Pesticidal indazole or benzotriazole derivatives

专利摘要:
A compound of formula (I): wherein G is (i) or (ii), M 1 or M 2 is defective in A; n is 0 or 1; When G is (i), D is S, NR 7 , CR 8 = CR 9 , CR 8 = N, CR 8 = N (O), N = CR 9 or N (O) = CR 9 ; When G is (ii), D is S or NR 7 ; E is N, N-oxide or CR 10 ; M 1 is OC (= Y), N (R 11 ) C (= Y), N = C (OR 12 ), N = (SR 13 ) or N = C (NR 14 R 15 ) and O or N is D And an atom attached to a ring containing E; M 2 is NC (= Y) and N is an atom attached to a ring containing D and E; Y is O, S or NR 16 ; J is N or CR 17 ; A, R 1, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are each specific organic Or weapon group. These compounds are useful in bactericidal, insecticidal, acaricidal, killing animals and bloody compositions.
公开号:KR20020008392A
申请号:KR1020017013285
申请日:2000-04-04
公开日:2002-01-30
发明作者:크리스토퍼 존 매튜；수잔 파트리샤 바네트；스테펀 크리스토퍼 스미스；나이젤 존 바네스；윌리엄 기 위팅햄；존 윌리암스；에릭 다니엘 클라크；앨런 존 화이틀；데이비드 존 휴그；사라 암스트롱；러셀 비너；토킬 에간 마클레오드 프레이저；패트릭 제프 크라울리；로저 샐먼
申请人:돈 리사 로얄；신젠타 리미티드；
IPC主号:

专利说明:

PestICIDAL INDAZOLE OR BENZOTRIAZOLE DERIVATIVES}
[1] The present invention relates to azine and azole derivatives, methods of making them, bactericidal, insecticidal, acaricides, acaricides and nematicide compositions comprising them, methods of using them to eradicate fungal diseases (particularly fungal diseases of plants) and the use thereof. The present invention relates to a method for eradicating and controlling insects, mites, molluscs and nematode parasites.
[2] Azole and azine derivatives are disclosed in WO95 / 31448, WO97 / 18198, WO98 / 02424 and WO98 / 05670.
[3] The present invention provides a compound of formula (I):
[4]
[5] [Wherein G is
[6]
[7] or
[8]
[9] In the formula, M^OneOr M²Is defective in A; n is 0 or 1; A is optionally substituted C_1-6Alkylene, optionally substituted C_2-6Alkenylene, optionally substituted C_2-6Alkynylene, optionally substituted C_1-6Alkyleneoxy, optionally substituted oxy (C_1-6Alkylene, optionally substituted C_1-6Alkylenethio, optionally substituted thio (C_1-6Alkylene, optionally substituted C_1-6Alkyleneamino, optionally substituted amino (C_1-6) Alkylene, optionally substituted [C_1-6Alkalineoxy (C_1-6) Alkylene], optionally substituted [C_1-6Alkylene thio (C_1-6) Alkylene], optionally substituted [C_1-6Alkylene sulfinyl (C_1-6) Alkylene], optionally substituted [C_1-6Alkylenesulfonyl (C_1-6) Alkylene] or optionally substituted [C]_1-6Alkyleneamino (C_1-6) Alkylene]; When G is (i), D is S, NR⁷, CR⁸= CR⁹, CR⁸= N, CR⁸= N (O), N = CR⁹Or N (O) = CR⁹; When G is (ii), D is S or NR⁷; E is N, N-oxide or CR¹⁰; M^OneIs OC (= Y), N (R¹¹C (= Y), N = C (OR¹²), N = (SR¹³) Or N = C (NR¹⁴R¹⁵) Or O or N is an atom attached to a ring containing D and E; M²Is N-C (= Y) and N is an atom attached to a ring containing D and E; Y is O, S or NR¹⁶; J is N or CR¹⁷; R^OneIs hydrogen, halogen, optionally substituted C_1-6Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_3-7Cycloalkyl, cyano, nitro or SF⁵; R²Is an optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or R¹⁸R¹⁹NS; R³, R⁴, And R⁵Is independently hydrogen, halogen, optionally substituted C_1-6Alkyl, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, cyano, nitro, optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkoxycarbonyl or SF⁵; R⁶Is hydrogen, cyano, optionally substituted C_1-20Alkyl, optionally substituted C_2-20Alkenyl (C_1-6Alkyl, optionally substituted C_2-20Alkynyl (C_1-6Alkyl, optionally substituted C_3-7Cycloalkyl, optionally substituted C_5-6Cycloalkenyl, formyl, optionally substituted C_1-20Alkoxycarbonyl, optionally substituted C_1-20Alkylcarbonyl, aminocarbonyl, optionally substituted C_1-20Alkylaminocarbonyl, optionally substituted di (C_1-20Alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbon Optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted Phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted C_1-20Alkylsulfonyl or optionally substituted arylsulfonyl; R⁷Silver c_1-6Alkyl; R⁸And R⁹Is independently hydrogen, halogen, cyano, nitro, optionally substituted C_1-6Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl or optionally substituted C_1-6Alkoxy; R¹⁰Is hydrogen, halogen, optionally substituted C_1-6Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, cyano, nitro, formyl, R²⁰ON = C (R²¹), Optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkoxycarbonyl or SF⁵; Or R^OneAnd R¹⁰Together with the atoms to which they are attached form a heterocyclic ring which may contain one or two heteroatoms selected from carbocyclic or O, N or S which is a 5, 6 or 7 membered saturated or unsaturated ring C_1-6Alkyl, C_1-6Optionally substituted by haloalkyl or halogen; R¹¹Is hydrogen, optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or R²²R²³NS; R¹²Is an optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, amino, optionally substituted C_1-6Alkylamino, optionally substituted di (C_1-6Alkylamino, optionally substituted phenoxycarbonyl, tri (C_1-4Alkylsilyl, aryldi (C)_1-4Alkylsilyl, (C_1-4Alkylalkylaryl or triarylsilyl; R¹³Is an optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10) Alkylaminocarbonyl or optionally substituted phenoxycarbonyl; R¹⁴And R¹⁵Is independently optionally substituted C_1-10Alkyl, optionally substituted C_1-6Alkoxy, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, hydroxy, amino, optionally substituted C_1-6Alkylamino, optionally substituted di (C_1-6) Alkylamino, or optionally substituted phenoxycarbonyl; R¹⁶Is hydrogen, cyano, nitro, optionally substituted C_1-6Alkyl, optionally substituted C_3-7Cycloalkyl, optionally substituted (C_2-6Alkenyl (C_1-6Alkyl, optionally substituted (C)_2-6Alkynyl (C_1-6Alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkoxycarbonyl, optionally substituted C_1-6Alkylamino, optionally substituted di (C_1-6Alkylamino, optionally substituted C_1-6Alkylcarbonylamino, optionally substituted C_1-6Alkoxycarbonylamino, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or C_1-6Acyloxy; R¹⁷Is hydrogen, halogen, nitro, cyano, optionally substituted C_1-8Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl, optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-6Alkoxycarbonyl, optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkylaminocarbonyl, optionally substituted di (C_1-6) Alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R¹⁸And R¹⁹Is Independently, optionally substituted C_1-6Alkyl or R¹⁸And R¹⁹May contain one or two or more heteroatoms selected from O, N or S together with the N atoms to which they are attached_1-6To form a 5, 6 or 7 membered heterocyclic ring which may be optionally substituted by an alkyl group; R²⁰Is hydrogen, optionally substituted phenyl, optionally substituted phenyl (C_1-4Alkyl or optionally substituted C_1-20Alkyl; R²¹Is hydrogen, optionally substituted phenyl or optionally substituted C_1-6Alkyl; And R²²And R²³Is independently an optionally substituted C_1-6Alkyl or R²²And R²³May contain one or two or more heteroatoms selected from O, N or S together with the N atoms to which they are attached_1-6To form a 5, 6 or 7 membered heterocyclic ring which may be optionally substituted by an alkyl group.
[10] The compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. The present invention includes all such isomers and tautomers and mixtures of all ratios thereof.
[11] If present, optional substituents on the alkylene, alkenylene, or alkynylene moiety may include one or more halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 cyanoalkyl, depending on the valence constraints. , C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkoxy, cyano, ═O, = NR ²⁴ and CR ²⁵ R ²⁶ , wherein R ²⁴ is C _1-6 alkyl, C _1-6 haloalkyl, OR ²⁷ or R ²⁸ R ²⁹ N; Wherein R ²⁵ and R ²⁶ are independently hydrogen, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 haloalkyl, cyano, C _1-6 alkoxycarbonyl, C _1-6 alkylcarbonyl Or R ³⁰ R ³¹ N; R ²⁷ is C _1-6 alkyl, C _1-6 haloalkyl or phenyl (C _1-2 ) alkyl; R ²⁸ and R ²⁹ are independently hydrogen, C _{1-8 alkyl} , C _3-7 cycloalkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _1-6 ) Alkyl, C _2-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl, carboxy (C _1-6 ) alkyl or phenyl (C _{1 -2)} alkyl or R ²⁸ and R ²⁹ may be the one containing at least one or two hetero atoms selected from O, N or S, together with the N atom to which they are attached, or two C _1-6 alkyl groups, optionally To form a 5, 6 or 7 membered heterocyclic ring which may be substituted; R ³⁰ and R ³¹ are independently hydrogen, C _1-8 alkyl, C _3-7 cycloalkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _1-6 ) Alkyl, C _2-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl, carboxy (C _1-6 ) alkyl or phenyl (C _{1 -2} ) alkyl; Or R ³⁰ and R ³¹ together with the N atom to which they are attached may contain one or two or more heteroatoms selected from O, N or S and may be optionally substituted by one or two C _1-6 alkyl groups To form a 5, 6 or 7 membered heterocyclic ring.
[12] Each alkyl moiety is straight or branched, for example methyl, ethyl, n -propyl, n -butyl, n -pentyl, n -hexyl, iso -propyl, n -butyl, sec -butyl, iso -butyl, tert -butyl or neo -pentyl. If present, the optional substituents on the alkyl include one or more halogen, nitro, cyano, HO ₂ C, C _1-10 alkoxy (which is itself substituted by C _1-10 alkoxy), aryl (C _1-4 Alkoxy, C _1-10 alkylthio, C _1-10 alkylcarbonyl, C _1-10 alkoxycarbonyl, C _1-6 alkylaminocarbonyl, di (C _1-6 alkyl) aminocarbonyl, (C _{1 Alkylcarbonyloxy} , optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C _3-7 cycloalkyl (which itself is (C _{1 6)} substituted by alkyl or halogen), C _3-7 cycloalkyloxy, C _5-7 cycloalkenyl, C _1-6 alkylsulfonyl, C _1-6 alkylsulfinyl, tri (C _1-4) Alkylsilyl, tri (C _1-4 ) alkylsilyl (C _1-6 ) alkoxy, aryldi (C _1-4 ) alkylsilyl, (C _1-4 ) alkyldiarylsilyl, triarylsilyl, = N-OR 'And = N-NR'R''; Wherein R 'and R''are independently C _1-6 alkyl or C _1-6 haloalkyl.
[13] Alkenyl and alkynyl moieties may be in straight or branched chain form and alkenyl moieties may be in the ( E ) -or ( Z ) -form, where appropriate. Examples are vinyl, allyl and propargyl. If present, any substituents on alkenyl or alkynyl are one or more halogen, aryl and C _3-7 cycloalkyl.
[14] Acyl in the context of the present specification is optionally substituted C _1-6 alkylcarbonyl (eg acetyl), optionally substituted C _2-6 alkenylcarbonyl, optionally substituted C _2-6 alkynylcarbonyl, optionally substituted Arylcarbonyl (eg benzoyl) or optionally substituted heteroarylcarbonyl.
[15] Halogen is fluorine, chlorine, bromine or iodine.
[16] Haloalkyl groups are optionally substituted with one or more identical or different halogen atoms, for example CF ₃ , CF ₂ Cl, CF ₃ CH ₂ or CHF ₂ CH ₂ .
[17] Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl.
[18] The term heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N. Examples of such rings are pyridine, pyrimidine, furan quinoline, quinazoline, pyrazole, thiophene, thiazole, oxazole and isoxazole.
[19] The term heterocyclyl refers to a non-aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N. Examples of such rings include 1,3-dioxolane, tetrahydrofuran and morpholine. Preferably heterocyclyl is optionally substituted with C _1-6 alkyl.
[20] Cycloalkyls include cyclopropyl, cyclopentyl and cyclohexyl. Optional substituents for cycloalkyl include halogen, cyano and C _1-3 alkyl.
[21] Cycloalkenyls include cyclopentyl and cyclohexenyl. Optional substituents for cycloalkenyl include C _1-3 alkyl, halogen and cyano.
[22] Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
[23] For substituted phenyl moieties, heterocyclyl and heteroaryl groups, one or more substituents are halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 haloalkylthio, C _1-6 alkylsulfinyl, C _1-6 haloalkylsulfinyl, C _1-6 alkylsulphur Ponyl, C _1-6 haloalkylsulfonyl, C _2-6 alkenyl, C _2-6 haloalkenyl, C _2-6 alkynyl, C _3-7 cycloalkyl, nitro, cyano, C0 ₂ H, C _1-6 alkylcarbonyl, C _1-6 alkoxycarbonyl, R ³² R ³³ N or R ³⁴ R ³⁵ NC (O), wherein R ³² , R ³³ , R ³⁴ and R ³⁵ are independently hydrogen or C _{1 -6} alkyl).
[24] Dialkylamino substituents may contain one or two or more heteroatoms selected from O, N or S together with the N atom to which the dialkyl group is attached and optionally be substituted by one or two C _1-6 alkyl groups It should be understood that this includes forming a 5, 6 or 7 membered heterocyclic ring which may be substituted. When the heterocyclic ring is formed by the bonding of two groups on the N atom, the resulting ring is suitably pyrrolidine, piperidine, thiomorpholine or morpholine, each of which is one or two (C _1-6 ) alkyl group.
[25] In another aspect, the present invention provides a compound of Formula (IA):
[26]
[27] Wherein A, G, J, R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above for the compound of formula (I).
[28] More preferred compounds of formula (IA) are those in which n is 0; A is C _1-6 alkylene, C _1-6 alkenylene, C _1-6 alkyleneoxy, oxy (C _1-6 ) alkylene, C _{1- 6} alkyleneamino or C _1-6 alkylenethio, each of which is C _1-3 alkyl, C _1-3 haloalkyl, C _1-3 cyanoalkyl, halogen, C _1-3 alkoxy, C _1-6 Optionally substituted by alkoxycarbonyl, cyano, = O, = NR ³⁶ or = CR ³⁷ R ³⁸ ; When G is (i) D is S, NR ⁷ , CR ⁸ = CR ⁹ , CR ⁸ = N, CR ⁸ = N (O), N = CR ⁹ or N (O) = CR ⁹ ; When G is (ii), D is S or NR ⁷ ; E is N or CR ¹⁰ ; M ¹ is N (R ¹¹ ) C (= Y) or N = C (SR ¹³ ) and O or N is an atom bonded to the ring containing D and E; M ² is NC (= Y) and N is an atom bonded to the ring containing D and E; Y is O, S or NR ¹⁶ ; J is N or CR ¹⁷ ; R ¹ is hydrogen, halogen, C _1-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, C _1-6 cyano Alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 haloalkylthio, C _3-6 cycloalkyl, C _3-7 cycloalkyl (C _1-4 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, cyano, nitro or SF ₅ ; R ² is C _1-10 alkyl, benzyloxymethyl, benzoyloxymethyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _1-6 ) alkyl, C _1-10 alkylcarbonyl or C _1-10 alkoxycarbonyl; R ^3, R ⁴ and R ⁵ are independently hydrogen, halogen, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1- 6 haloalkylthio, C _1-6 alkylsulfinyl, C _1-6 haloalkyl sulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkyl sulfonyl, C _1-6 haloalkyl, cyano, nitro, C _1-6 alkyl Carbonyl, C _1-6 alkoxycarbonyl or SF ₅ ; R ⁶ is C _1-10 alkyl or C _1-10 haloalkyl (each is C _1-6 alkyloxime, C _1-6 haloalkyloxime, C _1-6 alkylhydrazone or C _1-6 haloalkylhydrazone group Or cyano, C _1-6 cyanoalkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _1-6 ) alkyl, C _3-7 Cycloalkyl, C _3-7 halocycloalkyl, C _3-7 cyanocycloalkyl, C _1-3 alkyl (C _3-7 ) cycloalkyl, C _1-3 alkyl (C _3-7 ) halocycloalkyl, C _5-6 cycloalkenyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, C _5-6 cycloalkenyl (C _1-6 ) alkyl, C _2-6 haloalkenyl (C _1-6 ) alkyl , C _1-6 cyanoalkenyl (C _1-6 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _3-6 alkenyloxy (C _1-6 ) alkyl, C _3-6 alkynyl Oxy (C _1-6 ) alkyl, aryloxy (C _1-6 ) alkyl, formyl, C _1-6 carboxyalkyl, C _1-6 alkylcarbonyl (C _1-6 ) alkyl, C _2-6 alkenyl carbonyl (C _1-6) alkyl, C _2-6 alkynyl-carbonyl (C _1-6) alkyl, C _1-6 alkoxycarbonyl (C _1-6) alkyl, C _3-6 alkenyloxy car Carbonyl (C _1-6) alkyl, C _3-6 alkynyloxy-carbonyl (C _1-6) alkyl, aryloxy-carbonyl (C _1-6) alkyl, C _1-6 alkylthio (C _1-6) Alkyl, C _1-6 alkylsulfinyl (C _1-6 ) alkyl, C _1-6 alkylsulfonyl (C _1-6 ) alkyl, aminocarbonyl (C _1-6 ) alkyl, aminocarbonyl (C _{2- 6} ) alkenyl, aminocarbonyl (C _2-6 ) alkynyl, C _1-6 alkylaminocarbonyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) Alkyl, C _1-6 alkylaminocarbonyl (C _2-6 ) alkenyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _2-6 ) alkenyl (C _1-6 ) Alkyl, aminocarbonyl (C _2-6 ) alkynyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkynyl (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl, C _1-6 alkylcarbonyl, aminocarbonyl, C _1-6 alkylaminocarbonyl, di (C _1-6 ) alkylaminocarbonyl, phenyl (halo, nitro, cyano, C Optionally substituted with _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy, phenyl (C _1-4 ) alkyl, wherein the phenyl group is halo, Optionally substituted with nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), phenyl (C _2-4 ) alkenyl (C _1-6 Alkyl, wherein the phenyl group is optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkylsulfonyl or C _1-6 haloalkoxy Optionally substituted with heteroaryl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkylsulfonyl or C _1-6 haloalkoxy) ), Heterocyclyl (optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, or C _1-6 haloalkoxy), heteroaryl (C _{1 -4)} alkyl (wherein heteroaryl is selected from halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or optionally substituted by C _1-6 haloalkoxy), or heterocyclyl Aryl (C _1-4 ) alkyl (heterocyclyl is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 Optionally substituted with alkoxy or C _1-6 haloalkoxy); R ⁷ is C _1-6 alkyl; R ⁸ and R ⁹ are independently hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkylC _2-6 alkenyl, C _1-6 alkynyl, C _{1- 6} alkoxy or C _1-6 haloalkoxy; R ¹⁰ is hydrogen, halogen, C _1-6 alkyl, C _2-6 alkenyl, C _1-6 alkynyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkoxy (C _1-6 Alkyl, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 haloalkylthio, C _1-6 alkylsulfinyl, C _1-6 haloalkylsulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkylsulfonyl, C _1-6 haloalkyl, cyano, nitro, formyl, R ²⁰ ON = CH, C _1-6 alkylcarbonyl, C _1-6 alkoxycarbonyl or SF ₅ ; Or heterocyclic, wherein R ¹ and R ¹⁰ together with the atoms to which they are attached may contain one or two hetero atoms selected from carbocyclic or O, N or S which are 5, 6 or 7 membered saturated or unsaturated rings; A ring is formed which may be optionally substituted by C _1-6 alkyl, C _1-6 haloalkyl or halogen; R ¹¹ is hydrogen, C _1-10 alkyl, benzyloxymethyl, benzoyloxymethyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _2-6 alkenyl (C _1-6 ) alkyl (particularly allyl), C _2-6 alkynyl (C _1-6 ) alkyl (particularly propargyl), C _1-10 alkylcarbonyl or C _1-10 alkoxycarbonyl (particularly iso butoxycarbonyl); R ¹³ is C _1-10 alkyl, benzyloxymethyl, benzoyloxymethyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _2-6 alkenyl (C _1-6 ) alkyl (particularly allyl), C _{2 -6} alkynyl (C _1-6 ) alkyl (particularly propyl), C _1-10 alkylcarbonyl or C _1-10 alkoxycarbonyl (particularly iso butoxycarbonyl); R ¹⁶ is cyano, nitro, C _1-6 alkyl, C _1-6 haloalkyl, C _3-7 cycloalkyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, CH ₂ (C _2-6 ) Optionally with alkenyl, CH ₂ (C _2-6 ) alkynyl, phenyl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Heteroaryl (optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), C _1-6 alkylcarbo Neyl, C _1-6 alkoxycarbonyl, C _1-6 alkylamino, di (C _1-6 ) alkylamino, C _1-6 alkylcarbonylamino, C _1-6 alkoxycarbonylamino, C _1-6 alkoxy , C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkylthio, C _1-6 haloalkyl sulfinyl, C _1-6 haloalkyl-sulfonyl, Arylthio, arylsulfinyl, arylsulfonyl or (C _1-6 ) alkylC (O) O; R ¹⁷ is hydrogen, halogen, nitro, cyano, C _1-8 alkyl, C _1-6 haloalkyl, C _1-6 cyanoalkyl, C _2-6 alkenyl, C _2-6 alkynyl, C _{3- 7} cycloalkyl, C _2-6 haloalkenyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl, C _{1- 6} alkylcarbonyl, C _1-6 alkylaminocarbonyl, di (C _1-6 ) alkylaminocarbonyl, phenyl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C ₁ Optionally substituted with _-6 alkoxy or C _1-6 haloalkoxy) or heteroaryl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 halo Optionally substituted with alkoxy); R ²⁰ is C _1-6 alkyl or phenyl (C _1-2 ) alkyl, wherein phenyl is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1- Optionally substituted with ₆ haloalkoxy; R ³⁶ is C _1-6 alkyl, OR ³⁹ or NR ⁴⁰ R ⁴¹ ; R ³⁷ is hydrogen, C _1-6 alkyl or C _1-6 haloalkyl; R ³⁸ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, cyano, C _1-6 alkoxycarbonyl, C _1-6 alkylcarbonyl or NR ⁴² R ⁴³ ; R ³⁹ is C _1-6 alkyl or optionally substituted phenyl (C _1-2 ) alkyl; R ⁴⁰ and R ⁴¹ are independently hydrogen, C _1-8 alkyl or phenyl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Optionally substituted with; And R ⁴² and R ⁴³ are independently hydrogen, C _1-8 alkyl, C _3-7 cycloalkyl, C _3-6 alkenyl, C _3-6 alkynyl, C _2-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl, carboxy (C _1-6 ) alkyl or phenyl (C _1-2 ) alkyl; Or R ⁴² and R ⁴³ together with the N atom to which they are attached may contain one or two or more hetero atoms selected from O, N or S and may be optionally substituted by one or two C _1-6 alkyl groups To form a 5, 6 or 7 membered heterocyclic ring.
[29] Preferably n is zero.
[30] Preferably A is C _1-4 alkylene, -C (O) _-or C _1-4 alkyleneoxy.
[31] When G is (i), D is preferably S or CR ⁸ = CR ⁹ , wherein R ⁸ and R ⁹ are independently hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkylC _2-6 Alkenyl, C _1-6 alkynyl, C _1-6 alkoxy or C _1-6 haloalkoxy.
[32] When G is (ii), D is preferably S.
[33] Preferably E is N or CR ¹⁰ where R ¹⁰ is hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkoxy ( C _1-6 ) alkyl, C _1-6 alkylthio SF ₅ ; Or R ¹ and R ¹⁰ together with the atoms to which they are attached form a benzene ring optionally substituted with C _1-6 alkyl, C _1-6 haloalkyl or halogen.
[34] Preferably G is (i).
[35] Preferably M ¹ is N (R ¹¹ ) C (═O) where R ¹¹ is hydrogen, C _1-6 alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, benzyloxymethyl or benzoyloxymethyl .
[36] Preferably Y is O.
[37] Preferably J is N or CR ¹⁷ where R ¹⁷ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl, cyano, halogen or nitro.
[38] R ¹ is preferably hydrogen, halogen, C _1-6 alkyl, C _2-6 alkenyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 haloalkylthio, C _3-6 cycloalkyl, cyano, nitro or SF ₅ .
[39] R ² is preferably C _1-10 alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, allyl or propargyl.
[40] Preferably R ³ , R ⁴ and R ⁵ are independently hydrogen, C _1-3 alkyl or halogen.
[41] R ⁶ is preferably C _1-10 alkyl or C _1-10 haloalkyl (each C _1-6 alkyloxime, C _1-6 haloalkyloxime, C _1-6 alkylhydrazone or C _1-6 haloalkyl Hydrazone group), or C _1-6 cyanoalkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _1-6 ) alkyl, C _{3- 7} cycloalkyl, C _3-7 halocycloalkyl, C _3-7 cyanocycloalkyl, C _1-3 alkyl (C _3-7 ) cycloalkyl, C _1-3 alkyl (C _3-7 ) halocycloalkyl, C _5-6 cycloalkenyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, C _5-6 cycloalkenyl (C _1-6 ) alkyl, C _2-6 haloalkenyl (C _1-6 ) Alkyl, C _1-6 cyanoalkenyl (C _1-6 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _3-6 alkenyloxy (C _1-6 ) alkyl, C _3-6 alky Neyloxy (C _1-7 ) alkyl, aryloxy (C _1-6 ) alkyl, C _1-7 carboxyalkyl, C _1-6 alkylcarbonyl (C _1-6 ) alkyl, C _2-6 alkenylcarbonyl (C _1-6) alkyl, C _2-6 alkynyl-carbonyl (C _1-6) alkyl, C _1-6 alkoxycarbonyl (C _1-6) alkyl, C _3-6 alkenyloxy carbonyl (C _1-6) alkyl, C _3-6 alkynyloxy-carbonyl (C _1-6) alkyl, aryloxy-carbonyl (C _1-6) alkyl, C _1-6 alkylthio (C _1-6) alkyl , C _1-6 alkylsulfinyl (C _1-6 ) alkyl, C _1-6 alkylsulfonyl (C _1-6) alkyl, aminocarbonyl (C _1-6 ) alkyl, aminocarbonyl (C _2-6 ) Alkenyl, aminocarbonyl (C _2-6 ) alkynyl, C _1-6 alkylaminocarbonyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkyl , C _1-6 alkylaminocarbonyl (C _1-6 ) alkenyl (C _1-6 ) alkyl, alkylaminocarbonyl (C _1-6 ) alkynyl (C _1-6 ) alkyl, di (C _{1- 6} ) alkylaminocarbonyl (C _1-6 ) alkenyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkenyl (C _1-6 ) alkyl, phenyl (Optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), phenyl (C _1-4 ) alkyl, wherein Phenyl group is optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), phenyl (C _2-4) alkenyl (C _1-6) alkyl (wherein the phenyl group is (optionally substituted by halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 Optionally substituted with alkylsulfonyl or C _1-6 haloalkoxy, heteroaryl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 halo) Optionally substituted with alkoxy, heterocyclyl, wherein the heterocyclyl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Optionally substituted with heteroaryl (C _1-4 ) alkyl, wherein the heteroaryl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _{1 -6} alkylsulfonyl or optionally substituted with C _1-6 haloalkoxy) or heterocyclyl (C _1-4 ) alkyl, wherein the heterocyclyl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, optionally substituted with C _1-6 alkoxy or C _1-6 haloalkoxy).
[42] The optionally substituted ring of formula
[43]
[44] Optionally substituted isothiazolyl, optionally substituted pyridyl, optionally substituted pyrimidinyl, optionally substituted quinazolinyl and optionally substituted quinolinyl groups, wherein any substituent is C _1-6 alkyl, C _1-6 Haloalkyl, C _1-6 alkoxy, C _1-6 alkoxy (C _1-6 ) alkyl or C _1-6 haloalkoxy.
[45] The chemical formula below
[46]
[47] The optionally substituted ring of preferably
[48]
[49] or
[50]
[51] to be.
[52] More preferably A is CH ₂ or CH ₂ O, more preferably CH ₂ .
[53] More preferably M ¹ is N (R ¹¹ ) C (═O) where R ¹¹ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy (C _1-4 ) alkyl, benzyloxymethyl or benzoyloxymethyl to be. Particular preference is given to R ¹¹ being hydrogen, ethyl, ethoxymethyl, allyl or propargyl.
[54] More preferably J is N or CR ¹⁷ where R ¹⁷ is hydrogen, methyl or halogen.
[55] More preferably R ² is ethyl, ethoxymethyl, allyl or propargyl.
[56] More preferably R ³ , R ⁴ and R ⁵ are independently hydrogen or halogen (particularly fluorine); It is especially preferred that each of R ³ , R ⁴ and R ⁵ is hydrogen.
[57] More preferably R ⁶ is C _1-8 alkyl, C _2-8 haloalkyl, C _1-8 cyanoalkyl, C _3-7 cycloalkyl, C _1-3 alkyl (C _3-7 ) cycloalkyl, C _{Optionally with 1-6} alkoxy (C _1-6 ) alkyl, heterocyclic (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Substituted), phenyl (optionally substituted with halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, nitro, cyano or C _1-6 alkylsulfonyl) or heteroaryl (halogen, Optionally substituted with C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, nitro, cyano or C _1-6 alkylsulfonyl).
[58] Even more preferably R ⁶ is C _1-8 alkyl, C _2-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _3-7 cycloalkyl or C _3-7 cycloalkyl (C _{1- 6} ) alkyl.
[59] Group below
[60]
[61] Even more desirable
[62]
[63] or
[64]
[65] to be.
[66] The chemical formula below
[67]
[68] The optionally substituted ring of is most preferably
[69]
[70]
[71] or
[72]
[73] to be.
[74] In another aspect the present invention provides a compound of formula (IB):
[75]
[76] [Wherein R ¹ is hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _3-6 cycloalkyl or C _1-6 alkoxy (C _1-6 ) alkyl; R ¹⁰ is hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkyl, cyano, nitro, CHO, CH = NOR ²⁰ , C _1-6 alkylcarbonyl, C _1-6 alkoxycarbonyl or C _{1 -6} alkylS (O) _q ; Or R ¹ and R ¹⁰ together form a 5 or 6 membered saturated or unsaturated carbocyclic ring, which ring is optionally substituted with one or two C _1-6 alkyl groups; R ¹¹ is hydrogen, C _1-6 alkyl, CH ₂ (C _1-4 haloalkyl), C _3-6 alkenyl, C _3-6 alkynyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkylcarbonyl, C _1-6 alkoxycarbonyl, formyl, optionally substituted phenoxycarbonyl, optionally substituted phenyl (C _1-4 ) alkyl or S (O) _p R ⁴⁴ ; R ⁶ is hydrogen, C _1-8 alkyl, C _1-6 haloalkyl, C _1-6 cyanoalkyl, C _3-6 alkenyl, C _3-6 alkynyl, C _3-7 cycloalkyl, C _{3- 6} cycloalkyl (C _1-6 ) alkyl, C _3-6 haloalkenyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 carboxyalkyl, C _1-6 alkylcarbonyl (C _{1- 6} ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl, C _1-6 alkylthio (C _1-6 ) alkyl, C _1-6 alkylsulfinyl (C _1-6 ) alkyl, C _{1 -6} alkylsulfonyl (C _1-6 ) alkyl, aminocarbonyl (C _1-6 ) alkyl, C _1-6 alkylaminocarbonyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbo Aryl (C _1-6 ) alkyl, optionally substituted phenyl, optionally substituted phenyl (C _1-4 ) alkyl or optionally substituted heteroaryl; R ²⁰ is hydrogen, C _1-6 alkyl, optionally substituted phenyl or optionally substituted phenyl (C _1-4 ) alkyl; R ⁴⁴ is C _1-6 alkyl, C _1-6 haloalkyl or optionally substituted phenyl; Y is O or S; m is 0 or 1; And p and q are independently 0, 1 or 2; When R ⁶ is C _3-6 alkenyl, C _3-6 alkynyl or C _3-6 haloalkenyl, R ⁶ does not have an unsaturated carbon atom directly attached to N and R ¹¹ is C _3-6 alkenyl Or C _3-6 alkynyl, provided that R ¹¹ does not have an unsaturated carbon atom attached directly to N.
[77] It is preferred that R ¹ is ethyl or especially methyl.
[78] It is preferred that R ¹⁰ is hydrogen, halogen (particularly chloro) or cyano.
[79] It is preferable that m is zero.
[80] It is preferable that the compound of the present invention is formula (Ia).
[81] In a particular aspect the invention provides compounds of formula la, wherein R ¹ is C _1-4 alkyl (particularly methyl or ethyl); R ¹⁰ is hydrogen, halogen (particularly chloro or bromo) or cyano; Or R ¹ and R ¹⁰ together form a cyclopentyl, cyclohexyl or phenyl ring; R ¹¹ is hydrogen, C _1-4 alkyl (especially methyl or ethyl), phenyl (C _1-4 ) alkyl (especially benzyl), C _1-4 alkylcarbonyl (especially acetyl) or C _1-4 alkylsulfonyl ( Methanesulfonyl); m is 0; Y is oxygen; And R ⁶ is C _1-6 alkyl [halogen, C _1-4 alkoxy, phenyl (which itself is optionally substituted with halogen), C0 ₂ H, C0NH ₂ (which is optionally substituted with C _1-4 alkyl) , Cyano, C _3-6 cycloalkyl or CO (C _1-4 alkoxy)], C _3-6 alkenyl, C _3-6 alkynyl, C _3-6 cycloalkyl, phenyl [halogen, C _1-4 Haloalkyl (particularly CF ₃ ), nitro, CO ₂ H, or cyano] or heteroaryl (particularly pyridyl or pyrimidinyl) [optionally substituted with C _1-4 alkyl or C _1-4 haloalkyl].
[82] In another aspect, the present invention provides a compound of Formula (IC):
[83]
[84] [Wherein n is 0 or 1; A is optionally substituted C _1-6 -alkylene, optionally substituted C _2-6 -alkenylene, optionally substituted C _2-6 -alkynylene, optionally substituted C _1-6 -alkyleneoxy, optionally substituted Oxy (C _1-6 ) alkylene, optionally substituted C _1-6 -alkylenethio, optionally substituted thio (C _1-6 ) alkylene, optionally substituted C _1-6 -alkylamino, optionally substituted amino (C _1-6 ) alkylene, optionally substituted [C _1-6 -alkyleneoxy (C _1-6 ) alkylene], optionally substituted [C _1-6 -alkylenethio (C _1-6 ) alkyl Lene], optionally substituted C _1-6 -alkylenesulfinyl (C _1-6 ) alkylene], optionally substituted [C _1-6 -alkylenesulfonyl (C _1-6 ) alkylene] or optionally substituted [C _1-6 -alkyleneamino (C _1-6 ) alkylene]; D is S, NR ⁷ , CR ⁸ = CR ⁹ , CR ⁸ = N, CR ⁸ = N (O), N = CR ⁹ or N (O) = CR ⁹ ; R ⁷ is C _1-6 -alkyl; E is N, N-oxide or CR ¹⁰ ; M ¹ is OC (= Y), N (R ¹¹ ) C (= Y), N = C (OR ¹² ), N = C (SR ¹³ ) or N = C (NR ¹⁴ R ¹⁵ ), where O or N Is an atom attached to a ring containing E and D; Y is O, S or NR ¹⁶ ; J is N or CR ¹⁷ ; R ¹ is hydrogen, halogen, optionally substituted C _1-6 -alkyl, optionally substituted C _2-6 -alkenyl, optionally substituted C _2-6 -alkynyl, optionally substituted C _1-6 -alkoxy, optionally Substituted C _1-6 -alkylthio, optionally substituted C _3-7 -cycloalkyl, cyano, nitro or SF ₅ ; R ¹¹ is hydrogen, optionally substituted C _1-10 -alkyl, optionally substituted [C _2-6 -alkenyl (C _1-6 ) alkyl], optionally substituted [C _2-6 -alkynyl (C _{1- 6} ) alkyl], optionally substituted C _3-7 -cycloalkyl, optionally substituted C _1-10 -alkylcarbonyl, optionally substituted C _1-10 -alkoxycarbonyl, formyl, optionally substituted C _1-10 -Alkylaminocarbonyl, optionally substituted di (C _1-10 ) alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C _1-6 -alkylthio, optionally substituted C _1-6 -alkylsulphi Optionally substituted C _1-6 -alkylsulfonyl, optionally substituted C _1-6 -arylthio, optionally substituted C _1-6 -arylsulfinyl, optionally substituted C _1-6 -arylsulfonyl or R ²² R ²³ NS; R ¹² is optionally substituted C _1-10 -alkyl, optionally substituted [C _2-6 -alkenyl (C _1-6 ) alkyl], optionally substituted [C _2-6 -alkynyl (C _1-6) alkyl], optionally substituted C _3-7 - cyclo-alkyl, optionally substituted C _1-10 - alkyl-carbonyl, optionally substituted C _1-10 - alkoxycarbonyl, formyl, a random value A C _1-10 - alkyl-amino-carbonyl, optionally substituted di (C _1-10) alkyl aminocarbonyl, amino, optionally substituted C _1-6 - alkylamino, optionally substituted di (C _1-6) alkyl Amino, optionally substituted phenoxycarbonyl, tri (C _1-4 ) alkylsilyl, aryldi (C _1-4 ) alkylsilyl, (C _1-4 ) alkyldiarylsilyl or triarylsilyl; R ¹³ is optionally substituted C _1-10 -alkyl, optionally substituted [C _2-6 -alkenyl (C _1-6 ) alkyl], optionally substituted [C _2-6 -alkynyl (C _1-6 ) Alkyl], optionally substituted C _3-7 -cycloalkyl, optionally substituted C _1-10 -alkylcarbonyl, optionally substituted C _1-10 -alkoxycarbonyl, optionally substituted C _1-10 -alkylaminocarbonyl , Optionally substituted di (C _1-10 ) alkylaminocarbonyl or optionally substituted phenoxycarbonyl; R ¹⁴ and R ¹⁵ are independently optionally substituted C _1-10 -alkyl, optionally substituted C _1-6 -alkoxy, optionally substituted [C _2-6 -alkenyl (C _1-6 ) alkyl], optionally substituted [C _2-6 -alkynyl (C _1-6 ) alkyl], optionally substituted C _3-7 -cycloalkyl, optionally substituted C _1-10 -alkylcarbonyl, optionally substituted C _1-10 -alkoxy Carbonyl, formyl, optionally substituted C _1-10 -alkylaminocarbonyl, optionally substituted di (C _1-10 ) alkylaminocarbonyl, hydroxy, amino, optionally substituted C _1-6 -alkylamino, Optionally substituted di (C _1-6 ) alkylamino or optionally substituted phenoxycarbonyl; R ³ , R ⁴ and R ⁵ are independently hydrogen, halogen, optionally substituted C _1-6 -alkyl, optionally substituted C _1-6 -alkoxy, optionally substituted C _1-6 -alkylthio, optionally substituted C _1-6 -alkylsulfinyl, optionally substituted C _1-6 -alkylsulfonyl, cyano, nitro, optionally substituted C _1-6 -alkylcarbonyl, optionally substituted C _1-6 -alkoxycarbonyl or SF ₅ ; R ⁶ is hydrogen, cyano, optionally substituted C _1-20 -alkyl, optionally substituted C _2-20 -alkenyl (C _1-6 ) alkyl, optionally substituted C _2-20 -alkynyl (C _{1- 6} ) alkyl, optionally substituted C _3-7 -cycloalkyl, optionally substituted C _5-6 -cycloalkenyl, formyl, optionally substituted C _1-20 -alkoxycarbonyl, optionally substituted C _1-20- Alkylcarbonyl, aminocarbonyl, optionally substituted C _1-20 -alkylaminocarbonyl, optionally substituted di (C _1-20- ) alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbon Optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, Optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted hete Aryl, optionally substituted heteroaryl cycle one, optionally substituted C _1-20 - alkylsulfonyl or optionally substituted arylsulfonyl, and; R ⁸ and R ⁹ are independently hydrogen, halogen, cyano, nitro, optionally substituted C _1-6 -alkyl, optionally substituted C _2-6 -alkenyl, optionally substituted C _2-6 -alkynyl or optionally Substituted C _1-6 -alkoxy; R ¹⁰ is hydrogen, halogen, optionally substituted C _1-6 -alkyl, optionally substituted C _2-6 -alkenyl, optionally substituted C _2-6 -alkynyl, optionally substituted C _1-6 -alkoxy, optionally Substituted C _1-6 -alkylthio, optionally substituted C _1-6 -alkylsulfinyl, optionally substituted C _1-6 -alkylsulfonyl, cyano, nitro, formyl, R ²⁰ ON = C (R ²¹ ), Optionally substituted C _1-6 -alkylcarbonyl, optionally substituted C _1-6 -alkoxycarbonyl or SF ₅ ; R ¹ and R ¹⁰ together with the atoms to which they are attached form a 5, 6 or 7 membered saturated or unsaturated ring carbocyclic or bicyclic ring which may contain one or two heteroatoms selected from O, N or S and C May be optionally substituted with _1-6 -alkyl, C _1-6 -haloalkyl or halogen; R ¹⁶ is hydrogen, cyano, nitro, optionally substituted C _1-6 -alkyl, optionally substituted C _3-7 -cycloalkyl, optionally substituted (C _2-6 ) alkenyl (C _1-6 ) alkyl, Optionally substituted (C _2-6 ) alkynyl (C _1-6 ) alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C _1-6 -alkylcarbonyl, optionally substituted C _1-6 − Alkoxycarbonyl, optionally substituted C _1-6 -alkylamino, optionally substituted di (C _1-6 ) alkylamino, optionally substituted C _1-6 -alkylcarbonylamino, optionally substituted C _1-6 -alkoxy Carbonylamino, optionally substituted C _1-6 -alkoxy, optionally substituted C _1-6 -alkylthio, optionally substituted C _1-6 -alkylsulfinyl, optionally substituted C _1-6 -alkylsulfonyl, optionally Substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or C _1-6 -acyloxy; R ¹⁷ is hydrogen, halogen, nitro, cyano, optionally substituted C _1-8 -alkyl, an optionally substituted C _2-6 - alkenyl, optionally substituted C _2-6 - alkynyl, optionally substituted C _3-7 - cyclo-alkyl, optionally substituted C _1-6 - alkoxycarbonyl, optionally substituted C _1-6 - alkyl-carbonyl, optionally substituted C _1-6 - alkyl-amino-carbonyl, optionally substituted di ( C _1-6 ) alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R ²² and R ²³ are independently optionally substituted C _1-6 -alkyl or together with the N atom to which they are attached form a 5, 6 or 7 membered bicyclic ring which is an addition of one or two selected from O, N or S Contain hetero atoms and may be optionally substituted by one or two C _1-6 -alkyl groups; R ²¹ is hydrogen, optionally substituted phenyl or optionally substituted C _1-6 -alkyl; R ²⁰ is hydrogen, optionally substituted phenyl (C _1-2 ) alkyl or optionally substituted C _1-20 -alkyl.
[85] Compounds of formula (IC) may exist in different geometric or optical isomer or tautomeric forms. The present invention includes all such isomers and tautomers and mixtures thereof in all proportions.
[86] In another aspect, the present invention provides a compound of formula (ID)
[87]
[88] [Wherein A, D, E, M ¹ , Y, J, R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined for the compound of formula (IC) above.
[89] More preferred compounds of formula (ID) are those of formula (IE):
[90]
[91] [Wherein D is S, NR ⁷ , CR ⁸ = CR ⁹ , CR ⁸ = N, CR ⁸ = N (O), N = CR ⁹ or N (O) = CR ⁹ ; E is N or CR ¹⁰ ; R ¹ is hydrogen, halogen, C _1-6 -alkyl, C _2-6 -alkenyl, C _2-6 -alkynyl, C _1-6 -cycloalkyl, C _1-6 -haloalkyl, C _1-6 -Alkoxy, C _1-6 -haloalkoxy, C _1-6 -alkylthio, C _1-6 -haloalkylthio, C _3-6 -cycloalkyl, C _3-7 -cycloalkyl (C _1-4 ) alkyl , C _1-6 -alkoxy (C _1-6 ) alkyl, cyano, nitro or SF ₅ ; A is C _1-6 -alkylene, C _1-6 -alkenylene, C _1-6 -alkyleneoxy, oxy (C _1-6 ) alkylene, C _1-6 -alkyleneamino or C _1-6 Alkylenethio, each of which is C _1-3 -alkyl, C _1-3 -haloalkyl, C _1-3 -cyanoalkyl, halogen, C _1-3 -alkoxy, C _1-6 -alkoxycarbonyl, Optionally substituted with cyano, = O, = NR ³⁶ or = CR ³⁷ R ³⁸ ; M ¹ is N (R ¹¹ ) C (= Y) or N = C (SR ¹³ ) where O or N is an atom bonded to a ring containing E and D; Y is O, S or NR ¹⁶ ; J is N or CR ¹⁷ ; R ¹¹ is hydrogen, C _1-10 -alkyl, benzyloxymethyl, benzoyloxymethyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _2-6 alkenyl (C _1-6 ) alkyl (particularly allyl) , C _2-6 alkynyl (C _1-6) alkyl (especially propargyl), C _1-10 alkylcarbonyl or C _1-10 alkoxycarbonyl (especially iso butoxycarbonyl) and; R ¹³ is C _1-10 alkyl, benzyloxymethyl, benzoyloxymethyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _2-6 alkenyl (C _1-6 ) alkyl (particularly allyl), C _{2 -6} alkynyl (C _1-6) alkyl (especially propargyl), C _1-10 alkylcarbonyl or C _1-10 alkoxycarbonyl (especially iso butoxycarbonyl) and; R ³ , R ⁴ and R ⁵ are independently hydrogen, halogen, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 haloalkylthio, C _1-6 alkylsulfinyl, C _1-6 haloalkyl sulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkyl sulfonyl, C _1-6 haloalkyl, cyano, nitro, C _1-6 alkyl Carbonyl, C _1-6 alkoxycarbonyl or SF ₅ ; R ⁶ is cyano, C _1-8 alkyl, C _2-6 haloalkyl, C _1-6 cyanoalkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _{1 -6} ) alkyl, C _3-7 cycloalkyl, C _3-7 halocycloalkyl, C _3-7 cyanocycloalkyl, C _1-3 alkyl (C _3-7 ) cycloalkyl, C _1-3 alkyl (C _3-7) halo-cyclo-alkyl, cyclo C _5-6 alkenyl, C _3-7 cyclo-alkyl (C _1-6) alkyl, C _5-6) alkenyl, cyclo (C _1-6) alkyl, C _2-6 Haloalkenyl (C _1-6 ) alkyl, C _1-6 cyanoalkenyl (C _1-6 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _3-6 alkenyloxy (C _{1- 6} ) alkyl, C _3-6 alkynyloxy (C _1-6 ) alkyl, aryloxy (C _1-6 ) alkyl, formyl, C _1-6 carboxyalkyl, C _1-6 alkylcarbonyl (C _{1- 6} ) alkyl, C _2-6 alkenylcarbonyl (C _1-6 ) alkyl, C _2-6 alkynylcarbonyl (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl , C _3-6 alkenyloxycarbonyl (C _1-6 ) alkyl, C _3-6 alkynyloxycarbonyl (C _1-6 ) alkyl, aryloxycarbonyl (C _1-6 ) alkyl, C _{1- 6} alkylthio (C _1-6) alkyl, C _1-6 Kill sulfinyl (C _1-6) alkyl, C _1-6 alkylsulfonyl (C _1-6) alkyl, aminocarbonyl (C _1-6) alkyl, aminocarbonyl (C _2-6) alkenyl, amino Carbonyl (C _2-6 ) alkynyl, C _1-6 alkylaminocarbonyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkyl, C _1-6 Alkylaminocarbonyl (C _2-6 ) alkenyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _2-6 ) alkenyl (C _1-6 ) alkyl, alkylaminocarbon Nyl (C _2-6 ) alkynyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkynyl (C _1-6 ) alkyl, C _1-6 alkoxycarbo Nyl, C _1-6 alkylcarbonyl, aminocarbonyl, C _1-6 alkylaminocarbonyl, di (C _1-6 ) alkylaminocarbonyl, phenyl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, or C being optionally substituted with _1-6 haloalkoxy), phenyl (C _1-4) alkyl (wherein the phenyl group is halo, nitro, cyano, C _1-6 alkyl , optionally substituted by C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), phenyl (C _2-4) al Kenyl (C _1-6 ) alkyl, wherein the phenyl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkylsulfonyl or C _{1- 6} optionally substituted with haloalkoxy), heteroaryl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkylsulfonyl or C _1-6 Optionally substituted with haloalkoxy), heterocyclyl (optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), Heteroaryl (C _1-4 ) alkyl, wherein heteroaryl is optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy ) Or heterocyclyl (C _1-4 ) alkyl (optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy) ego; R ⁸ and R ⁹ are independently hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _2-6 alkenyl, C _1-6 alkynyl, C _1-6 alkoxy or C _1-6 halo Alkoxy; R ¹⁰ is hydrogen, halogen, C _1-6 alkyl, C _2-6 alkenyl, C _1-6 alkynyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkoxy (C _1-6 Alkyl, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 haloalkylthio, C _1-6 alkylsulfinyl, C _1-6 haloalkylsulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkylsulfonyl, C _1-6 haloalkyl, cyano, nitro, formyl, CH = NOR ²⁰ _A, C _1-6 alkylcarbonyl, C _1-6 alkoxycarbonyl or SF ₅ ; Or R ¹ and R ¹⁰ together with the atoms to which they are attached form a 5, 6 or 7 membered saturated or unsaturated ring carbocyclic or bicyclic ring which may contain one or two heteroatoms selected from O, N or S and C _1-6 - alkyl, C _1-6 - haloalkyl or halogen with any will be able to be substituted; R ¹⁶ is cyano, nitro, C _1-6 alkyl, C _1-6 haloalkyl, C _3-7 cycloalkyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, CH ₂ (C _2-6 ) Alkenyl, CH ₂ (C _2-6 ) alkynyl, phenyl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Substituted), heteroaryl (optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), C _1-6 alkyl Carbonyl, C _1-6 Alkoxycarbonyl, C _1-6 Alkylamino, Di (C _1-6 ) alkylamino, C _1-6 Alkylcarbonylamino, C _1-6 Alkoxycarbonylamino, C _1-6 alkoxy, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkylthio, C _1-6 haloalkyl sulfinyl, C _1-6 haloalkyl sulfonyl , Arylthio, arylsulfinyl, arylsulfonyl or OCO (C _1-6 ) alkyl; R ¹⁷ is hydrogen, halogen, nitro, cyano, C _1-8 alkyl, C _1-6 haloalkyl, C _1-6 cyanoalkyl, C _2-6 alkenyl, C _2-6 alkynyl, C _{3- 7} cycloalkyl, C _2-6 haloalkenyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, C _1-6 alkox (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl, C _{1 -6} alkylcarbonyl, C _1-6 alkylaminocarbonyl, di (C _1-6 ) alkylaminocarbonyl, phenyl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C Optionally substituted with _1-6 alkoxy or C _1-6 haloalkoxy or heteroaryl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 Optionally substituted with haloalkoxy); R ³⁶ is C _1-6 alkyl, OR ³⁹ or NR ⁴⁰ R ⁴¹ ; R ³⁷ is hydrogen, C _1-6 alkyl or C _1-6 haloalkyl; R ³⁸ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, cyano, C _1-6 alkoxycarbonyl, C _1-6 alkylcarbonyl or NR ⁴² R ⁴³ ; R ²² and R ²³ are independently hydrogen, C _1-6 alkyl, CH ₂ (C _1-4 ) haloalkyl, C _1-6 cyanoalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _{1 -6} alkylthio (C _1-6 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkoxy (C _1-6 ) alkyl, phenyl (C _1-4 ) alkyl, wherein the phenyl group is halo, nitro, Furnace, optionally substituted with C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy, heteroaryl (C _1-4 ) alkyl, wherein the heteroaryl group is halo, Optionally substituted with nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy, heterocyclyl (C _1-4 ) alkyl where heterocycle One group is optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy) or R ²² and R ²³ are bonded to Together with the N atoms to form a 5, 6 or 7 membered bicyclic ring, which is one or two additional atoms selected from O, N or S It may contain atoms and one or two of C _1-6 - alkyl group optionally will be able to be substituted; R ³⁹ is C _1-6 alkyl or optionally substituted phenyl (C _1-2 ) alkyl; R ⁴⁰ and R ⁴¹ are independently hydrogen, C _1-8 alkyl or phenyl (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Optionally substituted with; R ²¹ is hydrogen or C _1-3 alkyl; R ²⁰ is alkyl or phenyl (C _1-2 ) alkyl, wherein the phenyl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Optionally substituted with; R ⁴² and R ⁴³ are independently hydrogen, C _1-8 alkyl, C _3-7 cycloalkyl, C _3-6 alkenyl, C _3-6 alkynyl, C _2-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl, carboxy (C _1-6 ) alkyl or phenyl (C _1-2 ) alkyl; Or R ⁴² and R ⁴³ together with the N atom to which they are attached form a 5, 6 or 7 membered bicyclic ring which may contain one or two additional heteroatoms selected from O, N or S and one or two C Optionally substituted with _1-6 -alkyl groups.
[92] Preferably A is C _1-4 alkylene-C (O) _-or C _1-4 alkyleneoxy.
[93] Preferably D is S or CR ⁸ = CR ⁹ , wherein R ⁸ and R ⁹ are independently hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _2-6 alkenyl, C _{1- 6} alkynyl, C _1-6 alkoxy or C _1-6 haloalkoxy.
[94] Preferably E is N or CR ¹⁰ (wherein R ¹⁰ is hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkoxy) Or (C _1-6 ) alkyl, C _1-6 ) alkylthio or SF ₅ ; or R ¹ and R ¹⁰ together with the atoms to which they are attached are C _1-6 alkyl, C _1-6 haloalkyl or halogen To form an optionally substituted benzene ring).
[95] Preferred M ¹ is N (R ¹¹ ) C (═O), wherein N is an atom bonded to a ring comprising E and D; R ¹¹ is hydrogen, C _1-6 alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, benzyloxymethyl or benzoyloxymethyl.
[96] Preferably Y is O.
[97] Preferably J is N or CR ¹⁷ , wherein R ¹⁷ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl, cyano, halogen or nitro.
[98] R ¹ is preferably hydrogen, halogen, C _1-6 alkyl, C _2-6 alkenyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 haloalkylthio, C _3-6 cycloalkyl, cyano, nitro or SF ₅ .
[99] Preferably R ³ , R ⁴ and R ⁵ are independently hydrogen, C _1-3 alkyl or halogen.
[100] R ⁶ is preferably C _1-8 alkyl, C _1-6 haloalkyl, C _1-6 cyanoalkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _{1 -6} ) alkyl, C _3-7 cycloalkyl, C _3-7 halocyclo, C _3-7 cyanocycloalkyl, C _1-3 alkyl (C _3-7 ) cycloalkyl, C _1-3 alkyl (C _{3 -7)} halo-cyclo-alkyl, cyclo C _5-6 alkenyl, C _3-7 cyclo-alkyl (C _1-6) alkyl, C _5-6 cyclo alkenyl, (C _1-6) alkyl, C _2-6 haloalkenyl Kenyl (C _1-6 ) alkyl, C _1-6 cyanoalkenyl (C _1-6 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _3-6 alkenyloxy (C _1-6 ) Alkyl, C _3-6 alkynyloxy (C _1-6 ) alkyl, aryloxy (C _1-6 ) alkyl, C _1-6 carboxyalkyl, C _1-6 alkylcarbonyl (C _1-6 ) alkyl, C _2-6 alkenylcarbonyl (C _1-6 ) alkyl, C _2-6 alkynylcarbonyl (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl, C _3-6 Alkenyloxycarbonyl (C _1-6 ) alkyl, C _3-6 alkynyloxycarbonyl (C _1-6 ) alkyl, aryloxycarbonyl (C _1-6 ) alkyl, C _1-6 alkylthio (C _1-6) alkyl, C _1-6 alkyl sulfonic Carbonyl (C _1-6) alkyl, C _1-6 alkylsulfonyl (C _1-6) alkyl, aminocarbonyl (C _1-6) alkyl, aminocarbonyl (C _2-6) alkenyl, aminocarbonyl (C _2-6 ) alkynyl, C _1-6 alkylaminocarbonyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkyl, C _1-6 alkylamino Carbonyl (C _1-6 ) alkenyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkenyl (C _1-6 ) alkyl, alkylaminocarbonyl ( C _1-6 ) alkynyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _1-6 ) alkynyl (C _1-6 ) alkyl, phenyl (halo, nitro, cyano , Optionally substituted with C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy, phenyl (C _1-4 ) alkyl, wherein the phenyl group is halo, nitro, Furnace, optionally substituted with C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), phenyl (C _2-4 ) alkenyl (C _1-6 ) alkyl ( wherein the phenyl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 - alkyl sulfonic Carbonyl or optionally substituted by C _1-6 haloalkoxy), heteroaryl, (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy, Optionally substituted), heterocyclyl, wherein the heterocyclyl group is optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Heteroaryl (C _1-4 ) alkyl, wherein the heteroaryl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy Optionally substituted) or heterocyclyl (C _1-4 ) alkyl, wherein the heterocyclyl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C Optionally substituted with _1-6 haloalkoxy).
[101] More preferred optionally substituted formula
[102]
[103] The ring of is optionally substituted isothiazolyl, optionally substituted pyridyl, optionally substituted pyrimidinyl, optionally substituted quinazolinyl and optionally substituted quinolinyl group (wherein the optional substituents are halo, C _1-6 alkyl) , C _1-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl or C _1-6 haloalkoxy).
[104] Most preferred optionally substituted ring of the above formula is:
[105]
[106] More preferably A is CH ₂ or CH ₂ O, even more preferably CH ₂ .
[107] More preferably M ¹ is NR ¹¹ C (═O), wherein R ¹¹ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy (C _1-4 ) alkyl, benzyloxymethyl or benzoyloxymethyl Do. Particular preference is given to R ¹¹ being hydrogen, ethyl, ethoxymethyl, allyl or propargyl.
[108] It is more preferred that R ³ , R ⁴ and R ⁵ are independently hydrogen or halogen (particularly fluorine) and it is particularly preferred that R ³ , R ⁴ and R ⁵ are each hydrogen.
[109] More preferably J is N or CR ¹⁷ , wherein R ¹⁷ is hydrogen, methyl or halogen.
[110] More preferably R ⁶ is C _1-8 alkyl, C _2-8 haloalkyl, C _1-8 cyanoalkyl, C _3-7 cycloalkyl, C _1-3 alkyl (C _3-7 ) cycloalkyl, C Optionally substituted with _1-6 alkoxy (C _1-6 ) alkyl, bicyclic (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy ), Phenyl (optionally substituted with halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, nitro, cyano or C _1-6 alkylsulfonyl) or heteroaryl (halogen, C _{1 -6} alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, nitro, cyano or C _1-6 alkylsulfonyl.
[111] Particularly preferred R ⁶ is C _1-8 alkyl, C _2-6 haloalkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _3-7 cycloalkyl or C _3-7 cycloalkyl (C _1-6 ) Alkyl.
[112] Particularly preferred groups are the following:
[113]
[114] The compounds in the following table illustrate the compounds of the present invention.
[115] Table A1
[116] Table A1 presents 432 compounds of the formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is methyl.
[117]
[118]
[119]
[120]
[121]
[122]
[123]
[124]
[125]
[126]
[127]
[128]
[129] Table A2
[130] Table A2 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is ethyl.
[131] Table A3
[132] Table A3 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -propyl.
[133] Table A4
[134] Table A4 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is iso -propyl.
[135] Table A5
[136] Table A5 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -butyl.
[137] Table A6
[138] Table A6 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is sec -butyl.
[139] Table A7
[140] Table A7 sets forth 432 compounds of formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is iso -butyl.
[141] Table A8
[142] Table A8 sets forth 432 compound of formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is tert -butyl.
[143] Table A9
[144] Table A9 presents 432 compounds of formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -pentyl.
[145] Table A10
[146] Table A10 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 1-methylbutyl.
[147] Table A11
[148] Table A11 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2-methylbutyl.
[149] Table A12
[150] Table A12 shows 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 3-methylbutyl.
[151] Table A13
[152] Table A13 presents 432 compound of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is neopentyl.
[153] Table A14
[154] Table A14 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2-dimethylbutyl.
[155] Table A15
[156] Table A15 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2,2-trifluoroethyl. .
[157] Table A16
[158] Table A16 is a 432 compound of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2-difluoro-2-methoxyethyl To present.
[159] Table A17
[160] Table A17 sets forth 432 compounds of formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 3,3,3-trifluoropropyl .
[161] Table A18
[162] Table A18 presents 432 compound of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is para -fluorobenzyl.
[163] Table A19
[164] Table A19 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,4-dichlorophenyl.
[165] Table A20
[166] Table A20 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl .
[167] Table A21
[168] Table A21 presents 432 compounds of Formula A1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 4-trifluoromethylphenyl.
[169] Table B1
[170] Table B1 sets forth 288 compounds of the formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B 1 and R ⁶ is methyl.
[171]
[172]
[173]
[174]
[175]
[176]
[177]
[178]
[179]
[180] Table B2
[181] Table B2 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is ethyl.
[182] Table B3
[183] Table B3 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is n -propyl.
[184] Table B4
[185] Table B4 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B 1 and R ⁶ is iso -propyl.
[186] Table B5
[187] Table B5 sets forth 288 compounds of the formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B 1 and R ⁶ is n -butyl.
[188] Table B6
[189] Table B6 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is sec -butyl.
[190] Table B7
[191] Table B7 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B 1 and R ⁶ is iso -butyl.
[192] Table B8
[193] Table B8 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is tert -butyl.
[194] Table B9
[195] Table B9 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1 and R ⁶ is n -pentyl.
[196] Table B10
[197] Table B10 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is 1-methylbutyl.
[198] Table B11
[199] Table B11 shows 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B 1 and R ⁶ is 2-methylbutyl.
[200] Table B12
[201] Table B12 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is 3-methylbutyl.
[202] Table B13
[203] Table B13 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is neopentyl.
[204] Table B14
[205] Table B14 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is 2,2-dimethylbutyl.
[206] Table B15
[207] Table B15 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is 2,2,2-trifluoroethyl .
[208] Table B16
[209] Table B16 is a 288 compound of Formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B 1 and R ⁶ is 2,2-difluoro-2-methoxyethyl To present.
[210] Table B17
[211] Table B17 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is 3,3,3-trifluoropropyl .
[212] Table B18
[213] Table B18 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is para -fluorobenzyl.
[214] Table B19
[215] Table B19 sets forth 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is 2,4-dichlorophenyl.
[216] Table B20
[217] Table B20 presents 288 compounds of formula B1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table B1, and R ⁶ is 2-chloro-4-trifluoromethylphenyl .
[218] Table C1
[219] Table C1 sets forth 144 compounds of the formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is methyl.
[220]
[221]
[222]
[223]
[224]
[225] Table C2
[226] Table C2 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is ethyl.
[227] Table C3
[228] Table C3 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is n -propyl.
[229] Table C4
[230] Table C4 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is iso -propyl.
[231] Table C5
[232] Table C5 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is n -butyl.
[233] Table C6
[234] Table C6 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is sec -butyl.
[235] Table C7
[236] Table C7 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is iso -butyl.
[237] Table C8
[238] Table C8 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is tert -butyl.
[239] Table C9
[240] Table C9 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is n -pentyl.
[241] Table C10
[242] Table C10 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 1-methylbutyl.
[243] Table C11
[244] Table C11 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2-methylbutyl.
[245] Table C12
[246] Table C12 shows 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 3-methylbutyl.
[247] Table C13
[248] Table C13 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is neopentyl.
[249] Table C14
[250] Table C14 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2,2-dimethylbutyl.
[251] Table C15
[252] Table C15 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2,2,2-trifluoroethyl.
[253] Table C16
[254] Table C16 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2,2-difluoro-2-methoxyethyl.
[255] Table C17
[256] Table C17 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 3,3,3-trifluoropropyl.
[257] Table C18
[258] Table C18 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is para -fluorobenzyl.
[259] Table C19
[260] Table C19 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2,4-dichlorophenyl.
[261] Table C20
[262] Table C20 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2-chloro-4-trifluoromethylphenyl.
[263] Table D1
[264] Table D1 sets forth 96 compounds of the formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is methyl.
[265]
[266]
[267]
[268]
[269] Table D2
[270] Table D2 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is ethyl.
[271] Table D3
[272] Table D3 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is n -propyl.
[273] Table D4
[274] Table D4 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is iso -propyl.
[275] Table D5
[276] Table D5 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is n -butyl.
[277] Table D6
[278] Table D6 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is sec -butyl.
[279] Table D7
[280] Table D7 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is iso -butyl.
[281] Table D8
[282] Table D8 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is tert -butyl.
[283] Table D9
[284] Table D9 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is n -pentyl.
[285] Table D10
[286] Table D10 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 1-methylbutyl.
[287] Table D11
[288] Table D11 shows 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 2-methylbutyl.
[289] Table D12
[290] Table D12 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 3-methylbutyl.
[291] Table D13
[292] Table D13 sets forth 96 compounds of Formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is neopentyl.
[293] Table D14
[294] Table D14 sets forth 96 compounds of Formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 2,2-dimethylbutyl.
[295] Table D15
[296] Table D15 sets forth 96 compounds of Formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 2,2,2-trifluoroethyl.
[297] Table D16
[298] Table D16 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 2,2-difluoro-2-methoxyethyl.
[299] Table D17
[300] Table D17 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 3,3,3-trifluoropropyl.
[301] Table D18
[302] Table D18 sets forth 96 compounds of Formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is para -fluorobenzyl.
[303] Table D19
[304] Table D19 sets forth 96 compounds of Formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 2,4-dichlorophenyl.
[305] Table D20
[306] Table D20 sets forth 96 compounds of formula D1 wherein X, R ¹¹ , A and J are as defined in Table D1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl.
[307] Table E1
[308] Table E1 sets forth 432 compounds of the formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is methyl.
[309]
[310] Table E2
[311] Table E2 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is ethyl).
[312] Table E3
[313] Table E3 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -propyl).
[314] Table E4
[315] Table E4 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is iso -propyl).
[316] Table E5
[317] Table E5 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -butyl).
[318] Table E6
[319] Table E6 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is sec -butyl).
[320] Table E7
[321] Table E7 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is iso -butyl).
[322] Table E8
[323] Table E8 sets forth 432 compound of formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is tert -butyl.
[324] Table E9
[325] Table E9 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -pentyl).
[326] Table E10
[327] Table E10 sets forth 432 compounds of the formula El (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 1-methylbutyl).
[328] Table E11
[329] Table E11 shows 432 compound of formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2-methylbutyl.
[330] Table E12
[331] Table E12 sets forth 432 compounds of the formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 3-methylbutyl.
[332] Table E13
[333] Table E13 sets forth 432 compounds of formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1, and R ⁶ is neopentyl.
[334] Table E14
[335] Table E14 sets forth 432 compounds of formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2-dimethylbutyl.
[336] Table E15
[337] Table E15 shows the 432 compound of Formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2,2-trifluoroethyl. .
[338] Table E16
[339] Table E16 is a 432 compound of Formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2-difluoro-2-methoxyethyl To present.
[340] Table E17
[341] Table E17 sets forth 432 compounds of the formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 3,3,3-trifluoropropyl. .
[342] Table E18
[343] Table E18 sets forth 432 compound of formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is para -fluorobenzyl.
[344] Table E19
[345] Table E19 sets forth 432 compounds of formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,4-dichlorophenyl.
[346] Table E20
[347] Table E20 presents 432 compounds of Formula E1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl .
[348] TABLE F1
[349] Table F1 sets forth 432 compounds of the formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is methyl.
[350]
[351] TABLE F2
[352] Table F2 sets forth 432 compounds of the formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is ethyl.
[353] TABLE F3
[354] Table F3 sets forth 432 compounds of formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -propyl.
[355] TABLE F4
[356] Table F4 sets forth 432 compounds of the formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is iso -propyl.
[357] TABLE F5
[358] Table F5 sets forth 432 compounds of the formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -butyl.
[359] Table F6
[360] Table F6 sets forth 432 compounds of formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1, and R ⁶ is sec -butyl.
[361] Table F7
[362] Table F7 sets forth 432 compounds of formula F1, wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table F 1, and R ⁶ is iso -butyl.
[363] TABLE F8
[364] Table F8 sets forth 432 compounds of the formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is tert -butyl.
[365] Table F9
[366] Table F9 sets forth 432 compounds of formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is n -pentyl.
[367] Table F10
[368] Table F10 sets forth 432 compounds of formula F1, wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1, and R ⁶ is 1-methylbutyl.
[369] Table F11
[370] Table F11 shows 432 compounds of Formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2-methylbutyl.
[371] Table F12
[372] Table F12 sets forth 432 compounds of the formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 3-methylbutyl.
[373] Table F13
[374] Table F13 sets forth 432 compounds of formula F1, wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1, and R ⁶ is neopentyl.
[375] Table F14
[376] Table F14 sets forth 432 compounds of formula F1, wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1, and R ⁶ is 2,2-dimethylbutyl.
[377] Table F15
[378] Table F15 shows 432 compounds of Formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2,2-trifluoroethyl .
[379] Table F16
[380] Table F16 is a 432 compound of Formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,2-difluoro-2-methoxyethyl To present.
[381] TABLE F17
[382] Table F17 sets forth 432 compounds of Formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 3,3,3-trifluoropropyl .
[383] Table F18
[384] Table F18 sets forth 432 compounds of formula F1, wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1, and R ⁶ is para -fluorobenzyl.
[385] Table F19
[386] Table F19 sets forth 432 compounds of formula F1 (wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2,4-dichlorophenyl).
[387] Table F20
[388] Table F20 sets forth 432 compounds of formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl .
[389] Table F21
[390] Table F21 sets forth 432 compounds of formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1 and R ⁶ is 4-trifluoromethylphenyl.
[391] Table F22
[392] Table F22 sets forth 432 compounds of formula F1 wherein R ¹ , D, E, R ¹¹ , A and J are as defined in Table A1, and R ⁶ is COCH ₃ .
[393] Table G1
[394] Table G1 sets forth 144 compounds of the formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is methyl.
[395]
[396] Table G2
[397] Table G2 sets forth 144 compounds of the formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is ethyl.
[398] Table G3
[399] Table G3 presents 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is n -propyl.
[400] Table G4
[401] Table G4 presents 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is iso -propyl.
[402] Table G5
[403] Table G5 sets forth 144 compounds of the formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is n -butyl.
[404] Table G6
[405] Table G6 sets forth 144 compounds of the formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is sec -butyl.
[406] Table G7
[407] Table G7 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is iso -butyl.
[408] Table G8
[409] Table G8 presents 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is tert -butyl.
[410] Table G9
[411] Table G9 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is n -pentyl.
[412] Table G10
[413] Table G10 sets forth 144 compounds of the formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 1-methylbutyl.
[414] Table G11
[415] Table G11 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2-methylbutyl.
[416] Table G12
[417] Table G12 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 3-methylbutyl.
[418] Table G13
[419] Table G13 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is neopentyl.
[420] Table G14
[421] Table G14 presents 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2,2-dimethylbutyl.
[422] Table G15
[423] Table G15 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2,2,2-trifluoroethyl.
[424] Table G16
[425] Table G16 presents 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2,2-difluoro-2-methoxyethyl.
[426] Table G17
[427] Table G17 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 3,3,3-trifluoropropyl.
[428] Table G18
[429] Table G18 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is para -fluorobenzyl.
[430] Table G19
[431] Table G19 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2,4-dichlorophenyl.
[432] Table G20
[433] Table G20 sets forth 144 compounds of formula G1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl.
[434] TABLE H1
[435] Table H1 sets forth 144 compounds of the formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is methyl.
[436]
[437] Table H2
[438] Table H2 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is ethyl.
[439] Table H3
[440] Table H3 presents 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is n -propyl.
[441] Table H4
[442] Table H4 presents 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is iso -propyl.
[443] Table H5
[444] Table H5 sets forth 144 compounds of the formula H1, wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is n -butyl.
[445] Table H6
[446] Table H6 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is sec -butyl.
[447] Table H7
[448] Table H7 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is iso -butyl.
[449] Table H8
[450] Table H8 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is tert -butyl.
[451] Table H9
[452] Table H9 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is n -pentyl.
[453] Table H10
[454] Table H10 presents 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 1-methylbutyl.
[455] Table H11
[456] Table H11 presents 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2-methylbutyl.
[457] Table H12
[458] Table H12 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 3-methylbutyl.
[459] Table H13
[460] Table H13 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is neopentyl.
[461] Table H14
[462] Table H14 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2,2-dimethylbutyl.
[463] Table H15
[464] Table H15 sets forth 144 compounds of formula C1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2,2,2-trifluoroethyl.
[465] Table H16
[466] Table H16 presents 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1 and R ⁶ is 2,2-difluoro-2-methoxyethyl.
[467] Table H17
[468] Table H17 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 3,3,3-trifluoropropyl.
[469] Table H18
[470] Table H18 presents 144 compounds of formula H1, wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is para -fluorobenzyl.
[471] Table H19
[472] Table H19 sets forth 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2,4-dichlorophenyl.
[473] Table H20
[474] Table H20 presents 144 compounds of formula H1 wherein X, R ¹¹ , A and J are as defined in Table C1, and R ⁶ is 2-chloro-4-trifluoromethylphenyl.
[475] Table I1
[476] Table I1 sets forth 288 compounds of the formula (I1) wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is methyl.
[477]
[478]
[479]
[480]
[481]
[482]
[483]
[484]
[485] Table I2
[486] Table I2 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is ethyl.
[487] Table I3
[488] Table I3 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is n -propyl.
[489] Table I4
[490] Table I4 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is iso -propyl.
[491] Table I5
[492] Table I5 presents 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is n -butyl.
[493] Table I6
[494] Table I6 sets forth 288 compounds of the formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is sec -butyl.
[495] Table I7
[496] Table I7 presents 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is iso -butyl.
[497] Table I8
[498] Table I8 presents 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is tert -butyl.
[499] Table I9
[500] Table I9 shows 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is n -pentyl.
[501] Table I10
[502] Table I10 shows 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 1-methylbutyl.
[503] Table I11
[504] Table I11 sets forth 288 compounds of the formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 2-methylbutyl.
[505] Table I12
[506] Table I12 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 3-methylbutyl.
[507] Table I13
[508] Table I13 sets forth 288 compounds of Formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is neopentyl.
[509] Table I14
[510] Table I14 sets forth 288 compounds of Formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 2,2-dimethylbutyl.
[511] Table I15
[512] Table I15 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 2,2,2-trifluoroethyl.
[513] Table I16
[514] Table I16 presents 288 compounds of Formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 2,2-difluoro-2-methoxyethyl.
[515] Table I17
[516] Table I17 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 3,3,3-trifluoropropyl.
[517] Table I18
[518] Table I18 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is para -fluorobenzyl.
[519] Table I19
[520] Table I19 sets forth 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 2,4-dichlorophenyl.
[521] Table I20
[522] Table I20 presents 288 compounds of formula I1 wherein X, R ² , A and J are as defined in Table I1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl.
[523] Table J1
[524] Table J1 sets forth 288 compounds of the formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is methyl.
[525]
[526] Table J2
[527] Table J2 sets forth 288 compounds of the formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is ethyl.
[528] Table J3
[529] Table J3 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is n -propyl.
[530] Table J4
[531] Table J4 presents 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is iso -propyl.
[532] Table J5
[533] Table J5 sets forth 288 compounds of the formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is n -butyl.
[534] Table J6
[535] Table J6 presents 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is sec -butyl.
[536] Table J7
[537] Table J7 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is iso -butyl.
[538] Table J8
[539] Table J8 sets forth 288 compounds of the formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is tert -butyl.
[540] Table J9
[541] Table J9 sets forth 288 compounds of the formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is n -pentyl.
[542] Table J10
[543] Table J10 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 1-methylbutyl.
[544] Table J11
[545] Table J11 sets forth 288 compounds of Formula I1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2-methylbutyl.
[546] Table J12
[547] Table J12 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 3-methylbutyl.
[548] Table J13
[549] Table J13 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is neopentyl.
[550] Table J14
[551] Table J14 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,2-dimethylbutyl.
[552] Table J15
[553] Table J15 presents 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,2,2-trifluoroethyl .
[554] Table J16
[555] Table J16 is a 288 compound of Formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,2-difluoro-2-methoxyethyl To present.
[556] Table J17
[557] Table J17 sets forth 288 compounds of formula I1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I1 and R ⁶ is 3,3,3-trifluoropropyl .
[558] Table J18
[559] Table J18 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is para -fluorobenzyl.
[560] Table J19
[561] Table J19 sets forth 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,4-dichlorophenyl.
[562] Table J20
[563] Table J20 presents 288 compounds of formula J1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl .
[564] Table K1
[565] Table K1 sets forth 288 compounds of the formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is methyl.
[566]
[567] Table K2
[568] Table K2 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is ethyl.
[569] Table K3
[570] Table K3 shows 288 compounds of the formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is n -propyl.
[571] Table K4
[572] Table K4 sets forth 288 compounds of the formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is iso -propyl.
[573] Table K5
[574] Table K5 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is n -butyl.
[575] Table K6
[576] Table K6 sets forth 288 compounds of the formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is sec -butyl.
[577] Table K7
[578] Table K7 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is iso -butyl.
[579] Table K8
[580] Table K8 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is tert -butyl.
[581] Table K9
[582] Table K9 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is n -pentyl.
[583] Table K10
[584] Table K10 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 1-methylbutyl.
[585] Table K11
[586] Table K11 shows 288 compounds of the formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2-methylbutyl.
[587] Table K12
[588] Table K12 shows 288 compounds of the formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 3-methylbutyl.
[589] Table K13
[590] Table K13 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is neopentyl.
[591] Table K14
[592] Table K14 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,2-dimethylbutyl.
[593] Table K15
[594] Table K15 presents 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,2,2-trifluoroethyl .
[595] Table K16
[596] Table K16 is a 288 compound of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,2-difluoro-2-methoxyethyl To present.
[597] Table K17
[598] Table K17 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 3,3,3-trifluoropropyl .
[599] Table K18
[600] Table K18 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is para -fluorobenzyl.
[601] Table K19
[602] Table K19 sets forth 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I 1 and R ⁶ is 2,4-dichlorophenyl.
[603] Table K20
[604] Table K20 presents 288 compounds of formula K1 wherein R ¹ , D, E, R ² , A and J are as defined in Table I1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl .
[605] Table L1
[606] Table L1 sets forth 192 compounds of the formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is methyl.
[607]
[608]
[609]
[610]
[611]
[612]
[613] Table L2
[614] Table L2 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is ethyl.
[615] Table L3
[616] Table L3 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is n -propyl.
[617] Table L4
[618] Table L4 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is iso -propyl.
[619] Table L5
[620] Table L5 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is n -butyl.
[621] Table L6
[622] Table L6 sets forth 192 compounds of formula L1, wherein R ¹ , D, E, R ² , A and J are as defined in Table L ¹ , and R ⁶ is sec -butyl.
[623] Table L7
[624] Table L7 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is iso -butyl.
[625] Table L8
[626] Table L8 sets forth 192 compounds of the formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is tert -butyl.
[627] Table L9
[628] Table L9 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is n -pentyl.
[629] Table L10
[630] Table L10 sets forth 192 compounds of the formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1, and R ⁶ is 1-methylbutyl.
[631] Table L11
[632] Table L11 shows 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 2-methylbutyl.
[633] Table L12
[634] Table L12 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 3-methylbutyl.
[635] Table L13
[636] Table L13 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is neopentyl.
[637] Table L14
[638] Table L14 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 2,2-dimethylbutyl.
[639] Table L15
[640] Table L15 presents 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 2,2,2-trifluoroethyl .
[641] Table L16
[642] Table L16 is a 192 compound of Formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 2,2-difluoro-2-methoxyethyl To present.
[643] Table L17
[644] Table L17 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 3,3,3-trifluoropropyl .
[645] Table L18
[646] Table L18 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is para -fluorobenzyl.
[647] Table L19
[648] Table L19 sets forth 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 2,4-dichlorophenyl.
[649] Table L20
[650] Table L20 shows 192 compounds of formula L1 wherein R ¹ , D, E, R ² , A and J are as defined in Table L 1 and R ⁶ is 2-chloro-4-trifluoromethylphenyl .
[651] The following abbreviations are used in this specification:
[652] m.p. = Melting point ppm = parts per million
[653] s = single line br = wide area
[654] d = doublet dd = doublet of doublet
[655] t = triplet q = quartet
[656] m = polyline
[657] Table 1 lists all of the compounds of Tables A1-L20 as solvents (unless otherwise indicated; if a solvent mixture is present, this is indicated, for example (CDCl ₃ / d ₆ -DNSO)), using CDCl ₃ NMR data were presented (not all listing all characterization data).
[658]
[659]
[660]
[661] Compounds of the invention can be prepared in a variety of ways. For example, as shown in Scheme 1, where Y is 0 and A is alkylene, alkenylene, alkyleneoxy, alkyleneamino or alkylenethio, compounds (Ia) may be selected from the appropriate carboxylic esters ( III) (X ¹ = alkoxy or aryloxy) or carboxylic acid (III, X ¹ = OH), 1,3-dicyclohexylcarbodiimide or 1- (3-dimethylaminopropyl) -3-ethylka It is prepared by reacting in the presence of an arbitrary coupling agent, such as a bodyimide. Alternatively carboxylic acid (III, X ¹ = OH) may first be converted to an acid chloride, anhydride or chloroformate suitable for reaction with the amine to form an amide; Such processes are well known to those skilled in the art and are described, for example, in J. March, Advanced Organic Chemistry, 3rd Edition, John Wiley and Sons, New York, 1985, pages 370-376 and references incorporated therein.
[662]
[663] Thus, in another aspect, the present invention provides a compound of formula (II) wherein Y is oxygen and X ¹ is a leaving group (alkoxy, aryloxy, OH, chloro or ClC (O) O or the compound of formula (III) Provided is a process for the preparation of a compound of formula (I) wherein Y is oxygen comprising reacting with a compound of formula (III), wherein
[664] Compounds of formula (II) are known compounds or may be prepared by methods described in the literature from commercially available starting materials (e.g. C. Oliver Kappe, Robert Flammang, and Curt Wentrup, Heterocycles, Vol. 37, No. 3, 1615, (1994); A. Adams and R. Slack, J. Chem. Soc., 3061, (1959); and Ronald E Hackler, Kenneth W. Burrow, Jr., Sylvester V. Kaster and David I. Wickiser, J. Heterocyclic Chem, 26, 1575, (1989), Ronald E Hacker, Glen P Jourdan, Peter L Johnson, Brian R Thoreen and Jack G Samaritoni, PCT International Application, WO9304580 A1 and its references Reference).
[665] Synthesis of substituted benzotriazoles and indazoles is described in the chemical literature (see, eg, Alan R. Katritzky and Charles W. Rees, Comprehensive Heterocyclic Chemistry, Pergamon Press, 1984; Christoph Ruchardt and Volker Hassmann, Leibis Ann. Chem., 1980, 908; Jean-Jacques Vandenbossche and Alain Lagrange, Eur. Pat. Appl., EP 904769; F. Halley and X. Sava, Synth.Commun. 1997, 27 (7), 1199; Donald R. James , Don R. Baker, Steven D. Mielich, William J. Michaely, Steven Fitzjohn, Christopher G. Knudsen, Christopher Mathews and John M. Gerdes, PCT International Application, WO9318008 A1, Donald Richard James and Raymond Anthony Felix, PCT International Application , WO9425446A1) Similar methods can be used to prepare compounds of formula (III), starting with suitable substituted anilines known in the art. Alternatively, halobenzotriazoles and haloindazoles (particularly halogen dibromo or iodo) can be prepared by the above method, and Nitya G. Kundu et al., Tetrahedron, 53 (39), 13397, (1997). Processes involving transition metal catalyzed transformations similar to those described in Heterocycles, 36 (11), 2509 (1993), Motoi Kawatsura and John F. Hartwig, JACS, 1999, 121 , 1473, and others. To a compound of formula (III).
[666] Compounds of formula (Ia) in which Y is sulfur represent compounds of formula (Ia) in which Y is oxygen. , 4-disulfide (Lawesson reagent), 2,4-bis (methylthio) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4-bis such as ( para -tolyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent p -tolyl) or phosphorus pentasulfide in a suitable solvent such as toluene or fluorobenzene It can be prepared by reacting with a suitable sulfiding reagent.
[667] Therefore, in another aspect the invention provides a process for preparing a compound of formula (I) wherein Y is oxygen (by reacting a compound of formula (II) with a compound of formula (III) wherein Y is oxygen and X ¹ is a leaving group) Provided is a process for the preparation of a compound of formula (I) wherein Y is sulfur comprising reacting this compound with a sulfiding reagent.
[668] Compounds of formula (IV) may be prepared from compounds of formula (V) by treatment with N, N-dimethylformamide dialkyl acetal in a suitable solvent such as toluene or N, N-dimethylformamide. Often this reaction produces a mixture of E and Z isomers which can often be separated by standard techniques such as flash column chromatography and recrystallization. This invention includes isomers separated with a mixture of isomers.
[669]
[670] Compounds of formula (IV) may be subsequently treated with amines (HNRaRb) to afford formula (VI); Compounds of formula (V) may be treated with trialkylorthoformates (HC (ORd) ₃ ) in a similar manner to afford compounds of formula (VII):
[671]
[672] Compounds of formula (Ia) in which R ¹¹ is hydrogen are treated in the presence of a base with an optionally substituted alkylation reagent (such as an alkyl halide, chloromethylether, dialkyl sulfate or trialkyloxonium salt) to optionally substitute R ^11. In addition, a compound of formula (la) is obtained, which constitutes an additional part of the present invention. When Y is O, this reaction usually produces a mixture of isomeric products of formulas (la) and (lb). In contrast, when Y is S, the compound of formula (Ic) is the predominant product.
[673]
[674] Those skilled in the art will recognize that when Y is O, similar reactions involving sulfenation, sulfonation and acylation are possible.
[675] Compounds of formula (Ia) in which R ¹¹ is alkoxymethyl or acyloxymethyl can also be prepared from sequential reactions with formaldehyde and alkylation or acylating agents from compounds of formula (Ia) in which R ¹¹ is hydrogen.
[676] Formula (Ia) additional compound is R ¹¹ from a compound of formula (I) is hydrogen, hydroxymethyl benzotriazole or benzotriazole and an aldehyde and the like ARKatritzky, J. Org a. By reaction according to the method according to Chem., (1993), 58 , 2086.
[677] A compound of formula (Ic) wherein Y = S is reacted with an alcohol, amine, O-alkylhydroxylamine or hydrazine with a known method in the presence of a mercury salt (such as mercury chloride) according to known methods to form formula (Id) or ( Each compound of Ie) can be obtained:
[678]
[679] Wherein Re is H, optionally substituted alkyl, alkenyl or alkynyl, Rf is substituted alkyl, alkenyl alkynyl, amino, substituted amino or alkoxy and Rg is optionally substituted alkyl, alkenyl or ilkynyl.
[680] A compound of formula (Id) wherein Re is hydrogen is treated with an optionally substituted alkylating agent (such as an alkyl halide, chloromethylether, dialkyl sulfate or trialkyloxonium salt) in the presence of a base to give a compound of formula (If) You can get it.
[681]
[682] Heteroaryl N-oxides can be produced by methods known to those skilled in the art. Compounds of formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (IV), (V), (VI) and (VII) are all compounds of formula (I) to be.
[683] Compounds of formula (I) are susceptible to infection of insect parasites such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and other invertebrate parasites such as, for example, ticks, nematodes and molluscs parasites. Can be used to eradicate and control. Parasites that can be eradicated and controlled by the use of the compounds of the present invention include agriculture (the term includes crop cultivation for edible and textile products), horticulture, livestock raising, pets, forestry and plant origin products (fruit, Parasites associated with the storage of such grains and wood); Parasites associated with damage to artificial structures and transmission of diseases of humans and animals; Includes unpleasant parasites (such as flies).
[684] Examples of parasites which may be controlled by the compounds of formula (I) species include the following:. Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp (capsids), Dysdercus spp. (Capsid), Nilaparvata lugens (Plant Hopper), Nezara spp. (Stink Beetle), Euschistus spp. (Stink Beetle), Leptocorisa spp. (Stink Beetle), Frankliniella occidentalis (thrip), Thrips spp. ( Thrips ), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (weevil and beetle), Aonidiella spp. (Up bug), Trialeurodes spp. (White fly), Bemisia tabaci (white fly), Ostrinia ubilalis (European beetle moth), Spodoptera littoralis (cotton leaf beetle) ), Heliothis virescens (cigarette buds), Helicoverpa armigera (cotton pods), Helicoverpa Zea (cotton pods), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (chestnut and bug), Chilo suppressalis (Rice stalk perforated), Locusta migratoria (locust), Choriocetes terminifera (locust), Diarotica spp. (Root beetle), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus uriticae (2-stain red) mite), Tetranychus cinnabarinus (crimson red mite), Phyllocoptruta oleivora (citrus pest mites), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leaf moth), Musca domestica (housefly) Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (black flies), Blattella germanica (roaches), Periplaneta americana (roaches), Blattaorientalis (roaches), Mastotermitidae , termites (eg Mastotermes spp.), Kalotermitidae ( eg Neotermes spp.), Rhinotermitidae (eg C optotermes formosanus, Reticulitermes flavipes, R.speratu, R.verginicus, R.hesperus, and R.santonensis) and the Termitidae (for example Globitermes sulphreus), Solenopsis geminata (fire ant), Monomorium pharaonis (Pharaoh ant), Damalinia spp. And Linognathus spp. (Bitter suckling insects), Meloidogyne spp. (Root hump nematodes), Globodera spp. And Heterodera spp. ( Cystic nematodes), Pratylenchus spp. (Wound nematodes), Rhodopholus spp. (Banana perforation nematodes), Tylenchlus spp. (Citrus nematodes), Haemonchus contortus (barber pole nematodes), Caenorhabditis elegans ( herb nematodes) , Trichostrongylus spp. (Gastrointestinal nematodes) and Derocerae reticulatum (slugs).
[685] Compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae ( Magnaporthe grisea ) on rice and wheat and Pyricularia spp. On other hosts; Puccinia recondita for wheat, Puccinia striiformis and other rusts , Puccinia striiformis for barley and other rusts , and for other hosts (eg grass, rye, coffee, pears, apples, peanuts, sugar beets, vegetables and ornamental plants) Rust fungi); Erysiphe cichoracearum on gourds (eg melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and grass and Sphaerotheca macularis on hops, Sphaerotheca fuliginea on gourds (eg cucumbers), Leveillula taurica on potatoes, eggplants and bell peppers, on apples other mildew fungi on a variety of hosts such as Uncinulanecator on Podosphaera leucotricha and vines; Cochliobolus spp., Helminthosporiun spp., Drechslera spp. ( Pyrenophora spp.), Rhnechosporium spp., Mycosphaerella graminicola ( Septoria tritici ), and Phaeoshpaeria nodora ( Stagon ) against cereals (e.g. wheat, barley, rye), grass and other hosts nodorum or Septoria modorum ), Pseudocercosporell herpotrichoides and Gaeumannomyces graminis ; Cercospora arachidicola and Cercosporidium personatum for peanuts and other hosts such as beets, bananas, legumes and other Cercospora spp. For rice; Botrytis cinerea (gray mold) for tomatoes, strawberries, vegetables, vine plants and other hosts and other Botrytis spp. For other hosts; Alternaria spp. For vegetables (eg carrots), rape, apples, tomatoes, cereals (eg wheat) and other hosts; Venturia spp. (Including Venturia inaequalis (ohm)) on apples, pears, nuclei, nuts and other hosts; Cladosporium spp. For a range of hosts including cereals (eg wheat) and tomatoes; Monilinia spp. Against stone fruit, tree fruit, and other hosts; Didymella spp. On tomatoes, grass, wheat and other hosts; Phoma spp. For oil-seed rape, grass, rice, potatoes, wheat and other hosts; Aupergillus spp. For wheat, wood and other hosts. And Aureobasidium spp .; Ascochyta spp. Against peas, wheat, barley and other hosts; Stemphylium spp. ( Pleospora spp.) On apples, pears, onions and other hosts; summer diseases on apples and pears (eg bitter rotula ( Glomerella cingulata ), black rot or prog eye) (frogeye) (Botryosphaeria obtusa ), Brooks fruitspot ( Mycosphaerella pomi), Cedar apple rust ( Gymnosporangium juniperi-virginianae ), Sooty blotch ( Gloeodes pomigena ), Canteen flyspeck) ( Schizothyrium pomi ) and white rot ( Botryosphaeria dothidea ); Plasmopara ivticola on vine plants; . Bremia on lettuce lactucae, legumes, tobacco, onions, Peronospora for other host spp, Pseudoperonospora, such as downy mildew and other for the night and Pseudoperonospora humuli on hops and plants; Pythium spp. (Including Pythium ultimum ) on turf and other hosts; Phytophthora infestans for potatoes and tomatoes and other Phytophthora spp. For vegetables, strawberries, avocados, peppers, ornamental plants, tobacco, cocoa and other hosts; Thanatephorus cucumeris for rice and grass and other Rhizoctonia spp. For various hosts such as wheat and barley, peanuts, vegetables, cotton and grass; Sclerotinia spp. On grass, peanuts, oil-seed rape and other hosts; Sclerotium spp. On grass, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. For host ranges including grass, coffee and vegetables; Laetisaria fuciformis on grass; Mycosphaerella spp. Against bananas, peanuts, citrus fruits, pecans, papayas and other hosts; Diaporthe spp. For citrus fruits, legumes, melons, pears, lupines and other hosts; Elsinoe spp. For citrus fruits, vine plants, olives, pecans, roses and other hosts; Verticillium spp. For a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. For oil-seed rape and other hosts; Oncobasidium theobromae for cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochiym nivale, Ustilage spp., Urocystis spp., Tilletia spp. On various hosts, in particular wheat, barley, grass and corn . And Claviceps perpurea ; In particular, the training of fruit-growing diseases (eg Pencillium digitatum, Penicillium italicum and Trichoderma viride, Coleetotrichym musae and Gloeosporium musarum and Botrytis cinerea on grapes and bananas for on orange); Other pathogens for vine plants, in particular Eutypa lata , Guignardia bidwellii , Phellinus igniarus , Phomopsis viticola , Pseudopeziza tracheiphila and Stereum hirsutum ; . Trees (for example Lophodermium seditiosum) or other pathogens on lumber, especially Cephaloascus fragrans, Ceratocystis spp, Ophiostoma piceae , Penicillium spp, Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; Fungal and viral disease vectors (eg barley yellow mosaic virus (BYMV) Polymyxa graminis and candy Polymyxa betae as rhizomania of beet as the vector for the vector for the grains) of the.
[686] Compounds of formula (I) can be transported in a plant to be active against one or more fungi either spherically, acropetally, basipetally or locally. Furthermore, the compound of formula (I) may be volatile enough to be active against one or more fungi against plants in the vapor phase.
[687] The present invention therefore relates to a composition containing an effective amount of a compound of formula (I), or a compound of formula (I), against an insect, mite, nematode or mollusc, and is susceptible to being attacked by a parasite, a parasitic lesion, or a parasite. A method for eradicating and controlling insects, mites, nematodes or molluscs, comprising applying to a plant and a composition containing a fungal effective amount of a compound of formula (I) or a compound of formula (I), Provided are methods for eradication and control of fungi, including application to plant seeds, plant or seed lesions or soil. Compounds of formula (I) are preferably used against insects, mites, nematodes or fungi.
[688] The term "plant" in this specification includes seedlings, shrubs and trees. Furthermore, the fungicidal methods of the present invention include protective, therapeutic, systemic, pesticidal and antisposive treatments.
[689] As fungicides, the compounds of formula (I) are preferably used in the form of compositions for agricultural, horticultural and turfgrass applications.
[690] Insecticides, acaricides, insecticides or chelators for parasites, pathogenic parasites, or plants susceptible to attack by parasites, or for plants, plant seeds, plant or seed lesions or soil In order to apply the compound of formula (I) as a fungicide, the compound of formula (I) is usually in addition to the compound of formula (I) with a composition comprising a suitable inert diluent or carrier and optionally a surface active agent (SFA) Formulated. SFA can modulate the properties of the interface (eg liquid / solid, liquid / air or liquid / liquid interface) by lowering the surface tension and thus changing other properties (eg dispersion, emulsification and wetting). It is a chemical. It is preferred that all compositions (both solid and liquid formulations) comprise 0.0001-95% by weight, more preferably 1-85% by weight, for example 5-60% by weight of the compound of formula (I). The composition is generally used for control of parasites or fungi and is applied at a rate of 0.1 g-10 kg per hectare, preferably 1 g-6 kg, more preferably 1 g-1 kg per hectare.
[691] When used in seed dressing, the compound of formula (I) is used at a rate of 0.0001 g-10 g (eg 0.001 g or 0.05 g), preferably 0.005-10 g, more preferably 0.005 g-4 g per kg of seed do.
[692] In another aspect, the present invention provides an insecticidal composition comprising an insecticidal, acaricidal, nematicidal, chelator or fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent thereto Provided are agicidal, nematicidal, chelating or fungicidal compositions. The composition is preferably an insecticidal, acaricidal, nematicidal or fungicidal composition.
[693] In another aspect, the present invention comprises a parasitic or fungal or foci of a parasitic or fungal compound in an insecticidal, acaricidal, nematicidal, chelating or fungicidally effective amount of a compound of formula (I) It provides a method for eradicating and controlling parasites or fungi comprising treating with a composition.
[694] The composition is a dustable powder (DP), soluble powder (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (sustained release or rapid release), soluble concentrate Water (SL), oil soluble (OL), ultra low volume liquid (UL), emulsifiable concentrate (EC), dispersible concentrate (DC), emulsion (oil in water (EW) and oil) All)), micro-emulsions (ME), dispersible concentrates (SC), aerosols, mist / smoke preparations, capsule suspending agents (CS) and seed treatment preparations.
[695] Non-acidic powders contain one or more diluents (e.g., natural mud, kaolin, propyllite, bentonite, alumina, montmorillonite, kieselguhr, limestone, diatomaceous earth, calcium phosphate, calcium) And magnesium carbonate, sulfur, lime, milcar, talc and other organic and inorganic solid carriers) and mechanically ground the mixture into fine powders.
[696] Soluble powder (SP) may contain a compound of formula (I) as one or more water soluble inorganic salts (sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water soluble organic solids (such as polysaccharides) and, optionally, moisture It can be prepared by mixing one or more wetting agents, one or more dispersants or mixtures thereof to enhance acidity / solubility. The mixture is then ground to a fine powder. Similar compositions can also be granulated to form water soluble granules (SG).
[697] Wettable powders (WPs) may comprise a compound of formula (I) with one or more diluents or carriers, one or more wetting agents, and preferably one or more dispersants, and optionally one or more for promoting dispersion in a liquid. It can be prepared by mixing with more suspending agent. The mixture is then ground to a fine powder. Similar compositions can also be granulated to form water dispersible granules (WG).
[698] Granules (GR) granulate a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or granulate a compound of formula (I) (or a solution thereof in a suitable reagent) (Pumice, attapulgite mud, clay, kieselguhr, diatomaceous earth or corn cob), or a compound of formula (I) (or its solution in a suitable reagent) It may be formed by drying if necessary from the pre-formed blank granules by adsorption on the core material (sand, silicate, mineral carbonate, sulfate or phosphate). Commonly used reagents to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and adhesives (such as polyvinyl acetate, polyvinyl alcohol, dextrins, sugars and vegetable oils). ). One or more additives may be included in the granules (eg emulsifiers, wetting agents or dispersants).
[699] Dispersible concentrates (DC) may be prepared by dissolving the compound of formula (I) in water or in an organic solvent such as a ketone, alcohol or glycol ether. These solutions may include surface active materials (eg to enhance water dilution and prevent crystallization in the spray tank).
[700] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) dissolve a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers, or mixtures thereof). Can be prepared by Suitable organic solvents for use in EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes such as SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200 (SOLVESSO is a registered trademark)), ketones (cyclohexanone or methylcyclohexa). ) And alcohols (such as benzyl alcohol, perfuryl alcohol or butanol), N-alkylpyrrolidone (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amide (C _8- ) C ₁₀ fatty acids such as dimethylamide) and chlorinated hydrocarbons. The EC product may be effective in addition to water instantaneously, and it is possible to produce an emulsion with sufficient stability and spray application through suitable equipment. The preparation of EW can be accomplished by obtaining a compound of formula (I) as a liquid phase (not melt at room temperature or typically at a reasonable temperature of 70 ° C. or less) or as a solution (by dissolving in a suitable solvent) and the resulting liquid or solution Is emulsified under high shear with water containing one or more SFAs to produce an emulsion. Suitable solvents for use in EW include suitable organic solvents having low solubility in vegetable oyl, chlorinated hydrocarbons (such as chlorobenzene), aromatic solvents (such as alkylbenzene or alkylnaphthalene) and other waters.
[701] Microemulsions (ME) can be prepared by mixing water with a combination of one or more SFAs with one or more solvents to produce an instant thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in water or in a combination of solvent / SFA. Suitable solvents for use in ME include those previously described for use in EC or EW. The ME may be an oil-in-water or oil-in-oil system, which may be determined by conductivity measurement, and may be suitable for mixing water-soluble and fat-soluble pesticides in the same formulation. ME is suitable for dilution into water, or as a microemulsion, or for forming conventional oil-in-water emulsions.
[702] Suspension concentrate (SC) may comprise an aqueous or non-aqueous suspension of finely divided insoluble solid particles of the compound of formula (I). SC can be prepared by ball or bead milling a solid compound of formula (I) with one or more suspending agents in a suitable medium to produce a fine particle suspension of compound of formula (I). One or more wetting agents may be included in the composition and suspending agents may be included to reduce the rate at which the particles settle. Alternatively, the compound of formula (I) may be dry milled or added to water while containing the previously described reagents to produce the desired product.
[703] Aerosol formulations include a compound of formula (I) and an appropriate propellant (eg n-butane). Compounds of formula (I) may be dissolved or dispersed in a suitable medium (e.g., water or a liquid that can be mixed with water such as n-propanol) to provide a composition for a non-compressed, manually operated spray pump.
[704] The compound of formula (I) may be mixed with the flame compound in a dry state to produce a composition suitable for producing smoke containing the compound of formula (I) in a confined space.
[705] Capsule suspension (CS) is a method similar to the preparation of EW formulations, but an aqueous dispersion of oil droplets is obtained so that each oil droplet is encapsulated by the polymer shell and contains a compound of formula (I) and optionally a carrier or diluent thereto. It can be prepared by a method with an additional polymerization step. Polymer shells can be prepared by multicondensation reactions or coacervation processes at the interface. This composition can be provided for controlled release of the compound of formula (I) and can be used for seed treatment. Compounds of formula (I) may be formulated in biodegradable polymerization matrices to provide controlled slow release of compounds of formula (I).
[706] The composition may include one or more additives to enhance the biological performance of the composition (eg, wetting, retention or distribution to the surface; resistance to ratio on the treated surface; or of the compound of formula (I) By improving absorption or motility). Such additives include spray additives based on surface active substances, such as certain mineral oils or oils such as natural plant oils (such as soybean and rapeseed seed oils), and these and other bio-enhancing aids (compounds of formula (I)) Combinations of ingredients that assist or modulate action).
[707] The compound of formula (I) is a powder composition comprising powder (DS), water soluble powder (SS) or water dispersible powder (WS) for slurry treatment, or flow concentrate (FS), solution ( LS) or a liquid composition comprising capsule suspension (CS) and may be formulated for seed treatment. The preparation of the DS, SS, WS, FS and LS compositions is similar to the preparation for the DP, SP, WP, SC and DC compositions described above, respectively. The composition for treating seed may comprise a reagent that helps the composition adhere to the seed (eg mineral oil or film-forming barrier).
[708] Wetting agents, dispersants and emulsifiers may be SFAs of the surface cationic, anionic, zwitterionic or non-ionic type.
[709] Suitable SFAs of the cationic type include quaternary ammonium compounds (eg cetyltrimethyl ammonium bromide), imidazolines and amine salts.
[710] Suitable anionic SFAs are alkali metal salts of fatty acids, salts of aliphatic mother esters of sulfuric acid (eg sodium lauryl sulfate), salts of sulfonated aromatic compounds (eg sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfo Acetate, butylnaphthalene sulfonate and a mixture of sodium di- isopropyl- and tri- isopropyl -naphthalene sulfonate), ether sulfates, alcohol ether sulfates (e.g. sodium laurate-3-sulfate), ether carboxylates (e.g. Reactions between, for example, sodium laurate-3-carboxylate), phosphate esters (one or more aliphatic alcohols and phosphoric acid (mainly mono-esters) or tetraoxide phosphoric acid (mainly di-esters), for example lauryl alcohol. And products from the reaction of tetraphosphoric acid; in addition, these products can be ethoxylated), supportosuccinimate, wave And a pin or pen up sulfonates, taurates and lignoceric sulfonate.
[711] Suitable SFAs of the zwitterionic type include betaine, propionate and glycinate.
[712] Suitable SFAs of the non-ionic type are alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with fatty alcohols (oleyl alcohol or cetyl alcohol), or alkylphenols (octylphenol, nonylphenol). Or condensation products), such as octylcresol; Partial esters derived from long chain fatty acids or hexyl anhydrides; Condensation products of such partial esters with ethylene oxide; Block polymers (including ethylene oxide and propylene oxide); Alkanolamides; Simple esters (eg fatty acid polyethylene glycol esters); Amine oxides (eg lauryl dimethyl amine oxide); And lecithin.
[713] Suitable dispersants include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
[714] The compounds of formula (I) may be applied by any known means of applying insecticides or fungicide compounds. For example, a compound of formula (I) may be present in a parasite or in a lesion of a parasite (such as in a parasite's habitat or a cultivated plant susceptible to infection by a parasite) or in a portion of a plant comprising the mouth, stem, branch or root, It can be applied, formulated or unformulated, or sprayed, sprinkled or buried directly on the seed before it is cultivated, or on any other medium in which the plant is being cultivated or to be cultivated (soil surrounding the roots, general soil, paddy or hydroponic systems). Or as a cream or paste formulation, as a gas, or through a distribution or addition of a composition (such as a granulated composition or a composition filled in a water-soluble bag) into a soil or aqueous environment.
[715] The compounds of formula (I) can be injected into plants or sprayed onto plants using electrodynamic spraying techniques or other low volume methods or applied by paper or air irrigation systems.
[716] Compositions used as aqueous preparations are generally supplied in the form of concentrates containing a high proportion of active substance and added to water before use. These concentrates may include DC, SC, EC, EW, ME, SG, SP, agent, WG, CS, withstand extended storage and are added to water after such storage for uniform time It is required that it be possible to maintain and apply it as conventional spray equipment. Such aqueous formulations may comprise varying amounts of the compound of formula (I) (eg 0.0001-10 wt%), depending on the purpose used.
[717] The compound of formula (I) can be used as a mixture with fertilizers (nitrogen-, sodium- or phosphoric acid-containing fertilizers). Suitable formulation forms include granules of fertilizers. The mixture suitably contains up to 25% by weight of the compound of formula (I).
[718] The present invention therefore provides a fertilizer composition comprising a fertilizer and a compound of formula (I).
[719] Compositions of the present invention may include other compounds having biological activity, such as micronutrients or compounds having similar or supplemental fungicidal activity or having plant growth control, herbicidal, insecticidal, nematicide or acaricide activity Can be.
[720] By including other fungicides, the resulting composition may have a broader spectrum of activity or a higher level of intrinsic activity than the compound of formula (I) alone. Furthermore, other fungicides may have a synergistic effect with the fungicidal activity of the compound of formula (I).
[721] The compound of formula (I) may be the only active ingredient of the composition or may be admixed with one or more additional active ingredients such as insecticides, fungicides, synergists, herbicides or plant growth regulators if necessary. Additional active ingredients; Provide compositions with increased retention in a broader spectrum of activity or lesions; Increase the activity or supplement the activity of the compound of formula (I) (eg, by increasing the rate of expression and overcoming repulsion); Or assist in overcoming resistance or preventing the onset of each component. The particular additional active ingredient depends on the use of the composition. Examples of suitable pesticides are:
[722] a) permethrin, cypermethrin, penvalrate, espenvalrate, deltamethrin, sihalothrin (particularly lambda-cyhalothrin), bifenthrin, phenpropatrine, cyfluthrin, tefluthrin , Fish-safe pyrethroids (e.g. etofenprox), natural pyrethrins, tetramethrins, s-bioalltrins, fenfluthrins, praletins or 5-benzyl-3-furylmethyl- ( E )- Pyrethroids such as (1R, 3S) -2,2-dimethyl-3- (2-oxothioran-3-ylidinmethyl) cyclopropane carboxylate;
[723] b) propenops, sulfpropos, acetate, methyl parathion, azinfos-methyl, dimethone-s-methyl, dimethoate, phosphamidone, malathion, clopyriphos, posalon, terbufos, Organic phosphates such as pensulfothione, phonophos, forrate, poultice, pyrimifos-methyl, pyrimifos-ethyl, phenythrothione, phosphthiazate or diazinone;
[724] c) pyrimikab, triamate, chloretocarb, cabofuran, furathiocarb, ethioponcarb, aldicarb, thiofurox, carbosulphan, bendiocarb, phenobucarb, propoxur, Carbamate (including aryl carbamate) such as metomil or oxamil;
[725] d) benzoyl ureas such as diflubenzuron, triflumuron, bexaflumuron, flufenoxuron or clofluazuron;
[726] e) organic tin compounds such as cyhexatin, fenbutatin oxide or azocyclotin;
[727] f) pyrazoles such as tebufenpyrad and fenpyroxamate;
[728] g) macrolides such as avermectin or milbamycin, for example abamectin, imamectin, benzoate, ivermectin, milbamycin, spinosad or azadirachtin;
[729] h) hormones and pheromones;
[730] i) organic chlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordan or dieldrin;
[731] j) amidines such as chlordemeform or amitraz;
[732] k) fumigants such as chloropicrine, dichloropropane, methyl bromide or metham;
[733] l) chloronicotinyl compounds such as imidacloprid, tiacloprid, acetamiprid, nitenpyram or tymethoxam;
[734] m) diacylhydrazines such as tebufenozide, chromafenozide or methoxyphenozide;
[735] n) diphenyl esters such as diophenollan or pyriproxyfen;
[736] o) indoxacarb;
[737] p) chlorphenapr; or
[738] q) pymetrozine.
[739] In addition to the pesticides of the main chemical classes listed above, other pesticides with specific targets may be used in the composition if they are suitable for the use of the desired composition. For example, pesticides that are selective for certain crops may be used, for example stem-perforated specific insecticides (such as cartops) or hopper-specific insecticides (such as buprofezin) used in rice. Alternatively, insecticides or acaricides specific for a particular insect species / step may also be included in the composition (eg, acaricides such as clofentezin, flubenzimin, hexiathiax or tetradipon (B) salzid motility inhibitors, such as dicopol or propazide; acaricides such as bromopropylate or chlorobenzylate; or hydramides, cyromazines, metoprene, chlorfluzuron or diflubenzuron Growth regulators).
[740] Examples of fungicides that may be included in the compositions of the present invention include the following; ( E ) -N -methyl-2- [2- (2,5-dimethylphenoxymethyl) phenyl] -2-methoxy-iminoacetamide (SSF-129), 4-bromo-2-cyano -N, N-dimethyl-6-trifluoromethyl-benzimidazole-1-sulfonamide, α- [N- (3-chloro-2,6-silyl) -2-methoxy-acetamido] -γ-butyrolactone, 4-chloro-2-cyano-N, N-dimethyl-5- p -tolylamidazole-1-sulfonamide (IKF-916, cyamidazole sulfamide), 3,5 -Dichloro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -4-methylbenzamide (RH-7281, Xoxamide), N-allyl-4,5-dimethyl-2- Trimethylsilylthiophene-3-carboxamide (MOn65500), N- (1-cyano-1,2-dimethylpropyl) -2- (2,4dichlorophenoxy) propionamide (AC382042), N- ( 2-methoxy-5-pyridyl) -cyclopropane carboxamide, acibenzolar (CGA245704), alanicab, aldimorph, aniazine, azaconazole, azoxystrobin, benalacyl, benomil, bilixazole , Bitteranol, blasticidine s, bromuconazole, burilime , Captapol, captan, carbendazim, carbendazim chlorhydrate, carboxycin, capropamide, carbon, CGA41396, CGA41397, quinomethionate, chlorothalonil, chlorozolinate, clozilacon, copper oxychloride, Copper-containing compounds such as copper oxyquinolate, copper sulfate, copper calate and Bordeaux mixtures, cymoxanyl, cyproconazole, cyprodinyl, devacarb, di-2-pyridyl disulfide, 1,1'-dioxide, Dichlorofluanide, diclomezin, dichloran, dietofencarb, dipeniconazole, dipfenquat, diflumetorim, O , O -di- iso -propyl- S -benzyl thiophosphate, dimefluazole , Dimethconazole, dimethomorph, dimethirimol, diconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodyne, doguardin, etifenforce, epoxyconazole, eti rimol, ethyl (Z) - N - benzyl - N ([ Tyl (methyl-thioethylideneaminooxycarbonyl) amino] thio) -β-alanineate, erythrazole, pamoxadon, phenamidone (RPA407213), phenarimol, fenbuconazole, fenfuram, fen Hexamid (KBR2738), fenpiclonyl, fenpropidine, fenpropmorph, fentin acetate, fentin hydroxide, perbam, perimezone, fluazinam, fludiocionyl, flumetober, fluoroimide , Fluquinonezol, flusilazole, flutoranyl, flutriazole, flute, fuberidazole, furalasil, furametpyr, guazatin, hexaconazole, hydroxyisoxazole, hismexazole, imazaryl , Imibenconazole, iminottadine, iminottadine triacetate, ipconazole, ifprobenfos, ifprodione, isprovalicab (SZX0722), isopropanyl butyl carbamate, isoprothiolane, casukamycin, curry Core-methyl, LY1860954, LY211795, LY248908, mancozeb, maneb, mefenoxam, penny Rim, pepeu a carbonyl, metal rasil, meth to Kona sol, methicillin person, methicillin Ram-zinc, methoxy Tomino host robin, non-close-butanone carbonyl, Meo Oh depleted, nickel dimethyl dithiocarbamate benzoate, nitro-de-isopropyl, press Ari Moles, OFURACE, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxokazole, oxycarboxycin, pepurazoate, fenconazole, phensaicuron, phenazine oxide, pocetyl- Al, Phosphoric Acid, Phthalide, Pexycithrobbin (ZA1963), Polyoxin D, Polyram, Probenazole, Prochloraz, Prosaimidone, Propanocarb, Propiconazole, Propineb, Propionic Acid, Pyrazo Phos, pyriphenox, pyrimethanyl, pyroquilon, proxypur, pipelintrine, quaternary ammonium compound, quinomethionate, quinoxyphene, quintogen, sipoconazole (F-155), sodium pentachlorofe Nate, spiroxamine, streptomycin, sulfur, tebuconazole, teclophthalam, technazen, Traconazole, thibendazole, ticlozamide, 2- (thiocyanomethylthio) benzothiazole, thiofamate-methyl, thiram, thymibenconazole, tlclofos-methyl, tolylufluoride, tri Adimefon, Triadimenol, Triazbutyl, Triazoside, Tricyclazole, Tridemorph, Trixystrobin (CGA279202), Triporin, Triflumizol, Triticonazole, Validamycin A, Bafam, Bin Clozoline, Geneve, and Giram.
[741] Compounds of formula (I) may be mixed with media that take root of soil, peat or other plants to protect the plants against seed-derived, soil-derived, or leaf fungal diseases.
[742] Examples of suitable synergists for use in the composition include piperonyl butoxide, sesamex, saproxane and dodecyl imidazole.
[743] Suitable herbicides and plant-growth regulators for inclusion in the composition depend on the desired target and the desired effect.
[744] An example of a rice selective herbicide that may be included is propanyl. An example of a plant growth regulator for use in cotton is PIX ™.
[745] Some mixtures may contain active ingredients that have significantly different physical, chemical and biological properties and are not easy to make into the same conventional formulation type. In this environment other formulation types may be prepared. For example, if one active ingredient is a water insoluble solid and the other is a water insoluble liquid, the solid active ingredient is dispersed as a suspending agent (using a recipe similar to that of SC), while the liquid active ingredient is dispersed as an emulsion. It is possible to disperse each active ingredient (using a recipe similar to that of EW) in the same continuous aqueous phase. The resulting composition is a suspo emulsion (SE) formulation.
[746] The present invention is illustrated by the following examples.
[747] Example 1
[748] This example illustrates the preparation of N- (4-chloro-3-methylisothiazol-5-yl)-(2-propylbenzotriazol-5-yl) acetamide (Compound No. A3.1).
[749] Step 1-Preparation of Methyl 4-aminophenolacetate
[750] 4-aminophenylacetic acid (100 g) was suspended in methanol (1000 ml) and passed through liquid hydrogen chloride to saturate the mixture. The mixture was heated at 50 ° C. for 2 hours and then left to cool to room temperature. The solvent was evaporated in vacuo and the residue was taken up in aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate and the filtrate was evaporated in vacuo to afford methyl 4-aminophenylacetate as a pale brown liquid.
[751] ¹ H NMR (CDCl ₃ ) δ ppm: 3.5 (s, 2H); 3.7 (s, 3H); 6.65 (m, 2H); 7.05 (m, 2H).
[752] Step 2-Preparation of Methyl 4-acetamido-3-nitrophenylacetate
[753] Methyl 4-aminophenylacetate (110 g, 0.667 mol) was added dropwise to acetic anhydride (600 ml) and the temperature of the reaction mixture was cooled down to 30 ° C by external cooling. Once addition was complete, the mixture was cooled to 10 ° C. or lower and concentrated nitric acid (85 ml) was added dropwise. When the addition of acid was complete, the mixture was left to warm to room temperature and water and ice poured into the mixture. The precipitated solid was collected by filtration and dried to give methyl 4-acetamido-3-nitrophenylacetate (120 g) as a pale yellow solid.
[754] ¹ H NMR (CDCl ₃ ) δ ppm: 2.3 (s, 3H); 3.65 (s, 2H); 3.7 (s, 3H); 7.55 (dd, 1 H); 8.1 (d, 1 H); 8.7 (d, 1 H); 10.3 (b, 1 H).
[755] Step 3-Preparation of Methyl 4-acetamido-3-aminophenylacetate.
[756] Methyl 4-acetamido-3-nitrophenylacetate (40 g, 0.159 mol) was dissolved in methanol (400 ml) and hydrogenated over 5% palladium on carbon catalyst at 5 atmospheres. The catalyst was removed by filtration and the filtrate was evaporated in vacuo to afford methyl 4-acetamido-3aminophenylacetate.
[757] Step 4-Preparation of methyl (benzotriazol-5-yl) acetate
[758] Methyl 4-acetamido-3-aminophenylacetate (77 g, 0.373 mole) was added to a mixture of acetic acid (210 ml) and water (210 ml) and cooled to below 5 ° C. A solution in water (200 ml) of sodium nitrite (38.63 g, 0.559 mol) is added dropwise and once the addition is complete the mixture is stirred for 4 hours and slowly warmed up to room temperature. The mixture was diluted with ethyl acetate and the insoluble material was removed by filtration. The filtrate was washed with brine, dried over anhydrous magnesium sulfate, filtered and the solvent was evaporated in vacuo to give a viscous residue (51 g) which was then dissolved in a solution of methanol (400 ml) previously saturated with hydrogen chloride and the mixture was stirred for 2 hours. Was stirred. The solvent was removed in vacuo and the residue was taken in water, neutralized with saturated aqueous sodium bicarbonate and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate and the filtrate was evaporated in vacuo to afford methyl 5-benzotriazole acetate as a red liquid (crystallized when left).
[759] ¹ H NMR (CDCl ₃ ) δ ppm: 3.7 (s, 3H); 3.8 (s, 2H); 7.35 (d, 1H); 7.8 (b, 2H);
[760] 13.6 (b, 1 H).
[761] Step 5-Preparation of methyl (2-propylbenzotriazol-5-yl) acetate.
[762] A solution of methyl 5-benzotriazoacetate (10 g, 0.0523 mol) in N , N -dimethylformamide was cooled in sodium hydride (dispersion in 60% oil, 2.3 g, 0.0575 mol) in N , N -dimethylformamide. (Ice bucket) was added dropwise to the suspension. When the addition was complete, the ice bucket was removed and the mixture was stirred for 1 hour. N -propyl iodide (9.78 g, 0.0575 mol) was added dropwise and once the addition was complete the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into ice / water and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate and the filtrate was evaporated in vacuo. The residue was further purified by column chromatography to give methyl (2-propylbenzotriazol-5-yl) acetate (4.8 g).
[763] ¹ H NMR (CDCl ₃ ) δ ppm: 0.9 (t, 3H); 2.1 (m, 2H); 3.7 (s, 3H); 3.8 (s, 2H);
[764] 4.65 (t, 2H); 7.3 (dd, 1H); 7.7 (d, 1H); 7.8 (d, 1H).
[765] Step 6-Preparation of (2-propylbenzotriazol-5-yl) acetic acid.
[766] Acetate (4.8 g, 0.0206 mol) prepared in step 5 above was dissolved in methanol (60 ml) and potassium hydroxide pieces (1.27 g, 0.0226 mol) were added. The mixture was refluxed for 2 hours, then cooled and the solvent was evaporated in vacuo. The residual solid was dissolved in water and extracted with diethyl ether. The aqueous solution was acidified to pH 1 by addition of dilute aqueous hydrochloric acid and extracted with ethyl acetate. The ethyl acetate extract was washed with brine, dried over anhydrous magnesium sulfate and the filtrate was evaporated in vacuo to give (2-propylbenzenetriazol-5-yl) acetic acid (3.6 g) as a colorless solid.
[767] Step 7
[768] The acid (0.438 g, 0.002 mole) prepared in step 6 was dissolved in dichloromethane (5 ml) and a drop of N , N -dimethyl formamide was added. Oxalyl chloride (0.307 g, 0.0022 mol) was added dropwise and the mixture was stirred at room temperature for 2 hours. The solvent was removed in vacuo, the residue was placed in xylene and added to a mixture of 5-amino-4-chloro-3-methylisothiazole (0.446 g, 0.003 mol) in xylene and heated at reflux for 2 hours. . The mixture was cooled to room temperature and the solvent evaporated in vacuo. The residue was taken up in ethyl acetate, washed in saturated aqueous sodium bicarbonate solution and brine order, dried over anhydrous magnesium sulfate and the filtrate was evaporated in vacuo. The residue was further purified by flash column chromatography eluting with 2: 1 hexanes: ethyl acetate to give the title compound (0.34 g) as a sandy solid.
[769] Example 2
[770] This embodiment is N - (4- chloro-3-methyl-5-yl) - N - (ethoxymethyl) - (2-propyl-benzotriazol-5-yl) acetamide (Compound No. A3. 6) and N- [2-ethoxymethyl-4-chloro-3-methylisothiazoline-5-ylidene]-(2-propylbenzo-triazol-5-yl) acetamide (Compound No. I3.6 Exemplification of the production.
[771] Lithium bis (trimethylsilyl) amide (1.0M solution in tetrahydrofuran, 3.3 ml, 0.0033 mol) dropwise in N- (4-chloro-3-methylisothiazole-5- in tetrahydrofuran (10 ml) To a solution of yl)-(2-propylbenzotriazol-5-yl) acetamide (Compound No. A3.1) (0.699 g, 0.002 mole) and once addition was complete the mixture was stirred at room temperature for 30 minutes. Chloromethylethyl ether (0.620 g, 0.0066 mol) was added and the mixture was stirred at rt for 2 h. The mixture was poured into water, neutralized and extracted with ethyl acetate. The organic extract was dried over anhydrous magnesium sulfate and the filtrate was evaporated in vacuo. 1 hexane: 2 by flash column chromatography of the residue was further purified by elution with ethyl acetate as an orange gum N - (4- chloro-3-methyl-5-yl) - N - (ethoxymethyl Methyl)-(2-propylbenzotriazol-5-yl) acetamide (0.135 g) and colorless solid, N- [2-ethoxymethyl-4-chloro-3-methylisothiane as melting point 108-109 ° C Zoline-5-ylidene]-(2-propylbenzo-triazol-5-yl) acetamide (0.128 g) was obtained.
[772] Example 3
[773] This example provides for the preparation of N- (4-chloro-3-methylisothiazol-5-yl) [2- (2-methylpropyl) indazol-5-yl] acetamide (Compound No. A6.145). To illustrate.
[774] Step 1-Preparation of 4-bromo-2-methylacetanilide
[775] Droplet of acetic anhydride (15.2ml, 0.16mol) dropwise to a stirred mixture in toluene (150ml) of 4-bromo-2-methylaniline (10.0g, 0.054mol) and sodium acetate (2.52g, 0.056mol) Added. Once the addition was complete the mixture was warmed to 85 ° C. and stirred for 40 minutes. The mixture was cooled to room temperature, diluted with ethyl acetate and washed with water. The organic solution was evaporated in vacuo and additional amount of toluene was added followed by evaporation of the solvent to give 4-bromo-2-methylacetanilide (12.3 g) as a colorless solid.
[776] Step 2-Preparation of 5-bromoindazole
[777] tert -butyl nitrite (8.24 g, 0.0181 mol) was added dropwise to a suspension of 4-bromo-methylacetanilide (12.3 g) in toluene (300 ml) at 65 ° C. over 30 minutes and the mixture was 65 minutes for 45 minutes. Stir at C and then stir at 90 C for 3 hours. The mixture was cooled to room temperature and the solvent provided in vacuo. The residue was purified by flash karum chromatography eluting with 2: 1 diethylether: hexanes to give 5-bromoindazole (4.12 g) as a sandy solid.
[778] ¹ H NMR (CDCl ₃ ): 7.27 (m, 1H); 7.40-7.54 (m, 2H); 7.94 (m, 1H);
[779] 8.06 (br, 1 H) ppm.
[780] Step 3-Preparation of 5-bromo-1- (2-methylpropyl) andazole and 5-bromo-2- (2-methylpropyl) indazole.
[781] Sodium hydride (80% suspension in oil, 0.7 g, 0.023 mol) is suspended in N, N -dimethylpromamide (DMF) (10 ml) followed by DMF (40 ml of 5-bromoindazole (4.1 g, 0.021 mol)). ) Solution was added dropwise over 30 minutes. Once the addition was complete the mixture was stirred for 75 minutes at ambient temperature and then 1-bromo-2-methylpropane (37 g, 0.027 mol) in DMF (25 ml) was added over 10 minutes. The mixture was stirred for 5 hours and then left overnight at ambient temperature. The mixture was poured into water, extracted with diethyl ether and then the organic extract was further washed with water, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash chromatography on silica gel eluting with 1: 1 diethyl ether: hexanes to give 5-bromo-1- (2-methylpropyl) indazole (2.67 g) and 5-bromo-2- (2-methylpropyl) indazole (1.49 g) was obtained as an orange oil, respectively.
[782] 5-bromo-1- (2-methylpropyl) indazole:
[783] ¹ H NMR (CDCl ₃ ) δ: 0.92 (d, 6H); 2.32 (m, 1H); 4.16 (d, 2H); 7.28 (m, 1H);
[784] 7.44 (m, 1 H); 7.86 (m, 1 H); 7.92 (s, 1 H) ppm.
[785] 5-bromo-2- (2-methylpropyl) indazole:
[786] ¹ H NMR (CDCl ₃ ) δ: 0.94 (d, 6H); 2.38 (m, 1H); 4.18 (d, 2H); 7.32 (m, 1H);
[787] 7.58 (m, 1 H); 7.82 (m, 2 H) ppm.
[788] Step 4-Preparation of ethyl [2- (2-methylpropyl) indazol-5-yl] acetate
[789] 5-bromo-2- (2-methylpropyl) indazole (1.41 g, 0.0056 mol) and palladium acetate (0.063 g, 0.00028 mol) were stirred in toluene (10 ml) under a nitrogen atmosphere. A 10% w / v solution of tri- tert -butylphosphine in ethyl trimethylsilyl acetate (2.35 ml, 0.0115 mol), potassium tert -butoxide (0.66 g, 0.059 mol) and toluene (0.97 ml, 0.00048 mol) was sequentially And the mixture was then heated to 90 ° C. for 105 minutes. The mixture was cooled to room temperature, diluted with ethyl ether, filtered through diatomaceous earth and the filtrate was evaporated in vacuo.
[790] The residue was purified by flash chromatography on silica gel eluting with 2: 1 diethyl ether: hexanes to give ethyl [2- (2-methylpropyl) indazol-5-yl] acetate (1.85 g) as a yellow oil. .
[791] ¹ H NMR (CDCl ₃ ) δ: 0.96 (d, 6H); 1.27 (t, 3H); 2.39 (m, 1H); 3.68 (s, 2H);
[792] 4.12-4.22 (m, 4H); 7.22 (m, 1H); 7.68 (m, 1H); 7.84 (s, 1H) ppm.
[793] Step 5-Preparation of N- (4-chloro-3-methylisothiazol-5-yl)-[2- (2-methylpropyl) indazol-5-yl] acetamide
[794] Sodium methoxide (0.42 g, 0.0078 mol) is added to a solution of 5-amino-4-chloro-3 -methylisothiazole (0.46 g, 0.0031 mol) in tetrahydrofuran (THF) (15 ml) and the mixture is added. Stir at ambient temperature for 15 minutes. A solution of ethyl [2- (2-methylpropyl) indazol-5-yl] acetate (0.80 g, 0.0031 mol) in THF was added dropwise, and once addition was complete, the mixture was stirred at ambient temperature for 3 hours. I was. The mixture was partitioned between ethyl acetate and saturated aqueous ammonium chloride solution and the organic extracts were dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo.
[795] Trituration of the residue with diethyl ether gave N- (4-chloro-3-methylisothiazol-5-yl)-[2- (2-methylpropyl) indazol-5-yl] acetamide (0.78 g) Was obtained as a pale-brown solid (melting point 133-135 ° C.).
[796] Example 4
[797] This embodiment is N - (4- chloro-3-methyl-5-yl) - N - (ethoxymethyl) - [2- (2-methylpropyl) indazol-5-yl] acetamide ( Compound No. A6.150) and N- [2-ethoxymethyl-4-chloro-3-methylisothiazoline-5-ylidene]-[2- (2-methylpropyl) indazol-5-yl) acet Illustrates the preparation of amides (Compound No. I6.102).
[798] N- (4-chloro-3-methylisothiazol-5-yl)-[2- (2-methylpropyl) indazol-5-yl] acetamide (0.50 g, 0.0014 mol) was diluted with dichloromethane (15 ml ) And the solution was cooled to 5 ° C. Chloromethyl ethyl ether (0.32 ml, 0.0035 mol), 50% aqueous sodium hydroxide solution (0.56 ml) and benzyltriethylammonium chloride (0.018 g) were added sequentially and the mixture was then stirred for 2 hours. The mixture was diluted with dichloromethane, washed with water, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was first purified by flash column chromatography on silica gel, eluting with 3: 1 diethyl ether: hexanes, then with diethyl ether, and finally with ethyl acetate to give N- (4-chloro-3-methylisothia -5-yl) - N - (ethoxymethyl) - [2- (2-methylpropyl) indazol-5-yl] - acetamide was obtained (0.16g) as a yellow oil N - [2-ethoxy Methyl-4-chloro-3-methylisothiazoline-5-ylidene]-[2- (2-methylpropyl) indazol-5-yl) acetamide (0.20 g) was added to a cream solid (melting point 105-106). C) was obtained.
[799] Example 5
[800] This example illustrates the pesticidal properties of the compound of formula (I). The activity of the samples of the individual compounds of formula (I) and mixtures of compounds of formula (I) was determined using various pests. Pests were treated with liquid compositions containing 500 parts by weight (ppm) of the compound. Each composition was prepared by dissolving the compound in an acetone and ethanol mixture (50:50 volume ratio) and diluting this solution with water containing 0.05% wetting agent, SYNPERONIC NP8, so that the liquid composition contained the compound in the required concentration.
[801] Examples of samples used are shown in Table 2.
[802]
[803]
[804] The test procedure adopted for each pest is basically the same: supporting a large number of pests on a common substrate, a host plant or a medium for feeding and eating, and treating one or both of the medium and pests with the composition. Include. Pest mortality is usually measured between 2-5 days after treatment.
[805] The results of the test on Peach Aphid ( Myzus persicae) are presented below. In this test, Chinese cabbage leaves were infected with aphids, infected leaves were sprayed with the test composition, and mortality was measured after 3 days. Results are expressed as mortality grades (scores) designated as 9, 5 or 0, where 9 represents 80-10% mortality, 5 represents 40-79% mortality and 0 represents less than 40% mortality.
[806] Samples 2, 13, 15, 19, 20, 30, 31, 32, 36, 37, 39, and 40 had a lethality of 9, respectively, while samples 8, 9, 11, 17, 29, 34, 35, and 38 Each was 5 lethality.
[807] In addition, in a similar test for 2-stained red mite ( Tetranychus uriticae ), samples 1, 8, 11, 12, 13, 17, 18, 19, 20 and 30 each had a mortality of 9 while samples 9 It was a fatality rate of five.
[808] Example 6
[809] This example shows the antimicrobial properties of the compound of formula (I). The compound has been tested for fungal diseases of the leaves of various plants. The technique used is as follows.
[810] The plants were grown in John Innes Potting Compost (1 or 2) in small 4 cm diameter, 3.5 cm deep bowls. Test samples were made as solutions in acetone or acetone / ethanol (1: 1 volume ratio) respectively, and the solution was diluted to 100 ppm with deionized water immediately before use (ie 1 mg of compound in the final 10 ml volume). When the leaf spray was applied to monocotyledonous crops, TWEEN 20 (0.1% by volume) was added. TWEEN is a registered trademark.
[811] Individual compounds of formula (I), or mixtures of compounds of formula (I), were applied as a Flor application (wherein chemical solutions were applied to the leaves of the test plant by spraying the plants with maximum droplet retention). .
[812] These tests are for vine plantsUncinula necator(UNCINE), for tomatoesPhytophthora infestans lycopersici(PHYTIN); For wheatPuccinia recondita(PUCCRT); And for ricePyricularia oryzae(PYRIOR) was performed.
[813] Each treatment was applied to two or more cloned plants for Phytophthora infestans lycopersici and Uncinula necator . For testing for Puccinia recondita and Pyricularia oryzae , two replication vessels containing 6-10 plants each were used for each treatment. Plants were inoculated one day before chemical application (Erad) or one day after (Prot). Phytophtora infestans lycopersici , Puccinia recondita and Pyricularia oryzae plants were inoculated with calibrated fungal spore suspensions. Uncinula necator plants were inoculated using the 'blowing' inoculation technique.
[814] After chemical application and inoculation, the plants were incubated under high humidity conditions and then placed in a suitable environment in which the infection progresses and ready to measure disease. The time between chemical application and measurement varies from 5 to 14 days depending on the disease and the environment. However, each individual disease was measured after the same time for all samples.
[815] Measurements were performed on two leaves each for each of the cloned plants for Phytophthora infestans lycopersici . Measurements were performed on one leaf of each cloned plant for Uncinula necator . Measurements for Puccinia recondita and Pyricularia recondita were performed collectively for the plants in each replication vessel.
[816] The level of disease present (ie the percentage of leaf area occupied by actively spore forming diseases) was measured visually. For each treatment, measurements for all replicates were averaged to provide mean disease values. Untreated control plants were measured in the same way. The data is then processed by a method described later to provide a PRCO (Percentage Reduction from Control).
[817] An example of a representative calculation is as follows:
[818] Mean disease level for Treatment A = 25%
[819] Mean disease level for untreated control = 85%
[820] PRCO = 100- ｛ Average disease level for A treatment } × 100
[821] 질병 Average disease level for untreated controls｝
[822] = 100- ( 25 × 100) = 70.6
[823] 85
[824] PRCO is then rounded up to the nearest integer; Therefore, in this particular example, the PRCO result is 71.
[825] It is possible to obtain a negative PRCO value.
[826] The PRCO results are shown in Table 3 below, where the sample numbers are as defined in Example 5.
[827]

权利要求:
Claims (12)
[1" claim-type="Currently amended] Compound of Formula (I):

[Wherein G is

or

In the formula, M^OneOr M²Is defective in A; n is 0 or 1; A is optionally substituted C_1-6Alkylene, optionally substituted C_2-6Alkenylene, optionally substituted C_2-6Alkynylene, optionally substituted C_1-6Alkyleneoxy, optionally substituted oxy (C_1-6Alkylene, optionally substituted C_1-6Alkylenethio, optionally substituted thio (C_1-6Alkylene, optionally substituted C_1-6Alkyleneamino, optionally substituted amino (C_1-6) Alkylene, optionally substituted [C_1-6Alkalineoxy (C_1-6) Alkylene], optionally substituted [C_1-6Alkylene thio (C_1-6) Alkylene], optionally substituted [C_1-6Alkylene sulfinyl (C_1-6) Alkylene], optionally substituted [C_1-6Alkylenesulfonyl (C_1-6) Alkylene] or optionally substituted [C]_1-6Alkyleneamino (C_1-6) Alkylene]; When G is (i), D is S, NR⁷, CR⁸= CR⁹, CR⁸= N, CR⁸= N (O), N = CR⁹Or N (O) = CR⁹; When G is (ii), D is S or NR⁷; E is N, N-oxide or CR¹⁰; M^OneIs OC (= Y), N (R¹¹C (= Y), N = C (OR¹²), N = (SR¹³) Or N = C (NR¹⁴R¹⁵) Or O or N is an atom attached to a ring containing D and E; M²Is N-C (= Y) and N is an atom attached to a ring containing D and E; Y is O, S or NR¹⁶; J is N or CR¹⁷; R^OneIs hydrogen, halogen, optionally substituted C_1-6Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_3-7Cycloalkyl, cyano, nitro or SF⁵; R²Is an optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or R¹⁸R¹⁹NS; R³, R⁴, And R⁵Is independently hydrogen, halogen, optionally substituted C_1-6Alkyl, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, cyano, nitro, optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkoxycarbonyl or SF⁵; R⁶Is hydrogen, cyano, optionally substituted C_1-20Alkyl, optionally substituted C_2-20Alkenyl (C_1-6Alkyl, optionally substituted C_2-20Alkynyl (C_1-6Alkyl, optionally substituted C_3-7Cycloalkyl, optionally substituted C_5-6Cycloalkenyl, formyl, optionally substituted C_1-20Alkoxycarbonyl, optionally substituted C_1-20Alkylcarbonyl, aminocarbonyl, optionally substituted C_1-20Alkylaminocarbonyl, optionally substituted di (C_1-20Alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbon Optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted Phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted C_1-20Alkylsulfonyl or optionally substituted arylsulfonyl; R⁷Silver c_1-6Alkyl; R⁸And R⁹Is independently hydrogen, halogen, cyano, nitro, optionally substituted C_1-6Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl or optionally substituted C_1-6Alkoxy; R¹⁰Is hydrogen, halogen, optionally substituted C_1-6Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, cyano, nitro, formyl, R²⁰ON = C (R²¹), Optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkoxycarbonyl or SF⁵; Or R^OneAnd R¹⁰Together with the atoms to which they are attached form a heterocyclic ring which may contain one or two heteroatoms selected from carbocyclic or O, N or S which is a 5, 6 or 7 membered saturated or unsaturated ring C_1-6Alkyl, C_1-6Optionally substituted by haloalkyl or halogen; R¹¹Is hydrogen, optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or R²²R²³NS; R¹²Is an optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, amino, optionally substituted C_1-6Alkylamino, optionally substituted di (C_1-6Alkylamino, optionally substituted phenoxycarbonyl, tri (C_1-4Alkylsilyl, aryldi (C)_1-4Alkylsilyl, (C_1-4Alkylalkylaryl or triarylsilyl; R¹³Is an optionally substituted C_1-10Alkyl, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10) Alkylaminocarbonyl or optionally substituted phenoxycarbonyl; R¹⁴And R¹⁵Is independently optionally substituted C_1-10Alkyl, optionally substituted C_1-6Alkoxy, optionally substituted [C_2-6Alkenyl (C_1-6) Alkyl], optionally substituted [C_2-6Alkynyl (C_1-6) Alkyl], optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-10Alkylcarbonyl, optionally substituted C_1-10Alkoxycarbonyl, formyl, optionally substituted C_1-10Alkylaminocarbonyl, optionally substituted di (C_1-10Alkylaminocarbonyl, hydroxy, amino, optionally substituted C_1-6Alkylamino, optionally substituted di (C_1-6) Alkylamino, or optionally substituted phenoxycarbonyl; R¹⁶Is hydrogen, cyano, nitro, optionally substituted C_1-6Alkyl, optionally substituted C_3-7Cycloalkyl, optionally substituted (C_2-6Alkenyl (C_1-6Alkyl, optionally substituted (C)_2-6Alkynyl (C_1-6Alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkoxycarbonyl, optionally substituted C_1-6Alkylamino, optionally substituted di (C_1-6Alkylamino, optionally substituted C_1-6Alkylcarbonylamino, optionally substituted C_1-6Alkoxycarbonylamino, optionally substituted C_1-6Alkoxy, optionally substituted C_1-6Alkylthio, optionally substituted C_1-6Alkylsulfinyl, optionally substituted C_1-6Alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or C_1-6Acyloxy; R¹⁷Is hydrogen, halogen, nitro, cyano, optionally substituted C_1-8Alkyl, optionally substituted C_2-6Alkenyl, optionally substituted C_2-6Alkynyl, optionally substituted C_3-7Cycloalkyl, optionally substituted C_1-6Alkoxycarbonyl, optionally substituted C_1-6Alkylcarbonyl, optionally substituted C_1-6Alkylaminocarbonyl, optionally substituted di (C_1-6) Alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R¹⁸And R¹⁹Is Independently, optionally substituted C_1-6Alkyl or R¹⁸And R¹⁹May contain one or two or more heteroatoms selected from O, N or S together with the N atoms to which they are attached_1-6To form a 5, 6 or 7 membered heterocyclic ring which may be optionally substituted by an alkyl group; R²⁰Is hydrogen, optionally substituted phenyl, optionally substituted phenyl (C_1-4Alkyl or optionally substituted C_1-20Alkyl; R²¹Is hydrogen, optionally substituted phenyl or optionally substituted C_1-6Alkyl; And R²²And R²³Is independently an optionally substituted C_1-6Alkyl or R²²And R²³May contain one or two or more heteroatoms selected from O, N or S together with the N atoms to which they are attached_1-6To form a 5, 6 or 7 membered heterocyclic ring which may be optionally substituted by an alkyl group.
[2" claim-type="Currently amended] Compound of Formula (IA):

[Wherein A, G, J, R ³ , R ⁴ , R ⁵ and R ⁶ are as defined in claim 1.
[3" claim-type="Currently amended] When G is (i) as defined in claim 1, D is S or CR ⁸ = CR ⁹ , wherein R ⁸ and R ⁹ are independently hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkylC _2-6 alkenyl, C _1-6 alkynyl, C _1-6 alkoxy or C _1-6 haloalkoxy; when G is (ii) as defined in claim 1, then D is S; E is N or CR ¹⁰ where R ¹⁰ is hydrogen, halogen, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkoxy (C _{1- 6} ) alkyl, C _1-6 alkylthio SF ₅ ; Or R ¹ and R ¹⁰ together with the atoms to which they are attached form a benzene ring optionally substituted with C _1-6 alkyl, C _1-6 haloalkyl or halogen; M ¹ is N (R ¹¹ ) C (═O) wherein R ¹¹ is hydrogen, C _1-6 alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, benzyloxymethyl or benzoyloxymethyl A compound of formula (I) according to claim 2 or a compound of formula (IA) according to claim 2.
[4" claim-type="Currently amended] A compound of formula (I) according to claim 1 or 3 or a formula according to _claim 2, wherein A is C _1-4 alkylene, —C (O) — or C _1-4 alkyleneoxy Compound of (IA).
[5" claim-type="Currently amended] A compound of formula (I) according to claim 1, 3 or 4 wherein G is (i) as defined in claim 1 and n is 0 or a compound of formula (IA) according to claim 2, 3 or 4.
[6" claim-type="Currently amended] A compound of formula (I) according to claim 1, 3, 4 or 5 wherein R ³ , R ⁴ and R ⁵ are independently hydrogen, C _1-3 alkyl or halogen or a formula according to 2, 3, 4 or 5 Compound of (IA).
[7" claim-type="Currently amended] R ⁶ is C _1-10 alkyl or C _1-10 haloalkyl (each is C _1-6 alkyloxime, C _1-6 haloalkyloxime, C _1-6 alkylhydrazone or C _1-6 haloalkylhydrazone group Or C _1-6 cyanoalkyl, C _2-6 alkenyl (C _1-6 ) alkyl, C _2-6 alkynyl (C _1-6 ) alkyl, C _3-7 cycloalkyl , C _3-7 halocycloalkyl, C _3-7 cyanocycloalkyl, C _1-3 alkyl (C _3-7 ) cycloalkyl, C _1-3 alkyl (C _3-7 ) halocycloalkyl, C _{5- 6} cycloalkenyl, C _3-7 cycloalkyl (C _1-6 ) alkyl, C _5-6 cycloalkenyl (C _1-6 ) alkyl, C _2-6 haloalkenyl (C _1-6 ) alkyl, C _1-6 cyanoalkenyl (C _1-6 ) alkyl, C _1-6 alkoxy (C _1-6 ) alkyl, C _3-6 alkenyloxy (C _1-6 ) alkyl, C _3-6 alkynyloxy ( C _1-7 ) alkyl, aryloxy (C _1-6 ) alkyl, C _1-7 carboxyalkyl, C _1-6 alkylcarbonyl (C _1-6 ) alkyl, C _2-6 alkenylcarbonyl (C _{1 -6} ) alkyl, C _2-6 alkynylcarbonyl (C _1-6 ) alkyl, C _1-6 alkoxycarbonyl (C _1-6 ) alkyl, C _3-6 alkenyloxycarbonyl (C _1-6 Alkyl, C _3-6 alkynyloxycarbonyl (C _1-6 ) alkyl, aryloxycarbonyl (C _1-6 ) alkyl, C _1-6 alkylthio (C _1-6 ) alkyl, C _1-6 alkylsulfinyl ( C _1-6 ) alkyl, C _1-6 alkylsulfonyl (C _1-6) alkyl, aminocarbonyl (C _1-6 ) alkyl, aminocarbonyl (C _2-6 ) alkenyl, aminocarbonyl (C _2-6) alkynyl, C _1-6 alkyl, aminocarbonyl (C _1-6) alkyl, di (C _1-6) alkyl, aminocarbonyl (C _1-6) alkyl, C _1-6 alkylamino-carbonyl (C _1-6 ) alkenyl (C _1-6 ) alkyl, alkylaminocarbonyl (C _1-6 ) alkynyl (C _1-6 ) alkyl, di (C _1-6 ) alkylaminocarbonyl (C _{1 -6)} alkenyl (C _1-6) alkyl, di (C _1-6) alkyl, aminocarbonyl (C _1-6) alkenyl (C _1-6) alkyl, phenyl (optionally substituted by halo, nitro, cyano, C Optionally substituted with _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy, phenyl (C _1-4 ) alkyl wherein the phenyl groups are halo, nitro, cyano , Optionally substituted with C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy, phenyl (C _2-4 ) alkenyl (C _{1- 6} ) alkyl (wherein the phenyl group is (halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkylsulfonyl or C _1-6 haloalkoxy Optionally substituted with) heteroaryl (optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), heterocyclyl Wherein the heterocyclyl group is optionally substituted with halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy or C _1-6 haloalkoxy), heteroaryl (C _1-4) alkyl (wherein the heteroaryl group is selected from halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 alkylsulfonyl or C _1-6 Optionally substituted with haloalkoxy) or heterocyclyl (C _1-4 ) alkyl, wherein the heterocyclyl group is halo, nitro, cyano, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 Optionally substituted with alkoxy or C _1-6 haloalkoxy) Other compounds of formula (I) or compounds of formula (IA) according to 2, 3, 4, 5 or 6.
[8" claim-type="Currently amended] Wherein J is N or CR ¹⁷ wherein R ¹⁷ is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl, cyano, halogen or nitro (a formula according to claim 1, 3, 4, 5, 6 or 7) A compound of formula I) or a compound of formula (IA) according to claim 2, 3, 4, 5, 6 or 7.
[9" claim-type="Currently amended] (a) compounds of formula (II) when Y is oxygen

[Wherein D, E, R ¹ and R ¹¹ are as defined in claim 1
To the compound of formula (III)

[Wherein Y is oxygen and X ¹ is a leaving group and A, J, R ³ , R ⁴ , R ⁵ and R ⁶ are as defined in claim 1.
React with; or
(b) when Y is sulfur, a process comprising preparing a compound of formula (I) as defined in claim 1 wherein Y is oxygen using the method described in (a) and then reacting the compound with a sulfiding reagent A process for preparing the compound of formula (I) as claimed in claim 1.
[10" claim-type="Currently amended] Insecticidal, acaricidal, including an insecticidal, acaricidal, nematicidal, arachnid or fungicidally effective amount of a compound of formula (I) as claimed in claim 1 and an appropriate carrier or diluent thereto Mite, nematode, chelator or fungicidal composition.
[11" claim-type="Currently amended] A method of eradicating and controlling fungi comprising applying a bactericidal effective amount of a compound of formula (I) as claimed in claim 1 to a plant, seed of a plant, lesion or soil of a plant.
[12" claim-type="Currently amended] An insecticidal, acaricidal, nematicidal, chelating or a fungicidally effective amount of a compound of formula (I) as claimed in claim 1 is susceptible to attack by pests, pest lesions or pests. A method of exterminating and controlling insects, mites, nematodes or molluscs, comprising application to plants.

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同族专利:

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公开号 | 公开日

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KR100702064B1|2007-03-30|

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AR028821A1|2003-05-28|

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HU0201874A2|2002-09-28|

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CA2370265A1|2000-10-26|

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BR0009907A|2002-04-16|

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GT200000049A|2001-10-17|

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HU0201874A3|2002-12-28|

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AU3977200A|2000-11-02|

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NZ514948A|2003-05-30|

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PT1171437E|2004-03-31|

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CO5210890A1|2002-10-30|

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EG21945A|2002-04-30|

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EP1171437A1|2002-01-16|

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CN1351603A|2002-05-29|

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AT251621T|2003-10-15|

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EP1171437B1|2003-10-08|

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IL145962D0|2002-07-25|

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CN1156472C|2004-07-07|

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CN100509807C|2009-07-08|

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ES2208303T3|2004-06-16|

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CN1535966A|2004-10-13|

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PE20010254A1|2001-04-02|

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DE60005808D1|2003-11-13|

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DK1171437T3|2004-02-02|

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US7112553B1|2006-09-26|

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JP2002542244A|2002-12-10|

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DE60005808T2|2004-09-23|

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AU772298B2|2004-04-22|

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IL145962A|2007-07-24|

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WO2000063207A1|2000-10-26|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-04-20|Priority to GB9909062.3

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1999-04-20|Priority to GBGB9909062.3A

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2000-01-28|Priority to GB0002039.6

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2000-01-28|Priority to GB0002039A

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2000-04-04|Application filed by 돈 리사 로얄, 신젠타 리미티드

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2002-01-30|Publication of KR20020008392A

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2007-03-30|Application granted

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2007-03-30|Publication of KR100702064B1

优先权:

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申请号 | 申请日 | 专利标题

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GB9909062.3|1999-04-20|

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GBGB9909062.3A|GB9909062D0|1999-04-20|1999-04-20|Chemical compounds|

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GB0002039.6|2000-01-28|

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GB0002039A|GB0002039D0|2000-01-28|2000-01-28|Chemical compounds|