WO2000003580A2 - Utilization of 3,3-dichloro-2-fluoro-acrylic acid derivatives for pest control - Google Patents

Abstract

The invention relates to the partially known 3,3-dichloro-2-fluoro-acrylic acid derivatives of formula (I), wherein A has the meanings mentioned in the description. Said substances are suitable for protecting plants against the attack of undesired microorganisms and for controlling animal pests. The substances of formula (I) are also suitable for enhancing the effectiveness of azole fungicides. The invention further relates to novel 3,3-dichloro-2-fluoro-acrylic acid derivatives of formula (Ia), wherein A<1> has the meanings mentioned in the description, and to a method for producing said novel substances.

Description

Use of 3,3-dichloro-2-fluoro-acrylic acid derivatives to control pests

The present invention relates to the use of partially known 3,3-dichloro-2-fluoro-acrylic acid derivatives for controlling unwanted microorganisms and animal pests.

3,3-dichloro-2-fluoro-acrylic acid and some esters of this acid are already known (cf. J. Amer. Chem. Soc. 80 (1958), 6442 and Bull. Soc. Chim. Fr. DO (1993),

720). The use of these substances against plant or animal pests has not yet been described.

It has now been found that 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula

in welcher

in which

R ² A represents the groups -OR ¹ or - N, wherein

R ¹ for hydrogen, optionally substituted cycloalkyl, optionally sub-

R ⁴

substituted phenyl or represents the grouping of the formula R,

R ⁶ wherein R ^{4 represents} hydrogen, alkyl, alkoxyalkyl, dialkylaminoalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or the rest of the formula - (CH ₂ ) _n -COOR ⁷ ,

in which

R ^{7 represents} hydrogen or alkyl and

n stands for integers from 0 to 6,

R ^{5 represents} hydrogen, alkyl or optionally substituted phenyl and

R ^{6 represents} hydrogen or alkyl,

for hydrogen, optionally substituted cycloalkyl or optionally

worinsubstituted phenyl or represents the grouping of the formula,

wherein

R ^{8 represents} hydrogen, alkyl, alkenyl, optionally substituted phenyl, optionally substituted phenylalkyl, cyano or the rest of the formula - (CH ₂ ) _m -CO-R ^π ,

in which

R ¹ 1 represents hydroxy, alkoxy or amino and

m represents integers from 0 to 6, R ^{9 represents} hydrogen, alkyl, alkenyl, optionally substituted phenyl or optionally substituted heteroaryl and

R ^{10 represents} hydrogen or alkyl, or

R ⁹ and R ¹⁰ together represent an alkylene chain with 2 to 7 carbon atoms which is optionally substituted by alkyl and / or alkoxy, it being possible for one of the carbon atoms to be replaced by oxygen, sulfur or an 1 group, in which

R ¹²

R ^{12 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl,

and

R ^{3 represents} hydrogen, alkyl, alkoxyalkyl, optionally substituted phenyl or optionally substituted phenylalkyl or a radical of the formula

- C-C = CCL

I I

O stands

or

R ² and R ³ together represent an alkylene chain with 4 to 7 carbon atoms, one carbon atom not adjacent to the nitrogen atom passing through

Oxygen, sulfur or an I group can be replaced, wherein

R ¹³

R ^{13 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl, and wherein the alkylene chain can be substituted by alkyl and / or -CO-R ¹⁴ , wherein

R ^{14 represents} hydroxy, alkoxy or amino,

are very well suited for protecting plants against attack by undesired microorganisms and for combating animal pests.

It was also found that 3,3-dichloro-2-fluoro-acrylic acid derivatives of

Also use formula (I) very well to increase the effectiveness of azole fungicides.

Surprisingly, the 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (I) which can be used according to the invention are much better suited for protecting plants against attack by undesired microorganisms and for combating animal pests than the constitutionally most similar, known substances having the same direction of action . In addition, it could not be expected that the substances which can be used according to the invention can be used to improve the action of azole fungicides, since such a synergistic activity has not hitherto been known from substances of this type.

Formula (I) provides a general definition of the 3,3-dichloro-2-fluoro-acrylic acid derivatives which can be used according to the invention.

A also preferably represents the groups -OR ¹ or

R ¹ preferably represents hydrogen or cycloalkyl having 3 to 8 carbon atoms, which is monosubstituted to trisubstituted, identical or different can be by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 or 2 carbon atoms and 1 to 3 identical or different halogen atoms.

R ¹ furthermore preferably represents phenyl which can be monosubstituted to trisubstituted, identical or differently substituted by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy with 1 to

6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ¹ also preferably represents a radical of the formula.

R ⁴ preferably represents hydrogen, alkyl having 1 to 8 carbon atoms, alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and 1 to 6 carbon atoms in the alkyl part, dialkylaminoalkyl having 1 to 4 carbon atoms in each alkyl part or phenyl which is simple to triple, similar or can be substituted differently by flalogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms. R ⁴ also preferably represents phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, in the same way or differently, by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ⁴ also preferably represents a radical of the formula - (CH ₉ ) _n -COOR ⁷ , in which

R ⁷ preferably represents hydrogen or alkyl having 1 to 6 carbon atoms and

n stands for integers from 0 to 4.

R ⁵ preferably represents hydrogen, alkyl having 1 to 6 carbon atoms or phenyl which can be monosubstituted to triple, identical or differently substituted by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ⁶ preferably represents hydrogen or alkyl having 1 to 6 carbon atoms.

R ² preferably represents hydrogen or cycloalkyl having 3 to 8 carbon atoms, which is monosubstituted to trisubstituted, identical or different can be by halogen, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 3 identical or different halogen atoms, carboxyl, alkoxy having 1 to 6 carbon atoms and / or alkoxycarbonyl having 1 to 6 carbon atoms in the alkoxy part.

R ² furthermore preferably represents phenyl which can be monosubstituted to trisubstituted, identical or different, by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R °

IQR ² also preferably represents a radical of the formula PR

R ¹⁰

R ⁸ preferably represents hydrogen, cyano, alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 6 carbon atoms or phenyl, which can be mono- to trisubstituted, identical or different, by halogen, cyano, nitro, straight-chain or branched alkyl having 1 up to 6 carbon atoms, straight-chain or branched alkoxy with 1 to 6 carbon atoms, straight-chain or branched haloalkyl with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ⁸ also preferably represents phenylalkyl having 1 to 4 carbon atoms in the alkyl part, the phenyl part being simple to triple, similar or different can be substituted in various ways by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy with 1 to

6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ⁸ also preferably represents a radical of the formula - (CH ₂ ) _m -CO-R ^π , wherein

R ^{1 1} preferably represents hydroxyl, alkoxy having 1 to 6 carbon atoms or amino and

m stands for integers from 0 to 4.

R ⁹ preferably represents hydrogen, alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms or phenyl, which can be monosubstituted to trisubstituted, identical or different, by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 Carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ⁹ also preferably represents an optionally benzene-fused five- or six-membered heteroaromatic radical having 1 to 3 heteroatoms, such as

Nitrogen, oxygen and / or sulfur, it being possible for these radicals to be substituted one to three times, in the same way or differently, by halogen,

Cyano, nitro, straight-chain or branched alkyl with 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ¹⁰ preferably represents hydrogen or alkyl having 1 to 6 carbon atoms.

R ⁹ and R ¹⁰ also preferably together represent an alkylene chain with 2 to 7 carbon atoms which is optionally mono- or disubstituted by alkyl with 1 to 4 carbon atoms and / or alkoxy with 1 to 4 carbon atoms, it being possible for one of the carbon atoms to be replaced by acid

- N - erstoff, sulfur or an I group,

R ¹²

wherein

R ¹² preferably represents hydrogen, alkyl having 1 to 6 carbon atoms, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl part or alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy part.

R ³ preferably represents hydrogen, alkyl having 1 to 8 carbon atoms, alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and 1 to 6 carbon atoms in the alkyl part or phenyl which can be monosubstituted to trisubstituted, identical or different, by halogen, cyano, nitro , straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ³ also preferably represents phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, identically or differently, by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or by haloalkoxy having 1 to

6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ³ also preferably represents the rest of the formula

R ² and R ³ also preferably together represent an alkylene chain having 4 to 7 carbon atoms, a carbon which is not adjacent to the nitrogen atom

len atom replaced by oxygen, sulfur or an l group

R ¹³ can be where

R ¹³ preferably represents hydrogen, alkyl having 1 to 6 carbon atoms, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl part or alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy part,

and wherein the alkylene chain can be mono- to tetrasubstituted, identical or differently substituted by alkyl having 1 to 4 carbon atoms and / or -CO-R ¹⁴ , in which R ¹⁴ preferably represents hydroxy, alkoxy having 1 to 4 carbon atoms or amino.

The substituent definitions can be combined with one another as desired.

3,3-Dichloro-2-fluoroacrylic acid derivatives of the formula (I) in which

A stands for the groups -OR ¹ or, wherein

R ^{1 represents} hydrogen or cycloalkyl having 3 to 7 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -Butyl, iso-butyl, tert-butyl, and / or trifluoromethyl, or

R ^{1 represents} phenyl which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms,

Haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,

or

in welcherR ^{1 represents} a radical of the formula

in which

R ^{4 represents} hydrogen, alkyl having 1 to 6 carbon atoms, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 to 4

Carbon atoms in the alkyl part, dialkylaminoalkyl having 1 to 4 carbon atoms in each alkyl part or represents phenyl, which can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 Carbon atoms, straight-chain or branched alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, Chlorine and / or bromine atoms,

or

R ^{4 represents} phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or

Bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,

or R ^{4 represents} a radical of the formula - (CH ₂ ) _n -COOR ⁷ , in which

R ^{7 represents} hydrogen or alkyl having 1 to 4 carbon atoms and

n stands for integers from 0 to 3,

R ^{5 stands} for hydrogen, alkyl with 1 to 4 carbon atoms or for phenyl which can be subtituted by one to three times, in the same or different ways, by fluorine, chlorine, bromine, iodine,

Cyano, nitro, straight-chain or branched alkyl with 1 to 4 carbon atoms, straight-chain or branched alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or with haloalkoxy with 1 or 2

Carbon atoms and 1 to 5 fluorine. Chlorine and / or bromine atoms,

and

R ^{6 represents} hydrogen or alkyl having 1 to 4 carbon atoms,

represents hydrogen or cycloalkyl having 3 to 7 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -Butyl, iso-butyl, tert-butyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, carboxyl, alkoxy with 1 to 4 carbon atoms and / or alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, or R ^{2 represents} phenyl which can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, Haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,

or

R ^ä R ² is a radical of the formula - represents C- R ^9,

R ¹⁰

in which

R ^{8 represents} hydrogen, cyano, alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 4 carbon atoms or phenyl, which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, iodine, cyano, nitro , straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms - men and 1 to 5 fluorine, chlorine and / or bromine atoms,

or R ^{8 represents} phenylalkyl with 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, identically or differently, by fluorine, chlorine,

Bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched

Alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,

or

R ^{8 represents} a radical of the formula - (CH ₂ ) _m -CO-R ^1] , in which

R ^{1 1 represents} hydroxy, alkoxy having 1 to 4 carbon atoms or amino and

m represents integers from 0 to 3,

R ^{9 represents} hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms or phenyl, which can be substituted once to three times, in the same way or differently, by fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, or

R ^{9 represents} an optionally benzene-fused heteroaromatic radical having 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, it being possible for these radicals to be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, iodine, cyano, nitro straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5

Fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,

and

R ^{10 represents} hydrogen or alkyl having 1 to 4 carbon atoms,

or

R ⁹ and R ¹⁰ together represent an alkylene chain with 2 to 5 carbon atoms which is optionally mono- or disubstituted, identical or different, by alkyl having 1 to 4 carbon atoms or alkoxy by 1 to 4 carbon atoms, it being possible for one of the carbon atoms to be replaced by sow -

- Nitrogen, sulfur or a 1 ₁₂ group, in which

R

R ^{12 is} hydrogen, alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1 or 2 carbon atoms in the Alkyl part or for alkoxycarbonyl having 1 or 2 carbon atoms in the alkoxy part, and

R ^{3 represents} hydrogen, alkyl having 1 to 6 carbon atoms, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part or phenyl, which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, Iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,

or

R ^{3 represents} phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, in the same way or differently, by fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or Bromine atoms,

or

oderR ^{3 represents} the rest of the formula,

or

R ² and R ³ together represent an alkylene chain with 4 to 6 carbon atoms, a carbon atom which is not adjacent to the nitrogen atom being

- N - atom due to oxygen, sulfur or a | Group to be replaced

_R 13

can,

wherein

R ^{13 represents} hydrogen, alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1 or 2 carbon atoms in the alkyl part or alkoxycarbonyl having 1 or 2 carbon atoms in the alkoxy part,

and

where the alkylene chain can be mono- to tetrasubstituted, identical or different, by methyl, ethyl or -CO-R ¹⁴ ,

wherein

R ^{14 represents} hydroxy, methoxy, ethoxy or amino.

R ² also very particularly preferably represents the groups -OR ¹ and - N R ¹ very particularly preferably represents hydrogen or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl which is optionally monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, methyl, ethyl and / or trifluoromethyl.

R ¹ also very particularly preferably represents phenyl, which can be monosubstituted to trisubstituted in the same or different way by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, Trifluoromethyl, difluoromethoxy and / or trifluoromethoxy, or

R ¹ represents a radical of the formula

R ⁴ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxymethyl, methoxyethyl, ethoxyethyl, ethoxymethyl, dialkylaminomethyl having 1 or 2 carbon atoms in each alkyl part or dialkylaminoethyl having 1 or 2 carbon atoms in each alkyl part.

R ⁴ also very particularly preferably represents phenyl, which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy , Trifluoromethyl. Difluoromethoxy and / or trifluoromethoxy.

R ⁴ also very particularly preferably represents phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, in the same way or differently, by fluorine, Chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy.

R ⁴ also very particularly preferably represents a radical of the formula - (CH ₂ ) _n -COOR ⁷ , in which

R ^{7 represents} hydrogen, methyl, ethyl, n-propyl, isopropyl or n-butyl and

n stands for integers from 0 to 2.

R ⁵ very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl or phenyl, which can be substituted once to three times, identically or differently, by fluorine, chlorine, bromine, cyano

Nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy.

R ⁶ very particularly preferably represents hydrogen, methyl, ethyl, n-propyl or isopropyl.

R ² very particularly preferably represents hydrogen or optionally single to triple, identical or different by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl. Trichloromethyl, carboxyl, methoxy, ethoxy, methoxycarbonyl and / or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

R ² also very particularly preferably represents phenyl, which can be substituted once to three times, in the same way or differently, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, Methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy.

is also very particularly preferably a radical of the formula

R ⁸ very particularly preferably represents hydrogen, cyano, methyl, ethyl, n-propyl, isopropyl, vinyl, allyl or

Phenyl which can be monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy or for

Phenylalkyl with 1 or 2 carbon atoms in the alkyl part, the

Phenyl moiety can be monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy.

R ⁸ also very particularly preferably represents a radical of the formula - (CH ^ -CO-R ' ^l , in which

R ^{1 1 represents} hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy or amino and

m stands for 0, 1 or 2. R ⁹ very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, vinyl, allyl or phenyl, which can be monosubstituted to trisubstituted by identical or different substituents by fluorine, chlorine, bromine, cyano, nitro, methyl, Ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or

Trifluoromethoxy, or for

Pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl. Furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl, 1,2,3-triazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, quinazolinyl, indolyl,

Benzothienyl, benzofuranyl, benzothiazolyl or benzimidazolyl, where these radicals can be substituted once or twice, identically or differently by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy.

R ¹⁰ very particularly preferably represents hydrogen, methyl, ethyl, n-propyl or isopropyl.

R ⁹ and R ¹⁰ together also very particularly preferably represent an alkylene chain of the formula - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, -O- (CH ₂ ) ₃ -, -CH ₂ -O- (CH ₂ ) ₂ -, -O- (CH ₂ ) ₄ -, -CH ₂ -O- (CH ₂ ) ₃ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, -S- (CH ₂ ) ₃ -, -CH ₂ -S- (CH ₂ ) ₂ -, -S- (CH ₂ ) ₄ -, -CH ₂ -S- (CH _{2 3} -, - (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -N- (CH ₂ ) ₂ - or - (CH ₂ ) ₂ -N- (CH ₂ ) ₂ -,

H ^CH 3 where each of these chains can be substituted once or twice, in the same way or differently, by methyl, ethyl, methoxy and / or ethoxy.

R ³ very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl or phenyl, simple to triple, may be substituted in the same or different manner by fluorine, chlorine, bromine, cyano, nitro, methyl, n-propyl, isopropyl, tert-butyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy, or for phenylalkyl with 1 or 2 carbon atoms in the alkyl part, the phenyl part being monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, n-propyl, isopropyl, tert-butyl, ethyl, methoxy, ethoxy, Trifluoromethyl, Diflourmethoxy and / or

Trifluoromethoxy, or for the rest of the formula 9 P ^ '2.

O F

R ² and R ³ together also very particularly preferably represent an alkylene chain of the formula - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, -CH ₂ -O- (CH ₂ ) ₂ -, -CH ₂ -O - (CH ₂ ) ₃ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, -CH ₂ -S- (CH ₂ ) ₂ -, -CH ₂ -S- (CH ₂ ) ₃ -, - (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -N- (CH ₂ ) ₂ - or - (CH ₂ ) ₂ -N- (CH ₂ ) ₂ -,

H ^C 3 where each of these chains can be substituted once or twice, identically or differently by methyl, ethyl or -CO-R ¹⁴ -, in which

R ^{14 represents} hydroxy, methoxy, ethoxy or amino.

The specified substituent definitions can be combined with one another as desired. In addition, individual substituent definitions can also be omitted.

Some of the 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (I) which can be used according to the invention are known (cf. J. Amer. Chem. Soc. 80, 6442 (1958) and Bull. Chim. Soc. Fr. 130: 720 (1993).

in welcherThe 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula are new

in which

A ^{1 stands} for the groups -OR ^{l 5} or, wherein

R ^{l 5} for optionally substituted cycloalkyl, substituted phenyl or for the grouping of the formula

_R 1 ^β

- CR ⁵ is what

R ' ^{6 represents} alkoxyalkyl, dialkylaminoalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or a radical of the formula - (CH ₂ ) _n -COOR ⁷ , in which

R ^{7 represents} hydrogen or alkyl and

n stands for integers from 0 to 6,

R ^{5 represents} hydrogen, alkyl or optionally substituted phenyl and

R ^{6 represents} hydrogen or alkyl,

R ² for hydrogen, optionally substituted cycloalkyl or optionally substituted phenyl or for the grouping of the formula _R 1 ^β

- CR ⁵ is what

R ^{8 represents} hydrogen, alkyl, alkenyl, optionally substituted phenyl, optionally substituted phenylalkyl, cyano or the rest of the formula - (CH ₂ ) _m -CO-R ¹ ',

in which

Rl ^{1 represents} hydroxy, alkoxy or amino and

m represents integers from 0 to 6,

R ^{9 represents} hydrogen, alkyl, alkenyl, optionally substituted phenyl or optionally substituted heteroaryl and

R ¹ ° represents hydrogen or alkyl, or

R ⁹ and R ¹ ° together represent an alkylene chain with 2 to 7 carbon atoms which may be substituted by alkyl and / or alkoxy, it being possible for one of the carbon atoms to be replaced by oxygen, sulfur or an --N group,

R ¹² wherein

R ^{12 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl,

and R ^{3 represents} hydrogen, alkyl, alkoxyalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or the rest of the formula 9 9 Gd ₂ , or

O F

R ² and R ³ together represent an alkylene chain having 4 to 7 carbon atoms, a carbon atom not adjacent to the nitrogen atom being replaced by oxygen, sulfur or a

- N group can be replaced, where R ¹³

Rl ^{3 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl

and wherein the alkylene chain can be substituted by alkyl and / or -CO-R ¹⁴ , wherein

R ^{ϊ4 represents} hydroxy, alkoxy or amino.

In the compounds of formula (Ia)

A ¹ also preferably for the groups -ORI ⁵ or.

R ⁵ preferably represents cycloalkyl having 3 to 8 carbon atoms, which can be monosubstituted to triple, identical or differently substituted by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 or 2

Carbon atoms and 1 to 3 identical or different halogen atoms. R ¹⁵ furthermore preferably represents phenyl which can be monosubstituted to triple, identical or differently substituted by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 same or different halogen atoms and / or by haloalkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms.

R ¹⁵ also preferably represents a radical of the formula

R ^{l 6} preferably represents alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl part, dialkylaminoalkyl with 1 to 4 carbon atoms in each alkyl part, or phenyl which may be monosubstituted to trisubstituted by identical or different gene by halo , Cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or halogenoalkoxy having 1 to 6 Carbon atoms and 1 to 5 identical or different halogen atoms.

R ' ⁶ also preferably represents phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where the phenyl part can be monosubstituted to triple, identical or differently substituted by halogen, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy with 1 to 6 carbon atoms, straight-chain or branched haloalkyl with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms and / or haloalkoxy with 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms. R ^{! 6} also preferably represents a radical of the formula - (CH ₂ ) _n -COOR ⁷ , in which

R ⁷ and n preferably have those meanings which have already been mentioned as preferred for this radical and this index.

R ⁵ and R ⁶ and R ² and R ³ are also in the case of the compounds of the formula (Ia)

die für diese Substituenten bereits als bevorzugt genannt wurden.in the groups and preferably for those residues,

which have already been mentioned as preferred for these substituents.

Compounds of the formula (Ia) are particularly preferred. in which

A ^{1 stands} for the groups -OR ^{l 5} or, wherein

Rl ^{5 represents} cycloalkyl having 3 to 7 carbon atoms, which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- Butyl, tert-butyl, difluoromethyl and / or trifluoromethyl or

Rl ^{5 represents} phenyl which is monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms ,

Haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or with haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, or

represents a radical of the formula in which

R ^{l 6} alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl part, dialkylaminoalkyl with 1 to 4 carbon atoms in each alkyl part or represents phenyl which may be monosubstituted to trisubstituted by identical or different fluorine, chlorine Bromine

Iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 or 2

Carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, or

Rl ^{6 represents} phenylalkyl having 1 or 2 carbon atoms in the alkyl part, where the phenyl part can be substituted once to three times, identically or differently, by fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or

Bromine atoms and / or by haloalkoxy with 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, or Rl ^{6 represents} a radical of the formula - (CH ₂ ) _n -COOR ⁷ , in which

R ⁷ and n have those meanings which have already been mentioned as particularly preferred for this radical and this index, and

R ⁵ and R ⁶ and R ² and R ^{3 have} those meanings which have already been mentioned as particularly preferred for these radicals.

In the compounds of formula (Ia)

A ^{1 is} also very particularly preferred for the groups -OR ¹³ or

R ¹⁵ very particularly preferably represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl which is optionally mono- to triple, identical or different, substituted by fluorine, chlorine, methyl, ethyl and / or trifluoromethyl.

R ¹⁵ also very particularly preferably represents phenyl which is monosubstituted to trisubstituted by fluorine,

Chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy, or

R ¹⁶

I ₅ Rl ⁵ stands for a radical of the formula CR.

R ⁶

Rl ⁶ very particularly preferably represents methoxy methyl, methoxyethyl, ethoxyethyl, ethoxymethyl, dialkylaminomethyl with 1 or 2 carbon atoms in each alkyl part or for dialkylaminoethyl with 1 or 2 carbon atoms in each alkyl part.

R ¹⁶ also very particularly preferably represents phenyl, which can be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, Ethoxy, trifluoromethyl, difluoromethoxy and / or trifluoromethoxy.

R ¹⁶ also very particularly preferably represents phenylalkyl

1 or 2 carbon atoms in the alkyl part, the phenyl part being monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy,

Trifluoromethyl, difluoromethoxy and / or trifluoromethoxy.

Rl ⁶ also very particularly preferably represents a radical of the formula - (CH ₂ ) n-COOR ⁷ , in which

R ⁷ and n have the meanings which have already been mentioned as particularly preferred for this radical and this index.

R ⁶ and R ² and R ³ are also in the case of the compounds of the formula (Ia) in the groups

ganz besonders bevorzugt für diejenigen Reste, die für diese Substituenten bereits als ganz besonders bevorzugt genannt wurden.

very particularly preferred for those radicals which have already been mentioned as particularly preferred for these substituents.

3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (Ia) can be prepared by

a) 3,3-dichloro-2-fluoro-acrylic acid chloride of the formula

entweder

either

α) with amines of the formula

in welcher

in which

R ² and R ^{3 have} the meanings given above,

or

ß) with alcohols of the formula

HO-R ^{l 5} (IV)

in which R ^{15 has} the meanings given above,

if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,

or

b) 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula

in which

R ³ , R ⁹ , R ¹ ° and m have the meanings given above and

R ^{17 represents} alkoxy,

in the presence of a base and in the presence of water and optionally in the presence of an additional organic diluent.

The other 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (I) can also be prepared by the above processes.

The 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (I) which can be used according to the invention can optionally be obtained as mixtures of various possible isomeric forms, in particular in the form of optical isomers. The invention relates both to the pure isomers and to any mixtures thereof. If 3,3-dichloro-2-fluoro-acrylic acid chloride and L-leucine ethyl ester are used as starting materials, the course of the process (a, variant) according to the invention can be illustrated by the following formula.

If 3,3-dichloro-2-fluoro-acrylic acid chloride and ethylene glycol monomethyl ether are used as starting materials, the course of the process according to the invention (a, variant β) can be illustrated by the following formula.

If 3-N- (3,3-dichloro-2-fluoro-acryloyl) -N-methylamino-propionic acid ethyl ester is used as the starting material, sodium hydroxide as the base and water as the reaction medium, the course of the process according to the invention ( b) are illustrated by the following formula scheme.

The 3,3-dichloro-2-fluoro-acrylic acid chloride of the formula (II) required as starting material when carrying out process (a) according to the invention is known (cf. DE-A 44 01 099). Formula (III) provides a general definition of the amines required as reaction components when carrying out process (a, variant α) according to the invention. In this formula, R ² and R ³ preferably represent those radicals which have already been mentioned as preferred for these substituents.

The amines of the formula (III) can also be used in the form of their acid addition salts when carrying out the process (a, variant α) according to the invention. Both the amines of the formula (III) and their acid addition salts are known or can be prepared by known methods.

Formula (IV) provides a general definition of the alcohols required as reaction components when carrying out process (a, variant β) according to the invention. In this formula, R ' ⁵ preferably has those meanings which have already been mentioned as preferred for this substituent.

The alcohols of the formula (IV) are known or can be prepared by known methods.

All customary inorganic and organic bases are suitable as acid binders when carrying out the process according to the invention (a, variants α and β)

Question. Alkaline earth metal or alkali metal, hydroxides,

-alcoholates, -acetates. carbonates or bicarbonates, such as sodium methylate,

Sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, furthermore ammonium hydroxide, ammonium acetate or ammonium carbonate, or tertiary amines, such as trimethylamine, triethylamine, tributylamine , N, N-

Dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). In the case of process (a, variant α), an amine used in excess can also act as an acid binder.

Suitable diluents for carrying out the process according to the invention (a, variants α and β) are all inert organic solvents. Aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, can preferably be used. Toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,

Methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane or anisole; Nitriles such as acetonitrile, propionitrile. n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane.

When carrying out the process according to the invention (a, variants α and β), the reaction temperatures can be varied within a relatively wide range. In general, temperatures between -20 ° C and + 150 ° C, preferably between -10 ° C and + 100 ° C.

When carrying out the process according to the invention (a, variants .alpha. And .beta.) One generally works under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

When carrying out the process according to the invention (a, variant α), the following is used

3,3-dichloro-2-fluoro-acrylic acid chloride of the formula (II) and amine of the formula (III) in general in approximately equimolar amounts. However, it is also possible to use one of the components, preferably the amine, in a larger excess. If the amine of the formula (III) is used in the form of an acid addition salt, 1 mol or an excess of acid binder is generally added per mole of acid addition salt. The processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is filtered, the liquid phase is concentrated and the remaining product is freed of any impurities which may still be present, using customary methods.

When carrying out the process according to the invention (a, variant β), 1 mol or a larger excess of alcohol of the formula (IV) is generally employed per mol of 3,3-dichloro-2-fluoro-acrylic acid chloride of the formula (II) as well as 1 to

1.5 mol or a larger excess of acid binder. The processing is again carried out using customary methods. In general, the procedure is that the reaction mixture is filtered, the liquid phase is concentrated and the remaining product is freed of any impurities which may still be present using customary methods.

Formula (Ib) provides a general definition of the 3,3-dichloro-2-fluoro-acrylic acid derivatives required as starting materials when carrying out process (b) according to the invention. In this formula, R ³ , R ⁹ , R '° and m preferably have those meanings which have already been mentioned as preferred for these substituents and this index. R ^{l 7} is preferably alkoxy having 1 to 6 carbon atoms, more preferably alkoxy having 1 to 4 carbon atoms, and very particularly preferably represents methoxy, ethoxy, n-propoxy or isopropoxy.

The 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (Ib) are according to the invention

Fabrics. They can be produced by the process (a, variant α) according to the invention.

Suitable bases for carrying out process (b) according to the invention are all inorganic bases customary for such reactions. Alkali metal hydroxides and alkaline earth metal hydroxides, such as lithium hydroxide and calcium hydroxide, and also alkali metal carbonates and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate. Sodium hydroxide in the form of 10 to 45% sodium hydroxide solution is particularly preferably used.

In addition to water, suitable diluents for carrying out process (b) according to the invention are all organic solvents which are customary for such reactions and which are stable to bases and are at least partially miscible with water. Ethers such as dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or diethylene glycol dimethyl ether can preferably be used; and also lower alcohols, such as methanol, ethanol, i-propanol, ethanediol. Propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.

The reaction temperatures can be carried out when carrying out the process according to the invention

Process (b) can be varied within a certain range. Generally one works at temperatures between -20 ° C and + 70 ° C. preferably between -10 ° C and + 50 ° C.

The process (b) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

When carrying out process (b) according to the invention, 1 to 3 mol of 3,3-dichloro-2-fluoro-acrylic acid derivative of the formula (Ib) is generally from 1.2 to

50 equivalents, preferably 2 to 10 equivalents of base and 5 to 1000 mol, preferably 10 to 100 mol, of water. The processing takes place according to usual methods. In general, the procedure is that water is added to the reaction mixture, then acidified, extracted with an organic solvent which is not very miscible with water, and the organic phase is dried and concentrated. The received pro If necessary, the product can be freed of any impurities that may still be present using customary methods.

The 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (I) which can be used according to the invention are very suitable for protecting plants against attack by undesired microorganisms and for combating animal pests. In addition, the substances which can be used according to the invention also have a herbicidal action and can also be used as synergists to increase the effectiveness of azole fungicides.

The active substances which can be used according to the invention have a strong resistance-inducing action in plants. They are therefore suitable for creating resistance in plants to attack by undesirable microorganisms.

In the present context, resistance-inducing substances include those

To understand substances that are able to stimulate the immune system of plants so that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.

Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to produce resistance to the attack by the pests mentioned in plants within a certain period of time after the treatment. The period within which resistance is brought about generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active compounds.

In addition to the resistance-inducing action, the active compounds which can be used according to the invention also have a strong microbicidal action and are also used practically for the direct control of undesired microorganisms. The Active ingredients are suitable for use as crop protection agents, especially as fungicides.

Undesirable microorganisms in crop protection include fungi from the classes Plasmodiophoromycetes, Oomycetes, Chytriomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Bactericidal agents are used in crop protection to combat Pseudomonadaeae, Rliizobiaceae, 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; Pseudoperonospa 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: Helmihtosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus (Conidial form: Drechslera, Syn: Helminthosporium);

Uromycetes species, such as, for example, Uromycetes 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; Pseudocerosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

The active ingredients which can be used according to the invention are particularly successful in combating rice diseases, such as Pyricularia species, or diseases in wine, fruit and vegetable cultivation, such as, for example, Uncinula species, and also with good success against cereal diseases, such as powdery mildew, used.

Depending on their respective physical and / or chemical properties, the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV -Cold and warm mist formulations. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of using water as

Extenders can e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: 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. 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. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Possible solid carriers are: e.g. natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates. As solid carriers for granules come in

Question: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Possible emulsifiers and / or foaming agents are: e.g. non-ionic and anionic emulsifiers, such as

Polyoxyethylene fatty acid esters, poklyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, 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 94 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds which can be used according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases you get effects, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The active compounds which can be used according to the invention can be used as such, in the form of their commercially available formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, foaming, brushing, etc. If appropriate, the active ingredients are applied using the ultra-low-volume process or the active ingredient preparation or the active ingredient itself is injected into the soil. If necessary, the seeds of the plants are also treated. When using the active compounds according to the invention as fungicides or resistance inducers, the application rates can be varied within a substantial range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The active compounds which can be used according to the invention also act against plant, hygiene and stored-product pests and also in the veterinary sector against animal parasites (ect oparas iten) such as tick ticks, leather ticks, mite mites, running mites, flies (stinging and licking), parasitic fly larvae, lice and hair lice , Featherlings and fleas. These parasites include:

From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..

From the order of the Malophagida and the subordinates Amblycerina as well

Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Weneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..

From the order Diptera and the subordinates Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp.,

Eusimulium spp., Phletomous spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp ., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,

Hippobosca spp., Lipotena spp., Melophagus spp .. From the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..

From the order of the Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp.,

Panstrongylus spp ..

From the order of the Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp ..

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp.,

Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp ..

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) e.g.

Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypppterol spp ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..

For example, they show excellent activity against Musca domestica and Lucilia cuprina larvae.

The active substances which can be used according to the invention are also suitable for controlling arthropods which are used in agricultural animals, such as Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice. By fighting these arthropods, deaths and

Reductions in performance (for meat, milk, wool, skins, eggs, honey, etc.) be reduced, so that the use of the active ingredients which can be used according to the invention makes economical and simple animal husbandry possible.

The active ingredients which can be used according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example

Tablets, capsules, watering, drenching, granules, pastes, bokli, the feed-through method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), des

Washing, powdering and with the help of shaped articles containing active ingredients, such as collars, ear tags, tail tags, limb straps, holsters. Marking devices etc.

When used for cattle, poultry, pets etc., the active ingredients can be used as

Formulations (for example powders, emulsions, flowable agents), which contain the active ingredients in an amount of 1 to 80% by weight, can be used directly or after 100 to 10,000 times dilution or can be used as a chemical bath.

The substances which can be used according to the invention are also suitable as synergists for increasing the effectiveness of azole fungicides.

The invention therefore also relates to fungicidal compositions comprising an active ingredient combination

A) at least one 3,3-dichloro-2-fluoro-acrylic acid derivative of the formula

in welcher

in which

A has the meanings given above,

and

B) at least one azole fungicide

contain.

In the present case, azole fungicides are to be understood as meaning imidazole derivatives and triazole derivatives which are suitable for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection or in the protection of materials.

Examples of azole fungicides are:

(1) Azole derivatives of the formula

(VI) R ^{i 8} = _a - / \ / __ V / o- 'R ^l = -CH (OH) -C (CH ₃ ) ₃

(TRIADIMENOL)

(V-2) R ^{l 8} = ^C '\ _ / ^~ °' R ^{l 9} = -CO-C (CH ₃ ) ₃

R^l9 = -CH(OH)-C(CH₃)₃ (TRIADIMEFON) (V-3) R ^π

R ¹⁹ = -CH (OH) -C (CH ₃ ) ₃

(BITERTANOL)

(V-4) R ¹⁸ R ¹⁹ = -CH (OH) -C (CH ₃ ) ₃

(DICLOBUTRAZOL)

(2) Azole derivatives of the formula

R^2l=-C(CH₃)₃, R²² = OH(VI-1) R ²⁰ =

R ^2l = -C (CH ₃ ) ₃ , R ²² = OH

(TEBUCONAZOLE)

(VI-2) R ²⁰ = R ² 'and R ²² = -OCH ₂ CH (nC ₃ H ₇ ) O-

(PROPICONAZOLE)

(VI .3) R ² lundR ² = -OCH ₂ CH (CH ₃₎ O-

(DIFENCONAZOLE)

(CYPROCONAZOLE) R21 =

(CYPROCONAZOLE) R21 =

R ²² = OH

(VI-6) R ²⁰ = - (CH ₂ ) ₃ CH ₃ , R ² = OH

(HEXACONAZOLE)

(MYCLOBUTANIL)

(PENCONAZOLE)

(ETACONAZOLE)

(VI- 10) R ²⁰ -

(BROMUCONAZOLE)

R²¹ und R²² gemeinsam(VI-1 1) R ²⁰

R ²¹ and R ²² together

(EPOXICONAZOLE),

(TETRACONAZOLE)

(3) the azole derivative of the formula

(DINICONAZOLE)

(4) the azole derivative of the formula

(FLUSILAZOLE) (5) the azole derivative of the formula

(PROCHLORAZ)

(6) Azole derivatives of the formula

(Xl) R ²³ = CH ₃ , R ²⁴ = CH ₃

(METCONAZOLE)

(X-2) R ²³ = H, R ²⁴ = CH (CH ₃ ) ₂

(IPCONAZOLE)

(7) the azole derivative of the formula

(FLUQUINCONAZOLE) (8) the azole derivative of the formula

(TRITICONAZOLE)

(9) the azole derivative of the formula

(TRIFLUMIZOLE)

(10) the azole derivative of the formula

(IMIBENCONAZOLE) (11) the azole derivative of the formula

(IMAZALIL)

(12) the azole derivative of the formula

The azole derivatives of groups (1) to (12) are known.

Combinations according to the invention are preferred from

A) at least one 3,3-dichloro-2-fluoro-acrylic acid derivative of the formula (I)

and

B) at least one azole derivative of groups (1) to (12).

If the active compounds are present in the active compound combinations according to the invention in certain weight ratios, the effect-increasing is shown Effect particularly clear. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied within a relatively wide range. In general, 1 part by weight of active compound of the formula (I)

1 to 10 parts by weight, preferably

2 to 5 parts by weight of at least one azole fungicide, preferably an active ingredient from groups (1) to (12).

The preparation and the use of the active compounds which can be used according to the invention can be seen from the examples below.

Manufacturing examples

example 1

(Method a, variant α)

A solution of 17.7 g (100 mmol) is added to a mixture of 11 g (79.4 mmol) alanine methyl ester hydrochloride and 200 ml tetrahydrofuran at 0 ° C while stirring.

3,3-dichloro-2-fluoro-acrylic acid chloride in 20 ml of tetrahydrofuran and 28 ml (200 mmol) of triethylamine are added dropwise. After the addition has ended, the reaction mixture is stirred for a further hour at room temperature. The precipitate which has precipitated is then filtered off with suction and the liquid phase is concentrated under reduced pressure. The remaining precipitate is taken up in a mixture of hexane / ethyl acetate = 2: 1 and chromatographed on silica gel. By concentrating the eluate under reduced pressure, 16.6 g (68% of theory) of methyl 2-N- (3,3-dichloro-2-fluoro-acryloyl) aminopropionate are obtained in the form of an oil.

IH NMR spectrum (200 MHz; CDC1 ₃ ; TMS); δ = 1.50 (d, 3H, CHCH ₃ ); 3.80 (s,

3H, OCH ₃ ); 4.65 (m, 1H, _-CH-CH3) ppm. Example 2

(Method a, variant)

A solution of 3.54 g (20 mmol) of 3,3-dichloro-2-fluoro-acrylic acid chloride in 10 ml of tetrahydrofuran is added to a mixture of 5.1 ml (40 mmol) of phenylethylamine and 40 ml of tetrahydrofuran at 0 ° C. while stirring dropped in. After the addition has ended, the reaction mixture is stirred for a further hour at room temperature. The precipitate which has separated out is then filtered off with suction and the filtrate is concentrated under reduced pressure. In this way, 2.7 g (52% of theory) of 3,3-dichloro-2-fluoro-acrylic acid-1-phenyl-ethylamide are obtained in the form of an oil.

IH NMR spectrum (200 MHz; CDC1 ₃ ; TMS); δ = 1, 54 (d, 3H, _-CH-CH3); 5.17 (m,

1H, CHCH ₃ ); 7.30 (m, 5H, Ph-H) ppm.

Example 3

(Method a, variant ß)

A solution of 5.3 g (30 mmol) of 3,3-dichloro is added to a mixture of 2.5 ml (31.7 mmol) of ethylene glycol monomethyl ether, 5 ml of triethylamine and 100 ml of tetrahydrofuran at 0 ° C. while stirring -2-fluoro-acrylic acid chloride in 10 ml of tetrahydrofuran dropped in. After the addition has ended, the reaction mixture is stirred for a further hour at room temperature. The precipitate which has separated out is then filtered off with suction and the filtrate is concentrated under reduced pressure. In this way 6.2 g (95% of theory) of 3,3-dichloro-2-fluoro-acrylic acid-2-methoxyethyl ester are obtained in the form of an oil.

^I H NMR Spectrum (200 MH ₂ ; CDC1 ₃ ; TMS); 6 = 3.41 (s, 3H, OCH ₃ ); 3.68 (m, 2H, O-CH ₂ -); 4.44 (m, 2H, CO-O-CH ₂ ) ppm.

Example 4

(Method b)

A mixture of 14 ml of 45% sodium hydroxide solution and 14 ml of water is stirred in 12.2 g (50 mmol) of 2-N- (3,3-dichloro-2-fluoro-acryloyl) -amino- cooled to 10 ° C. methyl propionate added dropwise at such a rate that the temperature does not exceed 20 ° C. After the addition has ended, the reaction mixture is stirred for a further hour at 20 ° C. Then you add

Add 100 ml ice water and then acidify at temperatures between 0 ° C and 20 ° C with concentrated hydrochloric acid. The resulting mixture is extracted with dichloromethane, the combined organic phases are dried over magnesium sulfate and concentrated under reduced pressure. The remaining product is brought to crystallization by adding hexane. The precipitate is suctioned off, with n

Washed and dried hexane. In this way, 9.1 g (80% of theory) of 2-N- (3,3-dichloro-2-fluoro-acryloyl) -amino-propionic acid are obtained in the form of a solid with a melting point of 137-138 ° C. The 3,3-dichloro-2-fluoro-acrylic acid derivatives listed in the following table are also prepared by the methods given above.

Table 1

Spectroscopic data

Example 7

IH NMR spectrum (200 MHz; CDC1 ₃ ; TMS): δ = 5.32 (s, 2H. 0-CH ₂ ); 7.39 (m,

5H, aromatic protons) ppm.

Example 8 IH NMR spectrum (200 MHz; CDC1 ₃ ; TMS): δ = 2.55 (s, 6H, N (CH ₃ ) ₂ ); 4.55 (t,

2H, _O-CH2-CH2) ppm. Example 9

IH NMR spectrum (500 MHz; CDC1 ₃ ; TMS): δ = 1.04 (t, 6H, CH ₂ -CH ₃ ); 2.58 (q,

4H, _CH2-CH3); 2.67 (t, 2H, N-CH2) ppm.

Example 10

IH NMR spectrum (500 MHz; CDC1 ₃ ; TMS): δ = 1.59 (d, 3H, CH-CH ₃ ); 3.78 (s, 3H, OCH ₃ ); 5.15 (q, IH, -O-CH-CH ₃ ppm.

Example 11 ^I H-NMR spectrum (200 MHz; CDC1 ₃ ; TMS): δ = 1.60 (d, 3H, CH-CH ₃ ); 3.79 (s,

3H, OCH ₃ ); 5.26 (q, IH, O-CH-CH ₃ ) ppm.

Example 12

^I H-NMR spectrum (200 MHz; CDC1 ₃ ; TMS): δ = 1.25-1.97 (m, 10H); 5.0 (m, IH, OCH) ppm.

Example 13

! H NMR spectrum (400 MHz; D ₆ -DMSO; TMS): δ = 1.25 (t, 3H. O-CH -CH3); 6.05 (s, IH, -O-CH-CO) ppm.

Example 16 ¹ H-NMR spectrum (200 MHz; D ₆ -DMSO, TMS): δ = 1.45 (2s, 6H, C (CH ₃ ) ₂ ); 8.22

(b, 1H, NH) ppm.

Example 19

IH NMR spectrum (200 MHz; D ₆ -DMSO; TMS): δ = 0.95 (2d, 6H, CH (CH ₃ ) ₂ ; 2.24 (m, IH, CH (CH ₃ ) ₂ ); 3.77 (s, 3H, CH ₂ -CH ₃ ) ppm. Example 21

IH NMR spectrum (200 MHz; D ₆ -DMSO; TMS): δ = 1.35 (d, 6H, CH (CH ₃ ) ₂ ; 4.32

(m, 1H, NH-CH) ppm.

Example 23

IH NMR spectrum (400 MHz; D ₆ -DMSO; TMS): δ = 1.17 (d, 6H, CH (CH ₃ ) ₂ ); 4.05 (m, 1H, CH (CH ₃ ) ₂ ) ppm.

Example 24 IH NMR spectrum (400 MHz; D ₆ -DMSO; TMS): δ = 2.95 and 3.08 (s, 3H,

N-CH ₃ ); 4.21 and 4.29 (s, 2H, N-CF ^) ppm.

Example 25

IH NMR spectrum (400 MHz; D ₆ -DMSO; TMS): δ = 4.22 (m, IH, N-CH); 4.00 (m, 2H, N-CH ₇ -CO) ppm.

Example 26

Mass spectrum (m / e): 197 M® (3%); 141 (85%); 28 (100%).

Example 27

IH NMR spectrum (400 MHz; D ₆ -DMSO; TMS): δ = 3.62 (s, 3H, CO-OCH ₃ ); 3.20 and 3.23 (s, 3H, CH-OCH3) ppm.

Example 28 ¹ H-NMR spectrum (400 MHz; D ₆ -DMSO; TMS): δ = 1.23 (t, O-CH ₂ -CH ₃ ); 4.17

(q, 2H, O-CH ₂ -CH ₃ ); 4.75 (s, br.); 5.10 (d, IH, N-CH-CH ₂ p _pm .

COOC ₂ H ₅ Example 29

IH NMR spectrum (400 MHz; D ₆ -DMSO; TMS): δ = 1.22 (t, 3H, O-CH ₂ -CH ₃ );

4.21 (q, 2H, O-CH2-CH3); 5.13 (s); 5.43 (t, IH, N-CH-CH _{2 ppm} .

COOC ₂ H ₅

Examples of use

Example A

Pyricularia test (rice) / resistance induction

Solvent: 2.5 parts by weight of acetone

Emulsifier: 0.06 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.

To test for resistance-inducing activity, young rice plants are sprayed with the preparation of active compound in the stated application rate. 5 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then placed in a greenhouse at 100% relative atmospheric humidity and a temperature of 25 ° C.

Evaluation is carried out 4 days after the inoculation. 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active ingredients, application rates and test results come from the following

Table. Table A

Pyricularia test (rice) / resistance induction

Beispiel B

Example B

Erysiphe test (barley) / protective

Solvent: 25 parts by weight of N, N-dimethylacetamide

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate.

After the spray coating has dried on, the plants are covered with spores from Erysiphe graminis f.sp. hordei pollinated.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% to prevent the development of

Favor mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, application rates and test results are shown in the following table. Table B

Erysiphe test (barley) / protective

Example C

Erysiphe test (wheat) protective

Solvent: 25 parts by weight of N, N-dimethylacetamide

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate.

After the spray coating has dried on, the plants are covered with spores from Erysiphe graminis f.sp. tritici pollinated.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, application rates and test results are shown in the following table. Table C.

Erysiphe test (wheat) / protective

Example D

Nephotettix test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the green rice leafhopper (Nephotettix cincticeps) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all cicadas have been killed; 0% means that no cicadas have been killed.

Active substances, active substance concentrations and test results are shown in the following table.

Table D

plant-damaging insects Nephotettix test

Example E

Plutella test

Solvent: 7 parts by weight of dimethylformamide. Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping into the preparation of active compound of the desired concentration and populated with caterpillars of the cockroach (Plutella xylostella) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all the caterpillars have been killed, 0% means that none of the caterpillars have been killed.

Active ingredient. Active substance concentrations and test results are shown in the following table.

Table E plant-damaging insect PIutella test

Beispiel F

Example F

Tetranychus test (OP-resistant / immersion treatment)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of the common spider mite (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.

Active substance, active substance concentrations and test results are shown in the following table.

Table F

plant-damaging insect tetranychus test (OP-resistant / immersion treatment)

Claims

claims 1. Use of 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula / CI ₂ C: \ (I), in which R ² A for the groups -OR ^l or | _\ | stands in what R ¹ for hydrogen, optionally substituted cycloalkyl, optionally substituted phenyl or for the grouping of the formula stands in what

R ⁴ for hydrogen, alkyl, alkoxyalkyl, dialkylaminoalkyl, optionally substituted phenyl, optionally substituted Phenylalkyl or the radical of the formula - (CH ₂ ) _n -COOR ⁷ , in which R ^{7 represents} hydrogen or alkyl and n stands for integers from 0 to 6, R ^{5 represents} hydrogen, alkyl or optionally substituted phenyl and R ^{6 represents} hydrogen or alkyl, for hydrogen, optionally substituted cycloalkyl or optionally substituted phenyl or for the grouping of the formula stands in what

R ^{8 represents} hydrogen, alkyl, alkenyl, optionally substituted Phenyl, optionally substituted phenylalkyl, represents cyano or the radical of the formula - (CH ₂ ) _m -CO-R ¹ ', in which Rl 'represents hydroxy, alkoxy or amino and m represents integers from 0 to 6, R ^{9 represents} hydrogen, alkyl, alkenyl, optionally substituted Phenyl or optionally substituted heteroaryl and Rl ° represents hydrogen or alkyl, or R ⁹ and R ¹ ° together represent an alkylene chain with 2 to 7 carbon atoms optionally substituted by alkyl and / or alkoxy, one of the carbon atoms being replaced - N can be replaced by oxygen, sulfur or an l group, R ¹² wherein R ^{12 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl. and R ^{3 represents} hydrogen, alkyl, alkoxyalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or a radical of Formula - C - C = CCI 2. d or R ² and R ³ together represent an alkylene chain with 4 to 7 carbon atoms, a carbon atom not adjacent to the nitrogen atom being replaced by oxygen, sulfur or an 1 group R ¹³ can be where R ^{l 3 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl, and wherein the alkylene chain can be substituted by alkyl and / or -CO-R ' ⁴ , wherein Rl ^{4 represents} hydroxy, alkoxy or amino, to protect plants against infestation by undesirable microorganisms and to control animal pests. 2. A method for protecting plants against infestation by undesired microorganisms and for combating animal pests, characterized in that 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (I) according to claim 1 on the microorganisms or animal pests and / or their habitat. 3. 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula / CI ₂ C = C _χ (la) CA ¹ II O in what A 'represents the groups -OR' ⁵ or, wherein

Rl ⁵ for optionally substituted cycloalkyl, substituted phenyl or for the grouping of the formula stands in what

R ^{] 6 represents} alkoxyalkyl, dialkylaminoalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or a radical of the formula - (CH ₂ ) _n -COOR ⁷ , in which R ^{7 represents} hydrogen or alkyl and n stands for integers from 0 to 6, R ^{5 represents} hydrogen, alkyl or optionally substituted phenyl and R ^{6 represents} hydrogen or alkyl, for hydrogen, optionally substituted cycloalkyl or optionally substituted phenyl or for the grouping of the formula R ^{8 is} CR ⁹ , wherein _R ιo R ^{8 represents} hydrogen, alkyl, alkenyl, optionally substituted phenyl, optionally substituted phenylalkyl, cyano or the rest of the formula - (CH ₂ ) _m -CO-RH, in which Rl 'represents hydroxy, alkoxy or amino and m represents integers from 0 to 6, R ⁹ for hydrogen. Alkyl, alkenyl, optionally substituted phenyl or optionally substituted heteroaryl and R ¹ ° represents hydrogen or alkyl, or R ⁹ and R ¹⁰ together for an alkylene chain with 2 to 7 which is optionally substituted by alkyl and / or alkoxy 5 carbon atoms are available, whereby one of the carbon atoms can be replaced by oxygen, sulfur or an - N group. where R ¹² R ' ² for hydrogen. Is alkyl, alkylcarbonyl or 10 alkoxycarbonyl, and R ³ for hydrogen, alkyl, alkoxyalkyl, optionally 15 substituted phenyl. optionally substituted Phenylalkyl or the rest of the formula - C— C = CC stands, or II I O F R ² and R ³ together represent an alkylene chain with 4 to 7 carbon atoms, one carbon atom not adjacent to the nitrogen atom being caused by oxygen. Sulfur or a group N-t _{erse z} may be, 13 R where 25 Rl ^{3 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl and wherein the alkylene chain can be substituted by alkyl and / or -CO-R ¹⁴ , wherein R ^{14 stands} for hydroxy, alkoxy or amino. 4. A process for the preparation of 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (Ia) according to claim 3, characterized in that a) 3,3-dichloro-2-fluoro-acrylic acid chloride of the formula

either α) with amines of the formula

in which R ² and R ^{3 have} the meanings given above, or ß) with alcohols of the formula HO-RI ⁵ (IV) in which Rl ^{5 has} the meanings given above, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or b) 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula

in which R ³ , R ⁹ , R ¹ ° and m have the meanings given above and R ^{ϊ 7 represents} alkoxy, in the presence of a base and in the presence of water and optionally in the presence of an additional organic diluent. 5. Agents for protecting plants against attack by undesired microorganisms and for combating animal pests, characterized by a content of at least one 3,3-dichloro-2-fluoro-acrylic acid derivative of the formula (Ia) according to claim 3 in addition to extenders and / or surfactants. 6. A process for the preparation of agents for protecting plants against attack by undesirable microorganisms and for combating animal pests, characterized in that 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (Ia) according to claim 3 with extenders and / or surface-active substances are mixed. 7. Use of 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula (I) according to Claim 1 to increase the effectiveness of azole fungicides. 8. Fungicidal compositions, characterized by a content of an active ingredient combination A) at least one 3,3-dichloro-2-fluoro-acrylic acid derivatives of the formula \ / CI ₂ C: \ (I) in which R A stands for the groups -ORl or - N, in which V R ¹ for hydrogen, optionally substituted cycloalkyl, optionally substituted phenyl or for the grouping of the formula stands in what

R ^{4 represents} hydrogen, alkyl, alkoxyalkyl, dialkylaminoalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or the rest of the formula - (CH ₂ ) _n -COOR ⁷ , in which R ^{7 represents} hydrogen or alkyl and n stands for integers from 0 to 6, R ^{5 represents} hydrogen, alkyl or optionally substituted phenyl and R ^{6 represents} hydrogen or alkyl, for hydrogen, optionally substituted cycloalkyl or optionally substituted phenyl or for the grouping of the formula stands in what

R ^{8 represents} hydrogen, alkyl, alkenyl, optionally substituted Phenyl, optionally substituted phenylalkyl, represents cyano or the radical of the formula - (CH ₂ ) _m -CO-R ^]] , in which R ^{l 1 represents} hydroxy, alkoxy or amino and m represents integers from 0 to 6, R ^{9 represents} hydrogen, alkyl, alkenyl, optionally substituted phenyl or optionally substituted heteroaryl and Rl ° represents hydrogen or alkyl, or R ⁹ and Rl ° together for an optionally by alkyl and / or Alkoxy-substituted alkylene chain with 2 to 7 carbon atoms are available, one of the carbon atoms being replaced - N - can be due to oxygen, sulfur or an l group. R ¹² wherein R ' ^{2 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl, and R ^{3 represents} hydrogen, alkyl, alkoxyalkyl, optionally substituted phenyl, optionally substituted phenylalkyl or the rest of the Formula - C— C = CCI ₂ stands, OF or R ² and R ³ together represent an alkylene chain with 4 to 7 carbon atoms, with a carbon which is not adjacent to the nitrogen atom atom replaced by oxygen, sulfur or an l group R ¹³ can be where R ^{] 3 represents} hydrogen, alkyl, alkylcarbonyl or alkoxycarbonyl, and wherein the alkylene chain can be substituted by alkyl and / or -CO-R ¹⁴ , wherein R ^{14 represents} hydroxy, alkoxy or amino, and B) at least one azole fungicide. 3,3-dichloro-2-fluoro-acrylic acid derivative according to claim 3, characterized by the formula / CLC: \ -NH- CH- COOH 10. 3,3-dichloro-2-fluoro-acrylic acid derivative according to claim 3, characterized by the formula / CLC: \ C NH - CHr-COO CH, II O