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    • 专利摘要:
    Described herein are novel pyrimidin-4-ones and pyrimidin-4-thione derivatives of formula (I). The novel compounds of the invention have plant-protective properties and are suitable for protecting plants from invasion by phytopathogenic microorganisms, in particular fungi. Formula I In the above formula, A is phenyl, thienyl (including all three isomers), thiazolyl, pyridyl or pyridazinyl; X is oxygen or sulfur; R 1 is hydrogen, halogen or trimethylsilyl; R 2 is hydrogen, halogen or trimethylsilyl; At least one of R 1 and R 2 is not hydrogen; R 3 is C 1 -C 8 alkyl, C 1 -C 8 unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy Alkenyl, C 1 -C 8 alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 6 alkoxy; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl; R 4 is unsubstituted or mono- to trisubstituted C 1 -C 8 alkyl, C 1 by C 3 -C 6 cycloalkyl, halogen, cyano, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy -C 8 alkenyl, C 1 -C 8 alkynyl; C 1 -C 4 alkoxy-C 1 -C 4 alkoxy; C 1 -C 4 alkoxy-C 1 -C 4 alkylthio; Nitro; -CO-C 1 -C 6 alkyl; C 3 -C 6 cycloalkyl; Or unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, cyano, nitro, amino, mono-C 1 -C 6 Alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylthio, phenyl or phenoxy, wherein the phenyl moiety is unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl , Mono- to tri-substituted by C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy).
    公开号:KR20010023894A
    申请号:KR1020007002578
    申请日:1998-09-10
    公开日:2001-03-26
    发明作者:발터하랄트
    申请人:한스 루돌프 하우스；노파르티스 아게；헨리테 브룬너；베아트리체 귄터；
    IPC主号:
    专利说明:

    New pyrimidin-4-one and pyrimidin-4-thione as fungicide as fungicides
    The present invention relates to novel pyrimidin-4-ones and pyrimidine-4-thione derivatives of the general formula (I) having pesticide activity, in particular fungicidal activity:
    In the above formula,
    A is phenyl, thienyl (including all three isomers), thiazolyl, pyridyl or pyridazinyl;
    X is oxygen or sulfur;
    R 1 is hydrogen, halogen or trimethylsilyl;
    R 2 is hydrogen, halogen or trimethylsilyl;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 1 -C 8 alkyl, C 1 -C 8 unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy Alkenyl, C 1 -C 8 alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 6 alkoxy; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted or mono- to trisubstituted C 1 -C 8 alkyl, C 1 by C 3 -C 6 cycloalkyl, halogen, cyano, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy -C 8 alkenyl, C 1 -C 8 alkynyl; C 1 -C 4 alkoxy-C 1 -C 4 alkoxy; C 1 -C 4 alkoxy-C 1 -C 4 alkylthio; Nitro; -CO-C 1 -C 6 alkyl; C 3 -C 6 cycloalkyl; Or unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, cyano, nitro, amino, mono-C 1 -C 6 Alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylthio, phenyl or phenoxy, wherein the phenyl moiety is unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl , Mono- to tri-substituted by C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy).
    The invention also relates to a process for the preparation of said compounds, to agricultural chemical compositions comprising at least one of said compounds as active ingredient and to the use of the active ingredient or composition, particularly as fungicide, for pest control in agriculture and horticulture. Compounds of formula (I) and optionally tautomers thereof can be obtained in the form of their salts. Since the compounds of formula (I) have one or more basic centers, they can form acid addition salts, for example. The acid addition salts are for example inorganic acids (e.g. sulfuric acid, phosphoric acid or hydrogen halides), organic carboxylic acids (e.g. acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid), hydroxycarboxylic acids (e.g. ascorbic acid, lactic acid, Malic acid, tartaric acid or citric acid) or benzoic acid or organic sulfonic acid such as methanesulfonic acid or p-toluenesulfonic acid. In combination with one or more acidic groups, the compounds of formula (I) may also form salts with bases. Suitable salts with bases are, for example, metal salts, typically alkali metal or alkaline earth metal salts such as sodium, potassium or magnesium salts, or ammonia or organic amines such as morpholine, piperidine, pipe Lolidine, mono-, di- or trialkylamine, typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or trihydroxyalkylamine, typically mono-, di- Or triethanolamine). If appropriate, corresponding internal salts may also be formed. Within the scope of the present invention, agrochemically acceptable salts are preferred.
    If asymmetric carbon atoms are present in the compound of formula I, these compounds are in optically active form. Due to the presence of a double bond, the compound can be obtained in the form [E] and / or [Z]. In addition, rotational disorder isomerism may occur. The present invention relates to pure isomers such as enantiomers and diastereomers, as well as all possible mixtures of isomers, for example mixtures, racemates or racemate mixtures of diastereomers.
    The general terms used above and below have the following meanings unless defined otherwise:
    Alkyl groups, by themselves or as structural components of other groups such as alkoxy, may be linear or branched, depending on the number of carbon atoms, typically methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, Tert-butyl, n-amyl, tert-amyl, 1-hexyl, 3-hexyl, 1-heptyl or 1-octyl.
    Alkenyl may be straight or branched alkenyl, for example allyl, metallyl, 1-methylvinyl, but-2-en-1-yl, 1-pentenyl, 1-hexenyl, 1-heptenyl or 1-jade It is understood to mean tenyl. Preferred alkenyl radicals contain 3 or 4 carbon atoms in the chain.
    Likewise, alkynyl can be straight or branched depending on carbon number, typically propargyl, but-1-yn-1-yl, but-1-yn-3-yl, 1-pentynyl, 1-hexynyl , 1-heptinyl or 1-octynyl. Preferred meaning is propargyl.
    Halogen and halo substituents are generally understood to mean fluorine, chlorine, bromine or iodine. Preference is given to fluorine, chlorine or bromine.
    Haloalkyl contains the same or different halogen atoms and is typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2- Trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.
    Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, depending on the ring size.
    Preferred compounds are compounds of formula I (subgroup A) wherein A is thienyl, including all three isomers.
    Within the scope of subgroup A, R 1 is hydrogen, fluorine, chlorine, bromine or iodine;
    R 2 is hydrogen, fluorine, chlorine, bromine or iodine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is unsubstituted or C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkoxy; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkyloxy substituted with one to trisubstituted by C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Unsubstituted or mono- to trisubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy) Preference is given to compounds of the formula (I) which are substituted to trisubstituted phenyl (subgroup B).
    Oh specific group within the scope of the group B is R 3 is unsubstituted or C 3 -C 4 cycloalkyl, fluorine, chlorine, bromine or C 1 -C 4 alkoxy mono- to tri-substituted by C 1 -C 6 alkyl , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl; OC 1 -C 6 alkyl; OC 2 -C 6 alkenyl; OC 2 -C 6 alkynyl; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted C 3 -C 4 cycloalkyl, fluorine, chlorine, bromine or C 1 -C 4 alkoxy substituted with one to three alkenyl substituted C 1 -C 6 alkyl, C 2 -C 6 learned by, C 2 -C 6 alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Is a phenyl unsubstituted or mono- to tri-substituted by fluorine, chlorine or bromine) (subgroup C).
    Preferred groups within the scope of subgroup C are A is thienyl [2.3-d];
    X is oxygen;
    R 1 is hydrogen, chlorine or bromine;
    R 2 is hydrogen, chlorine or bromine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 3 -C 5 alkyl or OC 1 -C 4 alkyl;
    R 4 is C 2 -C 5 alkyl, or unsubstituted or fluorine, chlorine, bromine, C 1 -C 4 alkyl or phenoxy, wherein phenoxy is unsubstituted or mono- to trisubstituted by fluorine, chlorine or bromine Is a mono- or tri-substituted phenyl compound (subgroup D1).
    Another preferred group within the scope of subgroup C is A is thienyl [2.3-d];
    X is sulfur;
    R 1 is hydrogen, chlorine or bromine;
    R 2 is hydrogen, chlorine or bromine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 3 -C 5 alkyl or OC 1 -C 4 alkyl;
    R 4 is C 2 -C 5 alkyl, or unsubstituted or fluorine, chlorine, bromine, C 1 -C 4 alkyl or phenoxy, wherein phenoxy is unsubstituted or mono- to trisubstituted by fluorine, chlorine or bromine Is a mono- to trisubstituted phenyl compound (subgroup D2).
    Another preferred group within the scope of subgroup C is A is thienyl [3.2-d];
    X is oxygen;
    R 1 is hydrogen, chlorine or bromine;
    R 2 is hydrogen, chlorine or bromine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 3 -C 5 alkyl or OC 1 -C 4 alkyl;
    R 4 is C 2 -C 5 alkyl, or unsubstituted or fluorine, chlorine, bromine, C 1 -C 4 alkyl or phenoxy, wherein phenoxy is unsubstituted or mono- to trisubstituted by fluorine, chlorine or bromine Is a mono- or tri-substituted phenyl compound (subgroup E).
    Another preferred group of compounds of the invention is a compound of formula I (subgroup F) wherein A is pyridyl.
    Within the range of said group F, X is oxygen;
    R 1 is hydrogen, fluorine, chlorine, bromine or iodine;
    R 2 is hydrogen, fluorine, chlorine, bromine or iodine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is unsubstituted or C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl, unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkoxy ;
    R 4 is unsubstituted C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Unsubstituted or mono- to trisubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy) Preference is given to compounds of the formula (I) which are substituted to trisubstituted phenyl (subgroup G).
    Another preferred group of compounds of the invention is a compound of formula I (subgroup H) wherein A is phenyl.
    Within the range of said group H, X is oxygen;
    R 1 is hydrogen, fluorine, chlorine, bromine or iodine;
    R 2 is hydrogen, fluorine, chlorine, bromine or iodine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is unsubstituted or C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkoxy; NC 1 -C 6 alkyl or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Unsubstituted or mono- to trisubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy) Preference is given to compounds of the formula (I) (subgroup J1) which are substituted to trisubstituted phenyl.
    Another preferred group within the range of subgroups H is X is sulfur;
    R 1 is hydrogen, fluorine, chlorine or bromine;
    R 2 is hydrogen, fluorine, chlorine or bromine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is unsubstituted or C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl, unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkoxy ;
    R 4 is unsubstituted C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Unsubstituted or mono- to trisubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy) Is a substituted or trisubstituted phenyl compound of formula I (subgroup J2).
    Another preferred group of compounds of the invention is a compound of formula I wherein A is tazolyl (subgroup K).
    Within the range of said group K, X is oxygen;
    R 1 is hydrogen, fluorine, chlorine, bromine or iodine;
    R 2 is hydrogen, fluorine, chlorine, bromine or iodine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is unsubstituted or C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl, unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkoxy ;
    R 4 is unsubstituted C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Unsubstituted or mono- to trisubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy) Preference is given to compounds of the formula (I) which are substituted to trisubstituted phenyl (subgroup L).
    Another preferred group of compounds of the invention is a compound of formula (I) (subgroup M) wherein A is pyridazinyl.
    Within the range of said group M, X is oxygen;
    R 1 is hydrogen, fluorine, chlorine, bromine or iodine;
    R 2 is hydrogen, fluorine, chlorine, bromine or iodine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is unsubstituted or C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl, unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkoxy ;
    R 4 is unsubstituted C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Unsubstituted or mono- to trisubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy) Preference is given to compounds of the formula (I) which are substituted to trisubstituted phenyl (subgroup N).
    Compounds of formula (I) can be prepared by the following scheme 1:
    Compounds of formula (I) are prepared starting from an α-amino-β-carboalkoxy-heterocycle or an α-amino-β-carbocyclic acid heterocycle, some of which are Het is thienyl, commercially available. It is preferable (2 isomers). Methyl thiophene-2-amino-3-carboxylate is described, for example, in S. Gronowitz et al., Acta Pharm. Suecica 1968, Vol. 5, p. 563]. Other heterocycles can be prepared according to the instructions in the literature. For example, the synthesis of ethyl 5-aminothiazole-4-carboxylate and ethyl 5-amino-2-methylthiazole-4-carboxylate is described in Golankiewicz et al., Tetrahedron 1985, 41, 5989. It is described in. The reaction of an α-amino-β-carboalkoxyheterocycle or α-amino-β-carbocyclic acid heterocycle with an amide (R 4 CONHR 3 ) (step 1 of Scheme 1) may be a solvent (eg ClCH 2 CH 2). It is convenient to carry out in the presence of POCl 3 , SOCl 2 or SO 2 Cl 2 at a temperature ranging from room temperature to reflux in Cl, CHCl 3 , CH 2 Cl 2 , benzene, toluene, hexane, cyclohexane and the like. The resulting amidine (III) is spontaneously closed with pyrimidin-4-one, or at 20 ° C. to reflux temperature in a solvent (eg THF, dioxane, hexane, toluene, DMSO, DMF, dimethylacetamide, etc.) Treatment with a base (eg t-butyl-OK, NaH, KH, n-BuLi, NaOH, Na 2 CO 3, etc.) converts to the closed ring product. Substitution of the 4-one group with sulfur to the 4-thione group (step 3 of Scheme 1) is P 2 S 5 or Lawson-reagent from room temperature to reflux in tetrahydrofuran, dioxane or toluene as solvent. reaction with a reagent).
    This synthetic route is the first to describe a method for preparing a 3H-thieno [2.3-d] -pyrimidin-4-one derivative in the structural pattern of Formula (I) herein.
    Methods for preparing compounds of Formula I wherein R 1 and R 2 are both hydrogen are described in Chemical Scripta 1981, 18, 135, Synthesis 1977, 180, Chem. Pharm. Bull. 1989, 37,2122 and DE-OS-2411273.
    The invention also relates to intermediates of the formulas III, IV and V, in particular intermediates in which A is thienyl [2.3-d].
    The introduction of additional substituents into the 5-ring of thienopyrimidin-4-one will be convenient to carry out using organometallic methods. For example, thieno [3.2-d] pyrimidin-4-one and thieno [2.3-d] pyrimidin-4-one can be selectively deprotonated at position 6. Particularly suitable bases for this purpose are lithium diisopropylamide (LDA), lithium cyclohexylisopropylamide (LICA) or secondary butyl lithium / TMEDA. Most of the radicals R 1 or R 2 described above can be introduced by reacting the resulting anions with an electrophile, typically Br 2 , NBS, F 2 , ICl, Cl 2 , F + reagent, trimethylsilyl chloride (Scheme 2 Step 1).
    E + 1,2 are NBS (N-broxuccinimide), NCS (N-chlorsuccinimide), I 2 , Cl 2 , Br 2 , FCl, F + reagent, TMS and similar Si reagents.
    In addition, the following compounds can be generally prepared according to the method described in Scheme 2.
    Synthesis of Specific Thienopyrimidin-4-ones (Specific Methods of Introducing Halogen into the Thiophene Ring)
    a) thieno [2.3-d] pyrimidin-4-ones:
    a1)
    1-3 molar equivalents of N-bromosuccinimide or N-chlorosuccinimide (or Cl 2 gas or Br 2 ) are used for halogenation. The solvent used is for example pyridine at 0 ° C. to reflux temperature. The reaction time is 1 to 24 hours.
    a2)
    The reactions described above may optionally be cooled at room temperature or in the presence or absence of a suitable solvent or diluent or mixture thereof, or heated at about -20 ° C to the boiling point of the reaction medium, preferably from about -20 to about + 150 ° C. Accordingly in a closed vessel under pressure under an inert gas atmosphere and / or under dry conditions. Representative examples of such solvents or diluents are aromatic, aliphatic and cycloaliphatic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, chlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, Dichloroethane or trichloroethane); Ethers such as diethyl ether, tert-butylmethyl ether, tetrahydrofuran or dioxane; Ketones such as acetone or methyl ethyl ketone; Alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; Esters such as ethyl acetate or butyl acetate; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Nitriles such as acetonitrile; And sulfoxides such as dimethyl sulfoxide. Excess bases such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline can also be used as solvents or diluents. Suitable bases are, for example, alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal hydrides or alkaline earth metal hydrides, alkali metal amides or alkaline earth metal amides, alkali metal alkanolates or alkaline earth metal alkanolates, alkali metals. Carbonate or alkaline earth metal carbonate, alkali metal dialkylamide or alkaline earth metal dialkylamide, or alkali metal alkylsilylamide or alkaline earth metal alkylsilylamide, alkylamine, alkylenediamine, optionally N-alkylated, optionally unsaturated cycloalkylamine , Basic heterocycles, ammonium hydroxide and carbocyclic amines. Preferred examples include sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium carbonate, potassium tert-butanolate, potassium carbonate, lithium diisopropylamide, potassium bis (trimethylsilyl) amide, calcium hydride, triethyl Amines, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, N-methylmorpholine, Benzyltrimethylammonium hydroxide and 1,8-diazabicyclo [5.4.0] undec-5-ene (DBU).
    Compounds of formula (I) can be prepared by the following scheme 4:
    Wherein R 5 is C 1 -C 6 -alkyl.
    The amino carboxylic acid amide (VI) is reacted with orthoester (XIII) with heating in the presence or absence of a suitable solvent or diluent, optionally in the presence of an acid catalyst, at room temperature or at a temperature of, for example, about 20-200 ° C. Representative examples of solvents or diluents include ethers such as tertiary butylmethylether, tetrahydrofuran, dimethylether; Amides such as N, N-dimethylformamide or N-methyl-pyrrolidone; Sulfoxides such as dimethylsulfoxide and alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol. As the catalyst, hydrogen halide, methanesulfonic acid, trifluoromethyl acetic acid, p-toluenesulfonic acid and the like can be used in the absence of water. Commonly used bases are sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium hydride, potassium hydride, potassium carbonate and the like.
    Especially for thienopyrimidinone, Scheme 5 shows aminothiophene-carboxylic acid amides (VIa) and orthoesters (XIII) at temperatures ranging from 20 to 200 ° C., in the presence or absence of a solvent, optionally in the presence of an acid catalyst. Describe the reaction of The resulting intermediate (VIIa) is then halogenated at 20 ° C. to reflux temperature in the presence of a solvent. The halogenated intermediate (VIIIa) is then closed at 20 ° C. to reflux in the presence of a base, in the presence or absence of a suitable solvent. Halogenation reagents are typically N-bromosuccinimide, N-chlorsuccinimide, N-iosuccinimide, chlor gas, Br 2 , thionylchloride and the like. Preferred solvents used for halogenation are tert-butylmethylether, tetrahydrofuran, chloroform, methylenechloride, pyridine and quinoline.
    In the above formula,
    Hal + is NCS, NBS, NIS, Cl 2 , Br 2 , SO 2 Cl 2 ,
    Halogenated solvents are THF, TBME, CHCl 3 , CH 2 Cl 2 , pyridine, quinoline and the like.
    Another method is described in Scheme 6, wherein amino-carboalkoxy-thiophene (IIa) is reacted with orthoester (XIII) to give intermediate (IXa) and then compound (IXa) to amidine (IIIa) It is converted to ring closure to thienopyrimidinone (X). Halogenation of X to yield compound (I.1) is as described in Scheme 3.
    Wherein R 6 is C 1 -C 8 -alkyl.
    The reaction conditions from compound (IIa) to compound (IXa) are as described in Scheme 4 or 5, and the ring closure from compound (IIIa) to compound (X) is as described above. The reaction from compound (IXa) to compound (IIIa) requires, for example, tetrahydrofuran, N, N-dimethylformamide, or the like as a solvent at a temperature in the range of 0 ° C to reflux temperature.
    Scheme 7 describes the reaction of compound (IIa) with orthoester (XIII) to yield intermediate (IXa) and then conversion to intermediate (IIIa) to halogenate with thiophene (XIa). Compound (I.1) is obtained by ring closure of compound (XIa).
    Wherein R 6 is C 1 -C 8 -alkyl.
    The reaction conditions described in Method 4 are the same as those described in Scheme 4, 5 or 6.
    Scheme 8 describes another route comprising reacting compound (IIa) with orthoester (XIII) to yield intermediate (IXa) and then halogenating to intermediate (XIIa) to convert to thiophene (XIa). The ring closure of compound (XIa) affords the final product (I.1). The reaction conditions are the same as described in Schemes 4, 5, 6 and 7.
    Wherein R 6 is C 1 -C 8 -alkyl.
    Quinazolinones with fungicidal properties are known from WO-94 / 26722 or EP-A-276825 and thienopyrimidinones from WO-97 / 02262.
    Surprisingly, it has now been found that the novel compounds of formula (I) have a very advantageous range of activity which actually protects plants from diseases caused by fungi as well as bacteria and viruses.
    The compounds of formula (I) can be used in the agricultural or related fields as active ingredients for controlling plant pests. The novel compounds are characterized by good activity in low concentration applications, good resistance by plants and environmental safety. They have very useful curative, prophylactic and organizational properties and are used to protect many crops. Using the compounds of formula (I), the later growing plant parts are protected on, for example, phytopathogenic microorganisms, while on plant or plant parts (fruits, flowers, leaves, stems, tubers, roots) of various crops of useful plants. Pests can be suppressed or destroyed.
    The compounds of formula (I) are also used for the protection of fungal infections as well as phytopathogenic fungi occurring in the soil for the treatment of plant propagation substances, in particular seeds (fruits, tubers, granules) and plant cuttings (e.g. rice). It can be used as a thinner.
    The novel compounds of formula (I) include the following classes: Fungi imperfecti (e.g., Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alteraria, and Basidiomycetes (e.g. Rhizoctonia, Hemileia and Puccinia) Effective against phytopathogenic fungi They are also used in the Ascomycetes family (e.g., Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and especially Oh It is effective against the Mycetes family (e.g. Phytophthora, Pythium, Plasmopara). In addition, the novel compounds of formula (I) are effective against phytopathogenic bacteria and viruses such as Xanthomonas species, Pseudomonas species, Erwinia amylovora and tobacco mosaic viruses. .
    Target crops typically protected within the scope of the present invention typically include the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sugar cane and related species); Sugar beet (sugar beet and feed beet); Apples, nucleus and soft nucleus (eg apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); Leguminous plants (beans, lentils, peas, soybeans); Oil painting plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, peanuts); Cucumber plants (pumpkin, cucumber, melon); Fiber plants (cotton, flax, hemp, jute); Citrus fruits (orange, lemon, grapefruit, mandarin); Vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, paprika); Camphor (avocado, cassia, camphor) or plants such as tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, vine, hops, bananas and natural rubber plants, and edible plants.
    The compounds of formula (I) are usually used in the form of compositions and may be applied to crop parts or treated plants simultaneously or sequentially with further compounds. These other additional compounds may be fertilizers, micronutrient donors or other agents that affect plant growth. In addition, selective herbicides, as well as insecticides, fungicides, fungicides, nematicides, arachnids or some mixture of these agents may optionally be used with additional carriers, surfactants or application-promoting aids commonly used in the field of formulation. Can be used together
    Compounds of formula (I) may be mixed with other fungicides and in some cases may exhibit unexpected synergistic activity. Particularly preferred mixed components are azoles (e.g., azaconazole, bitertanol, propiconazole, diphenoconazole, diconazole, cyproconazole, epoxyconazole, fluquinconazole, flusilazole, flutriafol) Hexaconazole, imazaryl, imibenconazole, ifconazole, tebuconazole, tetraconazole, fenbuconazole, metconazole, michaelrobutanyl, perfurazoate, fenconazole, bromuconazole, Pyriphenox, prochloraz, triadimefon, triadimenol, triflumisol or triticazole; Pyrimidinyl carbinol (eg, animimidol, phenarimol or noarimol); 2-amino-pyrimidine (eg, volumerimate, dimethymol or etirimol); Morpholines such as dodemorph, fenpropidine, phenpropimod, spiroxamine or tridemorph; Anilinopyrimidines (eg, cyprodinyl, pyrimethanyl or mepanipyrim); Pyrrole (eg fenpiclonyl or fludioxonil); Phenylamides such as benalacyl, furalacyl, metallacyl, R-metallaxyl, opracese or oxadixyl; Benzimidazoles such as benomil, carbendazim, devacarb, fuberidazole, or thibendazole; Dicarboximide (eg, clozolinate, diclozoline, iprodine, michaelozoline, prosaimidone or vinclozoline); Carboxamides such as carboxycin, fenfuram, flutolanyl, mepronyl, oxycarboxycin or tifluzamide; Guanidines (eg guazin, dodine or iminottadine); Strobiliurine (e.g. azoxystrobin, cresoxime-methyl, metominostrobin, SSF-129 or 2- [α {[(α-methyl-3-trifluoromethyl-benzyl) imino] -oxy } -o-tolyl] -glyoxylic acid-methylester-O-methyloxime); Dithiocarbamates (eg, ferbam, mancozeb, manneve, metiram, propineb, tiram, geneb or ziram); N-halomethylthio-dicarboximide (eg, captapol, captan, diclofloanide, fluoromide, polpet or tolylufluoride); Copper compounds such as bordex mixtures, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or auxin-copper; Nitrophenol derivatives such as dinocap or nitrotal-isopropyl; Organophosphorus derivatives such as edifeneforce, ifprobenfos, isoprothiolane, phosphifene, pyrazophos or toclofos-methyl; And other compounds of varying structure, such as acibenzola-S-methyl, aniazine, blastetidine-S, cinnamethionate, chloroneve, chlorothalonil, cymoxanyl, diclones, diclomezin, Dichloran, dietofencarb, dimethomorph, dithianon, ethriazole, pamoxadon, fentin, perimzone, fluazinam, flusulfamid, phenhexamide, pocetyl-aluminum, hymexazole, Kasugamycin, Metasulfocarb, Pensaicuron, Phthalide, Polyoxine, Probenazole, Propamocarb, Pyroquilon, Quinoxyphene, Quintogen, Sulfur, Triazoside, Tricyclazole , Tripporin or validamycin).
    Preferred compounds for mixing with the above-mentioned mixing components are compounds of compound number 3.30.
    Another preferred compound for mixing with the above-mentioned mixing components is the compound of compound number 3.31.
    Another preferred compound for mixing with the above-mentioned mixing components is the compound of compound number 3.58.
    Another preferred compound for mixing with the above-mentioned mixing components is the compound of compound number 3.59.
    Suitable carriers and auxiliaries can be solid or liquid and are useful materials for the formulation technique, for example natural or regenerated inorganic materials, solvents, dispersants, wetting agents, tackifiers, thickening agents, binders or fertilizers. A preferred method of applying a compound of Formula 1, or an agrochemical composition comprising one or more of these compounds, is leaf application. The frequency of application and the rate of application depend on the risk of invasion by the corresponding pathogen. However, the compounds of formula (I) can penetrate plants through the roots (systemic action) through the soil by dipping plant parts in liquid formulations or by applying the compounds in soil (eg, in the form of granules) to the soil. have. For rice crops, these granules can be applied to soaked rice fields. The compounds of formula (I) can also be applied to seeds (coatings) by impregnating the seed or tuber into a liquid formulation of the fungicide or by coating them with a solid formulation.
    The compounds of formula (I) are used in unmodified form or preferably with adjuvant commonly used in the field of formulation. To this end, they are formulated by known methods, for example, into emulsifiable thickeners, coatable pastes, directly sprayable or dilutable liquids, diluents, wettable powders, soluble powders, dusting agents, granules and encapsulating agents in polymer materials. It is advantageous. With regard to the type of composition, the method of application, such as spraying, atomizing, dusting, spraying, coating or spinning, is selected according to the intended purpose and the usual environment.
    Advantageous application rates are usually from 5 g to 2 kg / ha, preferably from 10 g to 1 kg / ha, most preferably from 20 g to 600 g / ha of the active ingredient (a. I.). When used as seed soaking agents, convenient dosages are from 10 mg to 1 g / kg of seed active material.
    Formulations (i.e. compositions) comprising a compound of formula (I) and optionally a solid or liquid adjuvant are known methods, e.g., the compounds may be thickeners (e.g. solvents, solid carriers and optionally interfacial-active compounds (interfaces) Prepared by mixing homogeneously and / or polishing with the active agent)).
    Suitable carriers and auxiliaries may be solid or liquid and may correspond to materials conventionally used in formulation techniques, such as natural or recycled inorganic materials, solvents, dispersants, wetting agents, tackifiers, thickening agents, binders or fertilizers. have. Such carriers are described, for example, in WO97 / 33890.
    Additional surfactants commonly used in the formulation art are known to those skilled in the art or can be found in the literature.
    Agrochemical formulations typically comprise 0.1 to 99% by weight, preferably 0.1 to 95% by weight of the compound of formula I, 99.9% to 1% by weight, preferably 99.8% to 5% by weight of solid or liquid auxiliaries, And 0 to 25% by weight of surfactant, preferably 0.1 to 25% by weight. It may be desirable to formulate a commercial product as a concentrate, but end users typically use dilute formulations.
    The composition may also include additional auxiliaries such as stabilizers, antifoams, viscosity modifiers, binders or tackifiers as well as other fertilizers, micronutrient donors or other formulations for obtaining particular effects.
    The following non-limiting examples further illustrate the present invention described above. The temperature is given in degrees Celsius. The following abbreviations are used: Et is ethyl; i-propyl is isopropyl; Me is methyl and m.p. is the melting point. "NMR" is the nuclear magnetic resonance spectrum. MS is the mass spectrum. "%" Is% by weight unless the corresponding concentration is indicated in other units.
    Preparation Example:
    Example P-1: 2- (1-n-butyl-1-methoxymethyleneamino) thiophene-3-carboxylic acid propylamide
    In the distillation apparatus, a mixture of 1.84 g of 2-aminothiophene-3-carboxylic acid propylamide and 2.43 g of trimethyl orthovalerate is heated at 130 ° C. for 2 hours. Methanol produced during the reaction is distilled directly from the reaction flask. After cooling, the crude product is purified by column chromatography (eluent: hexane / ethyl acetate = 1: 2). Yield: 1.9 g of pure 2- (1-n-butyl-1-methoxymethyleneamino) thiophene-3-carboxylic acid propylamide; Melting point 68-70 ° C.
    Example P-2 5-chloro-2- (1-n-butyl-1-methoxymethyleneamino) thiophene-3-carboxylic acid propylamide
    In the sulfonated flask, 0.85 g of 2- (1-n-butyl-1-methoxymethyleneamino) thiophene-3-carboxylic acid propylamide is added to 10 ml of anhydrous pyridine under stirring. The internal temperature is then raised to 60 ° C. and 0.5 g of N-chlorosuccinimide (NCS) is added in two fractions. After stirring at 60 ° C. for 1 hour, pyridine is removed under water jet vacuum. The residue is taken up in ethyl acetate and the organic phase is washed twice with water. After drying the organic phase, the solvent is removed under a water jet vacuum and the raw material is purified by column chromatography on silica gel (eluent: hexane / ethylacetate = 3: 1). Yield: 0.6 g of 5-chloro-2- (1-n-butyl-1-methoxymethyleneamino) thiophene-3-carboxylic acid propylamide in the form of brown crystals; Melting point 110-112 ° C.
    Example P-3: 2-n-butyl-3-n-propyl-3H-thieno [2.3-d] pyrimidin-4-one
    In the sulfonated flask, 0.85 g of 2- (1-n-butyl-1-methoxymethyleneamino) -thiophene-3-carboxylic acid propylamide was dissolved in 20 ml of anhydrous THF and 0.15 g of about 55% NaH dispersion in small fractions. Is added. The mixture is stirred at room temperature for 15 minutes and at reflux temperature for 1 hour. The solvent is then removed under water jet vacuum and the residue is immersed in ethyl acetate. The organic phase is washed twice with water, the organic phase is dried over sodium sulfate and the solvent is removed under a water jet vacuum. The resulting crude product (yield: 0.8 g of 2-n-butyl-3-n-propyl-3H-thieno [2.3-d] -pyrimidin-4-one in brown liquid form) was subjected to halogenation without further purification. Can be used.
    Example P-4: 2-n-butyl-6-chloro-3-n-propyl-3H-thieno [2.3-d] pyrimidin-4-one
    In a sulfonated flask, 0.36 g of 5-chloro-2- (1-n-butyl-1-methoxymethyleneamino) thiophene-3-carboxylic acid propylamide is dissolved in 20 ml of dry THF and 0.085 g of about 55% NaH dispersion Is added in one fraction. The mixture is stirred at room temperature for 15 minutes and at reflux temperature for 1 hour. The solvent is then removed under water jet vacuum and the residue is immersed in ethyl acetate. The organic phase is washed twice with water, the organic phase is dried over sodium sulfate and the solvent is removed under a water jet vacuum. The resulting crude product is purified by column chromatography on silica gel (eluant: hexane / ethylacetate = 5: 1). Yield: 0.2 g of 2-n-butyl-6-chloro-3-n-propyl-3H-thieno [2.3-d] pyrimidin-4-one in the form of a slightly yellow powder; Melting point 67 to 69 ° C.
    Example P-3a: 2-n-butyl-3-n-propyl-3H-thieno [2.3-d] pyrimidin-4-one
    In a sulfonated flask, 11.0 g (70 mmol) of 2-amino-3-carbomethoxythiophene and 10.9 g (76 mmol) of valeric propylamide are added to 60 ml of 1,2-dichloroethane. 7 ml of phosphoroxychloride is slowly added dropwise under stirring at room temperature. After 3 hours at reflux temperature, the mixture is poured into ice water and adjusted slightly alkaline with sodium bicarbonate. The resulting mixture is then extracted three times with methylene chloride and the separated organic phase is dried over sodium sulfate. The solvent is then removed under a water-jet vacuum.
    In the sulfonated flask, the crude product is added to 100 ml of anhydrous tetrahydrofuran and, under stirring, 4.36 g (0.1 mol) of NaH in 50 ml of anhydrous THF is carefully added. After stirring at reflux for 2 hours, the solvent is removed under a water-jet vacuum and the residue is immersed in ethyl acetate / water. The aqueous phase is extracted with additional ethyl acetate. The organic phase is dried over sodium sulfate and the solvent is removed under water-jet vacuum. The crude product is purified by column chromatography on silica gel (eluant: TBME / hexane = 1: 2). 12.0 g of 2-n-butyl-3-n-propyl-3H-thieno [2.3-d] pyrimidin-4-one are obtained in the form of a yellow powder with a melting point of 70 to 72 ° C.
    Example P-4a: 2-n-butyl-6-chloro-3-n-propyl-3H-thieno- [2.3-d] pyrimidin-4-one
    In a sulfonated flask, 2.0 g (8 mmol) of 2-n-butyl-3-propyl-3H-thieno [2.3-d] pyrimidin-4-one are added to 15 ml of anhydrous pyridine with stirring. The internal temperature is then raised to 80 ° C. and 1.87 g (14 mmol) of N-chlorosuccinimide (NCS) are added in small fractions. After stirring at 90 ° C. for 3 hours, 1.0 g of NCS is added and the mixture is stirred at 90 ° C. for an additional 3 hours. Pyridine was removed under a water-jet vacuum, and the crude product thus obtained was purified by column chromatography on silica gel (eluant: n-hexane / 3 tert butylmethylether = 3: 1) to give 2-n-butyl-6. 0.9 g of -chloro-3-propyl-3H-thieno- [2.3-d] pyrimidin-4-one is obtained in the form of a beige powder having a melting point of 67 to 69 ° C.


























    Examples of specific formulation-combinations, for example wettable powders, emulsifiable thickeners, dusting agents, compressed granules, coated granules, solvents and suspending agent concentrates are described in WO97 / 33890.
    Biological Example: Fungicidal Activity
    Example B-1 Actions on False Collettricum lagenarium
    After a two week growth period, the cucumber plants are sprayed with an aqueous spray mixture (concentration 0.002%) prepared with a wettable powder formulation of the test compound, and after 2 days, infected with a fungal spore sac suspension (1.5 × 10 5 spores / ml) Incubate at 23 ° C. and high humidity for 36 hours. The incubation is then continued at normal humidity and 22 ° C. Assessment of fungal invasion is performed 8 days post infection.
    Compounds of Tables 1-7, preferably Compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171 , 4.36, 6.29, 7.6, 7.31 and 7.34 show good or excellent activity.
    Example B-2: Residual-Protective Action Against Venturia inaequalis on Apples
    Apple cuttings with a new sprig length of 10 to 20 cm are sprayed to a drip point with a spray mixture (0.02% a.i.) prepared with a wettable powder formulation of the test compound. After 24 hours the plants are infected with the fungal suspension of fungi. The plants are then incubated at 90-100% relative humidity for 5 days and placed in a greenhouse at 20-24 ° C. for a further 10 days. Assessment of fungal invasion is performed 12 days after infection.
    Compounds of Tables 1-7, preferably Compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118 , 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 show good activity.
    Example B-3: Action on Erysiphe graminis on barley
    a) residual-protective action
    Barley plants about 8 cm in height are sprayed to a drip point with a spray mixture (0.02% a.i.) prepared with a wettable powder formulation of the test compound and the treated plants are sprinkled with fungi conidia over 3-4 hours. Infected plants are placed in a greenhouse at 22 ° C. Evaluation of fungal infections is performed 12 days after infection.
    b) system action
    Barley plants about 8 cm in height are soaked in an aqueous spray mixture (0.002% a.i. based on soil volume) prepared in a wettable powder formulation of the test compound. Take care that the spray mixture does not come into contact with the growing part of the plant. After 48 hours, the treated plants are sprayed with fungi conidia. Infected plants are then placed in a greenhouse at 22 ° C. Assessment of fungal invasion is performed 12 days after infection.
    Compared to the control plants, the compounds of the formula 1 of Tables 1-7, for example compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, Invasion of plants treated with 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 is less than 20%.
    Example B-4: Action on Podosphaera leucotricha on Apple Sprigs
    Spray a new apple branch about 15 cm in length with a spray mixture (0.06% a.i.). The plants are infected 24 hours later with a fungal suspension of fungi and placed in a climatic chamber at 70% relative humidity and 20 ° C. Assessment of fungal invasion is performed 12 days after infection.
    The compounds of Tables 1-7 show good activity. The following compounds show particularly potent efficacy: 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118, 3.163 , 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 (0-5% invasion).
    Example B-5: Action on Plasmopara viticola on Vine
    a) residual-protective action
    Vine cuttings of the Chasselas variety are grown in greenhouses. In the tenth leaf, three plants are sprayed with a spray mixture (200 ppm a.i.). After the spray coating is dried, the plants are uniformly infected on the underside of the leaves with a fungal spore sac suspension. The plants are then kept in the wet chamber for 8 days, then significant signs of disease are observed on the control plants. The number and size of infected parts of untreated plants is considered as an indicator of the compound efficacy tested.
    b) healing action
    Vine cuttings of the Chasellas variety are grown in greenhouses, and the spore sac suspension of Plasmopara viticola is sprayed on the lower surface of the leaf at the 10th leaf. After 24 hours in the wetting chamber, the plants are sprayed with a spray mixture (200 ppm a.i.). The plants are then further maintained in the wet chamber for 7 days. At this time, the control plants show signs of the disease. The number and size of infected parts of untreated plants is considered as an indicator of the compound efficacy tested.
    Compounds of Tables 1-7, preferably Compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, 3.58, 3.59, 3.79, 3.117, 3.118 , 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 show good efficacy.
    Example B-6: Action on Uncinula necator on Vine
    Five week old vine cuttings are sprayed with a spray mixture (200 ppm a.i.) prepared as a wettable powder formulation of the test compound. After 24 hours, the plants are infected by conidia from strongly infected vine leaves shaken off the test plants. The plants are then incubated at 26 ° C. and 60% relative humidity. Assessment of fungal invasion is performed about 14 days after infection.
    Compared to control plants, the compounds of formula (I) of Tables 1-7, for example compounds 1.36, 2.30, 3.1, 3.6, 3.8, 3.15, 3.17, 3.26, 3.30, 3.31, 3.34, 3.36, 3.47, 3.52, 3.56, Invasion of plants treated with 3.58, 3.59, 3.79, 3.117, 3.118, 3.163, 3.171, 4.36, 6.29, 7.6, 7.31 and 7.34 is less than 20%.
    权利要求:
    Claims (17)
    [1" claim-type="Currently amended] Compounds of formula (I).
    Formula I

    In the above formula,
    A is thienyl, thiazolyl, pyridyl or pyridazinyl including all three isomers;
    X is oxygen or sulfur;
    R 1 is hydrogen, halogen or trimethylsilyl;
    R 2 is hydrogen, halogen or trimethylsilyl;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 1 -C 8 alkyl, C 1 -C 8 unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy Alkenyl, C 1 -C 8 alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 6 alkoxy; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted or mono- to trisubstituted C 1 -C 8 alkyl, C 1 by C 3 -C 6 cycloalkyl, halogen, cyano, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy -C 8 alkenyl, C 1 -C 8 alkynyl; C 1 -C 4 alkoxy-C 1 -C 4 alkoxy; C 1 -C 4 alkoxy-C 1 -C 4 alkylthio; Nitro; -CO-C 1 -C 6 alkyl; C 3 -C 6 cycloalkyl; Or unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, cyano, nitro, amino, mono-C 1 -C 6 Alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylthio, phenyl or phenoxy, wherein the phenyl moiety is unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl , Mono- to tri-substituted by C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy).
    [2" claim-type="Currently amended] 2. Compounds of formula I according to claim 1, wherein A is thienyl comprising all three isomers.
    [3" claim-type="Currently amended] The compound of claim 2, wherein R 1 is hydrogen, fluorine, chlorine, bromine or iodine;
    R 2 is hydrogen, fluorine, chlorine, bromine or iodine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is unsubstituted or C 3 -C 6 cycloalkyl, halogen or a substituted one by C 1 -C 4 alkoxy to trisubstituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkoxy; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted C 3 -C 6 cycloalkyl, halogen or C 1 -C 4 alkyloxy substituted with one to trisubstituted by C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is Unsubstituted or mono- to trisubstituted by fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy) A compound of formula I wherein substituted to trisubstituted phenyl.
    [4" claim-type="Currently amended] The C 1 -C 6 alkyl of claim 3, wherein R 3 is unsubstituted or mono- to trisubstituted by C 3 -C 4 cycloalkyl, fluorine, chlorine, bromine or C 1 -C 4 alkoxy, C 2- C 6 alkenyl, C 2 -C 6 alkynyl; OC 1 -C 6 alkyl; OC 2 -C 6 alkenyl; OC 2 -C 6 alkynyl; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted C 3 -C 4 cycloalkyl, fluorine, chlorine, bromine or C 1 -C 4 alkoxy substituted with one to three alkenyl substituted C 1 -C 6 alkyl, C 2 -C 6 learned by, C 2 -C 6 alkynyl; Or unsubstituted or substituted with fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, phenyl or phenoxy, wherein the phenyl moiety is A phenyl unsubstituted or monosubstituted to trisubstituted by fluorine, chlorine or bromine).
    [5" claim-type="Currently amended] The compound of claim 4, wherein A is thienyl [2.3-d];
    X is oxygen;
    R 1 is hydrogen, chlorine or bromine;
    R 2 is hydrogen, chlorine or bromine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 3 -C 5 alkyl or OC 1 -C 4 alkyl;
    R 4 is C 2 -C 5 alkyl, or unsubstituted or fluorine, chlorine, bromine, C 1 -C 4 alkyl or phenoxy, wherein phenoxy is unsubstituted or mono- to trisubstituted by fluorine, chlorine or bromine To phenyl mono- or trisubstituted.
    [6" claim-type="Currently amended] The compound of claim 4, wherein A is thienyl [2.3-d];
    X is sulfur;
    R 1 is hydrogen, chlorine or bromine;
    R 2 is hydrogen, chlorine or bromine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 3 -C 5 alkyl or OC 1 -C 4 alkyl;
    R 4 is C 2 -C 5 alkyl, or unsubstituted or fluorine, chlorine, bromine, C 1 -C 4 alkyl or phenoxy, wherein phenoxy is unsubstituted or mono- to trisubstituted by fluorine, chlorine or bromine To phenyl mono- or trisubstituted.
    [7" claim-type="Currently amended] The compound of claim 4, wherein A is thienyl [3.2-d];
    X is oxygen;
    R 1 is hydrogen, chlorine or bromine;
    R 2 is hydrogen, chlorine or bromine;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 3 -C 5 alkyl or OC 1 -C 4 alkyl;
    R 4 is C 2 -C 5 alkyl, or unsubstituted or fluorine, chlorine, bromine, C 1 -C 4 alkyl or phenoxy, wherein phenoxy is unsubstituted or mono- to trisubstituted by fluorine, chlorine or bromine To phenyl mono- or trisubstituted.
    [8" claim-type="Currently amended] 2. Compounds of formula I according to claim 1, wherein A is pyridyl.
    [9" claim-type="Currently amended] delete
    [10" claim-type="Currently amended] 2. Compounds of formula I according to claim 1, wherein A is thiazolyl.
    [11" claim-type="Currently amended] 2. Compounds of formula I according to claim 1, wherein A is pyridazinyl.
    [12" claim-type="Currently amended] A composition for controlling and preventing pests comprising the compound according to claim 1 as an active ingredient with a suitable carrier.
    [13" claim-type="Currently amended] Use of a compound of formula I according to claim 1 for protecting plants from invasion by phytopathogenic microorganisms.
    [14" claim-type="Currently amended] A method for controlling or preventing invasion of a cultivated plant by phytopathogenic microorganisms by applying the compound of formula (I) according to claim 1 to a plant, part thereof or a lesion thereof.
    [15" claim-type="Currently amended] The method of claim 14, wherein the phytopathogenic microorganism is a fungal organism.
    [16" claim-type="Currently amended] a) a step of using POCl 3 to the α- amino -β- carboalkoxy heterocycle of the general formula II in the presence of a solvent and R 4 CONHR 3 switch to the amidine of formula III;
    b) treating amidine with and without a solvent and with or without a base and ring closing to obtain a pyrimidin-4-one derivative of formula IV;
    c) pyrimidin-4-ones of the general formula (IV) by reacting the amino carboxylic acid amides of the following formula (VI) with orthoesters of the general formula (XIII) in the presence or absence of a solvent, at Obtaining a derivative; And
    d) when an intermediate of Formula VII is formed, treating the compound of Formula VII in the presence or absence of a solvent and in the presence or absence of a base and ring closing to obtain a pyrimidin-4-one derivative of Formula IV, Process for preparing the compound of formula I according to claim 1.






    In the above formula,
    R is hydrogen or C 1 -C 6 alkyl;
    R 1 , R 2 , R 3 , R 4 and A are as defined in claim 1;
    R 5 is C 1 -C 5 alkyl.
    [17" claim-type="Currently amended] Compound of Formula IIIa.

    In the above formula,
    A is thienyl [2.3-d] or thienyl [3.2-d];
    R 1 is hydrogen, halogen or trimethylsilyl;
    R 2 is hydrogen, halogen or trimethylsilyl;
    At least one of R 1 and R 2 is not hydrogen;
    R 3 is C 1 -C 8 alkyl, C 1 -C 8 unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy Alkenyl, C 1 -C 8 alkynyl; OC 1 -C 6 alkyl, OC 2 -C 6 alkenyl, OC 2 -C 6 alkynyl unsubstituted or mono- to trisubstituted by C 3 -C 6 cycloalkyl, halogen or C 1 -C 6 alkoxy; NC 1 -C 6 alkyl; Or N = CHC 1 -C 6 alkyl;
    R 4 is unsubstituted or mono- to trisubstituted C 1 -C 8 alkyl, C 1 by C 3 -C 6 cycloalkyl, halogen, cyano, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy -C 8 alkenyl, C 1 -C 8 alkynyl; C 1 -C 4 alkoxy-C 1 -C 4 alkoxy; C 1 -C 4 alkoxy-C 1 -C 4 alkylthio; Nitro; -CO-C 1 -C 6 alkyl; C 3 -C 6 cycloalkyl; Or unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, cyano, nitro, amino, mono-C 1 -C 6 Alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylthio, phenyl or phenoxy, wherein the phenyl moiety is unsubstituted or halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl Mono- to tri-substituted by C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy);
    R is hydrogen or C 1 -C 6 alkyl.
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    同族专利:
    公开号 | 公开日
    HU0002423A3|2001-02-28|
    AU9742998A|1999-04-05|
    HN1998000139A|1999-06-02|
    HU0002423A2|2000-11-28|
    AT216370T|2002-05-15|
    WO1999014202A3|1999-05-14|
    BR9812439A|2000-09-26|
    EP1015434A2|2000-07-05|
    EP1015434B1|2002-04-17|
    PL339053A1|2000-12-04|
    NZ503261A|2002-03-28|
    CA2301694A1|1999-03-25|
    JP2001516749A|2001-10-02|
    ES2175804T3|2002-11-16|
    GT199800142A|2000-03-02|
    WO1999014202B1|1999-06-17|
    KR100585571B1|2006-06-02|
    ZA9808336B|1999-02-12|
    AU743717B2|2002-01-31|
    DK1015434T3|2002-08-05|
    WO1999014202A2|1999-03-25|
    DE69804981T2|2002-11-28|
    TR200000713T2|2000-08-21|
    TW429254B|2001-04-11|
    CN1270593A|2000-10-18|
    AR015439A1|2001-05-02|
    EG22051A|2002-06-30|
    PT1015434E|2002-08-30|
    IL134779D0|2001-04-30|
    DE69804981D1|2002-05-23|
    US6277858B1|2001-08-21|
    GB9719411D0|1997-11-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-09-12|Priority to GBGB9719411.2A
    1997-09-12|Priority to GB9719411.2
    1998-09-10|Application filed by 한스 루돌프 하우스, 노파르티스 아게, 헨리테 브룬너, 베아트리체 귄터
    1998-09-10|Priority to PCT/EP1998/005790
    2001-03-26|Publication of KR20010023894A
    2006-06-02|Application granted
    2006-06-02|Publication of KR100585571B1
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB9719411.2A|GB9719411D0|1997-09-12|1997-09-12|New Pesticides|
    GB9719411.2|1997-09-12|
    PCT/EP1998/005790|WO1999014202A2|1997-09-12|1998-09-10|Novel pyrimidin-4-one and pyrimidin-4-thione as fungicide|
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