DE19829141A1 - Substituted alkenoic acids and their derivatives - Google Patents

Abstract

The invention relates to substituted alkenoic acids and their derivatives, said substituted alkenoic acids being of formula (I), wherein R<1> represents hydroxy, amino, alkoxy, alkylamino, dialkylamino, arylalkoxy or arylalkylamino, R<2> represents hydrogen, halogen or alkyl, R<3> represents hydrogen or alkyl, R<4> represents hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkylalkyl, R<5> represents hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkylalkyl, R<6> represents hydrogen or alkyl and Z represents the grouping R<7>-N or the grouping (R<8>) (R<9>)C, R<7> representing hydrogen, hydroxy, amino, alkyl, alkoxy, alkylamino, dialkylamino, alkenyl, alkinyl, alkenyloxy, cycloalkyl, cycloalkyloxy, cycloalkyloxy, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylamino, aryl, aryloxy, arylamino, arylalkyl, arylalkoxy, arylalkylamino, heterocyclyl, heterocyclylamino, heterocyclylalkyl or heterocyclylalkylamino, or one of the following groupings: A<3>-O-N=C(A<2>)-CH(A<1>)-O- or A<3>-O-N=C(A<2>-C(A<1>=N-, A<1> representing hydrogen or alkyl, A<2> representing hydrogen, cyano, alkyl, cycloalkyl or aryl, A<2> representing hydrogen, cyano, alkyl, cycloalkyl or aryl, A<3> representing hydrogen or alkyl, R<8> representing hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, and R<9> representing hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl. The invention also relates to methods for producing the substituted alkenoic acids and their derivatives, and to their use as fungicides.

Description

The invention relates to new substituted alkene acids and their derivatives, processes for their manufacture and their use as fungicides.

It is known that certain alkoxyacrylic acid derivatives, such as. B. Oudemansin, Strobilurin A, Strobilurin B and Myxothiazole (see J. Antibiot. 33 (1980), 1474-1479; loc. cit. 33: 1480-1490 (1980); FEBS Lett. 132: 329-333 (1981); Tetrahedron Lett. 34: 5151-5154 (1993); Nat. Prod. Rep. 10 (1993), 565-574) and Melithiazole A and melithiazole B (cf. DE 44 10 449) inhibit the respiration of cells and antibiotics have cal or antifungal or antifungal properties.

The new substituted alkene acids and their derivatives of the general formula (I) have now been found

in which
R ^{1 represents} hydroxy, amino or in each case optionally substituted alkoxy, alkyl amino, 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, and
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, arylalkyl amino, heterocyclyl, heterocyclylamino, heterocyclylalkyl or heterocyclyl alkylamino, or one of the following groups

A ³ -ON = C (A ² ) -CH (A ¹ ) -O- or A ³ -ON = C (A ² ) -C (A ¹ ) = N-

stands, where
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 registry no .: 153934-11-3] - known from Tetrahedron Lett. 34 (1993), 5151-5154 - are excluded by disclaimers.

The new substituted alkene acids and their derivatives of the general formula (I) are obtained if

• (a) alkenoic acids or their derivatives of the general formula (II)
  in which
  R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given above,
  with amino compounds of the general formula (III)
  R ⁷ -NH ₂ (III)
  in which
  R ^{7 has} the meaning given above,
  - or with acid adducts of compounds of the general formula (III) -
  or with olefining agents of the general formulas (IV) or (V)
  (R ⁸ ) (R ⁹ ) C = P (R ') ₃ (IV)
  (R ⁸ ) (R ⁹ ) CH-P (O) (R '') ₂ (V)
  in which
  R ⁸ and R ^{9 have} the meaning given above,
  R 'represents alkyl or aryl and
  R '' represents alkyl, alkoxy or aryl,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,
  or if you
• (b) bis-enolates of the general formula (VI)
  in which
  R ¹ , R ² and R ^{4 have} the meaning given above and
  M represents lithium, sodium, potassium or a magnesium equivalent,
  with aldehydes of the general formula (VII)
  in which
  R ⁶ and Z have the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,
  and optionally on the compounds of the general formula (I) obtained in this way, carry out further conversions in the context of the above definition of substituents by customary methods.

The new substituted alkene acids according to the invention and their derivatives of gen my formula (I) are characterized by strong fungicidal activity.

The compounds of the general formula (I) according to the invention, as well as all and intermediates contain asymmetrically substituted carbon atoms and / or double bonds. So they can be in different stereoisomeric forms available. The invention relates regardless of the spelling chosen here general formulas all different possible stereoisomers (and given if tautomeric) forms of the here outlined by the general formulas bonds individually and as mixtures of isomers.

In the definitions are the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkynyl, also in combination with heteroatoms, as in Alkoxy, alkylthio or alkylamino, in each case straight-chain or branched.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably Fluorine, chlorine or bromine, especially for fluorine or chlorine.  

Cycloalkyl stands for saturated, carbocyclic, ring-shaped compounds that opp optionally with other carbocyclic, fused or bridged rings form a polycyclic ring system.

Aryl stands for aromatic, mono- or polycyclic hydrocarbon rings, such as e.g. B. phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.

Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped Compounds in which at least one ring member has a heteroatom, i.e. H. one from Koh different atom, is. If the ring contains several heteroatoms, you can these be the same or different. Heteroatoms are preferably oxygen, stick substance or sulfur. If necessary, the annular connections form with wide ren carbocyclic or heterocyclic, fused or bridged rings together a polycyclic ring system. Mono- or bicyclic are preferred Ring systems, especially 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, for alkoxy, alkylamino or dialkylamino, each optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or for each optionally by halogen or C ₁ -C _4- alkyl substituted benzyloxy or benzylamino,
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 C ₁ -C ₄ alkoxy,
R ⁴ for hydrogen, for alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, for in each case optionally substituted by cyano or halogen alkenyl or alkynyl each with 2 to 6 carbon atoms, or for each optionally by Cyano, halo or C ₁ -C ₄ alkyl-substituted cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,
R ⁵ for hydrogen, for alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, for alkenyl or alkynyl each with 2 to 6 carbon atoms optionally substituted by cyano or halogen, or for each optionally by Cyano, halo or C ₁ -C ₄ alkyl-substituted cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,
R ^{6 represents} hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, and
Z stands for the grouping R ⁷ -N or the grouping (R ⁸ ) (R ⁹ ) C, where
R ⁷ for hydrogen, hydroxy, amino, for alkyl, alkoxy, alkylamino or dialkylamino, each optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, each optionally substituted by cyano or halogen Alkenyl, alkenyloxy or alkynyl each having 2 to 6 carbon atoms in the alkenyl or alkynyl groups, for each cycloalkyl, cycloalkyloxy, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy or cycloalkylalkylamino each having 3 to 6 substituted by cyano, halogen or C ₁ -C ₄ alkyl Carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, for each optionally by nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ - C ₄ - haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ finyl -Alkylsul, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ -Hal ogenalkyl sulfonyl or C ₁ -C ₄ alkoximino-C ₁ -C ₄ alkyl substituted aryl, aryloxy, arylamino, arylalkyl, arylalkoxy or arylalkylamino each having 6 or 10 carbon atoms in the aryl group and optionally up to 4 carbon atoms in the alkyl part, or for each optionally by cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ - haloalkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl, phenyl, phenoxy or phenylthio (the phenyl groups in each case where appropriate substituted by cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy) substituted and / or benzene-fused heterocyclyl, heterocyclylamino, heterocyclylalkyl or Heterocyclylalkylamino each having 3 to 7 ring members in the heterocyclyl group and optionally 1 to 4 carbon atoms is in the alkyl part, the heterocyclyl group each containing 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 groupings below

A ³ -ON = C (A ² ) -CH (A ¹ ) -O- or A ³ -ON = C (A ² ) -C (A ¹ ) = N-

stands, where
A ^{1 represents} hydrogen or alkyl having 1 to 6 carbon atoms,
Gen A ² represents hydrogen, cyano, represents in each case optionally cyano-, halogen or C ₁ -C ₄ alkoxy atoms substituted alkyl having 1 to 6 carbon atoms, represents optionally cyano-, halogen- or C ₁ -C ₄ -alkyl-substituted cycloalkyl having 3 to 6 carbon atoms or optionally substituted by cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy, and
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 C ₁ -C ₄ alkoxy, for alkenyl with 2 to 10 carbon atoms optionally substituted by cyano or halogen, for each optionally substituted by cyano, halogen or C. ₁ -C ₄ 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 in each case optionally by nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C _4- Haloalkylsul finyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl or C ₁ -C ₄ - alkoximino-C ₁ -C ₄ 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 alkyl with 1 to 10 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, for alkenyl with 2 to 10 carbon atoms optionally substituted by cyano or halogen, for each optionally substituted by cyano, halogen or C. ₁ -C ₄ 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 in each case optionally by nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C _4- Haloalkylsul finyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl or C ₁ -C ₄ - alkoximino-C ₁ -C ₄ 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,
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 registry no .: 153934-11-3] - known from Tetrahedron Lett. 34 (1993), 5151-5154 - are excluded by disclaimers.

The invention relates in particular to substituted alkene acids and their derivatives of the formula (I) in which
R ¹ for hydroxyl, amino or methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n-, in each case optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino,
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 for 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- 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 for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl,
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
Z stands for the grouping R ⁷ -N or the grouping (R ⁸ ) (R ⁹ ) C, where
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 in each case optionally substituted by cyano, fluorine, chlorine, methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyloxy, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopentylmethoxy, cyclohexyl methoxy, cyclopentylmethylamino or cyclohexylmethylamino, represents in each case optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s - or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromoxoxysulfomethyl, methoxymoximinoiminomethylmethyl, methoxymoximinoiminomethyl or ethoximinoethyl substituted phenyl, phenoxy, phenylamino, benzyl, benzyloxy, benzylamino or phenylethyl, or for each optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylcyllysulfonyl or phenyllyloxycylatedyl or phenyl Series oxiranyl, oxiranylmethyl, aziridinyl, oxetanyl, oxetanoyloxy, oxetanylmethyl, furyl, furylamino, furylmethyl, tetrahydrofuryl, thienyl, thienylamino, T. hienylmethyl, Benzofurylamino, Benzofurylmethyl, isobenzofuryl, benzothienyl, Benzothienylamino, benzo thienylmethyl, pyrrolyl, indolyl, oxazolyl, oxazolylmethyl, benzoxazolyl, benzoxazolylmethyl, isoxazolyl, isoxazolylmethyl, benzisoxazolyl, Benz isoxazolylmethyl, thiazolyl, thiazolylmethyl, benzothiazolyl, Benzthiazolylme methyl, oxadiazolyl, Oxadiazolylmethyl, thiadiazolyl , Thiadiazolylmethyl, pyridyl, pyridylamino, pyridylmethyl, quinolyl, quinolylamino, quinolylmethyl, pyrimidyl, pyrimidinylamino, pyrimidylmethyl, pyridazinyl, pyrazinyl, triazinyl, or one of the following groups

A ³ -ON = C (A ² ) -CH (A ¹ ) -O- or A ³ -ON = C (A ² ) -C (A ² ) = N-

stands, where
A ^{1 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
A ² for hydrogen, cyano, for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, for each optionally substituted by cyano , Fluorine, chlorine, methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or for optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t - Butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromoxy or trifluoromethoxy substituted phenyl, and
A ^{3 represents} hydrogen, methyl, ethyl, n- or i-propyl,
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 in each case optionally substituted by cyano, fluorine, chlorine or bromine ethenyl, propenyl, butenyl or pen tenyl, for in each case optionally substituted by cyano, fluorine, chlorine, methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl methyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy , Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or phenyl, benzyl and phenyl, benzyl, or phenylmethylethyl substituted phenyl
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 in each case optionally substituted by cyano, fluorine, chlorine or bromine ethenyl, propenyl, butenyl or pen tenyl, for in each case optionally substituted by cyano, fluorine, chlorine, methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl methyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy , Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or phenylimethylethyl substituted phenyl, benzyl
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 registry no .: 153934-11-3] - known from Tetrahedron Lett. 34 (1993), 5151-5154 - are excluded by disclaimers.

The compounds of the formula (I) in which

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.

Compounds of the formula (I) in which
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 with cyano, fluorine or chlorine-substituted ethenyl, propenyl, butenyl, propenyloxy, butenyloxy, ethynyl, propynyl or butynyl, for in each case optionally substituted by cyano, fluorine, chlorine, methyl or ethyl cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyloxy, cyclopentylamino, cyclohexylamino, cyclopentylmethyl, cyclopentylmethyl hexylmethyl, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylmethyl amino or cyclohexylmethylamino, each optionally with nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl , Methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromet hoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl optionally substituted by phenyl, phenoxy or benzyl, benzyl, phenylamino, phenylamino, phenylamino, phenylamino or phenylamino, phenylamino or phenylamino, for phenylamino, in each case Cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio , Ethylthio, n- or i-propylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl or phenyl-substituted heterocyclyl or heterocyclylalkyl from the series oxiranyl, oxiranylmethyl, aziridinyl, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanyloxy, oxetanylmethyl Thienylamino, Thienylme thyl, Benzofurylamino, Benzofurylmethyl, Isobenzofuryl, Benzothienyl, Ben zothienylamino, Benzothieny lmethyl, pyrrolyl, indolyl, oxazolyl, Oxazolylme methyl, benzoxazolyl, benzoxazolylmethyl, isoxazolyl, isoxazolylmethyl, Benz isoxazolyl, benzisoxazolylmethyl, thiazolyl, thiazolylmethyl, benzothiazolyl, Benzthiazolylmethyl, oxadiazolyl, Oxadiazolylmethyl, thiadiazolyl, thia diazolylmethyl, pyridyl, pyridylamino, pyridylmethyl, quinolyl, quinolylamino , Quinolylmethyl, Pyrimidyl, Pyrimidinylamino, Pyrimidylmethyl, Pyridazinyl, Pyrazinyl, Triazinyl.

The general or priority areas listed above Definitions apply both to the end products of formula (I) and accordingly to the starting or intermediate products required for the production. This Residual definitions can be between themselves, that is, between the specified ones areas can be combined as required.

Examples of the compounds of the general formula (I) are shown in the following Groups listed.  

Group 1

R ⁷ has, for example, the meanings given in the list below:

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyanomethyl, cyanoethyl, Fluoroethyl, fluoropropyl, methoxyethyl, ethoxyethyl, methoxy, ethoxy, n- or i- Propoxy, n-, i-, s- or t-butoxy, methoxyethoxy, ethoxyethoxy, methylamino, Ethylamino, dimethylamino, propenyl, butenyl, propenyloxy, propynyl, butynyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyloxy cyclohexyloxy, Cyclopentylamino, cyclohexylamino, phenyl, 2-cyano-phenyl, 3-cyano-phenyl, 4- Cyano-phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 3-fluorophenyl, 3- Chlorophenyl, 3-bromophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4- Difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 2,3-dichlorophenyl, 2,4- Dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 2- Methyl-phenyl, 3-methyl-phenyl, 4-methyl-phenyl, 2,3-dimethyl-phenyl, 2,4-dime thylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Dimethylphenyl, 2-chloro-6-methylphenyl, 2-chloro-4-methylphenyl, 4-chloro-2- methyl-phenyl, 3-chloro-4-methyl-phenyl, 4-chloro-3-methyl-phenyl, 4-ethyl-phenyl, 4- i-propyl-phenyl, 4-t-butyl-phenyl, 2-trifluoromethyl-phenyl, 3-trifluoromethyl-phenyl, 4-trifluoromethyl-phenyl, 2-methoxy-phenyl, 3-methoxy-phenyl, 4-methoxy-phenyl, 2,5-dimethoxy-phenyl, 3,4-dimethoxy-phenyl, 4-methoximinomethyl-phenyl, 4- Ethoximinomethylphenyl, 4-allyloximinomethylphenyl, 4-propargyloximinomethyl phenyl, 4- (1-methoximino) ethylphenyl, 4- (1-ethoximino) ethylphenyl, 4- (1- Allyloximino) ethyl phenyl, 4- (1-propargyloximino) ethyl phenyl, 2-methyl-4- methoximinomethyl-phenyl, 2-methyl-4-ethoximinomethyl-phenyl, 2-methyl-4- allyloximinomethyl-phenyl, 2-methyl-4-propargyloximinomethyl-phenyl, 2-methyl-4-  (1-methoximino) ethyl phenyl, 2-methyl-4- (1-ethoximino) ethyl phenyl, 2-methyl-4- (1-allyloximino) ethyl phenyl, 2-methyl-4- (1-propargyloximino) ethyl phenyl, 1- Naphthyl, 2-naphthyl, phenoxy, phenylamino, pyridin-3-yl, 2-chloropyridin-5-yl, Quinolin-6-yl, quinolin-8-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-methyl-pyrimi din-5-yl, 3-methyl-1,2,4-thiadiazol-5-yl, 3-phenyl-1,2,4-thiadiazol-5-yl, 6-phenoxy pyrimidin-4-yl, 6- (2-fluorophenoxy) pyrimidin-4-yl, 6- (2-chlorophenoxy) pyrimidine 4-yl, 6- (2-cyano-phenoxy) pyrimidin-4-yl, 6-phenoxy-5-fluoropyrimidin-4-yl, 6- (2- Fluorophenoxy) -5-fluoropyrimidin-4-yl, 6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yl, 6- (2-cyano-phenoxy) -5-fluoropyrimidin-4-yl, benzyl, 2-cyano-benzyl, 3-cyano-ben cyl, 4-cyano-benzyl, 2-fluoro-benzyl, 2-chloro-benzyl, 4-fluoro-benzyl, 4-chloro-benzyl, 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-pyridin-5-yl-methyl, 1- Phenyl-ethyl, 2-phenyl-ethyl, 1- (4-chlorophenyl) ethyl, 1- (4-methylphenyl) ethyl.

Group 2

R ⁷ has, for example, the meanings given above in Group 1.

Group 3

R ⁷ has, for example, the meanings given above in Group 1.

Group 4

R ⁷ has, for example, the meanings given above in Group 1.

Group 5

R ⁷ has, for example, the meanings given above in Group 1.

Group 6

R ⁷ has, for example, the meanings given above in Group 1.

Group 7

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.

Group 9

R ⁷ has, for example, the meanings given above in Group 1

Group 10

R ⁷ has, for example, the meanings given above in Group 1.

If, for example, 3,5-dimethoxy-6-formyl-4-methyl-2-hexenoic acid, methylamide and O-benzyl-hydroxylamine are used as starting materials, the reaction sequence in process (a) according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the alkenoic acids and their derivatives required as starting materials for carrying out process a) for the preparation of the compounds of formula (I). In the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ preferably or in particular have those meanings which are preferred above in connection with the description of the compounds of the formula (I) according to the invention or as particularly preferred for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ .

With the exception of the compound, the starting materials of the general formula (II) are E- (4S, 5S) -3,5-dimethoxy-5-formyl-4-methyl-2-hexenamide (alias 3, 5-dideoxy-3- methyl-2,4-di-O-methyl-DL-threo-hex-4-enuronamide - cf. Tetrahedron Lett. 34 (1993), 5151-5154) not yet known from the literature; they are exceptional of 3,5-dideoxy-3-methyl-2,4-di-O-methyl-DL-threo-hex-4-enuronamide as new Substances are also the subject of the present application.

The new alkene acids or their derivatives of the general formula (II) are obtained if (process c) hydroxyalkenoic acids or their derivatives of the general formula (VIII)

in which
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given above,
with an oxidizing agent suitable for the selective oxidation of hydroxyalkyl compounds to carbonyl compounds, such as, for. B. Trifluoroacetoxydimethylsulfonium trifluoroacetate in the presence of a diluent, such as. B. methylene chloride, at temperatures between -100 ° C and 0 ° C (see J. Org. Chem. 41 (1976), 957-962; preparation examples).

The hydroxy required to carry out process c) according to the invention alkene acids and their derivatives of the general formula (VIII) are not yet from the Literature known; as new substances they are the subject of another, not yet published registration.

The new hydroxyalkenoic acids and their derivatives of the general formula (VIII) are obtained if (process d) benzyloxyalkenoic acids or their derivatives of the general formula (IX)

in which
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given above,
with suitable means for the elimination of benzyl groups, such as. B. with hydrogen in the presence of a catalyst such as. As palladium, and in the presence of diluents such. B. ethyl acetate, at temperatures between 0 ° C and 150 ° C (see. The preparation examples).

The benzyloxy required as starting materials for carrying out process d) alkene acids and their derivatives of the general formula (IX) are not yet from the  Literature known; as new substances they are the subject of another, not yet published registration.

The new benzyloxyalkenoic acids or their derivatives of the general formula (IX) are obtained (process e) if substituted diketones of the general formula (X)

in which
R ² , R ⁴ , R ⁵ and R ^{6 have} the meaning given above,
with an alkylating agent, such as dimethyl sulfate, iodomethane, iodoethane, bromomethane, bromethane, dimethyl carbonic acid, trimethyl orthoformate or O-methylisourea, optionally in the presence of an acid acceptor, such as. B. sodium hydride, optionally in the presence of a catalyst, such as sulfuric acid and optionally in the presence of a diluent, such as. B. tetrahydrofuran, at temperatures between -20 ° C and 100 ° C (see also the preparation examples).

The substituted substances required as starting materials for carrying out process e) Diketones of the formula (X) are not yet known from the literature; they are as new Substances subject to another, not yet published application.  

The substituted diketones of the formula (X) are obtained (process f) if substituted dioxinones of the general formula (XI)

in which
R ² , R ⁴ , R ⁵ and R ^{6 have} the meaning given above,
with nucleophiles of the general formula (XII)

R ¹ -H (XII),

in which
R ^{1 has} the meaning given above,
optionally in the presence of a diluent, such as. B. diethyl ether, tetra hydrofuran, dioxane or toluene, and optionally in the presence of a reaction, such as. As butyllithium or magnesium, at temperatures between -50 ° C and + 150 ° C (see. Tetrahedron Asymmetry 3 (1992), 1157-1160; Her examples).

The substituted substances required to carry out process f) as starting materials Dioxinones of the formula (XI) are not yet known from the literature; they are as new Substances subject to another, not yet published application.  

The substituted dioxinones of the formula (XI) are obtained (process g) if silyloxydioxins of the general formula (XIII)

in which
R ² and R ^{4 have} the meaning given above,
with a benzyloxyacetaldehyde of the general formula (XIV),

in which
R ^{6 has} the meaning given above,
optionally in the presence of 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.

The silyloxy required as starting materials for carrying out process g) Dioxins of the formula (XIII) are known and can be obtained by known methods (see e.g. Tetrahedron Asymmetry 3 (1992), 1157-1160, hetero cycles 41 (1995), 1435-1444).  

They are obtained, for example (process h), if dioxinones of the general formula (XV),

in which
R ² and R ^{4 have} the meaning given above,
with 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.

Those used to carry out process h) according to the invention as starting materials required dioxinones of the formula (XV) are known and can be prepared according to known ones Methods are produced (compare e.g. Tetrahedron Asymmetry 3 (1992), 1157-1160 and literature cited there).

Those still required as starting materials for carrying out process g) Benzyloxyacetaldehydes of the formula (XIV) are known and can be prepared according to known ones Methods are prepared (see e.g. J.Chem.Soc.Perkin Trans. 1, 9, 1995, 1189-1198).  

The substituted diketones of the formula (X) are also obtained (process i) if bisenolates of the general formula (VI)

in which
R ¹ , R ² and R ^{4 have} the meaning given above and
M represents lithium, sodium, potassium or a magnesium equivalent,
with a benzyloxyacetaldehyde of the general formula (XIV),

in which
R ^{6 has} the meaning given above,
optionally in the presence of a diluent, such as N, N-dimethylformamide, at temperatures between -50 ° C and + 100 ° C (see. The preparation examples).

The bisenolates required for carrying out process i) as starting materials general formula (VI) are known and can by known methods can be produced (Tetrahedron Lett. 29 (1988) 2107-2110).

Those still required as starting materials for carrying out process i) Benzyloxyacetaldehydes of the general formula (XIV) are already above in the Connection with the description of the method g) has been described.  

The substituted diketones of the formula (X) are also obtained (process j) if carboxylic acids of the general formula (XVI)

in which
R ⁴ and R ^{6 have} the meaning given above,
with a reactive carbonic acid derivative such as phosgene or carbonyl bisimidazole, optionally in the presence of a diluent such as tetrahydrofuran, and then with sodium or potassium monomethyl or ethyl malonate, optionally in the presence of a catalyst such as magnesium chloride or bromide.

The carboxylic acids required as starting materials for carrying out process j) the general formula (XVI) are not yet known from the literature; they are as new substances subject to a further, not yet published application.

They are obtained (process k) if benzyloxyalkoxyalkenes of the general formula (XVII)

in which
R ⁴ and R ^{6 have} the meaning given above,
with an oxidizing agent, such as ozone or sodium or potassium periodate, optionally in the presence of a diluent, such as tetrahydrofuran, and optionally in the presence of a catalyst, such as ruthenium chloride.

The benzyloxy required as starting materials for carrying out process k) Alkoxyalkenes of the general formula (XVII) are not yet from the literature known; as new substances they are the subject of another, not yet published clear registration.

They are obtained (process 1) if benzyloxy-hydroxyalkenes of the general formula (XVIII),

in which
R ⁴ and R ^{6 have} the meaning given above,
with an alkylating agent, such as dimethyl sulfate, iodomethane, iodoethane, bromomethane, bromethane or dimethyl carbonate, optionally in the presence of an acid acceptor, such as. B. sodium hydride and optionally in the presence of a diluent, such as. B. tetrahydrofuran, at temperatures between -20 ° C and 100 ° C (see also the preparation examples).

The benzyloxy required as starting materials for carrying out process 1) hydroxyalkenes of the general formula (XVIII) are known and can according to known methods (Hoffmann, Reinhard W .; Helbig, Wilfried, Chem. Ber., 114.8, 1981, 2802-2807).  

The substituted diketones of the formula (X) are also obtained (process m) if benzyloxy-hydroxyketones of the general formula (XIX)

in which
R ⁴ and R ^{6 have} the meaning given above,
with a reactive carbonic acid derivative, such as, for example, methyl or ethyl cyan- or chloroform, or dimethyl carbonate, if appropriate in the presence of a diluent, for example tetrahydrofuran, if appropriate in the presence of a base, for example lithium-bis-trimethylsilylamide.

The benzyloxy required as starting materials for carrying out process m) Hydroxyketones of the general formula (XIX) are not yet from the literature known; as new substances they are the subject of another, not yet published clear registration.

You will get (method n) if you have benzyloxy alkoxyalkenes of the formula (XVII) with oxygen, optionally in the presence of a diluent, such as for example dimethylformamide, and optionally in the presence of a kata analyzers, such as, for example, palladium chloride, copper chloride or mixtures thereof, implements.

The benzyloxy required as starting materials for carrying out process n) Alkoxyalkenes of the formula (XVII) are already further above in the description of the Process k) has been described.  

Formula (III) provides a general definition of the amino compounds required to carry out process a) according to the invention for the preparation of the compounds of formula (I) which are furthermore required as starting materials. In this formula (III), R ⁷ preferably or in particular has the meaning which has already been given above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for R ⁷ .

The starting materials of the general formula (III) are known synthetic chemicals.

The olefins required alternatively as starting materials for carrying out the process a) for the preparation of the compounds of the formula (I) are generally defined by the formulas (IV) and (V). In the formulas (IV) and (V), R ⁸ and R ⁹ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R ⁸ and R ^{9 were} specified; R 'preferably represents alkyl having 1 to 6 carbon atoms or phenyl, in particular methyl, ethyl, n-propyl, n-butyl or phenyl; R '' preferably represents alkyl or alkoxy, each having 1 to 6 carbon atoms or phenyl, in particular methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy or phenyl.

The starting materials of the general formulas (IV) and (V) are known synthesis chemicals.

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). In the formula (VI), R ¹ , R ² and R ^{4 are} preferred or, in particular, those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for R. ¹ , R ² and R ^{4 have been} given; M preferably represents lithium, sodium, potassium or a magnesium equivalent.

The starting materials of the general formula (VI) are known and / or can be according to known processes can be prepared (cf. Tetrahedron Lett. 29 (1988), 2107-2110; Manufacturing examples).

The aldehydes to be used further as starting materials in the process (b) according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (VII). In 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 synthesis chemicals.

For the compounds of the general formulas (I), (II), (VIII), (IX), (X) and (XI), R ^{5 represents} hydrogen or in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl. Compounds of the formulas (I), (II), (VIII), (IX), (X) and (XI), in which R ⁵ represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl, can each be composed of 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.

As a diluent for carrying out processes (a) and (b) Inert organic solvents are particularly suitable. This includes in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chlorinated carbon, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran  or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or Methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N- Methyl pyrrolidone or hexamethyl phosphoric acid triamide; Esters such as acetic acid ethyl ester or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as Methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol colmonoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

As reaction aids for processes (a) and (b) according to the invention come in generally the usual inorganic or organic bases or acid acceptors other. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkano latex, 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 -i-propanolate, -n-, -i-, -s- or -t-butanolate; Farther also basic organic nitrogen compounds, such as trimethylamine, Triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl-2,4-dimethyl, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4- Dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), or 1,8-diazabicyclo [5,4,0] - undec-7-en (DBU).

The reaction temperatures can be carried out when carrying out the inventive Processes (a) and (b) can be varied over a wide range. In general one works at temperatures between -50 ° C and + 150 ° C, preferably between between -20 ° C and + 120 ° C.  

The processes of the invention are generally under normal pressure carried out. However, it is also possible to use the method according to the invention increased or reduced pressure - generally between 0.1 bar and 10 bar - to be carried out.

To carry out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible Lich to use one of the components in a larger excess. The order settlement is generally in a suitable diluent in the presence carried out a reaction auxiliary and the reaction mixture is generally NEN stirred for several hours at the required temperature. The workup is carried out according to customary methods (cf. the production examples).

The substances according to the invention have a strong microbicidal action and can to combat unwanted microorganisms, such as fungi and bacteria, in Plant protection and material protection are used. Fungicides can be used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Use Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae. Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

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, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or
Pseudoperonospora cubensis;
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 fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochlobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
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 caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the control of plants Concentrations necessary for diseases allow treatment above ground Parts of plants, of seedlings, and of the soil.

The active compounds according to the invention are particularly successful fighting cereal diseases, such as Erysiphe species, or Diseases in wine, fruit and vegetable growing, such as Phytophthora or Venturia species, or also rice diseases, such as, for example, Pyricularia Species used. Other cereal diseases such as  Septoria, Cochliobolus and Pyrenophora species fought. They also show Active substances according to the invention have a particularly strong and broad in vitro effect.

The active compounds according to the invention are also suitable for increasing the crop yield. she are also less toxic and have good plant tolerance.

In material protection, the substances according to the invention can be used to protect technical ones Use materials against infestation and destruction by unwanted microorganisms. In the present context, technical materials include non-living ones Understand materials that have been prepared for use in the art. For example, technical materials can be provided by active ingredients according to the invention microbial change or destruction should be protected, adhesives, glues, Paper and cardboard, textiles, leather, wood, paints and plastic articles, Cooling lubricants and other materials that are infested with microorganisms or can be decomposed. Parts of are also within the scope of the materials to be protected Production facilities, such as cooling water circuits, called by multiplication can be affected by microorganisms. As part of the present Invention as technical materials are preferably adhesives, glues, papers and Cardboard boxes, leather, wood, paints, coolants and heat transfer called liquids, particularly preferably wood.

As microorganisms that break down or change the technical Materials such as bacteria, fungi, yeasts, algae and Called slime organisms. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against mucous organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora 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, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The active ingredients can depend on their respective physical and / or chemical properties can be converted into the usual formulations, such as Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric substances and in coating compositions for seeds, as well as ULV Cold and warm fog formulations.

These formulations are prepared in a known manner, e.g. B. by mixing the Active ingredients with extenders, i.e. liquid solvents, under pressure liquid gases and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foaming agents. In the case of the use of water as an extender e.g. B. organic solvents can also be used as auxiliary solvents. As a liquid Solvents are essentially possible: 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, e.g. B. petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfate oxide, as well as water. With liquefied gaseous extenders or carriers such liquids are meant, which at normal temperature and under normal pressure are gaseous, e.g. B. aerosol propellants, such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide. As solid carriers come into question: B. natural Liche rock powder, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmo rillonite or diatomaceous earth and synthetic stone powder, such as finely divided pebbles acid, aluminum oxide and silicates. The following are suitable as solid carriers for granules: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, Dolomite and synthetic granules from inorganic and organic flours as well Granules from organic material such as sawdust, coconut shells, corn cobs and Tobacco stem. Suitable emulsifying and / or foam-generating agents are: B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxy  ethylene fatty alcohol ether, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are: B. Lignin Leaches of sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as Cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alzarin, 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 Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, too in a mixture with known fungicides, bactericides, acaricides, nematicides or Insecticides can be used, e.g. B. to broaden the spectrum of activity or To prevent the development of resistance. In many cases you get synergistic Effects, d. H. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

Fungicides

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyphodinconol, cypodinconol, cypodinconol
Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxinodonine, dithorphononine
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimolol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusilazolutol, flusilazolutolol Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
Guazatin,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifen, pyifenox, pyrroyilonil
Quinconazole, quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Uniconazole,
Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G,
OK-8705,
OK-8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-1,3-dioxan-5-yl) -β - [[4-trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazole-1-ethanol,
(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -a (methoxylimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-methyl-1 - [[[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester,
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulfonyl] -4-methyl-benzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,
2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -aD-glucopyranosyl] amino] -4- methoxy-1H-pyrrolo [2,3-d] pyrimidine- 5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) pentandinitrile
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) oxy] methyl] benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,
4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis- (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethylmorpholine hydrochloride,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
Potassium hydrogen carbonate,
Methane tetrathiol sodium salt,
Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,
Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide,
N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,
N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,
N-formyl-N-hydroxy-DL-alanine sodium salt,
O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,
O-methyl-S-phenyl-phenylpropylphosphoramidothioate,
S-methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one.

Bactericides

Bromopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, oc thilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, Copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, 4-Bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) - 1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, Brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butyl pyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidamide , Chlorpyrifos, Chlor pyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fen oxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenproionophonin, Flufenproionfonium, Fufonxionfonium, Fufonxionfonium, Fufonxionfonium, Fufonxionfonium, Fufonoxophon, Fufon, Fufon, Fufon, Fufon ,
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamido phos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, 21067 00070 552 001000280000000200012000285912095600040 0002019829141 00004 20948 NC 184, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phos phamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetroion, Pyridaphrinophin, Pyridaphrinophin , Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Ter bam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhrononium, Triomenethriazonium, Tri
Vamidothione,
XMC, xylylcarb,
Zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible. The active substances can be used as such, in the form of their formulations or in the form thereof riding application forms, such as ready-to-use solutions, suspensions, wettable powders, Pastes, soluble powders, dusts and granules can be used. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, scattering, Dusting, foaming, brushing, etc. It is also possible to add the active ingredients to apply the ultra-low-volume process or the preparation of active ingredients or Inject active ingredient into the soil yourself. It can also be the seed of the plants be treated.

When using the active compounds according to the invention as fungicides, the effort can be reduced quantities can be varied within a wide range depending on the type of application. At the treatment of plant parts, the amounts of active ingredient are in all generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. At the seed treatment, the application rates of active ingredient are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per Kilogram of seeds. When treating the soil, the application amounts are applied Active ingredient generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.  

The agents used to protect technical materials contain the active ingredients in generally in an amount of 1 to 95%, preferably 10 to 75%.

The application concentrations of the active compounds according to the invention depend on the Type and the occurrence of the microorganisms to be controlled and according to the Composition of the material to be protected. The optimal amount can be Test series can be determined. In general, the application concentrations are Range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight on the material to be protected.

The effectiveness and spectrum of activity of the invention in material protection using active ingredients or the agents, concentrates or wholly produced therefrom general formulations can be increased if necessary further antimicro biologically active compounds, fungicides, bactericides, herbicides, insecticides or others Active substances to enlarge the spectrum of effects or to achieve special effects such as B. added protection against insects. These blends can have a broader spectrum of activity than the compound according to the invention fertilize.  

Manufacturing examples example 1

Procedure a)

770 mg (2.67 mmol) of 3,5-dimethoxy-4-methyl-6-oxo-hex-2-enoic acid methyl ester (crude product approx. 75%) together with 540 mg (5.3 mmol) triethylamine in 10 ml Dissolved methanol. At room temperature 280 mg (4.0 mmol) of hydroxylamine hydrochloride and 411 mg (5.3 mmol) pyridine added and then overnight stirred at room temperature. The reaction mixture is under reduced pressure concentrated and the residue in water (20 ml) and ethyl acetate taken. The organic phase is dried with sodium sulfate and min reduced pressure. The residue is mixed with cyclohexane / ethyl acetate (1: 1, + 1% Triethylamine) chromatographed on silica gel. 100 mg (17% of theory) are obtained. 6-Hydroxyimino-3,5-dimethoxy-4-methyl-hex-2-enoic acid methyl ester.

The diastereoisomers (syn / anti) are characterized by ¹ H-NMR spectra. (E) -configured products are created.

Isomer 1 (syn) (CDCl ₃ / TMS): δ = 1.19 (d, J = 6.8Hz, 3H, CHC H ₃ ), 3.32, 3.61, 3.68 (s, 3H, OC H ₃ ), 5.02 (s, 1H , H C = C) ppm.
HPLC-MS: m / e = 232 (M⁺) standard gradient, 6.07 min.

Example 2

Procedure a)

43 mg (0.2 mmol) of 3,5-dimethoxy-4-methyl-6-oxo-hex-2-enoic acid methyl ester dissolved in 5 ml of methylene chloride and with 50 mg (0.25 mol) of 3-trifluoromethylacetophe nonhydrazone and 200mg molecular sieve 4A (powdered) added. It gets over night stirred at room temperature and then filtered. The filtrate is min concentrated pressure and the crude product with cyclohexane / ethyl acetate (2: 1) Chromatographed silica gel. 15 mg (15% of theory) of 3,5-dimethoxy-4- are obtained. methyl-6 - {[1- (3-trifluoromethylphenyl) ethylidene] hydrazono} hex-2-enoic acid methyl ester.

The diastereoisomers (syn / anti) are characterized by 1H NMR spectra. (E) -configured products are created.

Isomer 1 (syn) (CDCl ₃ / TMS): δ = 1.11 (d, J = 7.0Hz, 3H, CHC H ₃ ), 3.38, 3.68, 3.69 (s, 3H, OC H ₃ ), 5.11 (s, 1H , H C = C) ppm.
HPLC-MS: M⁺ = 401.

Production of raw materials Preparation of precursors of formula (XVII) Example (XVII-1)

Procedure 1)

2.06 g (10 mmol) of 1-benzyloxy-3-methyl-4-penten-2-ol (Hoffmann, Reinhard W .; Helbig, Wilfried, Chem. Ber., 114, 8, 1981, 2802-2807) and 2.84g (20 mmol) Me thyl iodide are dissolved in 50 ml of tetrahydrofuran and at 0 ° C in portions with 120 mg (40 mmol) sodium hydride (80%) added. After 2 hours in the room temperature is hydrolyzed by adding 10 ml of water. It is extracted with Ethyl acetate, the organic phase dries with sodium sulfate and concentrated reduced pressure. The residue is mixed with cyclohexane / ethyl acetate (4: 1) Chromatographed silica gel. 1.16 g (53% of theory) (2-methoxy-3- methyl-pent-4-enyloxymethyl) benzene.

The diastereoisomers are characterized by ¹ H NMR spectra.

Isomer 1: (CDCl ₃ / TMS): δ = 1.04 (d, J = 6.9Hz, 3H, CHC H ₃ ), 3.22 (m, 1H, C H OCH ₃ ), 3.45 (s, 3H, OC H ₃ ) ppm.
Isomer 2: (CDCl ₃ / TMS): δ = 1.04 (d, J = 6.9Hz, 3H, CHC H ₃ ), 3.28 (m, 1H, C H OCH ₃ ), 3.45 (s, 3H, OC H ₃ ) ppm.
HPLC: log P (neutral) = 3.70

Production of precursors of the formula (XVI) Example (XVI-1)

Procedure k)

220 mg (1.0 mmol) (2-methoxy-3-methyl-pent-4-enyloxymethyl) benzene and 546 mg (6.5 mmol) sodium hydrogen carbonate are dissolved in 3 ml carbon tetrachloride, 3 ml acetonitrile and 4.5 ml water and at room temperature in portions with 1.18 g (5.5 mmol) sodium periodate added. After adding 41 mg (0.2 mmol) of ruthenium III chloride, the mixture is stirred at room temperature for 3 days. The reaction mixture is taken up in 100 ml of diethyl ether / 50 ml of water and, after acidification, the aqueous phase is extracted with 10% HCl with ethyl acetate. The combined organic phases are dried with sodium sulfate and concentrated under reduced pressure. 0. 12 g (50% of theory) of 4-benzyloxy-3-methoxy-2-methyl-butanoic acid are obtained.
The raw product is used without further purification.

The diastereoisomers are characterized by ¹ H NMR spectra.

Isomer 1: (CDCl ₃ / TMS): δ = 1.18 (d, J = 7.1Hz, 3H, CHC H ₃ ), 3.45 (s, 3H, OC H ₃ ) ppm.
HPLC: log P (acidic) = 1.91
Isomer 2: (CDCl ₃ / TMS): δ = 1.19 (d, J = 7.1Hz, 3H, CHC H ₃ ), 3.28 (m, 1H, C H OCH ₃ ), 3.48 (s, 3H, OC H ₃ ) ppm.
HPLC: log P (acidic) = 1.94

Production of precursors of the formula (XIX) Example (XIX-1)

Procedure n)

18 mg (0.1 mmol, 10 mol%) palladium-II-chloride and 27 mg (0.2 mmol) copper-II- chloride are dissolved in a mixture of 5 ml of dimethylformamide and 5 ml of water and at room temperature under an oxygen atmosphere with a solution of 220 mg (1.0 mmol) (2-methoxy-3-methyl-pent-4-enyloxymethyl) benzene in 1 ml of dimethyl formamide offset. The mixture is stirred under an oxygen atmosphere for 3 days and then diluted reaction with 50 ml of water. It is extracted with ethyl acetate ester, dries with sodium sulfate and concentrates under reduced pressure. The back stand is chromatographed on silica gel using cyclohexane / ethyl acetate (4: 1). Man receives 180 mg (76% of theory) of 5-benzyloxy-4-methoxy-3-methyl-pentan-2-one.

The diastereoisomers can be separated by chromatography and are characterized by 1H NMR spectra.

Isomer 1: (syn) (CDCl ₃ / TMS): δ = 1.12 (d, J = 7.1Hz, 3H, CHC H ₃ ), 2.16 (s, 3H, COC H ₃ ), 3.42 (s, 3H, OC H ₃ ) ppm.
HPLC: log P (neutral) = 2.59
Isomer 2 (anti) (CDCl ₃ / TMS): δ = 0.99 (d, J = 7.1Hz, 3H, CHC H ₃ ), 2.20 (s, 3H, COC H ₃ ), 3.36 (s, 3H, OC H ) ppm.
HPLC: log P (neutral) = 2.54

Production of precursors of formula (XIII) Example (XIII-1)

Procedure h)

A solution of 6.5 g (64 mmol) diisopropylamine in 150 ml tetrahydrofuran at -10 ° C while stirring with 40 ml of a solution of butyllithium in hexane added and the mixture is stirred at -10 ° C to 0 ° C for 15 minutes. Then 5.0 g (32 mmol) of 2,2-dimethyl-6-ethyl-4-oxo-1,3-dioxin are added at -78 ° C give, the mixture is stirred for 45 minutes at -78 ° C and then with 10.2 ml (80 mmol) trimethylchlorosilane were added and the mixture was stirred at -78 ° C. for a further 2 hours. Man allows to come to room temperature, concentrated in a water jet vacuum and distilled the residue under reduced pressure. 5.78 g (79% of theory) are obtained. Ethylidene-3-trimethylsilyloxy-2,2-dimethyl-1,3-diox-5-ene with a boiling point of 50 ° C (at 0.1 mbar).  

Production of precursors of formula (XI) Example (XI-1)

Procedure g)

A mixture of 3.0 g (20 mmol) benzyloxyacetaldehyde and 100 ml methylene chloride is cooled to -78 ° C and at this temperature with stirring in succession with 20 ml of a 1M solution of titanium (IV) chloride in methylene chloride (20 mmol of TiCl ₄ ) and a solution of 4.57 g (20 mmol) of 6-ethylidene-3-trimethylsilyloxy-2,2-dimethyl-1,3-diox-5-ene in 30 ml of methylene chloride were added dropwise. The reaction mixture is then stirred for a further 3 hours at -78 ° C. For working up, saturated aqueous sodium bicarbonate solution is added until foaming is no longer observed with further addition. The organic phase is then separated off and the aqueous phase is extracted twice with 100 ml of methylene chloride each time. The combined organic phases are washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated and the crude product which remains as a residue is purified by column chromatography (silica gel, ethyl acetate / hexane, vol .: 3: 1).

2.74 g (45% of theory) of 6- (3-benzyloxy-2-hydroxy-1-methyl-propyl) are obtained. 2,2-dimethyl-2,4-dihydro-1,3-diox-5-en-4-one as an amorphous product.

The separation of the syn and anti isomers can be carried out in a customary manner, for example by column chromatography.

The syn and anti isomers were characterized by their ¹ H NMR spectra:

Isomer 1 (CDCl ₃ , δ, ppm): 1.20 (d, J = 7.0Hz, 3H, CHC H ₃ ), 1.66 (s, 6H, 2 × CH ₃ ), 2.35 (d, J = 4.7Hz, 1H), 3.42 (dd, J = 9.5Hz / 6.7Hz, 1H), 3.53 (dd, J = 9.5Hz / 3.5Hz, 1H), 4.54 (s, 2H,), 5.29 (s, 1H).
Isomer 2 (CDCl ₃ , δ, ppm): 1.10 (d, J = 7.0Hz, 3H, CHC H ₃ ), 1.67 and 1.68 (s, 6H, 2 × CH ₃ ), 2, 40 (d, J = 5.4Hz, 1H), 5.31 (s, 1H).
Mass spectrum: (M + H) ⁺: 307.

Example (XI-2)

450 mg (1.5 mmol) 6- (3-benzyloxy-2-hydroxy-1-methyl-propyl) -2,2-dimethyl-2,4- dihydro-1,3-diox-5-en-4-one and 2.25 ml (6.9 mmol) methyl iodide are dissolved in 15 ml Di dissolved ethyl ether and stirred with 2.1 g (6.0 mmol) of silver 1-oxide in the dark for 3 days. The reaction mixture is filtered and the precipitate thoroughly with diethyl ether washed. The filtrate is concentrated under reduced pressure and the residue is chromatographed on silica gel using cyclohexane / ethyl acetate (1: 1). You get 270 mg (57% of theory) 6- (3-benzyloxy-2-methoxy-1-methyl-propyl) -2,2-dime thyl- [1,3] dioxin-4-one.

The diastereoisomers are characterized by ¹ H NMR spectra.

Isomer 1: (syn) (CDCl ₃ / TMS): δ = 1.13 (d, J = 7.1Hz, 3H, CHC H ₃ ), 3.42 (s, 3H, OC H ₃ ), 5.29 (s 1H H C = C ) ppm.
Isomer 2: (anti) (CDCl ₃ / TMS): δ = 1.09 (d, J = 7.1Hz, 3H, CHC H ₃ ), 338 (s, 3H, OC H ₃ ), 5.47 (s, 1H H C = C) ppm.
HPLC: log P (neutral) = 3.13

Production of precursors of formula (X) Example (X-1)

Procedure m)

236 mg (1.0 mmol) of 5-benzyloxy-4-methoxy-3-methyl-pentan-2-one are added Argon in a mixture of 20 ml tetrahydrofuran and 5 ml 1,3-dimethyltetrahy dro-2 (1H) -pyrimidinone dissolved and cooled to -78 ° C. 4.0 ml (4.0 mmol a 1M solution) lithium bistrimethylsilylamide at -78 ° C, stirred for 30 min. and drips then a solution of 430 mg (5.0 mmol) methyl cyano formate in 2 ml of tetrahydrofuran at -78 degrees. After another 15 min. is achieved by adding 20 ml of saturated ammonium chloride solution hydrolyzed. It is extracted with vinegar Acid ethyl ester, dries with sodium sulfate and concentrated under reduced pressure. Of the The residue is chromatographed on silica gel using cyclohexane / ethyl acetate (2: 1). Man receives 230 mg (80% of theory) of 6-benzyloxy-5-methoxy-4-methyl-3-oxo-hexane acid methyl ester.

The diastereoisomers can be separated by chromatography and are characterized by ¹ H-NMR spectra.

Isomer 1: (syn) (CDCl ₃ / TMS): δ = 1.14 (d, J = 7.0Hz, 3H, CHC H ₃ ), 3.42 (s, 3H, OC H ₃ ), 3.70 (s, 3H, OC H ₃ ) ppm.
HPLC: log P (acidic) = 2.50
Isomer 2: (anti) (CDCl ₃ / TMS): δ = 1.02 (d, J = 7.0Hz, 3H, CHC H ₃ ), 3.33 (s, 3H, OC H ₃ ), 3.72 (s, 3H, OC H ₃ ) ppm.
HPLC: log P (acidic) = 2.50

Example (X-1)

Procedure j)

240 mg (1.0 mmol) of 4-benzyloxy-3-methoxy-2-methyl-butanoic acid are dissolved in 20 ml of tetrahydrofuran under argon, 165 mg (1.0 mmol) of carbonyldiimidazole are added and the mixture is stirred at room temperature for 2 hours. 95 mg (1.0 mmol) of magnesium chloride and 165 mg (1.0 mmol) of potassium monomethylmalonate are added, and the mixture is stirred at room temperature for 1 hour and then at 40-45 ° C. for 6 hours. After cooling, the reaction mixture is filtered, the filtrate is concentrated under reduced pressure and taken up in ethyl acetate. The organic phase is washed successively with 1N hydrochloric acid, saturated sodium hydrogen carbonate and saturated sodium chloride solution, dried with sodium sulfate and concentrated under reduced pressure. 100 mg (34% of theory) of 6-benzyloxy-5-methoxy-4-methyl-3-oxo-hexanoic acid methyl ester are obtained.
The raw product is used without further purification.

Example (X-1)

Procedure f)

1.04 g (3.25 mmol) of 6- (3-benzyloxy-2-methoxy-1-methyl-propyl) -2,2-dimethyl- [1,3] - dioxin-4-one are dissolved in 150 ml of toluene and mixed with 680 mg (19.5 mmol) of methanol heated under reflux for 6 hours. The reaction mixture is concentrated under reduced pressure. 740 mg (78% of theory) of crude methyl 6-benzyloxy-5-methoxy-4-methyl-3-oxo-hexanoate are obtained.
The crude product is used for further syntheses without further purification.

Production of precursors of formula (IX) Example (IX-1)

Procedure e)

198 mg (1.73 mmol) of potassium hydride (35%) are argon twice with pentane washed and then in a mixture of 4 ml of tetrahydrofuran and 4 ml 1,3-Dimethyltetrahydro-2 (1H) -pyrimidinone dissolved. The suspension is at 0 ° C cooled and with 660 mg (5.2 mmol) of dimethyl sulfate and a solution of 510 mg (1.73 mmol) 6-Benzyloxy-5-methoxy-4-methyl-3-oxo-hexanoic acid methyl ester in 4 ml Tetrahydrofuran and 2 ml of 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone were added. It is stirred for one hour at 0 ° C and then by adding water hydrolyzed. It is extracted with hexane, dried with sodium sulfate and concentrated at ver reduced pressure. The residue is mixed with cyclohexane / ethyl acetate (3: 1) on silica gel chromatographed. 250 mg (47% of theory) of 6-benzyloxy-3,5- dimethoxy-4-methyl-hex-2-enoic acid methyl ester.  

The diastereoisomers (syn / anti) are characterized by ¹ H-NMR spectra. (E) -configured products are created.

Isomer 1: (syn) (CDCl ₃ / TMS): δ = 1.17 (d, J = 7.0Hz, 3H, CHC H ₃ ), 3.48, 3.55, 3.66 (s, 3H, OC H ₃ ), 4.96 (s, 1H, H C = C) ppm.
HPLC: log P (neutral) = 3.37

Preparation of precursors of formula (VIII) Example (VIII-1)

Procedure d)

180 mg (0.612 mmol) of 6-benzyloxy-3,5-dimethoxy-4-methyl-hex-2-enoic acid methyl esters are dissolved in 30 ml of ethyl acetate and after the addition of catalytic Amounts of Pd-C (10%) hydrogenated for 1.5 hours. When the reaction has ended, the reac tion mixture filtered and the filtrate concentrated under reduced pressure. You get 6-Hydroxy-3,5-dimethoxy-4-methyl-hex-2-enoic acid methyl ester. The product decomposes itself and will be implemented directly raw.

Production of intermediates of formula (II) Example (II-1)

Procedure c)

42 mg (0.2 mmol) of the crude product 6-hydroxy-3,5-dimethoxy-4-methyl-hex-2-en- Acid methyl ester are dissolved in 10 ml of methylene chloride. One gives with stirring 100 mg molecular sieve 4 Å (powdered), 41 mg (0.3 mmol) N-methyl-morpholine-N-  oxide and 14 mg (20 mol%) of tetrapropylammonium perruthenate and stirred for 2 hours at room temperature. The reaction mixture is filtered through Celite and under reduced pressure. 3,5-Dimethoxy-4-methyl-6-oxo-hex-2-ene is obtained. acid methyl ester. The product is volatile and unstable and continues to be used raw.

The diastereoisomers (syn / anti) are characterized by ¹ H-NMR spectra. (E) -configured products are created.

Isomer 1 (syn) (CDCl ₃ / TMS): δ = 1.20 (d, J = 7.1Hz, 3H, CHCH ₃ ), 3.43, 3.64, 3.68 (s, 3H, OCH ₃ ), 5.07 (s, 1H, HC = C) ppm.
FAB-MS: m / e = 217 (M +)

Claims (18)

1. Compounds of formula (I)
in which
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, and
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, arylamino, arylamino , Heterocyclyl, Heterocyclyl amino, Heterocyclylalkyl or Heterocyclylalkylamino, or one of the following groupings
A ³ -ON = C (A ² ) -CH (A ¹ ) -O- or A ³ -ON = C (A ² ) -C (A ¹ ) = N-
stands, where
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. 2. Compounds of formula (I) according to claim 1, in which
R ¹ for hydroxy, amino, for alkoxy, alkylamino or dialkylamino each optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, or for each optionally substituted by halogen or C ₁ -C _4- alkyl substituted benzyloxy or benzylamino,
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 C ₁ -C ₄ -alkoxy,
R ⁴ for hydrogen, for alkyl optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy having 1 to 6 carbon atoms, for each alkenyl or alkynyl optionally substituted by cyano or halogen each having 2 to 6 carbon atoms, or for where appropriate cycloalkyl or cycloalkylalkyl which is substituted by cyano, halogen or C ₁ -C ₄ -alkyl and has in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,
R ⁵ for hydrogen, for optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy alkyl having 1 to 6 carbon atoms, for each optionally substituted by cyano or halogen alkenyl or alkynyl each having 2 to 6 carbon atoms, or for where appropriate cycloalkyl or cycloalkylalkyl which is substituted by cyano, halogen or C ₁ -C ₄ -alkyl and has in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,
R ^{6 represents} hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy, and
Z stands for the grouping R ⁷ -N or the grouping (R ⁸ ) (R ⁹ ) C, where
R ⁷ for hydrogen, hydroxy, amino, for alkyl, alkoxy, alkylamino or dialkylamino, each optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy, each having 1 to 6 carbon atoms in the alkyl groups, each optionally substituted by cyano or halogen Alkenyl, alkenyloxy or alkynyl each having 2 to 6 carbon atoms in the alkenyl or alkynyl groups, for each cycloalkyl, cycloalkyloxy, cycloalkylamino, cycloalkyl alkyl, cycloalkylalkoxy or cycloalkylalkylamino each substituted by cyano, halogen or C ₁ -C ₄ alkyl to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, for each optionally by nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ -Ha logenalkylsulfonyl or C ₁ -C ₄ alkoximino-C ₁ -C ₄ alkyl substituted aryl, aryloxy, arylamino, arylalkyl, arylalkoxy or arylalkylamino each having 6 or 10 carbon atoms in the aryl group and optionally up to 4 carbon atoms in the alkyl part, or for each optionally by cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ - C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ halo alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl, phenyl, phenoxy or phenylthio (where the phenyl groups in each case ge by cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ -halogen alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ -haloalkoxy substituted) substituted and / or benzannelliertes heterocyclyl, heterocyclyl amino, Heterocyclylalkyl or heterocyclylalkylamino each having 3 to 7 ring members in the heterocyclyl group and optionally 1 to 4 carbon atoms n is in the alkyl part, the heterocyclyl group in each case containing 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 groups below
A ³ -ON = C (A ² ) -CH (A ¹ ) -O- or A ³ -ON = C (A ² ) -C (A ¹ ) = N-
stands, where
A ^{1 represents} hydrogen or alkyl having 1 to 6 carbon atoms,
Substituted A ² represents hydrogen, cyano, represents in each case optionally cyano-, halogen or C ₁ -C ₄ -alkoxy-substituted alkyl having 1 to 6 carbon atoms, represents optionally cyano-, halogen- or C ₁ -C ₄ -alkyl cycloalkyl having 3 to 6 Carbon atoms or phenyl optionally substituted by cyano, halo, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy, and
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 C ₁ -C ₄ -alkoxy, for alkenyl with 2 to 10 carbon atoms optionally substituted by cyano or halogen, for each optionally substituted by cyano, halo or C ₁ -C ₄ 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, if appropriate, in each case by nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkyl sulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl or C ₁ - C ₄ alkoximino-C ₁ -C ₄ 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 alkyl with 1 to 10 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy, for alkenyl with 2 to 10 carbon atoms optionally substituted by cyano or halogen, for each optionally substituted by cyano, halo or C ₁ -C ₄ 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, if appropriate, in each case by nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkyl sulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl or C ₁ - C ₄ alkoximino-C ₁ -C ₄ 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,
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 registry no .: 153934-11-3] - known from Tetrahedron Lett. 34 (1993), 5151-5154 - are excluded by disclaimers. 3. Compounds of formula (I) according to claim 1, in which
R ¹ for hydroxyl, amino or methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n-, in each case optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino,
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, each optionally substituted by cyano, fluorine, chlorine, methyl or ethyl,
R ⁵ 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, each optionally substituted by cyano, fluorine, chlorine, methyl or ethyl,
R ^{6 represents} hydrogen or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and
Z stands for the grouping R ⁷ -N or the grouping (R ⁸ ) (R ⁹ ) C, where
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 each optionally substituted by cyano, fluorine or chlorine, ethenyl, propenyl, butenyl, propenyloxy, butenyloxy, ethynyl, propynyl or butynyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyloxy optionally substituted by cyano, fluorine, chlorine, methyl or ethyl, Cyclohexyloxy, Cyclopentylamino, Cyclohexylamino, Cyclopropylmethyl, Cyclo-butyl methyl, Cyclopentylmethyl, Cyclohexylmethyl, Cyclopentylmethoxy, Cyclohexylmethoxy, Cyclopentylmethylamino or Cyclohexylmethyl amino, for each optionally by nitro, cyano, fluorine, chloro, nyl, methyl or ethyl, Eth , n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonethyl, methoximino-methylethyl , Methoximinoethyl or ethoximinoethyl substituted phenyl, phenoxy, phenylamino, benzyl, benzyloxy, benzylamino or phenylethyl, or for each optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethyl substituted sulfonyl Heterocyclyl or heterocyclic alkyl from the series oxiranyl, oxiranylmethyl, aziridinyl, oxetanyl, oxetanoyloxy, oxetanylmethyl, furyl, furylamino, furyl methyl, tetrahydrofuryl, thienyl, thienylami no, thienylmethyl, Benzofurylamino, Benzofurylmethyl, isobenzofuryl, benzothienyl, Benzothienylamino, benzothienylmethyl, pyrrolyl, indolyl, oxazolyl, oxazolylmethyl, benzoxazolyl, benzoxazolylmethyl, isoxazolyl, isoxazolylmethyl, benzisoxazolyl, benzisoxazolylmethyl, thiazolyl, thiazolylmethyl, benzothiazolyl, Benzthiazolylmethyl, oxadiazolyl, Oxadiazolylmethyl, thiadiazolyl, Thiadiazolylmethyl, pyridyl, pyridylamino, pyridylmethyl, quinolyl, quinolylamino, quinolylmethyl, pyrimidyl, pyrimidinylamino, pyrimidylmethyl, pyridazinyl, pyrazinyl, triazinyl, or one of the following groups
A ³ -ON = C (A ² ) -CH (A ¹ ) -O- or A ³ -ON = C (A ² ) -C (A ² ) = N-
stands, where
A ^{1 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
A ² for hydrogen, cyano, 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, chlorine, methyl or ethyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or for optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -Butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromoxy or trifluoromethoxy substituted phenyl, and
A ^{3 represents} hydrogen, methyl, ethyl, n- or i-propyl,
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 in each case optionally substituted by cyano, fluorine, chlorine or bromine, propenyl, butenyl or pentenyl, for in each case optionally substituted by cyano, fluorine, chlorine, methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, Cyclobutylmethyl, Cyclo pentylmethyl or Cyclohexylmethyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl substituted phenyl, benzyl or benzyl
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 in each case optionally substituted by cyano, fluorine, chlorine or bromine, propenyl, butenyl or pentenyl, for in each case optionally substituted by cyano, fluorine, chlorine, methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, Cyclobutylmethyl, Cyclo pentylmethyl or Cyclohexylmethyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl substituted phenyl, benzyl
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 registry no .: 153934-11-3] - known from Tetrahedron Lett. 34 (1993), 5151-5154 - are excluded by disclaimers. 4. Compounds of formula (I) according to claim 1, in which
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. 5. Compounds of formula (I) according to claim 1, in which
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, if appropriate by cyano, fluorine or chlorine-substituted ethenyl, propenyl, butenyl, propenyloxy, butenyloxy, ethynyl, propynyl or butynyl, for cyclopentyl, cyclohexyl, cyclopentyloxy, cyclohexyl oxy, cyclopentylamino, cyclohexylamino, cyclopentylmethyl, cyclohexylamino, cyclohexylamethyl, cyclohexylamino, cyclohexylamethyl, cyclohexylamino, cyclohexylamethyl, cyclohexylamino, cyclohexylamino, cyclohexylamino, cyclohexylamino, cyclohexylamino, cyclohexylamino, cyclohexylamino, cyclohexylamino and cyclohexylamino , Cyclopentylmethoxy, Cyclohexylmethoxy, Cyclopentyl methylamino or Cyclohexylmethylamino, for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, Methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluorme thoxy, methylthio, ethyl thio, n- or i-propylthio, trifluoromethylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, methoximino methyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl each substituted by phenyl, phenoxy, phenylamino or benzyl for benzylamino or benzyl Cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio , ethylthio, n- or i-propylthio, trifluoro methylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, fluoromethylsulfonyl tri or phenyl substituted heterocyclyl or heterocyclylalkyl from the series oxiranyl, oxiranylmethyl, aziridinyl, oxetanyl, Oxetanoyloxy, Oxetanylmethyl, furyl, Furylamino, furyl methyl, tetrahydrofuryl , Thienyl, Thienylamino, Thienylmethyl, Benzofurylamino, Benzofurylmethyl, Isobenzofuryl, Benzothienyl, Benzothienylamino, Benzothie nylmethyl, pyrrolyl, indolyl, oxazolyl, oxazolylmethyl, benzoxazolyl, benzoxazolylmethyl, isoxazolyl, isoxazolylmethyl, benzisoxazolyl, benzisoxazolylmethyl, thiazolyl, thiazolylmethyl, benzothiazolyl, Benzthiazolylmethyl, oxadiazolyl, Oxadiazolylmethyl, thiadiazolyl, Thiadiazolylmethyl, pyridyl, pyridyl amino, pyridylmethyl, quinolyl, quinolylamino, quinolylmethyl , Pyrimidyl, pyrimidinylamino, pyrimidylmethyl, pyridazinyl, pyrazinyl, triazinyl. 6. Agent, characterized by a content of at least one compound of Formula (I) according to claim 1. 7. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 for pests and / or lets their living space take effect.   8. Use of compounds of formula (I) or agents according to the claims Chen 1 to 6 to control pests. 9. Process for the preparation of pesticides, thereby ge indicates that compounds of the formula (I) according to Claims 1 to 5 mixed with extenders and / or surfactants. 10. A process for the preparation of compounds of formula (I) as defined in claim 1, characterized in that

• (a) alkenoic acids or their derivatives of the general formula (II)
  in which
  R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given in claim 1,
  with amino compounds of the general formula (III)
  R ⁷ -NH ₂ (III)
  in which
  R ^{7 has} the meaning given in claim 1,
  -or with acid adducts of compounds of the general formula (III) -
  or with olefining agents of the general formulas (IV) or (V)
  (R ⁸ ) (R ⁹ ) C = P (R ') ₃ (IV)
  (R ⁸ ) (R ⁹ ) CH-P (O) (R '') ₂ (V)
  in which
  R ⁸ and R ^{9 have} the meaning given in claim 1,
  R 'represents alkyl or aryl and
  R '' represents alkyl, alkoxy or aryl,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,
  or if you
• (b) bis-enolates of the general formula (VI)
  in which
  R ¹ , R ² and R ^{4 have} the meaning given in claim 1 and
  M represents lithium, sodium, potassium or a magnesium equivalent,
  with aldehydes of the general formula (VII)
  in which
  R ⁶ and Z have the meaning given in claim 1,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,
  and optionally on the compounds of the general formula (I) thus obtained, further conversions within the scope of the above substituent definition by conventional methods.

11. Compounds of the formula (II)
in which
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meanings given in Claim 1. 12. Compounds of formula (VIII)
in which
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given in claim 1. 13. Compounds of formula (IX)
in which
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given in claim 1. 14. Compounds of formula (X)
in which
R ² , R ⁴ , R ⁵ and R ^{6 have} the meaning given above. 15. Compounds of the formula (XI)
in which
R ² , R ⁴ , R ⁵ and R ^{6 have} the meaning given in claim 1. 16. Compounds of the formula (XVI)
in which
R ¹ , R ² and R ^{4 have} the meaning given in claim 1 and
M represents lithium, sodium, potassium or a magnesium equivalent. 17. Compounds of the formula (XVII)
in which
R ⁴ and R ^{6 have} the meaning given in claim 1. 18. Compounds of the formula (XIX)
in which
R ⁴ and R ^{6 have} the meaning given in claim 1.