WO1999012892A1 - Acides d'alcene substitues et leurs derives - Google Patents

Acides d'alcene substitues et leurs derives Download PDF

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Publication number
WO1999012892A1
WO1999012892A1 PCT/EP1998/005406 EP9805406W WO9912892A1 WO 1999012892 A1 WO1999012892 A1 WO 1999012892A1 EP 9805406 W EP9805406 W EP 9805406W WO 9912892 A1 WO9912892 A1 WO 9912892A1
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Prior art keywords
cyano
alkyl
methyl
optionally
optionally substituted
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PCT/EP1998/005406
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German (de)
English (en)
Inventor
Dirk Backhaus
Peter Gerdes
Thomas Seitz
Martin Vaupel
Karl-Heinz Kuck
Astrid Mauler-Machnik
Klaus Stenzel
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Bayer Aktiengesellschaft
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Priority claimed from DE19829141A external-priority patent/DE19829141A1/de
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to EP98947455A priority Critical patent/EP1015420A1/fr
Priority to AU94369/98A priority patent/AU9436998A/en
Priority to JP2000510704A priority patent/JP2001518448A/ja
Publication of WO1999012892A1 publication Critical patent/WO1999012892A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/88—Hydrazones having also the other nitrogen atom doubly-bound to a carbon atom, e.g. azines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/40—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton

Definitions

  • the invention relates to new substituted alkene acids and their derivatives, processes for their preparation and their use as fungicides
  • alkoxyacrylic acid derivatives such as, for example, oudemansin, strobilurin A, strobilurin B and myxothiazole (cf. J Antibiot 33 (1980), 1474-1479, loc cit 33 (1980), 1480-1490, FEBS Lett 132 (1981) , 329-333, Tetrahedron Lett 34 (1993), 5151-5154; Nat. Prod Rep 10 (1993), 565-574) as well as melithiazole A and melithiazole B (cf. DE 4410449) inhibit the respiration of cells and antibiotic or have anti-fertilizing or antifungal properties
  • R 1 represents hydroxy, amino or in each case optionally substituted alkoxy, alkylamino, dialkylamino, arylalkoxy or arylalkylamino,
  • R 2 represents hydrogen, halogen or optionally substituted alkyl
  • R 3 represents hydrogen or optionally substituted alkyl
  • R 4 represents hydrogen or represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl
  • R 5 represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl
  • R 6 represents hydrogen or optionally substituted alkyl
  • Z stands for the grouping R 7 -N or the grouping (R 8 ) (R 9 ) C, where
  • R 7 for hydrogen, hydroxy, amino, in each case optionally substituted alkyl, alkoxy, alkylamino, dialkylamino, alkenyl, alkynyl, alkenyloxy, cycloalkyl, cycloalkyloxy, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylamino, aryl, aryloxy, arylamino, arylalkyl, arylalkoxy, Arylalkylamino, heterocyclyl, heterocyclylamino, heterocyclylalkyl or heterocyclylalkylamino, or one of the groupings below
  • a 1 represents hydrogen or alkyl
  • a 2 represents hydrogen, cyano or in each case optionally substituted alkyl, cycloalkyl or aryl, and
  • a 3 represents hydrogen or alkyl
  • R 8 stands for hydrogen or for optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, and
  • R 9 represents hydrogen or represents optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, where the previously known compounds [R *, S * - (E, E)] - (+ -) -3,5-dimethoxy-4-methyl-7-phenyl-2,6-heptadienamide [CAS Registry No. 153934- 17-9] and [R *, S * - (E, E)] - (+ -) -3,5-dimethoxy-4-methyl-7-phenyl-2,6-heptadienoic acid methyl ester [CAS-
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meaning given above,
  • R 7 has the meaning given above
  • R s and R 9 have the meaning given above,
  • R ' represents alkyl or aryl
  • R represents alkyl, alkoxy or aryl
  • R 1 , R 2 and R 4 have the meaning given above and
  • M represents lithium, sodium, potassium or a magnesium equivalent
  • the new substituted alkene acids according to the invention and their derivatives of the general formula (I) are notable for strong fungicidal activity
  • the compounds of the general formula (I) according to the invention, and also all the preliminary and intermediate products contain asymmetrically substituted carbon atoms and / or double bonds. They can therefore exist in various stereoisomeric forms.
  • the invention relates to all different possible stereoisomers (and optionally tautomeric) forms of the compounds outlined here by the general formulas individually and as isomer mixtures
  • saturated or unsaturated hydrocarbon chains such as alkyl, alkenyl or alkynyl, are also linked to heteroatoms, as in
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine
  • Cycloalkyl stands for saturated, carbocyclic, ring-shaped compounds which optionally form a polycyclic ring system with further carbocyclic, fused or bridged rings
  • Aryl stands for aromatic, mono- or polycyclic hydrocarbon rings, such as phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl
  • Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped
  • ring member is a heteroatom, ie an atom different from carbon, If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur.
  • the ring-shaped compounds optionally form with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems
  • the present application preferably relates to substituted alkene acids and their derivatives of the formula (I), in which
  • R 1 for hydroxy, amino, each optionally by cyano, halogen or
  • alkoxy C1-C4-alkoxy-substituted alkoxy, alkylamino or dialkylamino each having 1 to 6 carbon atoms in the alkyl groups, or for benzyloxy or, where appropriate, substituted by halogen or Ci-Cz ⁇ -alkyl
  • R 2 represents hydrogen, halogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by halogen,
  • R 3 represents hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C1-C4-alkoxy
  • R 4 for hydrogen, for alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C ] -C4-alkoxy, for each alkenyl or alkynyl with 2 to 6 carbon atoms optionally substituted by cyano or halogen, or for each optionally substituted by cyano
  • R 5 for hydrogen, for alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy, for each alkenyl or alkynyl optionally substituted by cyano or halogen each with 2 to 6 carbon atoms, or for each optionally substituted by cyano , Halogen or C] -C4-alkyl substituted cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms in the cycloalkyl group and optionally
  • R 6 represents hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C1-C4-alkoxy, and
  • R 7 represents hydrogen, hydroxy, amino, each alkyl, alkoxy, alkylamino or dialkylamino, each optionally substituted by cyano, halogen or C1-C4alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, each alkenyl optionally substituted by cyano or halogen, Alkenyloxy or alkynyl, each with 2 to 6 carbon atoms in the alkenyl or alkynyl groups, for cycloalkyl, cycloalkyloxy, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy or cycloalkylalkylamino, each with 3 to 6, each optionally substituted by cyano, halogen or C1-C4alkyl
  • Phenyl, phenoxy or phenylthio (where the phenyl groups are each optionally substituted by cyano, halogen, C1-C4-alkyl, C ] -C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy) substituted and / or benzene-fused heterocyclyl, Heterocyclylamino, heterocyclylalkyl or heterocyclylalkylamino, each with 3 to 7 ring members in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl part, the heterocyclyl group in each case 1 to 3 identical or different heteroatoms (1 to 3 for nitrogen atoms and / or 1 or 2 oxygen - or sulfur atoms), or (R 7 ) for one of the following groupings
  • a 1 represents hydrogen or alkyl having 1 to 6 carbon atoms
  • a 3 represents hydrogen or alkyl having 1 to 6 carbon atoms
  • R 8 for hydrogen, for alkyl with 1 to 10 carbon atoms optionally substituted by cyano, halogen or CJ-C4-alkoxy, for optionally by
  • Cyano or halogen substituted alkenyl with 2 to 10 carbon atoms for each cycloalkyl or cycloalkylalkyl with 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part optionally substituted by cyano, halogen or C ] -C4-alkyl, or for each optionally by nitro, cyano, halogen, C1-C4-alkyl,
  • C 1 -C 4 haloalkyl C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 4 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C] -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 -Alkylsulfonyl, C ⁇ -C4-haloalkylsulfonyl or C1 -C4- Alkoximino-C ⁇ -C4-alkyl substituted aryl or arylalkyl having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, and
  • R 9 for hydrogen, for optionally substituted by cyano, halogen or C1-C4-alkoxy alkyl having 1 to 10 carbon atoms, for optionally substituted by cyano or halogen alkenyl having 2 to 10 carbon atoms, each optionally substituted by cyano, halogen or -C -C4 -Alkyl-substituted cycloalkyl or cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, or for each optionally by nitro, cyano, halogen, CJ-C4- alkyl, -C-C4-haloalkyl, CJ-C4 - Alkoxy, -C-C4-haloalkoxy, -C-C4-alkylthio, C ⁇ -C4-haloalkylthio, C ⁇ -C4-alkylsulfiny
  • the invention relates in particular to substituted alkene acids and their derivatives of the formula (I) in which
  • R 1 for hydroxy, amino or in each case optionally through cyano, fluorine, chlorine,
  • R 2 represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine and / or chlorine,
  • R 3 represents hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl alkyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
  • R 4 for hydrogen, for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, for each optionally by cyano, fluorine or chlorine-substituted ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, or represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl,
  • R 5 for hydrogen, for each methyl, ethyl, n- or i-propyl, n-, i-, s- which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy or t-butyl, for in each case optionally substituted by cyano, fluorine or chlorine, ethenyl, propenyl, butenyl, ethynyl, propynyl or butinyl, or for in each case optionally substituted by cyano, fluorine, chlorine, methyl or ethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
  • R 6 stands for hydrogen or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and
  • R 7 for hydrogen, hydroxy, amino, for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, for in each case optionally substituted by cyano, fluorine or chlorine, ethenyl, propenyl, butenyl, propenyloxy, butenyloxy, ethynyl, propynyl or butynyl, for cyclopropyl, cyclo
  • a 1 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
  • R 8 for hydrogen, for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy - or t-pentyl, for each optionally by cyano,
  • R 9 for hydrogen, for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s, which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy - or t-pentyl, for ethenyl, propenyl, butenyl or pentyl, each optionally substituted by cyano, fluorine, chlorine or bromine, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, each optionally substituted by cyano, fluorine, chlorine, methyl or ethyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl,
  • R 1 represents methoxy or methylamino
  • R 2 represents hydrogen, chlorine or methyl
  • R 3 represents methyl or ethyl
  • R 4 represents hydrogen, methyl or ethyl
  • R 5 represents hydrogen, methyl or ethyl
  • R 6 represents hydrogen
  • Z stands for the grouping R 7 -N, in which
  • R 7 for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, each optionally by cyano, Fluorine or chlorine substituted ethenyl, propenyl, butenyl, propenyloxy, butenyloxy, ethynyl, propynyl or butynyl, for each cyclopentyl, cyclohexyl, cyclopentyloxy
  • Majorylamino is, benzo lacnzo lacmethyl, isobenzo colryl, benzothienyl, benzothienylamino, benzothienylmethyl, pyrrolyl, indolyl, oxazolyl, o
  • R 7 has, for example, the meanings given in the list below:
  • 2,6-dichlorobenzyl 2-methyl-benzyl, 4-methyl-benzyl, 2-chloro-6-methyl-benzyl, 2,6-dimethyl-benzyl, 2-trifluoromethyl-benzyl, 3-trifluoromethyl-benzyl, 4-trifluoromethyl-benzyl, 2-methoxy-benzyl, 3-methoxy-benzyl, 4-methoxy-benzyl, 2-trifluoromethoxy-benzyl, benzyloxy, benzylamino, pyridin-3-yl-methyl, 2-chloro-pyridine-5- yl-methyl, 1-phenyl-ethyl, 2-phenyl-ethyl, 1 - (4-chlorophenyl) -ethyl, l- (4-methyl-phenyl) -ethyl.
  • R 7 has, for example, the meanings given above in Group 1.
  • R 7 has, for example, the meanings given above in Group 1.
  • R 7 has, for example, the meanings given above in Group 1.
  • R 7 has, for example, the meanings given above in Group 1.
  • R 7 has, for example, the meanings given above in Group 1.
  • R 7 has, for example, the meanings given above in Group 1.
  • Group 8
  • R 7 has, for example, the meanings given above in Group 1
  • R 7 has, for example, the meanings given above in Group 1
  • R 7 has, for example, the meanings given above in Group 1
  • Formula (II) provides a general definition of the alkene acids required as starting materials for carrying out process a) for the preparation of the compounds of the formula (I) and their derivatives.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 preferably or in particular those meanings which have already been described above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 1 , R 2 , R 3 , R 4 , R 5 and R 6 were given
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meaning given above,
  • an oxidizing agent suitable for the selective oxidation of hydroxyalkyl compounds to carbonyl compounds such as, for example, trifluoroacetoxydimethylsulfonium trifluoroacetate in the presence of a diluent, such as methylene chloride, at temperatures between -100 ° C and 0 ° C (see J Org Chem 41 (1976), 957-962, preparation examples)
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meaning given above,
  • agents suitable for splitting off benzyl groups such as, for example, hydrogen in the presence of a catalyst, such as, for example, palladium, and in the presence of diluents, such as, for example, ethyl acetate, at temperatures between 0 ° C. and 150 ° C. (cf. the preparation examples)
  • R 2 , R 4 , R 5 and R 6 have the meaning given above,
  • alkylating agent such as dimethyl sulfate, iodomethane, iodoethane, bromomethane, bromethane, dimethyl carbonate, ortho formate methyl ester or O-methyl urea
  • an acid acceptor such as sodium hydride
  • a catalyst optionally in the presence of sulfuric acid a diluent, such as tetrahydrofuran, at temperatures between -20 ° C and 100 ° C (see also the preparation examples)
  • substituted diketones of the formula (X) required as starting materials for carrying out the process e) are not yet known from the literature; as new substances, they are the subject of a further, not yet published application
  • the substituted diketones of the formula (X) are obtained (process f) if substituted dioxinones of the general formula (XI)
  • R 2 , R 4 , R 5 and R 6 have the meaning given above,
  • R 1 has the meaning given above
  • a diluent such as, for example, diethyl ether, tetrahydrofuran, dioxane or toluene, and, if appropriate, in the presence of a reaction auxiliary, such as butyllithium or magnesium, at temperatures between -50 ° C. and + 150 ° C. (cf. Tetrahedron Asymmetry 3 (1992), 1157-1160, preparation examples)
  • substituted dioxinones of the formula (XI) required as starting materials for carrying out the process f) are not yet known from the literature; as new substances, they are the subject of a further, not yet published application
  • the substituted dioxinones of the formula (XI) are obtained (process g) if silyloxydioxins of the general formula (XIII)
  • R ⁇ and R ⁇ have the meaning given above,
  • a diluent such as dichloromethane and optionally in the presence of a Lewis acid such as aluminum trichloride or titanium tetrachloride, at temperatures from -100 to -20 ° C.
  • a Lewis acid such as aluminum trichloride or titanium tetrachloride
  • silyloxydioxins of the formula (XIII) required as starting materials for carrying out the process g) are known and can be prepared by known methods (compare, for example, Tetrahedron Asymmetry 3 (1992), 1 157-1 160, Heterocycles 41 (1995), 1435-1444) They are obtained, for example (process h), if dioxinones of the general formula (XV),
  • R ⁇ and R ⁇ have the meaning given above,
  • trimethylsilyl chloride optionally in the presence of a diluent such as diethyl ether or tetrahydrofuran and optionally in the presence of a base such as sodium amide or lithium diisopropylamide, at temperatures from -100 to 0 ° C.
  • a diluent such as diethyl ether or tetrahydrofuran
  • a base such as sodium amide or lithium diisopropylamide
  • dioxinones of the formula (XV) required as starting materials for carrying out the process h) according to the invention are known and can be prepared by known methods (compare, for example, Tetrahedron Asymmetry 3 (1992),
  • benzyloxyacetaldehydes of the formula (XIV which are also required as starting materials for carrying out process g) are known and can be prepared by known methods (compare, for example, J Chem.Soc Perkin Trans 1, 9, 1995,
  • R 1 , R 2 and R 4 have the meaning given above and
  • M represents lithium, sodium, potassium or a magnesium equivalent
  • a diluent such as N, N-dimethylformamide
  • R 4 and R 6 have the meaning given above
  • a reactive Kohlensaurede ⁇ vat such as phosgene or carbonyl bisimidazole
  • a diluent such as tetrahydrofuran
  • sodium or potassium monomethyl or ethyl malonate optionally in the presence of a catalyst, such as magnesium chloride or bromide
  • R 4 and R 6 have the meaning given above, with an oxidizing agent such as ozone or sodium or potassium podate, optionally in the presence of a diluent such as tetrahydrofuran, and optionally in the presence of a catalyst such as ruthenium chloride
  • R 4 and R 6 have the meaning given above
  • alkylating agent such as dimethyl sulfate, iodomethane, iodoethane,
  • an acid acceptor such as sodium hydride
  • a diluent such as tetrahydrofuran
  • the benzyloxy-hydroxyalkenes of the general formula (XVIII) required as starting materials for carrying out process 1) are known and can be prepared by known methods (Hoffmann, Reinhard W, Heibig, Wilfried, Chem Ber, 1 14, 8, 1981, 2802- 2807)
  • the substituted diketones of the formula (X) are also obtained (process m) if benzyloxy-hydroxyketones of the general formula (XIX)
  • R 4 and R 6 have the meaning given above
  • a reactive carbonic acid derivative such as methyl or ethyl cyanate or chloroformate, or dimethyl carbonate
  • a diluent such as tetrahydrofuran
  • a base such as lithium bis-trimethylsilylamide
  • R 8 and R have 9 preferably or in particular those meanings which have already been given above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 8 and R 9
  • R ' preferably represents alkyl having 1 to 6 carbon atoms or phenyl , in particular for methyl, ethyl, n-propyl, n-butyl or phenyl
  • the bis-enolates to be used as starting materials for carrying out process b) according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (VI).
  • R 1 , R 2 and R 4 preferably or in particular those meanings which have already been mentioned above in connection with the description of the compounds of the formula according to the invention
  • R 1 , R 2 and R 4 M is preferably lithium, sodium, potassium or a magnesium equivalent
  • aldehydes to be used further as starting materials in process (b) according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (VII).
  • R 6 and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 6 and Z.
  • the starting materials of the general formula (VII) are known organic synthetic chemicals
  • R 5 represents hydrogen or in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl compounds of the formulas (I), (II), (VIII),
  • R 5 stands for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl, can in each case be obtained from compounds of the general formulas (I), (II), (VIII), (IX), (X) and (XI) in which R 5 is hydrogen can be obtained by alkylation under customary conditions
  • Suitable diluents for carrying out processes (a) and (b) according to the invention are, above all, inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene,
  • Dichlorobenzene petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride ether, such as diethyl ether, dnsopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones, such as acetone, butanone or methyl isobutyl ketone, nitins, such as acetonitol, propionitol or butyronitol, amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N, methylformane N-methyl-pyrrone or hexamethylphosphoric acid, esters such as ethyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols, such as
  • Suitable reaction auxiliaries for processes (a) and (b) according to the invention are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogen carbonates, hydrides , hydroxides or alkanols, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium,
  • Potassium or calcium hydrogen carbonate lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium or potassium - methanolate, ethanolate, -n- or -l -propanolate, -n-, -I-, -s- or -t-butanolate, and also basic organic nitrogen compounds, such as, for example, t ⁇ methylamine, t ⁇ ethylamine, t ⁇ propylamine, t ⁇ butylamine, ethyl-dnsopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, Ethyl-dicyclohexylamm, N, N-dimethyl-an ⁇ l ⁇ n, N, N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl- , 3,4-dimethyl- and 3,5-dimethyl
  • reaction temperatures can be varied within a substantial range when carrying out processes (a) and (b) according to the invention. In general, temperatures between -50 ° C and + 150 ° C, preferably between -20 ° C and + 120 ° C.
  • the processes according to the invention are generally carried out under normal pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
  • the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess.
  • the reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred for several hours at the required temperature. Working up is carried out by customary methods (see the preparation examples).
  • the substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria
  • Fungicides can be used to control Plasmodiophoromycetes
  • Bactericides can be used in plant protection to combat Pseudomonadaceae,
  • pathogens of fungal and bacterial are exemplary but not limiting
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. Oryzae
  • Pseudomonas species such as, for example, Pseudomonas syringae pv lachrymans,
  • Erwinia species such as, for example, Erwinia amylovora,
  • Pythium species such as Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Bremia lactucae
  • Peronospora species such as, for example, Peronospora pisi or P brassicae,
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca sselina, Podosphaera species, such as, for example, Podosphaera leucot ⁇ cha,
  • Ventu ⁇ a species such as, for example, Ventu ⁇ a inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P graminea
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidia form Drechslera, Syn Helminthospo ⁇ um),
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • Tilletia species such as, for example, Tilletia ca ⁇ es
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae
  • Pelhcula ⁇ a species such as, for example, Pel culana sasakii
  • Py ⁇ cula ⁇ a species such as, for example, Py ⁇ cula ⁇ a oryzae,
  • Fusa ⁇ um species such as, for example, Fusa ⁇ um culmorum
  • Botrytis species such as, for example, Botrytis cinerea, Septo ⁇ a species, such as, for example, Septo ⁇ a nodorum,
  • Leptosphae ⁇ a species such as, for example, Leptosphae ⁇ a nodorum
  • Cercospora species such as, for example, Cercospora canescens,
  • Alternaria species such as, for example, Alternaria brassicae,
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpot ⁇ choides
  • the fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of topical plants
  • the active compounds according to the invention are particularly successful in combating cereal diseases, such as, for example, Erysiphe species, or
  • the active compounds according to the invention also have a particularly strong and broad in vitro activity.
  • the active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance
  • the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • Technical materials are non-living in the present context
  • Bacteria, fungi, yeasts, algae and slime organisms may be mentioned as microorganisms which can cause degradation or a change in the industrial materials
  • microorganisms of the following genera may be named Alternaria, such as Alterna ⁇ a tenuis,
  • Aspergillus such as Aspergillus niger
  • Chaetomium like Chaetomium globosum
  • Coniophora such as Comophora puetana
  • Lentinus such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli,
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus
  • the active compounds can be converted into the customary formulations, such as
  • formulations are prepared in a known manner, for example by mixing the
  • Active ingredients with extenders i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, i.e. emulsifiers and / or dispersants and / or foaming agents.
  • surface-active agents i.e. emulsifiers and / or dispersants and / or foaming agents.
  • water e.g.
  • Organic solvents can be used as auxiliary solvents
  • Solvents are essentially suitable aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as
  • Liquefied gaseous extenders or carriers are liquids which are gaseous at normal temperature and under normal pressure, for example aerosol Propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
  • Suitable solid carrier materials are, for example, natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as finely divided silica, aluminum oxide and silicates
  • solid carrier materials for granulates there are, for example, broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well Granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.
  • Suitable emulsifiers and / or foam-producing agents are, for example, ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkylsulfonates, alkylsulfonates, alkylsulfonates, sulfonates and protein hydrolyzates.
  • Suitable dispersants are, for example, ligmn
  • adhesives such as carboxymethylceulose, natural and synthetic powder, comedy or latex-shaped polymers can be used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as
  • Kephalme and lecithins and synthetic phospholipids
  • Other additives can be mineral and vegetable oils
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizine, azo and metal phthalocyanine dyes and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc, can be used
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%
  • the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acacids, nematrzides or insecticides, in order to broaden the spectrum of action or to prevent development of resistance, for example. In many cases, synergistic results are obtained
  • fen Famoxadone, fenapanil, fenarimol, fenbuconazole, fen
  • fen Famoxadone, fenapanil, fenarimol, fenbuconazole, fen
  • fen Famoxadone, fenapanil, fenarimol, fenbuconazole, fen
  • fen Famoxadone, fenapanil, fenarimol, fenbuconazole, fen
  • fen Famoxadone, fenapanil, fenarimol, fenbuconazole, fen
  • fen Famoxadone, fenapanil, fenarimol, fenbuconazole, fen
  • Flutolanil Flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl-sodium, fthalide, fuberidazole,
  • Iodocarb Ipconazole, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan,
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl,
  • Metconazole methasulfocarb, mefh tartroxam, metiram, metomeclam, metsulfovax,
  • Nickel dimethyldithiocarbamate Nitrothal-isopropyl, Nuarimol, O requirementsace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
  • Polyoxin Polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb, propanosine
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen,
  • Triadimefon Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemo ⁇ h, Triflumizol, Triforin, Triticonazol,
  • Bacillus thuringiensis 4-bromo-2- (4-chl ⁇ henyl) - 1 - (ethoxymethyl) -5- (trifluoromethyl) - 1H-pyrrole-3-carbonitrile, bendiocarb, ben Divisionacarb, bensultap, betacyfluthrin, bifenthrin,
  • Etrimphos Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil,
  • HCH Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
  • Lamda-cyhalothrin Lufenuron, Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymethionos, Pyridaphrinophone, Pyridaphrinin, Pyridaphrin Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,
  • Tebufenozide Tebufenpyrad
  • Tebupirimiphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhriazon, Tralomenhriazon, Tronomenhrononium,
  • the active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusting agents and granules.
  • the application is carried out in the customary manner, for example by pouring, spraying, spraying, Scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume process or to prepare the active ingredient or the like
  • the application rates can be varied within a substantial range depending on the type of application.
  • the application amounts of active compound generally lie between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha
  • the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. The application rates are applied when treating the soil
  • Active ingredient generally between 0.1 and 10,000 g / ha, preferably between 1 and 5000 g / ha
  • the agents used to protect industrial materials generally contain the active ingredients in an amount of 1 to 95%, preferably 10 to 75%.
  • the optimum amount to be used can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected
  • the diastereoisomers are characterized by ⁇ NMR spectra
  • the diastereoisomers can be separated by chromatography and are characterized by 1H NMR spectra
  • the separation of the syn and anti isomers can be carried out in a conventional manner, for example by column chromatography
  • the diastereoisomers can be separated by chromatography and are characterized by ⁇ NMR spectra
  • the crude product is used for further syntheses without further purification

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

L'invention concerne des acides d'alcène substitués et leurs dérivés de la formule (I) où R1 représente hydroxy, amino, alcoxy, alkylamino, dialkylamino, arylalcoxy ou arylalkylamino; R2 représente de l'hydrogène, halogène, alkyle; R3 représente de l'hydrogène, alkyle; R4 représente de l'hydrogène, alkyle, alcényle, alcynyle, cycloalkyle ou cycloalkylalkyle; R5 représente de l'hydrogène, alkyle, alcényle, alkinyle, cycloalkyle ou cycloalkylalkyle; R6 représente de l'hydrogène ou alkyle, et Z représente le groupe R7-N ou le groupe (R?8)(R9)C; R7¿ représentant de l'hydrogène, hydroxy, amino, alkyle, alcoxy, alkylamino, dialkylamino, alcényle, alcynyle, alcènyloxy, cycloalkyle, cycloakyloxy, cycloalkylamino, cycloalkylalkyle, cycloalkylalcoxy, cycloalkylalkylamino, aryle, aryloxy, arylamino, arylalkyle, arylacoxy, arylalkylamino, hétérocyclyle, hétérocyclylamino, hétérocyclylalkyle ou hétérocyclylalkylamino, ou un des groupes suivants A3-O-N=C(A?2)-CH(A1¿)-O- ou A3-O-N=C(A2)-C(A1)=N- où A1 représente de l'hydrogène ou alkyle; A2 représente de l'hydrogène, cyano, alkyle, cycloalkyle ou aryle et A3 représente de l'hydrogène ou alkyle; R8 représente de l'hydrogène, alkyle, alcényle, cycloalkyle, cycloalkylalkyle, aryle ou arylalkyle et R9 représente de l'hydrogène, alkyle, alcényle, cycloalkyle, cycloalkylalkyle, aryle ou arylalkyle. L'invention concerne également leur procédé de production et leur utilisation comme fongicide.
PCT/EP1998/005406 1997-09-08 1998-08-26 Acides d'alcene substitues et leurs derives WO1999012892A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP98947455A EP1015420A1 (fr) 1997-09-08 1998-08-26 Acides d'alcene substitues et leurs derives
AU94369/98A AU9436998A (en) 1997-09-08 1998-08-26 Substituted alkenoic acids and their derivatives
JP2000510704A JP2001518448A (ja) 1997-09-08 1998-08-26 置換アルケン酸及びその誘導体

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19739199 1997-09-08
DE19739199.0 1997-09-08
DE19829141A DE19829141A1 (de) 1997-09-08 1998-06-30 Substituierte Alkensäuren und ihre Derivate
DE19829141.8 1998-06-30

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WO1999012892A1 true WO1999012892A1 (fr) 1999-03-18

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JP (1) JP2001518448A (fr)
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WO (1) WO1999012892A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6225484B1 (en) 1999-08-12 2001-05-01 American Cyanamid Co. Process for the preparation of beta-methoxyacrylates

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US2438241A (en) * 1945-05-17 1948-03-23 Mallinckrodt Chemical Works Metallation of beta-keto esters
DE2400429A1 (de) * 1974-01-05 1975-07-17 Basf Ag Verfahren zur herstellung von 4-ketotetrahydro-alpha-pyronen
DE2708871A1 (de) * 1976-03-01 1977-10-27 Sagami Chem Res Verfahren zur herstellung von allylalkohol-derivaten

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KAZUAKI KUDO ET AL.: "Anti-selective reaction of alpha-sulfenyl acetals with silylated carbon nucleophiles. Scope, limitation, and mechanism", JOURNAL OF ORGANIC CHEMISTRY, vol. 58, 1993, EASTON US, pages 579 - 587, XP002091291 *
M.M. MIDLAND ET AL.: "Asymmetric hetero-Diels-Alder reaction of alpha-alkoxy aldehydes with activated dienes. The scope of Lewis acid chelation-controlled cycloadditions", JOURNAL OF ORGANIC CHEMISTRY, vol. 55, 1990, EASTON US, pages 5058 - 5065, XP002091288 *
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6225484B1 (en) 1999-08-12 2001-05-01 American Cyanamid Co. Process for the preparation of beta-methoxyacrylates

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AU9436998A (en) 1999-03-29
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