WO2004067527A1

WO2004067527A1 - Thiophene derivatives as microbicides and herbicides

Info

Publication number: WO2004067527A1
Application number: PCT/EP2004/000388
Authority: WO
Inventors: Dorothee Hoischen; Otto Schallner; Hans-Ludwig Elbe; Herbert Gayer; Franz Kunisch; Ulrike Wachendorff-Neumann; Karl-Heinz Kuck; Mark Wilhelm Drewes; Yuan Liping; Wang Min; Zhao Qing
Original assignee: Bayer Cropscience Ag
Priority date: 2003-01-30
Filing date: 2004-01-20
Publication date: 2004-08-12
Also published as: CN1521165A

Abstract

Novel thiophene derivatives of the formula (I) wherein R1, R2, R3 and n have the meanings given in the specification, several processes for the preparation of the new compounds and their use as microbicides and herbicides.

Description

THIOPHENE DERIVATIVES AS MICROBICIDES ND HERBICIDES

The present invention relates to novel thiophene derivatives, to several processes for their preparation and to their use as microbicides and herbicides.

It has aheady been known that various thiophene derivatives show fungicidal properties (cf. EP-A 0 234 622; J. Med. Chem. 42 (10), 1849-1854 (1999); Pharmazie 50 (10), 675-678 (1995) and DD-A 294485). The fungicidal activity of such known compounds is good. However, it is not always satisfactory, if the compounds are applied at low dosages.

There have now been found novel thiophene derivatives of the formula

in which

R¹ represents a hydrogen atom or alkyl,

R² represents a hydrogen atom or alkyl,

R³ represents optionally substituted aryl, optionally substituted heteroaryl, optionally substituted benzoheteroaryl, optionally substituted alkoxy having 3 to 10 carbon atoms, optionally substituted cycloalkoxy or optionally substituted aryloxy, and

n represents 0, 1 or 2, with the proviso that

4-amino-5-(4-chlorobenzoyl)-2-methylthio-3-thiophene-carbonitril of the formula

4-amino-5-benzoyl-2-methylsulfonyl-3-thiophene-carbonitril of the formula

4-amino-5-(4-nitrobenzoyl)-2-memylsulfonyl-3-thiophene-carbonitril of the formula

are excluded.

Further, it has been found that thiophene derivatives of the formula (I) can be prepared by

a) reacting dicyano-methylthio-ethenthiolates of the formula

in which

M represents an alkalimetal atom,

with halogenoacetyl compounds of the formula

in which

R³ has the above-mentioned meanings and

X represents a halogen atom,

if appropriate, in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent,

or

b) reacting thiophene derivatives of the formula

in which R³ has the above-mentioned meanings,

with alkylating agents of the formula

Y -R⁴ (IN)

in wliich

R⁴ represents alkyl and

Y represents chloro, bromo, iodo, methylsulfonyloxy, methoxysulfonyl- oxy or tolylsulfonyloxy,

or

c) reacting thiophene derivatives of the formula

in which

R³ and R⁴ have the above-mentioned meanings,

with alkylating agents of the formula Y - R⁴ (IN)

in which

R⁴ and Y have the above-mentioned meanings,

or

d) reacting thiophene derivatives of the formula

in which

R¹, R² and R³ have the above-mentioned meanings,

with oxidizing agents, if appropriate, in the presence of a diluent.

Finally, it has been found that the thiophene derivatives of the formula (I) are outstandingly active as microbicides and herbicides. The compounds are particularly suitable for the direct control of plant disease or for causing resistance in plants against plant pathogens. Surprisingly, the thiophene derivatives according to the invention have a much better microbicidal activity than the already known compounds, which are structurally most similar and have the same type of action.

Formula (I) provides a general definition of the thiophene derivatives according to the invention. Preferred compounds of the formula (I) are those, in which

R¹ represents a hydrogen atom or alkyl having 1 to 4 carbon atoms,

R² represents a hydrogen atom or alkyl having 1 to 4 carbon atoms,

n represents 0 and

R³ represents unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of fluoro, bromo, iodo, cyano, nitro, amino hydroxy, formyl, carboxy, carbamoyl, tbio- carbamoyl,

in each case straight-chained or branched alkyl, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsufinyl or alkylsufonyl having in each case 1 to 8 carbon atoms,

in each case straight-chained or branched alkenyl or alkenyloxy having in each case 2 to 6 carbon atoms,

in each case straight-chained or branched halogenoalkyl, halogeno- alkoxy, halogenoalkylthio, halogenoalkylsulfϊnyl or halogenoalkyl- sulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chained or branched halogenoalkenyl or halo- genoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms,

in each case straight-chained or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, phenylalkylaminocarbonyl dialkylamino- carbonyloxy, hydroxyiminoalkyl or alkoximinoalkyl having in each case 1 to 6 carbon atoms in each of the carbon atoms chains,

in each case straight-chained or branched alkenylcarbonyl or alkinyl- carbonyl having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl chain,

cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms,

phenyl, phenoxy, phenylthio, heterocyclyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, phenylalkyl having 1 to 3 carbon atoms in the alkyl group, phenylalkoxy having 1 to 3 carbon atoms in the alkoxy group, phenylalkylthio having 1 to 3 carbon atoms in the alkylthio group, and heterocyclylalkyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, in the heterocyclyl group, and having 1 to 3 carbon atoms in the alkyl group, wherein each of the aforementioned radicals may be substituted in the phenyl group by or in the heterocyclyl group by 1 to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and/or alkoxy having 1 to 4 carbon atoms, represents di- to penta-substituted phenyl, the substitutents being selected from the group consisting of

halogeno, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

in each case straight-chained or branched alkyl, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl having in each case 1 to 8 carbon atoms,

in each case straight-chained or branched halogenoalkyl, halogeno- alkoxy, halogenoalkylthio, halogenoalkylsufinyl or halogenoalkyl- sulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

in each case straight-chained or branched halogenoalkenyl or halo- genoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms,

in each case straight-chained or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, ^alkylaminocarbonyl, phenylalkylaminocarbonyl, dialkylamino- carbonyloxy, hydroxyiminoalkyl or alkoximinoalkyl having in each case 1 to 6 carbon atoms in each of the carbon atom chains,

in each case straight-chained or branched alkenylcarbonyl or alkinylcarbonyl having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl chain, cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms,

phenyl, phenoxy, phenylthio, heterocyclyl having 5 to 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, phenylalkyl having 1 to 3 carbon atoms in the alkyl group, phenyl- alkoxy having 1 to 3 carbon atoms in the alkoxy group, phenylalkylthio having 1 to 3 carbon atoms in the alkylthio group, and heterocyclylalkyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, in the heterocyclyl group and having 1 to 3 carbon atoms in the alkyl group, wherein each of the aforementioned radicals may be substituted in the phenyl group or in the heterocyclyl group by 1 to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and/or alkoxy having 1 to 4 carbon atoms,

or

R³ represents phenoxy, which is unsubstituted or substituted by 1 to 5 identical or different substituents selected from the group consisting of

in each case straight-chained or branched alkenyl or alkenyloxy having in each case 2 to 6 carbon atoms, in each case straight-chained or branched halogenoalkyl, halogeno- alkoxy, halogenoalkylthio, halogenoalkylsulfinyl or halogenoalkyl- sulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

in each case straight-chained or branched alkylamino, dialtylanriino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, diall-ylaminocarbonyl, phenylalkylaminocarbonyl, dialkylamino- carbonyloxy, hydroxyiminoalkyl in each case 1 to 6 carbon atoms in each of the carbon atom chains,

cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms,

phenyl, phenoxy, phenylthio, heterocyclyl having 5 to 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, phenylalkyl having 1 to 3 carbon atoms in the alkyl group, phenyl- alkoxy having 1 to 3 carbon atoms in the alkoxy group, phenylalkylthio having 1 to 3 carbon atoms in the alkylthio group, and heterocyclylalkyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen oxygen and/or sulfur, in the heterocyclyl group and having 1 to 3 carbon atoms in the alkyl group, wherein each of the aforementioned radicals may be substituted in the phenyl group or in the heterocyclyl group by 1 to 3 identicals or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and or alkoxy having 1 to 4 carbon atoms,

or

R³ represent heteroaryl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, or represents benzoheteroaryl having 5 or 6 ring members in the heteroaryl group and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, wherein the aforementioned radicals may be substituted by up to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms,

or

R³ represents alkoxy having 3 to 8 carbon atoms, or represents cycloalkoxy having 3 to 8 carbon atoms.

Another group of preferred compounds are those thiophene derivatives of the formula (I), in which

R¹ represents a hydrogen atom or alkyl having 1 to 4 carbon atoms,

R² represents a hydrogen atom or alkyl having 1 to 4 carbon atoms,

n represents 1 and

R³ represents phenyl or phenoxy, wherein each of these radicals may be unsubstituted or may be substituted by 1 to 5 identical or different radicals selected from the group consisting of halogeno, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, in each case straight-chained or branched alkyl, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfinyl or alkyl- sulfonyl having in each case 1 to 8 carbon atoms,

in each case straight-chained or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulfinyl or halogenoaUcylsulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

in each case straight-chained or branched halogenoalkenyl or halogeno- alkenyloxy having each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms,

in each case straight-chained or branched alkylamino, dialkylamino, alkyl- carbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkyl- amino-carbonyl, phenylalkylaminocarbonyl, dialkylamino-carbonyloxy, hydroxyimmoalkyl or alkoxyiminoalkyl having in each case 1 to 6 carbon atoms in each of the carbonatom chains,

in each case straight-chained or branched alkenylcarbonyl or alkinylcarbonyl having in each case 2 to 6 carbon atoms in the alkenyl or alkinyl chain,

cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms,

phenyl, phenoxy, phenylthio, heterocyclyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen oxygen and/or sulfur, phenylalkyl having 1 to 3 carbon atoms in the alkyl group, phenylalkoxy having 1 to 3 carbon atoms in the alkoxy group, phenylalkylthio having 1 to 3 carbon atoms in the alkylthio group, and heterocyclylalkyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, in the heterocyclyl group and having 1 to 3 carbon atoms in the alkyl group, wherein each of the aforementioned radicals may be substituted in the phenyl group or in the heterocyclyl group by 1 to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and/or alkoxy having 1 to 4 carbon atoms,

or

R³ represents heteroaryl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, or represents benzoheteroaryl having 5 or 6 ring members in the heteroaryl group and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, wherein the aforementioned radicals may be substituted by up to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and halogenalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms,

or

R¹ represents a hydrogen atom or alkyl having 1 to 4 carbon atoms,

R² represents a hydrogen atom or alkyl having 1 to 4 carbon atoms,

n represents 2 and represents mono-substituted phenyl, the substituents being selected from the group consisting of

halogen, cyano, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

in each case straight-chained or branched alkyl, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfinyl or alkyl- sulfonyl having in each case 1 to 8 carbon atoms,

in each case straight-chained or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoa cylsulfinyl or halogenoaUcylsulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

in each case straight-chained or branched alkylamino, dialkylamino, alkyl- carbonyl, aUcylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, diaUcyl- aminocarbonyl, phenylalkylaminocarbonyl, diaUcylamino-carbonyloxy, hydroxyiminoalkyl or alkoximinoalkyl having in each case 1 to 6 carbon atoms in each of the carbon atom chains,

in each case straight-chained or branched alkenylcarbonyl or alkinylcarbonyl having in each case 2 to 6 carbon atoms in the alkenyl or aUcinyl chain, cycloalkyl or cycloal yloxy having in each case 3 to 6 carbon atoms,

phenyl, phenoxy, phenylthio, heterocyclyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, phenylalkyl having 1 to 3 carbon atoms in the alkyl group, phenylalkoxy having 1 to 3 carbon atoms in the alkoxy group, phenylalkylthio having 1 to 3 carbon atoms in the alkylthio group, and heterocyclylakyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, in the heterocyclyl group and having 1 to 3 carbon atoms in the alkyl group, wherein each of the aforementioned radicals may be substituted in the phenyl group or in the heterocyclyl group by 1 to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and/or alkoxy having 1 to 4 carbon atoms,

or

R³ represents di- to penta-substituted phenyl, the substituents being identical or different and being selected from the group consisting of

halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, tbio- carbamoyl,

in each case straight-chained or branched alkyl, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylthioaUcyl, dialkoxyaUcyl, alkylthio, alkylsulfinyl or alkyl- sulfonyl having in each case 1 to 8 carbon atoms,

in each case straight-chained or branched halogenoaUcyl, halogenoalkoxy, halogenoalkylthio, halogenoaUcylsulfinyl or halogenoaUcylsulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

in each case straight-chained or branched halogenoalkenyl or halogeno- aUcenyloxy, having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms,

in each case straight-chained or branched alkylamino, dialkylamino, alkyl- carbonyl, aUcylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkyl- aminocarbonyl, phenylalkylaminocarbonyl, diaUcylamino-carbonyloxy, hydroximinoalkyl or alkoximinoaUcyl having in each case 1 to 6 carbon atoms in each of the carbon atoms chains,

cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms,

phenyl, phenoxy, phenylthio, heterocyclyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, phenylalkyl having 1 to 3 carbon atoms in the alkyl group, phenylaUcoxy having 1 to 3 carbon atoms in the alkoxy group, phenylalkylthio having 1 to 3 carbon atoms in the alkylthio group, and heterocyclylalkyl having 5 or 6 ring members and

1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, in the heterocyclyl group and having 1 to 3 carbon atoms in the alkyl group, wherein each of the aforementioned radicals may be substituted in the phenyl group or in the heterocyclyl group by 1 to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and/or alkoxy having

1 to 4 carbon atoms, represents phenoxy, which is unsubstituted or can be substituted by 1 to 5 identical or different radicals selected from the group consisting of

halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thio- carbamoyl,

in each case straight-chained or branched alkyl, hydroxyalkyl, alkoxy, alkoxyaUcyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfϊnyl or alkylsulfonyl having in each case 1 to 8 carbon atoms,

in each case straight-chained or branched alkenyl or aUcenyloxy having in each case 2 to 6 carbon atoms,

in each case straight-chained or branched halogenoaUcenyl or halogeno- alkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms,

in each case straight-chained or branched alkylamino, diaUcylamino, alkyl- carbonyl, alkylcarbonyloxy, alkoxycarbonyl, aUcylaminocarbonyl, dialkyl- aminocarbonyl, phenylaUcylaminocarbonyl, cUalJkylarnino-carbonyloxy, hydroximinoalkyl or aUcoximinoalkyl having in each case 1 to 6 carbon atoms in each of the carbon atom chains,

phenyl, phenoxy, phenylthio, heterocyclyl having 5 or 6 ring members and 1 to 3 nitrogen, oxygen and/or sulfur, phenylalkyl having 1 to 3 carbon atoms in the alkyl group, phenylaUcoxy having 1 to 3 carbon atoms in the alkoxy group, phenylalkylthio having 1 to 3 carbon atoms in the alkylthio group, and heterocyclylalkyl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, in the heterocyclyl group and having 1 to 3 carbon atoms in the alkyl group, wherein each of the aforementioned radicals may be substituted in the phenyl group or in the heterocyclyl group by 1 to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and/or alkoxy having 1 to 4 carbon atoms,

or

R³ represents heteroaryl having 5 or 6 ring members and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, or represents benzoheteroaryl having 5 or 6 ring members in the heteroaryl group and 1 to 3 heteroatoms selected from nitrogen, oxygen and/or sulfur, wherein the aforementioned radicals may be substituted by up to 3 identical or different radicals selected from halogen, alkyl having 1 to 4 carbon atoms and halogenaUcyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms,

or

R³ represent alkoxy having 3 to 8 carbon atoms, or represents cycloaUcoxy having 3 to 8 carbon atoms.

Particularly preferred are those thiophene derivatives of the formula (I), in which R¹ represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, i- butyl, sec-butyl or tert-butyl,

R² represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, i- butyl, sec-butyl or tert-butyl,

n represents 0, and

R³ represents unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of

fluoro, bromo, iodo, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl, cyclopropyl, phenyl, phenoxy and benzyloxy,

or

R³ represents phenyl, which is substituted by 2 or 3 identical or different substitutents selected from the group consisting of

fluoro, chloro, bromo, iodo, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl, cyclopropyl, phenyl, phenoxy and benzyloxy, or R³ represents phenoxy which is unsubstituted or substituted by 1 to 3 identical or different radicals selected from

or

R³ represents pyridyl, thienyl, thiazolyl or benzothiazolyl, each of which is unsubstituted or substituted by 1 or 2 identical or different radicals selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl and trifluromethyl,

or

R³ represents alkoxy having 3 to 8 carbon atoms, or cycloaUcoxy having 3 to 8 carbon atoms.

Another group of particularly preferred compounds are those thiophene derivatives of the formula (I), in which

R¹ represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, i- butyl, sec-butyl or tert-butyl,

R² represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, i- butyl, sec-butyl or_. tert-butyl, n represents 1, and

R³ represents phenyl or phenoxy, each of which may be unsubstituted or substituted by 1 to 3 identical or different radicals selected from the group consisting of

or

R³ represents pyridyl, thienyl, thiazolyl or benzothiazolyl, each of which is unsubstituted or substituted by 1 or 2 identical or different radicals selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl and trifluoromethyl,

or

R³ represents alkoxy having 3 to 8 carbon atoms, or cycloalkoxy having 3 to 8 carbon atoms.

R¹ represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, i- butyl, sec-butyl or tert-butyl, R² represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, i- butyl, sec-butyl or tert-butyl,

n represents 2, and

R³ represents mono-substituted phenyl, wherein the substituents are selected from the group consisting of

fluoro, chloro, bromo, iodo, cyano, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

or

R³ represents phenyl, which is di or tri-substituted by identical or different radicals selected from the group consisting of

fluoro, chloro, bromo, iodo, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl, cyclopropyl, phenyl, phenoxy and benzyloxy,

or

R³ represents phenoxy, which is unsubstituted or substituted by 1 to 3 identical or different substitutents selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl,

or

represents pyridyl, thienyl, thiazolyl or benzothiazolyl, each of which is unsubstituted or substituted by 1 or 2 identical or different radicals selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl and trifluoromethyl,

or

The above-mentioned radical definitions can be combined in any manner, even between the different ranges. The definitions relate to the final products as well as to the starting materials and intermediates. Some of the definitions can also be left out.

If 3-mercapto-3-methylmercapto-2-cyano-acrylonitrile potassium salt and 2-bromo- l-(4-bromo-phenyl)-ethanon are used as starting materials, the course of process (a) according to the invention can be illustrated by the following formula scheme

If 4-amino-5-(4-bromo-benzoyl)-2-methylthio-3-thiophen-carbonitrile and an equivalent amount of methyliodide are used as starting materials, the course of process (b) according to the invention can be illustrated by the following formula scheme

If 4-methylamino-5-(3,4-dichlorobenzoyl)-2-methylthio-3-tMophen-carbonitrile and methyliodide are used as starting materials, the course of process (c) according to the invention can be illustrated by the following formula scheme

If 4-amino-5-(4-bromo-berιzoyl)-2-memyltMo-3-thiophen-carbonitrile is used as starting material and 3-chloro-perbenzoic acid is employed as oxidizing agent, the course of process (d) according to the invention can be illustrated by the following formula scheme

3-chloro-perbenzoic acid

Formula (II) provides a general definition of the dicyano-methylthio-efhenthiolates, which are required as starting materials for carrying out process (a) according to the invention. In this formula, M preferably represents sodium or potassium. The dicyano-methylthio-ethenthiolates of the formula (II) are known or can be prepared by known processes (cf. Heterocycles 45 (3), (1997), 493-500 and Arch. Pharm. Ber. Dtsch. Pharm. Ges. 301, (1968) 601-610). The compounds can also be prepared by reacting malodinitrile and carbondisulfide in the presence of aqueous sodium hydroxide or potassium hydroxide immediately prior to their use.

Formula (III) provides a general definition of the halogenoacetyl compounds, which are furthermore required as starting materials for carrying out process (a) according to the invention. In this formula, R³ preferably has those meanings, 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 radical. X preferably denotes chloro or bromo.

The halogenoacetyl compounds of the formula (III) are known or can be prepared by known methods.

Formula (la) provides a general definition of the thiophene derivatives, which are required as starting materials for carrying out process (b) according to the invention. In this formula, R³ preferably has those meanings, which have aheady been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this radical.

The thiophene derivatives of the formula (la) are sub-group of the compounds according to the invention. They can be prepared by process (a) according to the invention.

Formula (IN) provides a general definition of the alkylating agents, which are furthermore required as starting materials for carrying out processes (b) and (c) according to the invention. In this formula, R⁴ preferably represents alkyl having 1 to 4 carbon atoms, and Y preferably represents chloro, bromo, iodo, methylsulfonyloxy, methoxysulfonyloxy or tolylsulfonyloxy.

The alkylating agents of the formula (IN) are known or can be prepared by known processes.

Formula (lb) provides a general definition of the thiophene derivatives, which are required as starting materials for carrying out process (c) according to the invention. In this formula, R³ preferably has those meanings, which have aheady been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this radical. R⁴ preferably represents alkyl having 1 to 4 carbon atoms.

The thiophene derivatives of the formula (lb) are a sub-group of the compounds according to the invention. They can be prepared by process (b) according to the invention.

Formula (Tc) provides a general definition of the thiophene derivatives, which are required as starting materials for carrying out process (d) according to the invention. In this formula, R¹, R² and R³ preferably have those meanings, which have aheady been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these radicals. They can be prepared by processes (a) to (c) according to the invention.

Suitable oxidizing agents for carrying out process (d) according to the invention are all customary compounds, which can be employed for oxidizing sulfur. Preferred are hydrogenperoxide or organic peracids, such as peracetic acid, 4-nitro-ρerbenzoic acid and 3-chloro-perbenzoic acid, as well as inorganic materials, such as periodic acid, potassium permanganate, chromic acid and oxones. These oxidizing agents are known compounds. Suitable diluents for carrying out process (a) according to the invention are all customary organic solvents. Preferred are ketones, such as acetone, butanone, methyl-isobutyl-ketone or cyclohexanone; 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 hexamethyl- phosphoric triamide; sulfoxides, such as dimethyl sulfoxide; sulfones, such as sulfolane, and alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethandiol, propan-l,2-diol, ethoxy ethanol, methoxyethanol, diethylene glycol monomethylether or diethylene glycol mono-ethyl ether; as well as mixtures of these diluents with water. Further, water can also be employed as a diluent.

Suitable acid-binding agents for carrying out process (a) according to the invention are all customary inorganic or organic bases. With preference it is possible to use alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate and sodium carbonate, and also ammonium compounds, such as ammonium hydroxide, ammonium acetate and ammonium carbonate. As organic bases mention may be made of the following: tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N- dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N- methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonene (DBN) or diazabicycloundecene (DBU).

When carrying out the process (a) according to the invention, the reaction temperatures may be varied within a relatively wide range. In general, the process is carried out at temperatures between 0°C and 150°C, preferably at temperatures between 0°C and 50°C. Process (a) as well as processes (b) to (d) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

When carrying out process (a) according to the invention, in general from 1 to 5 mol, preferably from 1 to 1.5 mol of a halogenoacetyl compound of the formula (III) are employed per 1 mol of dicyanomethylthio-ethenthiolate of the formula (II). Work-up is carried out by customary methods.

Suitable diluents for carrying out processes (b) and (c) according to the invention are all customary inert organic solvents. With preference it is possible to use ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; ketones, such as acetone, butanone, methyl-isobutyl-ketone or cyclohexanone; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl- formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile, as well as sulfones, such as sulfolane.

Suitable acid-binding agents for carrying out processes (b) and (c) according to the invention are all customary inorganic or organic bases. With preference it is possible to use those acid-binding agents, which have already been mentioned in connection with the description of process (a) according to the invention as being preferred as bases.

When carrying out processes (b) and (c) according to the invention, the reaction temperatures may in each case be varied within a relatively wide range. In general, processes (b) or (c) are carried out at temperatures between 0°C and 150°C, preferably at temperatures between 0°C and 50°C. When carrying our process (b) according to the invention, in general from 1 to 2.0 mol, preferably from 1 to 1.5 mol of an alkylating agent of the formula (IN) are employed per 1 mol of thiophene derivative of the formula (la). Work-up is carried out by customary methods.

When carrying our process (c) according to the invention, in general from 2.0 to 15.0 mol, preferably from 2.5 to 3.0 mol of an alkylating agent of the formula (IN) are employed per 1 mol of thiophene derivative of the formula (lb). Work-up is again carried out by customary methods.

Suitable diluents for carrying out process (d) according to the invention are water as well as customary inert organic solvents. With preference it is possible to use aliphatic, alicyclic or aromatic hydrocarbons, such as pertroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloro- methane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; amides, such as Ν,Ν-dimethylformamide, N,N-diemthylacetamide, N-methyl- formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethandiol, propandiol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether or diethylen glycol mono-ethyl ether, as well as mixtures of these diluents with water.

When carrying out process (d) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, process (d) is carried out at temperatures between 0°C and 150°C, preferably between 0°C and 80°C.

When carrying out process (d) according to the invention for preparing of thiophene derivatives of the formula (I), wherein n is 1, in general from 1.0 to 1.5, preferably from 1.0 to 1.2 equivalents of an oxidizing agent are employed per 1 mol of thiophene derivative of the formula (Ic). Work-up is carried out by customary methods.

When carrying out process (d) according to the invention for the preparation of thiophene derivatives of the formula (I), wherein n is 2, in general from 2.0 to 5.0, preferably from 2.0 to 3.0 equivalents of an oxidizing agent are employed per 1 mol of thiophene derivative of the formula (Ic). Work-up is again carried out by customary methods.

The substances according to the invention have potent microbicidal activity and can be employed for controlling undesired microorganisms, such as fungi and bacteriae, in crop protection and in the protection materials.

Fungicides can be employed in crop protection for controlling Plasmodio- phoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomyetes, Basidio- mycetes and Deuteromycetes.

Bactericides can be employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come 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 spieces, such as, for example Phytophthora infestans;

Pseudoperonospora species, such as, for example Pseudoperonospora humuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphera leucotricha;

Nenturia species, such as, for example, Nenturia 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;

Sclerotinia species, such as, for example, Sclerotinia schlerotiorum; 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, Bortytis cinerea;

Septoria species, such as, for example, Septoria nodorum; r 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 active compound according to the invention also have very good fortifying action in plants. Accordingly, they can be used for mobilizing the defences of the plant against attack by unwanted microorganisms.

In the present context, plant-fortifying (resistance-inducing) substances are to be understood as meaning those which are capable of stimulating the defence system of plants such that, when the treated plants are subsequently inoculated with unwanted microorganisms, they show substantial resistance against these microorganisms. In the present case, unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteriae and viruses. Accordingly, the substances according to the invention can be used to protect plants for a certain period after the treatment against attack by the pathogens mentioned. The period for which protection is provided generally extends over 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.

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

The compounds according to the invention are particularly suitable for the control of diseases in vine, fruits and vegetables. For example, the compounds according to the invention can be used against Nenturia species, Alternaria species, Phytophthora species as well as against Plasmopara species.

The active compounds according to the invention are also suitable for increasing the yield of crops. In addition, they show reduced toxicity and are well tolerated by plants.

At certain concentrations and application rates, the active compounds according to the invention can also be used as herbicides, for influencing plant growth and for controlling animal pests. They can also be used as intermediates and precursors for the synthesis of further active compounds.

The active compounds according to the invention can be used to treat all plants and parts of plants. By plants are understood here all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by varietal property rights. Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.

The treatment of the plants and the parts of plants with the active compounds according to the invention is carried out directly or by action on their surroundings, habitat or storage space, according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, spreading-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multi-layer coating.

In the protection of materials, the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, undesired microorganisms.

Industrial materials in the present context are understood as meaning non-living materials wliich have been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood, paints and plastic article, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may be mentioned within the scope of the present invention are preferably adhesives, sizes, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids particularly preferably wood.

Microorganisms capable of degrading or changing the industrial materials which may be mentioned are, for example, bacteria, fungi, yeast, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coh,

Pseudomonas, such as Pseudomonas aeruginosa, and

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, the active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powder, foams, pastes, granules, aerosols and micro- encapsulations in polymeric substances and in coating compositions for seeds, and

ULN cool and warm fogging 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 surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example pertroleum fractions, alcohol 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 or dimethyl sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic materials such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, aryl- sulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.

Tackifiers 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, or else natural phosphohpids such as cephalins and lecithin and synthetic phosphohpids can be used in the formulations. Other possible additives are 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 generally comprise 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 used as such or in their formulations, also in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden, for example, the activity spectrum or to prevent development of resistance. In many case, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.

Examples of suitable mixing components are the following: Fungicides

2-phenyl-phenol, 8-hydroxyquinoline sulphate;

acibenzolar-S-methyl; aldimorph; amidoflumet; ampropylfos; ampropylfos-potas- sium; andoprim; anilazine; azaconazole; azoxystrobin;

benalaxyl; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzama- cril-isobutyl; bialafos; binapacryl; biphenyl; bitertanol; blasticidin-S; bromucon- azole; bupirimate; buthiobate; butylamin;

calcium polysulphide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone; quinomethionat; chlobenthiazone; chlorofenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram;

dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon;

edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;

famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fen- hexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprirnidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al; fosetyl-sodium; fuberidazole; furalaxyl; fttrametpyr; furcarbanil; furmecyclox;

guazatine; hexachlorobenzene; hexaconazole; hymexazol;

imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione;

kasugamycin; kresoxim-methyl;

mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam; metiram; metominostrobin; met- sulfovax; mildiomycin; myclobutanil; myclozolin;

natamycin; nicobifen; nitrothal-isopropyl; noviflumuron; nuarimol;

ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin;

paclobutrazol; pefurazoate; penconazole; pencycuron; phosdiphen; phthalide; pic- oxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymi- done; propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid; pro- thioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolnitrine;

quinconazole; quinoxyfen; quintozene;

simeconazole; spiroxamine; sulfur;

tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tri- cyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole;

uniconazole;

validamycin A; vinclozolin;

zineb; ziram; zoxamide;

(2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-ρroρinyl]oxy]-3-methoxyphenyl]ethyl]-3- methyl- 2-[(methylsulfonyl)amino]-butanamide;

l-(l-naphthalenyl)-lH-pyrrol-2,5-dion;

2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine;

2-amino-4-methyl-N-phenyl-5-thiazolcarboxamid;

2-chloro-N-(2,3-dihy(ho-l,l,3-trimemyl-lH-inden-4-yl)-3-pyridmcarboxamide;

3,4,5-trichloro-2,6-pyridindicarbonitril;

actinovate;

cis- 1 -(4-chlorophenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol;

methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazol-5-carboxylate; mono-potassium carbonate;

N-(6-methoxy-3-pyridinyl)-cyclopropancarboxamide; sodium tetrathiocarbonate as well as copper salts and copper preparations, such as Bordeanux mixture, copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, cufraneb, copper oxide, mancopper, oxine-copper.

Bactericides

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracylin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides, acaricides, nematicides

abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole, acrinathrm, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb, aldoxycarb, allethrin, allethrin lR-isomers, alpha-cypermethrin (alphamethrin), amidoflumet, arninocarb, amitraz, avermectin, AZ-60541, azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, Baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, Beta- cypermethrin, bifenazate, bifenthrin, binapacryl, bioallethrin, bioallethrin-S-cyclo- pentyl-isomer, bioethmomethrin, biopermethrin, bioresmethrin, bistrifluron, BPMC, brofenprox, bromophos-ethyl, bromopropylate, bromfenvinfos (-methyl), BTG-504,

BTG-505, bufencarb, buprofezin, butathiofos, butocarboxim, butoxycarboxim, butyl- pyridaben,

cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA-50439, chlorodane, chlorodimeform, chloethocarb, chlorethoxyfos, chlorofena- pyr, chlorofenvinphos, chlorofluazuron, chloromephos, chlorobenzilate, chloropicrin, chloroproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl), chlovaporthrin, chroma- fenozide, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin, clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene, cycloprothrin, cydia pomonella, cyfluthrin, cyhalothrin, cy- hexatin, cypermethrin, cyphenothrin (lR-trans-isomer), cyromazine,

DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dichlofenthion, dichlorovos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimethoate, dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan, disulfoton, docusat-sodium, dofenapyn, DOWCO-439,

eflusilanate, emamectin, emamectin-benzoate, empenthrin (lR-isomer), endosulfan, entomopthora spp., EPN, esfenvalerate, ethiofencarb, ethiprole, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,

famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobu- carb, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulfothion, fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin (flufenzine), fluvalinate, fonofos, formetanate, formothion, fosmethilan, fosthiazate, fubfenprox (fluproxyfen), furathiocarb,

gamma-HCH, gossyplure, grandlure, granulosis viruses,

halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron, hexy- thiazox, hydramethylnone, hydroprene,

IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, japonilure,

kadethrin, kinoprene,

lambda-cyhalothrin, lindane, lufenuron,

malathion, mecarbam, mesulfenfos, metaldehyd, metam-sodium, methacrifos, methamidophos, metharhizium anisopliae, metharhizium flavoviride, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin, MTI-800,

naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, novaluron, noviflumuron, nuclear polyhedrosis viruses,

OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-methyl,

paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (lR-trans isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl, pirimiphos-ethyl, prallethrin, profenofos, promecarb, propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphen- thion, pyridathion, pyrimidifen, pyriproxyfen,

quinalphos,

resmethrin, RH-5849, ribavirin, RU-12457, RU-15525, S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad, spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos, SZI-121,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, temivinphos, terbam, terbufos, tetrachlorovinphos, tetradifon, tetra- methrin, teframethrin (lR-isomer), tetrasul, theta-cypermethrin, thiacloprid, thia- methoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thio- fanox, thiometon, thiosultap-sodium, thuringiensin, tolfenpyrad, fralocythrin, tralo- methrin, fransfluthrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,

vamidothion, vaniliprole, verbutin, Nerticillium lecanii,

WL-108477, WL-40027,

YI-5201, YI-5301, YI-5302,

XMC, xylylcarb,

ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,

3-methyl-phenyl-propylcarbamate (tsumacide Z),

3-(5-cUoro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]-octan-3-carbo- nitrile (CAS No. 185 982-80-3) as well as the corresponding 3-endo isomer

(CAS No. 185 984-60-5) (cf. WO 96-37 494 and WO 98-25923)

and also preparations comprising insecticidally active plant extracts, nematodes, fungi or viruses. A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, safeners or semiochemicals, is also possible.

In addition, the compounds of the formula (I) according to the invention also have very good antimycotic activity. They have a very broad antimycotic activity spectrum in particular against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as Candida albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi by no means limits the mycotic spectrum covered, but is only for illustration.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. Application is carried out in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading, etc. It is furthermore possible to apply the active compounds by the ultra-low volume method, or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat the seeds of the plants.

When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the kind of application. For 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

1000 g/ha. For seed dressing, the active compound application rates are generally between 0.001 and 60 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. For the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g ha, preferably between 1 and 5000 g/ha. The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. Weeds in the broadest sense are understood to mean all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda,

Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala,

Rumex, Salsola, Senecio. Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon,

Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis,

Eriochloa, Festuca, Fimbristylis, Heteranthera, hnperata, Eschaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena,

Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea. However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

The active compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on path and areas with and without tree plantings. Similarly, the active compounds according tot he invention can be employed for controlling weeds in perennial crops, for example forests, decorative free plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns, turf and pastureland, and for the selective control of weeds in annual crops.

The compounds of the formula (I) according to the invention have strong herbicidal activity and a broad active spectrum when used on the soil and on above-ground parts of plants. To a certain extent they are also suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.

For controlling weeds, the active compounds according to the invention, as such or in then formulations, can also be used as mixtures with known herbicides and/or substances which improve the compatibility with crop plants ("safeners"), finished formulations or tank mixes being possible. Also possible are mixtures with weed- killers comprising one or more known herbicides and a safener.

Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafemdin, azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron

(-methyl), bentazon, benzfendizone, benzobicyclon, benzofenap, benzoyl- prop(-ethyl), bialaphos, bifenox, bispyribac (-sodium) bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron, (-ethyl), chlornitrogen, chlorsulfuron, chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop

(-propargly), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cylosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyfiam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, fiorasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol, (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (-ammonium), glyphosate (-isopropyl- ammonium), halosafen, haloxyfop (-ethoxyethyl, -P-methyl), hexazinone, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, ketospiradox, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanihde, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfiuorfen, paraquat, pelargonic acid, pendimethalin, pendralin, penoxysulam, pentoxazone, pethoxamid, phenmedipham, picolinafen, piperophos, pretilachlor, primisulfuron (-methyl), profluazol, profoxydim, prometryn, propachlor, propanil, propaquizafop, propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol, pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl, -P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), trichlopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.

Furthermore suitable for the mixture are known softeners, for example AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil, 2,4-D, DKA-

24, dichlormid, dymron, fenclorim, fenchlorazol (-ethyl), flurazole, fluxofenim, flurilazole, isoxadifen (-ethyl), MCPA, mecoprop (-P), mefenpyr (-diethyl), MG-191 oxabetrinil, PPG-1292, R-29148.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agent which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in a customary manner, for example by watering, spraying, atomizing or broadcasting.

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing. The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.

As aheady mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetical engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.

Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivar are to be understood as meaning plants having certain properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, bio- or genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced apphcation rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions to be used according to the invention - also in combiantion with other agro-chemical acitve compounds -, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by genetical engineering) which are preferably treated according to the invention include all plants which, in the genetic modification, received genetic material wliich imparted particularly advantageous useful properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape. Traits that are emphasized are in particular increased defence of the plant against insects by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes (CryΙA(a), CryIA(b), CryIA(c), CrylLA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (hereinbelow referred to as "Bt plants"). Traits that are also particularly emphasized are the increased defence of the plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the

"PAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade name YIELD GARD® (for example maize, cotton, soya beans), KnockOut^® (for example maize), StarLink^® ( for example maize), Bollgard^® (cotton), Nucotn^® (cotton) and NewLeaf^® (potato).

Examples of herbicide-tolerant plants wliich may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready^® (tolerance to glyphosate, for example maize, cotton, soya bean). Liberty Link^® (tolerance to phosphinotricin, for example oilseed rape), IMI^® (tolerance to imidazolinones) and STS^® (tolerance to sulphonylurea, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield^® (for example maize). Of course, these statements also supply to plant cultivars having these genetic traits or genetic traits still to be developed, which plants will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula (I) or the active compound mixtures according to the invention where in addition to the good control of weed plants, the above-mentioned synergistic effects with the transgenic plants of plant cultivars occur. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.

The following examples show the preparation and use of the active compounds according to the invention: Preparation Example

Example 1

Process (a)

22.3 g (0.558mol) of sodium hydroxide are added to a solution of 108.4 g (0.558 mol) of 3-mercapto-3-methylmercapto-2-cyano-acrylonitrile potassium salt and 155 g (0.558 mol) of 2-bromo-l-(3-bromo-phenyl)-ethanone in 1.2 litres of ethanol at room temperature with stirring. The temperature of the reaction mixture rises up to 50°C in the course of the addition. The mixture is stirred for 6 hours whereupon it cools down to room temperature again. The precipitate is filtered off, washed with water and dried. In this manner, 44.9 g (22% of theory) of 4-amino-5- (3-bromo-benzoyl)-2-memylthio-3-thiophenecarbonitril are obtained in the form of a solid product. HPLC: logP = 3.39

1H-NMR (DMSO-dβ, TMS): δ = 2.70 (3H); 7.47-7.51 (1H); 7.69-7.71 (1H); 7.76- 7.81 (2H); 7.94 (2H) ppm.

Example 2

Process (d)

1.6 g (6.8 mmol) of 3-chloro-perbenzoic acid are added to a solution of 2.0 g (5.66 mmol) of 4-ammo-5-(3-bromobenzoyl)-2-methylthio-3-thiophenecarbonitril in 160 ml of dichloromethane. The reaction mixture is stirred for 12 hours at room temperature, and is then successively washed with an aqueous sodiumcarbonate solution and with water. After drying the organic phase over sodium sulfate, it is concentrated under reduced pressure. The residue is treated with diisopropyl ether whilst stirring, and the solid product is then sucked off. In this manner, 1.47 g (65.2 % of theory) of 4-amino-5-(3-bromobenzoyl)-2-(methylsulfinyl)-3- thiophenecarbonitril are obtained in the form of a crystalline product.

HPLC: logP=2.33.

1H-NMR (DMSO-d₆, TMS): δ = 3.08 (3H); 7.51-7.56 (1H); 7.75-7.77 (1H); 7.82- 7.85 (1H); 7.88-7.92 (1H); 7.95 (2H) ppm.

Example 3

Process (a)

A solution of 39.6 g (0.6 mol) of potassium hydroxide in 40 ml of water is slowly dropped into a solution of 18.0 g (01272 mol) of malonic acid dinitril and 37.34 g (0.49 mol) of carbondisulfide in 250 ml of dimethylformamide at a temperature between 0°C and 10°C whilst stirring. After having completed the addition, the reaction mixture is stirred for 10 minutes at a temperature between 0°C and 10°C, and then 38.6 g (0.272 mol) of methyliodide are added dropwise while keeping the temperature between 0°C and 10°C. After 30 minutes of stirring, a solution of 47.6 (0.272 mol) of chloroacetic acid 2-fluorophenylester in 50 ml of dimethyl-formamide are added. The reaction mixture is stirred for 30 minutes without cooling, and when a temperature of 25°C has been reached, 0.6 g of potassium hydroxide powder are added. The reaction mixture is stirred for an additional hour and then poured into 300 ml of water. The resulting precipitate is filtered off and is then successively washed with isopropanol and diethylether. In this manner, 34.0 g (40.5% of theory) of 3-ammo-4-cyano-5-methyltWo-2-thiophene-carboxylic acid 2-fluoro-phenyl-ester are obtained in the form of a crystalline product.

HPLC: logP = 3.22

1H-NMR (DMSO-d₆, TMS): δ = 2.76 (3H); 7.12 (2H); 7.16-7.28 (1H); 7.3-7.4 (3H) ppm. Example 4

Process (d)

A solution of 100.1 g (0.407 mol) of 3-chloro-perbenzoic acid (70%-ic material) in 1.1 litres of dichloromethane is added to 35.9 g (0.116 mol) of 3-amino-4-cyano-5- methylthio-2-thiophene-carboxylic acid 2-fluoro-phenyl-ester, and the resulting mixture is stirred for 12 hours at room temperature. The reaction mixture is then washed with an aqueous sodium carbonate solution several times, and the organic phase is dried over sodium sulphate. The solvent is then distilled off under reduced pressure, and the residue is recrystallized from toluene. In this manner, 25.0 g (63.3% of theory) of 3-amino-4-cyano-5-methylsulphonyl-2-fhiophene-carboxylic acid 2- fluorophenyl-ester are obtained in the form of a crystalline product.

HPLC:logP=2.61.

iH-NMR (DMSO-d₆, TMS): δ=3.56 (3H) ppm.

Example 5

Process (a)

A solution of 33.5 g (0.5 mol) of potassium hydroxide in 40 ml of water is slowly dropped into a solution of 15.2 g (0.231 mol) of malonic acid dinitril and 31.6 g (0.415 mol) of carbondisulphide in 260 ml of dimethylformamide at a temperature between 0°C and 10°C whilst stirring. After having completed the addition, the reaction mixture is stirred for 10 minutes at the same temperature. 32.74 g (0.231 mol) of methyliodide are then added dropwise while keeping the temperature of the reaction mixture between 0°C and 10°C. Stirring is continued for 30 minutes at the same temperature, and then a solution of 61.8 g (0.231 mol) of 2-bromo-l-(3,4- dichlor-ρhenyl)-ethanone in 60 ml of dimethylformamide is added. The reaction mixture is stirred for another 30 minutes without cooling, and when a temperature of about 25°C has been reached, 2.0 g of potassium hydroxide powder are added. After further stirring for 1 hour, the reaction mixture is poured into 400 ml of water. The precipitate formed is filtered off and then successively washed with isopropanol and with diethyl ether. In this manner, 62.3 g (69% of theory) of 4-amino-5-(3,4- dichloro-berιzoyl)-2-memyltMo-3-thiophene-carbonitril are obtained in the form of a crystalline product.

HPLC: logP=3.87 Example 6

Process (b)

2.33 g (0.058 mol) of sodium hydride (60%-ic) are added portionwise to a solution of 10.0 g (0.0291 mol) of 4-amino-5-(3,4-dcWoro-benzoyl)-2-methylthio-3-thiophene- carbonitril in 30 ml of dimethylformamide whilst stirring at room temperature. Stirring is continued until the formation of gas has stopped. 8.27 g (0.058 mol) of methyliodide are then added dropwise, and the reaction mixture is stirred for 12 hours at room temperature. For work-up, the reaction mixture is poured into water, and the resulting mixture is extracted with ethyl acetate. After drying the organic phase over sodium sulphate, the solvent is distilled off under reduced pressure. In this manner, 8.5 g (78.6% of theory) of 4-dimethyl-amino-5-(3,4-dichloro-benzoyl)- 2-methylthio-3-thiophene-carbonitril are obtained.

HPLC: logP=4.33.

Example 7

Process (d)

A mixture of 25.5 g (0.0686 mol) of 4-dimethylan ino-5-(3,4-dichloro-benzoyl)-2- methylthio-3-thiophene-carbonitril and 18.6g (0.075 mol) of 3-chloro-perbenzoic acid (70%-ic) in 500 ml of dichloromethane is stirred for 12 hours at room temperature. The reaction mixture is then washed with an aqueous sodium carbonate solution several times. After drying the organic phase over sodium sulphate, the solvent is distilled off under reduced pressure, and the residue is recrystallized from toluene. In this manner, 36.0 g (77.6% of theory) of 4-dimethylamino-5-(3,4- dichlorobenzoyl)-2-methylsulfinyl-3-thiophene-carbonitril are obtained in the form of a crystalline product.

HPLC: logP=3.15

The compounds of the formula (I) listed in the following Table 1 can also be prepared according to the aforementioned processes.

Table 1

The logP values were determined in accordance with EEC directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile/0.1% aqueous phosphoric acid) Use Examples

Example A

Phytophthora test (tomato)/protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide Emulsifier: 1.0 part by weight of alkyl-aryl 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 to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabin at about 20°C and 100% relative atmospheric humidity.

Evaluation is carried out 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

Active compounds, application rates and test results are shown in the table below. Table A

Phytophthora Test (tomato) / protective

Table A (continuation) Phytophthora Test (tomato) / protective

Example B

Plasmopara Test (grapevine)/-protective

Solvent: 24.5 parts by weight of acetone

To produce a suitable preparation of the 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 a preparation of active compound at the stated apphcation rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in an incubation cabin at approximately 20°C and 100% relative atmospheric humidity for 1 day. The plants are then placed in a greenhouse at approximately 21°C and approximately 90% atmospheric humidity for 4 days. The plants are then moistened and placed in an incubation cabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

Active compounds, application rates and test results are shown in the table below. Table B

Plasmopara Test (grapevine) / protective

Table B (continuation)

Plasmopara Test (grapevine) / protective

Example C

Venturia Test (Apple) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of a dimethylacetamide Emulsifier: 1.0 part by weight of alkyl-aryl 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 at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causative organism of apple scab Venturia inaequalis and then remain in an incubation cabin at approximately 20°C and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at approximately 21°C and a relative atmospheric humidity of approximately 90%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no injection is observed.

Active compounds, application rates and test results are shown in the table below. Table C

Venturia Test (apple) / protective

Example D

Alternaria test (tomato)/protective

Solvent: 49 parts by weight of N,N-dimethylformamide

Emulsifier: 1.0 part by weight of alkylaryl polyglycol ether

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants are then placed in an incubation cabinet for 24 hours at approximately 20°C and a relative atmospheric humidity of 100%. Thereafter, the plants are kept at a temperature of 20°C and at a relative atmospheric humidity of 96%.

The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control while an efficacy of 100% means that no disease is observed.

The active compounds, active compound concentrations and results can be seen from the following table: Table D

Alternaria Test (tomato) / protective

Example E

Pre-emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of aUcylaryl polyglycol ether

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

Seeds of the test plants are sown in normal soil. After 24 hours, the soil is sprayed with the preparation of active compound such that the particular amount of active compound desired is applied per unit area. The concentration of active compound in the spray liquor is chosen such that the particular amount of active compound desired is applied in 1000 liters of water per hectare.

After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated controls. The figures denote:

0 % = no effect (like untreated control) 100 % = total destruction

The active compounds, application rates and test results are shown in the table below. Table E

Pre-emergence Test / Greenhouse

Active compound Application rate Maize Setaria Abutilon Amaranthus Galium g/ha

Example F

Post-emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier 1 part by weight alkylaryl polyglycol ether

Test plants of a height of 5-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 1000 1 of water/ha.

After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

The figures denote:

0 % = no effect (like untreated control) 100 % = total destruction

The active compounds, application rates and test results are shown in the following table. Table F-

Post-emergence Test / Greenhouse

Active compound Application rate Setaria Abutilon Amaranthus Ipomoea Sinapis

Table F-2

Post-emergence Test / Greenhouse

Active compound Application rate Wheat Soybeans Abutilon Amaranthus Datura Ipomoea Sinapis Solanum g ai/ha

0

Claims

Patent Claims

1. Thiophene derivatives of the formula

in which

R¹ represents a hydrogen atom or alkyl,

R² represents a hydrogen atom or alkyl,

R³ represents optionally substituted aryl, optionally substituted heteroaryl, optionally substituted benzoheteroaryl, optionally substituted alkoxy having 3 to 10 carbon atoms, optionally substituted cyclo- alkoxy or optionally substituted aryloxy, and

n represents 0, 1 or 2,

with the proviso that

4-amino-5-(4-chlorobenzoyl)-2-methylthio-3-thiophene-carbonitril of the formula

4-amino-5-benzoyl-2-methylsulfonyl-3-thiophene-carbonitril of the formula

4-amino-5-(4-nitrobenzoyl)-2-methylsulfonyl-3-thiophene-carbonitril of the formula

are excluded.

2. Process for the preparation of thiophene derivatives of the formula (I) according to claim 1 , characterized in that

a) dicyano-methylthio-ethenthiolates of the formula

in which

M represents an alkalimetal atom,

are reacted with halogenoacetyl compounds of the formula

in which

R³ has the above-mentioned meanings and

X represents a halogen atom,

or

b) thiophene derivatives of the formula

in which R³ has the above-mentioned meanings,

are reacted with alkylating agents of the formula

Y-R⁴ (IV)

in which

R⁴ represents alkyl and

Y represents chloro, bromo, iodo, methylsulfonyloxy, methoxy- sulfonyloxy or tolylsulfonyloxy,

or

c) thiophene derivatives of the formula

in which

R³ and R⁴ have the above-mentioned meanings,

are reacted with alkylating agents of the formula

Y- R⁴ (IV) in which

R⁴ and Y have the above-mentioned meanings,

or

d) thiophene derivatives of the formula

in which

R¹, R² and R³ have the above-mentioned meanings,

are reacted with oxidizing agents, if appropriate, in the presence of a diluent.

3. Compositions for the control of undesired microorganisms, characterized in that they comprise at least one thiophene derivative of the formula (I) according to claim 1 in addition to extenders and/or surface-active agents.

4. Use of thiophene derivatives of the formula (I) according to claim 1 for the confrol of undesired microorganisms.

5. Use of thiophene derivatives of the formula (I) according to claim 1 for the control of weeds.

6. Method for the control of undesired microorganisms, characterized in that thiophene derivatives of the formula (I) according to claim 1 are applied to the microorganisms and/or their habitat.

7. Method for the confrol of weeds, characterized in that thiophene derivatives of the formula (I), according to claim 1 are applied to the weeds and/or their habitat.

8. Process for the preparation of microbicidal compositions, characterized in that thiophene derivatives of the formula (I) according to claim 1 are mixed with extenders and/or surface-active agents.