Fungicidal substituted acrylic acid esters of the formula ##STR1## in which R.sup.1 and R.sup.2 independently of one another each stand for hydrogen, alkyl, alkenyl or for in each case optionally substituted aralkyl, aralkenyl, aryl or heteroaryl, PA0 R.sup.3 stands for alkyl or for optionally substituted aralkyl, PA0 R.sup.4 stands for dialkylamino or for a radical --Z--R.sup.5, PA0 X stands for oxygen or sulphur and PA0 Y stands for oxygen, sulphur or for a radical ##STR2## wherein R.sup.5 stands for alkyl or for optionally substituted aralkyl, PA1 R.sup.6 stands for hydrogen, alkyl, alkanoyl or for in each case optionally substituted aralkyl or aryl and PA1 Z stands for oxygen or sulphur. Some intermediates are also new.

The invention relates to new substituted acrylic acid esters, several 
processes for their preparation and their use in pesticides. 
It has been disclosed that certain substituted acrylic acid esters, such 
as, for example, the compound methyl 
2-(2-benzoyl-pyrrol-1-yl)-3-methoxy-acrylate or the compound methyl 
3-methoxy-2-(2-methylphenyl)-acrylate or the compound phenyl 
2-(2-benzyloxyphenyl)-3-methoxy-acrylate, possess fungidal properties 
(cf., for example, EP No. 206,523; EP No. 178,816; DE-OS (German Published 
Specification) No. 3,519,282 corresponding to U.S. Pat. No. 4,709,078). 
However, the activity of these previously known compounds is not completely 
satisfactory in all fields of use, in particular at low application rates 
and when low concentrations are used. 
New substituted acrylic acid esters of the general formula (I) 
##STR3## 
in which R.sup.1 and R.sup.2 independently of one another each stand for 
hydrogen, alkyl, alkenyl or for in each case optionally substituted 
aralkyl, aralkenyl, aryl or heteroaryl, 
R.sup.3 stands for alkyl or for optionally substituted aralkyl, 
R.sup.4 stands for dialkylamino or for a radical --Z-R.sup.5, 
X stands for oxygen or sulphur and 
Y stands for oxygen, sulphur or for a radical 
##STR4## 
wherein R.sup.5 stands for alkyl or for optionally substituted aralkyl, 
R.sup.6 stands for hydrogen, alkyl, alkanoyl or for in each case optionally 
substituted aralkyl or aryl and 
Z stands for oxygen or sulphur, 
have been found. 
The compounds of the formula (I) can be present as geometric isomers or 
isomer mixtures having a varying composition. The invention relates both 
to the pure isomers and to the isomer mixtures. 
Furthermore, it has been found that the new substituted acrylic acid esters 
of the general formula (I) 
##STR5## 
in which R.sup.1 and R.sup.2 independently of one another each stand for 
hydrogen, alkyl, alkenyl or for in each case optionally substituted 
aralkyl, aralkenyl, aryl or heteroaryl, 
R.sup.3 stands for alkyl or for optionally substituted aralkyl, 
R.sup.4 stands for dialkylamino or for a radical --Z-R.sup.5, 
X stands for oxygen or sulphur and 
Y stands for oxygen, sulphur or for a radical 
##STR6## 
wherein R.sup.5 stands for alkyl or for optionally substituted aralkyl, 
R.sup.6 stands for hydrogen, alkyl, alkanoyl or for in each case optionally 
substituted aralkyl or aryl and 
Z stands for oxygen or sulphur, 
are obtained by one of the processes described below: 
(a) substituted acrylic acid esters of the formula (Ia) 
##STR7## 
in which R.sup.1, R.sup.2, R.sup.3, R.sup.5, X and Y have the 
abovementioned meaning, 
are obtained when hydroxyacrylic acid esters or their alkali metal salts of 
the formula (II) 
##STR8## 
in which M stands for hydrogen or for an alkali metal cation and 
R.sup.1, R.sup.2, R.sup.3, X and Y have the abovementioned meaning, 
are reacted with alkylating agents of the formula (III) 
EQU R.sup.5 --E.sup.1 (III) 
in which 
E.sup.1 stands for an electron-withdrawing leaving group and 
R.sup.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 (Ib) 
##STR9## 
in which R.sup.4-1 stands for dialkylamino and 
R.sup.1, R.sup.2, R.sup.3, X and Y have the abovementioned meaning, 
are obtained when substituted acetic acid esters of the formula (IV) 
##STR10## 
in which R.sup.1, R.sup.2, R.sup.3, X and Y have the abovementioned 
meaning, 
are reacted with formamides of the formula (Va) 
##STR11## 
in which R.sup.4-1 has the abovementioned meaning, 
or with the derivatives of the formula (Vb) 
##STR12## 
in which R.sup.7 and R.sup.8 independently of one another each stand for 
alkoxy or dialkylamino and 
R.sup.4-1 has the abovementioned meaning, 
if appropriate in the presence of a diluent; 
(c) substituted acrylic acid esters of the formula (Ic) 
##STR13## 
in which Y.sup.1 stands for sulphur or for a radical 
##STR14## 
and R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6 and X have the 
abovementioned meaning, 
are obtained when oxalic acid derivatives of the formula (VI) 
##STR15## 
in which R.sup.1, R.sup.2, R.sup.3, X and Y.sup.1 have the abovementioned 
meaning, 
are reacted with organometal compounds of the formula (VII) 
##STR16## 
in which R.sup.5 has the abovementioned meaning, 
if appropriate in the presence of a diluent; 
(d) substituted acrylic acid esters of the formula (Id) 
##STR17## 
in which R.sup.1, R.sup.2, R.sup.3, R.sup.5 and X have the abovementioned 
meaning, 
are obtained when substituted acrylic acid esters of the formula (VIII) 
##STR18## 
in which E.sup.2 stands for an electron-withdrawing leaving group and 
R.sup.1, R.sup.2, R.sup.3 and X have the abovementioned meaning, 
are reacted with thiols of the formula (IX) 
EQU R.sup.5 --SH (IX) 
in which 
R.sup.5 has the abovementioned meaning, 
if appropriate in the presence of a diluent and if appropriate in the 
presence of a reaction auxiliary. 
Finally, it has been found that the new substituted acrylic acid esters of 
the general formula (II) possess a good action against pests. 
Surprisingly, the substituted acrylic acid esters of the general formula 
(I) according to the invention show, for example, a considerably better 
fungicidal activity than the acrylic acid esters known from the prior art, 
such as, for example, the compound methyl 
2-(2-benzoylpyrrol-1-yl)-3-methoxyacrylate or the compound methyl 
3-methoxy-2-(2-methylphenyl)-acrylate or the compound phenyl 
2-(2-benzyloxyphenyl)-3-methoxyacrylate, which are chemically similar 
compounds of a similar type of action.

Formula (I) provides a general definition of the substituted acrylic acid 
esters according to the invention. Preferred compounds of the formula (I) 
are those in which 
R.sup.1 and R.sup.2 independently of one another each stand for hydrogen, 
for straight-chain or branched alkyl which has 1 to 8 carbon atoms, for 
straight-chain or branched alkenyl which has 2 to 8 carbon atoms, or for 
aralkyl which has 1 to 6 carbon atoms in the straight-chain or branched 
alkyl moiety, aralkenyl which has 2 to 6 carbon atoms in the 
straight-chain or branched alkenyl moiety or aryl which has 6 to 10 carbon 
atoms in the respective aryl moiety and each of which is optionally 
substituted once or more than once in the aryl moiety by identical or 
different substituents, suitable aryl substituents in each case being: 
halogen, cyano, nitro, in each case straight-chain or branched alkyl, 
alkoxy or alkylthio each of which has 1 to 4 carbon atoms, in each case 
straight-chain or branched halogenoalkyl, halogenoalkoxy or 
halogenoalkylthio each of which has 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 of which has 1 to 8 carbon 
atoms in the individual alkyl moieties, cycloalkyl with 3 to 7 carbon 
atoms, doubly linked alkandiyl with 3 to 5 carbon atoms or aryl, aralkyl, 
aryloxy or aralkyloxy each of which has 6 to 10 carbon atoms in the aryl 
moiety and where appropriate 1 to 4 carbon atoms in the straight-chain or 
branched alkyl moiety and each of which is optionally substituted once or 
more than once in the aryl moiety by identical or different substituents 
from the series comprising halogen, alkyl, alkoxy, alkylthio, 
halogenoalkyl, halogenoalkoxy or halogenoalkylthio each of which has 1 to 
4 carbon atoms and where appropriate 1 to 9 identical or different halogen 
atoms, or heteroarylalkyl or heteroaryl each of which has 2 to 9 carbon 
atoms and 1 to 4 identical or different hetero atoms, in particular 
nitrogen, oxygen and/or sulphur, in the heteroaryl moiety and where 
appropriate 1 to 4 carbon atoms in the straight-chain or branched alkyl 
moiety and each of which is optionally substituted once or more than once 
in the heteroaryl moiety by identical or different substituents from the 
series comprising halogen, alkyl, alkoxy, alkylthio, halogenoalkyl, 
halogenoalkoxy or halogenoalkylthio each of which has 1 to 4 carbon atoms 
and where appropriate 1 to 9 identical or different halogen atoms; 
furthermore stand for a heteroaryl radical which has 2 to 9 carbon atoms 
and 1 to 4 identical or different hetero atoms, in particular nitrogen, 
oxygen and/or sulphur, and which is optionally substituted once or more 
than once by identical or different substituents, suitable substituents 
being the abovementioned aryl substituents, 
R.sup.3 stands for straight-chain or branched alkyl which has 1 to 6 carbon 
atoms or for aralkyl which has 1 to 4 carbon atoms in the straight-chain 
or branched alkyl moiety and 6 to 10 carbon atoms in the aryl moiety and 
which is optionally substituted once or more than once in the aryl moiety 
by identical or different substituents, suitable aryl substituents being 
those which have been mentioned for R.sup.1 and R.sup.2, 
R.sup.4 stands for dialkylamino, each of which has 1 to 6 carbon atoms in 
the individual alkyl moieties, or for a radical --Z-R.sup.5, 
X stands for oxygen or sulphur and 
Y stands for oxygen, sulphur or for a radical 
##STR19## 
wherein R.sup.5 stands for straight-chain or branched alkyl which has 1 to 
6 carbon atoms or for aralkyl which has 1 to 4 carbon atoms in the 
straight-chain or branched alkyl moiety and 6 to 10 carbon atoms in the 
aryl moiety and which is optionally substituted once or more than once in 
the aryl moiety by identical or different substituents, suitable aryl 
substituents being those which have been mentioned for R.sup.1 and 
R.sup.2, 
R.sup.6 stands for hydrogen, for straight-chain or branched alkyl which has 
1 to 6 carbon atoms, for straight-chain or branched alkanoyl which has 1 
to 6 carbon atoms in the alkyl moiety or for aralkyl which has 1 to 6 
carbon atoms in the straight-chain or branched alkyl moiety and which is 
optionally substituted once or more than once in the aryl moiety by 
identical or different substituents, or for aryl, each of which has 6 to 
10 carbon atoms in the respective aryl moiety, suitable substituents in 
the aryl moiety being those which have been mentioned for R.sup.1 and 
R.sup.2, and 
Z stands for oxygen or sulphur. 
Particularly preferred compounds of the formula (I) are those in which 
R.sup.1 and R.sup.2 independently of one another each stand for hydrogen, 
methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for allyl, n- or 
i-butenyl, for benzyl, phenylethyl, phenylethenyl, phenyl, naphthyl, 
pyridyl, thienyl or furyl each of which is optionally substituted once, 
twice or three times in the aryl moiety or in the heteroaryl moiety by 
identical or different substituents, suitable substituents in each case 
being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or 
i-propyl, n-, 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 phenyl, benzyl, phenoxy or 
benzyloxy each of which is optionally substituted once, twice or three 
times in the phenyl moiety by identical or different substituents from the 
series comprising fluorine, chlorine, bromine, methyl, ethyl, methoxy, 
ethoxy, methylthio, trifluoromethyl, difluoromethoxy, trifluoromethoxy 
and/or trifluoromethylthio, 
R.sup.3 stands for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or 
for benzyl which is optionally substituted once, twice or three times by 
identical or different substituents, suitable substituents being those 
which have been mentioned for R.sup.1 and R.sup.2, 
R.sup.4 stands for dialkylamino which has in each case 1 to 4 carbon atoms 
in the individual alkyl moieties or for a radical --Z-R.sup.5, 
X stands for oxygen or sulphur and 
Y stands for oxygen, sulphur or for a radical 
##STR20## 
wherein R.sup.5 stands for methyl, ethyl, n- or i-propyl, n-, i-, s- or 
t-butyl or for benzyl which is optionally substituted once, twice or three 
times by identical or different substituents, suitable substituents being 
those which have been mentioned for R.sup.1 and R.sup.2 ; 
R.sup.6 stands for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or 
t-butyl, for acetyl, propionyl, n- or i-butyryl, or for benzyl or phenyl 
each of which is optionally substituted once, twice or three times by 
identical or different substituents, suitable substituents being those 
which have been mentioned for R.sup.1 and R.sup.2, and 
Z stands for oxygen or sulphur. 
Very particularly preferred compounds of the formula (I) are those in which 
R.sup.1 and R.sup.2 independently of one another each stand for hydrogen, 
methyl, ethyl, n- or i-propyl or for phenyl or naphthyl each of which is 
optionally substituted once, twice or three times by identical or 
different substituents, suitable substituents in each case being: 
fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, 
n-, 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 phenyl, phenoxy, benzyl or benzyloxy 
each of which is optionally substituted once or twice by identical or 
different substituents from the series comprising fluorine, chlorine, 
bromine, methyl, and/or ethyl, 
R.sup.3 stands for methyl, ethyl or benzyl, 
R.sup.4 stands for dimethylamino, diethylamino or for a radical 
--Z-R.sup.5, 
X stands for oxygen or sulphur and 
Y stands for oxygen, sulphur or for a radical 
##STR21## 
wherein R.sup.5 stands for methyl, ethyl, n- or i-propyl or benzyl, 
R.sup.6 stands for hydrogen, methyl, ethyl, acetyl, propionyl or for benzyl 
or phenyl, each of which is optionally substituted once or twice by 
identical or different substituents from the series comprising fluorine, 
chlorine, bromine, methyl, ethyl and/or trifluoromethyl and 
Z stands for oxygen or sulphur. 
Especially preferred compounds of the formula (I) are those in which 
R.sup.1 stands for hydrogen, methyl, ethyl, n- or i-propyl, or for phenyl 
which is optionally substituted once or twice by identical or different 
substituents, suitable substituents being: fluorine, chlorine, bromine, 
cyano, nitro, methyl, ethyl, methoxy, ethoxy, methylthio, trifluoromethyl, 
trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, 
methoximinomethyl, methoximinoethyl, cyclopentyl, 1,3-propanediyl, or 
phenyl, phenoxy, benzyl or benzyloxy each of which is optionally 
substituted once or twice by identical or different substituents from the 
series comprising fluorine, chlorine, bromine or methyl, 
R.sup.2 stands for hydrogen, methyl, ethyl, n- or i-propyl, 
R.sup.3 stands for methyl or ethyl, 
R.sup.4 stands for methoxy, ethoxy, methylthio or dimethylamino, 
X stands for oxygen or sulphur and 
Y stands for an N-methyl radical. 
The following substituted acrylic acid esters of the general formula (I) 
may be mentioned individually in addition to the compounds mentioned in 
the Preparation Examples: 
##STR22## 
__________________________________________________________________________ 
R.sup.1 R.sup.2 
R.sup.3 
R.sup.4 
X Y 
__________________________________________________________________________ 
H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR23## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR24## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR25## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR26## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR27## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR28## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR29## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR30## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR31## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR32## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR33## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR34## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR35## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR36## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR37## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR38## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR39## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR40## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR41## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR42## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR43## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR44## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR45## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR46## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR47## H CH.sub. 3 
OCH.sub.3 
S NCH.sub.3 
##STR48## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR49## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR50## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR51## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR52## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR53## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR54## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR55## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR56## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR57## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR58## H CH.sub.3 
OCH.sub.3 
S 
##STR59## 
##STR60## CH.sub.3 
CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR61## H CH.sub.3 
OCH.sub.3 
O 
##STR62## 
##STR63## CH.sub.3 
CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR64## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR65## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR66## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR67## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR68## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR69## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR70## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR71## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR72## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR73## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR74## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR75## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR76## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR77## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR78## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR79## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR80## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR81## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR82## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR83## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR84## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR85## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR86## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR87## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR88## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR89## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR90## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR91## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR92## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR93## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR94## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR95## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR96## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR97## H CH.sub.3 
SCH.sub.3 
S NCH.sub.3 
##STR98## H CH.sub.3 
SCH.sub.3 
S NCH.sub.3 
##STR99## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR100## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR101## H CH.sub.3 
##STR102## 
S NCH.sub.3 
##STR103## H CH.sub.3 
##STR104## 
O NCH.sub.3 
##STR105## H CH.sub.3 
OCH.sub.3 
S S 
##STR106## H CH.sub.3 
OCH.sub.3 
O S 
##STR107## H C.sub.2 H.sub.5 
OCH.sub.3 
S NCH.sub.3 
##STR108## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR109## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR110## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR111## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 
##STR112## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR113## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR114## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
##STR115## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 
__________________________________________________________________________ 
If, for example, methyl 
2-{N[4-(3,4-dichlorophenyl)-thiazol-2-yl]-N-methylamino}-3-hydroxyacrylate 
and dimethyl sulphate are used as starting substances, the course of the 
reaction of the process (a) according to the invention may be represented 
by the following equation: 
##STR116## 
If, for example, methyl 2-[4-(4-chlorophenyl)-thiazol-2-yl-oxy]-acetate and 
dimethylformamide dimethyl acetal are used as starting substances, the 
course of the reaction of process (b) according to the invention may be 
represented by the following equation: 
##STR117## 
If, for example, methyl 
2-[4-(2,4-dichlorophenyl)-thiazol-2-yl-thio]-2-oxo-acetate and 
(methylthio)-(trimethylsilyl)-methylenelithium are used as starting 
substances, the course of the reaction of process (c) according to the 
invention may be represented by the following equation: 
##STR118## 
If, for example, methyl 
2-[4-(4-chlorophenyl)-oxazol-2-yl-oxy]-3-methylsulphonyloxy-acrylate and 
methyl mercaptan are used as starting substances, the course of the 
reaction of process (d) according to the invention may be represented by 
the following equation: 
##STR119## 
Formula (II) provides a general definition of the hydroxyacrylic acid 
esters or their alkali metal salts required as starting substances for 
carrying out process (a) according to the invention. In this formula (II), 
R.sup.1, R.sup.2, R.sup.3, X and Y preferably stand for 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. M preferably stands for hydrogen or for 
a sodium or potassium cation. 
Some of the hydroxyacrylic acid esters of the formula (II) are known (cf. 
EP No. 61,425; U.S. Pat. No. 4,451,471). 
The invention also relates to compounds which were hitherto unknown, of the 
formula (IIa), 
##STR120## 
in which R.sup.1, R.sup.2, R.sup.3, X, Y and M have the abovementioned 
meaning, 
with the exception of the compound ethyl 
2-[4,5-bis(4-methoxyphenyl)-thiazol-2-yl-thio]-3-hydroxyacrylate. 
They are obtained when substituted acetic acid esters of the formula (IV) 
##STR121## 
in which R.sup.1, R.sup.2, R.sup.3, X and Y have the abovementioned 
meaning, with the exception of the compound ethyl 
2-[4,5-bis(4-methoxyphenyl)-thiazol-2-yl-thio]-acetate, 
are reacted with formic acid esters of the formula (X) 
##STR122## 
in which R.sup.9 stands for alkyl, in particular for methyl or ethyl, 
if appropriate in the presence of a diluent, such as, for example, 
dimethylformamide, and if appropriate in the presence of a basic reaction 
auxiliary, such as, for example, sodium hydride, at temperatures between 
-20.degree. C. and +50.degree. C. 
Formic acid esters of the formula (X) are generally known compounds of 
organic chemistry. 
Formula (III) provides a general definition of the alkylating agents also 
required as starting substances for carrying out process (a) according to 
the invention. In this formula (III), R.sup.5 preferably stands for 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.sup.1 stands for a leaving group customary in alkylating agents, 
preferably for an optionally substituted alkyl, alkoxy or arylsulphonyloxy 
radical, such as, for example, a methoxysulphonyloxy radical, an 
ethoxysulphonyloxy radical or a p-toluenesulphonyloxy radical, or for 
halogen, in particular for chlorine, bromine or iodine. 
The alkylating agents of the formula (III) are generally known compounds of 
organic chemistry. 
Formula (IV) provides a general definition of the substituted acetic acid 
esters required as starting substances for carrying out process (b) 
according to the invention and for the synthesis of the precursors of the 
formula (II). In this formula (IV), R.sup.1, R.sup.2, R.sup.3, X and Y 
preferably stand for 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 or can be 
obtained in analogy to known processes (cf., for example, J. Ind. Chem. 
Soc. 46, 441- 443 [1963]; FR 2,152,345; FR 2,146,161; Chem. Ber. 92, 1928 
[1959]; Arzneimittel-Forsch. 36, 1391-1393 [1986]. GB 1,552,126; DE-OS 
(German Published Specification) No. 2,129,012, U.S. Pat. Nos. 3,933,840 
and 4,051,250 and the Preparation Examples). 
Formulae (Va) and (Vb) provide general definitions of the formamides and 
their derivatives which are also required as starting substances for 
carrying out process (b) according to the invention. In these formulae 
(Va) and (Vb), R.sup.4-1 preferably stands for dialkylamino which has in 
each case 1 to 6, in particular 1 to 4, carbon atoms in the individual 
straight-chain or branched alkyl moieties. R.sup.4-1 very particulary 
preferably stands for dimethylamino or diethylamino. 
R.sup.7 and R.sup.8 preferably independently of one another in each case 
stand for straight-chain or branched alkoxy which has 1 to 4 carbon atoms, 
in particular for methoxy or ethoxy, or for a dialkylamino radical which 
has in each case 1 to 6, in particular 1 to 4, carbon atoms in the 
individual straight-chain or branched alkyl moieties. 
The formamides of the formula (V) and their derivatives of the formula (Vb) 
are generally known compounds of organic chemistry. 
Formula (VI) provides a general definition of the oxalic acid derivatives 
required as starting substances for carrying out process (c) according to 
the invention. In this formula (VI), R.sup.1, R.sup.2, R.sup.3 and X 
preferably stand for 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. 
Y.sup.1 preferably stands for sulphur or for a radical 
##STR123## 
wherein R.sup.6 preferably stands for 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. 
Most of the oxalic acid derivatives of the formula (VI) are known (cf., for 
example, Arzneimittel-Forsch. 36, 1391-1393 [1986]; J. med. chem. 26, 
1158-1163 [1983]; DE-OS (German Published Specification) No. 2,828,091; EP 
No. 6,368; U.S. Pat. Nos. 4,238,496; 4,246,271), or they can be obtained 
in analogy to known processes (cf., for example, Synthetic Communications 
11, 943 [1981] or Organic Reactions 26, 1 [1979]), for example when oxalic 
esters of the formula (IX) 
##STR124## 
in which E.sup.3 stands for alkoxy or halogen, in particular for methoxy, 
ethoxy or chlorine and 
R.sup.3 has the abovementioned meaning, 
are reacted with heterocyclic compounds of the formula (XII) 
##STR125## 
in which R.sup.1, R.sup.2, X and Y.sup.1 have the abovementioned meaning, 
if appropriate in the presence of a diluent, such as, for example, 
dichloromethane or tetrahydrofuran, and if appropriate in the presence of 
a base, such as, for example, n-butyllithium, sodium hydride, potassium 
t-butoxide, triethylamine or pyridine, at temperatures between -80.degree. 
C. and +80.degree. C. 
Oxalic esters of the formula (XI) are generally known compounds of organic 
chemistry. 
Heterocyclic compounds of the formula (XII) are also generally known or can 
be obtained in analogy to generally known processes (cf., for example, 
Organic Reactions 6, 367 et seq., and their Preparation Examples). 
Formula (VII) provides a general definition of the organometal compounds 
also required as starting substances for carrying out process (c) 
according to the invention. In this formula (VII), R.sup.5 preferably 
stands for 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 organometal compounds of the formula (VII) are known (cf., for example, 
J. org. Chem. 33, 780 [1968]; J. org. Chem. 37, 939 [1972]). 
Formula (VIII) provides a general definition of the substituted acrylic 
acid esters required as starting substances for carrying out process (d) 
according to the invention. In this formula (VIII), R.sup.1, R.sup.2, 
R.sup.3 and X preferably stand for 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.sup.2 preferably stands for a suitable acyloxy or sulphonyloxy radical, 
in particular for an acetoxy, a methanesulphonyloxy or a 
p-toluenesulphonyloxy radical. 
The substituted acrylic acid esters of the formula (VIII) were hitherto 
unknown. 
They are obtained when hydroxyacrylic acid esters of the formula (IIb) 
##STR126## 
in which R.sup.1, R.sup.2, R.sup.3 and X have the abovementioned meaning, 
are reacted with acid chlorides of the formula (XIII) 
EQU R.sup.10 --Cl (XIII) 
in which 
R.sup.10 stands for an acyl or sulphonyl radical, in particular for an 
acetyl, a methanesulphonyl or a p-toluenesulphonyl radical, 
if appropriate in the presence of a diluent, such as, for example, 
dichloromethane, and if appropriate in the presence of an acid-binding 
agent, such as, for example, triethylamine or pyridine, at temperatures 
between -20.degree. C. and +120.degree. C. 
Acid chlorides of the formula (XIII) are generally known compounds of 
organic chemistry. 
Formula (IX) provides a general definition of the thiols also required as 
starting substances for carrying out process (d) according to the 
invention. In this formula (IX), R.sup.5 preferably stands for 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 the formula (IX) are generally 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, benzine, benzene, toluene, xylene, chlorobenzene, petroleum 
ether, hexane, cyclohexane, dichloromethane, chloroform or carbon 
tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran, 
ethylene glycol dimethyl ether or ethylene glycol diethyl ether, nitriles, 
such as acetonitrile or propionitrile, amides, such as dimethylformamide, 
dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or 
hexamethylphosphoric triamide, or sulphoxides, such as dimethyl 
sulphoxide. 
If appropriate, process (a) according to the invention can also be carried 
out in a two-phase system, such as, for example, water/toluene or 
water/dichloromethane, if necessary in the presence of a phase transfer 
catalyst. Examples of such catalysts which may be mentioned are: 
tetrabutylammonium iodide, tetrabutylammonium bromide, 
tributyl-methylphosphonium bromide, trimethyl-C.sub.13 /C.sub.15 
-alkylammonium chloride, dibenzyldimethyl-ammoniummethyl sulphate, 
dimethyl-C.sub.12 /C.sub.14 -alkylbenzylammonium chloride, 
tetrabutylammonium hydroxide, 15-crown-5, 18-crown-6, 
triethylbenzylammonium chloride, trimethylbenzylammonium chloride or 
tris-[2-(2-methoxyethoxy)-ethyl]-amine. 
Process (a) according to the invention is preferably carried out in the 
presence of a suitable basic reaction auxiliary. Suitable basic reaction 
auxiliaries are all inorganic and organic bases which can customarily be 
used. The hydrides, hydroxides, amides, alkoxides, carbonates or hydrogen 
carbonates of alkali metals, such as, for example, sodium hydride, sodium 
amide, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium 
t-butoxide, sodium carbonate or sodium hydrogen carbonate, and also 
tertiary amines, such as, for example, triethylamine, N,N-dimethylaniline, 
pyridine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), 
diazabicyclononene (DBN) or diazabicycloundecene (DBU). 
When carrying out process (a) according to the invention, the reaction 
temperatures can be varied within a relatively wide range. In general, the 
process is carried out at temperatures between -30.degree. C. and 
+120.degree. C., preferably at temperatures between -20.degree. C. and 
+60.degree. C. 
For carrying out process (a) according to the invention, 1.0 to 10.0 moles, 
preferably 1.0 to 5.0 moles, of alkylating agent of the formula (III) and 
if appropriate 1.0 to 5.0 moles, preferably 1.0 to 2.0 moles, of reaction 
auxiliary are generally employed per mole of 3-hydroxyacrylic acid ester 
or of a corresponding alkali metal salt of the formula (II). The reaction 
is carried out, and the reaction products are worked up and isolated by 
generally customary methods (cf. also the Preparation Examples). 
Suitable diluents for carrying out process (b) according to the invention 
are inert organic solvents. These include in particular aliphatic, 
alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for 
example, benzine, benzene, toluene, xylene, chlorobenzene, petroleum 
ether, hexane, cyclohexane, dichloromethane, chloroform, carbon 
tetrachloride, or ethers, such as diethyl ether, dioxane, tetrahydrofuran, 
ethylene glycol dimethyl ether or ethylene glycol diethyl ether. 
However, it is also possible to carry out process (b) according to the 
invention without the addition of a diluent. 
When carrying out process (b) according to the invention, the reaction 
temperatures can be varied within a relatively wide range. In general, the 
process is carried out at temperatures between -20.degree. C. and 
+200.degree. C., preferably at temperatures between 0.degree. C. and 
150.degree. C. 
For carrying out process (b) according to the invention, 1.0 to 30.0 moles, 
preferably 1.0 to 15.0 moles, of formamide of the formula (Va) or of a 
corresponding derivative of the formula (Vb) are employed per mole of 
substituted acetic acid ester of the formula (IV). The reaction is carried 
out, and the reaction products are worked up and isolated by generally 
customary methods (cf. in this context also G. Mathieu; J. Weill-Raynal 
"Formation of C-C-Bonds", Vol. 1; 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, such, as, for example, benzine, 
benzene, toluene, xylene, petroleum ether, hexane or cyclohexane, or 
ethers, such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol 
dimethyl ether or ethylene glycol diethyl ether. 
When carrying out process (c) according to the invention, the reaction 
temperatures can be varied within a relatively wide range. In general, the 
process is carried out at temperatures between -100.degree. C. and 
+100.degree. C., preferably at temperatures between -80.degree. C. and 
+50.degree. C. 
For carrying out process (c) according to the invention, 1.0 to 1.5 moles, 
preferably 1.0 to 1.2 moles, of organometal compound of the formula (VII) 
are generally employed per mole of oxalic acid derivative of the formula 
(VI). The reaction is carried out, and the reaction products are worked up 
and isolated by generally customary 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, benzine, benzene, toluene, xylene, chlorobenzene, petroleum 
ether, hexane, cyclohexane, dichloromethane, chloroform or carbon 
tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran, 
ethylene glycol dimethyl ether or ethylene glycol 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 sulphoxides, such as dimethyl 
sulphoxide. 
Process (d) according to the invention is preferably carried out in the 
presence of a suitable reaction auxiliary. Suitable reaction auxiliaries 
are all customary inorganic or organic bases. 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 hydrogen carbonate, or tertiary amines, such as triethylamine, 
N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, 
diazabicyclooctane (DABCO), diazabicyclononene (DBN) or 
diazabicycloundecene (DBU). 
When carrying out process (d) according to the invention, the reaction 
temperatures can be varied within a relatively wide range. In general, the 
process is carried out at temperatures between -20.degree. C. and 
180.degree. C., preferably at temperatures between 0.degree. C. and 
150.degree. C. 
If appropriate, the process according to the invention can also be carried 
out under pressure, depending on the boiling point of the reactants used, 
for example when low-boiling thiols of the formula (IX) are employed. In 
this case, the reaction is preferably carried out under the pressure which 
arises under the reaction conditions during heating to the reaction 
temperature required. 
For carrying out process (d) according to the invention, 1.0 to 20.0 moles, 
preferably 1.0 to 5.0 moles, of thiol of the formula (IX) and if 
appropriate 1.0 to 5.0 moles, preferably 1.0 to 1.5 moles, of reaction 
auxiliary are generally employed per mole of substituted acrylic acid 
ester of the formula (VIII). The reaction is carried out, and the reaction 
products are worked up and isolated by generally customary methods. 
The active compounds according to the invention exhibit a powerful action 
against pests and can be employed in practice for combating undesired 
harmful organisms. The active compounds are suitable for the use as plant 
protection agents, in particular as fungicides. 
Fungicidal agents in plant protection are employed for combating 
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, 
Ascomycetes, Basidiomycetes and Deuteromycetes. 
Some causative organisms of fungal diseases which come under the generic 
names listed above may be mentioned as examples, but not by way of 
limitation: Pythium species, such as, for example, Pythium ultimum; 
Phytophthora species, such as, for example, Phytophthora infestans; 
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli 
or Pseudoperonospora cubensis; Plasmopara species, such as, for example, 
Plasmopara viticola; 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 (conidia form: Drechslera, syn: Helminthosporium); 
Cochliobolus species, such as, for example, Cochliobolus sativus (conidia 
form: Drechslera, syn: Helminthosporium); Uromyces species, such as, for 
example, Uromyces appendiculatus; Puccinia species, such as, for example, 
Puccinia recondita; 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 and Pseudocercosporella species, such as, for example, 
Pseudocercosporella herpotrichoides. 
The good toleration, by plants, of the active compounds, at the 
concentrations required for combating plant diseases, permits treatment of 
above-ground parts of plants, of vegetative propagation stock and seeds, 
and of the soil. 
Here, the active compounds according to the invention can be employed with 
particularly good success for combating cereal diseases, such as, for 
example, against the causative organism of powdery mildew of cereals 
(Erysiphe graminis) or for combating rice diseases, such as, for example, 
against the causative organism of rice blast disease (Pyricularia oryzae), 
or for combating diseases in fruit growing and vegetable growing, such as, 
for example, against the causative organism of apple scab (Venturia 
inaequalis) or against the causative organism of tomato blight 
(Phytophthora infestans), and also against Cercospora species in beans. 
Furthermore, the active compounds according to the invention show a good in 
vitro activity. 
Depending on their particular physical and/or chemical properties, the 
active compounds can be converted to the customary formulations, such as 
solutions, emulsions, suspensions, powders, foams, pastes, granules, 
aerosols, very fine capsules in polymeric substances as well as ULV cold 
mist and warm mist formulations. 
These formulations are produced 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 
surface-active agents, that is, emulsifying agents and/or dispersing 
agents, and/or foam-forming agents. In the case of the use of water as an 
extender, organic solvents can, for example, also be used as auxiliary 
solvents. As liquid solvents, there are suitable in the main: aromatics, 
such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or 
chlorinated aliphatic hydrocarbons, such as chlorobenzenes, 
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as 
cyclohexane or paraffins, for example mineral oil fractions, alcohols, 
such as butanol or glycol as well as their ethers and esters, ketones, 
such as acetone, methyl ethyl ketone, methyl isobutyl ketone or 
cyclohexanone, strongly polar solvents, such as dimethylformamide and 
dimethylsulphoxide, as well as water; by liquefied gaseous extenders or 
carriers are meant liquids which are gaseous at normal temperature and 
under normal pressure, for example aerosol propellants, such as 
halogenated hydrocarbons as well as butane, propane, nitrogen and carbon 
dioxide; as solid carriers there are suitable: for example ground natural 
minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, 
montmorillonite or diatomaceous earth, and ground synthetic minerals, such 
as highly-disperse silicic acid, alumina and silicates; as solid carriers 
for granules there are suitable: for example crushed and fractionated 
natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as 
well as synthetic granules of inorganic and organic meals, and granules of 
organic material such as sawdust, coconut shells, corn cobs and tobacco 
stalks; as emulsifying and/or foam-forming agents there are suitable: for 
example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty 
acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl 
polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as 
well as albumin hydrolysis products; as dispersing agents there are 
suitable, for example, ligninsulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, as well as natural phospholipids, such as 
cephalins and lecithins, and synthetic phospholipids, can be used in the 
formulations. Other additives can be mineral and vegetable oils. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain between 0.1 and 95 per cent by weight 
of active compound, preferably between 0.5 and 90%. 
The active compounds according to the invention can be present in the 
formulations as a mixture with other known active compounds, such as 
fungicides, insecticides, acaricides and herbicides, as well as in 
mixtures with fertilizers and growth regulators. 
The active compounds can be used as such or 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. They are used in the customary manner, for example by 
watering, spraying, atomizing, scattering, dusting, foaming, brushing on 
and the like. It is furthermore possible to apply the active compounds by 
the ultra-low volume method or to inject the active compound formulation 
or the active compound itself into the soil. The seeds of the plants can 
also be treated. 
In the treatment of parts of plants, the active compound concentrations in 
the use forms can be varied within a substantial range. They are, in 
general, between 1 and 0.0001% by weight, preferably between 0.5 and 
0.001%. 
In the treatment of seeds, amounts of active compound of 0.001 to 50 g per 
kilogram of seed, preferably 0.01 to 10 g, are generally required. 
For the treatment of soil, active compound concentrations of 0.00001 to 
0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the 
place of action. 
PREATION EXAMPLES 
EXAMPLE 1 
##STR127## 
(process a) 
In a first step, 19.3 g (0.14 mol) of ground potassium carbonate are added 
to 13 g (0.035 mol) of methyl 
2-{N-[4-(3,4-dichlorophenyl)-thiazol-2-yl]-N-methylamino}-3-hydroxy-acryla 
te in 60 ml of dry dimethylformamide, 4.63 g (0.037 mol) of dimethyl 
sulphate in 10 ml of dry dimethylformamide are then added dropwise, with 
stirring and in the course of 10 minutes, and the mixture is then stirred 
for 16 hours at room temperature. For working up, the reaction mixture is 
poured into 70 ml of saturated aqueous sodium hydrogen carbonate solution, 
the mixture is extracted three times with 100 ml portions of diethyl 
ether, the combined ether phases are washed with 80 ml of saturated 
aqueous sodium chloride solution, dried over sodium sulphate and 
evaporated in vacuo, and the residue is purified by chromatography on 
silica gel (eluant: toluene/n-propanol 10:1). 
9.6 g (74% of theory) of methyl 
2-{N-[4-(3,4-dichlorophenyl)-thiazol-2-yl]-N-methylamino}-3-methoxyacrylat 
e of melting point 96.degree. C.-98.degree. C. are obtained. 
PREATION OF THE STARTING COMPOUND 
EXAMPLE II-1 
##STR128## 
11.6 g (0.035 mol) of methyl 
2-{N-[4-(3,4-dichlorophenyl)-thiazol-2-yl]-N-methylamino}-acetate in 69.7 
g (1.16 mol) of dry methyl formate are added dropwise at 5.degree. C. to 
10.degree. C. and with stirring and ice-cooling to a suspension of 2.1 g 
(0.07 mol) of sodium hydride (80 percent strength in paraffin) in 40 ml of 
dry dimethylformamide, and, when the addition is complete, the mixture is 
stirred for 4 hours at room temperature. For working up, the reaction 
mixture is poured with stirring and ice-cooling into 50 ml of saturated 
aqueous sodium carbonate solution, the mixture is diluted with 50 ml of 
water and washed three times with 75 ml portions of diethyl ether, and the 
aqueous phase is acidified with 5N hydrochloric acid to a pH of 5 and 
extracted three times with 100 ml portions of diethyl ether. The combined 
ether phases are dried over sodium sulphate and concentrated in vacuo. 
13 g (100% of theory) of methyl 
2-{N-[4-(3,4-dichlorophenyl)-thiazol-2-yl]-N-methylamino}-3-hydroxyacrylat 
e are obtained as an oil. .sup.1 H-NMR (DMSO tetramethylsilane): 
.differential.=12 ppm (OH). 
EXAMPLE IV-1 
##STR129## 
33.7 g (0.22 mol) of methyl bromoacetate are added dropwise with stirring 
at 80.degree. C. and in the course of 20 minutes to a suspension of 27.6 g 
(0.195 mol) of ground potassium carbonate and 50.5 g (0.195 mol) of 
4-(3,4-dichlorophenyl)-2-methylaminothiazole in 350 ml of dry 
acetonitrile, and the mixture is then heated to reflux temperature for 26 
hours. For working up, the cooled reaction mixture is filtered, the 
filtrate is evaporated in vacuo, the residue is taken up in 
dichloromethane, washed several times with water, dried over sodium 
sulphate and evaporated in vacuo, and the residue is chromatographed on 
silica gel (eluant: toluene/propanol 10:1). 
14.6 g (22% of theory) of methyl 
2-{N-[4-(3,4-dichlorophenyl)-thiazol-2-yl]-N-methyl-amino}-acetate of 
melting point 88.degree. C.-89.degree. C. are obtained. 
EXAMPLE XII-1 
##STR130## 
67.05 g (0.3 mol) of 3,4-dichlorophenacyl chloride in 300 ml of ethanol are 
added dropwise with stirring at room temperature and in the course of 25 
minutes to a solution of 27.1 g (0.3 mol) of N-methylthiourea in 300 ml of 
ethanol, which solution had been heated to 60.degree. C.-80.degree. C., 
the mixture is then heated to reflux temperature for 1 hour and then 
allowed to cool slowly to room temperature, and the crystalline 
precipitate is filtered off and recrystallized from ethanol. 
70.9 g (91% of theory) of 4-(3,4-dichlorophenyl)-2-methylaminothiazole of 
melting point 220.degree. C.-221.degree. C. are obtained. 
The substituted acrylic acid esters below, of the general formula (I), are 
obtained in a corresponding manner and following the general instructions 
for the preparation: 
##STR131## 
__________________________________________________________________________ 
Physical 
Ex. No. 
R.sup.1 R.sup.2 R.sup.3 
R.sup.4 
X Y properties 
__________________________________________________________________________ 
H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 104-105.degree. 
C. 
3 
##STR132## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 108-109.degree. 
C. 
4 
##STR133## H CH.sub.3 
OCH.sub.3 
S 
##STR134## 
m.p. 154.degree. C. 
5 
##STR135## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 m.p. 87-88.degree. 
C. 
6 
##STR136## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 .sup.1 H-NMR*: 3.28; 
3.73; 3.92; 7.3-7.8 
7 
##STR137## H CH.sub.3 
OCH.sub. 3 
S NCH.sub.3 n.sub.D.sup.22.5 
1.5941 
8 
##STR138## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 66-67.degree. 
C. 
9 
##STR139## H CH.sub.3 
OCH.sub.3 
S 
##STR140## 
m.p. 68.degree. C. 
10 
##STR141## CH.sub.3 CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.5915 
11 
##STR142## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 81-82.degree. 
C. 
12 
##STR143## H CH.sub.3 
OCH.sub.3 
S S m.p. 89-90.degree. 
C. 
13 
##STR144## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6065 
14 
##STR145## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 m.p. 102.degree. C. 
15 
##STR146## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6111 
16 
##STR147## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6258 
17 
##STR148## H CH.sub.3 
OCH.sub.3 
S 
##STR149## 
m.p. 60-61.degree. 
C. 
18 
##STR150## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 123-124.degree. 
C. 
19 
##STR151## H CH.sub.3 
OCH.sub.3 
S NC.sub.2 H.sub.5 
n.sub.D.sup.20 
1.6043 
20 
##STR152## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 138-139.degree. 
C. 
21 
##STR153## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6178 
22 
##STR154## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 100-101.degree. 
C. 
23 
##STR155## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 118-119.degree. 
C. 
24 
##STR156## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 128-129.degree. 
C. 
25 
##STR157## H CH.sub.3 
OCH.sub.3 
S O m.p. 114-115.degree. 
C. 
26 
##STR158## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.5943 
27 
##STR159## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6073 
28 
##STR160## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 126-127.degree. 
C. 
29 
##STR161## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 95-96.degree. 
C. 
30 
##STR162## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 115-116.degree. 
C. 
31 
##STR163## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 182-183.degree. 
C. 
32 
##STR164## 
##STR165## 
CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6059 
33 
##STR166## CH.sub.3 CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 67-69.degree. 
C. 
34 
##STR167## H CH.sub.3 
OCH.sub.3 
S S m.p. 89-90.degree. 
C. 
35 
##STR168## C.sub.2 H.sub.5 
CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6109 
36 
##STR169## CH.sub.3(CH.sub.2).sub.2 
CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.5755 
37 
##STR170## H CH.sub.3 
OCH.sub. 3 
S S n.sub.D.sup.20 
1.6171 
38 
##STR171## H CH.sub.3 
OCH.sub.3 
S S m.p. 110-111.degree. 
C. 
39 
##STR172## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 104-105.degree. 
C. 
40 
##STR173## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.6073 
41 
##STR174## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 n.sub.D.sup.20 
1.5982 
42 
##STR175## H CH.sub.3 
OCH.sub.3 
S NCH.sub.3 m.p. 154-155.degree. 
C. 
43 
##STR176## H CH.sub.3 
OCH.sub.3 
O NCH.sub.3 .sup.1 H-NMR*: 
3.3(s); 3.73(s); 
3.9(s); 
44 
##STR177## C.sub.2 H.sub.5 
CH.sub.3 
OCH.sub.3 
O NCH.sub.3 .sup.1 H-NMR*: 
1.2(t); 2.71(t); 
2.20(c); 
__________________________________________________________________________ 
3.71(c); 
*The .sup.1 HNMR spectra were recorded in deuterochloroform (CDCl.sub.3) 
or hexadeuterodimethyl sulphoxide (DMSOd.sub.6) with tetramethylsilane 
(TMS) as the internal standard. The chemical shift is indicated as a valu 
in ppm. 
USE EXAMPLES 
In the following Use Examples, the compounds listed below were employed as 
comparison substances: 
##STR178## 
EXAMPLE A 
Venturia test (apple)/protective 
Solvent: 4.7 parts by weight of acetone 
Emulsifier: 0.3 parts 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 
preparation of active compound until dripping wet. After the spray coating 
has dried on, the plants are inoculated with an aqueous conidia suspension 
of the apple scab causative organism (Venturia inaequalis) and then remain 
in an incubation cabin at 20.degree. C. and 100% relative atmospheric 
humidity for 1 day. 
The plants are then placed in a greenhouse at 20.degree. C. and a relative 
atmospheric humidity of about 70%. 
Evaluation is carried out 12 days after the inoculation. 
In this test, a clearly superior activity compared with the prior art is 
shown, for example, by the compound according to Preparation Example 1. 
EXAMPLE B 
Phytophthora Test (tomato)/protective 
Solvent: 4.7 parts by weight of acetone 
Emulsifier: 0.3 parts 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 
preparation of active compound until dripping wet. After the spray coating 
has dried on, the plants are inoculated with an aqueous spore suspension 
of Phytophthora infestans. 
The plants are placed in an incubation cabin at 100% relative atmospheric 
humidity and at about 20.degree. C. 
Evaluation is carried out 3 days after the inoculation. 
In this test, a clearly superior activity compared with the prior art is 
shown, for example, by the compound according to Preparation Example 1. 
EXAMPLE C 
Pyricularia test (rice)/protective 
Solvent: 12.5 parts by weight of acetone 
Emulsifier: 0.3 parts 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 with water and the stated 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. After the spray coating 
has dried on, 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 25.degree. C. 
Evaluation of the disease infestation is carried out 4 days after the 
inoculation. 
In this test, a clearly superior activity compared with the prior art is 
shown, for example, by the compound according to Preparation Example 1. 
EXAMPLE D 
Erysiphe test (wheat)/protective 
Solvent: 100 parts by weight of dimethylformamide 
Emulsifier: 0.25 parts 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 
preparation of active compound until dew-moist. After the spray coating 
has dried on, the plants are dusted with spores of Erysiphe graminis f. 
sp. tritici. 
The plants are placed in a greenhouse at a temperature of about 20.degree. 
C. and a relative atmospheric humidity of about 80%, in order to promote 
the development of powdery mildew pustules. 
Evaluation is carried out 7 days after the inoculation. 
In this test, a clearly superior activity compared with the prior art is 
shown, for example, by the compound according to Preparation Example 1. 
It will be understood that the specification and examples are illustrative 
but not limitative of the present invention and that other embodiments 
within the spirit and scope of the invention will suggest themselves to 
those skilled in the art.