EP0973771A1

EP0973771A1 - Thiazolimine derivatives

Info

Publication number: EP0973771A1
Application number: EP98912471A
Authority: EP
Inventors: Guido Mayer; Martina Otten; Uwe Kardorff; Ernst Baumann; Wolfgang Von Deyn; Stefan Engel; Regina Luise Hill; Joachim Rheinheimer; Matthias Witschel; Roland Götz; Michael Rack; Karl-Otto Westphalen; Ulf Misslitz; Helmut Walter
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1997-03-24
Filing date: 1998-03-12
Publication date: 2000-01-26
Also published as: AU6729498A; WO1998042703A1; AR015576A1; CA2283925A1; JP2001518918A; US6165943A; ZA982436B

Abstract

The invention relates to thiazolimines derivatives of formula (I), wherein the substituents have the following meanings: X, Y independently of each other stand for hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, Z means hydrogen, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkinyl, C1-C8-alkoxy, C1-C8-alkylthio, wherein these groups can be substituted by 1-5 halogen or C1-C4-alkoxy; aryl, hetaryl, benzyl, wherein these groups can be substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, halogen, nitro or cyano; or one of the following groups (a...); R1, R2 are hydrogen, halogen; C¿1?-C4-alkyl, C2-C4-alkenyl, C2-C4-alkinyl, wherein these groups can be substituted by 1-5 halogen or by C1-C4-alkoxy; n is 1 or 2; m is 0, 1 or 2, and R?3-R6¿ have the meaning cited in the application. The invention further relates to salts of compound I which can be used in agriculture.

Description

Thiazolimine derivatives

description

The present invention relates to new thiazolimine derivatives with herbicidal activity, a process for the preparation of the thiazolimine derivatives, compositions which contain them and the use of these derivatives or compositions containing them for weed control.

Herbicidal thiazolimine derivatives are known from the literature (US Pat. No. 5,244,863; EP 529 482, EP 446 802).

However, the herbicidal properties of the known compounds and the tolerability can only satisfy to a limited extent.

The task was to find new thiazolimine derivatives with improved properties.

New thiazolimine derivatives of the formula I have now been found

R ¹ R2

in which the substituents have the following meaning:

X, Y independently of one another hydrogen, halogen, -CC ₄ alkyl, -C ₄ -haloalkyl;

Z is hydrogen;

Cι-C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, Cι-C ₈ -alkoxy, C ₈ alkylthio, where these groups substituted by one to five halogen or C_-C ₄ Alkoxy can be substituted; Aryl, hetaryl, benzyl, these groups with

C 1 -C ₄ -alkyl, C_-C ₄ -alkoxy, C_-C ₄ -haloalkyl, C_-C ₄ -haloalkoxy, halogen, nitro or cyano may be substituted; or one of the following groups: R ³ ; S R6;

0 0

OR ³ OR ³ OR ³ OR ³

OR ^{3 '} NR ⁴ R ⁵ ^' OR ³ ; ^' NR ⁴ R ⁵ ;

R ¹ , R ^{2 are} hydrogen, halogen;

Cι * C ₄ alkyl, C ₂ -C ₄ alkenyl, C -C alkynyl, where these groups may be substituted by one to five halogen or by Ci _j alkoxy;

R ^{3 is} hydrogen;

C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ -alkynyl, C ₂ -C ₈ -alkylcarbonyl, C ₃ -C ₈ -alkenylcarbonyl, C ₃ -C ₈ -alkynylcarbonyl, where these groups can be substituted by one to eight halogen or by -CC ₄ alkoxy;

C ₃ -C ₇ cycloalkyl, C ₃ -C cycloalkenyl, where these groups can be substituted by one to eight halogen atoms, C_-C ₄ alkoxy, C_-C ₄ alkyl or C_-C ₄ haloalkyl; Aryl, hetaryl, benzyl, where these groups with C_-C -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C -Halo- alkoxy, halogen, cyano, or nitro;

R ⁴ , R ^{5 are} hydrogen;

Cχ-C ₆ alkyl, C -C ₆ alkenyl, C -Ce alkynyl, these

Groups can be substituted by one to four halogen or by C_-C ₄ alkoxy;

C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkenyl through one to four halogen or through C_-C ₄ alkyl, -CC ₄ -haloalkyl,

C 1 -C ₄ alkoxy, C 1 -C haloalkoxy may be substituted;

Aryl, hetaryl, these groups being C 1 -C ₄ -alkyl,

_{Cι-C4-alkoxy,} _Cι-C4 haloalkyl, _Cι-C4 haloalkoxy, halogen,

Nitro or cyano can be substituted; R ⁴ , R ⁵ together form a 3- to 7-membered heterocycle which can carry a further heteroatom of N, 0 or S, can contain at least one double bond and with C 1 -C ₄ alkyl, C 1 -C ₄ haloalkyl, C 1 -C ₄ -alkoxy, C_-C ₄ -haloalkoxy, halogen, nitro or cyano groups may be substituted;

R ^{6 is} hydrogen;

Ci-Cβ-alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, where these groups can be substituted by one to four halogen or by alkoxy;

C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkenyl, the foundation with one to four halogen atoms or C_-C ₄ - alkyl, Cι-C ₄ -Halo- alkyl, C ₁ -C ₄ alkoxy, haloalkoxy substituted could be;

Aryl, hetaryl, where these groups can be substituted by C ₁ -C ₄ -alkyl C_-C -haloalkyl, -CC -alkoxy, C ₁ -C ₄ -haloalkoxy, halogen, nitro or cyano;

n 1 or 2;

m 0, 1 or 2

as well as agriculturally useful salts of the compounds I.

To prepare the thiazolimine derivatives of the formula I, anilines of the formula II, which are known from DE 41 33 156, are used in the presence of an organic or inorganic base in a ratio of 0.5 to 5 equivalents with substituted propargyl derivatives of the general Formula III reacted in an inert solvent at temperatures between 0 and 100 ° C.

II III

IV

LG (leaving group) stands for a nucleophilically exchangeable leaving group such as halogen, mesylate, tosylate or acetate.

The reaction is generally carried out by adding the alkylating agent to the aniline derivative of the general formula II and the base. Suitable bases are tertiary amines, pyridine, the aniline derivative of the general formula II or potassium carbonate and cesium carbonate, which are used in a range from 0.5 to 5 molar equivalents.

For example, methylene chloride, chloroform, dioxane, tetrahydrofuran, dimethylformamide, acetonitrile, toluene or ethyl acetate can be used as solvents.

During the addition of the alkylating agent of the general formula III, the reaction mixture is preferably stirred at a temperature between 0 and 150 ° C.

The processing takes place in the usual way, e.g. the reaction mixture is poured into water and the product of value is extracted by extraction with, for example, methylene chloride. Further purification can be carried out, for example, by chromatography, crystallization or distillation. (Organikum, 16th edition, VEB German Publishing House of Sciences, Berlin 1986; J. Fluorine Chem. 1993, 60, 31-38)

For the preparation of compounds of the general formula VIII

IV VI

VII

Aniline derivatives of the general formula IV reacted with a mixture of KSCN and acetyl chloride. The product mixtures obtained are subsequently converted into N-acetyl-thiazolimine derivatives VIII by acidic or basic treatment (EP 446 820).

The reaction is generally carried out by adding the aniline derivative of the general formula IV to a reaction mixture of KSCN and acetyl chloride in an inert solvent such as methylene chloride, chloroform, dioxane, tetrahydrofuran, dimethylformamide, acetonitrile, toluene or ethyl acetate. During the entire reaction time, the reaction mixture is preferably stirred at temperatures between -15 ° C and 150 ° C.

The processing takes place in the usual way, e.g. the reaction mixture is poured onto water and the product of value is separated off by extraction with, for example, methylene chloride.

The further implementation takes place after drying. For this purpose, the reaction mixture is either dissolved in an inert solvent such as methylene chloride, chloroform, tetrahydrofuran, ethyl acetate or reacted in bulk with an auxiliary reagent. The temperature is in a range between -15 ° C and 150 ° C. The catalyst can be an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, an organic acid such as acetic acid, trifluoroacetic acid, toluenesulfonic acid, a base such as potassium tert. -butylate, sodium methoxide, pyridine, triethylamine, dimethylaminopyridine. working up is carried out in the customary manner, for example the reaction mixture is poured into water and the product of value is then separated off by extraction with, for example, methylene chloride. The cleaning can be carried out by crystallization or chromatography (EP 446 802).

To prepare compounds of the general formula IX, N-acetylthiazolimines of the general formula VIII are converted into their salts by acid hydrolysis.

_R ι _R2

acid

ix X->

^ - _H. salt

N-acetylthiazolimines of the general formula VIII are generally dissolved in an inert organic solvent such as methylene chloride, chloroform, tetrahydrofuran, dimethylformamide, toluene, diethyl ether, methanol, ethanol and reacted with 1 to 100 equivalents of an organic or inorganic acid brought. The temperature is usually between 0 and 150 ° C. Suitable acids are organic and inorganic acids such as acetic acid, trifluoroacetic acid, p- Toluenesulfonic acid or sulfuric acid, hydrochloric acid and phosphoric acid.

The processing is generally carried out in such a way that the solvent is removed in vacuo and the salt which remains is purified by crystallization from an inert solvent (T.W. Greene, Protective Groups in Organic Synthesis, Wiley, InterScience, N.Y.).

Compounds of the general formula I are prepared as follows:

-H salt

Ri R2

I z

N-substituted thiazolimine derivatives of the general formula I are generally in an inert solvent such as, for example, methylene chloride, chloroform, tetrahydrofuran, dimethylformamide, toluene, diethyl ether, ethyl acetate, methanol or ethanol by reacting thiazolimine derivatives of the general formula IX with one to ten Equivalents of an organic base and subsequent reaction with one to ten equivalents of the radical Z, which carries a leaving group (LG). Halogen atoms, ester groups and OH groups are particularly suitable as leaving groups. In the latter case, dehydrating agents such as dicyclohexylcarbodiimide and related substances can be added to the reaction. The temperature during the reaction is in a range between -15 ° C and + 100 ° C. The up work is generally carried out so that the reaction mixture is poured into water and the product of value is then extracted with an organic solvent such as methylene chloride or ethyl acetate.

The product of value can be purified by chromatography, distillation or crystallization.

Reaction scheme summarized

In the definition of compounds I given at the outset, collective terms were used which are generally representative of the following groups:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: straight-chain or branched alkyl group with 1 to 4, 6, 8 or 10 carbon atoms, for example Ci-C _δ- alkyl w methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, Methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1- Methylpentyl, 2-methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl,

2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl and 1-ethyl- 2-methylpropyl;

Alkylcarbonyl; straight-chain or branched alkyl groups with 1 to 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-C0-);

Haloσenalkyl: straight-chain or branched alkyl groups with 1 to 4 carbon atoms, in which groups the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C ₁ -C ₂ -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro- methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, Chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, -

1,1, 2-trimethylpropyloxy, 1,2, 2-trimethylpropyloxy,

1-ethyl-l-methylpropyloxy and l-ethyl-2-methylpropyloxy;

Haloalkenoxy; straight-chain or branched alkyl groups with 1 to 4 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, and where these groups are bonded to the skeleton via an oxygen atom;

Alkylthio: straight-chain or branched alkyl groups with 1 to 4, 6 or 8 carbon atoms as mentioned above, which are bonded to the structure via a sulfur atom (-S-), for example C_-C ₆ -alkylthio such as methylthio, ethylthio, propylthio, 1- Methyl-ethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-di-methylpropylthio, 1-ethylpropylthio, Hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1,2-dimethylbutylthio, 1, 3- Dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-l-methylpropylthio and l-ethyl-2-methylpropylthio;

Cvcloalky: monocyclic alkyl groups with 3 to 7 carbon ring members, e.g. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl;

Cycloalkenyl: as under cycloalkyl with at least one double bond;

Alkenyl: straight-chain or branched alkenyl groups with 2 to 6, 8 or 10 carbon atoms and a double bond in any position, for example CC ₆ ~ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl , 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4 -Pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl , l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l-dimethyl-2-propenyl, 1, 2-dimethyl-l-propenyl, 1, 2-dimethyl -2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-l-pentenyl,

2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2- Methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1, 2-dimethyl l-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-l-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl 3-butenyl, 2, 2-dimethyl-3-butenyl, 2, 3-dimethyl-l-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3,3-dimethyl l-butenyl, 3, 3-dimethyl-2-butenyl,

1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, l, 2-trimethyl-2-propenyl, 1-ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-l-propenyl and l-ethyl-2-methyl-2-propenyl;

Alkenylcarbonyl: straight-chain or branched alkenyl groups with 2 to 10 carbon atoms and a double bond in any position, which are bonded to the skeleton via a carbonyl group (-C0-);

Alkynyl: straight-chain or branched alkynyl groups with 2 to 8 or 10 carbon atoms and a triple bond in any position, for example CC ₆ -alkynyl such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 2 -Pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2 propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl , 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, l-dimethyl-2-butynyl, 1, l-dimethyl-3-butynyl, 1, 2-dimethyl - 3-butynyl, 2, 2-dimethyl-3-butynyl, l-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl ;

Alkynylcarbonyl: straight-chain or branched alkynyl groups with 3 to 10 carbon atoms and a triple bond in any position, which are bonded to the skeleton via a carbonyl group (-C0-);

Aryl: aromatic mono- or polycyclic hydrocarbon residues e.g. Phenyl, naphthyl and phenanthrenyl;

Hetaryl: aromatic mono- or polycyclic radicals which, in addition to carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, for example 5-αliedriσes heteroaryl, containing one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three nitrogen atoms as ring members, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5 -Pyrazolyl, 2-imidazolyl, 4-imidazolyl, l, 2,4-triazol-3-yl and 1, 3, 4-triazol-2-yl;

5-σliedriσes heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three May contain nitrogen atoms and a sulfur or oxygen atom or an oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-0xazolyl, 4-oxazolyl, 5-0xazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-0xadiazol- 3-yl, l, 2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, l, 2,4-thiadiazol-5-yl, 1,2,4-triazol-3- yl, 1,3, 4-oxadiazol-2-yl, 1,3, 4-thiadiazol-2-yl, 1,3, 4-triazol-2-yl;

benzo-fused 5-σliedriσes heteroaryl. containing one to three nitrogen atoms or a nitrogen atom and / or an oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom

May contain oxygen atom or an oxygen or a sulfur atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group,

5-σliedriσes heteroaryl bound via nitrogen. containing one to four nitrogen atoms. or a 5-σ-linked heteroaryl bonded via nitrogen. containing one to three nitrogen atoms: 5-ring heteroaryl groups, which in addition to carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member through a buta -1, 3-diene-1,4-diyl group can be bridged, these rings being bound to the frame via one of the nitrogen ring members;

6-σliedriσes heteroaryl, containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups, which in addition to carbon atoms can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3, 5-triazin-2-yl, 1, 2, 4-triazin-3-yl and 1,2,4,5-etrazin-3 -y1;

benzo-fused 6-σliedriσes heteroaryl. containing one to four nitrogen atoms: 6-ring heteroaryl groups in which two adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, e.g. Quinoline, isoquinoline, quinazoline and quinoxaline,

With regard to their biological action, preference is given to compounds of the formula I in which X and Y each independently represent hydrogen, halogen or C ₁ -C ₄ -alkyl.

Compounds of the formula I in which X and Y each independently represent hydrogen or halogen are particularly preferred.

Compounds of the formula I in which X and Y are fluorine are very particularly preferred.

Equally preferred are compounds of the formula I in which

Z is hydrogen;

Cx-Cs alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, -C-C ₈ alkoxy, C_-C ₈ alkylthio means, these groups by one to five halogen atoms or C ₁ -C ₄ -alkoxy may be substituted; or stands for one of the following groups: OR ³

NR ⁴ R ⁵ ;

0

0 0 0 0

II

- S - R ³ ; - S - R ³ ; S NR R ⁵

Compounds of the formula I in which

Z represents one of the following groups:

0

R ³ ; - S - R ³ ; - S - NRR ⁵

Equally preferred are compounds of the formula I in which

R ⁱ , R ² hydrogen, halogen; or

C ₁ -C ₄ alkyl, C -C ₄ alkenyl, C ₂ -C ₄ alkynyl, where these groups can be substituted by one to five halogen atoms,

mean.

Compounds of the formula I in which

Rl is hydrogen, halogen or C ₁ -C ₄ alkyl, and

R ^{2 is} hydrogen, halogen; or

C1-C ₄ alkyl, which can be substituted by one to five halogen atoms, mean.

Compounds of the formula I in which

R ¹ for hydrogen and

R represents methyl or ethyl.

Equally preferred are compounds of the formula I in which

R3 Cχ-C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ alkyl carbonyl, these groups being substituted by one to eight halogen or by C ₁ -C ₄ - Alkoxy may be substituted; C ₃ -C cycloalkyl, which can be substituted by one to eight halo atoms, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl or C_-C ₄ haloalkyl;

Aryl, which can be substituted by C ₁ -C ₄ alkyl, C_-C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, haloagen,

means.

Compounds of the formula I in which

R -CC ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ alkylcarbonyl, where these groups can be substituted by one to eight halogen; or

C ₃ -C _. Cycloalkyl, which can be substituted by one to eight halogen atoms, C ₁ -C ₄ -alkyl or C_-C ₄ -haloalkyl,

means.

Equally preferred are compounds of the formula I in which

R ⁴ , R ^{5 are} hydrogen; -C-C ₆ alkyl, C ₂ -C ₆ alkenyl, C -C ₆ "alkynyl, where these groups can be substituted by one to four halogen or by C ₁ -C ₄ alkoxy;

Aryl which can be substituted by C ₁ -C 4 -alkyl, C ₁ -C ₄ -alkoxy, Ci-haloalkyl, C ₁ -C ₄ -haloalkoxy or halogen,

mean or

R ⁴ , R ⁵ together form a 3- to 7-membered heterocycle which can carry a further hetero atom of N, 0 or S, can contain a double bond and with one to four C_-C ₄ -alkyl, Cι-C ₄ - Haloalkyl, -C-C ₄ alkoxy, C_-C ₄ halo alkoxy, halogen, nitro or cyano groups can be substituted.

Compounds of the formula I in which

R ⁴ , R ^{5 are} hydrogen or C_-C ₆ alkyl, which can be substituted by one to four halogen,

mean or

R, R ⁵ together form a 3- to 7-membered heterocycle which can carry a further heteroatom from N, 0 or S, can contain a double bond and can be substituted by C_-C ₄ -alkyl.

Equally preferred are compounds of the formula I in which

R ^{6 is} hydrogen;

C_-C ₆ alkyl, C ₂ -C ₆ alkenyl, where these groups can be substituted by one to four halogen or by alkoxy;

C ₃ -C cycloalkyl, which can be substituted by one to four halogen or C_-C ₄ alkyl, C_-C ₄ haloalkyl, C ₁ -C ₄ alkoxy, haloalkoxy; Aryl, hetaryl, these groups being substituted by C ₁ -C ₄ alkyl,

C_-C ₄ -haloalkyl, Cι-C ₄ -alkoxy, C_-C_ -haloalkoxy, halogen, nitro or cyano may be substituted,

means.

Equally preferred are compounds of the formula I in which

n means 1.

Also preferred are compounds of formula I in which

n means 2.

Equally preferred are compounds of the formula I in which

m means 0.

Also preferred are compounds of formula I in which

m means 1. Preference is furthermore given to compounds of the formula I in which

m 2 means.

Preference is also given to compounds of the formula I in which the thiazo limine substituent is linked to the benzene ring ortho to one of the oxygen atoms of the heterocycle.

Equally preferred are compounds of the formula I in which the thiazolimine substituent is meta to one and para to the other

Oxygen atom of the heterocycle is linked to the benzene ring.

Equally preferred are compounds of the formula I in which the substituents have the following meaning:

X, Y independently of one another are hydrogen, halogen or C 1 -C ₄ -alkyl;

Z is hydrogen; C ₁ -C ₈ -alkyl, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ -alkynyl, C_-C ₈ -alkoxy,

C ₁ -C ₈ -alkylthio, where these groups can be substituted by one to five halogen or C ₁ -C ₄ -alkoxy, or one of the following groups:

0

0 0 0 0

II

- s— - R ³ ; - S - R ³ ; x Ss NR R ⁵

R, R ^{2 are} hydrogen, halogen; or

C ₁ -C ₄ alkyl, C ₂ -C alkenyl, C ₂ -C ₄ alkynyl, where these groups can be substituted by one to five halogen atoms; R ³ Cι - C ₈ alkyl, C ₂ - C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ alkyl - carbonyl, these groups being substituted by one to eight halogen or by C ₁ -C ₄ -Alkoxy can be substituted; C ₃ -C ₇ cycloalkyl, ₄ alkyl or Cι-C ₄ haloalkyl may be substituted by one to eight halogen atoms, C ₁ -C ₄ alkoxy, C ₁ -C;

Aryl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -haloalkoxy or halogen may be substituted by Cι-C alkyl, C_-C ₄ haloalkyl;

R ⁴ , R ^{5 are} hydrogen;

-C-C ₆ alkyl, C -C ₆ alkenyl, C ₂ -C ₆ alkynyl, these

Groups by one to four halogen or by

C ₁ -C ₄ alkoxy may be substituted;

Aryl which can be substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C_-C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy or halogen;

R ⁴ , R ⁵ together form a 3- to 7-membered heterocycle, which can carry a further heteroatom from N, 0 or S, can contain a double bond and with C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C1 -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, halogen, nitro or cyano groups;

R ^{6 is} hydrogen; Ci-Cβ-alkyl or C ₂ -C ₆ alkenyl, where these groups can be substituted by one to four halogen or by alkoxy;

C ₃ -C ₇ cycloalkyl, which can be substituted by one to four halogen atoms, C ₁ -C alkyl, C_-C ₄ haloalkyl, C_-C ₄ alkoxy or haloalkoxy;

Aryl or hetaryl, where these groups can be substituted by C_-C ₄ -alkyl, -C-C ₄ -haloalkyl, -C-C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy, halogen, nitro or cyano;

n 1 or 2;

m 0, 1 or 2.

Compounds of the formula I in which the substituents have the following meanings are particularly preferred:

X, Y independently of one another are hydrogen or halogen;

Z one of the following groups:

0

0 0 0 0

- _s II— - R ³ ; - s - R ³ ; x Ss NR R ⁵

R ^{1 is} hydrogen, halogen or C_ -C alkyl;

R ^{2 is} hydrogen, halogen; or

C ₁ -C alkyl, which can be substituted by one to five halogen atoms;

R ^{3 is} C_-C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl or

C ₂ -C ₈ alkylcarbonyl, where these groups can be substituted by one to eight halogen; C ₃ -C cycloalkyl, which may be substituted by one to eight halogen atoms, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

R ⁴ , R ^{5 are} hydrogen;

-CC ₆ alkyl, which can be substituted by one to four halogen atoms, or

R ⁴ , R ⁵ together form a 3- to 7-membered heterocycle which can carry a further heteroatom from N, 0 or S, can contain a double bond and can be substituted by C ₁ -C ₄ alkyl;

n 1 or 2;

m 0.

Compounds of the formula I in which the substituents have the following meanings are very particularly preferred:

X, Y fluorine;

Z one of the following groups:

Rl hydrogen f;

R ^{2 is} methyl or ethyl;

R ³ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ alkylcarbonyl, where these groups can be substituted by one to eight halogen;

C ₃ -C cycloalkyl, which can be substituted by one to eight halogen atoms, C ₁ -C ₄ alkyl or -C-C ₄ haloalkyl;

R ⁴ , R ^{5 are} hydrogen;

C_-C ₆ alkyl, which can be substituted by one to four halogen atoms, or

R, R ⁵ together form a 3- to 7-membered heterocycle which can carry a further heteroatom from N, 0 or S, can contain a double bond and can be substituted by C ₁ -C alkyl;

n 1 or 2;

m 0.

Compounds of the formula I in which the substituents are selected from a combination of the preferred substituents listed above are also preferred.

In particular, in view of their use, the compounds I of the formulas I.1-1.12 listed in the following tables are preferred. Table 1: Compounds 1.1-1.258 compounds of the general formula 1.1,

in which R ^{1 is} water, R ^{2 is} methyl and the substituent Z corresponds to one row of Table A for each individual compound.

Table 2: Compounds 2.1-2.258 compounds of the general formula 1.2,

in which R ^{1 is} hydrogen, R ^{2 is} methyl and the substituent Z corresponds to one row of Table A for each individual compound.

Table 3: Compounds 3.1-3.258 compounds of the general formula 1.3,

Table 4: Connections 4.1-4.258

Compounds of the general formula 1.3 in which R ^{1 is} hydrogen, R ^{2 is} ethyl and the substituent Z corresponds to one row of Table A for each individual compound.

Table 5: Connections 5.1-5.258

Compounds of the general formula 1.4,

in which Ri is hydrogen, R ^{2 is} methyl and the substituent Z corresponds to one row of Table A for each individual compound.

Table 6: Connections 6.1-6.258

Compounds of the general formula 1.5,

Z

in which R ^{i is} hydrogen, R ^{2 is} methyl and the substituent Z corresponds to one row of Table A for each individual compound. Table 7: Compounds 7.1-7.258 compounds of the general formula 1.6,

in which R ^{i is} hydrogen, R ^{2 is} methyl and the substituent Z corresponds to one row of Table A for each individual compound.

Table 8: Connections 8.1-8.258

Compounds of the general formula 1.6 in which R ^{1 is} hydrogen, R ^{2 is} ethyl and the substituent Z corresponds to one row of Table A for each individual compound.

Table 9: Compounds 9.1-9.258 compounds of the general formula 1.7,

Table 10: Compounds 10.1-10.258 compounds of the general formula 1.8,

Table 11: Compounds 11.1-11.258 compounds of the general formula 1.9,

Table 12: Compounds 12.1-12.258 compounds of the general formula 1.10,

Z

in which R ^{i is} hydrogen, R ^{2 is} methyl and the substituent Z corresponds to one row of Table A for each individual compound. Table 13: Connections 13.01-13.258

Compounds of the general formula 1.3 in which R ^{1 is} hydrogen, R ^{2 is} vinyl and the substituent Z corresponds to one row of the table for each individual compound.

Table 14: Compounds 14.1-14.258

Compounds of the general formula 1.6, in which R ^{i is} hydrogen, R ^{2 is} vinyl and the substituent Z corresponds to one row of the table for each individual compound.

Table 15: Connections 15.1-15.258

Compounds of the general formula 1.8 in which R is hydrogen, R ^{2 is} vinyl and the substituent Z corresponds to one row of the table for each individual compound.

Table 16: Connections 16.1-16.258

Compounds of the general formula 1.10 in which R is hydrogen, R ^{2 is} vinyl and the substituent Z corresponds to one row of the table for each individual compound.

Table A:

No.

177, 0

<\

178. 0

Me

179,

Et

180,

Ph

181.

S CF ₃

182 O

CC1 ₃

183,

SC ₂ F ₅

184,

CH ₃

185.

CF ₃

186,

CHF ₂

187.

Et

188.

^" C ₂ F ₅

189,

Ph No.

190.

o- Ph

191.

192,

193,

0 CH ₃

194,

0 CF ₃

195.

0 C ₂ F ₅

196,

^■ 0 CH ₂ - CF ₃

197,

^' 0 CH ₂ "CH ₂ F

198,

0 CH ₂ CHF ₂

199,

200.

201.

No.

202.

CF ₃ o-

203,

0 'CF ₂ CF ₃

204,

Me

N

Me

205,

Et

N

Et

206, S CH ₃ CH ₃

N CH ₃

<CH ₃

207,

Ph

N

Ph

208.

N 0

209,

.Cl

N

^' Cl

210.

S Me

211,

S CF ₃

212.

S Ph

Manufacturing examples

1. To a solution of 120 g (0.67 mol) of 4-amino-2,2-difluoro-benzo-1,3-dioxole in 150 ml of toluene, 53.3 g of an 80% solution are obtained at 20-25 ° C Solution of propargyl bromide in toluene (6th

0.36 mol of propargyl bromide) was added dropwise. After 2 hours at 80 ° C., the reaction mixture is cooled to room temperature and the precipitate is filtered off with suction and washed with n-hexane. The filtrate is concentrated in vacuo and the residue is purified over silica gel with cyclohexane / ethyl acetate mixtures and then crystallized from pentane. This gives 33.2 g (44% of theory) of N-proparyl-4-amino-2, 2, difluorobenzo-1, 3-dioxole, mp: 66-68 ° C.

NMR: (CDC1 ₃ ): 2.25 (t, 1H); 3.9 (2 * s, 3H); 6.30 (dd, 1H);

6.50 (d, 1H); 6.85 (d, 1H)

2. 8.75 g of acetyl chloride (0.087 mol) are dissolved in 150 ml of abs. Dissolved acetonitrile and mixed with 8.75 g (0.09 mol) of potassium rhodanide at 0 ° C. After 6 hours at 0 ° C., 18.3 g of N-propyl-4-amino-2,2-difluorobenzo-1,3-dioxole (0.087 mol) in 20 ml of CH ₃ CN are added dropwise. After the addition, the mixture is stirred at room temperature for 16 hours. The solvent is then concentrated in vacuo and the residue is washed with ethyl acetate. The organic phases are washed 3 times with water and 1 time with saturated NaCl solution and then dried over Na ₂ S0 ₄ . The residue obtained after evaporation of the solvent is concentrated at 0 ° C to 61 ml. Added sulfuric acid and stirred for 30 min at 0 ° C and 1 hour at 20 ° C. The solution is then poured onto ice water and neutralized with 50% sodium hydroxide solution at 20-25 ° C. The aqueous phase is then extracted 3 times with methylene chloride and the combined organic phases are washed 2 times with water and 1 time with saturated NaCl solution. After the solvent has been dried and evaporated, the residue is recrystallized from diethyl ether.

This gives 11.4 g of 4- (N '-acetyl-2' -imino-5 '-methylthiazol-3-yl) -2,2-difluorobenzo-1,3-dioxole (0.036 mol; 42 % of theory), mp .: = 203-205 ° C.

ⁱ H NMR: CDC1 ₃ : 2.22 (s, 3H); 2.30 (s, 3H); 6.65 (s, 1H); 7.18 (m. 2H); 7.30 (s, 1H)

3. 21.5 g (0.069 mol) of 4- (N '-acetyl-2' -imino-5 '-methylthiazol-3-yl) -2, 2-difluorobenzo-1,3-dioxole are added in 111 ml Dissolved ethanol and 111 ml of water and with 22.1 ml of conc. Salt- acid added. The reaction mixture is heated under reflux for 3 hours and then concentrated to dryness. The solid is taken up twice in methylene chloride and isolated again.

This gives 21.2 g of 4- (2'-imino-5 '-methylthiazol-3-yl) -2, 2-difluorobenzo-1,3-dioxolohydrochloride (100% of theory), mp .:> 220 ° C decomposition.

H (DMSO): 2.25 (s, 3H); 7.25 (s. 1H); 7.50 (d. 1H);

7.72 (d. 1H); 7.90 (s, 1H); 9.70 (s, br.2H)

4. Active ingredients

a) 1.2 g of 4- (2'-imino-5 '-methyl-thiazole -3 -yl) -2, 2-difluoro-benzo-1, 3-dioxole hydrochloride are dissolved in 40 ml of ethyl acetate and 1.2 g of triethylamine (0.0119 mol) and then 0.47 g of isopropenyl chloroformate (0.0039 mol) were added at 0 ° C. The reaction mixture is stirred at 20-25 ° C for 16 hours. A further 150 ml of ethyl acetate are then added, the precipitate which has separated out is filtered off with suction and the filtrate is washed 3 times with water and 1 time with saturated NaCl solution. After the organic phase has dried, the solvent is evaporated off in vacuo and the residue is purified by column chromatography on silica gel using cyclohexane / ethyl acetate mixtures as the eluent.

This gives 0.75 g of 4- (N '-isopropenyloxycarbonyl-2' -imino-5-methylthiazol-3-yl) -2, 2 -difluorobenzo-1,3-dioxole (54% of theory . Th.), Mp .: 82-84 ° C.

b) 1.2 g of 4- (2'-imino-5 '-methylthiazole -3 -yl) -2, 2-difluorobenzo-l, 3-dioxole hydrochloride (0.0039 mol) are added in 40 ml of ethyl acetate dissolved and first with 1.2 g of triethylamine (0.0119 mol) and then with 0.85 g of diethyl. butyl dicarbonate (0.0039 mol) at 0 ° C. The mixture is then stirred for 3 hours at 20-25 ° C. and the reaction mixture is then mixed with 150 ml of ethyl acetate. The precipitate which has separated out is filtered off with suction and the filtrate is washed 3 times with water and 1 time with saturated NaCl solution. After drying the org. Phase, the solvent is evaporated in vacuo and the residue is purified by column chromatography on silica gel using cyclohexane / ethyl acetate mixtures.

This gives 0.95 g of 4- (N'-tert. -Butyloxycarbonyl-2'-imino-5 '-methylthiazole -3 -yl) -2, 2-difluorobenzo-1,3-dioxole (66% of theory), oil.

NMR: CDC1 ₃ : 1.50 (s, 9H); 2.25 (s, 3H); 6.65 (s, 1H); 7.12 (m; 2H); 7.32 (s, 1H)

CH ₃

0 ^C 0.8 g of 4- (2'-imino-5 '-methylthiazol-3-yl) -2,2-difluoro-benzo-1,3-dioxole hydrochloride are dissolved in 30 ml of chloroform and mixed with 4 , 1 g (0.04 mol) of triethylamine, 1.4 g of N-ethyl-N '- (3-dimethylaminopropyl) carbodiimide hydrochloride (0.0074 mol) and 3.0 g of 3-nitrobenzoic acid were added. The reaction mixture is then boiled under reflux for 5 hours. After cooling, it is washed with dilute hydrochloric acid and dilute potassium carbonate solution and the organic phase is dried. After removing the solvent in vacuo, the crude product is purified by column chromatography on silica gel using cyclohexane / ethyl acetate mixtures.

0.7 g of 4- [N '- (3 "-nitrobenzoyl) -2' -imino-5 'methylthiazol-3-yl] -2,2-difluorobenzo-1,3-dioxole (64% d.Th.), m.p .: 211-213 ° C

d) 1.0 g of 4- (2'-imino-5 '-methylthiazole -3 -yl) -2, 2-difluoro-benzo-1, 3-dioxole hydrochloride (0.0033 mol) are in

40 ml of tetrahydrofuran dissolved and 1.0 g of triethylamine (0.01 mol) and 0.62 g of phenylchlorodithioformate (0.0033 mol) were added. The reaction mixture is then stirred at 20-25 ° C. for 16 hours, evaporated, taken up in 100 ml of ethyl acetate and 3 times with water and

Washed once with saturated NaCl solution. After drying the organic phase and removing the solvent in vacuo, the crude product is purified by column chromatography on silica gel using cyclohexane / ethyl acetate mixtures.

This gives 0.42 g of 4- (N '-phenyldithioformyl-2' -imino-5 '-methylthiazol-3-yl) -2, 2 -difluorobenzo-l, 3-dioxole (30% d.Th.), oil

NMR: CDC1 ₃ : 2.30 (s, 3H); 6.85 (m. 3H); 7.15 (m. 2H); 7.25 (m, 3H)

e) 1.5 g of 4- (2'-imino-5 '-methyl-thiazol-3-yl) -2, 2-difluoro-benzo-1, 3-dioxole hydrochloride (0.005 mol) are in 90 ml of methylene chloride dissolved and with 0.94 g of thiophosphoric acid diethyl ester chloride (0.005 mol) and 1.01 g of triethylamine

(0.01 mol) was added. The reaction mixture is stirred for 3 hours at 20-25 ° C. and then shaken out with dilute hydrochloric acid. The organic phase is then washed 3 times with water and 1 time with saturated NaCl solution. After drying the organic phase over Na ₂ SÜ ₄ , the solvent is evaporated in vacuo and the The residue was purified by column chromatography on silica gel using cyclohexane / ethyl acetate mixtures.

This gives 1.0 g of 4 - [(N '-diethoxythiophosphoric acid amido) -2' -imino-5 '-methylthiazole -3 -yl] -2,2 -difluorobenzo-l, 3-dioxole ( 47% of theory), mp: 90-92 ° C.

1.0 g of 4- (2'-imino-5 '-methyl-thiazol-3 -yl) -2, 2 -difluoro-benzo-1, 3 -dioxole-hydrochloride (0.0033 mol) are in 40 ml of ethyl acetate dissolved and at 0 ° C with 1.0 g of triethylamine (0.01 mol) and 0.95 g of trifluoromethanesulfonic anhydride (0.0033 mol). The mixture is then stirred at 20-25 ° C for 3 hours. The reaction mixture is then mixed with 150 ml of ethyl acetate and the precipitate which has separated out is filtered off with suction. The filtrate is washed 3 times with water and 1 time with saturated NaCl solution and then dried over Na ₂ S0 _4. After removing the solvent in vacuo, the residue is purified by column chromatography on silica gel using cyclohexane / ethyl acetate mixtures.

This gives 1.1 g of 4- (N '-trifluoromethylsulfonyl-2' -imino-5 '-methylthiazole -3 -yl) -2, 2-difluorobenzo-1,3-dioxole (83% d.Th.), mp: 124-135 ° C.

Table 17: Compounds synthesized

The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.

Depending on the particular application method, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoealumisisumisum , Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium prate nse, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.

The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are, if possible not be hit while the active ingredients get on the leaves of unwanted plants growing underneath or the uncovered floor area (post-directed, lay-by).

The compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules , Atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The following are essentially considered as inert additives:

Mineral oil fractions from medium to high boiling point, such as kerosene or diesel oil, also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the thiazolimine derivatives, or those dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.

The surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenyl glycolphenyl, alkylphen - aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene xid condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite waste liquors or methyl cellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. The formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The compounds I according to the invention can be formulated, for example, as follows:

I 20 parts by weight of compound no. 13.13 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzene sulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

II 20 parts by weight of compound no. 13.13 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide There is 1 mole of castor oil. Through a- pour and finely distribute the solution in 100,000

Parts by weight of water give an aqueous dispersion which contains 0.02% by weight of the active ingredient.

III 20 parts by weight of active ingredient no. 13.13 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring and finely distributing the solution in

100,000 parts by weight of water are obtained in an aqueous dispersion which contains 0.02% by weight of the active ingredient.

IV 20 parts by weight of active ingredient no. 13.13 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

V 3 parts by weight of active ingredient no. 13.13 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of the active ingredient.

VI 20 parts by weight of active ingredient No. 13.13 are mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid,

8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

VII 1 part by weight of compound 13.13 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII 1 part by weight of compound 13.13 is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (non-ionic Emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained.

To broaden the spectrum of activity and to achieve synergistic effects, the thiazolimine derivatives can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, 1,2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2-aroyl come as mixing partners -l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinoline carboxylic acids and their derivatives, chloroacetanilides, cyclohexane-1, 3-dione derivatives, diazines, dichloropropionic acid and their derivatives,

Dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3, 4, 5, 6-tetrahydropholeimides, oxadiazane oxiroxanes , Phenols, aryloxy or heteroaryloxyphenoxypropionic acid esters,

Phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and their derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils.

It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

Depending on the control target, the season, the target plants and the growth stage, the active compound application rates are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (see also) Examples of use

The herbicidal activity of the thiazolimine derivatives formula I was demonstrated by greenhouse experiments.

Plastic pots with loamy sand with about 3.0% humus served as the culture vessels. The seeds of the test plants were sown separately according to species.

In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients. The application rate for the pre-emergence treatment was 0.5 or 0.25 kg / ha a. S.

For the purpose of post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the growth habit, and then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.

The plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.

Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.

The plants used in the greenhouse experiments are composed of the following types:

Table 14

Selective herbicidal activity when pre-emergence in a greenhouse

Table 15

Selective herbicidal activity when pre-emergence in a greenhouse

Claims

claims

1. thiazolimine derivatives of the formula I o

5 in which the substituents have the following meaning:

X, Y independently of one another hydrogen, halogen, C_-C-alkyl, -C-C ₄ haloalkyl;

0 Z hydrogen;

-C-C ₈ alkyl, C ₂ -C ₈ alkenyl, C -C ₈ alkynyl, Ci-Cβ-alkoxy, Ci-Cβ-alkylthio, these groups by one to five halogen or C ₁ -C ₄ alkoxy can be substituted; Aryl, hetaryl, benzyl, these groups with

Cι-C ₄ -alkyl, C -alkoxy, C haloalkyl, C ₁ -C ₄ -haloalkoxy, halogen, nitro or cyano groups; or one of the following groups:

0

0 0 0 0

II

- S - R ³ ; - S - R ³ ; - S - NR R ⁵

Ri, R ^{2 is} hydrogen, halogen;

C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C alkynyl, these groups being substituted by one to five halogen or by

C ₁ -C ₄ alkoxy may be substituted;

R ^{3 is} hydrogen;

-CC ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C -C ₈ alkylcarbonyl, C ₃ -C ₈ alkenylcarbonyl,

C ₃ -C ₈ alkynylcarbonyl, where these groups can be substituted by one to eight halogen or by C ₁ -C ₄ alkoxy; C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkenyl, these groups being represented by one to eight halogen atoms,

C_-C alkoxy, -C-C ₄ alkyl or C_-C ₄ haloalkyl may be substituted;

Aryl, hetaryl, benzyl, where these groups with Cι-C ₄ -alkyl, C ₄ haloalkyl, C_-C ₄ alkoxy, C ₁ -C ₄ -haloalkoxy, halogen, cyano, or nitro;

R ⁴ , R ^{5 are} hydrogen;

Ci-Cg-alkyl, C -C ₆ alkenyl, C ₂ -C ₆ "alkynyl, where these groups can be substituted by one to four halogen or by -C-C ₄ alkoxy; C ₃ -C cycloalkyl, C ₃ - C -cycloalkenyl, the alkyl substituted by one to four halogen or C ₁ -C ₄ -alkyl, C ₄ -Halo-, Cι-C ₄ alkoxy, C ₁ -C ₄ haloalkoxy groups;

Aryl, hetaryl, these groups being separated by C_-C ₄ -alkyl, C ₁ -C ₄ alkoxy, C_-C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, halogen, nitro- or cyano may be substituted;

R ⁴ , R ⁵ together form a 3- to 7-membered heterocycle which can carry a further heteroatom from N, 0 or S, can contain at least one double bond and with C ₁ -C ₄ alkyl, C ₁ -C ₄ - Haloalkyl, C_-C ₄ alkoxy, -C-C ₄ haloalkoxy, halogen, nitro or cyano groups can be substituted;

R ^{6 is} hydrogen;

C_-C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, where these groups can be substituted by one to four halogen or by alkoxy; C ₃ -C cycloalkyl, C ₃ -C ₇ cycloalkenyl, which can be substituted by one to four halogen atoms or by C ₁ -C ₄ alkyl, C_-C ₄ haloalkyl, C_-C alkoxy, haloalkoxy; Aryl, hetaryl, where these groups can be substituted by C_-C ₄ -alkyl -C-C -haloalkyl, -C-C ₄ -alkoxy, Cι-C ₄ -haloalkoxy, halogen, nitro or cyano;

n 1 or 2;

m 0, 1 or 2

as well as agriculturally useful salts of the compounds I.

2. thiazolimine derivatives of the formula I according to claim 1, in which X and Y each independently of one another are hydrogen, halogen or C ₁ -C ₄ -alkyl.

3. thiazolimine derivatives of the formula I according to claim 1 or 2, in which n = 1.

4. thiazole imines of formula I according to any one of claims 1 to 4, in which n = 2.

5. thiazolimine derivatives of the formula I according to one of claims 1 to 4, in the thiazolimine substituent ortho to one of the

Oxygen atoms of the heterocycle are attached to the benzene ring.

6. thiazolimine derivatives of the formula I according to one of claims 1 to 4, in which the thiazolimine substituent is linked meta to the one and para to the other oxygen atom of the heterocycle with the benzene ring.

5

7. thiazolimine derivatives of the formula I according to one of claims 1 to 6, in which m = 0.

8. thiazolimine derivatives of the formula I according to any one of claims 1 10 to 6, in which m = 1.

9. thiazolimine derivatives of the formula I according to one of claims 1 to 6, in which m = 2.

10. A process for the preparation of the thiazolimine derivatives of the formula I as claimed in claim 1, characterized in that anilines of the formula II are reacted with propargyl derivatives of the formula III,

R ^l

IV 5 where LG stands for a nucleophilically exchangeable leaving group and the substituent R ^{7 has the} following meaning:

R ^{7 is} hydrogen, halogen;

-C-C ₃ alkyl, C ₂ -C ₃ alkenyl, C ₂ -C ₃ alkynyl, these 0 groups by one to five halogen or by

C ₁ -C ₄ alkoxy may be substituted;

the resulting aniline derivative of the formula IV is reacted with KSCN and acetyl chloride and converted with a base or acid into the 5 N-acetyl-thiazolimine derivatives of the formula VIII,

IV

which are converted into their salts by acid, which are then reacted with the compounds of the formula X to give the thiazolimine derivatives of the formula I,

acid

Rl R2

N

IX ^" S.

H . salt

where LG stands for a nucleophilically exchangeable leaving group.

11. Herbicidal composition containing a herbicidally effective amount of at least one compound of the formula I according to claim 1 and at least one inert liquid and / or solid carrier and, if desired, at least one adjuvant.

12. A method for controlling undesirable plant growth, characterized in that a herbicidally effective amount of a compound of the formula I according to claim 1 is allowed to act on the plants, their habitat or their seeds.

13. Use of a compound of general formula I according to

Claim 1 as a herbicide.