EP1157012A1 - 1-aryl-1,3,5-triazine-4-thione-2,6-diones, production thereof and use thereof as herbicides - Google Patents

Abstract

The invention relates to novel 1-aryl-4-thiotriazines of formula (I), wherein R1 = H, NH¿2?, C1-C4-alkyl, C1-C4-alkyl halide; R?2¿ = H, NH¿2?, C1-C4-alkyl, C1-C4-alkyl halide; R?3¿ = H, halogen; R4 = CN, halogen; Y = nitrogen, the methine group or together with R5, a bridge ⊃C-O-C(R?6)=N-; R5¿ = 1) hydrogen, hydroxy, mercapto, nitro, halogen, C¿1?-C6-alkyl, C1-C6-alkyl halide, 2) C1-C6-alkoxy, C1-C6-alkylthio, C3-C6-cycloalkoxy, C3-C6-cycloalkylthio, C2-C6-alkenyloxy, C2-C6-alkenylthio, C2-C6-alkinyloxy or C2-C6-alkinylthio, each of these 8 radicals optionally bearing one of the following substituents: halogen, cyano, -CO-R?8¿, -CO-OR8 or -CO-N(R8)-R9; 3) -CO-R?11, -C(R11)(OR13)(OR14), -C(R11)=C(R15)-CO-R16, -CH(R11)-CH(R15)-CO-R16¿, -CO-OR?20, -C(R10)=N-OR7, -N(R21)-R22¿ or -CO-N(R?21)-R22; and R6¿ = H, halogen, optionally substituted C¿1?-C6-alkyl, C3-C6-alkenyl, C3-C6-alkinyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkinyloxy, C3-C6-cycloalkyl or C3-C6-cycloalkoxy. The invention also relates to salts and enol ethers of the inventive compounds (I), to a method for producing them and to their use as herbicides.

Description

L-ARYL-L, 3,5-TRIAZINE-4 _~ TILION-2,6-DIONE, THEIR PRODUCTION AND THEIR USE AS HERBICIDES ^'

Description 5

The present invention relates to novel l-aryl-4-thiotriazines of the formula I.

5 in which the variables have the following meanings:

R ¹ is hydrogen, amino, Cι-C ₄ alkyl or _{Cι-C4-haloalkyl,} -

R ^{2 is} hydrogen, amino, -CC ₄ alkyl or C _! -C ₄ haloalkyl; 0

R ^{3 is} hydrogen or halogen;

R ⁴ cyano or halogen;

5 Y nitrogen, the methine group or together with R ⁵ a bridge> C-0-C (R ⁶ ) = N-;

R ⁵

0 1) hydrogen, hydroxy, mercapto, nitro, halogen, -CC ₆ alkyl, Ci - Cβ -haloalkyl,

2) -CC ₆ alkoxy, Ci -C ₆ alkylthio, C ₃ -C ₆ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, C ₂ ~ C ₆ alkenyloxy, C ₂ -C ₆ alkenylthio, C ₂ -C ₆ alkynyl-5 oxy or C ₂ -Cg -alkynylthio, where each of these 8 radicals can optionally carry one of the following substituents: halogen, cyano, -CO-R ⁸ , -CO-OR ⁸ or -CO- N (R ⁸ ) -R ⁹ ;

3) -CO-R ¹¹ , -CfR ¹¹ ) (OR ¹³ ) (OR ¹⁴ ), -C (R ¹¹ ) = C (R ¹⁵ ) -CO-R ¹⁶ , 0 -CH (R ^{1: L} ) -CH (R ¹⁵ ) -CO-R ¹⁶ , -CO-OR ²⁰ , - C (R ¹⁰ ) = N-OR ⁷ , -N (R ²¹ ) -R ²² or -CO-N (R ²¹ ) -R ²² ;

R ^{6 is} hydrogen, halogen, -CC ₆ alkyl, C ₃ -C ₆ alkenyl,

C ₃ -C ₆ alkynyl, -C-C ₆ alkoxy, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyl - 5 oxy, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkoxy, each of the latter 8 residues, if desired, one to three Can carry substituents, each selected from the group consisting of halogen, -CC ₆ alkoxy and -CO-OR ⁸ ';

R ⁷ are hydrogen, C ₆ -alkyl, C ₆ haloalkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ -alkynyl, (C ι-C _6- alkoxy) carbonyl-C ₆ alkyl or benzyl;

R ⁸ , R ⁸ 'independently of one another

Are hydrogen, C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ -cycloalkyl-Cι-C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, Cι-C ₆ -alk- oxy-Cι-C ₆ alkyl, _{(C! -C6} alkoxy) carbonyl-Cι-C ₆ -alkyl, (C ₃ -C ₆ -alkenyloxy) carbonyl-C ₁ -C ₆ -alkyl, phenyl or phenyl-Ci-C _ö -alkyl, where the phenyl group and the phenyl ring of the phenylalkyl group may be unsubstituted or may carry one to three radicals, each selected from the group consisting of halogen, nitro, cyano, Cι -C ₆ -alkyl, C ₆ haloalkyl, _Cι-C6 alkoxy, and (Ci-C _ö alkyl) carbonyl;

R ^{9 is} hydrogen or C; _L -C ₆ alkyl;

R ¹⁰ are hydrogen, C ₆ alkyl or Ci-C _ö -alkoxy, where the 2 last-mentioned radicals to carry one of the following substituents: Ci-C _ß alkoxy, (Cι-C ₆ alkoxy) carbonyl or phenoxycarbonyl;

R ^{11 is} hydrogen, -CC ₆ alkyl or Ci-C _δ -haogenoalkyl;

R ¹³ , R ¹⁴ independently of one another C] _. -C ₆ alkyl or together for a saturated 2- to 4-membered carbon - chain of substances which can carry a Ci-Cβ-alkyl radical;

R ^{15 is} hydrogen, cyano, halogen or -CC ₆ alkyl;

_R 16 ₀ _ _R 23 _or -N (R ²¹ ) R ²² ;

R ²⁰ , R ²³ independently of one another are hydrogen, C ₁ -C ₆ -alkyl,

Ci-Ce-haloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, where the latter 4 groups can each carry one or two of the following radicals: cyano, halogen, hydroxy, hydroxycarbonyl, Ci-Cδ-alkoxy , Ci-Cβ-alkylthio,

(C] _. -C ₆ -alkyl) carbonyl, (-C-C ₆ -alkoxy) carbonyl, (Cι-C ₆ -alkyl) carbonyloxy, (C ₃ -C ₆ -alkenyloxy) carbonyl, (C ₃ -Cβ-alkynyloxy ) carbonyl or Ci-Cδ-alkoxy- (CI-C _Ö -alkoxy) carbonyl; or C ₃ -C ₆ cycloalkyl, Phenyl or phenyl -CC ₆ alkyl, where the phenyl rings may be unsubstituted or in turn carry one to three substituents, each selected from the group consisting of cyano, nitro, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ - Haloalkyl, C _! -C ₆ -alkoxy and (Cι-C ₆ alkoxy) carbonyl;

R ²¹ , R ²² independently of one another

Is hydrogen, Cx-Cg-alkyl, C ₃ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, Cι-C ₆ haloalkyl, Cι-C ₆ -alkoxy-Cι-C ₆ -alkyl,

(-CC ₆ alkyl) carbonyl, (-C ₆ alkoxy) carbonyl, (-C ₆ -C alkoxy) carbonyl -C ₆ -C ₆ alkyl or C ₁ -C ₆ -alkylsulfonyl, or R ²¹ and R ²² together with the common nitrogen atom for a saturated or unsaturated 4- to 7-membered aza-heterocycle which, in addition to carbon ring members, can contain one of the following members if desired: -0-, -S-,

-N =, -NH- or -N (-C -C ₆ alkyl) -;

and the agriculturally useful salts and enol ethers of the compounds I.

The invention also relates to the use of the compounds I as herbicides, herbicidal compositions which comprise the compounds I as active substances,

Process for the preparation of the compounds I and herbicidal compositions using the compounds I, and process for controlling unwanted vegetation with the compounds I.

DE-A 40 00 624 describes specially substituted 1-phenyltriazines which are said to have a fungicidal action. A herbicidal effect is not mentioned. Thiotriazines are not mentioned.

EP-A 640 600 describes substituted 4-thiotriazines with herbicidal activity which have a 4-5 annulation in the phenyl substituent.

The subject of EP-A 584 655 and - to a small extent - also WO 99/05125 are aryl-triazinetrione of the type of compounds I and their use as herbicides. A large number of aryltriazines and arylthiotriazines fall under the general formulas; However, individual compounds with a thioketone group in the triazine part are not mentioned in either publication. Surprisingly, it has now been found that arylthiotriazines of the formula I as defined above have a particularly good herbicidal action. Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.

Depending on the substitution pattern, the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers. In the case of compounds I with at least one olefinic radical, E / Z isomers may also be possible. The invention relates both to the pure enantiomers or diastereomers and to their mixtures.

Agriculturally useful salts include, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I. So come as cations in particular the ions of the alkali metals, preferably sodium and potassium, the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion, which if desired one to four Cι -C ₄ alkyl and / or a phenyl or benzyl substituent can carry, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, further phosphonium ions, sulfonium ions, preferably tri (-C ₄ alkyl) sulfonium and sulfoxonium ions, preferably Tri (-C ₄ alkyl) sulfoxonium, into consideration.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C] _. -C ₄ -alkanoic acids, preferably formate, acetate, propionate and butyrate.

The organic molecule parts mentioned in the definition of R ¹ to R ³ , R ⁵ to R ²³ and on phenyl, cycloalkyl and heterocyclyl rings represent collective terms for individual lists of the individual group members. All carbon chains, ie all (optionally substituted) alkyl -, Alkenyl or alkynyl parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms.

Halogen is fluorine, bromine, chlorine or iodine, in particular fluorine or chlorine.

Furthermore, for example:

-C-C ₄ alkyl for: CH ₃ , C ₂ H ₅ , n-propyl, CH (CH ₃ ) ₂ , n-butyl, CH (CH ₃ ) -C ₂ H ₅ , 2-methylpropyl or C (CH ₃ ) ₃ , in particular for CH ₃ , C ₂ H ₅ or CH (CH ₃ ) ₂ ;

For Cι-C ₄ -haloalkyl: a _Cι-4 alkyl C as mentioned above, the, chlorine, bromine and / or iodine is partially or fully substituted by fluorine, eg CH ₂ F, CHF _2, CF _3, CHC1, Dichloromethyl, trichloroethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2 -Chlor-2,2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl, C ₂ F ₅ , 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3- Difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, CH ₂ -C ₂ F ₅ , CF ₂ -C ₂ F ₅ , 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4- Bromobutyl or nonafluorobutyl, in particular for CH ₂ F, CHF ₂ , CF ₃ , CH ₂ C1, 2-fluoroethyl, 2-chloroethyl or 2, 2, 2-trifluoret hyl;

- Ci-C _δ- alkyl for: -C-C ₄ alkyl as mentioned above, and for example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl , 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpenyl, 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 or l-ethyl-2-methylpropyl, in particular for CH ₃ , C ₂ H ₅ , n-propyl, CH (CH ₃ ) ₂ , n-butyl, C (CH ₃ ) ₃ , n-pentyl or n-hexyl;

Cι-C ₆ -haloalkyl: as mentioned above _Cι-C6 alkyl which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, eg one of said at Cι-C ₄ haloalkyl radicals or 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6- Fluoro-l-hexyl, 6-chloro 1-hexyl, 6-bromo-l-hexyl, 6-iodo-l-hexyl, 6, 6, 6-trichloro-l-hexyl or dodecafluorohexyl, especially for chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2- Chloroethyl or 2, 2, 2-trifluoroethyl;

Phenyl-Cx-C _ö -alkyl for: e.g. benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-1-yl, 1-phenylbut -l-yl, 2-phenylbut-l-yl, 3-phenylbut-l-yl, 4-phenylbut-l-yl, l-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2 -yl, 4-phenylbut-2-yl, 1- (phenylmethyl) -eth-1-yl, 1- (phenylmethyl) -1- (methyl) -eth-l-yl or 1- (phenylmethyl) prop -1-yl, especially for benzyl or 2-phenylethyl;

(-CC ₆ alkyl) carbonyl for: CO-CH ₃ , CO-C ₂ H ₅ ,, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1, 1- Dimethylethylcarbonyl, n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1, 1-dimethylpropylcarbonyl, 1, 2-dimethylpropylcarbonyl, 2, 2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1-methylpentyl carbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1, 1-dimethylbutylcarbonyl,

1, 2-dimethylbutylcarbonyl, 1, 3-dimethylbutylcarbonyl, 2, 2-dimethylbutylcarbonyl, 2, 3-dimethylbutylcarbonyl,

3, 3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1, 1, 2-trimethylpropylcarbonyl, 1,2,2-trimethylpropylcarbonyl, 1-ethyl-l-methylpropylcarbonyl or l-ethyl-2-methylpropylcarbonyl, especially for CO-CH ₃ , CO-C2H5 or CO-CH (CH ₃ ) ₂ ;

-C-C ₆ alkoxy for: for example OCH ₃ , OC ₂ H ₅ , OCH ₂ -C ₂ H ₅ , OCH (CH ₃ ) ₂ , n-butoxy, OCH (CH ₃ ) -C ₂ H ₅ , OCH ₂ - CH (CH ₃ ) ₂ , OC (CH ₃ ) ₃ , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethyl-propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy,

2, 3-dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-ethyl-l-methylpropoxy and l-ethyl 2-methylpropoxy, especially for OCH ₃ , OC ₂ H ₅ or OCH (CH ₃ ) ₂ ;

(-C-C ₆ alkoxy) carbonyl for: for example CO-OCH ₃ , CO-OC ₂ H ₅ , CO-CH ₂ -C ₂ H ₅ , CO-OCH (CH ₃ ) ₂ , n-butoxycarbonyl, CO-OCH (CH ₃ ) -C ₂ H ₅ , CO-OCH ₂ -CH (CH ₃ ) ₂ , CO-OC (CH ₃ ) ₃ , n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxy- carbonyl, 2, 2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hexoxycarbonyl, 1, 1-dirnethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methyl - pentoxycarbonyl, 1, 1-dimethylbutoxycarbonyl, 1, 2-dimethylbutoxycarbonyl, 1, 3-dimethylbutoxycarbonyl, 2, 2-dimethylbutoxycarbonyl, 2, 3-dimethylbutoxycarbonyl, 3, 3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1, 1, 2-trimethylpropoxycarbonyl, 1,2, 2-trimethylpropoxycarbonyl, 1-ethyl-l-methyl-propoxycarbonyl or l-ethyl-2-methyl-propoxycarbonyl, especially for CO-OCH ₃ , CO-OC ₂ H ₅ , CO-OCH (CH ₃ ) ₂ or CO-CH ₂ -CH (CH ₃ ) ₂ ;

(-C-C ₆ -alkoxy) carbonyloxy for: methoxycarbonyloxy, ethoxycarbonyloxy, n-propoxycarbonyloxy, 1-methylethoxycarbonyloxy, n-butoxycarbonyloxy, 1-methylpropoxycarbonyloxy, 2-methyl-propoxycarbonyloxy, 1, 1-dimethylethoxycarbonyloxy, n-pentoxycarbonyloxy , 1-methylbutoxycarbonyloxy, 2-methylbutoxycarbonyloxy, 3-methylbutoxycarbonyloxy, 2, 2-dimethylpropoxycarbonyloxy, 1-ethylpropoxycarbonyloxy, n-hexoxycarbonyloxy,

1, 1-dimethylpropoxycarbonyloxy, 1, 2-dimethylpropoxycarbonyloxy, 1-methylpentoxycarbonyloxy, 2-methylpentoxycarbonyloxy, 3-methylpentoxycarbonyloxy, 4-methylpentoxycarbonyloxy,

1, 1-dimethylbutoxycarbonyloxy, 1, 2-dimethylbutoxycarbonyloxy, 1, 3-dimethylbutoxycarbonyloxy, 2, 2-dimethylbutoxycarbonyloxy,

2, 3-dimethylbutoxycarbonyloxy, 3, 3-dimethylbutoxycarbonyloxy, 1-ethylbutoxycarbonyloxy, 2-ethylbutoxycarbonyloxy,

1,1, 2-Trimethylpropoxycarbonyloxy, 1,2, 2-Trimethylprop-oxycarbonyloxy, 1-ethyl-l-methyl-propoxycarbonyloxy or l-ethyl-2-methyl-propoxycarbonyloxy, especially for

Methoxycarbonyloxy, ethoxycarbonyloxy or 1-methylethoxycarbonyloxy;

Cx-Ce-alkylthio for: SCH ₃ , SC ₂ H ₅ , SCH ₂ -C ₂ H ₅ , SCH (CH ₃ ) _{2 '} n-butylthio, 1-methylpropylthio, 2-methylpropylthio, SC (CH ₃ ) ₃ , n -Pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, n-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-ethylbutyl - thio, 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-l-methylpropylthio and 1-ethyl-2-methylpropylthio, especially for SCH ₃ or SC ₂ H ₅ ; -C-C ₆ alkylsulfonyl for: S0 ₂ -CH ₃ , S0 ₂ -C ₂ H ₅ , n-propylsulfonyl,

S0 -CH (CH ₃ ) ₂ , n-butylsulfonyl, 1-methylpropylsulfonyl,

2-methylpropylsulfonyl, S0 ₂ -C (CH ₃ ) ₃ , n-pentylsulfonyl,

1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n-hexylsulfonylsulfonyl, 1 sulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl,

1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutylsulfonyl, 1, 3-dimethylbutylsulfonyl, 2, 2-dimethylbutylsulfonyl, 2, 3-dimethylbutylsulfonyl, 3, 3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 1-ethylsulfonyl, 2 Trimethyl - propylsulfonyl, 1,2, 2-trimethylpropylsulfonyl, 1-ethyl-l-methylpropylsulfonyl or l-ethyl-2-methylpropylsulfonyl, especially for S0 ₂ -CH ₃ ;

Cι-C ₆ -alkoxy-Cι-C6-alkyl viewed by C _δ alkoxy - as mentioned above - substituted _Cι-C6 alkyl, that is CH ₂ OCH _3, CH ₂ -0C ₂ H ₅ for example, , n-propoxymethyl, CH ₂ -OCH (CH ₃ ) ₂ , n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH ₂ -OC (CH ₃ ) ₃ , 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (1-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (1-methylpropoxy) ethyl, 2- ( 2-methylpropoxy) ethyl, 2- (1, 1-dimethylethoxy) ethyl, 2- (methoxy) ropyl, 2- (ethoxy) propyl, 2- (n-propoxy) propyl, 2- (1-methylethoxy) propyl,

2- (n-butoxy) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl, 2- (1, 1-dimethylethoxy) propyl, 3- (methoxy) propyl, 3- (Ethoxy) propyl, 3- (n-propoxy) propyl, 3- (l-methylethoxy) propyl, 3- (n-butoxy) propyl, 3- (1-methylpropoxy) propyl, 3- (2-methylpropoxy ) propyl, 3- (1, 1-dimethylethoxy) propyl, 2- (methoxy) butyl, 2- (ethoxy) bu yl, 2- (n-propoxy) butyl, 2- (l-methylethoxy) butyl, 2- (n-butoxy) butyl, 2- (l-methylpropoxy) butyl, 2- (2-methylpropoxy) butyl, 2- (1, 1-dimethylethoxy) butyl, 3- (methoxy) butyl, 3- ( Ethoxy) butyl, 3- (n-propoxy) butyl, 3- (1-methylethoxy) butyl, 3- (n-butoxy) butyl, 3- (1-methylpropoxy) butyl, 3- (2-methylpropoxy) butyl, 3- (1, 1-dimethylethoxy) butyl, 4- (methoxy) butyl, 4- (ethoxy) butyl, 4- (n-propoxy) butyl, 4- (1-methylethoxy) butyl, 4- (n-butoxy ) butyl, 4- (1-methylpropoxy) butyl, 4- (2-methylpropoxy) butyl or 4- (1, 1-dimethylethoxy) butyl, especially for CH ₂ -OCH ₃ or 2-methoxyethyl;

Ci-C _δ -alkoxy- (Ci-Cδ-alkoxy) carbonyl for: (Ci-C _δ- alkoxy) carbonyl substituted by Ci-C _δ- alkoxy as mentioned above, for example for CO-OCH ₂ -0CH ₃ , CO -OCH ₂ -0C ₂ H ₅ , C0-0CH ₂ -OCH ₂ -C ₂ H ₅ , CO-OCH ₂ -OCH (CH ₃ ) ₂ , n-butoxymethoxycarbonyl, (1-methylpropoxy) methoxycarbonyl, CO-OCH ₂ -OCH ₂ -CH (CH ₃ ) ₂ , CO-OCH ₂ -OC (CH ₃ ) ₃ , 2- (methoxy) ethoxycarbonyl, 2- (ethoxy) ethoxycarbonyl, 2- (n-propoxy) ethoxycarbonyl, 2- (l-methylethoxy) ethoxycarbonyl, 2- (n -Butoxy) ethoxycarbonyl, 2- (1-methylpropoxy) ethoxycarbonyl, 2- (2-methylpropoxy) ethoxycarbonyl, 2- (1, 1-dimethylethoxy) ethoxycarbonyl,

2- (methoxy) propoxycarbonyl, 2- (ethoxy) propoxycarbonyl, 2- (n-propoxy) propoxycarbonyl, 2- (1-methylethoxy) propoxycarbonyl, 2- (n-butoxy) propoxycarbonyl, 2- (l-methyl-propoxy) propoxycarbonyl, 2- (2-methylpropoxy) propoxycarbonyl, 2- (1, 1-dimethylethoxy) propoxycarbonyl, 3- (methoxy) propoxycarbonyl, 3- (ethoxy) ropoxycarbonyl, 3- (n-propoxy) propoxycarbonyl, 3- (1- Methylethoxy) propoxycarbonyl, 3- (n-butoxy) propoxycarbonyl, 3- (1-methylpropoxy) propoxycarbonyl, 3- (2-methylpropoxy) propoxycarbonyl, 3- (1, 1-dimethylethoxy) propoxycarbonyl, 2- (methoxy) butoxycarbonyl, 2 - (Ethoxy) butoxycarbonyl, 2- (n-propoxy) butoxycarbonyl, 2- (1-methylethoxy) butoxycarbonyl, 2- (n-butoxy) butoxycarbonyl, 2- (1-methylpropoxy) butoxycarbonyl, 2- (2-methylpropoxy) butoxycarbonyl , 2- (1, 1-Dirnethy1-ethoxy) butoxycarbonyl, 3- (methoxy) butoxycarbonyl,

3- (ethoxy) butoxycarbonyl, 3- (n-propoxy) butoxycarbonyl,

3- (1-methylethoxy) butoxycarbonyl, 3- (n-butoxy) butoxycarbonyl, 3- (1-methylpropoxy) butoxycarbonyl, 3- (2-methylpropoxy) butoxycarbonyl, 3- (1, 1-dimethylethoxy) butoxycarbonyl, 4 - (Methoxy) butoxycarbonyl, 4- (ethoxy) butoxycarbonyl, 4- (n-propoxy) butoxycarbonyl, 4- (1-methylethoxy) butoxycarbonyl, 4- (n-butoxy) butoxycarbonyl, 4- (1-methylpropoxy) butoxycarbonyl, 4 - (2-Methylpropoxy) butoxycarbonyl, 4- (1, 1-dimethylethoxy) butoxycarbonyl, 5- (methoxy) pentoxycarbonyl, 5- (ethoxy) pentoxycarbonyl, 5- (n-propoxy) pentoxycarbonyl, 5- (1-methylethoxy ) pentoxycarbonyl, 5- (n-butoxy) pentoxycarbonyl, 5- (1-methylpropoxy) pentoxycarbonyl, 5- (2-methylpropoxy) pentoxycarbonyl, 5- (1, 1-dimethylethoxy) pentoxycarbonyl, 6- (methoxy) hexoxycarbonyl, 6- (ethoxy) hexoxycarbonyl, 6- (n-propoxy) hexoxycarbonyl, 6- (l-methylethoxy) hexoxycarbonyl, 6- (n-butoxy) hexoxycarbonyl, 6- (1-methylpropoxy) exoxycarbonyl, 6- ( 2-methylpropoxy) hexoxycarbonyl or 6- (1, 1-dimethylethoxy) hexoxycarbonyl, in particular for CO-OCH ₂ -OCH ₃ or CO-OCH ₂ -OC ₂ H ₅ ;

_{(! C-C6} alkoxy) carbonyl-Ci-C _ö alkyl of: by (Cι-C ₆ alkoxy) - carbonyl as mentioned above substituted _Cι-C6 alkyl, eg methoxycarbonylmethyl, ethoxycarbonylmethyl, 1 - (Methoxycarbonyl) ethyl, 2 - (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 3 - (methoxycarbonyl) propyl, 4- (meth- oxycarbonyl) butyl, 5 - (methoxycarbonyl) pentyl or 6- (methoxycarbonyl) hexyl;

C ₃ -C ₆ alkenyl for: for example prop-2-en-l-yl, n-buten-4-yl, l-methyl-prop-2-en-l-yl, 2-methyl-prop-2- en-l-yl, 2-butene

1-yl, n-penten-3-yl, n-penten-4-yl, l-methyl-but-2-en-l-yl, 2-methyl-but-2-en-l-yl, 3- Methyl-but-2-en-l-yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-en-l-yl, 3-methyl-but-3-en- 1-yl, 1, l-dimethyl-prop-2-en-l-yl, 1, 2-dimethyl-prop-2-en-1-yl, l-ethyl-prop-2-en-l-yl, n-hex-3-en-l-yl, n-hex-4-en-1-yl, n-hex-5-en-l-yl, l-methyl-pent-3-en-l-yl, 2-methyl-pent-3-en-l-yl, 3-methyl-pent-3-en-l-yl, 4-methyl-pent-3-en-l-yl, l-methyl-pent-4- en-l-yl, 2-methyl-pent-4-en-l-yl, 3-methyl-pent-4-en-l-yl, 4-methyl-pent-4-en-l-yl, 1, l-dimethyl-but-2-en-l-yl, 1, l-dimethyl-but-3-en-l-yl, 1, 2-dimethyl-but-2-en-l-yl, 1, 2- Dimethyl-but-3-en-l-yl, 1, 3-dimethyl-but-2-en-l-yl, 1, 3-dimethyl-but-3-en-l-yl, 2, 2-dimethyl but-3-en-l-yl, 2, 3-dimethyl-but-2-en-l-yl, 2, 3-dimethyl-but-3-en-l-yl, 3, 3-dimethyl-but- 2-en-l-yl, l-ethyl-but-2-en-l-yl, l-ethyl-but-3-en-l-yl, 2-ethyl-but-2-en-l-yl, 2-ethyl-but-3-en-1-yl, 1, 1, 2-trimethyl-prop-2-en-1-yl, 1-ethyl-1-methyl-prop-2-en-1-yl or l-ethyl-2 -methyl-prop-2-en-l-yl, in particular for prop-2 -en-l-yl or n-buten-4-yl;

C ₂ -Cg alkenyl for: ethenyl or one of the radicals mentioned under C ₃ - Cβ alkenyl, in particular for ethenyl or prop-2-en-yl;

C ₃ -C ₆ alkenyloxy for: prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2-yloxy, n -Butene-3-yloxy, 1-methyl-prop-1-en-1-yloxy, 2-methyl-prop-1-en-1-yloxy, 1-methyl-prop-2-en-1-yloxy, 2 -Methyl-prop-2-en-l-yloxy, n-penten-1-yloxy, n-penten-2-yloxy, n-penten-3-yloxy, n-penten-4-yloxy ,, 1-methyl- but-l-en-l-yl-oxy, 2-methyl-but-l-en-l-yloxy, 3-methyl-but-l-en-l-yloxy, l-methyl-but-2-en- l-yloxy, 2-methyl-but-2-en-l-yloxy, 3-methyl-but-2-en-l-yloxy, l-methyl-but-3-en-l-yloxy, 2-methyl but-3-en-l-yloxy, 3-methyl-but-3-en-l-yloxy, 1, l-dimethyl-prop-2-en-l-yloxy, 1, 2-dimethyl-prop-l- en-l-yl - oxy, 1, 2-dimethyl-prop-2-en-l-yloxy, l-ethyl-prop-l-en-2-yl - oxy, l-ethyl-prop-2-en- l-yloxy, n-hex-1-en-l-yloxy, n-hex-2-en-1-yloxy, n-hex-3-en-l-yloxy, n-hex-4-en-l- yloxy, n-hex-5- en-1-yloxy, 1-methyl-pent-l-en-l-yloxy, 2-methyl-pent-l-en-1-yloxy, 3-methyl-pent-l- en-l-yloxy, 4-methyl-pent-l-en-l-yl-oxy, l-methyl-pent-2-en-l-yloxy, 2-methyl-pent-2-en-l-yloxy, 3-methyl-pent-2-en-l-yloxy, 4-methyl-pent-2-en-l-yloxy, l-methyl-pent-3-en-l-yloxy, 2-methyl-pent-3-en-l-yloxy, 3-methyl-pent-3-en-l-yloxy, 4-methyl-pent-3- en-l-yloxy, l-methyl-pent-4-en-l-yloxy, 2-methyl-pent-4-en-l-yloxy, 3-methyl-pent-4-en-l-yloxy, 4- Methyl-pent-4-en-l-yloxy, 1, l-dimethyl-but-2-en-l-yloxy, 1, l-dimethyl-but-3-en-l-yloxy, 1, 2-dimethyl but-l-en-l-yloxy, 1, 2-dimethyl-but-2-en-l-yloxy, 1, 2-dimethyl-but-3-en-l-yloxy, 1, 3-dirnethy1-but- l-en-l-yloxy,

1,3-dimethyl-but-2-en-l-yloxy, 1,3-dimethyl-but-3-en-l-yloxy,

2,2-dimethyl-but-3-en-l-yloxy, 2,3-dimethyl-but-l-en-l-yloxy, 2,3-dimethyl-but-2-en-l-yloxy, 2, 3-dimethyl-but-3-en-l-yloxy,

3,3-dimethyl-but-l-en-l-yloxy, 3,3-dimethyl-but-2-en-l-yloxy, 1-ethyl-but-l-en-l-yloxy, l-ethyl but-2-en-l-yloxy, 1-ethyl-but-3-en-l-yloxy, 2-ethyl-but-l-en-l-yloxy, 2-ethyl-but-2-en-1- yloxy, 2-ethyl-but-3-en-l-yloxy, 1, 1, 2-trimethyl-prop-2-en-1-yloxy, l-ethyl-l-methyl-prop-2-en-l- yloxy, 1-ethyl-2-methyl-prop-1-en-1-yloxy or 1-ethyl-2-methyl-prop-2-en-1-yloxy, in particular for prop-2-en-1-yloxy;

C ₂ -C ₆ alkenyloxy for: ethenyloxy or one of the radicals mentioned under C3-C6-alkenyloxy, in particular for ethenyloxy or prop-2-en-1-yloxy;

C ₂ -C ₆ alkenylthio for: ethenylthio, prop-1-en-l-ylthio, prop-2-en-l-ylthio, 1-methylethenylthio, n-buten-1-ylthio, n-buten-2-ylthio , n-buten-3-ylthio, 1-methyl-prop-l-en-l-yl-thio, 2-methyl-prop-l-en-l-ylthio, l-methyl-prop-2-en-l -yl-thio, 2-methyl-prop-2-en-l-ylthio, n-penten-1-ylthio, n-penten-2-ylthio, n-penten-3-ylthio, n-penten-4-ylthio , 1-methyl-but-l-en-l-ylthio, 2-methyl-but-l-en-l-ylthio, 3-methyl-but-l-en-l-ylthio, l-methyl-but-2 -en-l-ylthio, 2-methyl-but-2-en-l-ylthio, 3-methyl-but-2-en-l-ylthio, l-methyl-but-3-en-l-ylthio, 2-methyl-but-3-en-l-ylthio, 3-methyl-but-3-en-l-ylthio, 1, 1-dirnethy1-prop-2-en-l-ylthio, 1, 2-dirnethyl- prop-1-en-l-ylthio, 1, 2-dimethyl-prop-2-en-1-ylthio, l-ethyl-prop-l-en-2-ylthio, l-ethyl-prop-2-en-

1-ylthio, n-hex-1-en-l-ylthio, n-hex-2-en-l-ylthio, n-hex-3-en-l-ylthio, n-hex-4-en-l- ylthio, n-hex-5-en-l-ylthio, 1-methyl-pent-l-en-l-ylthio, 2-methyl-pent-l-en-l-ylthio, 3-methyl-pent-l- en-l-ylthio, 4-methyl-pent-l-en-l-ylthio, l-methyl-pent-2-en-l-ylthio, 2-methyl-pent-2-en-l-ylthio, 3- Methyl-pent-2-en-l-ylthio, -methyl-pent-2-en-l-ylthio, 1-methyl-pent-3-en-l-ylthio, 2-methyl-pent-3-en-l -ylthio, 3-methyl-pent-3-en-l-ylthio, 4-methyl-pent-3-en-l-ylthio, 1-methyl-pent-4-en-l-ylthio, 2-methyl-pent -4-en-l-ylthio, 3-methyl-pent-4-en-l-ylthio, 4-methyl-pent-4-en-l-ylthio,

1, l-dimethyl-but-2-en-l-ylthio, 1, l-dimethyl-but-3-en-l-ylthio, 1,2-dimethyl-but-l-en-l-ylthio, 1, 2-dimethyl-but- 2-en-l-ylthio, 1, 2-dimethyl-but-3-en-l-ylthio, 1, 3-dimethyl-but-1-en-l-ylthio, 1, 3-dimethyl-but-2- en-l-ylthio, 1,3-dimethyl-but-3-en-l-ylthio, 2, 2-dimethyl-but-3-en-l-ylthio, 2, 3-dimethyl-but-l- en-l-ylthio, 2, 3-dimethyl-but-2-en-l-yl-thio, 2, 3-dimethyl-but-3-en-l-ylthio, 3, 3-dimethyl-but-l- en-1-ylthio, 3,3-dimethyl-but-2-en-l-ylthio, 1-ethyl-but-l-en-1-ylthio, l-ethyl-but-2-en-l-ylthio, l-ethyl-but-3-en-l-ylthio, 2-ethyl-but-l-en-l-ylthio, 2-ethyl-but-2-en-l-ylthio, 2-ethyl-but- 3-en-l-ylthio, 1, 1, 2-trimethyl-prop-2-en-l-yl-thio, l-ethyl-l-methyl-prop-2-en-l-ylthio, l-ethyl- 2-methyl-prop-1-en-1-ylthio or 1-ethyl-2-methyl-prop-2-en-1-ylthio, in particular for ethenylthio or prop-2-en-1-ylthio;

C ₃ -C ₆ alkynyl for: prop-1-in-l-yl, prop-2-in-l-yl, n-but-1-in-l-yl, n-but-l-in-3 -yl, n-but-l-in-4-yl, n-but-2-in-l-yl, n-pent-1-in-l-yl, n-pent-l-in-3-yl , n-pent-1-in-4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n Pent-2-in-5-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, n-hex-1-in-l-yl , n-hex-1-in-3-yl, n-hex-1-in-4-yl, n-hex-1-in-5-yl, n-hex-1-in-6-yl, n -Hex-2-in-1-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex -3-in-1-yl, n-hex-3-in-2-yl, 3-methyl-pent-1-in-1-yl, 3-methyl-pent-1-in-3-yl, 3 -Methyl-pent-1-in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2-in -4-yl or 4-methyl-pent-2-yn-5-yl, especially for prop-2-yn-yl;

C ₂ -C ₆ alkynyl for: ethynyl or one of the radicals mentioned under C ₃ - Qς, -alkynyl, in particular for ethynyl or prop -2-in-l-yl;

C ₃ -C ₆ alkynyloxy for: prop-1-in-l-yloxy, prop-2-in-l-yloxy, n-but-1-in-l-yloxy, n-but-l-in-3 -yloxy, n-but-l-in-4-yloxy, n-but-2-in-l-yloxy, n-pent-1-in-yloxy, n-pent-1-in-3-yloxy , n-pent-1-yn-4-yloxy, n-pent-1-yn-5-yloxy, n-pent-2-yn-yl-oxy, n-pent-2-yn-4-yloxy , n-Pent-2- in-5-yloxy, 3-methyl-but-l-in-3-yloxy, 3-methyl-but-l-in-4-yloxy, n-hex-1- in-l -yl-oxy, n-hex-1-in-3-yloxy, n-hex-1-in-4-yloxy, n-hex-1-in-5-yl-oxy, n-hex-1 -in -6-yloxy, n-hex-2 -in-1-yloxy, n-hex-2-in-4 -yl-oxy, n-hex-2 -in-5-yloxy, n-hex-2 -in -6-yloxy, n-hex-3-in-1-yloxy, n-hex-3-in-2-yloxy, 3-methylpent-1-in-1-yloxy, 3-methylpent-1 -in-3-yloxy, 3-methyl-pent-l-in-4-yloxy, 3-methyl-pent-l-in-5-yloxy, 4-methyl-pent-l-in-l-yloxy, 4 -Methyl-pent-2-in-4-yloxy or 4-methylpent-2-in-5-yloxy, especially for prop-2-in-1-yloxy; C ₂ -C ₆ alkynyloxy for: ethynyloxy or one of the radicals mentioned under C ₃ -C ₆ -alkynyloxy, in particular for ethynyloxy or prop-2-yn-l-yloxy;

C ₂ -C ₆ alkynylthio for: ethynylthio or one of the below

Radicals called C ₃ -C ₆ -alkynylthio, in particular for ethynylthio or prop-2-yn-1-ylthio;

(C ₃ -C ₆ alkenyloxy) carbonyl for: prop-1-en-l-yloxycarbonyl, prop-2-en-l-yloxycarbonyl, 1-methylethenyloxycarbonyl, n-buten-1-yloxycarbonyl, n-buten-2- yloxycarbonyl, n-butene-3-yloxycarbonyl, 1-methyl-prop-l-en-l-yloxycarbonyl, 2-methyl-prop-1-en-l-yloxycarbonyl, l-methyl-prop-2-en-l- yloxycarbonyl, 2-methyl-prop-2-en-l-yloxycarbonyl, n-pentene-1-yloxycarbonyl, n-pentene-2-yloxycarbonyl, n-pentene-3-yloxycarbonyl, n-pentene-4- yloxycarbonyl, 1-methyl-but-l-en-l-yloxycarbonyl, 2-methyl-but-l-en-l-yloxycarbonyl, 3-methyl-but-1-en-l-yloxycarbonyl, l-methyl-but- 2-en-l-yloxycarbonyl, 2-methyl-but-2-en-l-yloxycarbonyl, 3-methyl-but-2-en-l-yloxycarbonyl, l-methyl-but-3-en-l- yloxycarbonyl, 2-methyl-but-3-en-1-yloxycarbonyl, 3-methyl-but-3-en-l-yloxycarbonyl, 1, l-dimethyl-prop-2-en-l-yloxycarbonyl, 1, 2- Dimethyl-prop-l-en-1-yloxycarbonyl, 1, 2-dimethyl-prop-2-en-l-yloxycarbonyl, l-ethyl-prop-l-en-2-yloxycarbonyl, l-ethyl-prop-2- en-l-yloxycarbonyl, n-hex-1-en-l-yloxycarbonyl, n-hex-2-en-l-yloxycarbonyl, n-hex-3-en-l-yloxycarbonyl, n-hex-4-en-l-yloxycarbonyl, n-hex-5-en-l- yloxycarbonyl, 1-methyl-pent-l-en-l-yloxycarbonyl, 2-methyl-pent-l-en-l-yloxycarbonyl, 3-methyl-pent-1-en-l-yloxycarbonyl, 4-methyl-pent- l-en-l-yloxycarbonyl, l-methyl-pent-2-en-l-yloxycarbonyl, 2-methyl-pent-2-en-l-yloxycarbonyl, 3-methyl-pent-2-en-l- yloxycarbonyl, 4-methyl-pent-2-en-l-yloxycarbonyl, l-methyl-pent-3-en-l-yloxycarbonyl, 2-methyl-pent-3-en-l-yloxycarbonyl, 3-methyl-pent- 3-en-l-yloxycarbonyl, 4-methyl-pent-3-en-l-yloxycarbonyl, l-methyl-pent-4-en-l-yloxycarbonyl, 2-methyl-pent-4-en-l- yloxycarbonyl, 3-methyl-pent-4-en-l-yloxycarbonyl, 4-methyl-pent-4-en-1-yloxycarbonyl, 1, l-dimethyl-but-2-en-l-yloxycarbonyl, 1, l- Dimethyl-but-3-en-l-yloxycarbonyl, 1, 2-dimethyl-but-1-en-l-yloxycarbonyl, 1, 2-dimethyl-but-2-en-l-yloxycarbonyl, 1, 2-dimethyl- but-3-en-1-yloxycarbonyl, 1,3-dimethyl-but-1-en-1-yloxycarbonyl, 1, 3-dimethyl-but-2-en-1-yloxycarbonyl, 1, 3-di methyl-but-3-en-l-yloxycarbonyl, 2, 2-dimethyl-but-3-en-l-yloxycarbonyl, 2, 3-dimethyl-but-l-en-l-yloxycarbonyl, 2, 3-dimethyl but-2-en-l-yloxycarbonyl, 2,3-dimethyl-but-3-en-l-yloxycarbonyl, 3, 3-dimethyl-but-l-en-l-yloxycarbonyl, 3, 3-dimethyl- but-2-en-l-yloxycarbonyl, 1-ethyl-but-l-en-l-yloxycarbonyl, l-ethyl-but-2-en-l-yloxy- carbonyl, 1-ethyl-but-3-en-l-yloxycarbonyl, 2-ethyl-but-l-en-1-yloxycarbonyl, 2-ethyl-but-2-en-l-yloxycarbonyl, 2-ethyl-but- 3-en-l-yloxycarbonyl, 1,1, 2-trimethyl-prop-2-en-1-yloxycarbonyl, l-ethyl-l-methyl-prop-2-en-l-yloxycarbonyl, l-ethyl-2- methyl-prop-1-en-1-yloxycarbonyl or 1-ethyl-2-methyl-prop-2-en-1-yloxycarbonyl, in particular for prop-2-en-1-yloxycarbonyl;

(C ₃ -C ₆ alkenyloxy) carbonyl -CC ₆ alkyl for: by (C3-C6-alkenyloxy) carbonyl as mentioned above, preferably prop-2-en-1 -yloxycarbonyl, substituted Ci-C _δ Alkyl, for example prop-2 -en-1-yloxycarbonylmethyl;

(C ₃ -C ₆ alkynyloxy) carbonyl for: prop-1-in-l-yloxycarbonyl, prop-2-in-l-yloxycarbonyl, n-but-1-in-l-yloxycarbonyl, n-but-l- in-3-yloxycarbonyl, n-but-l-in-4-yloxycarbonyl, n-but-2-in-l-yloxycarbonyl, n-pent-1-in-l-yloxycarbonyl, n-pent-l-in- 3-yloxycarbonyl, n-pent-l-in-4-yloxycarbonyl, n-pent-l-in-5-yloxycarbonyl, n-pent-2-in-l-yloxycarbonyl, n-pent-2-in-4- yloxycarbonyl, n-pent-2-yn-5-yloxycarbonyl,

3-methyl-but-l-in-3-yloxycarbonyl, 3-methyl-but-1-in-yloxycarbonyl, n-hex-1-in-l-yloxycarbonyl, n-hex-1-in-3-yloxycaryl bonyl, n-hex-1-in-4-yloxycarbonyl, n-hex-1-in-5-yloxycarbonyl, n-hex-1-in-6-yloxycarbonyl, n-hex-2-in-1 -yloxycarbonyl, n-Hex-2-in-4-yloxycarbonyl, n-Hex-2-in-5-yloxycarbonyl, n-Hex-2-in-6-yloxycarbonyl, n-Hex-3-in-l-yloxycarbonyl , n-Hex-3-in-2-yloxycarbonyl, 3-methylpent-1-in-1-yloxycarbonyl, 3-methyl-pent-l-in-3-yloxycarbonyl, 3-methyl-pent-l-in-4 -yl-oxycarbonyl, 3-methyl-pent-1-in-5-yloxycarbonyl, 4-methyl-pent-1-in-1-yloxycarbonyl, 4-methyl-pent-2-in-4-yloxycarbonyl or 4 -Methylpent-2-in-5-yloxycarbonyl, in particular for ethynyloxycarbonyl or prop-2-yn-1-yloxycarbonyl;

C ₃ -C ₆ cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

C ₃ -C ₆ cycloalkyl -CC ₄ alkyl for: z. B. cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, 1- (cyclopropyl) ethyl, 1- (cyclobutyl) ethyl, 1- (cyclopentyl) ethyl, 1- (cyclohexyl) ethyl, 2- (cyclopropyl) ethyl,

2- (cyclobutyl) ethyl, 2- (cyclopentyl) ethyl, 2- (cyclohexyl) ethyl, 3- (cyclopropyl) propyl, 3- (cyclobutyl) ropyl, 3- (cyclopentyl) propyl, 3- (cyclohexyl) propyl, 4 - (Cyclopropyl) butyl, 4- (cyclobutyl) butyl, 4- (cyclopentyl) butyl or 4- (cyclohexyl) butyl, especially for cyclopentylmethyl or cyclohexylmethyl; C ₃ -C ₆ cycloalkoxy for: cyclopropyloxy, cyclobutyloxy, cyclopentyloxy or cyclohexyloxy;

C ₃ -C ₆ cycloalkylthio for: cyclopropylthio, cyclobutylthio, cyclopentylthio or cyclohexylthio.

4- to 7-membered azaheterocycles, which in addition to carbon ring members may also contain an oxygen or sulfur atom as a ring member, are e.g. Azetidin-1-yl, pyrrolidin-1-yl, isoxazolidin-2-yl, isothiazolidin-2-yl, oxazolidin-3-yl,

Thiazolidin-3-yl, piperidin-1-yl, morpholin-1-yl, thiomorpholine-l-yl and azepin-1-yl.

With regard to the use of the 1-aryl-4-thiotriazines of the formula I according to the invention as herbicides, the variables preferably have the following meanings, individually or in combination:

R ^{1 is} hydrogen, amino or methyl, especially methyl;

R ^{2 is} hydrogen, amino or methyl, especially methyl;

R ^{3 is} hydrogen or fluorine, in particular fluorine,

R ⁴ cyano or halogen, in particular a) cyano; b) chlorine;

Y is the methine group or together with R ⁵ a bridge> C-0-C (R ⁶ ) = N-, in particular a) the methine group; b) together with R ⁵ a bridge> C-0-C (R ⁶ ) = N-;

R5 1) on the one hand hydrogen, nitro or halogen; on the other hand, -C ₆ "alkyl or Ci -C _ß haloalkyl;

2) C ₁ -C ₆ alkoxy or C ₆ -C ₆ alkylthio, where each of these two radicals can, if desired, bear one of the following substituents: cyano, -CO-R ⁸ , -CO-OR ⁸ or -C0-N (R ⁸ ) -R ⁹ , in particular methoxy, ethoxy, n-propyloxy, isopropoxy, methylthio, ethylthio, n-propylthio or isopropylthio, where each of these 8 radicals can optionally carry a substituent -CO-OR ⁸ , particularly preferred

(C ₃ -C ₆ alkenyloxy) carbonyl methoxy, (C ₃ -Cβ-alkynyloxy) carbonyl-methoxy, 1- [(C ₃ -C ₆ alkenyloxy) carbonyl] eth-1-yloxy, 1- [(C -C6-Alkynyloxy) carbonyl] eth-1-yloxy, C _3. -C ₄ -alkoxy- (Cι-C ₄ -alkoxy) carbonyl-methoxy, 1- [Cι-C ₄ -alkoxy- ( -C-C ₄ -alkoxy) carbonyl] eth-1-yloxy, (C ₃ -C ₆ -alkenyloxy) carbonyl -methylthio, (C ₃ -C ₆ -alkynyl-oxy) carbonyl -methylthio, 1- [(C ₃ - C ₆ alkenyloxy) carbonyl] eth-1-ylthio, 1- [(C ₃ -C ₆ alkynyloxy) carbonyl] eth-1-ylthio, C ₁ -C ₄ alkoxy- (Ci -C ₄ alkoxy ) carbonylmethylthio or 1- [C ₁ -C ₄ alkoxy- (-C-C ₄ - alkoxy) carbonyl] eth- 1 -ylthio;

on the other hand C ₃ -C ₆ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, C -C ₆ alkenyloxy, C ₂ -C ₆ alkenylthio, C ₂ -C ₆ alkynyloxy or C ₂ -C ₆ alkynylthio, each of which if desired, these 6 radicals can carry one of the following substituents:

Cyano, -CO-R ⁸ , -CO-OR ⁸ or -CO-N (R ⁸ ) -R ⁹ , in particular cyclopentyloxy, cyclopentyl thio, allyloxy,

Allylthio, propargyloxy or propargylthio;

3) on the one hand -CO-R ¹¹ , -C (R ¹¹ ) = C (R ¹⁵ ) -CO-R ¹⁶ ,

-CH (R ¹¹ ) -CH (R ¹⁵ ) -CO-R ¹⁶ , -C (R ¹⁰ ) = N-OR ⁷ , -N (R ²¹ ) -R ²² or -CO-N (R ²¹ ) -R ²² , in particular CHO, -CH = C (R ¹⁵ ) -CO-R ¹⁶ , -CH ₂ -CH (R ¹⁵ ) -CO-R ¹⁶ , -CH = N-OR ⁷ , -C (CH ₃ ) = N -OR ⁷ , -N (R ¹ ) -R ²² or -CO-N (R ²¹ ) -R ²² ; on the other hand, -CO-OR ²⁰ ;

R ^{8 is} hydrogen, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

C ₃ -C ₅ cycloalkyl -CC ₄ alkyl or -C ₄ alkoxy-C ₁ -C ₄ alkyl, in particular C ₃ -C 6 alkenyl;

R ⁸ 'is hydrogen, -CC ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ alkenyl,

C ₃ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl -Ci -C ₄ alkyl or Cι-C ₄ -alkoxy-Cι-C alkyl, in particular Ci -C ₆ alkyl;

R ^{9 is} hydrogen;

R ^{11 is} hydrogen;

R ^{15 is} hydrogen, halogen or -CC ₆ alkyl, especially hydrogen, chlorine, bromine or methyl, particularly preferably chlorine;

R ²⁰ C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, _± -C ₄ alkoxy-C _! -C ₄ alkyl,

(C ₃ -C ₆ alkenyloxy) carbonylmethyl, (C ₃ -C ₆ alkynyloxy) carbonylmethyl, 1- (C ₃ -C ₆ alkenyloxy) carbonyl -eth-1 -yl, 1- (C ₃ -C ₆ -alkynyloxy) carbonyl-eth-1 -yl,

Ci -C ₄ alkoxy- (C ₁ -C ₄ alkoxy) carbonylmethyl,

1- [C ₁ -C ₄ alkoxy- (C ₁ -C ₄ alkoxy) carbonyl] -eth-1-yl, 2- [(C ₃ -C ₆ - Alkenyloxy) carbonyl] -prop-2 -yl, C ₃ -C _δ -cycloalkyl or

C ₃ -C ₆ cycloalkyl-Ci -C-alkyl;

Are hydrogen, C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl, where the last 3 groups may carry one of the following radicals, respectively: _Cι-C6 alkoxy, (Cι-C ₆ -Alkoxy) carbonyl or (C ₃ -C ₆ -alkenyloxy) carbonyl.

The 1-aryl -4-thiotriazines of the formula Ia are very particularly preferred (= I with R ² = methyl and Y = the methine group)

in particular the compounds la.l to Ia.720 listed in the following Table 1:

Table 1

Furthermore, the l-aryl-4-thiotriazines of the formula Ib are particularly preferred, in particular the compounds Ib.l to Ib.720, which differ from the corresponding compounds la.l to la.720 only in that R ^{2 is} amino stands:

In addition, the l-aryl-4-thiotriazines of the formula Ic {= I with

particularly preferred, in particular the compounds Ic.l to Ic.55 listed in Table 2 below:

Table 2

The l-aryl-4-thiotriazines of the formula I can be obtained in various ways, in particular by one of the following processes:

A) Analog J. Chem. Soc. Perkin Trans. (1982), 1321

Ch OH

Well,

I (R ² = CH ₃ )

For the conditions when carrying out the reaction, reference is made to the literature reference mentioned.

B) Analog J. Chem. Soc. Perkin Trans. (1992), 1139

III IV For the conditions of the reaction, reference is made to the literature reference mentioned.

According to a preferred process, which is a further subject of the invention, the l-aryl-4-thiotriazines according to the invention are prepared by reacting aryl isocyanates with thioureas and subsequent cyclization.

According to a particularly preferred embodiment of process C according to the invention, the isocyanate is reacted with the thiourea in the presence of an activated carbon dioxide source. Examples include carbodiimidazole, phosgene, diphosgene and triphosgene, and chloroformic acid esters.

Process (C)) according to the invention and processes (A>) and (B)) for the preparation of the compounds of the formula (I) are preferably carried out in the presence of a suitable reaction auxiliary.

The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogen carbonates, hydrides, hydroxides or alkanolates, for example 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 iso- propanolate, n-, iso-, sec- or tert. -butanolate; also basic organic nitrogen compounds, for example trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N, N-dimethylcyclohexylamine, di-cyclohexylamine, ethyldicyclohexylamine, 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-dimethylpyridine, 5 -Ethyl-2-methylpyridine, 4-dimethylanimopyridine, N-methylpiperidine, 1, 4-diazabicyclo [2, 2, 2] octane (DABCO), 1, 5-diazabicyclo [4,3, 0] -non-5-ene (DBN) or 1.8 diazabicyclo [5, 4, 0] -undec-7-ene (DBU).

Process (C>) according to the invention and processes (A)) and (B)) for the preparation of the compound of the formula (I) are preferably carried out in the presence of a diluent. The usual organic solvents are generally suitable as diluents. These preferably include aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons, for example pentane, hexane, heptane, petrol ether, ligroin, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane (Chloroform) or carbon tetrachloride, dialkyl ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether (MTBE), ethyl tert. -butyl ether, methyl tert. - pentyl ether (TAME), ethyl tert-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethyl ether; Dialkyl ketones such as acetone, butanone (methyl ethyl ketone), methyl isopropyl ketone and methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile; Amides such as N, N-dimethylformamide (DMF), N, N-dimethyl-acetamide, N-methylformanilide, N-methylpyrrolidone and hexamethyl-phosphoric acid triamide; Esters such as methyl acetate, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester and sec-butyl ester; Sulfoxides such as dimethyl sulfoxide;

Alkanols such as methanol, ethanol, n-propanol, isopropanol, n-, iso-, sec- and tert. Butanol; Glycol ethers such as ethylene glycol monomethyl ether, monoethyl ether, diethylene glycol monomethyl ether and monoethyl ether; their mixtures with water or pure water.

The reaction temperatures can be varied within a substantial range when carrying out processes (B)) and (C)). In general, temperatures from 0 to 200 ° C, preferably at 10 to 150 ° C, in particular at 20 ° C to the boiling point of the reaction mixture.

To carry out processes (A)), (B)) and (C>), 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, for example up to twice the molar amount of the other component.

The processes (A)), (B>) and (C>) are expediently used in

Atmospheric pressure or under the autogenous pressure of the respective reaction mixture. However, it is also possible to ren under increased or reduced pressure - generally at

0.1 to 10 bar.

The respective reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and then isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and working up the organic phase towards the product.

In general, the l-aryl-4-thiotriazines I can be prepared by one of the synthesis methods mentioned above. For economic or procedural reasons, however, it may be more expedient to produce some compounds I from similar l-aryl-4-thiotriazines - which differ, however, in particular in the meaning of the radicals R ⁵ - in a manner known per se, for example by hydrolysis Esterification

Transesterification, amidation, acetalization, acetal hydrolysis, condensation reaction, Wittig reaction, Peterson olefination, etherification, alkylation, oxidation or reduction.

The l-aryl-4-thiotriazines I can be used in the preparation as

Mixtures of isomers are obtained, which, however, can, if desired, be separated into the pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.

Agricultural salts of the compounds I can be formed by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride, or by reaction with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

Salts of I, the metal ion of which is not an alkali metal ion, can also be prepared in a conventional manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides. 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, maize, soybeans and cotton, they work against weeds and grass weeds without causing any significant damage to crops. This effect occurs especially at low application rates.

Depending on the particular application method, the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants. For example, the following crops are suitable: Allium cepa, pineapple 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 brasiliensiε, Hordeum vulgare, Humulus lupulus, Linpusumumumumisas , 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 sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticitic aestum Vicia faba, Vitis vinifera and 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 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, sprays or granules , Atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should be as possible ensure the finest distribution of the active ingredients according to the invention.

The following are essentially considered as inert auxiliaries: mineral oil fractions of medium to high boiling point such as

Kerosene and diesel oil, also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. Amines such as N-methylpyrrolidone and 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 oldispersions, the l-aryl-4-thiotriazines I as such or 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 alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanoien as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl ethoxylated, polyethylenethoxy alcohol, fatty alcohol alcohol, fatty alcohol Polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor 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, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, 5 chalks, boluses, 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 10 solid carriers.

The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. In general, the formulations contain about 0.001 to 15 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).

20 The following formulation examples illustrate the preparation of such preparations:

I. 20 parts by weight of compound no. 3 are dissolved in a mixture which is alkylated from 80 parts by weight

25 benzene, 10 parts by weight of the adduct of

There are 8 to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanol amide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide in 1 mole of castor oil. By training

Pouring 30 and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

II. 20 parts by weight of compound No. 5 are dissolved in a 35 mixture consisting of 40 parts by weight of cyclohexanone,

30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the additive of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

III. 20 parts by weight of active ingredient No. 12 are dissolved in a 45 mixture consisting of 25 parts by weight of cyclohexanone,

65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the addition Product of 40 moles of ethylene oxide to 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous solution

Dispersion containing 0.02% by weight of the active ingredient.

IV. 20 parts by weight of active ingredient No. 32 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic 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. 36 are with

97 parts by weight of finely divided kaolin mixed. In this way, a dusting agent is obtained which contains 3% by weight of the active ingredient.

VI. 20 parts by weight of active ingredient No. 41 are 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 mixed intimately. A stable oily dispersion is obtained.

VII. 1 part by weight of compound no. 42 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone,

20 parts by weight of ethoxylated isooctylphenol and

There are 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII. 1 part by weight of compound no. 64 is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol * EM 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG). A stable emulsion concentrate is obtained.

The active ingredients I or the herbicidal compositions 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 not hit, if possible, while the active ingredients are applied to the leaves including growing unwanted plants or the uncovered

Floor space (post-directed, lay-by).

The application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.

In order to broaden the spectrum of action and to achieve synergistic effects, the l-aryl-4-thiotriazines I 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, aryloxy- / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2- (Hetaroyl / Aroyl) - 1, 3 -cyclohexanediones, heteroaryl-aryl-ketones, benzylisoxazolidinones, meta-CF ₃ -phenyl derivatives, carbamates, quinolinecarboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3-dione derivatives, diazine acid and dichloro 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-tetrahydrophthalimides azoles, oxiranes, phenols, aryloxy and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridine carbon Acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and 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. Manufacturing examples

Example 1 (Compound No. 38)

3- (2,4-difluorophenyl) -1,5-dimethyl-6-thioxo- [1,3,5] tri-5 azinane-2,4-dione

31 g of 2,4-difluorophenyl isocyanate and 64.9 g of carbodiimidazole were added in succession to 20.8 g of N, N'-dimethylthiourea in 500 ml of toluene and 1 ml of triethylamine. This mixture was only

15 3 hours at 60-65 ° C and then 12 hours at 80-85 ° C. After cooling to room temperature, the mixture was washed three times with 100 ml of water each time and the organic phase was dried over sodium sulfate. After the low-boiling fractions had been distilled off, 48 g of the desired product with a melting point of

20 156-159 ° C.

Example 2 (Compound No. 40)

2-chloro-5- (3,5-dimethyl-2,6-dioxo-4-thioxo - [1,3,5] criazanan-1-yl) -benzaldehyde-O-ethyl-oxime

25

To 1.3 g of N, N'-dimethylurea in 20 ml of toluene and 0.4 ml of triethylamine, 2.8 g of 3-ethoxyiminoethyl-4-chloro -

35 phenyl isocyanate and 4 g of carbodiimidazole. This mixture was first stirred at 60 ° C. for 2 hours and then at 80 ° C. for 4 hours. After cooling to room temperature, the mixture was washed four times with 20 ml of water each time and the organic phase was dried over sodium sulfate. The remaining residue after the solvent has been distilled off

40 was cleaned chromatographically on silica gel (mobile phase: cyclohexane / ethyl acetate). Yield: 2.02 g; Mp: 139-141 ° C.

Example 3 (Compound No. 1) 45 3- (4-chloro-2-fluoro-5-hydroxyphenyl) -1, 5-dimethyl-6-thioxo [1,3,5] triazinan-2, 4-dion

3 ml of triethylamine and then a solution of 22.4 g (91.2 mmol.) Were added to a solution of 9.5 g (91.2 mmol) of N, N'-dimethylthiourea in 20 ml of toluene at approx. 20 ° C ) 4

Drops of chloro-2-fluoro-5- (methoxycarbonyloxy) phenyl isocyanate in 100 ml of toluene. After adding 29.6 g (182.5 mmol) of carbodiimidazole, the mixture was heated at 80 ° C. for 3 hours. The reaction mixture was stirred at about 20 ° C. overnight, then washed three times with water and finally concentrated under reduced pressure. The crude product was purified by column chromatography (mobile phase: cyclohexane / ethyl acetate = 10: 1). Yield: 18.1 g (63%); Mp: 242-246 ° C.

Example 4 (Compound No. 11)

2- [2-chloro-5- (3,5-dimethyl-2,6-dioxo [1,3,5] triazinan-1-yl) -4-fluoro-phenoxy] propionic acid allyl ester (racemate)

To a solution of 0.80 g (2.52 mmol) of 3- (4-chloro-2-fluoro-5-hydroxy-phenyl) -1,5-dimethyl-6-thioxo- [1,3,5 ] triazinan-2, 4-dione in 15 ml of dimethylformamide were 0.37 g (2.65 mmol) of K ₂ CO ₃ and 0.51 g (2.65 mmol) of rac at about 20 ° C. Given 2-Bromopropionic acid allyl ester. After two hours of stirring at about 20 ° C, the reaction mixture was stirred into ice water. The product was three times with methyl tert. -butyl ether extracted. The combined organic phases were dried over magnesium sulfate and then concentrated. The crude product (1.18 g) was purified by column chromatography (mobile phase: cyclohexane / ethyl acetate = 15: 1). Yield: 0.88 g (81%);

ⁱ H-NMR (270 MHz, in CDCI3): δ [ppm] = 1.7 (d, 3H), 3.8 (s, 6H), 4.6 (m, 2H), 4.7 (q, 1H), 5.2 (d, 1H) ), 5.3 (d, 1H), 5.9 (m, 1H), 6.9 (d, 1H), 7.3 (d, 1H). Example 5 (Compound No. 12)

(R) -2- [2-chloro-5- (3,5-dimethyl-2,6-dioxo- [1,3,5] triazinane

1-yl) -4-fluorophenoxy] propionic acid allyl ester (R isomer)

CH ₃

To a mixture of 0.50 g (1.58 mmol) of 3- (4-chloro-2-fluoro-5-hydroxy-phenyl) -1,5-dimethyl-6-thioxo- [1,3,5 ] triazinan-2, 4-dione, 0.20 g (1.58 mmol) S-lactic acid allyl ester and 0.48 g (1.81 mmol) triphenylphosphine were added at 0 ° C within 5 minutes to 0.38 g (1, 89 mmol) diisopropyl azodicarboxylate added dropwise. The mixture was then stirred at 0-5 ° C. for 2 hours, after which the reaction mixture was concentrated under reduced pressure. The crude product was taken up in methylene chloride. The solution obtained was washed twice with water, then dried over magnesium sulfate and finally concentrated. The crude product (1.88 g) was purified by column chromatography (mobile phase: cyclohexane / ethyl acetate = 9: 1). Yield: 0.64 g (94%); iH-NMR see example 4.

Example 6 (Compound No. 24)

(R) -2- [2-chloro-5- (3,5-dimethyl-2,6-dioxo-4-thioxo- [1,3,5] triazanan-1-yl) -4-fluoro- phenoxy] propionic acid cyclobutyl methyl ester (R isomer)

CH ₃

To a solution of 504 mg (1.25 mmol) (R) -2 - [2-chloro-5- (3, 5-dimethyl-2, 6-dioxo- [1,3,5] triazinan-1 -yl) -4-fluoro-phenoxy] -propionic acid methyl ester in 10 ml cyclobutylmethanol gave 36 mg (0.125 mmol, 10 mol%) Ti [OCH (CH ₃ ) ₂ ] ₄ . The resulting mixture was heated to reflux for 5 hours, after which the reaction mixture was poured onto ice water. The resulting product of value was extracted with ethyl acetate (4 times). The combined organic phases were then dried over magnesium sulfate and then concentrated. The crude product obtained was by means of Column chromatography (eluent: cyclohexane / ethyl acetate = 25: 1) cleaned. Yield: 410 mg (72%);

iH-NMR (400 MHz, in CDC1 ₃ ): δ [ppm] = 1.7 (d, 3H), 1.7 (m, 2H), 1.85 (m, 2H), 2.0 (m, 2H), 2.6 (quint., 1H), 3.8 (2s, 3H each), 4.1 (m, 2H), 4.7 (q, 1H), 6.9 (d, 1H), 7.35 (d, 1H).

Example 7 (Compound No. 28)

2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo- [1, 3, 5] tri-azinan-1-yl) -4-fluoro-benzoic acid

Method A:

4.98 g (12.9 mmol) of 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thi - oxo [1,3,5] triazinan-1-yl) -4 -fluorobenzoic acid isopropyl ester were concentrated together with 25 ml. Sulfuric acid heated to 80 ° C for 7 hours. The reaction mixture was then carefully poured onto ice water. The resulting solid was separated and washed neutral with water. After drying, 2.62 g (59%) of the desired acid were obtained; Mp: 225-229 ° C.

Method B:

108 mg (0.30 mmol) of 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thi - oxo [1,3,5] triazinan-1-yl) -4-fluorine -benzoic acid methyl ester were heated together with 150 mg (0.75 mmol) iodotrimethylsilane at 100 ° C for 2 hours. After cooling, methyl-tert was added to the reaction mixture. -butyl ether and saturated aqueous sodium bicarbonate solution (up to pH 8). The aqueous phase was then separated off and acidified with 10% hydrochloric acid (pH 5). Then extracted three times with methylene chloride. The combined methylene chloride phases were dried over magnesium sulfate and finally concentrated. Yield: 70 mg (67%); Mp: 225-229 ° C.

In addition to the active ingredients described above, Table 3 below lists further l-aryl-4-thiotriazines of the formula I which were prepared or can be prepared in an analogous manner: Table 3

No.R ³ R ⁴ RS Fp. Or HPLC / MS ^*)

42 H CI CH = C (CD-C0-0C ₂ H ₅ 212 -218 ° C

43 H CI CH = C (CI) -CO-OCH ₂ -CH = CH ₂ 171 -173 ° C

44 F CI OCH ₂ -CO-CH ₃ M = 374, t = 3.91

45 F CI OCH ₂ -CO-C (CH ₃ ) ₃ M = 416, t = 5.07

46 F CI OCH ₂ -CO-cyclopropyl M = 400, t = 4.17

47 F CI OCH ₂ -CO-phenyl M = 436, t = 5.07

48 F CI OCH ₂ -CO- (4-fluorophenyl) M = 454, t = 4.45

49 F CI OCH ₂ -CO- (4-chlorophenyl) M = 470, t = 5.24

50 F CI OCH ₂ -CO- (4-bromophenyl) M = 515, t = 4.70

51 F CI OCH ₂ -CO- (4-cyanophenyl) M = 461, t = 5.01

52 F CI OCH ₂ -CO- (4-methoxyphenyl) M = 466, t = 5.09

53 F CI OCH ₂ -CO- (4-nitrophenyl) M = 481, t = 5.08

54 F CI OCH ₂ -CO- (2-nitrophenyl) M = 481, t = 4.39

55 F CI OCH ₂ -CO- (3-nitrophenyl) M = 481, t = 4.40

56 F CI OCH ₂ -CO- (3-methoxyphenyl) M = 466, t = 4.46

57 F CI OCH ₂ -CO- (2,4-dichlorophenyl) M = 505, t = 4.82

58 F CI OCH ₂ -CO- (2,4-dibromophenyl) M = 594, t = 4.88

59 F CI OCH ₂ -CO- (2,4-dimethoxyphenyl) M = 496, t ⁼ 4.52

60 F CI OCH ₂ -CO- (3,4-dichlorophenyl) M = 505, t = 4.83

61 F CI OCH ₂ -CO- (2,3,4-trichlorophenyl) M = 539, t = 4.97

62 F CI OCH ₂ -CO- (2,4-dichloro-3-methyl- M = 519, t = 4.97 phenyl)

63 F CI OCH (CH ₃ ) -CO-phenyl (rac.) M = 450, t = 4.58

HPLC / MS conditions: column GROM-SIL 80, ODS-7pH, 4μm, 40 x 2 mm; Flow 0.7 ml / min, UV detector

Example 8 (Compound No. 64)

3- (4-Chloro-2-cyclopropyl-6-fluoro-benzoxazol-7-yl) -1, 5-dimethyl-6-thioxo- [1, 3, 5] triazinan-2, 4-dione (R. ⁶ = cyclopropyl)

A mixture of 370 mg (1.11 mmol) of 3- (3-amino-4-chloro-6-fluoro-2-hydroxyphenyl) -1,5-dimethyl-6-thioxo- [1,3,5] Triazinan-2, 4-dione and 226 mg (1.67 mmol) of imidomethyl ester hydrochloride cyclopropanoate in 20 ml of methanol (distilled off over Na) were stirred at approx. 20 ° C. for two hours. Then it was narrowed. The residue was suspended in water, after which the undissolved portions were separated off and dissolved in ethyl acetate. The ester phase was dried over magnesium sulfate and then concentrated under reduced pressure. 160 mg of crude product were obtained. product, which was purified by column chromatography (mobile phase: cyclohexane / ethyl acetate = 20: 1). Yield: 90 mg (21%); Oil;

ⁱ H-NMR (400 MHz, in CDC1 ₃ ): δ [pp] = 1.2-1.35 (m, 4H), 2.2 (m, 1H), 3.8 (s, 6H), 7.15 (d, 1H).

Preliminary stage 8

3- (3-Amino-4-chloro-6-fluoro-2-hydroxyphenyl) -1, 5-dimethyl-6-thioxo [1,3,5] triazinan-2,4-dione

0.46 g (1.33 mmol) of 3- (3-amino-4-chloro-6-fluoro-2-methoxy) were added to 8 ml of an 1M solution of boron tribromide in methylene chloride (= 8 mmol of BBr ₃ ) at 0 ° C -phenyl) -1, 3-dimethyl-6-thioxo- [1,3,5] tri-azinan-2, 4-dione in 5 ml of methylene chloride. The mixture was then stirred at 0 ° C. for two hours, after which the reaction mixture was slowly stirred into ice water. The product of value was extracted from the aqueous phase with methylene chloride (twice). The combined organic phases were dried over magnesium sulfate and then concentrated under reduced pressure. 0.21 g (48%) of valuable product was obtained.

The aqueous phase was adjusted to pH 10 with sodium hydroxide solution.

The mixture was then extracted again with methylene chloride. The methylene chloride phases were again dried over magnesium sulfate and concentrated. A further 0.16 g (36%) of valuable product was obtained.

Overall yield: 84%;

ⁱ H-NMR (270 MHz, in CDC1 ₃ ): δ [ppm] = 3.8 (s, 6H), 6.9 (d, 1H).

Precursor 8ß 3- (3-amino-4-chloro-6-fluoro-2-methoxy-phenyl) -1, 3-dimethyl-6-thi-oxo [1,3,5] triazinan-2, 4-dione

A mixture of 0.22 g (3.98 mmol) iron powder and 2.5 ml acetic acid in 5 ml methanol was heated to the reflux temperature.

10 At this temperature, a suspension of 0.50 g (1.33 mmol) of 3- (4-chloro-6-fluoro-2-methoxy-3-nitro-phenyl) -1, 5-dimethyl-6- thioxo- [1, 3, 5] triazinan-2, 4-dione in 3 ml of methanol in the reaction mixture. The mixture was then stirred at reflux temperature for two hours. After cooling and concentrating the reac

15 tion mixture, the crude product was filtered through silica gel

(Eluent: ethyl acetate). The filtrate was concentrated under reduced pressure. After drying, 0.45 g (98%) of product of value was obtained;

ⁱ H-MR (400 MHz, in CDC1 ₃ ): δ [ppm] = 3. 75 (s, 3H), 3. 8 (s, 6H), 20 4. 05 (bs, 2H), 7. 05 (d, 1H).

Precursor 8γ

3- (4-chloro-6-fluoro-2-methoxy-3-nitro-phenyl) -1, 5-dimethyl-6-thioxo [1,3,5] triazinan-2,4-dione

25

A solution was added to a solution of 3.0 g (13.6 mmol) of 4-chloro-6-fluoro-2-meth-oxy-3-nitro-phenylamine in 15 ml of toluene at approx

35 solution of 3.0 g (15.0 mmol) of diphosgene in 5 ml of toluene was added dropwise. Then it was slowly heated to the reflux temperature and stirred under reflux for a further 6 hours. After concentrating and drying the reaction mixture, the crude isocyanate was redissolved in 5 ml of toluene for further reaction. One dripped to this solution at approx.

40 20 ° C 6 ml triethylamine and a solution of 3.55 g (14.4 mmol) dimethylthiourea. Then 4.7 g (28.8 mmol) of carbonyldiimidazole were added to the reaction mixture. The mixture was heated to 80 ° C. for 5 hours and then allowed to cool. For working up, it was first washed four times with water. Then you dried them

45 organic phase over magnesium sulfate and concentrated under reduced pressure. The red product (6.58 g) was purified by silica gel Chromatography (eluent: cyclohexane / ethyl acetate = 10: 1) cleaned. Yield: 1.31 g (24%);

iH-NMR (270 MHz, in CDC1 ₃ ): δ [ppm] = 3.8 (s, 6H), 3.9 (s, 3H), 7.2 (d, 1H).

Precursor 8δ

4-chloro-6-fluoro-2-methoxy-3-nitro-phenylamine

A suspension of 40.0 g (152 mmol) of N- (4-chloro-6-fluoro-2-meth-oxy-3-nitro-phenyl) -acetamide in 800 ml of 6M hydrochloric acid was heated at reflux temperature for 5 hours, after which it was heated Stirred at about 20 ° C overnight. For working up, the reaction mixture was stirred into ice water. A pH of 8-9 was set by adding sodium hydroxide solution. The mixture was then extracted six times with ethyl acetate. The combined organic phases were dried over magnesium sulfate and then concentrated under reduced pressure. Yield: 33 g (98%);

! H NMR (270 MHz, in CDC1 ₃ ): δ [ppm] = 3.9 (s, 3H), 4.0 (bs, 2H), 7.0 (d, 1H).

Precursor 8ε N- (4-chloro-6-fluoro-2-methoxy-3-nitro-phenyl) acetamide

A solution of 72 was added to a solution of 81 g (323 mmol) of N- (4-chloro-2, 6-difluoro-3-nitro-phenyl) -acetamide in 490 ml of dioxane and 50 ml of methanol at approx. 20 ° C , 5 g (647 mmol) of NaOSi (CH ₃ ) ₃ in 25 ml of tetrahydrofuran were added dropwise. The mixture was then heated to the reflux temperature for two hours. After cooling and concentration, the crude product (black oil) in ice cold 10 percent. Hydrochloric acid stirred in. Then the resulting product of value was extracted with ethyl acetate (3 times). The combined organic phases were dried over magnesium sulfate and concentrated under reduced pressure. The residue was stirred once with water. The un- soluble fractions were separated off and washed three times with water. After drying, 53.1 g (63%) of product of value were obtained;

iH-NMR (270 MHz, in d ⁶ -dimethylsulfoxide): δ [ppm] = 2.1 (s, 3H), 3.85 (s, 3H), 7.75 (d, 1H), 9.9 (bs, 1H).

Preliminary stage 8ς

N- (4-chloro-2, 6-difluoro-3-nitro-phenyl) acetamide

To a solution of 100 g (487 mmol) N- (4-chloro-2, 6-difluorophenyl) acetamide in 500 ml conc. 30.7 g (487 mmol) of concentrated nitric acid were added dropwise to sulfuric acid at 0-5 ° C. After stirring for one hour at 0-5 ° C, the reaction mixture was stirred into ice water. The resulting solid was separated, washed twice with water and dried. Yield: 81.3 g (72%),

ⁱ H-NMR (270 MHz, in d ⁶ -dimethylsulfoxide): δ [ppm] = 2.1 (s, 3H), 7.95 (dd, 1H), 10.2 (bs, 1H).

Preliminary stage 8Θ

N- (4-chloro-2, 6-difluorophenyl) acetamide

126 g (930 mmol) of sulfuryl chloride were added dropwise to a solution of 100 g (775 mmol) of difluoroaniline in 700 ml of glacial acetic acid at 80 ° C. The mixture was then stirred at 100 ° C. for three hours. After cooling and concentration, the residue was mixed with 200 ml of acetic anhydride. Then the mixture was stirred at about 20 ° C. overnight. For working up, the reaction mixture was stirred into 1.5 l of ice water. The valuable product was extracted from the aqueous phase with ethyl acetate (3 times). The combined organic phases were dried over magnesium sulfate and concentrated under reduced pressure. Yield: 163 g; ⁱ -H NMR (270 MHz, in d ⁶ -dimethyl sulfoxide): δ [ppm] = 2.05 (s, 3H) 7.4 (d, 2H), 9.8 (bs, 1H).

In an analogous manner, compound no. 65 3- (4-chloro-6-fluoro-benzoxazol-7-yl) -1, 5-dimethyl-6-thioxo [1,3,5] triazinan-2, 4-dione (R ⁶ = H; mp: 209-211 ° C) and compound no. 66

3- (4-Chloro-2-ethyl-6-fluoro-benzoxazol-7-yl) -1,5-dimethyl-6-thioxo [1,3,5] triazinane-2,4-dione (R. ⁶ = C ₂ H ₅ ; mp: 156-159 ° C).

Example 9 (Compound No. 67)

3- (4-chloro -6-fluoro-benzoxazole - 7 -yl) -1, 5 - dimethyl -6 - thioxo- [1, 3, 5] triazinan-2, 4-dione (R ⁶ = hydrogen)

To a solution of 502 mg (1.50 mmol) of 3 - (3-amino-4-chloro-6-fluoro-2-hydroxyphenyl) -1,5-dimethyl -6 -thioxo- [1,3,5 ] triazinan-2,4-dione in 10 ml of methanol, 5.0 g (48.1 mmol) of tri-methylformamide were added dropwise. Then heated to reflux for 9 hours. The reaction mixture was then concentrated under reduced pressure. The crude product thus obtained was purified by column chromatography (mobile phase: cyclohexane / ethyl acetate = 20: 1). Yield: 240 mg (46%); Mp : 209-211 ° C.

In an analogous manner, compound no. 68

3- (4-Chloro-2 -ethyl -6-fluoro-benzoxazole -7 -yl) -1, 5 -dimethyl -6 - thi- oxo- [1, 3, 5] triazinane-2,4-dione (R. ⁶ = ethyl).

Examples of use

The herbicidal activity of the l-aryl-4-thiotriazine I was demonstrated by the following greenhouse tests:

Plastic flower pots with loamy sand with about 3.0% humus as substrate served as 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 covers until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.

For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only 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 post-emergence treatment costs were 125, 62.5, 7.81 and 3.91 g / ha a.S. (active substance).

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:

With application rates of 7.81 and 3.91 g / ha aS, the active ingredient no. 30 fought Amaranthus retroflexus, Chenopodium album, Commelina benghalensis and Setaria faberii much better than the comparative compound A in the post-emergence process

With application rates of 125 and 62.5 g / ha a.S. the active ingredient no. 39 showed a significantly better herbicidal action against Abutilon theophrasti, Chenopodium album, Ipomoea species, Solanum nigrum and Veronica species in the post-emergence process than the comparative compound B

Claims

claims

1. New l-aryl-4-thiotriazines of the formula I.

where the variables have the following meanings:

R ^{1 is} hydrogen, amino, C ₁ -C ₄ alkyl or C -C haloalkyl;

R ² is hydrogen, amino, Cι-C ₄ alkyl or Cι-C ₄ haloalkyl;

R ^{3 is} hydrogen or halogen;

R ⁴ cyano or halogen;

Y nitrogen, the methine group or together with R ⁵ a bridge> C-0-C (R ⁶ ) = N-;

R ⁵

1) hydrogen, hydroxyl, mercapto, nitro, halogen, Cι-C ₆ -alkyl, C ₆ haloalkyl,

2) Ci-C _δ alkoxy, Ci -Cε alkylthio, C ₃ -C ₆ cycloalkoxy, ₃ -C ₆ cycloalkylthio, C ₂ -C ₆ alkenyloxy, C -C ₆ alkenyl thio, C ₂ - C ₆ -alkynyloxy or C ₂ -C ₆ -alkynylthio, where each of these 8 radicals can optionally carry one of the following substituents: halogen, cyano, -CO-R ⁸ , -CO-OR ⁸ or -CO-N (R ⁸ ) -R ⁹ ;

3) -CO-R ¹¹ , -C (R ¹¹ ) (OR ¹³ ) (OR ¹⁴ ), -C (R ¹¹ ) = C (R ¹⁵ ) -CO-R ¹⁶ , -CH (R ^{1: L} ) - CH (R ¹⁵ ) -CO-R ¹⁶ , -CO-OR ²⁰ , -C (R ¹⁰ ) = N-OR ⁷ , -N (R ²¹ ) -R ²² or -CO-N (R ²¹ ) -R ²² ;

R ^{6 is} hydrogen, halogen, -CC ₆ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, -C-C ₆ -alkoxy, C ₃ -C ₆ -alkenyloxy, C ₃ -C ₆ - Alkynyloxy, C ₃ -C ₆ -cycloalkyl or C ₃ -C ₆ -cycloalkoxy, where each of the latter 8 radicals can optionally carry one to three substituents, in each case selects from the group consisting of halogen, Ci-Cβ-alkoxy and -CO-OR ⁸ ';

R ^{7 is} hydrogen, -CC ₆ -alkyl, -C-C ₆ -haloalkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, (-C-C ₆ - Alkoxy) carbonyl -C ₆ alkyl or benzyl;

R ⁸ , R ⁸ 'independently of one another

Are hydrogen, C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ -cycloalkyl C ₁ -C ₄ - alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl ,

Ci-Ce-alkoxy-C-Ce-alkyl, _{(C! -C6} alkoxy) carbonyl-Cι-C ₆ -alkyl, (C ₃ -C ₆ alkenyloxy) carbonyl -Cι-C ₆ alkyl, phenyl or Phenyl-Ci-C _δ- alkyl, where the phenyl group and the phenyl ring of the phenylalkyl group can be unsubstituted or can carry one to three radicals, each selected from the group consisting of halogen, nitro, cyano, C ₁ -C ₆ alkyl, C 1 -C ₆ -haloalkyl, Ci-Cε-alkoxy and (-C-C ₆ alkyl) carbonyl;

R ^{9 is} hydrogen or -CC ₆ alkyl;

R ^{10 is} hydrogen, -CC ₆ -alkyl or Ci-Ce-alkoxy, where the latter 2 radicals can carry one of the following substituents: -C ₆ -alkoxy, (Ci-C _ß -alkoxy) carbonyl or phenoxycarbonyl;

R ¹¹ hydrogen, C _! -C ₆ alkyl or Cι-C ₆ haloalkyl;

R ¹³ , R ¹⁴ independently of one another C ₁ -C ₆ -alkyl or together for a saturated 2- to 4-membered carbon chain which can carry a C ₁ -C ₆ -alkyl radical;

R ^{15 is} hydrogen, cyano, halogen or -CC ₆ alkyl;

R ¹⁶ OR ²³ or -N (R ²¹ ) R ²² ;

R ²⁰ , R ²³ independently of one another are hydrogen, C ₁ -C ₆ -alkyl,

Cι-C ₆ haloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, where the last 4 groups may carry one or two of the following radicals, respectively: cyano,

Halogen, hydroxy, hydroxycarbonyl, C ₁ -C ₆ -alkoxy, Ci-Ce-alkylthio, (Cx-Ce-alkyl) carbonyl, (Cι-C ₆ -alkoxy) carbonyl, (Ci-C _δ- alkyl) carbonyloxy, (C ₃ -C ₆ alkenyloxy) carbonyl, (C ₃ -Cβ-alkynyloxy) carbonyl or C _x -C ₆ alkoxy- (-C-C ₆ alkoxy) carbonyl; or C ₃ -C ₆ cycloalkyl, Phenyl or phenyl-Ci-C _δ- alkyl, where the phenyl rings can be unsubstituted or in turn can carry one to three substituents, each selected from the group consisting of cyano, nitro, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ - Haloalkyl, -CC ₆ alkoxy and

(-C ₆ alkoxy) carbonyl;

R ²¹ , R ²² independently of one another

Are hydrogen, C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, Cι-C ₆ haloalkyl,

C ₁ -C ₆ -alkoxy-C ₆ -alkyl, (C ₁ -C ₆ -alkyl) carbonyl, (C ₁ -C ₆ -alkoxy) carbonyl, (C ₁ -C ₆ -alkoxy) carbonyl-C ₆ -C ₆ -alkyl or -CC ₆ alkyl sulfonyl, or R ²¹ and R ²² together with the common nitrogen atom for a saturated or unsaturated 4- to

7-membered azaheterocycle which, in addition to carbon ring members, can optionally contain one of the following members: -O-, -S-, -N =, -NH- or -N (-C-C ₆ -alkyl) -;

and the agriculturally useful salts and enol ethers of the compounds I.

2. l-aryl-4-thiotriazines of the formula I according to claim 1, where Y is nitrogen or the methine group.

3. l-aryl-4-thiotriazines of formula I according to claim 1, wherein Y together with R ^{5 is} a bridge> C-0-C (R ⁶ ) = N-.

4. l-aryl-4-thiotriazines of formula I according to claim 1, wherein R ^{5 is} hydroxy, 2) C _! -C ₆ alkoxy, C ₃ -C ₆ cycloalkoxy, C ₂ -C ₆ alkenyloxy or

C ₆ -C ₆ -alkynyloxy, where each of these 4 radicals can, if desired, bear one of the following substituents: halogen, cyano, -CO-R ⁸ , -CO-OR ⁸ or -CO-N (R ⁸ ) R ⁹ .

5. l-aryl-4 - thiotriazines of formula I according to claim 1, wherein R ⁵ for mercapto, 2) -C-C ₆ -alkhio, C ₃ -C ₆ -cycloalkylthio, C ₂ -C ₆ -alkenylthio or C ₂ - C ₆ -alkynylthio, where each of these 4 radicals can optionally carry one of the following substituents: halogen, cyano, -CO-R ⁸ , -CO-OR ⁸ or -CO-N (R ⁸ ) R ⁹ .

l-aryl-4-thiotriazines of the formula I according to claim 1, where R ^{5 is} C -C-alkyl, -C-C ₆ haloalkyl, 3) -CO-R ¹¹ , -C (R ¹¹ ) (OR ¹³ ) (OR ¹⁴ ), -C (R ¹¹ ) = C (R ¹⁵ ) -CO-R ¹⁶ ,

-CH (R ¹¹ ) -CH (R ¹⁵ ) -CO-R ¹⁶ , -CO-OR ²⁰ , - C (R ¹⁰ ) = N-OR ⁷ or - CO-N (R ²¹ ) - R ²² . 5

7. 1-aryl -4-thiotriazines of formula I according to claim 1, wherein R ^{5 is} hydrogen, nitro, halogen or -N (R ²¹ ) -R ²² .

8. Use of the l-aryl-4-thiotriazines of the formula I and their 10 agriculturally useful salts and enol ethers, in accordance with

Claim 1 as a herbicide.

9. Herbicidal composition containing a herbicidally effective amount of at least one l-aryl-4-thiotriazine of the formula I or

15 an agriculturally useful salt or enol ether of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one surfactant.

10. A process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount of at least one l-aryl-4-thiotriazine of the formula I or an agriculturally useful salt or enol ether of I, according to claim 1, and at least one inert fluid

25 gene and / or solid carrier and, if desired, at least one surfactant mixes.

11. A method for controlling undesirable plant growth, characterized in that a herbicidally effective amount 30 of at least one l-aryl-4-thiotriazine of the formula I or an agriculturally useful salt or enol ether of I, according to claim 1, on plants, their habitat or can act on seeds.

35 12. A process for the preparation of l-aryl-4-thiotriazines of the formula I according to claim 1, characterized in that isocyanates of the formula V

45 with thioureas of the formula IV R ¹

NH

IV

NH

R ² '

in the presence of an activated form of carbonic acid.

10

15

20th

25

30

35

40

45