DD298394A5 - SUBSTITUTED ACRYLIC ACID ESTERS - Google Patents

Abstract

Substituted acrylic acid esters of the general formula * in which R1, R2, R3, R4, X and Y have the meaning given in the description, their use for the control of pests and new intermediates. The novel compounds are defined by the formula (I) and can be prepared by analogy methods, e.g. B. from suitable hydroxyacrylic acid esters with suitable alkylating agents, or from suitable substituted acetic acid esters with suitable formamides or their derivatives, or from suitable Oxalsaeurederivaten and suitable organometallic compounds, or from suitable acrylic acid esters and suitable thiols. Some intermediates are new and can be prepared by analogy. Formula (I)

Description

R ¹ ^ ₇ . N COOR ³

JI I ₂ '(viii)

RZxVxXVo-C = CH-E "

in which

R ^{1 is} hydrogen, alkyl, alkenyl or optionally substituted aralkyl, aralkenyl, aryl or heteroaryl,

R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl.-alkoxyalkyl, alkylchioalkyl, hydroximinoalkylmycoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, aryloxy, Arylthio, alkanoyl, alkoxycarbonyl, N, N-dialkylcarbamoyl or heterocyclylcarbonyl,

R ^{3 is} alkyl or optionally substituted aralkyl, X is oxygen or sulfur and E ^{2 is} an electron attracting leaving group, characterized in that hydroxyacrylic acid esters of the formula (II b),

R ¹ V. N COOR ³

2X \ xX \ q -C =

CH-OH

in which

R ¹ , R ² , R ³ and X have the abovementioned meaning, with acid chlorides of the formula (XIV),

R ¹⁰ -CI (XIV)

in which

R ^{10 is} an acyl or sulfonyl radical, if appropriate in the presence of a diluent and optionally in the presence of an acid binder at temperatures between -2O ⁰ C and + 12O ⁰ C reacted.

17. Use of compounds of the formulas (II), (IVa) and (VIII) according to claims 11, 13 and 15 as intermediates.

The invention relates to novel substituted acrylic acid esters, to a plurality of processes for their preparation, to their use in Pesticides and new intermediates. It is known that certain substituted acrylic esters, such as the compound 3-methoxy-2- (2-methylphenyl) -

methyl acrylate have fungicidal properties (see, e.g., EP178826).

However, the effectiveness of these vorb-recognized compounds is especially at low application rates and Concentrations are not completely satisfactory in all fields of application. There have been new substituted acrylic acid esters of the general formula (I),

COOR ³

I _IA

^ Y - C = CH-R ⁴

C = CH-R ⁴

in which

R 'is hydrogen, alkyl, alkenyl or any substituted aralkyl, aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl,

N-alkyliminoalkyl, N-aryliminoalkyl. Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, aryloxy, arylthio, alkanoyl, alkoxycarbonyl, Ν, Ν-dialkylcarbamoyl or heterocyclylcarbonyl,

R ^{3 is} alkyl or optionally substituted aralkyl, R ^{4 is} dialkylamino or a residual ZR ⁶ , X is oxygen or sulfur and Y is oxygen, sulfur or a residual N-,

R ^e

R ^{5 is} alkyl or optionally substituted aralkyl, R ^{6 is} hydrogen, alkyl, alkanoyl or each optionally substituted aralkyl or aryl; and Z is oxygen or sulfur,

found.

The compounds of the formula (I) can be different than geometric isomers or mixtures of isomers Composition present. Both the pure isomers and the isomer mixtures are according to the invention

claimed.

Furthermore, it has been found that the novel substituted acrylic acid esters of the general formula (I)

R ¹ X ₁ N COOR ³

Tl I ₄ (η

in which

R 'is hydrogen, alkyl, alkenyl or each optionally substituted aralkyl, aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, for alkoxy, alkylthio, haloalkoxy, haloalkylthio, for

Aryloxy, arylthio, alkanoyl, alkoxycarbonyl, Ν, Ν-dialkylcarbamoyl or heterocyclylcarbonyl, R ^{3 is} alkyl or optionally substituted aralkyl, R ^{4 is} dialkylamino, a residual ZR ^s , X is oxygen or sulfur and Y is oxygen, sulfur or stands for a remnant N,

R ^e

R ^{s is} alkyl or optionally substituted aralkyl, R ^{6 is} hydrogen, alkyl, alkanoyl, or each optionally substituted aralkyl or aryl; and Z is oxygen or sulfur,

obtained by one of the processes described below: (a) substituted acrylic acid esters of the formula (Ia) are obtained,

R ¹ VN COOR ³

(La)

= CH-O-R ⁵

in which

R ', R ² , R ³ , R ^& , X and Y have the abovementioned meaning, if hydroxyacrylates or their Alkali metal salts of the formula (II),

COOR ³ '-C = CH-OM

in which

M is hydrogen or an alkali metal cation and R ¹ , R ² , R ³ , X and Y have the abovementioned meaning, with alkylating agents of the formula (III),

R ⁵ -E '(III)

in which

E ^{1 stands} for an electron attracting leaving group and

R ^{5 has} the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary; (b) substituted acrylic acid esters of the formula (I b) are obtained

N COOR ³

, , (Ib)

X ₁ N

9TlL

in which

R ⁴ "'represents dialkylamino and

R ¹ , R ¹ , R ³ , X and Y have the abovementioned meaning, if substituted acetic acid esters of the formula (IV)

Χΐί "( ^{| V} >

..- ^ Y-CH ₂ -COOR ³

in which R ¹ , R ² , R ³ , X and Y have the abovementioned meaning, with formamides of the formula (Va),

O HCR ⁴ - '(Va)

in which R ⁴ * 'has the abovementioned meaning, or with derivatives thereof of the formula (Vb),

R ⁷ R *

> _CH . _R 4-1 (Vb)

in which

R ⁷ and R ⁸ are each independently alkoxy or dialkylamino and R ⁴ * ^{1 has} the abovementioned meaning, if appropriate in the presence of a diluent; (c) substituted acrylic esters of the formula (Ic) are obtained,

-N COOR ³

I _c (IO

-C = CH-SR ⁰

in which Y 'is sulfur or a radical -N-,

R "and R ¹ , R ² , R ³ , R ⁵ , R ^s and X have the abovementioned meaning, if the fatty acid derivatives of the formula (VI),

¹ -C-COOR ^J (VI)

in which R ¹ , R ² , R ³ , X and Y 'have the abovementioned meaning, with organometallic compounds of the formula (VII)

-, - - < ^VII >

R ⁵ -S

in which

R ^{5 has} the abovementioned meaning, if appropriate in the presence of a diluent; (d) substituted acrylic acid esters of the formula (I d) are obtained,

COOR ³

j (id)

-C = CH-SR ⁵

in which R ¹ , R ² , R ³ , R ⁵ and X have the abovementioned meaning, if substituted acrylic acid esters of the formula (VIII)

COOR ³

I (viii)

-C = CH-E ²

in which E ^{2 is} an electron-attracting leaving group and R ¹ , R ² , R ³ and X have the abovementioned meaning, with thiols of the formula (IX),

(IX)

in which R ^{5 has} the abovementioned meaning, if appropriate in the presence of a diluent and optionally in

Reacting the presence of a reaction auxiliary.

Finally, it has been found that the new substituted acrylic esters of the general formula (I) have a good action against Own pests. Surprisingly, the substituted acrylic acid esters of the general formula (I) according to the invention exhibit z. Legs

significantly better fungicidal activity than the known from the prior art acrylic acid esters, such as

Compound 3-Methoxy-2- (2-methyl-phenyl) -acrylic acid methyl ester, which is chemically and operatively obvious Connections are. The substituted acrylic acid esters according to the invention are generally defined by the formula (I). Preferred are Compounds of the formula (I), b '< which

R ^{1 represents} hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, or straight-chain or branched alkenyl having 2 to 8 carbon atoms, aralkyl having 1 to 6 carbon atoms in the straight-chain or mono- or polysubstituted by identical or different substituents optionally substituted once or twice in the alkyl moiety branched alkyl part, aralkenyl with

2 to 6 carbon atoms in the straight-chain or branched alkenyl part or aryl having 6 to 10 carbon atoms in the respective aryl part, in each case being suitable as aryl substituents:

Halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy or alkylthio having in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case straight-chain or branched Alkoxycarbonyl or alkoximinoalkyl having in each case 1 to 8 carbon atoms in the individual alkyl moieties, cycloalkyl with

3 to 7 carbon atoms, doubly linked alkanediyl having 3 to 5 carbon atoms, each optionally in the aryl moiety mono- to polysubstituted by identical or different halo, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or Haliogenalkylthio each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms substituted aryl, aralkyl, aryloxy or aralkyloxy having in each case 6 to 10 carbon atoms in the aryl moiety and optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety or in each case optionally in the heteroaryl moiety singly or multiply, identically or differently, by halogen, alkyl, alkoxy, Alkylthio, haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms substituted heteroarylalkyl or heteroaryl having in each case 2 to 9 carbon atoms and 1 to 4 identical or different heteroatoms, - esp Other nitrogen, oxygen and / or sulfur - in the heteroaryl and optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety;

R 'furthermore represents an optionally mono- to polysubstituted, identically or differently substituted heteroaryl radical having 2 to 9 carbon atoms and 1 to 4 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur -, the abovementioned aryl substituents being suitable as substituents .

R ^{2 is} fluorine, chlorine, bromine, iodine, cyano, nitro, formyl, straight-chain or branched haloalkyl having 1 to 4

Carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine, bromine or iodine, in each case straight-chain or branched alkoxyalkyl or alkylthioalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties, in each case straight-chain or branched hydroximinoalkyl, alkoximinoalkyl, N-alkyliminoalkyl or Ν, Ν-dialkylhydrazonoalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties, in each case straight-chain or branched alkoxy or alkylthio having in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkoxy or halogenoalkylthio having in each case 1 to 4 carbon atoms and in each case 1 to 9 the same or different halogen atoms, in particular fluorine, chlorine or bromine, in each case straight-chain or branched alkanoyl, alkoxycarbonyl or Ν, Ν-Oialkylcarbamoyl each having 1 to 4 carbon atoms in the individual alkyl moieties or heterocyclylcarbonyl, where as Heterocyc lylrest a saturated five- to seven-membered N-linked Heterocyc'us in question, which may optionally contain a further heteroatom, in particular oxygen, sulfur or nitrogen, and which may optionally be substituted one to four times by methyl and / or ethyl;

R ² also in each case optionally mono- to polysubstituted, identical or different, in the aryl moiety, in each case

6 to 10 carbon atoms substituted N-aryliminoalkyl, aryloxy or arylthio, wherein the straight-chain or branched alkyl part has 1 to 4 carbon atoms and wherein as aryl substituents in question: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy or alkylthio with in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case straight-chain or branched alkoxycarbonyl or alkoximinoalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties, optionally monosubstituted multiply, identically or differently by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted phenyl,

R ^{3 is} straight-chain or branched alkyl having 1 to 6 carbon atoms or optionally in the aryl part mono- to polysubstituted, identically or differently substituted aralkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl part and 6 to 10 carbon atoms in the aryl part, wherein as aryl substituents at R ¹ mentioned come into question,

R ^{4 represents} dialkylarrino with in each case 1 to 6 carbon atoms in the individual straight-chain or branched alkyl parts or represents a radical ZR ⁶ ,

X is oxygen or sulfur and Y is oxygen, sulfur or a residual N-,

R ^e

R ^{5 is} straight-chain or branched alkyl having 1 to 6 carbon atoms or optionally in the aryl part mono- to polysubstituted, identically or differently substituted aralkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl part and 6 to 10 carbon atoms in the aryl part, wherein as aryl substituents at those mentioned R ¹ in question, R ⁶ represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkanoyl having 1 to 6 carbon atoms in the alkyl or in each case optionally in the aryl moiety to polysubstituted by identical or different substituents aralkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety or aryl having in each case 6 to 10 carbon atoms in the respective aryl moiety, the substituents in the aryl moiety being in each case those mentioned for R 'and Z being oxygen or sulfur.

Particular preference is given to compounds of the formula (I) in which

R 'represents hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, allyl, η- or I-butenyl, in each case optionally in the aryl part or in the heteroaryl part benzyl, phenylethyl, phenytethenyl, phenyl, naphthyl, pyridyl, thionyl or furyl, where each substituent is suitable: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i- Propy I, η-, i-, s- or t-butyl I, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarboryl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, Ethoximinoethyl, cyclopentyl, cyclohexyl, 1,3-propanediyl, 1,4-butanediyl or in each case optionally in the phenyl moiety one to three times, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, trifluoromethyl, Difluoromethoxy, trifluoromethoxy and / or trifluoromethylthio substituted phenyl, B enyl, phenoxy or benzyloxy,

R ^{2 represents} chlorine, bromine, iodine, cyano, nitro, formyl, chloromethyl, bromomethyl, iodomethyl, moihoxymethyl, ethoxymethyl, n- or i-propoxymethyl, methylthiomethyl, ethylthiomethyl, n- or i-propylthiomethyl I, for hydroximinomethyl I, hydroximinoethyl, Hydroximinopropyl, for methoximinomethyl, ethoximinomethyl, n- or i-propoximinomethyl, methoximinoethyl, ethoximinoethyl, n- or i-propoximinoethyl, for Mothyliminomethyl, ethyliminomethyl, n- or i-Propyliminomethyl, for methyliminoethyl, ethylimime. 3-ethyl, n- or i-propyliminoethyl, for Ν, Ν-dimethylhydrazonomethyl, N, N-diethylhydrazonomethyl, N-methyl-N-ethylhydrazonomethyl, N-methyl-N-propylhydrazonomethyl, Ν, Ν-dipropylhydrazonomethyl, Ν, Ν-dimethylhydrazonoethyl, Ν, Ν-Dlethylhydrazonoethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, for TrifJuormethoxy, difluoromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, trichloromethoxy, trifluoromethylthio, trichloromethylthio, difluoromethylthio, Dichlorfluormethyl'hio, difluorochloromethylthio for acetyl, propionyl, butyryl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, N, -dipropylaminocarbonyl, N-methyl-N-ethylaminocarbonyl, N-methyl-N-propylaminocarbonyl, for 1 Piperidinylcarbonyl, 4-morpholinylcarbonyl or N-phenyliminomethyl, N-phanylimionomethyl, phenoxy or phenylthio, each of which is optionally monosubstituted to trisubstituted by identical or different substituents in the phenyl moiety in each case suitable substituents being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl or optionally mono- to trisubstituted by identical or different substituents by fluorine, chlorine, bromine, methyl and / or ethyl-substituted phenyl,

R ^{3 is} methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl or optionally mono- to trisubstituted by identical or different substituents benzyl, where as substituents mentioned in R ¹ in Come question

R ^{4 is} dialkylamino having in each case 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts or is a radical ZR ⁵ ,

X is oxygen or sulfur and Y is oxygen, sulfur or a residual N-,

R ^e

R ^{5 is} methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl or optionally mono- to trisubstituted, identical or different

substituted benzyl, wherein as substituents those mentioned in R 'come into question; R "is hydrogen, methyl, ethyl, η- or i-propyl, n-, I-, s- or t-butyl, f Or acetyl, propionyl, n- or i-butyryl or, if appropriate, one to three times, the same or differently substituted benzyl or phenyl,

wherein as substituents those mentioned in R ¹ come into question and Z is oxygen or Schwofel.

Very particular preference is given to compounds of the formula (I) in which

R ^{1 is} hydrogen, methyl, ethyl, η- or i-propyl or is in each case optionally mono- to disubstituted, identical or different substituted phenyl or naphthyl, where as substituents in question: fluorine, chlorine, bromine, cyano, nitro , Methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, Methoxyiminomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl, cyclopentyl, cyclohexyl, 1,3-propanediyl, 1,4-butanediyl or in each case optionally monosubstituted or disubstituted by identical or different substituents by fluorine, chlorine, bromine, methyl and / or ethyl-substituted phenyl, phenoxy, Benzyl or benzyloxy,

R ^{2 is} chlorine, bromine, cyano, nitro, formyl, methoxymethyl, ethoxymethyl, methylthiomethyl, hydroximinomethyl, methoximinomethyl, ethoximinomethyl, methyiminiminethyl, ethyliminomethyl, Ν, Ν-dimethylhydrazonomethyl, N, N-diethylhydrazonomethyl, for methoxy, ethoxy, methylthio, ethylthio, Trifluoromethylthio, dichlorofluoromethylthio, difluorochloromethylthio, trichloromethylthio, acetyl, methoxycarbonyl, ethoxycarbonyl, Ν, Ν-dimethylaminocarbonyl, Ν, Ν-diethylaminocarbonyl, N-methyl-N-ethylaminocarbonyl or phenylthio which is optionally monosubstituted or disubstituted by identical or different substituents, where Substituents come into question: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, Mothylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,

R ^{3 is} methyl, ethyl or benzyl, R ^{4 is} dimethylamino, diethylamino or a residual ZR ⁵ , X is oxygen or sulfur and Y is oxygen, sulfur or a radical -N-,

R ^e

R ^{5 is} methyl, ethyl, η- or i-propyl or benzyl, R ^{e is} hydrogen, methyl, ethyl, acetyl, propionyl or in each case optionally single or twice, identical or different, by fluorine, chlorine, bromine, methyl, ethyl and / or trifluoromethyl

substituted benzyl or phenyl and Z represents oxygen or sulfur.

Particular preference is given to compounds of the formula (I) in which

R ^{1 is} hydrogen, methyl, ethyl, η- or i-propyl or optionally mono- or disubstituted by identical or different substituents phenyl, where possible substituents are: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, Methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy.trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, cyclopentyl, 1,3-propanediyl methoximinoethyl or optionally mono- or disubstituted by identical, different or by fluorine, chlorine, bromine or methyl-substituted phenyl, phenoxy, benzyl or benzyloxy,

R ^{2 is} chlorine, bromine, cyano, nitro, formyl, methoxymethyl, methylthiomethyl, methoxycarbonyl, ethoxycarbonyl, methylthio, trifluoromethylthio or methoximinomethyl,

R ^{3 is} methyl or ethyl, R ^{4 is} methoxy, ethoxy, methylthio or dimethylamines, X is oxygen or sulfur and Y stands for an N-methyl radical.

Specifically, in addition to the compounds mentioned in the preparation examples, the following substituted acrylic acid esters of the general formula (I) may be mentioned:

R 'R ^;

COOR ³ -C = CH-R ⁴

CN

OCH.

N-CH ₃

CN

CN

CHq OCHr

CH.

OCH

N-CH ₃

A.D

CN

CHo OCHr

N-CH ₃

Cl Cl

ö-

CN

ochr

N-CH ₃

CN

CHo OCHr

N-CH ₃

CN

CN

CHq OCHr

CH-

ochr

N-CHRN-CHr

R ³ R ⁴ XY

br

CN CH ₃ OCH ₃ S N-CH ₃ CN CH ₃ OCH ₃ S N-CH ₃ CN CH ₃ OCH ₃ S N-CH ₃ CN CH ₃ OCH ₃ S N-CH ₃

CN CH ₃ OCH ₃

CN CH ₃ OCH ₃ S N-CH ₃

Cl

CN CH ₃ OCH ₃ S N-CH ₃ CN CH ₃ OCH ₃ S N-CH ₃

O ₂ N

CN CH ₃ OCH ₃ S N-CH ₃

OCH

CN CH ₃ OCH ₃

N-CH ₃

CH.

CN CH ₃ OCH ₃ S N-CH ₃

Cl

CN CH ₃ OCH ₃ S N-CH ₃

CH ₃ O,

,, CN CH ₃ OCH ₃

S N -CH _:

ochr

CN CH ₃ OCH ₃

S N-CH ₃

CN CH ₃ OCH ₃ S N-CH ₃

° ^CH :

CN CH ₃ OCH ₃ S _N-CH;

R ² R ³ R ⁴

XY

-CHO CH ₃ OCH ₃ S

-CHO CH ₃ OCH ₃ S N-CH ₃

-CHO CH ₃ OCH ₃ S N-CH _:

-CHO CH ₃ OCH ₃ S N-CH ₃

-CHOCH ₃ OCH ₃ S N-CH _;

-CHO CH ₃ OCH ₃ S N-CH ₃

-CHO CH ₃ OCH ₃ S N-CH ₃

-CHO CH ₃ OCH ₃

N-CH ₃

-CHO CH ₃ OCH ₃ S N-CH ₃

Η- \

₃ - ^ ^ - CHO CH ₃ OCH ₃ S N-CH;

R ³ R ⁴

XY

R ² R ³ R ⁴ XY

egg:

-COOCH ₃ CH ₃ OCH ₃ S N-CH ₃

egg:

-COOCH ₃ CH ₃ OCH ₃ 0 N-CH ₃

-CHO CH ₃ OCH ₃

S N

-CHOCH ₃ OCH ₃ S N-CH _;

Cl CH ₃ OCH ₃ 0 N

Cl CH ₃ OCH ₃ 0 _N-CH:

Cl CH ₃ OCH ₃ 0 N-CH ₃

Cl

Cl CH ₃ OCH ₃ 0 N-CH ₃

Cl CH ₃ OCH ₃ 0 N-CH ₃

Cl

Cl CHq OCHq 0 N-CH,

R ² R ³ R ⁴

XY

Cl Cl

ff

Cl CH ₃ OCH ₃

0 N-CH.

Cl

Cl

Cl

Br CH ₃ OCH ₃

0 N-CH ₃

Br CH ₃ OCH ₃ 0 N-CHr Br CH ₃ OCH ₃ 0 _N-CH:

ochr

Br CH ₃ OCH ₃ 0 N-CH ₃

CH ₃ O

OCH

Br CH ₃ OCH ₃ 0 N-CH _C

CH ₃ O

Br CH ₃ OCH ₃ 0 N-CHr Br CH ₃ OCH ₃ 0 N-CH ₃

XY

CH ₃ O,

CH ₃ O '

NO ₂ CH ₃ OCH ₃ 0 N-CH ₃

NO ₂ CH ₃ OCH ₃ 0 N-CH ₃

NO ₂ CH ₃ OCH ₃ 0 N-CH ₃

NO, CHO OCHO O N-CHr

-COOCH ₃ CH ₃ OCH ₃

O N-CHr

Br CH ₃ OCH ₃ O N-CH ₃

^CH 3 \ // -COOCH ₃ CH ₃ OCH ₃ O N-CH ₃

br

-CH = N-OCH ₃ CH ₃ OCH ₃ O-N-CH ₃

-CH = N-OCH ₃ CH ₃ OCH ₃ O-N-CH ₃

-CH = N-OCH ₃ CH ₃ OCH ₃ O N-CH *

-CH ₂ -OCH ₃ CH ₃ OCH ₃ 0 N-CH ₃

-CH ₂ -OCH ₃ CH ₃ OCH ₃ 0 N-CH ₃

Cl

-CH ₂ -OCH ₃ CH ₃ OCH ₃

0N-CH-;

Cl

-CH ₂ -OCH ₃ CH ₃ OCH ₃

0 N-CH ^

O ₂ N

-CH ₂ -OCH ₃ CH ₃ OCH ₃ 0 N-CH ₃

OCH.

-CH ₂ -OCH ₃ CH ₃ OCH ₃

0 N-CH-

CH.

-CH ₂ -OCH ₃ CH ₃ OCH ₃

0 N-CH <

R ¹ R ²

R ³ R ⁴ XY

Cl

Br CH ₃ OCH ₃ S N-CH ₃

Cl

-SCH ₃ CH ₃ OCH ₃ S

Cl

> -COOCH ₃ CH ₃ OCH ₃

S N-CH ₃

Cl

Cl-C > - -OCH ₃ CH ₃ SCH ₃

S N-CH-

-OCHo CHo SCHo S N-CH

Cl

NO

CH ₃ OCH ₃ S N-CHr

-COOCH ₃ CH ₃ OCH ₃ S N-CH _:

CN

CH ₃ -N <S N-CH-

Cl

-CHO CK

N-CH ₃

F ³ F ⁴

XY

F ³ F ⁴

XY

-COOCH ₃ CH ₃ OCH ₃ S N-CHj

br

CH ₃ OCH ₃ S N-CH ₃

CH:

Cl

CH ₃ OCH ₃ S N-CH ₃

br

CH ₃ OCH ₃ S N-CH ₃

Cl

₃ OCH ₃ 0 N-CH ₃

NO.

CH "OCHO O N-CH-

CH-

I | l -COOCH ₃ CH ₃ OCH ₃ O _N-CH;

I

-CH ₂ -S-CH ₃ CH ₃ OCH ₃ ON-CH ₃

CHo OCH, S S

br

CH ₃ OCH ₃

0 s

-COOCH ₃ C ₂ H ₅ OCH ₃ S N-CH ₃

For example, use is made of 2 - {- [4- (3,4-dichlorophenyl) -5-bromothiazol-2-yl-N-methylamino} -3-

hydrofoxyacrylic Buf ethyl ester and dimethyl sulfate as starting materials, so can the reaction sequence of the invention

Method yes) by the following formula scheme:

CH ₃ COOCHo

I ³ I ³

= CH-OH + CH ₃ O-SO ₂ -OCH ₃

- CH ₃ OSO ₃ H (Base)

CH ₃ COOCH ₃

C = CH-OCH ₃

If, for example, 2- [4- (4-chlorophenyl) -5-methoxycarbonylthiazol-2-yl-oxy] -acetic acid methyl ester and dimethylformamide dimethylacetal are used as starting materials, the course of the reaction of process (b) according to the invention can be represented by the following formula scheme:

0-CH ₂ -COOCH ₃

"-O-CI

COOCH ₃

CH ₃ O CH ₃

> CH-N <CH ₃ OCH ₃

COOCH-

-2CH ₃ OH

> egg

0-C = CH-N <

CHr

If, for example, 2-I4- {2,4-dichlorophenyl) -5-chlorothiazol-2-yl-thio) -2-oxo-acetic acid methyl ester and (methylthio) - (trimethylsilyl) -methylenlithium are used as starting materials, the course of the reaction of process (c) according to the invention by the following formula scheme:

SC-COOCH ₃

Cl Cl

(CH 2) 3Si-CH 3 i 3 3,

Cho

H ₂ O

- <CH ₃ ) ₃ Si0H / Li0H

-> Ci-

COOCH ₃ SC = CH-SCH-:

= \ N = I

Cl Cl

If, for example, 2-l4- (4-chloronon-5-cyanooxazol-2-yl-oxy] -3-methylsulfonyloxy-acrylic acid methyl ester and methylmercaptan are used as starting materials, the reaction sequence of process (d) according to the invention can be represented by the following equation :

COOCH ₃

0-C = CH-O-SO ₂ -CH ₃ I + CH ₃ SH

COOCH ₃ 0-C = CH-SCH ₃

-CH ₃ SO ₃ H (base)

The hydroxyacrylic acid esters or their alkali metal salts required as starting materials for carrying out the process (a) according to the invention are generally defined by the formula (II). In this formula (II), R ¹ , R ² , R ³ , X and Y are preferably those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these Substiuenten.

M is preferably hydrogen or a sodium or potassium cation.

The hydroxyacrylic esters of the formula (II) are not yet known and are likewise the subject of the invention.

They are obtained when substituted acetic acid esters of the formula (IV),

(IV)

^p -CH ₂ -COOR ^d

in which

R ¹ , R ² , R ³ , X and Y have the abovementioned meaning,

with formic esters of the formula (X),

OR ⁹ -OCH

(X)

R ^{9 is} alkyl, in particular methyl or ethyl, optionally in the presence of a diluent such as dimethylformamide and optionally in the presence of a basic reaction auxiliary such as sodium hydride at temperatures between -20 ° C and + 5O ⁰ C reacted.

Formic acid esters of the formula (X) are generally known compounds of organic chemistry.

The alkylating agents which are furthermore required as starting materials for carrying out the process (a) according to the invention are generally defined by the formula (III). In this formula (III), R ⁶ preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent.

E ¹ is a leaving group which is customary for alkylating agents, preferably an optionally substituted alkyl, alkoxy or arylsulfonyloxy radical, such as, for example, a methoxysulfonyloxy radical, an ethoxysulfonyloxy radical or a p-toluenesulfonyloxy radical or halogen, in particular chlorine, bromine or iodine.

The alkylating agents of the formula (III) are generally known compounds of organic chemistry.

The substituted acetic acid esters required as starting materials for carrying out the process (b) according to the invention and for the synthesis of the precursors of the formula (II) are generally defined by the formula (IV). In this formula (IV), R ', R ² , R ³ , X and Y are preferably those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

The substituted acetic acid esters of the formula (IV) are known in some cases (see, for example, J. Med. Chem., 15.951-954 [1972]; J. Med.

Chem. 14, 10-16 [1971]; J. Med. Chem. 16, 1030-1034 [19731].

Not yet known and also the subject of the invention are substituted acetic acid esters of the formula (IVa),

(IVa)

^ CH ₂ -COOR *

in which

Y ^{2 is} oxygen, sulfur or an N-alkyl radical, preferably having 1 to 4 carbon atoms, in particular an -N-methyl radical or an -N-ethyl radical and

R ¹ , R ² , R ³ and X have the abovementioned meaning.

They are obtained in analogy to known processes, for example, when thiazole or oxazole derivatives of the formula (XI a), R ¹

It 11th

(XIa)

in which

R ', R ^2, X and Y ² have the above mentioned EANING L, or thiazole or oxazole derivatives of the formula (Xl b),

¹ Jl 2

(XIb)

in which

R ¹ , X and Y ^{2 have} the abovementioned meaning, with bromoacetic esters of the formula (XII),

Br-CH _r COOR ³ (XII)

in which

R ^{3 has} the abovementioned meaning, if appropriate in the presence of a diluent such as dimethylformamide and optionally in the presence of a reaction auxiliary such as sodium hydride at temperatures between -2O ⁰ C and + 150 ° C and optionally then in the 5-position of the thiazole · or Oxazole ring substituted with conventional electrophilic substitution reactions or derivatized already existing functional groups in this position by means of well-known methods (see also the preparation examples). Thus, for example, by customary electrophilic substitutions, the nitro group with nitric acid, the halogen radicals with elemental chlorine or bromine or other conventional halogenating agents, the formyl group by the Vilsmeier reaction with phosphorus oxychloride and dimethylformamide, alkanoyl groups by Friedel-Crafts acylations with alkanoyl chlorides in the presence of aluminum trichloride, Alkylthio, haloalkylthio and arylthio radicals by direct sulfenylation with the corresponding sulfenyl chlorides or by rhodanation with potassium thiocyanate or ammonium thiocyanate, subsequent reduction to the mercapto group and alkylation of the same.

Iminoalkylsubstituenten ui 5-position of the heterocycle is obtained by reacting formyl or alkanoyl substituents with aliphatic or aromatic amines, hydroxylamines or hydrazines in the usual manner. Amide substituents are obtained from methoxy or ethoxycarbonyl groups by reaction with amines, the cyano group by dehydration of the thus obtainable N-unsubstituted carbamoyl group or by dehydration of the Hydroximinomethylgruppe.

Alkoxymethyl groups, alkylthiomethyl groups and halomethyl groups can be introduced by reduction of the formyl group, for example with sodium borohydride and subsequent alkylation of the hydroxymethyl group thus obtained or subsequent nucleophilic substitution with halogen or subsequent sulfonylation with a conventional alkyl or arylsulfonyl chloride and subsequent substitution with alcohols or thiols with evolution of alkyl or arylsulfonyloxy radicals.

If appropriate, it may also be advantageous to carry out the substitution and / or derivatization reactions described above at the stage of the thiazole or oxazole derivatives of the formulas (XI a) or (XI b) before the reaction with the bromoacetic esters of the formula (XII) (See also the preparation examples).

Thiazole and oxazole derivatives of the formulas (XI a) and (XI b) are known or obtainable in analogy to known processes (cf.

e.g. Heterocycles23, 2645-2649 [1985]; GB 2020661; Indian J. Chem. Sect. B, 16B, 749-751 [1978]; J. org. Chem. 32, 3132-3134 [1967]; J. Heterocycl. Chem. 22, 1621-1630 [1985]; JP 63/112572; JP 63/112573; JP 63/112574; JP 62/132 871). Bromoacetic esters of the formula (XII) are generally known compounds of organic chemistry.

For carrying out the process (b) further required as starting materials formamides and their derivatives are generally defined by the formulas (Va) and (Vb). In these formulas (Va) and (Vb), R ⁴ * ¹ preferably represents dialkylamino having in each case 1 to 6, in particular 1 to 4, carbon atoms in the individual straight-chain or branched alkyl parts. R ⁴ " ¹ is very particularly preferably dimethylamino or diethylamino.

R ⁷ and R ⁸ are each, independently of one another, in each case straight-chain or branched alkoxy having 1 to 4 carbon atoms, in particular methoxy or ethoxy, or a dialkylamino radical having 1 to 6, in particular 1 to 4, carbon atoms in the individual straight-chain or branched alkyl parts.

The formamides of the formula (Va) and derivatives thereof of the formula (Vb) are generally known compounds of organic chemistry.

The oxalic acid derivatives required as starting materials for carrying out the process (c) according to the invention are generally defined by the formula (VI). In this formula (VI), R ¹ , R ² , R ³ and X preferably represent those radicals which, in connection with the description of the substances of the formula (I) according to the invention, are preferred for these substituents

were called. , ^

Y ¹ is preferably sulfur or a radical -N-, wherein R ^e preferably represents those radicals which are already in the

R ⁶

In connection with the description of the substances of the formula (I) according to the invention have been mentioned as preferred for this substituent.

The oxalic acid derivatives of the formula (VI) are either known (cf., for example, FR 1306603) or can be obtained in analogy to known processes (cf., for example, US 4321372, Synthetic Communications 11,943 [1981] or Organic Reactions 26,1 [1979]), for example if oxalates of the formula (XIII),

in which

E ^{3 is} alkoxy or halogen, in particular methoxy, ethoxy or chlorine, and R ^{3 has} the abovementioned meaning, with heterocycles of the formula (XIc)

R ²

(XIc)

in which

R ', R ² , X and Y ^{1 have} the abovementioned meaning, if appropriate in the presence of a diluent such as dichloromethane or tetrahydrofuran and optionally in the presence of a base such as n-butyllithium, sodium hydride, potassium t-butylate, triethylamine or Pyridine at temperatures between -80 ⁰ C and + 8O ⁰ C reacted.

Oxal esters of the formula (XIII) are generally known compounds of organic chemistry.

Heterocycles of the formula (XIc) are also generally known or can be obtained in analogy to generally known processes (cf., for example, Organic Reactions 6,367 et seq. And the preparation examples).

The organometallic compounds which are furthermore required as starting materials for carrying out the process (c) according to the invention are generally defined by the formula (VII). In this formula (VII), R ⁶ preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent.

The organometallic compounds of formula (VII) are known (see, for example, J. Org. Chem., 33, 780 (1968); J. Org. Chem. 37,939

The substituted acrylic acid esters required as starting materials for carrying out the process (d) according to the invention are generally defined by the formula (VIII). In this formula (VIII), R ¹ , R ² , R ³ and X preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

E ² is preferably a suitable acyloxy or sulphonyloxy radical, in particular an acetoxy, a methanesulfonyloxy or a p-toluenesulfonyloxy radical.

The substituted acrylic acid esters of the formula (VIII) are not yet known.

They are obtained when hydroxyacrylates of the formula (II b),

COOR ³

-C = CH-OH

in which

R ¹ , R ² , R ³ and X have the abovementioned meaning, with acid chlorides of the formula (XIV),

R ¹⁰ -CI (XIV)

in which

R ^{10 is} an acyl or sulfonyl radical, in particular an acetyl, a methanesulfonyl or a p-toluenesulfonyl radical, if appropriate in the presence of a diluent such as dichloromethane and optionally in the presence of an acid binder such as triethylamine or pyridine at temperatures between -20 ° C and + 12O ⁰ C implemented.

Acid chlorides of the formula (XIV) are generally known compounds of organic chemistry.

The thiols which are furthermore required as starting materials for carrying out the process (d) according to the invention are generally defined by the formula (IX). In this formula (IX), R ⁵ preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent.

The thiols of formula (IX) are well-known compounds of organic chemistry.

Suitable diluents for carrying out process (a) according to the invention are inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, nitriles, such as acetonitrile or propionitrile, amides, such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide or sulfoxides, such as dimethyl sulfoxide.

If appropriate, process (a) according to the invention can also be carried out in a two-phase system, for example water / toluene or water / dichloromethane, if appropriate in the presence of a phase transfer catalyst. As examples of such catalysts may be mentioned are: tetrabutylammonium iodide, tetrabutylammonium bromide, tributylmethylphosphonium bromide, trimethyl-Ci ₃ / C ₁ 5-alkylammonium chloride, Dibenzyldimethyl ammonium methylsulfate, dimethyl C ^ / Cu alkylbenzylammoniumchlorid, tetrabutylammonium hydroxide, 15-crown-5,18-crown- 6, triethylbenzylammonium chloride, trimethylbenzylammonium chloride or tris [2- (2-methoxyethoxy) ethyll-amine.

The process (a) according to the invention is preferably carried out in the presence of a suitable basic reaction auxiliary. As such, all commonly used inorganic and organic bases are suitable.

Preference is given to using alkali metal hydrides, hydroxides, amides, alkoxides, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, sodium hydroxide, sodium methoxide, sodium ethylate, potassium t-butylate, sodium carbonate or sodium bicarbonate or else tertiary amines, for example triethylamine, Ν, Ν-dimethylaniline, pyridine, Ν, Ν-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicyctoundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out the process (a) according to the invention. In general, one works at temperatures between -3O ⁰ C and +120 ⁰ C, preferably at temperatures between -2O ⁰ C and + 6O ⁰ C.

For carrying out process (a) according to the invention, 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, of alkylating agent of the formula (III) are generally employed per mole of 3-hydroxyacrylic acid ester or of a corresponding alkali metal salt of the formula (II). and optionally 1.0 to 6.0 moles, preferably 1.0 to 2.0 moles of reaction auxiliary.

It is also possible to prepare the required as starting compounds for carrying out the process (a) 3-hydroxyacrylic acid ester or alkali metal salts of the formula (II) in an upstream reaction directly in the reaction vessel and directly from the reaction mixture without isolation with the alkylating agent of the formula (III) according to the process (a) further to implement ("one-pot process").

The reaction is carried out, workup and isolation of the reaction products by generally customary methods (see.

also the production examples).

Suitable diluents for carrying out the process (b) according to the invention are inert organic solvents. These include, in particular, aliphatic, acyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride or ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether.

However, it is also possible to carry out the process (b) according to the invention without addition of a diluent.

The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, one works at temperatures between -2O ⁰ C and +200 "C, preferably at temperatures between ^{0 0} C and 150 ⁰ C.

In order to carry out process (b) according to the invention, in general 1.0 to 30.0 mol, preferably 1.0 to 15.0 mol, of formamide of the formula (Va) or a corresponding derivative of the formula (IV) are employed per mole of substituted acetic acid ester of the formula (IV) Formula (Vb). The reaction is carried out, working up and isolation of the reaction products by generally customary methods (see also G. Mathieu, J. Weill-Raynal "Formation of CC bonds", Vol.l; p.229-244, Thieme Verlag Stuttgart 1973) ,

Suitable diluents for carrying out process (c) according to the invention are inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic hydrocarbons, for example benzine, benzene, toluene, xylene, petroleum ether, hexane or cyclohexane or ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether.

The reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general carried out at temperatures between -100 ⁰ C and +100 ⁰ C, preferably at temperatures between -8O ⁰ C and + 5O ⁰ C.

For carrying out process (c) according to the invention, 1.0 to 1.5 mol, preferably 1.0 to 1.2 mol, of organometallic compound of the formula (VII) are generally employed per mole of oxalic acid derivative of the formula (VI).

The reaction is carried out, working up and isolation of the reaction products by known methods (cf., for example, J.

org. Chem. 33,780 (1968); J. org. Chem. 37; 939 [1972]).

Suitable diluents for carrying out process (d) according to the invention are inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.

The process (d) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. As such, all customary inorganic or organic bases are suitable. These include, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate or sodium bicarbonate, or tertiary amines such as triethylamine, Ν, Ν-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or Diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out process (d) according to the invention. In general, one works at temperatures between -20 ° C and -180 ⁰ C, preferably at temperatures between ^{0 0} C and 150 ° C.

The inventive method can be carried out, depending on the boiling point of the reactants used, for example, when using low-boiling thiols of the formula (IX) optionally under pressure.

The reaction is then preferably carried out at the pressure which, when heated to the required reaction temperature, is established under the reaction conditions.

For carrying out the process (d) according to the invention, eester dsr forms are used per mole of substituted acrylic acid! (VMI) generally 1.0 to 20.0 moles, preferably 1.0 to 5.0 moles of thiol of formula (IX) and optionally 1.0 to 5.0 moles, preferably 1.0 to 1.5 moles of reaction auxiliary.

The reaction is carried out, workup and isolation of the reaction products by generally customary methods.

The active compounds according to the invention have a strong action against pests and can be used practically for controlling unwanted harmful organisms. The active ingredients are for use z. B. suitable as crop protection agents, in particular as fungicides.

Fungicidal agents in crop protection are used to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Dauteromycetes.

By way of example but not limitation, some pathogens of fungal diseases, which fall under the above-enumerated generic terms, are named:

Pythium species such as Pythium ultimum; Phytophthora species, such as Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as Plasmopara viticola; Peronospora species such as Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Eryslphe graminls; Sphaerotheca species, such as Sphaerotheca fuliginea; Podosphaera species, such as Podosphaera leucotricha; Venturia species, such as Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea;

(Conidia form: Drechslera.Syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus

(Conidia form: Drechslera.Syn: Helminthosporium);

Uromyces species, such as Uromyces appandiculatus; Puccinia species, such as Puccinia recondita; Tilletia species, such as Tilletia caries; Ustilago species such as Ustilago nuda or Jstilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as Pyricularia oryzae; Fusarium species such as Fusarium culmorum; Botrytis species, such as Botrytis cinerea; Septoria species such as Septoria nodorum; Leptosphaeria species, such as Leptosphaerla nodorum; Cercospora species, such as Cercospora canescens; Alternaria species, such as Alternaria brassicae; Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of aboveground plant parts, of plant and seed, and the soil.

In this case, the active compounds according to the invention can be used to combat cereal diseases, for example against the causative agent of cereal powdery mildew (Erysiphe graminis) or against the causative agent of net blotch of barley (Pyrenophora teres) or against the causative agent of cereal pollen (Pseudocercosporella herpotrichoides or against the brown fever pathogen of wheat (Leptosphaeria nodorum) or for the control of rice diseases such as, for example, against the causative agent of rice blotch disease (Pyricularia oryzae) or against the pathogen of rice sickle disease (Pellicularia sasakii) or for the control of diseases in fruit and vegetable crops , such as against the causative agent of apple scab (Venturia inaequalis) use. In addition, the active compounds according to the invention show a broad in vitro activity.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, ultrapure encapsulations in polymeric substances and in seed coating compositions, as well as ULV products. KaIt and warm mist formulations. These formulations are prepared in a known manner, for. Example, by mixing the active compounds with extenders, that is liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers are: z. Natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; suitable solid carriers for granules are: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam producing agents come in Fraga: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. I.ignin sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and Metallohthalocyaninfarbstoffe 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% by weight of active compound, preferably between 0.5 and 90%. The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds such as fungicides, insecticides, acaricides and herbicides and in mixtures with fertilizers and growth regulators. The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or the active ingredient preparation or the active ingredient itself in the soil to their. It can also be the seed of the plants to be treated.

In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001 %. In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g are needed.

When treating the soil, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

Herstellungsbelsplele example 1

CH ₃ COOCH ₃

J = CH-OCH ₃

Br Procedure (a) - One-pot variant

A solution of 5.4 g (0.013 mol) of N- [5-bromo-4- (4-bromophenyl) -thiazol-2-yl] -N-methyl-acetic acid methyl ester in a mixture of 25 ml of dimethylformamide and 25 ml of methyl formate is added dropwise with stirring and Cooling and with careful exclusion of moisture to a suspension of 0.8 g (0.0335 mol) of sodium hydride in 75 ml of dimethylformamide, wherein the temperature of the reaction mixture should not exceed 0 ° C. After complete addition, it is stirred for 15 hours at room temperature, 4.9 g (0.039 mol) of dimethyl sulfate, stirred for a further 15 hours at room temperature, then 300 ml of water, extracted several times with ethyl acetate, the combined organic phases are dried over sodium sulfate, concentrated reduced pressure and the residue is purified by chromatography on silica gel. This gives 3.0 g (51% of theory) of N-l5-bromo-4- (4-bromophenyl) -thiazol-3-yl] -N-methyl-2-methoxymethylidenglycinmethylester a melting point of 112 ⁰ C.

Bolspiel 2

CH-OCH ₃

Method (a) - one pot variant A solution of 4 g (0.01 mol) of N- [5-methoxycarbonyl-4- (4-blyphenylyl) -thiazol-2-yl] -N-methyl-acetic acid methyl ester in a Mixture c.us 10 ml of dimethylformamide and 10 ml of methyl formate are added dropwise with stirring and cooling

and under careful moisture rejection and an argon protective gas atmosphere to a suspension of 0.66 g (0.022 mol) of sodium hydride in 10 ml of dimethylformamide, the temperature of the reaction mixture not exceeding 0 ° C. After completion of the addition, the mixture is stirred for another four to five hours at ^{0 0} C, then added dropwise with stirring 3g (0.02 mol)

Dimethyl sulfate and then allowed the reaction mixture slowly come to room temperature. You stir more

12 hours at room temperature, then the reaction mixture is poured into ice, extracted several times with dichloromethane, the combined organic phases are dried over sodium sulfate, concentrated under reduced pressure and the residue is purified by passage

Chromatography on silica gel (eluent: dichloromethane / ethyl acetate 20: 1). You get as 1st fraction

2.5 g (56.4% of theory) of N- [5-methoxycarbonyl-4- (4-biphenylyl) -thiazol-2-yl] -N-methyl-2-methoxymethylidenglycinmethylester as Z-isomer of melting point 132 ⁰ C.

and as 2nd fraction

0.6 g (13.5% of theory) of N-15-methoxycarbonyl-4- (4-biphenylyl) -thiazol-2-yl] -N-methyl-2-methoxymethylidenglycinmoihylester as Ε-isomer of melting point 223 ⁰ C.

In a corresponding manner and in accordance with the general information on the preparation, the following substituted acrylic acid esters of the general formula (I) are obtained:

N COOR ³

-C = CH-R ⁴

Ex. R ¹ no.

R ² R ³ R ⁴ XY physical

properties

Cl

> Br CH ₃ OCH ₃ S

Cl-ς / λ "-CH CH ₃ OCH ₃ S

-N-

¹ H-NMR **: 3.26; 3.78;

I 3.97; 7.46; CH ₃ 7.5; 7.9

¹ H-NMR * ⁾ : N-3.37; 3.8; I 4.0; 7.45; CH ₃ 7.5; 7.66;

9.68

> -CN CH ₃ OCH ₃ S -N-Fp. 129 ⁰ C

CHO

br

br

-CH CH ₃ OCH ₃ S

¹ H-NMR * ⁾ : -N- 3,4; 3.8;

I O QO ·

I J> "" I

CH ₃ 7.2-7.7; 9.68

y- -CN CH ₃ OCH ₃ S -N- Fp. 151-152 ⁰ C

Cl-C /) -Br CH ₃ OCH ₃ S

Cl

CH-

-N- mp. 137 ° C

CHr

br

Cl

Cl

Br CH ₃ OCH ₃ S

Cl CH ₃ OCH ₃ S

Cl CH ₃ OCH ₃ S

-N-CH ₃

-N- mp 108-110 ⁰ C CH ₃

-N- Mp. 136 ⁰ C CHo

* Ή NMR spokes were recorded in deuterochloroform (CDCl ₃ ) with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as the δ value in ppm.

Ex. R ¹ no.

R ² R ³ R ⁴

12 cl

Br CH *

X Y physical properties

S -N-CH ₃

3r

CH ₃ OCH ₃ S -N- Fp. 87-89 ⁰ C

CH.

H ₃ C Cl

Cl CH-

Br CHo OCHo S -N- Fp. 111- ^{3 3} I 112 ⁰ C CHo

Br CHo OCHo S -N- Mp. 77-79 ⁰ C

CH *

00 (3

OC ' "

Br CH ₃ OCH ₃ S -N-Fp. 87-88 ⁰ C

CHO

^{17 F} ~ ^ // ^{Br CH} :

-N-

18 PC j- Cl CHr

S -N-

CH,

Br CHo OCHo S -N-

CHr

20 cl

/ CH ₃ * 3

Br CH ₃ NS -N-

CHr

Ex. R ¹ no.

R ² R ³ R ⁴

X Y Physical properties

br

Br CH ₃ OCH ₃ S -Ά- mp. 76-77 ⁰ C

CH

F ₃ C

SCCl ₂ F CH ₃ OCH ₃ S -N-

CH ₃

Br CH ₃ OCH ₃ S -N- Fp. 83-87 ⁰ C

CHO

/ CH ₃

24 Br- < _v .) - SCCl ₂ F CH ₃ NS -N- Fp. 122-123 ⁰ C

\ I

Cl

CH

Br CHo OCHo S -N-

3 3 j

CH-

Br CH ₃ OCH ₃ S -N- Fp. 94-95 ⁰ C

CHO

Preparation of the starting compounds Example IV-1

CHr

N-CH ₂ -COOCH ₃

To a mixture of 4.5 g (0.013 mol) of N- [4- (4-bromophenyl) -thiazol-2-yl] -N-methylaminoacetic acid methyl ester and 2.5 g

(0.03 mol) of sodium acetate in 30 ml of glacial acetic acid is added dropwise with stirring at room temperature in the course of 45 minutes a solution of 2.34 g (0.015 mol) of bromine in 5 ml of glacial acetic acid, then stirred with excess aqueous saturated

Sodium bicarbonate solution and sucks off the precipitate. After drying, 5.4 g (97% of theory) of N- [5-bromo-4- (4-bromophenyl) -thiazol-2-yl) -N-

Methylaminoessigsäuremethylester as an oil.

¹ H-NMR (CDClA / tetramethylsilane):

δ = 3.13 (s, 3H); 3.75 (s, 3H); 4.30 (s, 2H); 7.51 (d, 2H); 7.80 (d, 2H) ppm.

In a mixture of 4.5 g (0.013 mol) of N-I4- (4-bromophenyl) -thiazol-2-yll-N-methylaminoessigsäuremethylester and 2.5 g (0.03 mol) Natriumacevct in 30ml of glacial acetic acid at 35 ⁰ C eitet while stirring, chlorine gas until a starting compound is no longer detectable in the thin-layer chromatogram of the reaction mixture. Then the mixture is stirred with excess saturated aqueous sodium bicarbonate solution, the precipitate is filtered off with suction and purified by chromatography on silica gel (eluent: 1: 1 eluent: eluent).

0.58 g (12% of theory) of methyl N-IS-chloro-methyl-bromopheny-1-thiazolyl-N-methylamino-pepsoate is obtained. MS: m / e = 376 (Μ ^φ ); 317 (base peak, M ^ COOCH ₁ ).

Example IV-3

To a solution of 2.0 g (0.006 mol) of N- [4- (4-bromophenyl) -thiazol-2-yl) -N-methylamino-acetic acid in 15 ml of dimethylformamide is added with stirring and Feuchtiqkeits exclusion, dropwise 5g (0.03 Mol) of phosphorus oxychloride so that the temperature of the reaction mixture does not exceed 45 ^° C. After completion of the addition, the reaction mixture is allowed to stand for 2 hours at room temperature, then poured onto ice, neutralized by the addition of aqueous sodium bicarbonate solution, filtered off with suction and dried.

This gives 1.62 g (71% of theory) of N- [4- (4-bromophenyl) -5-formylthiazol-2-yl) -N-methylaminoessigsäuremethylester as monohydrate of melting point 105-106 ⁰ C.

Example IV-4

CHO

I ³

N-CH ₂ -COOCH ₃

HO-N = CH

A mixture of 5 g (0.0146 mol) of N- [4- (4-chlorophenyl) -5-formylthiazol-2-yl) -N-methylaminoacetic acid methyl ester and 1.6 g (0.023 mol) of hydroxylamine hydrochloride in 50 ml of ethanol and 5 ml of glacial acetic acid becomes 45 Heated to reflux with stirring for minutes, cooled, poured into ice, neutralized by addition of sodium bicarbonate, extracted with ethyl acetate, the organic phase dried over sodium sulfate and concentrated under reduced pressure. This gives 4.56 g (92% of theory) of methyl N- | 4- (4-chlorophenyl) -5-hydroximinomethylthiazol-2-yl-N-methylacetate of melting point 147 ° C to 149 ⁰ C as a Z / E isomer mixture.

Example IV-5

CHO

I ³

N-CH ₂ -COOCH ₃

A mixture of 4.16 g (0.0122 mol) of N - ^ - W-chlorophenyl-S-hydroximinomethylthiazole -yl-N-

methylaminoacetic acid methyl ester and 30 ml of acetic anhydride is 4 hours. With stirring, heated to reflux temperature, cooled, neglected in ice water, neutralized in the cold with saturated aqueous sodium bicarbonate solution, extracted with ethyl acetate, the organic phase dried over sodium sulfate, concentrated and the crystalline residue purified by stirring with a mixture of diisopropyl ether and η-hexane.

After filtering off with suction and drying, 3.01 g (77% of theorlor) of N-H-M-chlorophenyl-B-cyanothlazolyl-n-N-

methylaminoessigsäuremethylester.

MS: m / e = 321 (Μ ^φ ); 262 (base peak, M ¹ MX) OCH ₃ ). Example IV-6

CH-

N-CH ₂ -COOCK ₃

Choo-C

³ Il

To a mixture of 8.1 g (0.025 mol) of 2- (N-methylamino) -4- (4-biphenylyl) -thiazol-5-yl-carboxylic acid methyl ester and 30 ml of dimethylformamide are added with stirring and cooling in portions 0.9 g (0 , 03 mol) of sodium hydride, so that the temperature of the reaction mixture does not exceed 20 ° C, then stirred for 45 minutes at room temperature and then added dropwise with stirring at room temperature over 30 minutes 18.3g (0.199 mol) bromoacetate z, u, stirred After completion of addition for a further 12 hours at room temperature, then the reaction mixture is poured into ice water, extracted several times with dichloromethane, the combined organic phases are dried over sodium sulfate, concentrated under reduced pressure and the crystalline residue is purified by stirring with diisopropyl ether

 This gives 5.1 g (52% of theory) of N-t4- (4-biphenylyl) -5-methoxycarbonylthiazol-2-yl) -N-methylaminoessigsäuremethylester of melting point 141 ° C. In a corresponding manner and in accordance with the general information on the preparation, the following substituted acetic acid esters of the general formula (IV) are obtained,

N = I

Y-CH ₂ -COOR ^

Ex. R no.

IV-7 IV-8

IV-9

Cl

Br CH-.

-C-H CHr

X γ Melting point / ° C S -N- 92-94 CH ₃ S -N- 115-118

CH-

Br CHo S -N-

CH-

105-106

IV-IO

Cl

Br CH ₃ S -N-

CH,

109

IV-H

CN CHo S -N-133-136

CHO

N-CH ₂ -COOCH ₃

To 2.73 g (0.114 mol) of sodium hydride in 20OmI of dimethylform, amid yibt dropwise with stirring and under Exclusion of moisture and ice cooling, a solution of 9.0 g (0.036 mol) of 4- (4-bromophenyl) -2-methylamirothiazole in 50 ml Dimethylformamide, so that the temperature of the reaction mixture 1O ⁰ C does not exceed. After completion of the addition, stirring

One hour at room temperature, then cooled to 10 ° C and added dropwise with stirring over an hour 21.4g (0.14 mol) of methyl bromoacetate, then stirred for 15 hours at room temperature, then the

Reaction mixture in ice-water, extracted several times with dichloromethane, the combined organic phases are dried over Sodium sulfate, concentrated under reduced pressure and the residue is purified by chromatography on silica gel (mobile phase: Dichloromethane). 10.0 g (42% of theory) of N- [4- (4-bromophenyl) -thiazol-2-yl] -N-methylaminoacetic acid methyl ester are obtained Melting point 95 ^° C. In a corresponding manner and according to the general information on the preparation is obtained

CHO

N-CH ₂ -COOCH ₃

Melting point 86 ^° C.

 Example XM

NH-CH.

CH ₃ OC

A mixture of 17.1 g (0.06 mol) of 2-chloro-2- (4-phenylbenzoyl) acetic acid methyl ester (by chlorination with sulfuryl chloride

according to standard procedures; see. Also DE-OS 2343974) 10.8 g (0.12 mol) of N-methylthiourea and 200 ml of methanol is heated for 3 hours at reflux temperature, cooled, in excess dilute aqueous Natriumhydrogencarbonatlösungeinger, the precipitate was filtered off with suction and dried.

This gives 18.2 g (95% of theory) of 2- (N-methylamino) -4- (4-biphenylyl) -thiazol-5-ylcarboxylic acid methyl ester of melting point Example XI-2

NH-CH ₃

A mixture of 27.8 g (0.1 mol) of 2,4'-dibromoacetophenone (see, for example, Tetrahedron Lett. 1975, 373-376), 9.0 g (0.115 mol) of N- Methylthiourea and 400ml of ethanol is heated at reflux for 3 hours, then cooled, in

Excess diluted aqueous sodium bicarbonate solution, extracted with dichloromethane, the combined organic phases dried over sodium sulfate and concentrated.

This gives 20.8 g (78% of theory) of 2- (N-methylamino) -4- (4-bromophenyl) -thlazol a melting point of 147 ⁰ C. In appropriate catfish one obtains example XI-3:

NH-CH '

Melting point 14O ⁰ C

-37- 298 394 Application Examples In the following application examples, the following compound was used as reference substance:

(A) CH ₃ O-CH = C-COOCH ₃

Methyl 3-methoxy-2- (2-methylphenyl) acrylate (known from EP 178826)

Example A Venturia test (apple) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3% by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated Amounts of solvent and emu 'or and dilutes the concentrate with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. To When the spray coating is dried, the plants are treated with an aqueous conidia suspension of the apple scab pathogen (Venturia

inaequalis) and then remain for 1 day at 20 ° C and 100% relative humidity in an incubation cabin.

The plants are then raised in the greenhouse at 20 ° C and a relative humidity of about 70%.

12 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this test z. B. the compounds

according to Preparation Examples 1 and 3.

Example B Pyrenophora teres test (Gerstel / protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether To prepare a suitable Wirkstoffzubereitimg one mixes 1 part by weight of active compound with the indicated Amounts solvent and emulsifier and dilute the concentrate with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound in a dewy manner. After drying

spraying the plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain for 48 hours at 2O ⁰ C and 100% relative humidity in an incubation cabin.

The plants are grown in a greenhouse at a temperature of about 2O ⁰ C and a relative humidity of about 80%

established.

7 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art shows in this test z. B. the connection

according to Preparation Example 3.

Example C Pyricularia test (rice) / protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount Solvent and dilute the concentrate with water and the specified amount of emulsifier to the desired Concentration. To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. To

the spray coating is dried, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae.

Subsequently, the plants in a greenhouse at 100% rel. Humidity and 25 ⁰ C set up.

4 days after the inoculation, the evaluation of the disease infestation takes place.

Clear superiority in efficacy over the prior art is shown in this test, e.g. the connections

according to Preparation Examples 1 and 3.

Claims (10)

1. Substituted acrylates of the general formula (I),
, N COOR ³ - C = CH - R ⁴ in which R ^{1 is} hydrogen, alkyl, alkenyl or each optionally substituted aralkyl, aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, N, N-dialkylhydrazonoalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, aryloxy, arylthio, is alkanoyl, alkoxycarbonyl, Ν, Ν-dialkylcarbamoyl or heterocyclylcarbonyl, R ^{3 is} alkyl or the optionally substituted aralkyl, R ^{4 is} dialkylamine or a residual ZR ⁵ , X is oxygen or sulfur and Y represents oxygen sulfur or a residual N, R ⁶ in which R ^{5 is} alkyl or optionally substituted aralkyl; R ^{6 is} hydrogen, alkyl, alkanoyl, or aralkyl, or each substituted aralkyl; Aryl stands and
Z is oxygen or sulfur, their geometric isomers and mixtures thereof. Substituted acrylic esters of the formula (I) according to claim 1, wherein R ^{1 is} hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms, each optionally in the aryl part mono- to polysubstituted by identical or different substituents aralkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety , Aralkenyl having 2 to 6 carbon atoms in the straight-chain or branched alkenyl part or aryl having 6 to 10 carbon atoms in the respective aryl part, in each case being suitable as aryl substituent: Halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy or alkylthio having in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case straight-chain or branched Alkoxycarbonyl or alkoximinoalkyl having in each case 1 to 8 carbon atoms in the individual alkyl moieties, cycloalkyl having 3 to 7 carbon atoms, di-linked alkanediyl having 3 to 5 carbon atoms, each optionally in the aryl moiety mono- to polysubstituted by identical or different halogen, alkyl, alkoxy, alkylthio, Haloalkyl, haloalkoxy or haloalkylthio each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms substituted aryl, aralkyl, aryloxy or aralkyloxy each having 6 to 10 carbon atoms in the aryl and optionally 1 to 4 carbon atoms in the straight branched or branched alkyl moiety or in each case optionally in the heteroaryl moiety mono- to polysubstituted by identical or different halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms substituted heteroarylalkyl or heteroaryl in each case 2 to 9 carbon atoms and 1 to 4 identical or different heteroatoms in the heteroaryl moiety and optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety; R ¹ also represents an optionally mono- to polysubstituted by identical or different substituents heteroaryl radical having 2 to 9 carbon atoms and 1 to 4gleichet. or different heteroatoms, suitable substituents being the abovementioned aryl substituents, R ^{2 is} fluorine, chlorine, bromine, iodine, cyano, nitro, formyl, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different Halogen atoms, in each case straight-chain or branched alkoxyalkyl or alkylthioalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties, in each case straight-chain or branched hydroxyiminoalkyl, alkoximinoalkyl, N-alkyliminoalkyl or N, N-dialkylhydrazonoalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties straight-chain or branched alkoxy or alkylthio having in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and in each case 1 to 9 identical or different halogen atoms, for each straight-chain or branched alkanoyl, alkoxycarbonyl or Ν, Ν-dialkylcarbamoyl with in each case 1 to 4 carbon atoms in the individual alkyl moieties or for heterocyclylcarbonyl, heterocyclyl being a saturated five- to seven-membered N-linked heterocyclic radical which optionally represents a further heteroatom and may optionally be substituted one to four times by methyl and / or ethyl; R ² furthermore represents N-aryliminoalkyl, aryloxy or arylthio which is optionally monosubstituted to polysubstituted by identical or different substituents in the aryl moiety of in each case 6 to 10 carbon atoms, where the straight-chain or branched alkyl moiety has up to 4 carbon atoms and where as aryl substituents in each case h: halogen , Cyano, nitro, in each case straight-chain or branched alkyl, alkoxy or alkylthio having in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case straight-chain or branched alkoxycarbonyl or Alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl moieties, optionally mono- to polysubstituted, identically or differently by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted phenyl, R ³ represents straight-chain or branched alkyl having up to 6 carbon atoms or represents aryl moiety of from 1 to 4 carbon atoms in the aryl moiety which is mono- to polysubstituted, identically or differently substituted in the straight-chain or branched alkyl moiety and 6 to 10 carbon atoms, suitable aryl substituents being those mentioned for R ¹ , R ^{4 is} dialkylamino having in each case 1 to 6 carbon atoms in the individual straight-chain or branched alkyl parts or is a radical ZR ⁶ , X is oxygen or sulfur and Y is oxygen, sulfur or a radical N-, R ⁸ R ^{5 is} straight-chain or branched alkyl having 1 to 6 carbon atoms or optionally in the aryl part mono- to polysubstituted, identically or differently substituted aralkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl part and 6 to 10 carbon atoms in the aryl part, wherein as aryl substituents at R ¹ mentioned come into question, R ^{6 is} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkanoyl having 1 to 6 carbon atoms in the alkyl moiety or aryl moiety optionally mono- or polysubstituted by identical or different substituents in the aryl moiety having from 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety or aryl having in each case 6 to 10 carbon atoms in the respective aryl part, where as substituents in the aryl part in each case those mentioned for R ¹ come into question and Z is oxygen or sulfur.
3. Substituted acrylic acid esters of the formula (I) according to claim 1, wherein R ^{1 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, allyl, η- or i-butenyl, for each optionally in the aryl part or in the heteroaryl part one to four times, benzyl, phenylethyl, phenylethyl, phenyl, naphthyl, pyridyl, thienyl or FuryI, which are each the same or different, are suitable as substituents: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl, cyclopentyl, cyclohexyl, 1 , 3-propanediyl, 1,4-butanediyl or in each case optionally in the phenyl part one to three times, identical or different phenyl, benzyl, phenoxy or benzyloxy substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethoxy, trifluoromethoxy and / or trifluoromethylthio, R ^{2 is} chloro, bromo, iodo, cyano, nitro, formyl, chloromethyl, bromomethyl, iodomethyl, methoxymethyl, ethoxymethyl, n- or i-propoxymethyl, methylthiomethyl, ethylthiomethyl, n- or i-propylthiomethyl for hydroximinomethyljhydroximinoethyl, hydroximinopropyl, for methoximinomethyl, ethoximinomethyl , n- or i-propoximinomethyl, methoximinoethyl, ethoximinoethyl, n- or i-propoximinoethyl, for methyliminomethyl, ethyliminomethyl, n- or i-propyliminomethyl, for methyliminoethyl, ethyliminoethyl, η- or i-propyliminoethyl, for Ν, Ν-dimethylhydrazonomothyl, N, N-diethylhydrazonomethyl, N-methyl-N-ethylhydrazonomethyl, N-methyl-N-propylhydrazonomethyl, Ν, Ν-dipropylhydrazonomethyl, Ν, Ν-dimethylhydrazonoethyl, Ν, Ν-diethylhydrazonoethyl, for methoxy, ethoxy, n- or i- Propoxy, methylthio, ethylthio, n- or i-propylthio, for trifluoromethoxy, difluoromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, trichloromethoxy, trifluoromethylthio, trichloromethylthio, dif luormethylthio, you lorfluoromethylthio, difluorochloromethylthio, for acetyl, propionyl, butyryl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, Ν, Ν-dipropylaminocarbonyl, N-methyl-N-ethylaminocarbonyl, N- Methyl-N-propyl-aminocarbonyl.füri-Piperidinylcarbonyl ^ -Morpholinylcarbonyl or for each optionally in the phenyl moiety to one to three, the same or different substituted N-phenyliminomethyl, N-phenyliminoethyl, phenoxy or phenylthio, where as substituents in question: Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy , Trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl or optionally mono- to trisubstituted by identical or different phenyl, fluorine, chlorine, bromine, methyl and / or ethyl, R ^{3 is} methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl or optionally mono- to trisubstituted by identical or different substituents benzyl, where as substituents mentioned in R ¹ in question come, R ^{4 represents} dialkylamino having in each case 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts or represents a radical ZR ⁵ , X is oxygen or sulfur and Y is oxygen, sulfur or a residual N-, R ^e in which R ^{5 is} methyl, ethyl, η- or i-propyl, n-, i-, s-tert-butyl or optionally mono- to trisubstituted by identical or different substituents benzyl, wherein as substituents those mentioned in R ¹ come into question ; R ^{6 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, for acetyl, propionyl, n- or i-butyryl or in each case optionally mono- to trisubstituted, the same or substituted benzyl or phenyl, wherein as substituents those mentioned in R ¹ come into question and
Z is oxygen or sulfur.
4. Substituted acrylic acid esters of the formula (I) according to claim 1, wherein R ^{1 is} hydrogen, methyl, ethyl, η- or i-propyl or is in each case optionally mono- to disubstituted, identical or different substituted phenyl or naphthyl, where as substituents in question: fluorine, chlorine, bromine, cyano, nitro , Methyl, ethyl, η- or i-propyl, η-, i-, s-tert-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl , Ethoximinomethyl, methoximinoethyl, ethoximinoethyl, cyclopentyl, cyclohexyl, 1,3-propanediyl, 1,4-butanediyl or each optionally optionally once or twice, identically or differently, fluorine, chlorine, bromine, methyl and / or ethyl-substituted phenyl, phenoxy, Benzyl or benzyloxy, R ^{2 represents} chlorine, bromine, cyano, nitro, formyl, methoxymethyl, ethoxymethyl, methylthiomethyl, hydroximinomethyl, methoximinomethyl, ethoximinomethyl, methyliminomethyl, Ethyliminomethyl, Ν, Ν-dimethylhydrazonomethyl, Ν, Ν-diethylhydrazonomethyl, for methoxy, ethoxy, methylthio, ethylthio, trifluoromethylthio, dichlorofluoromethylthio, difluorochloromethylthio, trichloromethylthio, for acetyl, methoxycarbonyl, ethoxycarbonyl, N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, N-methyl- N-ethylaminocarbonyl or optionally once or twice, same or different substituted phenylthio, suitable substituents being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, η- or i-propyl, η-, i-, s- or t-butyl, methoxy, ethoxy, n- or i- Propoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, R ^{3 is} methyl, ethyl or benzyl, R ^{4 is} dimethylamino, diethylamine, or a residual ZR ⁵ , X is oxygen or sulfur, and Y is oxygen, sulfur or a radical -N-, R ^e in which R ^{5 is} methyl, ethyl, η- or i-propyl or benzyl,
R ^{6 represents} hydrogen, methyl, ethyl, acetyl, propionyl, or each optionally optionally mono- or disubstituted, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl and / or Trifluoromethyl substituted benzyl or phenyl and Z is oxygen or sulfur. 5. Substituted acrylic acid esters of the formula (I) according to claim 1, wherein R ^{1 is} hydrogen, methyl, ethyl, n- or i-propyl or optionally mono- or disubstituted by identical or different substituents phenyl, wherein suitable substituents are: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy , Ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, cyclopentyl, 1,3-propanediyl, methoximinoethyl or optionally mono- or disubstituted by identical or different fluorine, chlorine, bromine or methyl-substituted phenyl, phenoxy, benzyl oderBenzyloxy, R ^{2 is} chlorine, bromine, cyano, nitro, formyl, methoxymethyl, methylthiomethyl, methoxycarbonyl, ethoxycarbonyl, methylthio, trifluoromethylthio or methoximinomethyl, R ^{3 is} methyl or ethyl, R ^{4 is} methoxy, ethoxy, methylthio or dimethylamino, X is oxygen or sulfur and Y is an N-methyl radical. 6. Process for the preparation of substituted acrylic acid esters of the general formula (I), - C = CH - R ⁴ in which R ^{1 is} hydrogen, alkyl, alkenyl or each optionally substituted aralkyl.Aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio.Halogenalkoxy, haloalkylthio, aryloxy, arylthio, is alkanoyl, alkoxycarbonyl, N, N-dialkylcarbamoyl or heterocyclylcarbonyl, R ^{3 is} alkyl or the optionally substituted aralkyl, R ^{4 is} dialkylamino or a residual ZR ⁵ , X stands for oxygen or sulfur and Y is oxygen, sulfur or a radical N-, R ⁶
in which R ^{5 is} alkyl or optionally substituted aralkyl, R ^{6 is} hydrogen, alkyl, alkanoyl or each optionally substituted aralkyl or Aryl and Z is oxygen or sulfur, their geometric isomers and mixtures thereof, characterized in that (a) substituted acrylic acid esters of the formula (Ia), R ¹ "N COOR ³ 2JOI's ^(la) R ^z x ^a v X ^ XY - C = CH - O - R ⁵ in which R ¹ , R ² , R ³ , R ⁵ , X and Y have the abovementioned meaning, is obtained by reacting hydroxyacrylic acid esters or their alkali metal salts of the formula (II) N COOR ³ Jl ' ^(ll) rxx ^ y - c = CH - OM in which M is hydrogen or an alkali metal cation and R ¹ , R ² , R ³ , X and Y have the abovementioned meaning, with alkylating agents of the formula (III), RS-E ¹ (III) in which E ^{1 is} an electron-withdrawing leaving group and R ^{5 has} the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary (b) substituted acrylic acid esters of the formula (I b), N COOR ³ II I XxVy-C = CH- in which R ⁴ " ^{1 is} dialkylamino and R ¹ , R ² , R ³ , X and Y have the abovementioned meaning, is obtained by reacting substituted acetic acid esters of the formula (IV) R ¹ VN J Il _R 2 / S _X / SY - CH 2 - COOR ^J in which R ¹ , R ² , R ³ , X and Y have the abovementioned meaning, with formamides of the formula (Va), O HCR ⁴ " ¹ (Va) in which R ⁴ " ^{1 has} the abovementioned meaning, or with derivatives thereof of the formula (Vb) R ⁷ > Ch-r4-1 (Vb) R ⁸ in which R ⁷ and R ⁸ are each independently alkoxy or dialkylamino and R ^{4-1 has} the abovementioned meaning, if appropriate in the presence of a diluent or (c) substituted acrylic acid esters of the formula (Ic), , N COOR ³ - c = CH - S - R ^ in which Y ^{1 is} sulfur or a residual N-position, R ⁶ and R ¹ , R ² , R ³ , R ^B , R ⁸ and X have the abovementioned meaning, in which oxalic acid derivatives of the formula (VI) ¹ N γ1-c-COOR ³ (VI) in which R ¹ , R ² , R ³ , X and Y ^{1 have} the abovementioned meaning, with organometallic compounds of the formula (VII), (CHO) ₃ Si Q _Θ ³ > CH Li (VII) R ⁵ -S in which R ^{5 has} the abovementioned meaning, if appropriate in the presence of a diluent or (d) substituted acrylic acid esters of the formula (Id), - N COOR ³ 5 ^(ld) CH - S - R ^b N CO
^^ - 0 - C = in which R ¹ , R ² , R ³ , R ⁵ and X have the abovementioned meaning, is replaced by substituted. Acrylic acid esters of the formula (VIII), N COOR ³ I (VIII) -C = CH-E ² in which E ^{2 is} an electron withdrawing leaving group and R ¹ , R ² , R ³ and X are as defined above, with thiols of the formula (IX), R ⁵ -SH (IX) in which R ^{5 has} the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary. 7. pesticides, characterized by a content of at least one substituted acrylic acid ester of the formula (I) according to the Ansj, Sue 1 and 6. 8. Use of substituted acrylic acid esters of the formula (I) according to claims 1 and 6 for combating pests. 9. A process for combating pests, characterized in that it is possible to act substituted pesticides of the formula (I) according to claims 1 and 6 on pests and / or their habitat. 10. A process for the preparation of pesticides, characterized in that one mixes substituted acrylic acid esters of the formula (I) according to claims 1 and 6 with extenders and / or surface-active agents. 11. Hydroxyacrylsäureester or their alkali metal salts of the formula (II), -N COOR ³ H 1 ' ^(II) .. ^ X '- ^ Y- C = CH-OM in which R ^{1 is} hydrogen, alkyl, alkenyl or each optionally substituted aralkyl, aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, aryloxy, arylthio, is alkanoyl, alkoxycarbonyl, Ν, Ν-dialkylcarbamoyl or heterocyclylcarbonyl, R ^{3 is} alkyl or optionally substituted aralkyl, X is oxygen or sulfur, M is hydrogen or an alkali metal cation and Y is oxygen, sulfur or a radical N, in which R ^{6 is} hydrogen, alkyl, alkanoyl or each optionally substituted aralkyl or aryl. 12. Process for the preparation of hydroxyacrylic esters or their alkali metal salts of the formula (II) N COOR ³ I (II) -C = CH-OM in which R ^{1 is} hydrogen, alkyl, alkenyl or each optionally substituted aralkyl, aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, mkoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, aryloxy, arylthio, is alkanoyl, alkoxycarbonyl, Ν, Ν-dialkylcarbamoyl or heterocyclylcarbonyl, R ^{3 is} alkyl or optionally substituted aralkyl, X is oxygen or sulfur, M is hydrogen or an alkali metal cation and Y is oxygen, sulfur or a radical N-, ie in which R ^{6 is} hydrogen, alkyl, alkanoyl or each optionally substituted aralkyl or aryl, characterized in that substituted acetic acid esters of the formula (IV) R ¹ ^ t- N (IV) in which R ¹ , R ² , R ³ , X and Y have the abovementioned meaning, with formic acid esters of the forms! (X) r9_0-C-H (X) in which R ^{9 is} alkyl, if appropriate in the presence of a diluent and optionally in the presence of a basic reaction auxiliary at temperatures between -2O ⁰ C and + 50 ⁰ C reacted. 13. Substituted acetic esters of formula (IVa),
¹ ₇ - N J Ii 7 3 < ^IVa > ^ x / ^ y 2 - CH ₂ - COOR- * -CH ₂ - in which Y ^{2 is} oxygen, sulfur or an N-alkyne, R ^{1 is} hydrogen, alkyl, alkenyl or each optionally substituted aryl, aralkenyl, aryl or heteroaryl, R ^{2 is} halo, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl, N -alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio.Halogenalkoxy, haloalkylthio, arryloxyjAiylthiOjfür alkanoyliAlkoxycarbonyliN.N-dialkylcarbamoyl or heterocyclylcarbonyl stands, R ^{3 is} alkyl or optionally substituted Aralky! stands and X is oxygen or sulfur.
14. Process for the preparation of substituted acetic esters of the formula (IVa) 3 (IVa) • -Chg-COOR ^ in which Y ^{2 is} oxygen, sulfur or an N-alkyl radical, R ^{1 is} hydrogen, alkyl, alkenyl or each optionally substituted aralkyl.Aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, aryloxy, arylthio, alkanoyl, Alkoxycarbonyl, N, N -dialkylcarbamoyl or heterocyclylcarbonyl, R ^{3 is} alkyl or optionally substituted aralkyl and X is oxygen or sulfur, characterized in that thiazole or oxazole derivatives of the formula (XI a) (XIa) R ² in which R ¹ , R ² , X and Y ^{2 have} the abovementioned meaning, or thiazole or oxazole derivative of the formula (XIb) (XIb) in which R ¹ , X and Y ^{2 have} the abovementioned meaning, with bromoacetic esters of the formula (XII), Br-CH ₂ -COOR ³ (XII) in which R ^{3 has} the abovementioned meaning, if appropriate in the presence of a diluent and optionally in the presence of a reaction auxiliary at temperatures between -2O ⁰ C and + 15 ⁰ C and optionally subsequently substituted in the 5-position of the thiazole or oxazole ring with conventional electrophilic substitution reactions or derivatizing existing functional groups in this position by well-known methods. 15. Substituted acrylic esters of the formula (VIII) - N COOR ^{3 1n} -j- N CO - E ² (vim CH - E in which R ^{1 is} hydrogen, alkyl, alkenyl or each optionally substituted aralkyl, aralkenyl, aryl or heteroaryl, R ^{2 is} halogen, cyano, nitro, formyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, hydroximinoalkyl, alkoximinoalkyl, N-alkyliminoalkyl, N-aryliminoalkyl, Ν, Ν-dialkylhydrazonoalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, arryloxy-arylthio, arylalkanoyl, alkoxycarbonyl. N, N-dialkylcarbamoyl or heterocyclylcarbonyl, R ^{3 is} alkyl or the optionally substituted aralkyl, X is oxygen or sulfur, E ^{2 stands} for an electron attracting leaving group. 16. Process for the preparation of substituted acrylic acid esters of the formula (VIII)