EP1286968A2

EP1286968A2 - Substituted iminoazines

Info

Publication number: EP1286968A2
Application number: EP01936338A
Authority: EP
Inventors: Klaus-Helmut Müller; Mark Wilhelm Drewes; Peter Dahmen; Dieter Feucht; Rolf Pontzen
Original assignee: Bayer AG
Current assignee: Bayer CropScience AG
Priority date: 2000-05-19
Filing date: 2001-05-08
Publication date: 2003-03-05
Also published as: RU2265596C9; DE10024938A1; UA73173C2; PL363841A1; WO2001090071A3; JP2004525067A; AU2001262271B2; AU6227101A; CN1227234C; KR20030016252A; RU2265596C2; US7329757B2; BR0110824A; AR028393A1; CA2409142A1; US20040029881A1; CN1430608A; US20060122062A1; WO2001090071A2; US7186834B2

Abstract

The invention relates to novel substituted iminoazines of general formula (I), in which R<1>, R<2>, R<3>, R<4>, Z<1>, Z<2> and Z<3> are defined as cited in the description. The invention also relates to several methods and intermediate compounds for producing said substituted iminoazines and to their use as herbicides.

Description

Substituted iminoazines

The invention relates to new substituted iminoazines, processes for their preparation and their use as plant treatment agents, in particular as herbicides.

It is known that certain substituted iminopyridines have herbicidal properties (cf. EP-A-432 600). However, the effectiveness of these compounds is not satisfactory in all respects.

The new substituted iminoazines of the general formula (I)

in which

R for nitro, cyano, or one of the groupings -R, -CQ -Q -R,

-NH-CQ -QR ⁵ , or -SO ₂ -R ⁶ ,

R ^{2 represents} nitro, cyano, SF ₅ , halogen or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfmyl, alkylsulfonyl or alkylsulfonyloxy,

R ^{3 represents} hydrogen or halogen, or together with R ^{2 represents} optionally substituted alkylenedioxy,

R ^{4 represents} hydrogen, cyano, carboxy, carbamoyl, halogen or optionally substituted alkyl, Q ^{1 represents} O (oxygen), S (sulfur) or NR ⁵ ,

Q ^{2 represents} a single bond or O (oxygen), S (sulfur) or NR ⁵ ,

R ^{5 represents} hydrogen, amino or optionally substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylideneamino, alkenyl, alkenyloxy, alkynyl, cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl, arylamino, arylalkyl, heterocyclyl or heterocyclylalkyl,

R ^{6 represents} in each case optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,

Z ^{1 represents} N (nitrogen) or CR ⁴ ,

Z ^{2 represents} N (nitrogen) or CR ⁴ , and

Z ^{3 represents} N (nitrogen) or CR ⁴ ,

found.

In the definitions, the hydrocarbon chains, such as alkyl, alkenyl or alkynyl - also in connection with heteroatoms, such as in alkylamino - are in each case straight-chain or branched. R ³ is preferably in the meta or para position on the phenyl ring.

Preferred substituents or preferred ranges of the radicals present in the formulas listed above and below are defined below.

R ¹ preferably represents cyano or one of the groupings -R ⁵ , -CQ'-Q ^ -R, -NH-CO -QR ⁵ , or -SO ₂ -R ⁶ . R ² preferably represents nitro, cyano, SF ₅ , halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylsulfonyloxy each having 1 to 5 carbon atoms in each case substituted by cyano, halogen or dC ₄ -alkoxy.

R preferably represents hydrogen or halogen, or together with R represents halogen-substituted alkylenedioxy having 1 to 3 carbon atoms.

R ⁴ preferably represents hydrogen, cyano, carboxy, carbamoyl, halogen or alkyl having 1 to 5 carbon atoms which is optionally substituted by cyano, halogen or C 1 -C ₄ -alkoxy.

Q ¹ preferably represents O (oxygen) or S (sulfur).

R ⁵ preferably represents hydrogen or amino, alkyl or alkoxy each optionally substituted by cyano, halogen or dC ₄ -alkoxy, each having 1 to 6 carbon atoms, alkylamino having 1 to 6 carbon atoms, dialkylamino each having 1 to 6 carbon atoms in the Alkyl groups, for alkylidene amino with up to 6 carbon atoms, for each alkenyl optionally substituted by cyano or halogen, alkenyloxy or alkynyl each with 2 to 6 carbon atoms, for cycloalkyl, cycloalkylamino or cycloalkylalkyl optionally substituted by cyano, halogen or C 1 -C ₄ -alkyl each with 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, for each optionally by nitro, cyano, phenyl, phenoxy, phenylthio, halogen, C ₁ -C 4 -alkyl, C ₁ -C ₄ -haloalkyl , C ₁ -C - Alkoxy, Ci-C -haloalkoxy, -C-C ₄ - alkylthio, C ₁ -C ₄ -haloalkylthio, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ -Halogenalkylsulfmyl, Cι-C ₄ - alkylsulphonyl, C ₁ -C ₄ haloalkylsulfonyl or di- (C ₁ -C ₄ alkyl) amino-sulfonyl substituted aryl, arylamino or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, or for each optionally by nitro, cyano, phenyl, phenoxy, phenylthio, halogen, C ₁ -C 4 -alkyl, C ₁ -C ₄ -haloalkyl, C1 _. -C ₄ - alkoxy, C ₁ -C ₄ haloalkoxy, -C-C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfmyl, C ₁ -C ₄ haloalkylsulfinyl, Ci-C - alkylsulfonyl .

C ₁ -C ₄ haloalkylsulfonyl or di (C ₁ -C ₄ alkyl) aminosulfonyl substituted, monocyclic or bicyclic heterocyclyl or heterocyclylalkyl each having up to 10 carbon atoms and up to 4 nitrogen atoms and / or 1 or 2 oxygen or sulfur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl part.

preferably represents alkyl optionally substituted by halogen with 1 to 6 carbon atoms, alkenyl optionally substituted by halogen with 2 to 6 carbon atoms, cycloalkyl or cycloalkylalkyl optionally substituted by halogen or -CC-alkyl, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, represents in each case optionally substituted by nitro, cyano, halo, Cι-C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - haloalkoxy, C1 -C4- alkylthio, C ₁ -C ₄ -haloalkylthio, C ₁ -C ₄ -alkylsulfmyl, -C-C ₄ -haloalkylsulfinyl, Qd-alkylsulfonyl, C ₁ -C ₄ -haloalkylsulfonyl or di- (C ₁ - C ₄ -alkyl) -aminosulfonyl-substituted aryl or arylalkyl each having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, or for each optionally by nitro, cyano, halogen, QQ-alkyl, Cι _. -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ - alkylthio, C ₁ -C ₄ haloalkyl thio, C ₁ -C alkylsulfinyl, C ₁ - C -haloalkylsulfinyl, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C -haloalkylsulfonyl or di- (C ₁ -C -alkyl) -aminosulfonyl-substituted, monocyclic or bicyclic heterocyclyl or heterocyclylalkyl each having up to 10 carbon atoms and up to 4 nitrogen atoms and / or 1 or 2 oxygen or sulfur atoms in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl part. Z ¹ preferably represents CR ⁴ .

Z ² preferably represents CR ⁴ .

Z ³ preferably represents CR ⁴ .

R ² particularly preferably represents nitro, cyano, SF ₅ , fluorine, chlorine or bromine, or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy - or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, n- or i-propylsulfonyloxy.

R ³ particularly preferably represents hydrogen, fluorine, chlorine or bromine, or together with R represents methylene dioxy or ethylenedioxy which are optionally substituted by fluorine and / or chlorine.

R ⁴ particularly preferably represents hydrogen, cyano, carboxy, carbamoyl,

Fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy.

Q ¹ preferably represents O (oxygen).

R ⁵ particularly preferably represents hydrogen or amino, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methylamino, which are each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, Ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, for dimethylamino or diethylamino, for propylidenamino or butylidenamino, each optionally substituted by cyano, fluorine, chlorine and / or bromine - ized propenyl, butenyl, propynyl or butynyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, each optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl. Cyclobutylmethyl, Cyclopentylmethyl or Cyclohexy nethyl, for each optionally by nitro, cyano, phenyl, phenoxy, phenylthio, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Dichloromethyl, difluoromethyl, trichloromethyl, trifhiormethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difϊuormethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethyl-methyl-thio , Trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosulfonyl substituted phenyl, naphthyl, phenylamino, benzyl or phenylethyl, or for each against also by cyano, phenyl, phenoxy, phenylthio, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, Chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfonyl, ethyltrifluoromethylsulfonyl, ethyltrifluoromethylsulfonyl, ethyltrifluoromethylsulfonyl, ethyltrifluoromethylsulfonyl, ethyltrifluoromethylsulfonyl, methyltrifluoromethylsulfonyl Heterocyclyl or heterocyclylalkyl from the series furyl, tetrahydrofuryl, benzofuryl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzthiazolyl, pyridylmethyl, methyladylmethyl, methyladylmethyl, methyladylmethyl, methyladylmethyl

Pyrrolylmethyl, pyrazolylmethyl, oxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl.

particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine and / or chlorine, each optionally substituted by fluorine, chlorine and / or bromine Propenyl or butenyl, for each optionally by. Fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally with nitro, cyano, fluorine, chlorine, bromine, methyl , Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, Methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosulfonyl, optionally substituted phenyl or naphthyl, methyl, for chlorine, naphthyl, or for methyl Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- o i-propoxy, difluoromethoxy, trifluoromethoxy,

Methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosylfyl, benzyl, benzyl, pyrrolyl, benzol, benzol, benzol, benzol, benzol

Benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzthiazolyl, pyridinyl, quinolinyl, pyrimidinyl, furylmethyl, thienylmethyl, pyrrolylmethyl, pyrazolylmethyl, oxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyriminyl.

Z ¹ particularly preferably represents CH.

Z ² particularly preferably represents CH.

Z ³ particularly preferably represents CH. R very particularly preferably represents cyano, fluorine, chlorine or bromine, or methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy or ethylsulfonyloxy, each optionally substituted by fluorine, chlorine, methoxy or ethoxy ,

R ⁴ very particularly preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or methyl or ethyl optionally substituted by fluorine, chlorine, methoxy or ethoxy.

R ⁵ very particularly preferably represents hydrogen or amino, for methyl, ethyl, n- or i-propyl, methylamino, ethylamino, n- or i-propylamino, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy Dimethylamino, for propenyl, butenyl, propynyl or butinyl, each optionally substituted by fluorine, chlorine and / or bromine, for cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclopentylamino, cyclohexylamino, each optionally substituted by fluorine, chlorine, bromine, methyl or ethyl , Cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl , Trifluoromethylsulfonyl or dimethylaminosulfonyl substituted phenyl, phenylamino, benzyl or phenylethyl.

R ⁶ very particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine and / or chlorine, in each case optionally by fluorine, chlorine, bromine, Methyl or ethyl substituted cyclopropyl, cyclopentyl or cyclohexyl, or for optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, Trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosulfonyl substituted phenyl.

R ² most preferably represents trifluoromethyl.

R ⁴ most preferably represents methyl.

A very particularly preferred group are those compounds of the formula (I) in which

R ¹ for cyano or one of the groupings -CQ ^! -Q ² -R ⁵ or -SO ₂ -R ⁶ ,

R ^{2 represents} trifluoromethyl, difluoromethoxy or trifluoromethoxy,

R stands for hydrogen, fluorine or chlorine, or together with R — in the ortho position — stands for difluoromethylene dioxy or tetrafluoroethylene dioxy,

R ^{4 represents} hydrogen, fluorine, chlorine, bromine or methyl,

Q ^{1 represents} O (oxygen) or S (sulfur),

Q represents a single bond or O (oxygen), S (sulfur) or N-R,

R ⁵ for hydrogen, for each optionally by cyano, fluorine, chlorine,

Methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine, chlorine and / or bromine

Propenyl, butenyl, propynyl or butynyl, each for where appropriate Fluorine, chlorine or methyl substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopenthenethyl or cyclohexylmethyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfonyl, methylifluoromethylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, or dimethylaminosulfonyl substituted phenyl or benzyl,

R for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine and / or chlorine, for cyclopropyl, cyclopentyl or cyclohexyl, each optionally substituted by fluorine, chlorine or methyl , or for optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl,

Methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethyl or sulfylethylsulfonyl, trifluoromethylsulfonyl,

Z ¹ stands for CH,

Z ² stands for CH, and

stands for CH.

Those compounds of the formula (I) in which a combination of the meanings listed above as preferred are present according to the invention. According to the invention, particular preference is given to those compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.

According to the invention, the particular compounds of the

Formula (I) in which there is a combination of the meanings given above as being particularly preferred.

The general definitions of radicals listed above or those specified in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation.

These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.

The new substituted iminoazines of the general formula (I) have interesting biological properties. They are particularly characterized by their strong herbicidal activity.

The new substituted iminoazines of the general formula (I) are obtained if

(a) iminoazines of the general formula (II)

in which R, R, R, Z, Z and Z have the meanings given above,

- or acid adducts of rminoazines of the general formula (II), such as e.g. the hydrochloride -

with compounds of the general formula (Tfl)

X ^ R ¹ (in)

in which

R ^{1 has} the meaning given above,

X ^{1 represents} halogen, -SO ₂ CH ₃ , -O-CO-R ⁵ or -O-SO ₂ -R ⁶ and

R ⁵ and R ^{6 have} the meanings given above,

or with iso (thio) cyanates of the general formula (TV)

QC = NR ⁵ (IV)

in which

Q ¹ and R ^{5 have} the meanings given above,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

or if you

(b) Azinthions of the general formula (V) in which

R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meanings given above,

with compounds of the general formula (VI)

in which

R has the meaning given above and

M stands for a metal equivalent,

if appropriate in the presence of one or more diluents,

or if you

(c) chlorazinium compounds of the general formula (VII) in which

9 "A 1 ^

R, R, R, Z, Z and Z have the meanings given above, and

Y stands for Cl, PC1 ₄ , POCl ₄ or PC1 ₆ ,

with amino compounds of the general formula (VIII)

HzN-R ¹ (Vπi)

in which

R ^{1 has} the meaning given above,

or if you

(d) iminoazines of the general formula (II) in which

R> 2, τ R> 3, τ R> 4, Z ^ 1, Z ₇ 2, u_ndJ Z ₇ 3 have the meanings given above,

- or acid adducts of iminoazines of the general formula (II), such as e.g. the hydrochloride -

with nitric acid, optionally in the presence of a reaction auxiliary and / or diluent.

If, for example, 5-chloro-l- (3-cyano-phenyl) -2 (1H) -pyridinimine and acetyl chloride are used as starting materials, the course of the reaction in process (a) according to the invention can be outlined using the following formula:

If, for example, 1- (3-chlorophenyl) -5-ethyl-2 (1H) -pyridinethione and N-chlorobenzenesulfonamide sodium salt are used as starting materials, the course of the reaction in process (b) according to the invention can be outlined using the following formula :

If, for example, 1- (3-bromo-phenyl) -2-chloro-5-trifluoromethyl-pyridium chloride and dimethylhydrazine are used as starting materials, the course of the reaction in process (c) according to the invention can be outlined using the following formula:

If, for example, 5-bromo-1- (3-chlorodifluoromethyl-phenyl) -2 (1H) -pyridinimine and nitric acid are used as starting materials, the course of the reaction in process (d) according to the invention can be outlined using the following formula:

The iminos to be used as starting materials in processes (a) and (d) according to the invention for the preparation of compounds of the general formula (I) Azines are generally defined by the formula (IT). In the general formula (H)

9 4 1 9 "R, R, R, Z, Z and Z preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have been} specified.

The starting materials of the general formula (II) are not yet known from the literature; as new substances, they are also the subject of the present application.

You get the new iminoazines of the general formula (II) if you

(α) azinones of the general formula (IX)

in which

R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meaning given above,

in a first stage with chlorinating agents, e.g. Phosgene, diphosgene, oxalyl chloride, thionyl chloride, phosphorus (πi) chloride, phosphoryl chloride or

Phosphorus (V) chloride, optionally in the presence of reaction auxiliaries, such as e.g. N, N-dimethylformamide, and optionally in the presence of diluents such as e.g. 1,2-dichloroethane, reacted at temperatures between 0 ° C and 150 ° C (see the production examples)

and the chlorazinium compounds of the general formula (VII) obtained in this way in which

3 4 1 3

R, R, R, Z, Z and Z have the meanings given above, and

Y stands for Cl, PC, POC or PC1 ₆ ,

in a second stage with ammonia, optionally in the presence of a diluent, e.g. Methanol, and optionally in the presence of an acid acceptor, e.g. Sodium methylate, reacted at temperatures between 0 ° C and 80 ° C (see the production examples),

or if you

(β) substituted iminoazines of the general formula (Ia)

in which

R ² , R ³ , R ⁴ , R ⁶ , Z ¹ , Z ² and Z ^{3 have} the meanings given above, with a strong acid, such as sulfuric acid, which may be diluted with water, at temperatures between 0 ° C and 100 ° C (cf. the preparation examples).

Some of the starting materials of the general formula (IX) are known and / or can be prepared by processes known per se (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1900947, DE-A- 2362958, DE-A-2555411, see also the preparation examples).

The starting materials of the general formula (LXa)

in which

R ² , R ³ and R ^{4 have} the meaning given above,

are new compounds according to the present invention for the preparation of compounds of general formula (II).

In the general formula (IXa), R ² , R ³ and R ⁴ preferably have those

Meanings which have already been given above in connection with the description of the compounds of the general formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for R ² , R ³ and R ⁴ .

The starting materials of the general formula (IXa) are not yet known from the literature; as new substances, they are also the subject of the present application. The new compounds of the general formula (IXa) can be prepared by processes known per se (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A 19 00 947, DE-A 23 62 958, DE -A 25 55 411, see also the manufacturing examples).

Like the compounds of the general formula (LXa), the compounds of the general formula (IX) have interesting biological properties. In particular, they show a strong herbicidal action.

The substituted iminoazines of the general formula (Ia) are new compounds according to the invention; they are preferably produced by process (b) according to the invention.

The compounds to be used further as starting materials in process (a) according to the invention for the preparation of compounds of the general formula (I) are generally defined by the formulas (III) and (IV). In the general formulas (III) and (IV), R ¹ preferably has the meaning which has already been given as preferred, particularly preferred or very particularly preferred for R ¹ in connection with the description of the compounds of the general formula (I) according to the invention has been; X ¹ preferably represents fluorine, chlorine, bromine or the group -O-CO-R ¹ , in particular chlorine or bromine; Q ¹ preferably represents O or S.

The starting materials of the general formulas (III) and (IV) are known organic

Chemicals for synthesis.

Formula (V) provides a general definition of the azinthiones to be used as starting materials in process (b) according to the invention for the preparation of compounds of the general formula (I). In the general formula (V), R ² , R ³ , R ⁴ ,

Z ¹ , Z ² and Z ^{3 are} preferably those meanings which have already been described The description of the compounds of the general formula (I) according to the invention have been given as preferred, particularly preferred or very particularly preferred for R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ³ .

The starting materials of the general formula (V) are not yet known from the literature; as new substances, they are also the subject of the present application.

The new azinthiones of the general formula (V) are obtained if azinones of the general formula (IX)

in which

3 3

R, R, R, Z, Z and Z have the meanings given above,

with a sulfurizing agent, such as phosphorus (V) sulfide (P ₂ S ₅ or P ₄ S _K )), optionally in the presence of a reaction auxiliary, such as pyridine, at temperatures between 10 ° C and 150 ° C (cf. the manufacturing examples).

The starting materials of the general formula (IX) are known and / or can be prepared by processes known per se (cf. Chem. Pharm. Bull. 45 (1997), 719-721, DE-A-1900947, DE-A-2362958 , DE-A-2555411, see also the preparation examples).

The azinones of the general formula (IX) are obtained if azinones of the general formula (X) in which

R> 4, Z ryi, Z ryl, u, ndι Z r _j i 'have the meanings given above,

with halogen arenes of the general formula (XI)

in which

R2. u_nd R have the meanings given above and

X represents fluorine, chlorine, bromine or iodine,

optionally in the presence of a catalyst, e.g. Copper (I) iodide, optionally in the presence of an acid acceptor, e.g. Potassium carbonate, and optionally in the presence of a diluent, e.g. N, N-dimethyl-formamide, at temperatures between 20 ° C and 200 ° C (see. Preparation Examples).

The chlorazinium compounds to be used as starting materials in the process (c) according to the invention for the preparation of compounds of the general formula (I) are generally defined by the formula (VII). In the general formula (VII), R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ³ preferably have those meanings which have already been mentioned above in connection with the description of the invention Compounds of the general formula (I) have been indicated as preferred, particularly preferred or very particularly preferred for R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ³ .

The starting materials of the general formula (VII) are not yet known from the literature; as new substances, they are also the subject of the present application.

The new chlorazinium compounds of the general formula (VH) are obtained if azinones of the general formula (IX)

in which

R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meanings given above,

with chlorinating agents, e.g. Phosgene, diphosgene, oxalyl chloride, thionyl chloride, phosphorus (ιII) chloride, phosphoryl chloride or phosphorus (V) chloride, optionally in the presence of reaction aids such as e.g. N, N-dimethylformamide, and optionally in the presence of diluents, e.g. 1,2-dichloroethane, at temperatures between 0 ° C and 150 ° C (see the manufacturing examples).

Formula (VIII) provides a general definition of the amino compounds to be used as starting materials in process (c) according to the invention for the preparation of compounds of the general formula (I). In the general formula (VIII), R ¹ preferably has the meaning already given above in connection with the description of the compounds according to the invention of the general my formula (I) has been given as preferred, particularly preferred or very particularly preferred for R ¹ .

The starting materials of the general formula (VHI) are known synthetic chemicals.

Suitable reaction auxiliaries for processes (a) and (c) according to the invention are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogen carbonates, hydrides, hydroxides or

alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium , Sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium or potassium methoxide, ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or

t-butoxide; also basic organic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethylaniline, N, N- Dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2.0.0] octane (DABCO), 1,5-diazabicyclo [4.0.0] -non-5-ene (DBN), or 1.8 diazabicyclo [5.0.0] -undec-7-ene (DBU).

Phase transfer catalysts are also suitable as further reaction auxiliaries for processes (a) and (c) according to the invention. Examples of such catalysts are:

Tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetrabutylammonium hydrogen sulfate, methyl trioctylammonium chloride,

Hexadecyl-trimethylammonium chloride, hexadecyl-trimethylammonium bromide, Benzyl-trimethylammonium chloride, benzyl-triethylammonium chloride, benzyl-trimethylammonium hydroxide, benzyl-triethylammonium hydroxide, benzyl-tributylammonium chloride, benzyl-tributylammonium bromide, tetrabutylphosphonium bromide, tetrabutylphomide hexadecylphosphonium bromide, butyl triphenylphosphonium chloride, ethyl trioctylphosphonium bromide, tetraphenylphosphonium bromide.

Substances used in nitrations are generally suitable as reaction auxiliaries and / or diluents for process (d) according to the invention. These preferably include sulfuric acid, acetic acid and acetic anhydride.

The processes (a), (b) and (c) according to the invention for the preparation of the compounds of the general formula (I) are preferably carried out using one or more diluents. In addition to water, diluents for carrying out processes (a), (b) and (c) according to the invention are, above all, inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or

Ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be carried out when the inventive

Processes (a), (b), (c) and (d) can be varied over a wide range. In general I think you work at temperatures between -30 ° C and 150 ° C, preferably between -10 ° C and 120 ° C.

The processes according to the invention are generally carried out under normal pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the processes according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. 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 e.g. can be used for the following plants:

Dicotyledon weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Gupopsisia, Euphorbia , 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, Xanth.

Dicotyledon cultures 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, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, ScHaum, Setha, Sagarum, Sagarum, Sagarum, Sagarum, Sagarum, Setha

Monocot cultures of the genera: Allium, pineapple, asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to others

Plants.

Depending on the concentration, the active compounds according to the invention are suitable for combating total weeds, for example on industrial and rail tracks and on paths and squares with and without tree growth. Likewise, the active compounds according to the invention for weed control in permanent crops, for example forests, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants , on ornamental and sports turf and pasture land as well as for selective weed control in annual crops. The compounds of formula (I) according to the invention and the compounds of formula (LX) and (LXa) show strong herbicidal activity and a broad spectrum of activity 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 monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence process.

In certain concentrations or application rates, the active compounds according to the invention can also be used to control animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants). Cultivated 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 cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space using the customary treatment methods, for example by diving, Spraying, evaporation, nebulization, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by means of single-layer or multi-layer coating.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as diethyl formamide and dimethyl sulfoxide, and water.

Possible solid carriers are: e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite,

Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight

Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations as a mixture with known herbicides and / or with substances which improve crop tolerance (“safeners”) for weed control, finished formulations or tank mixes being possible. Mixtures are therefore also possible possible with weed control agents which contain one or more known herbicides and a safener. Known herbicides are suitable for the mixtures, for example

Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Beflubutamid, Benazolin (-ethyl), Benulfureson -methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoyl-prop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofen-oxime, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylates, Cafe- strole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chlorambene, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlorotoluron, Cinidon (-ethyl), Cinmethylin, Cinosulfuron, Clefoxydim, Clethod Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Cloransulam (-methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-Dutyl) 2,4-DB, Desmedipham, Diallate, Dicamba, Dichlorprop (-P), Diclofop (-methyl), D iclosulam, diethatyl

(-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epropodan, EthTCam-, Sulfur methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop (-isopropyl, -isopropyl-L,

-methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone (fluoroglorochloridone) ), Fluoxoxam, flupropacil, fluorsulfüron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone, fluothiacet (-methyl), flutiamide, fomesafen , Foramsulfiiron, Glufosinate (-ammomum), Glyphosate (-isopropylammonium), Halosafen, Haloxyfop (-ethoxy-ethyl, -P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin Imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlorotole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Naproanilonon, Napropamide, Nebropamide, Nebropamide, Nebropamide, Nebropamide Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfonon, Oxaziclomefone, Oxyfluorfen, Paraquat, Pelargonic acid, Pendimethalin,

Pendralin, Pentoxazone, Phenmedipham, Picolinafen, Piperophos, Pretilachlor, Primisulfuron (-methyl), Profluazol, Prometryn, Propachlor, Propanil, Propaquiza- fop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocon, Pyraflufen-urosulfufen ), Pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridate, pyridatol, pyriftalid, pyriminobac

(-methyl), pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quinoclamine, Quizalofop (-P-ethyl, -P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sultrione, Sulfentrazone, Sulfometuron (-methyl ), Sulfosate, Sulfosulfuron, Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Tnidiazimin, Thifensulfuron (-methyl), Thiobencarb, Tiocarbazil,

Tralkoxydim, Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifluralin, Trifloxysulfuron, Triflusulfuron (-methyl), Tritosulfuron.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents 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 the usual way, e.g. by pouring, spraying, spraying, sprinkling.

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing. The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.

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

Manufacturing examples:

example 1

(Method (a))

A mixture of 2.3 g (10 mmol) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine, 2.1 g (10 mmol) of trifluoroacetic anhydride, 1.0 g (10 mmol) Triethylamine and 50 ml of ethyl acetate are stirred for 60 minutes at room temperature (approx. 20 ° C). The reaction mixture is then washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue is digested with diisopropyl ether and the crystalline product is isolated by suction.

0.5 g (14% of theory) of 2,2,2-trifluoro-N- [5-methyl-1- (3-trifluoromethylphenyl) -2 (1H) -pyridinylidene] -acetamide with a melting point of 115 ° is obtained C.

Example 2

(Method (a)) A mixture of 1.1 g (4 mmol) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine, 5 ml (5 mmol) of isopropyl chloroformate, 0.5 g (5 mmol) Triethylamine and 50 ml of ethyl acetate are stirred for 60 minutes at room temperature (approx. 20 ° C). The reaction mixture is then washed with water, the aqueous phase is extracted with methylene chloride, the combined organic phases are dried with sodium sulfate and filtered. The solvents are carefully distilled off from the filtrate under reduced pressure.

0.6 g (46% of theory) of N- [5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinylidene] -O-methyl-carbamic acid ester is obtained as an amorphous residue.

logP = 1.59 (determination of log P values see page 40).

Example 3

(Method (a))

A mixture of 1.1 g (4 mmol) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine, 0.6 g (5 mmol) of cyanogen bromide, 0.5 g (5 mmol) Triethylamine and 50 ml

Ethyl acetate is stirred for 30 minutes at room temperature (approx. 20 ° C). The reaction mixture is then washed with water, the aqueous phase is extracted with methylene chloride, the combined organic phases are dried with sodium sulfate and filtered. The solvents are carefully distilled off from the filtrate under reduced pressure. 0.35 g (32% of theory) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinylideasanamide with a melting point of 165 ° C. is obtained.

Example 4

(Method (a))

A mixture of 2.6 g (10 mmol) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine, 0.6 g (10 mmol) of methyl isocyanate and 100 ml of acetonitrile becomes two

Let stand at room temperature (approx. 20 ° C) for hours. It is then concentrated in a water-jet vacuum, the residue is digested with diisopropyl ether and the crystalline product is isolated by suction.

2.1 g (68% of theory) of N-methyl-N '- [5-methyl-1- (3-trifluoromethylphenyl) -2 (1H) -pyridinylidene] urea with a melting point of 114 ° C. are obtained.

Example 5

(Method (a)) 2.9 g (10 mmol) of 5-methyl-l- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine hydrochloride, 3.1 g (30 mmol) of triethylamine and 100 ml of acetonitrile are at room temperature ( approx. 20 ° C) while stirring with 2.9 g (10 mmol) of trifluoromethanesulfonic acid anhydride. The reaction mixture is stirred for 60 minutes at room temperature and then concentrated in a water jet vacuum. The crude product obtained as a residue is purified by column chromatography (silica gel, ethyl acetate / hexane, 9: 1).

0.40 g (10% of theory) of N- [5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinylidene] -trifluoromethanesulfonic acid amide with a melting point of 206 ° C. is obtained.

Example 6

(Method (a))

A mixture of 2.9 g (10 mmol) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine hydrochloride, 2.3 g (10 mmol) of 2-methylsulfonyl-5-trifluoromethyl- l, 3,4-thiadiazole, 4.2 g (30 mmol) of potassium carbonate and 30 ml of dimethyl sulfoxide is stirred for 60 minutes at 100 ° C. and, after cooling, poured onto approximately the same volume of methylene chloride. After washing with water and saturated aqueous sodium chloride solution, the organic phase is dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by suction.

2.3 g (57% of theory) of N- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) are obtained. -pyridinimine with a melting point of 179 ° C. Example 7

(Method (b))

2.7 g (10 mmol) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridmthione are placed in 50 ml of chloroform and stirred at room temperature (approx. 20 ° C.) with a solution of 2.9 g (10 mmol) of N-chloro-p-toluenesulfonamide sodium salt hydrate (chloramine-T hydrate) in 50 ml of ethanol were added dropwise. The reaction mixture is stirred for 15 hours at room temperature, then concentrated in a water jet vacuum, the residue is taken up in chloroform, washed with water and then with saturated aqueous sodium bicarbonate solution, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and the residue is kept at 180 ° C. for 15 minutes in a high vacuum. To

Cooling and digesting with diisopropyl ether, the crystalline product is isolated by suction.

1.8 g (49% of theory) of 4-methyl-N- [5-methyl-1- (3-trifluoromethylphenyl) -2 (1H) -pyridinylidene] -benzenesulfonamide with a melting point of 174 ° C. are obtained. Example 8

(Method (c))

A mixture of 1.6 g (5 mmol) of 2-chloro-5-methyl-l- (3-trifluoromethylphenyl) pyridinium chloride, 0.9 g (15 mmol) of cyclopropylamine and 50 ml of methanol is stirred for 15 hours at room temperature ( approx. 20 ° C) and then concentrated in a water jet vacuum. The residue is taken up in methylene chloride, washed with water, dried with sodium sulfate and filtered. The

The filtrate is concentrated in a water jet vacuum, the residue is taken up in methanol and hydrochloric acid and the volatile components are carefully distilled off under reduced pressure. The crude product obtained as a residue is purified by column chromatography (silica gel, ethyl acetate / hexane, 5: 1).

1.5 g (91% of theory) of N-cyclopropy 1-5 -methyl-1 - (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine are obtained as an oily product.

logP = 1.51 (determination of log P values see page 40).

Analogously to Examples 1 to 8 and in accordance with the general description of the production processes according to the invention, it is also possible, for example, to prepare the compounds of the general formula (I) listed in Table 1 below.

Table 1: Examples of the compounds of the formula (I)

The logP values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.

(a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a) .

(b) Eluents for determination in the neutral range: 0.01 molar aqueous

Phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^b) .

The calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the

Retention times by linear interpolation between two consecutive alkanones).

The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. Starting materials of formula (II):

Example (II-l)

(Method (α))

step 1

A mixture of 2.5 g (10 mmol) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridone, 3.9 g (30 mmol) of oxalyl chloride, 40 ml of 1,2-dichloro- ethane and 2 drops of N, N-dimethylformamide are heated to boiling under reflux until the evolution of gas has ended. After cooling to room temperature, the crystalline product is isolated by suction.

2.1 g (65% of theory) of 2-chloro-5-methyl-1- (3-trifluoromethyl-ρhenyl) pyridinium chloride with a melting point of 194 ° C. are obtained. Level 2

3.1 g (10 mmol) of 2-chloro-5-methyl-1- (3-trifluoromethyl-phenyl) pyridinium chloride are taken up in 40 ml of methanol and ammonia is passed into this mixture at temperatures between 20 ° C. and 30 ° C. until the solution is saturated. Then 3.6 g (20 mmol) of sodium methylate in the form of a 30% strength methanolic solution are added, and the mixture is then concentrated in a water jet vacuum.

The product thus obtained (5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinimine) can be reacted without further purification by the process (a) according to the invention.

Example (II-l)

(Procedure (ß))

A mixture of 10 g (24 mmol) of 4-methyl-N- [5-methyl-1- (3-trifluoromethylphenyl) -2 (1H) -pyridinylidene] -benzenesulfonamide and 50 g of 80% sulfuric acid is added for 15 hours Stirred 50 ° C and then to a 1 molar aqueous

Sodium carbonate solution added dropwise. Then with ethyl acetate extracted, the organic phase dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

2.3 g (38% of theory) of 5-methyl-1- (3-trifluoromethyl-ρhenyl) -2 (1H) -pyridinimine are obtained, which can be reacted by process (a) according to the invention without further purification.

Analogously to Example (II-1), the compounds of the general formula (II) listed in Table 2 below can also be prepared, for example.

Table 2: Example of the compounds of the formula (II), these being the hydrochlorides

Example (11-26) 5-methyl-l- (2,3-difluoromethylenedioxy-ρhenyl) -2 (1H) -pyridinimine, Example (11-27) 5-methyl-l- (3,4-difluoromethylenedioxy-phenyl) -2 (lH) -pyridinimine, example (π-28) 5-methyl-l- (2,3-tetrafluoroethylenedioxy-phenyl) -2 (lH) -pyridinimine, example (11-29) 5-methyl-l- ( 3,4-tetrafluoroethylenedioxy-phenyl) -2 (1H) -pyridinimine, example (11-30) 5-Memyl-l- (2,3-chlorotrifluoro-ylenώoxy-phenyl) -2 (1H) -pyridinimine in example (11-31 ) 5-Methyl-l- (3,4-cωortrifluoremylenedioxyphen-^ Starting materials of formula (V):

Example (V-1)

A mixture of 18.7 g (74 mmol) of 5-methyl-1- (3-trifluoromethyl-ρhenyl) -2 (1H) -pyridinone, 16.4 g (74 mmol) of phosphorus (V) sulfide and 75 ml of pyridine is heated under reflux for two hours and, after cooling, poured onto 300 ml of water. After stirring overnight, the crystalline product is isolated by suction.

12.8 g (64% of theory) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinethione with a melting point of 96 ° C. are obtained.

Analogous to example (V-1), for example, those in the following can also be used

Compounds of general formula (V) listed in Table 3 can be prepared.

Table 3: Example of the compounds of the formula (V)

Example (V-26): 5-methyl-1- (2,3-difluoromethylenedioxy-phenyl) -2 (1H) -pyridinethione, example (N-27): 5-methyl-1-- (3,4-difluoromethylenedioxy- phenyl) -2 (1H) -pyridine thione, example (V-28): 5-methyl-1- (2,3-tetrafluoroethylenedioxy-phenyl) -2 (1H) -pyridmthione, example (V-29): 5-methyl -l- (3,4-tetrafluoroethylenedioxy-phenyl) -2 (1H) -pyridinthione, example (V-30): 5-MeII- (2,3-cωorrrifluoromylenedioxy-phenyl) -2 (1H) -pyridomthione, example (V-31): 5-Memyl-l- (3,4-Co-Utrifluoromylenedoxyphenyl) -2 (1H) -pyridethione.

Products of formula (VII):

Example (VII-1)

2.1 g (65% of theory) of 2-chloro-5-methyl-1- (3-trifluoromethyl-phenyl) pyridinium chloride with a melting point of 194 ° C. are obtained.

Analogously to Example (VII-1), for example, the compounds of the general formula (VII) listed in Table 4 below can also be prepared.

Table 4: Examples of the compounds of the formula (VTI)

stands for Cl

Example (Vπ-26): 2-chloro-5-methyl-l- (2,3-difluoromethylenedioxy-phenyl) -pyridinium chloride, example (Vπ-27): 2-chloro-5-methyl-l- (3rd , 4-difluoromethylenedioxy-phenyl) pyridium chloride, example (NII-28): 2-chloro-5-methyl-l- (2,3-tetrafluoroethylenedioxy-ρhenyl) -ρyridium chloride, example (VTI-29): 2-chloro-5-methyl-1- (3,4-tetrafluoroethylene dioxy-phenyl) pyridine chloride, example (VII-30): 2-chloro-5-methyl-1 - (2,3-chlorotrifluoroethylene dioxy-phenyl) pyridinium chloride,

Example (NII-31): 2-chloro-5-methyl-1 - (3, 4-chlorotrifluoroethylenedioxy-phenyl) pyridinium chloride.

Starting materials of formula (IX):

Example (TX-1)

A mixture of 21.8 g (0.20 mol) of 5-methyl-2-pyridone, 54 g (0.24 mol) of 3-bromo-benzotrifluoride, 27.7 g (0.20 mol) of potassium carbonate, 2 g ( 10 mmol) of copper (I) iodide and 300 ml of N, N-dimethylformamide are stirred at 100 ° C. for 15 hours and at 140 ° C. for a further 6 hours. After cooling to room temperature, 300 ml of ethyl acetate are added and the mixture is then diluted to about twice the volume with water. The organic phase is separated off and the aqueous phase is subsequently extracted with ethyl acetate. The combined organic phases are washed with water, dried with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

20.7 g (41% of theory) of 5-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinone with a melting point of 95 ° C. are obtained.

Analogously to example (IX-1), for example, those in the following can also be used

Compounds of the general formula (IX) listed in Table 5 can be prepared.

Table 5: Examples of the compounds of the formula (IX)

Example (IX-28): 5-methyl-1- (2,3-difluoromemylenemoxyphenyl) -2 (1H) pyridinone

(logP = 3.95 a)),

Example (IX-29): 5-Memyl-l- (3,4-difluoromethylenedioxy-phenyl) -2 (1H) -pyridinone, Example (IX-30): 5-Memyl-l- (2,3-tetiafluoroethylene-dioxy- phenyl) -2 (1H) -pyridinone, example (IX-31): 5-memyl-1- (3,4-tetrafluoroemylenedioxy-phenyl) -2 (1IT; -pyridinone, example (IX-32): 5-memyl -l- (2,3-chlorotrifluoroethylenedioxy-phenyl) -2 (1H) -pyridinone, example (IX-33): 5-methyl-1 - (3, 4-chlorotrifluoroethylenedioxy-phenyl) -2 (1 H) -pyridi - non.

Example (IX-34): 3-methyl-1- (3-trifluoromethyl-phenyl) -2 (1H) -pyridinone (mp .: 122 ° C.), Example (IX-35): 5-trifluoromemyl-1- ( 3-trifluoromethyl-phenyl) -2 (lH) -pyridinone

(logP = 2.78 ^)).

(Determination of log P values see page 40)

Application examples:

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of 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 active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area. The concentration of active ingredient in the spray liquor is chosen so that the desired amount of active ingredient is applied in 1000 liters of water per hectare.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:

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

In this test, for example, the compounds according to Preparation Example 1, 2, 3, IX-1, IX-3, IX-11 and IX-16 show, with good tolerance to cultivated plants, such as rice, in part, strong action against weeds. Example B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

Concentration.

Test plants which have a height of 5 to 15 cm are sprayed with the active compound preparation in such a way that the desired amounts of active compound are applied per unit area. The concentration of the spray liquor is chosen so that in

10001 water / ha the desired amounts of active ingredient are applied.

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

It means:

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

In this test, for example, the compounds according to Preparation Examples 1, 3, IX-1 and IX-16 show a strong action against weeds.

Claims

Patentansprfiche

1. Substituted iminoazines of the general formula (I)

in which

R ^{1 represents} nitro, cyano, or one of the groupings -R ⁵ , -CQ QR ⁵ , -NH-CQ -QR ⁵ or -SO ₂ -R ⁶ ,

R ^{2 represents} nitro, cyano, SF ₅ , halogen or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylsulfonyloxy,

R represents hydrogen or halogen, or together with R represents optionally substituted alkylenedioxy,

R ^{4 represents} hydrogen, cyano, carboxy, carbamoyl, halogen or optionally substituted alkyl,

Q ^{1 represents} O (oxygen), S (sulfur) or NR ⁵ ,

Q ^{2 represents} a single bond or O (oxygen), S (sulfur) or NR ⁵ ,

R ^{5 represents} hydrogen, amino or in each case optionally substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylideneamino, alkenyl, Alkenyloxy, alkynyl, cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl, arylamino, arylalkyl, heterocyclyl or heterocyclylalkyl,

Z ^{1 represents} N (nitrogen) or CR ⁴ ,

Z ^{2 represents} N (nitrogen) or CR ⁴ , and

Z ^{3 represents} N (nitrogen) or CR ⁴ .

Compounds according to claim 1, characterized in that

R ¹ for cyano or one of the groupings -R ⁵ , -CQ ^ -Q ^ -R ⁵ , or -SO ₂ -R ⁶ ,

R ² for nitro, cyano, SF ₅ , halogen or in each case, if appropriate

Cyano, halogen or C ₁ -C ₄ -alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylsulfonyloxy each having 1 to 5 carbon atoms,

R ^{3 represents} hydrogen or halogen, or together with R ^{2 represents} alkylenedioxy with 1 to 3 carbon atoms optionally substituted by halogen,

R ^{4 represents} hydrogen, cyano, carboxy, carbamoyl, halogen or optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy

Alkyl having 1 to 5 carbon atoms, Q ^{1 represents} O (oxygen) or S (sulfur),

R ⁵ for hydrogen or amino, each optionally substituted by cyano, halogen or -CC ₄ -alkoxy-substituted alkyl or alkoxy each having 1 to 6 carbon atoms, for alkylamino having 1 to 6 carbon atoms, for dialkylamino each having 1 to 6 carbon atoms in the Alkyl groups, for alkylidene amino having up to 6 carbon atoms, for alkenyl, alkenyloxy or alkynyl each optionally substituted by cyano or halogen, each having 2 to 6

Carbon atoms, each for cycloalkyl, cycloalkylamino or cycloalkylalkyl optionally substituted by cyano, halogen or C ₁ -C ₄ alkyl, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, for each optionally substituted by nitro , Cyano, phenyl, phenoxy,

Phenylthio, halogen, ^ alkyl, haloalkyl, Cj-C - alkoxy, Cι-C ₄ -haloalkoxy, C ₁ -C ₄ - alkylthio, C ₁ -C ₄ haloalkyl thio, C 1-C ₄ - alkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl, -C ₄ - alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl or di- (C ₁ -C ₄ alkyl) amino sulfonyl substituted aryl, arylamino or arylalkyl, each with 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, or for each optionally by nitro, cyano, phenyl, phenoxy, phenylthio, halogen, C1-C4-alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, - haloalkylthio, CC ₄ - alkylsulfinyl, C1-C4-

Haloalkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl or di (C ₁ -C ₄ alkyl) amino sulfonyl substituted, monocyclic or bicyclic heterocyclyl or heterocyclylalkyl, each having up to 10 carbon atoms and up to 4 nitrogen atoms and / or 1 or 2 oxygen or sulfur atoms in the hetero- cyclyl group and optionally 1 to 4 carbon atoms in the alkyl part,

R ⁶ for optionally halogen-substituted alkyl having 1 to 6 carbon atoms, for optionally substituted with halogen

Alkenyl with 2 to 6 carbon atoms, for cycloalkyl or cycloalkylalkyl, each substituted by halogen or C ₁ -C ₄ alkyl, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, each optionally by nitro, cyano, halogen , C1-C ₄ - alkyl,

C ₁ -C ₄ haloalkyl, _Cι-C4 alkoxy, -C ₄ -haloalkoxy, C ₁ -C -Al- alkylthio, _{Cι-C4-haloalkylthio,} alkylsulfinyl dC, - -Halo- genalkylsulfinyl, Ci- alkylsulfonyl, C ₁ -C ₄ haloalkylsulfonyl or di (C ₁ -C ₄ alkyl) aminosulfonyl substituted aryl or arylalkyl each having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, or for each optionally substituted by nitro, cyano, halogen, C ₁ -C ₄ - alkyl, C ₁ -C ₄ haloalkyl, Cι-C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C1-C4-AI alkylthio, C ₁ - C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl, CrC ^ alkylsulfonyl, haloalkylsulfonyl or di (C ₁ -C ₄ alkyl) amino sulfonyl substituted, monocyclic or bicyclic heterocyclyl or heterocyclylalkyl each having up to 10 carbon atoms and up to 4 nitrogen atoms and / or 1 or 2 oxygen or sulfur atoms in the heterocyclyl group and optionally 1 to 4 Koh is in the alkyl part,

Z ^{1 stands} for CR ⁴ ,

Z ^{2 stands} for CR ⁴ ,

Z ^{3 stands} for CR ⁴ . Compounds according to claim 1 or 2, characterized in that

R ² for nitro, cyano, SF, fluorine, chlorine or bromine, or for methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy Propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfmyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylsulfonyloxy, ethylsulfonyloxy, n- or i-propylsulfonyloxy

R represents hydrogen, fluorine, chlorine or bromine, or together with R represents methylenedioxy or ethylenedioxy optionally substituted by fluorine and / or chlorine,

R ^{4 represents} hydrogen, cyano, carboxy, carbamoyl, fluorine, chlorine, bromine, or represents methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,

Q ^{1 stands} for O (oxygen),

R ⁵ for hydrogen or amino, for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methylamino, ethylamino, n, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy - or i-Propylamino, n-, i-, s- or t-butylamino, for dimethylamino or diethylamino, for propylidenamino or butyhdenamino, for propenyl, butenyl, propynyl or butynyl which are optionally substituted by cyano, fluorine, chlorine and / or bromine , for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclob tylamino, cyclopentylamino, each optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, Cyclohexylamino, Cyclopropylrnethyl, Cyclobutylmethyl, Cyclopentylmethyl or Cyclohexylmethyl, for each optionally by nitro, cyano, phenyl, phenoxy, phenylthio, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s - or t-butyl, dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl,

Fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonylsulfonyl, ethylsulfonylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfonyl

Phenyl, naphthyl, phenylamino, benzyl or phenylethyl, or for each optionally by cyano, phenyl, phenoxy, phenylthio, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t -Butyl, dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethylsulfyl, difluoromethylsulfyl , Trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosulfonyl substituted heterocyclyl or heterocyclylalkyl from the series

Furyl, tetrahydrofuryl, benzofuryl, thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzthiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, quinolethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethylmethyl

Pyridinylmethyl, pyrimidinylmethyl,

for each optionally substituted by fluorine and / or chlorine

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine, chlorine and / or bromine

Propenyl or butenyl, each optionally by fluorine, chlorine, Bromine, methyl, ethyl, n- or i-propyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopenthenethyl or cyclohexylmethyl, each optionally with nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n - or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosulfonyl, substituted phenyl or naphthyl, or for each optionally substituted by cyano, methyl, chlorine, ethyl, chlorine or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propox y, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, dimethylylsulfonyl, dimethylaminosylonylethylsulfonyl, or

Thienyl, benzothienyl, pyrrolyl, benzopyrrolyl, pyrazolyl, benzopyrazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzothiazolyl, pyridinyl, quinolinyl, pyrimidinyl, furylmethyl, thienylmethyl, pyrrolylmethyl, pyazololylmethyl, oxazolylmethyl, oxazolylmethyl, oxazolylmethyl, oxazolylmethyl, oxazolylethyl, Pyrimidinylmethyl,

stands for CH,

stands for CH. Compounds according to one of claims 1 to 3, characterized in that

R ^{2 represents} cyano, fluorine, chlorine or bromine, or represents methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy or ethylsulfonyloxy, each optionally substituted by fluorine, chlorine, methoxy or ethoxy,

R ^{4 represents} hydrogen, cyano, fluorine, chlorine, bromine or methyl or ethyl optionally substituted by fluorine, chlorine, methoxy or ethoxy,

R ^{5 represents} hydrogen or amino, in each case optionally by cyano,

Fluorine, chlorine, methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl, methylamino, ethylamino, n- or i-propylamino, for dimethylamino, for propenyl, butenyl, propynyl or optionally substituted by fluorine, chlorine and or bromine Butinyl, for cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclopentylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by fluorine, chlorine, bromine, or ethyl, or for each optionally substituted by nitro, cyano, fluorine, chlorine, Bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl,

Methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfylethylsulfonyl, trifluoromethylsulfonyl, trifluoromethyl

Is benzyl or phenylethyl, R ⁶ for each optionally substituted by fluorine and / or chlorine methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for each optionally substituted by fluorine, chlorine, bromine, methyl or ethyl ized cyclopropyl, cyclopentyl or cyclohexyl, or for optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl,

Ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosulfonyl substituted phenyl.

5. Compounds according to any one of claims 1 to 4, characterized in that

R ^{2 represents} trifluoromethyl and / or

R ^{4 represents} methyl.

6. Compounds according to any one of claims 1 to 5, characterized in that

R ¹ for cyano or one of the groupings -CQ ^! -Q ² -R ⁵ or -SO ₂ -R ⁶ ,

R ^{2 represents} trifluoromethyl, difluoromethoxy or trifluoromethoxy,

R represents hydrogen, fluorine or chlorine, or together with R — m ortho position — represents difluoromethylene dioxy or tetrafluoroethylene dioxy, R ^{4 represents} hydrogen, fluorine, chlorine, bromine or methyl,

Q ^{1 represents} O (oxygen) or S (sulfur),

Q ^{2 represents} a single bond or O (oxygen), S (sulfur) or NR ⁵ ,

R ⁵ for hydrogen, for each methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, for propenyl, butenyl, propynyl or butinyl, each optionally substituted by fluorine, chlorine and / or bromine, for each cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopenthenethyl or cyclohexylmethyl optionally substituted by fluorine, chlorine or methyl, or for each optionally substituted by nitro,

Cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio , Ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl,

Trifluoromethylsulfonyl or dimethylaminosulfonyl substituted phenyl or benzyl,

R ⁶ for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine and / or chlorine, for cyclopropyl, cyclopentyl or, in each case optionally substituted by fluorine, chlorine or methyl Cyclohexyl, or for optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i Propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, Ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl or dimethylaminosulfonyl substituted phenyl,

stands for CH,

stands for CH, and

Z ³ stands for CH.

7. A process for the preparation of substituted iminoazines of the formula (I) according to any one of claims 1 to 6, characterized in that

(a) iminoazines of the general formula (II)

in which

R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meanings given in one of Claims 1 to 6,

- or acid adducts of iminoazines of the general formula (II),

with compounds of the general formula (III)

in which

R ^{1 has} the meaning given in one of claims 1 to 6,

X ^{1 represents} halogen, -SO ₂ CH ₃ , -O-CO-R ⁵ or -O-SO ₂ -R ⁶ and

R ⁵ and R ^{6 have} the meanings given in one of Claims 1 to 6,

or with iso (tbio) cyanates of the general formula (TV)

QC = NR ⁵ (IV)

in which

Q ¹ and R ^{5 have} the meanings given in one of Claims 1 to 6,

if appropriate in the presence of a reaction auxiliary and, if appropriate, in the presence of a diluent,

or that one

(b) Azinthions of the general formula (V)

in which R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meanings given in one of Claims 1 to 6,

with compounds of the general formula (VT)

M ⁺ CΓN-SO ₂ -R ⁶ (VI)

in which

R ^{6 has} the meaning given in one of claims 1 to 6 and

M stands for a metal equivalent,

if appropriate in the presence of one or more diluents,

or that one

(c) chlorazinium compounds of the general formula (VII)

in which

R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meanings given in one of claims 1 to 6, and Y stands for Cl, PC1 ₄ , POC or PC1 ₆ ,

with amino compounds of the general formula (VIII)

H ₂ NR ^! (VHI)

in which

R ^{1 has} the meaning given in one of claims 1 to 6,

or that one

(d) iminoazines of the general formula (II)

in which

- or acid adducts of iminoazines of the general formula (II) - with nitric acid, optionally in the presence of a reaction auxiliary and / or diluent.

8. Iminoazines of the general formula (II)

in which

R, R, R, Z, Z and Z have the meanings given in one of claims 1 to 6,

or their acid adducts.

9. Azinthione of the general formula (V)

in which

R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meanings given in one of claims 1 to 6.

10. Chlorazinium compounds of the general formula (NTf)

in which

R ² , R ³ , R ⁴ , Z ¹ , Z ² and Z ^{3 have} the meanings given in one of claims 1 to 6, and

Y stands for Cl, PC1 ₄ , POCl ₄ or PC1 ₆ .

11. Compounds of the general formula (IXa)

in which

R ² , R ³ and R ^{4 have} the meanings given in one of claims 1 to 6.

12. A method for controlling undesirable plant growth, characterized in that at least one compound according to one of claims 1 to 6 and 11 is allowed to act on undesired plants and / or their habitat.

13. Use of at least one compound according to one of claims 1 to 6 and 11 for controlling unwanted plants.

14. Use of compounds of the general formula (IX)

in which

to control unwanted plants.

15. Herbicidal agent, characterized by a content of a compound according to one of claims 1 to 6 and 11 and conventional extenders and / or surface-active agents.

16. Herbicidal agent, characterized by a content of a compound of

Formula (IX) according to claim 14 and conventional extenders and / or surface-active agents.

17. A process for the preparation of a herbicidal composition, characterized in that at least one compound according to one of Claims 1 to 6 and 11 is mixed with extenders and / or surface-active agents.