1 eq.) and cesium carbonate (eq. 2). Argon was bubbled into the solvent for 5 min and the reactor was purged with argon, Pd (OAc) 2 (0.05 eq.) Was added and the tube was sealed. The reaction was heated to 100 ° C until LCMS did not indicate any remaining raw material. The reaction was diluted with EA and filtered through celite. The solvent was removed in vacuo and the residue dissolved in DCM. TFA (10 eq.) Was added. It was refluxed for 5 h, cooled, quenched with sat. NaHCCh, extracted with EA, dried with MgSCU and concentrated. The residue was purified on silica gel to obtain material
101/116 pure.
[313] Example: Preventive test in vivo with Alternaria brassicae (leaf spot on radish) [314] The active ingredients tested are prepared by homogenization in a mixture of acetone / tween / DMSO and dilution with water to obtain the desired concentration of material active.
[315] Radish plants (variety “Pernod Clair”), sown in starter cups on a 50/50 truffle-pozzolan substrate and grown at 17 ° C, were treated in the cotyledon phase by spraying with the active ingredient prepared as described behind. The plants used as controls were treated with an acetone / Tween / DMSO / water mixture without active material.
[316] After 24 hours, the plants were contaminated by spraying the cotyledons with an aqueous spore suspension of Alternaria brassicae (50,000 spores per ml). The spores were collected after 15 days of culture. The contaminated radish plants were incubated at 20 ° C and 100% relative humidity.
[317] A classification (% of effectiveness) was carried out 6 days after the contamination, in comparison with the control plants.
[318] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
Ex. % Effective 1 92 2 98 3 86 4 71 6 71 7 79 13 93 33 100 37 96 38 80 42 83 43 100
102/116
46 98 49 89 51 93 52 86 56 93 57 97 59 88 60 100 62 100
[319] Under these conditions, good protection (at least
70%) or total at a dose of 100 ppm with the following compounds:
Ex. % Effective 71 88 76 75 77 75 78 80 81 70 90 93
[320] Example: Preventive test in vivo with Botrytis cinerea (gray mold) [321] The tested active ingredients are prepared by homogenization in a mixture of acetone / tween / DMSO and dilution with water to obtain the desired concentration of active material.
[322] Itchy plants ('Vert petit de Paris' variety), sown in starter cups on a 50/50 truffle-pozzolan substrate and grown at 24 ° C, were treated in the cotyledon Z11 phase by spraying with the active ingredient prepared as described above. The plants used as controls were treated with an acetone / Tween / DMSO / water mixture without active material.
[323] After 24 hours, the plants were contaminated by spraying the cotyledons with a cryopreserved aqueous spore suspension of Botrytis cinerea (50,000 spores per ml). The spores were suspended in a nutrient solution composed of 10 g / L of PDB, 50 g / L of D-Fructose, 2 g / L of NH4NO3 and 1 g / L of KH2PO4. The contaminated itch plants were incubated at 17 ° C and 90% relative humidity.
[324] A rating (% effectiveness) was carried out after 4 to 5
103/116 days after contamination, compared to control plants.
[325] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
Ex. % Effective 1 100 2 97 10 100 11 99 12 100 20 90 25 96 27 100 33 97 42 99 46 83
[326] Under these conditions, good (at least 70%) or total protection was observed at a dose of 100 ppm, with the following compounds:
Ex. % Effective 65 100 76 98 78 98 79 80 80 70 81 100 82 80 84 99 85 98 88 89 90 80
[327] Under the same conditions, full protection was observed at a dose of 100 ppm of active ingredient with the compound of Example 1, while no protection was observed with the compound P1 disclosed in the patent application of WO2010109301 and neither with 2 - (difluoromethyl) -N- (1,1,3-trimethyl-2,3-dihydro-1 H- inden-4-yl) benzamide:
Example Dose (PPm) Efficiency (%) 1 of the present patent 100 100
104/116
Compound P1 of WO2010109301 100 0 2- (difluoromethyl) -N- (1,1,3-trimethyl-2,3-dihydro-1Hinden-4-yl) benzamide 100 0
[328] Example: Preventive test in vivo with Pyrenophora teres (reticular-reticular in barley) [329] The tested active ingredients are prepared by homogenization in an acetone / tween / DMSO mixture and dilution with water to obtain the desired concentration of active material.
[330] Barley plants ('Plaisant' variety), sown in starter cups on a 50/50 truffle-pozzolan substrate and allowed to grow at 22 ° C, were spray-treated at the stage of 1 leaf (height 10 cm) with the active ingredient prepared as described above. The plants used as controls were treated with an acetone / Tween / DMSO / water mixture without active material.
[331] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous spore suspension of Pyrenophora teres (12,000 spores per ml). Spores were harvested from a 12-day culture. The contaminated barley plants were incubated for 48 hours at 20 ° C and 100% relative humidity, and then for 12 days at 20 ° C and 70-80% relative humidity.
[332] A classification (% of effectiveness) was carried out 14 days after the contamination, in comparison with the control plants.
[333] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
Ex. Eff. % 1 100 3 83 4 75 9 86 12 86 13 100 14 92 27 83 36 75
105/116
39 83 51 83 52 75 56 92 57 97
[334] Under these conditions, good (at least 70%) or total protection was observed at a dose of 100 ppm, with the following compounds:
Ex. Eff. % 65 70 69 70 71 92 76 92 84 75 90 86
[335] Under the same conditions, full protection was observed at a dose of 100 ppm of active ingredient with the compound of Example 1, while a lower protection was registered with compound P1 disclosed in patent application WO2010109301, Ex 3, in Table 1 by J. Pesticide Sei. 18, 1993, 245-251 (and also Ex 17 in Table 1 by J. Pesticide Sci. 18, 1993, 49-57) and with 2- (difluoromethyl) -N- (1,1,3-trimethyl-2 , 3-dihydro-1H-inden-4-yl) benzamide:
Example Dose (ppm) Efficiency (%) 1 of the present patent 100 100 Compound P1 of WO2010109301 100 40 Ex 3 of Table 1 by J. Pesticide Sci. 18, 1993, 245-251 and also Ex 17 of Table 1 by J. Pesticide Sei. 18, 1993, 49-57 100 79 2- (difluoromethyl) -N- (1,1,3-trimethyl-2,3-dihydro-1Hinden-4-yl) benzamide 100 0
[336] Example: Preventive test in vivo with Puccinia recondita (brown rust in wheat) [337] The tested active ingredients are prepared by homogenization in a mixture of acetone / tween / DMSO and dilution with water to obtain the desired concentration of material active.
106/116 [338] Wheat plants ('Scipion' variety), sown in starter cups on a 50/50 truffle-pozzolan substrate and grown at 22 ° C, were treated in the 1-leaf stage (10 cm height) ) by spraying with the active ingredient prepared as described above. The plants used as controls were treated with an acetone / Tween / DMSO / water mixture without active material.
[339] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous spore suspension of Puccinia recondita (100,000 spores per ml). The spores were harvested from an infected plant and suspended in water containing 2.5 ml / l of 10% Tween 80. The contaminated wheat plants were incubated for 24 hours at 20 ° C and 100% relative humidity, and then for 10 days at 20 ° C and 70-80% relative humidity.
[340] A classification (% of effectiveness) was carried out 12 days after the contamination, in comparison with the control plants.
[341] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
Ex. % Effective 1 100 2 100 3 97 4 97 8 78 9 100 10 100 11 98 12 100 13 100 14 100 15 86 17 100 18 89 19 100 20 94 21 72 22 83 23 94 24 89 25 98
107/116
Ex. % Effective 27 100 30 86 33 100 34 93 35 93 36 98 37 100 38 94 39 98 40 81 41 98 42 100 43 98 44 83 45 89 46 98 47 72 49 100 50 94 51 75 55 72 56 88 57 98 58 81 59 98 60 98 61 78 62 100 63 83 64 98
[342] Under these conditions, good (at least 70%) or total protection was observed at a dose of 100 ppm, with the following compounds:
Ex. % Effective 65 98 66 98 67 89 68 100 69 100 70 98 71 98 73 78 74 72
108/116
Ex. % Effective 76 94 77 98 78 100 79 89 80 94 81 100 82 94 83 83 84 97 85 97 88 88 90 98 91 94
[343] Under the same conditions, full protection was observed at a dose of 100 ppm of active ingredient with the compound of Example 1, while a low protection was registered with the compound P1 disclosed in patent application WO2010109301 and with 2- (difluoromethyl) -N- (1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl) benzamide:
Example Dose (ppm) Efficiency (%) 1 of the present patent 100 100 Compound P1 of WO2010109301 100 40 2- (difluoromethyl) -N- (1, 1,3-trimethyl-2,3dihydro-1 H-inden-4-yl) benzamide 100 83
[344] Example: Preventive test in vivo with Septoria tritici (leaf spot in wheat) [345] The active ingredients tested are prepared by homogenization in an acetone / tween / DMSO mixture and dilution with water to obtain the desired concentration of material active.
[346] Wheat plants ('Scipion' variety), sown in starter cups on a 50/50 truffle-pozzolan substrate and allowed to grow at 22 ° C, were sprayed in the 1-leaf stage (10 cm height). with the active ingredient prepared as described above. The plants used as controls were
109/116 treated with the acetone / Tween / DMSO / water mixture without active material.
[347] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous spore suspension of Septoria trittici (500,000 spores per ml). The contaminated wheat plants were incubated for 72 hours at 18 ° C and 100% relative humidity, and then for 21 days at 90% relative humidity.
[348] A classification (% of effectiveness) was carried out 24 days after the contamination, in comparison with the control plants.
[349] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
Ex. % Effective 1 100 2 100 3 90 4 100 9 98 12 96 13 83 14 97 15 83 23 71 25 86 27 86 30 88 33 100 34 100 37 97 39 86 40 71 42 79 43 86 46 71 47 71 49 86 52 86 56 93 59 75 60 100 62 100
110/116 [350] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
Ex. % Effective 65 80 69 80 76 97 77 93 84 100 85 79 90 96
[351] Example: In vivo preventive test with Sphaerotheca fuliginea (powdery mildew in cucurbits) [352] The tested active ingredients are prepared by homogenization in an acetone / tween / DMSO mixture and dilution with water to obtain the desired concentration of active material .
[353] Itchy plants ('Vert petit de Paris' variety), sown in starter cups on a 50/50 truffle-pozzolan substrate and grown at 24 ° C, were treated in the cotyledon Z11 phase by spraying with the active ingredient prepared as described above. The plants used as controls were treated with an acetone / Tween / DMSO / water mixture without active material.
[354] After 24 hours, the plants were contaminated by spraying the cotyledons with an aqueous spore suspension of Sphaerotheca fuliginea (100,000 spores per ml). Spores were harvested from infected plants. The contaminated itch plants were incubated at 20 ° C and a relative humidity of 70-80%.
[355] A classification (% of effectiveness) was carried out 12 days after the contamination, in comparison with the control plants.
[356] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
Ex. % Effective 1 100 2 100 3 95 9 100
111/116
13 100 14 98 23 94 27 100 33 100 34 100 37 100 39 94 42 89 43 100 46 100 49 100 56 98 57 98 59 98 60 100 62 98 64 94
[357] Under these conditions, good (at least 70%) or total protection was observed at a dose of 100 ppm, with the following compounds:
Ex. % Effective 65 98 69 100 71 100 76 98 77 98 78 98 81 94 84 100 85 100 90 100 91 98
[358] Under the same conditions, full protection was observed at a dose of 100 ppm of active ingredient with the compound of Example 1, while a lower protection was registered with the compound P1 disclosed in patent application WO2010109301, Ex 3 of Table 1 by J. Pesticide Sei. 18, 1993, 245-251 (and also Ex 17 of Table 1 by J. Pesticide Sci. 18, 1993, 49-57) and with 2 (difluoromethyl) -N- (1, 1,3-trimethyl-2, 3-dihid ro-1 H-inden-4-yl) benzamide:
112/116
Example Dose (ppm) Efficiency (%) 1 of the present patent 100 100 Compound P1 of WO2010109301 100 20 Ex 3 in Table 1 by J. Pesticide Sci. 18, 1993, 245-251 and also Ex 17 in Table 1 by J. Pesticide Sei. 18, 1993, 49-57 100 78 2- (difluoromethyl) -N- (1,1,3-trimethyl-2,3-dihydro-1 Hinden-4-yl) benzamide 100 0
[359] Example: Preventive test in vivo with Uromyces appendiculatus (rust on beans) [360] The tested active ingredients are prepared by homogenization in an acetone / tween / DMSO mixture and dilution with water to obtain the desired concentration of active material .
[361] Bean plants («Saxa» variety), sown in starter cups on a 50/50 truffle-pozzolan substrate and grown at 24 ° C, were sprayed in the 2-leaf stage (9 cm height) with the active ingredient prepared as described above. The plants used as controls were treated with an acetone / Tween / DMSO / water mixture without active material.
[362] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous spore suspension of Uromyces appendiculatus (150,000 spores per ml). The spores were collected from infected plants and suspended in water containing 2.5 ml / l of 10% Tween 80. The contaminated bean plants were incubated for 24 hours at 20 ° C and 100% relative humidity, and then for 10 days at 20 ° C and 70-80% relative humidity.
[363] A classification (% of effectiveness) was carried out 11 days after the contamination, in comparison with the control plants.
[364] Under these conditions, good (at least 70%) or total protection was observed at a dose of 500 ppm, with the following compounds:
113/116
Εχ. η. ° % Effective 1 100 2 100 3 100 4 100 7 71 9 100 10 99 12 100 13 100 14 100 15 81 17 100 19 79 20 100 21 88 23 93 24 100 25 100 27 100 30 98 33 100 36 100 37 100 38 100 39 100 40 100 41 100 42 100 43 100 44 93 45 88 46 100 49 100 50 100 51 70 52 93 56 100 57 100 58 95 59 100 60 100 62 100 64 84
114/116 [365] Under these conditions, good (at least 70%) or total protection was observed at a dose of 100 ppm, with the following compounds:
Ex. % Effective 65 100 66 85 67 100 69 100 70 100 71 100 76 96 77 100 78 100 80 91 81 99 82 88 83 72 84 100 90 100 91 100
[366] Example: Test with Phakopsora (soy) / preventive [367] Solvent:
24.5 parts by weight of acetone • 24.5 parts by weight of dimethylacetamide [368] Emulsifier: 1 part by weight of alkylaryl polyglycolic ether [369] In order to obtain a suitable preparation of the active compound, 1 part by weight of the compound active was mixed with the indicated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
[370] To test the preventive activity, young plants were sprayed with the preparation of active compound at the indicated application rate. After drying the spray coating, the plants were inoculated with an aqueous spore suspension of the soybean rusting agent (Phakopsora pachyrhizi) and left for 24 hours in an incubator, without light, at about 24 ° C and relative humidity 95%.
[371] The plants remained in the incubator at about 24 ° C and a relative humidity of about 80%, at a day / night interval of 12h.
115/116 [372] The test was evaluated 7 days after inoculation. An efficacy of 0% corresponds to the untreated control, while an efficacy of 100% means that no disease was observed.
[373] In this test, the following compounds according to the invention showed an efficiency of 70% or greater at a concentration of 100 ppm of active ingredient.
Ex. Eff. % 1 99 3 100 9 99 13 99
[374] In this test, the following compounds according to the invention showed an efficiency of 70% or greater at a concentration of 100 ppm of active ingredient.
Ex. % Effective 14 100 37 95 43 98 46 90 57 93 71 94 81 100
[375] Example: Venturia test (apples / preventive [376] Solvent: 24.5 parts by weight of acetone • 24.5 parts by weight of N, N-dimethylacetamide [377] Emulsifier: 1 part by weight of alkylaryl polyglycolic ether [378] In order to obtain a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with the indicated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.
[379] To test the preventive activity, young plants were sprayed with the preparation of active compound at the indicated application rate. After drying the spray coating, the plants were inoculated with an aqueous conidia suspension of the agent causing the stoned apple (Venturia
116/116 inaequalis) and left for 1 day in an incubator, at about 20 ° C and 100% relative humidity.
[380] The plants were then placed in a greenhouse at about 21 ° C and a relative atmospheric humidity of about 90%.
[381] The test was evaluated 10 days after inoculation. An efficacy of 0% corresponds to the untreated control, while an efficacy of 100% means that no disease was observed.
[382] In this test, the following compounds according to the invention showed an efficiency of 70% or greater than a concentration of 100 ppm of active ingredient.
Ex. % Effective 1 100

权利要求:
Claims (12)
[1]
1. Indanyl difluoramethylnicotinic carboxamides characterized by
present the formula (1) Y li^Ra “T Í1 r * »6 ϊιΠR 2 ^ " ^r5QR ¹ -4 “ -y (x’íY R ² O) in whichn represents 0; T represents an oxygen atom or sulfur;
Q represents hydrogen;
R ^a represents hydrogen, halogen, methyl, ethyl or cyclopropyl;
Y represents O, or CR ³ R ⁴ ;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of each other represent hydrogen; C 1 -C 6 alkyl; halo-C 1 -C 6 alkyl with 1 to 6 equal or different halogen atoms; C3-C6-cycloalkyl; (C3-C6-cycloalkyl) -Ci-C4-alkyl or
R ¹ and R ² together with the carbon atom to which they are attached can represent a group = C (Y ¹ ) Y ² or a group = NOR ^C ; or
R ⁵ and R ⁶ together with the carbon atom to which they are attached may represent a cycloalkyl-Cs-Ce; or a group = C (Y ¹ ) Y ² or a group = NO-R ^c ;
Y ¹ and Y ² independently of each other represent hydrogen or halogen;
R ^c represents C 1 -C 6 alkyl or C 1 -C 6 haloalkyl having 1 to 9 equal or different halogen atoms.
[2]
2. Difluoromethylnicotinic indanyl carboxamides according to claim 1, characterized by having formula (I), in which
T represents an oxygen atom;
Petition 870190042706, of 05/06/2019, p. 9/19
2/5
R ^a represents hydrogen, fluorine, chlorine, methyl, trifluoromethyl, cyclopropyl.
[3]
3. Indanyl difluoromethylnicotinic carboxamides according to claim 1, characterized by presenting formula (I), in which
Q represents hydrogen,
R ^a represents hydrogen;
Y represents CR ³ R ⁴ ;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of each other represent hydrogen, fluorine, chlorine; C1-6 alkyl-halo-C1-2 alkyl with 1 to 5 same or different fluorine atoms; or R ¹ and R ² can form, together with the carbon atom to which they are attached, a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; or they can form the group = C (Y ¹ ) Y ² or a group = NOR ^C ; or
R ⁵ and R ⁶ can form, together with the carbon atom to which they are attached, a cyclopropyl; or they can form the group = C (Y ¹ ) Y ² or a group = NOR ^C ;
R ^c represents C 1 -C 4 alkyl
Y ¹ and Y ² represent, independently of each other, fluorine, chlorine, methyl; ethyl, propyl, isopropyl.
[4]
4. Process for the preparation of compounds of formula (I) as defined in claim 1, characterized in that in a process (a), carbonyl halides or acids of formula (II) in which X ^{1 and} n have the meanings as defined in the claim
1 and X ² represents halogen, hydroxyl or an activated hydroxyl group, to be reacted with amines of the formula (lll-a)
Petition 870190042706, of 05/06/2019, p. 10/19
3/5 in which Q, R ^a , R ¹ , R ² , Y, R ⁵ and R ⁶ have the meanings as defined in claim 1, to obtain compounds of the formula (la) (Ia) in which X ¹ , n , Q, R ^a , R ¹ , R ² , Y, R ⁵ and R ⁶ have the meanings as defined in claim 1, which are reacted with a thioning agent selected from the group consisting of sulfur (S), acid sulfide (H2S), sodium sulfide (Na2S), sodium hydrogen sulfide (NaHS), boron trisulfide (B2S3), bisdiethylaluminiosulfide ((AIEt2) 2S), ammonium sulfide ((NH4) 2S), phosphorus pentasulfide (P2S5) or Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,2,3,4ditiadiadiphosfetano 2,4-disulfide), if T represents sulfur to obtain compounds of the formula (lb) (ib) in which X ¹ , n, Q, R ^a , R ¹ , R ² , Y, R ⁵ and R ⁶ have the meanings as defined in claim 1.
Petition 870190042706, of 05/06/2019, p. 11/19
4/5
[5]
5. Method for controlling harmful phytopathogenic fungi, characterized in that the compounds of formula (I) as defined in any one of claims 1 to 3 are applied to harmful phytopathogenic fungi and / or in their habitat.
[6]
6. Composition for controlling harmful phytopathogenic fungi, characterized in that it contains at least one compound of the formula (I) as defined in any one of claims 1 to 3, in addition to extenders and / or surfactants.
[7]
Composition according to claim 6, characterized in that it comprises at least one additional active ingredient selected from the group of insecticides, attractants, sterilizers, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, phytotoxicity and semi-chemical protectors .
[8]
8. Use of compounds of formula (I) as defined in any one of claims 1 to 3 or of compositions as defined in claim 7, characterized in that they are intended for the control of harmful phytopathogenic fungi.
[9]
9. Production process for compositions to control harmful phytopathogenic fungi, characterized in that the compounds of formula (I) as defined in any one of claims 1 to 3 are mixed with extenders and / or surfactants.
[10]
10. Use of compounds of formula (I) as defined in any one of claims 1 to 3 or of the compositions as defined in claim 7, characterized in that it is in the treatment of transgenic plants.
[11]
11. Use of compounds of formula (I) as defined in any one of claims 1 to 3 or of compositions as defined in claim 7, characterized in that they are in the treatment of seeds and seeds of transgenic plants.
[12]
12. Compound characterized by presenting the formula (lll-a)
Petition 870190042706, of 05/06/2019, p. 12/19
5/5 where:
Q represents hydrogen,
R ^a represents hydrogen, halogen, methyl or cyclopropyl,
R ¹ represents C ¹ -C 6 -alkyl, difluoromethyl or dichloromethyl,
R ² , represents hydrogen, or
R ¹ and R ² can form together with the carbon to which they are attached the group = C (Y ¹ ) Y ² ,
Y represents O or CR3R4,
R ⁵ , R ⁶ represent, independently of each other, hydrogen or C 1 -C 6 alkyl, or
R ⁵ and R ⁶ can form together with the carbon to which a cyclopropyl is attached, or they can form the group = C (Y ¹ ) Y ² or a group = N-OR ^c ,
R ^c represents C 1 -C 4 -alkyl;
Y ¹ and Y ² , independently of each other, represent fluorine, chlorine, methyl; ethyl, propyl or isopropyl.

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法律状态:
2018-05-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-02-05| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2019-06-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-08-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2013, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2013, OBSERVADAS AS CONDICOES LEGAIS |

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2021-01-12| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 7A ANUIDADE. |

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2021-05-04| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2610 DE 12-01-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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EP12198296|2012-12-19|

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PCT/EP2013/076636|WO2014095675A1|2012-12-19|2013-12-16|Difluoromethyl-nicotinic-indanyl carboxamides as fungicides|

---