EP1077954A1

EP1077954A1 - Substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines

Info

Publication number: EP1077954A1
Application number: EP99926328A
Authority: EP
Inventors: Peter Schäfer; Michael Rack; Roland Götz; Gerhard Hamprecht; Olaf Menke; Markus Menges; Robert Reinhard; Cyrill Zagar; Martina Otten; Karl-Otto Westphalen; Helmut Walter
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1998-05-20
Filing date: 1999-05-19
Publication date: 2001-02-28
Also published as: CN1306523A; PL344369A1; HUP0103541A2; IL139463A0; BG104977A; JP2002515495A; CA2332352A1; SK17302000A3; NO20005821L; AU4362999A; EA200001213A1; KR20010025048A; HUP0103541A3; WO1999059983A1; TR200003403T2; AR017487A1; BR9910595A; NO20005821D0

Abstract

The invention relates to substituted 6-aryl-3-thioxo-5-(thi)oxo-2,3,4,5-tetrahydro-1,2,4-triazines of formula (I) and to their salts. In said formula, R1 is C1-C6-alkyl, C1-C6-halogen alkyl, and possibly substituted phenyl; R2 is NH¿2?, C1-C6-alkyl, C1-C6-halogen alkyl, C2-C6-alkenyl, C3-C6-alkinyl, (C1-C6-alkoxy) carbonyl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkylthio-C1-C6-alkyl, C3-C6-cycloalkyl; Ar is a group corresponding to formula (Ar?1), (Ar2), (Ar3¿) or (Ar4); Y is O, S; Z is O, S, NH, N(C¿1?-C6-alkyl) and R?3, R4, R5, R6, R7 and R8¿ have the meaning given in the description. Said compounds are used as herbicides and for the desiccation/defoliation of plants.

Description

Substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetra-hydro-1, 2, 4-triazines

description

The present invention relates to new substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetrahydro-l, 2, 4-triazines of the formula I.

/

R ^l

where the variables have the following meanings:

X oxygen or sulfur;

R ^l Cχ-Cg-alkyl, Ci-Cg-haloalkyl or phenyl, which if desired can carry one to three substituents, each selected from the group consisting of nitro, halogen, -C-C ₆ alkyl, Ci-Cg-haloalkyl and Ci-Cg-alkoxy;

R ² amino, Cχ-Cg-alkyl, Ci-Cg-haloalkyl, C ₂ -Cg-alkenyl, C ₃ -Cg-alkynyl, (Ci-Cg-alkoxy) carbonyl-Cχ-Cg-alkyl, Cι-C ₆ - Alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkylthio-C ₁ -C ₆ -alkyl or C ₃ -Cg-cycloalkyl;

Ar is a substituted aryl radical of the formula Ar ¹ to Ar ⁴ :

Ar ⁴

Ar ¹ Ar ² Ar ³

R3 is hydrogen or halogen; R ⁴ cyano, halogen, -CS-NH ₂ , hydroxy, C _.- C ₆ alkoxy,

Ci-Cg-haloalkoxy, C ₂ -C -alkenoxy, C ₂ -C ₄ -alkynyloxy, (-C-C ₄ -alkoxy) carbonyl -C-C ₄ -alkoxy or benzyloxy, which are unsubstituted or one to three substituents on the phenyl ring can wear, each selected from the group consisting of halogen, Ci-Cg-alkyl, Ci-Cg-alkoxy and Ci-Cg-haloalkoxy;

R ^{5 is} hydrogen, nitro, cyano, amino, hydroxylamino, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl, formyl, -CH = N-OR ⁹ ,

-CH (0R ^l °) ₂ , _f -co-Cl, -CO-OR ¹³ ,

-CO-OR ¹ -CO-OR ¹³ , -CO-N (R ") - Rl6 _f -CO-OR ¹ -CO-N (R ¹⁵ ) -R ¹⁶ , -CH ₂ -CH (R ¹⁷ ) -CO -OR ¹³ , -CH = C (R ¹⁷ ) -CO-OR ¹³ , -OCH (CH ₃ ) -COOH, -OCH (CH ₃ ) -COOCH ₃ , -N (R2 ⁰ ) -R19, -SO ₂ - C1, -S0 ₂ -N (R ¹⁵ ) -R ¹⁶ ,

OR ²¹

-CO-NH-OR ¹⁵ , -c, -CO-N (R22) -oR ¹ 5 or V

N-OR ¹⁵ together with R ^{4 is} a chain 0-CH ₂ -CH ₂ -0, which is a cyano-, halogen-, Ci-Cg-alkyl-, oxo-, hydroxycarbonyl- or (Ci-Cg-alkoxy) carbonyl- Can carry substituents;

R ^{6 is} hydrogen, hydroxy, Ci-Cg-alkyl, Ci-Cg-alkoxy, (-C-C ₆ -alkoxy) carbonyl -CC-Cg-alkyl, Ci-Cg-alkoxy- (Ci-Cg-alkoxy) carbonyl -Ci-Cg-alkyl, (Ci-Cg-alkoxy) carbonyl-Cι-Cg-alkoxy, C ₃ -Cg-alkenyl, C ₃ -Cg-alkynyl, C3-Cg-alkenyloxy or C ₃ -Cg-alkynyloxy ;

R ^{7 is} hydrogen, Ci-Cg-alkyl or (Ci-Cg-alkoxy) carbonyl;

R ^{8 is} hydrogen, hydroxy, mercapto, halogen, Ci-Cg-alkyl, -C-Cg-alkoxy-Cι-Cg-alkyl, hydroxycarbonyl, hydroxycarbonyl-Ci-Cg-alkyl, (Ci-Cg-alkoxy) carbonyl-Ci -Cg-alkyl, (Ci-Cg-alkoxy) carbonyl, Ci-Cg-alkoxy, Cι ~ Cg-alkoxy-Ci-Cg-alkoxy, C ₃ -Cg-alkenyloxy, C ₃ -Cg-alkynyloxy, (Ci-Cg -Alkoxy) carbonyl-Ci-Cg-alkoxy, Ci-Cg-alkylthio, (Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkylthio, C ₃ -Cg-alkenylthio, C ₃ -C ₆ -alkynylthio, -N ( R2) -R24, -CH ₂ -CH (R ¹⁷ ) -CO-OR ¹³ or -CH = C (R ¹⁷ ) -CO-OR ¹³ ;

n zero or 1;

Oxygen or sulfur; Z Sauers tof f, sulfur or -N (R ² 3) - _;

R ⁹ water tof f, Ci-Cg-alkyl or (Ci-Cg-alkoxy) carbonyl-

Ci-Cg-alkyl;

R ¹⁰ Ci-Cg-alkyl;

R11 R12 independently of one another at position 4 or 5 of the dioxolane ring are hydrogen, Ci-Cg-alkyl, hydroxycarbonyl or (Ci-Cg-alkoxy) carbonyl;

R ^{13 is} hydrogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-Cg-alkoxy-Ci-Cg-alkyl, cyano-Cι ~ Cg-alkyl, C ₃ -C ₇ cycloalkyl, 3-oxetanyl, C ₃ -Cg alkenyl, C ₃ -Cg haloalkenyl or C ₃ -Cg alkynyl;

R ¹⁴ Ci-Cg alkylene;

R15 is hydrogen or Ci-Cg-alkyl;

R ^{15 is} hydrogen, Ci-Cg-alkyl, C ₃ -C ₇ cycloalkyl, (Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkyl, Ci-Cg-alkylsulfonyl or together with R ¹⁵ a tetramethylene or pentarethylene - chain which can be interrupted by an oxygen bridge and / or substituted by a (Ci-Cg-alkoxy) carbonyl group;

R ^{17 is} hydrogen, halogen or Ci-Cg-alkyl;

R ¹⁹ Ci-Cg-alkylsulfonyl;

_R ^{20 is} hydrogen, Ci-Cg-alkyl or Ci-Cg-alkylsulfonyl;

R ²¹ , R22 independently of one another Ci-Cg-alkyl, (Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkyl, C ₃ -Cg-alkenyl, C ₃ -Cg-alkynyl or benzyl;

R ^{23 is} hydrogen or Ci-Cg-alkyl;

R ^{4 is} hydrogen, Ci-Cg-alkyl, (Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkyl, C ₃ -Cg-alkenyl, C ₃ ~ Cg-alkynyl or benzyl;

and the agriculturally useful salts of the compounds I.

The invention also relates to the use of these compounds I as herbicides or for the desiccation / defoliation of plants, herbicidal agents and agents for the desiccation / defoliation of plants which contain the compounds I as active substances,

Process for combating undesired plant growth and for desiccating / defoliation of plants with the compounds I,

Process for the preparation of herbicidal agents and agents for the desiccation / defoliation of plants using the compounds I, and - new intermediates of the formula Va '.

The following two 6-phenyl-3-thioxo-5- (thi) oxo-2, 3,4, 5-tetra-hydro-1, 2, 4-triazines are already known from the following publications, but no information about possible herbicidal shadows are made:

• Daunis et al .; BSCFAS; Bull. Soc. Chim. Fr .; 1972; 1511, 1513, 1514, 1517;

• prystas; Good; CCCCAK; Collect. Czech. Che. Commun. 21 (1962), 1898, 1903;

• Mansour; Ibrahim; JPCEAO; J. Prakt. Chem. 315 (1973), 221, 223;

Ibrahim; IJSBDB; Indian J. Chem. Sect. B, 14: 273 (1976);

• prystas; Good; CCCCAK; Collect. Czech. Chem. Commun. 27 (1962), 1898, 1903;

• Daunis et al .; BSCFAS; Bull. Soc. Chim. Fr .; 1972; 1975, 1980-1982. WO 94/03454 describes herbicidally active triazinones, including formula II

C ₁ -C ₄ alkyl /

-C-C ₄ haloalkyl.

wherein R ^a is Cι-C -alkyl, C ₄ haloalkyl, C ₃ -C alkenyl or C ₃ -C ₄ alkynyl substituents and Q is o-halophenyl containing 1 or 2 further substituents or certain heterocycles fused can stand.

In EP-A 044 696 herbicidally active triazinones are taught, i.a. Compounds of formula III:

H ₂ N / -CC ₄ alkyl

In U.S. 3,671,523, U.S. 3,966,715, U.S. 3,544,570 and in W. Oettmeier et al. , Pestic. Be. 22. (1991), 399-409 further herbicidally active triazinones are described.

JP-A 10/053 508 finally relates to 1,2,4-triazines of the formula X.

wherein R ^b is C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ -alkynyl or Cι-C ₄ haloalkyl, R ^c is hydrogen or R ^b and

R ^{d are,} inter alia, H, Ci-Cg-alkyl or -CH (Ci -C ₄ alkyl) -COO (H / -C-C ₆ alkyl), which is also attributed to a herbicidal activity there.

However, the herbicidal properties of the known herbicides with regard to the harmful plants are not always completely satisfactory. The object of the present invention was therefore to develop new herbicides To provide effective compounds with which undesirable plants can be controlled better than before. The task also extends to the provision of new desiccant / defoliant connections.

We have found that this object is achieved by the substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetrahydro-l, 2, 4-triazines of formula I as well as their herbicidal activity. 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.

Furthermore, it was found that the compounds I are also suitable for the desiccation and / or defoliation of parts of plants, for which crop plants such as cotton, potatoes, oilseed rape, sunflower, soybeans or field beans, in particular cotton, are suitable. In this regard, agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with 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 slide ereomers and to their mixtures.

The substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetra-hydro-1,2, 4-triazines can be in the form of their agriculturally useful salts, depending on the type of the salt usually does not arrive. In general, the salts of I with such bases and those acid addition salts into which the herbicidal action is not adversely affected in comparison with the free compound I are suitable.

Particularly suitable as basic salts are those of the alkali metals, preferably the sodium and potassium salts, those of the alkaline earth metals, preferably calcium and magnesium salts, those of the transition metals, preferably zinc and iron salts, and ammonium salts in which the ammonium ion is present if desired can carry up to four C 1 -C ₄ alkyl, hydroxy C 1 -C ₄ alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimethyl (2nd -hydroxyethyl) -ammonium- Salts, furthermore phosphonium salts, sulfonium salts such as preferably tri- (C 1 -C ₄ -alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri- (C 1 -C ₄ -alkyl) sulfoxonium salts.

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 1 -C ₄ -alkanoic acids, preferably formate, acetate, propionate and butyrate.

The organic molecule parts mentioned in the definition of R ¹ , R ² and R ⁴ to R ²⁴ represent collective terms for individual lists of the individual group members. All carbon chains, that is to say all alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylthio, alkylsulfonyl, cyanoalkyl, hydroxycarbonylalkyl, alkoxycarbonyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenyl hi and alkynylthio parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms.

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

Furthermore, for example:

Ci-Cg-alkyl for: CH ₃ , C ₂ H ₅ , n-propyl, CH (CH ₃ ) ₂ , n-butyl, CH (CH ₃ ) -C ₂ H ₅ , CH ₂ -CH (CH ₃ ) ₂ , C (CH ₃ ) ₃ , n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2- Dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3- Wench hylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl and 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;

Ci-Cg-haloalkyl for: Ci-Cg-alkyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CH ₂ F, CHF ₂ , CF ₃ , CH ₂ C1, CH (C1) ₂ , C (C1) ₃ , CHFC1, CF (C1) ₂ , CF ₂ C1, CF ₂ Br, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2.2 -Difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 1,2-dichloroethyl, 2, 2 , 2-trichloroethyl, CF 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 Fs, CF -C ₂ F ₅ , 1- (Fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nC F ₉ , 5- Fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, 5, 5, 5-trichloropentyl, undecafluoropentyl, 6-fluorhexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl, 6, 6, 6-trichlorohexyl or Dodeca- fluorhexyl, in particular for C 1 -C -haloalkyl such as CH ₂ F, CHF ₂ , CF ₃ , CH ₂ C1, 2-fluoroethyl, 2-chloroethyl, 1,2-dichloroethyl, 2, 2, 2-trifluoroethyl or CF ₅ ;

C ₃ -C ₇ cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, in particular for cyclopentyl or cyclohexyl;

Hydroxycarbonyl-Ci-Cg-alkyl for: eg CH ₂ -COOH, 2-hydroxycarbonyl-eth-1-yl, 2-hydroxycarbonyl-prop-1-yl, 3-hydroxycarbonyl-prop-1-yl, l -Hydroxycarbonyl-prop-2-yl, 2-hydroxycarbonyl-but-1-yl, 3-hydroxycarbonyl-but-l-yl, 4-hydroxycarbonyl-but-l-yl, l-hydroxycarbonyl-but-2-yl , 1-Hydroxycarbonyl-but-3-yl, 2-Hydroxycarbonyl-but-3-yl, l-Hydroxycarbonyl-2-methyl-prop-3-yl, 2-Hydroxycarbonyl-2-methyl-prop-3-yl or 2 - (Hydroxycarbonylmethyl) prop-2-yl, especially for 2-hydroxycarbonyl-ethyl;

Cyano-Ci-Cg-alkyl for: e.g. CH ₂ CN, 1-cyanoeth-l-yl, 2-cyano-eth-l-yl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3- Cyano-prop-1-yl, l-cyanoprop-2-yl, 2-cyanoprop-2-yl, 1-cyanobut-1-yl, 2-cyanobut-l-yl, 3-cyanobut-l-yl, 4- Cyanobut-l-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, l-cyanobut-3-yl, 2-cyano-but-3-yl, l-cyano-2-methyl-prop- 3-yl, 2-cyano-2-methyl-prop-3-yl, 3-cyano-2-methyl-prop-3-yl or 2-cyanomethyl-prop-2-yl, especially for CH ₂ CN or 2- Cyanoethyl;

Ci-Cg-alkoxy for: -C-C ₄ alkoxy as mentioned above, and for example n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbu oxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy, 2, 3-dirnethylb toxy, 3, 3-dirnethylbutoxy, 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 , 0C ₂ Hs or OCH (CH ₃ ) ₂ ; Ci-Cg-haloalkoxy for: a Ci-Cg-alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, e.g. 0CHF, OCHF ₂ , 0CF ₃ , 0CH ₂ C1, OCH ( CI) ₂ , 0C (C1) ₃ , OCHFC1, 0CF ₂ C1, 0CF (C1) ₂ , 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2- Trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC F ₅ , 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2, 3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2, 3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3, 3, 3-trifluoropropoxy, 3, 3, 3- Trichloropropoxy, OCH ₂ -C ₂ F ₅ , 0CF ₂ -C ₂ F ₅ , 1- (fluoromethyl) -2-fluoroethoxy, l- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, n-CFg, 5-fluor-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1-pe toxy, 5-iodine-1 -pentoxy, 5, 5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexo xy, 6-chloro-l-hexoxy, 6-bromo-l-hexoxy, 6-iodo-l-hexoxy, 6, 6, 6-trichloro-l-hexoxy or dodecafluorohexoxy, in particular for C 1 -C 6 -haloalkoxy such as OCH ₂ F, OCHF ₂ , 0CF ₃ , CH ₂ C1, 2-fluoroethoxy, 2-chloroethoxy, 1, 2-dichloroethoxy, 2,2,2-trifluoroethoxy or OC ₂ Fs;

(Ci-Cg-alkoxy) carbonyl for: e.g. CO-OCH ₃ , CO-OC ₂ Hs, CO-OCH 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-methylbutoxycarbonyl, 2 , 2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hexoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 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, in particular for CO-OCH ₃ , CO-OC ₂ H ₅ , CO-OCH (CH ₃ ) ₂ or C0-0CH ₂ -CH (CH ₃ ) ₂ ;

(Cι-Cg-alkoxy) carbonyloxy for: O-CO-OCH ₃ , 0-CO-OC ₂ H ₅ , n-propoxycarbonyloxy, 1-methylethoxycarbonyloxy, n-butoxycarbonyloxy, 1-methylpropoxycarbonyloxy, 2-methylpropoxycarbonyloxy, 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-methyl pentoxycarbonyloxy, 2-methylpentoxycarbonyloxy, 3-methylpentoxycarbonyloxy, 4-methylpentoxycarbonyloxy, 1, 1-dimethylbutoxycarbonyloxy, 1, 2-dimethylbutoxycarbonyloxy, 1, 3-dimethylbutoxycarbonyloxy, 2, 2-dimethylbutoxycarbonyloxy, 2, 3-dimethylbutylcarbonyloxy , 3-dimethylbutoxycarbonyloxy, 1-ethylbutoxycarbonyloxy, 2-ethylbutoxycarbonyloxy, 1,1, 2-trimethylpropoxycarbonyloxy, 1, 2,2-trimethylpropoxoxycarbonyloxy, 1-ethyl-l-methyl-propoxycarbonyloxy or l-ethyl-2-methyl-propoxycarbonyloxy , in particular for methoxycarbonyloxy, ethoxycarbonyloxy or 1-methylethoxycarbonyloxy;

(Ci-Cg-alkoxy) carbonylthio for: methoxycarbonylthio, ethoxycarbonylthio, n-propoxycarbonylthio, 1-methylethoxycarbonylthio, n-butoxycarbonylthio, 1-methylpropoxycarbonylthio,

2-methylpropoxycarbonylthio, 1, 1-dimethylethoxycarbonylthio, n-pentoxycarbonylthio, 1-methylbutoxycarbonylthio, 2-methylbutoxycarbonylthio, 3-methylbutoxycarbonylthio, 2, 2-dimethylpropoxycarbonylthio, 1-ethylpropoxycarbonylthio, n-hexoxycarbonyl -Dimethylpropoxycarbonylthio, 1, 2-dimethyl-propoxycarbonylthio, 1-methylpentoxycarbonylthio, 2-methyl-pentoxycarbonylthio, 3-methylpentoxycarbonylthio, 4-methyl-pentoxycarbonylthio, 1, 1-dimethylbutoxycarbonylthio, 1,2-dimethylbutoxycarbonylthio, 1,2-dimethylbutoxycarbonylthio Dimethylbutoxycarbonylthio, 2, 2-dimethylbutoxycarbonylthio, 2, 3-dimethylbutoxycarbonylthio, 3, 3-dimethylbutoxycarbonylthio, 1-ethylbutoxycarbonylthio, 2-ethylbutoxycarbonylthio, 1, 1, 2-trimethylpropoxycarbonylthioprop, 1 1-ethyl-1-methyl-propoxycarbonylthio or l-ethyl-2-methyl-propoxycarbonylthio, especially for methoxycarbonylthio, ethoxycarbonylthio or 1-methylethoxycarbonylthio;

Ci-Cg-alkylthio for: SCH ₃ , SC ₂ H ₅ , SCH ₂ -C ₂ H ₅ , SCH (CH ₃ ) ₂ , n-butylthio, SCH (CH ₃ ) -C ₂ H ₅ , SCH ₂ -CH ( CH ₃ ) ₂ , 1, l-dimethylethylthio, 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 -Dimethylb tylthio, 1, 2-Dimethylbutyl - thio, 1,3-Dirnethylbutylthio, 2, 2-Dirnethylb tyl hio,

2, 3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-l-methylpropylthio or l- Ethyl 2-methylpropylthio, especially for SCH ₃ or SC ₂ H ₅ ; -C-Cg-alkoxy-Cι-Cg-alkyl for: Ci-Cg-alkoxy substituted by Ci-Cg-alkyl as mentioned above, for example for methoxymethyl, ethoxymethyl, n-propoxymethyl, (1-methylethoxy) methyl, n -Butoxymethyl, (l-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dirnethylethoxy) methyl,

2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (1-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (l-methyl-propoxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- (1, 1-dimethylethoxy) ethyl, 2- (methoxy) propyl, 2- (ethoxy) ropyl, 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- (1-methylethoxy) propyl, 3- (n-butoxy) propyl, 3- (1-methylpropoxy) ropyl, 3- ( 2-methyl-propoxy) propyl, 3- (1, 1-dimethylethoxy) propyl, 2- (methoxy) butyl, 2- (ethoxy) butyl, 2- (n-propoxy) butyl, 2- (l-methyl ethoxy) butyl, 2- (n-butoxy) butyl, 2- (1-methylpropoxy) butyl, 2- (2-methylpropoxy) butyl, 2- (1, 1-dimethylethoxy) butyl, 3- (methoxy) butyl, 3- (ethoxy) butyl, 3- (n-propoxy) butyl, 3- (l-methylethoxy) butyl, 3- (n-butoxy) butyl, 3- (l-methylprooxy) butyl, 3- (2- Methylpropoxy) butyl, 3- (1, 1-dimethyl- ethoxy) 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 methoxymethyl or 2-methoxyethyl;

-C-Cg-alkoxy-Cι-Cg-alkoxy for: Ci-Cg-alkoxy substituted by Ci-Cg-alkoxy as mentioned above, e.g. for methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, (1-methylethoxy) methoxy, n-butoxymethoxy, (1-methylpropoxy) methoxy, (2-methylpropoxy) methoxy, (1, 1-dimethylethoxy) methoxy, 2- (methoxy) ethoxy, 2- (ethoxy) ethoxy, 2- (-propoxy) ethoxy, 2- (1-methylethoxy) ethoxy, 2- (n-butoxy) ethoxy, 2- (l-methylpropoxy) ethoxy, 2- (2nd -Methylpropoxy) ethoxy, 2- (1, 1-dimethylethoxy) ethoxy, 2- (methoxy) propoxy, 2- (ethoxy) propoxy, 2- (n-propoxy) propoxy, 2- (1-methylethoxy) propoxy, 2- (n-butoxy) propoxy, 2- (1-methylpropoxy) propoxy, 2- (2-methylpropoxy) propoxy, 2- (1, 1-dimethylethoxy) propoxy, 3- (methoxy) propoxy, 3- (Ethoxy) propoxy, 3- (n-propoxy) propoxy,

3- (1-methylethoxy) propoxy, 3- (n-butoxy) propoxy, 3- (l-methylpropoxy) propoxy, 3- (2-methylpropoxy) propoxy, 3- (1, 1-dimethylethoxy) propoxy , 2- (methoxy) butoxy, 2- (ethoxy) butoxy, 2- (n-propoxy) butoxy, 2- (1-methylethoxy) butoxy, 2- (n-butoxy) butoxy, 2- (1-methylpropoxy) butoxy, 2- (2-methylpropoxy) butoxy, 2- (1, 1-dimethylethoxy) butoxy, 3- (methoxy) butoxy, 3- (ethoxy) butoxy, 3- (n-propoxy) butoxy, 3- (1st -Methylethoxy) butoxy, 3- (n-butoxy) butoxy, 3- (1-methylpropoxy) butoxy, 3- (2-methylpropoxy) butoxy, 3- (1, 1-dimethylethoxy) butoxy, 4- (methoxy) butoxy, 4- (Ethoxy) butoxy, 4- (n-propoxy) butoxy, 4- (l-methylethoxy) butoxy, 4- (n-butoxy) butoxy, 4- (1-methylpropoxy) butoxy, 4- (2-methylpropoxy) butoxy, 4- (1, 1-dimethylethoxy) butoxy,

5- (methoxy) pentoxy, 5- (ethoxy) pentoxy, 5- (n-propoxy) pentoxy, 5- (l-methylethoxy) pentoxy, 5- (n-butoxy) pentoxy, 5- (1-methyl-propoxy) pentoxy, 5- (2-methylpropoxy) pentoxy, 5- (1, 1-dimethylethoxy) pentoxy, 6- (methoxy) hexoxy, 6- (ethoxy) hexoxy, 6- (n-propoxy) hexoxy, 6- ( 1-methylethoxy) hexoxy, 6- (n-butoxy) - hexoxy, 6- (1-methylpropoxy) exoxy, 6- (2-methylpropoxy) exoxy or 6- (1, 1-dimethylethoxy) hexoxy, especially for methoxyethoxy or ethoxymethoxy;

(C -C ₄ alkoxy) carbonyl -Cι-C ₄ alkoxy for: Cι-C ₄ alkoxy such as OCH3, OC ₂ H ₅ , OCH ₂ -C ₂ H ₅ , OCH (CH ₃ ) ₂ , OCH (CH ₃ ) -C ₂ H ₅ , 0CH ₂ -CH (CH ₃ ) ₂ or OC (CH ₃ ) ₃ , which is a residue CO-OCH ₃ , CO-OC ₂ H ₅ , C0-0CH ₂ -C ₂ H ₅ , C0- OCH (CH ₃ ) ₂ , CO-0 (CH ₂ ) ₂ -C ₂ H ₅ , CO-OCH (CH ₃ ) -C ₂ H ₅ , CO-OCH ₂ -CH (CH ₃ ) ₂ or CO- OC (CH ₃ ) ₃ carries, for example OCH -CO-OCH ₃ , OCH (CH ₃ ) -CO- OCH ₃ , OCH ₂ -CO-OC ₂ H ₅ or OCH (CH ₃ ) -CO-OC ₂ H ₅ ;

(Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkoxy for: Ci-Cg-alkoxy substituted by (Ci-Cg-alkoxy) - carbonyl as mentioned above, e.g. for OCH ₂ -CO-OCH ₃ , OCH ₂ - CO-OC ₂ H ₅ , OCH ₂ -CO-OCH ₂ -C ₂ H ₅ , 0CH ₂ -CO-OCH (CH ₃ ), n-butoxycarbonyl-methoxy, 1- (methoxycarbonyl) ethoxy, 2- (methoxycarbonyl) ethoxy , 2- (ethoxycarbonyl) ethoxy, 2- (n-propoxycarbonyl) ethoxy, 2- (n-butoxycarbonyl) ethoxy, 3- (methoxycarbonyl) propoxy, 3- (ethoxycarbonyl) propoxy, 3- (n-propoxycarbonyl ) ropoxy, 3- (n-butoxycarbonyl) propoxy, 4- (methoxycarbonyl) butoxy, 4- (ethoxycarbonyl) butoxy, 4- (n-propoxycarbonyl) butoxy, 4- (n-butoxy ^¬ carbonyl) butoxy, 5- (methoxycarbonyl) entoxy, 5- (ethoxycarbonyl) pentoxy, 5- (n-propoxycarbonyl) pentoxy, 5- (n-butoxycarbonyl) butoxy, 6- (methoxycarbonyl) exoxy, 6- (ethoxycarbonyl) hexoxy, 6- (n-propoxycarbonyl) hexoxy or

6- (n-butoxycarbonyl) hexoxy, especially for OCH -CO-OCH ₃ or 1- (methoxycarbonyl) ethoxy;

(Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkyl for: Ci-Cg-alkyl substituted by (Cι ~ Cg-alkoxy) carbonyl as mentioned above, for example for methoxycarbonylmethyl, ethoxycarbonylmethyl, 1 - (methoxycarbonyl) ethyl, 2 - (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 3 - (methoxycarbonyl) ropyl, 4- (methoxycarbonyl) butyl, 5- (methoxycarbonyl) pentyl or 6- (methoxycarbonyl) hexyl; Ci-Cg-alkylthio-Ci-Cg-alkyl for: Ci-Cg-alkylthio substituted by Ci-Cg-alkylthio as mentioned above, for example for CH ₂ -SCH ₃ , CH ₂ -SC ₂ H ₅ , n-propylthiomethyl, CH ₂ -SCH (CH ₃ ) ₂ , n-butylthiomethyl, (1-methylpropylthio) methyl, CH ₂ -SCH ₂ -CH (CH ₃ ) ₂ , CH ₂ -SC (CH ₃ ) ₃ , 2-methylthioethyl, 2- Ethyl - thioethyl, 2- (n-propylthio) ethyl, 2- (1-methylethylthio) ethyl, 2- (n-butylthio) ethyl, 2- (1-methylpropylthio) ethyl, 2- (2-methylpropylthio) ethyl, 2 - (1, 1-Dimethylethylthio) ethyl, 2- (methylthio) propyl, 3- (methylthio) propyl, 2- (ethylthio) propyl, 3- (ethylthio) propyl, 3- (propylthio) propyl, 3- (butyl - thio) ropyl, 4- (methylthio) butyl, 4- (ethylthio) butyl, 4- (n-propylthio) butyl or 4- (n-butylthio) butyl, especially for 2- (methylthio) ethyl;

- Ci-Cg-alkoxy- (Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkyl for: substituted by Ci-Cg-alkoxy as mentioned above (Cι ~ Cg-alkoxy) carbonyl-Cι-Cg-alkyl, so for example for CH ₂ -COOCH ₂ -OCH ₃ , CH ₂ -COOCH ₂ -OC ₂ H ₅ , CH ₂ -COOCH ₂ -OCH (CH ₃ ) ₂ or CH ₂ -COOCH ₂ -OC (CH ₃ ) ₃ ;

- C ₃ -Cg alkenyl for: prop-1-en-l-yl, prop-2-en-l-yl, 1-methyl-ethenyl, n-buten-1-yl, n-buten-2-yl , n-buten-3-yl, 1-methyl-prop-1-en-l-yl, 2-methylprop-l-en-l-yl, l-methylprop-2-en-1-yl, 2-methylprop -2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-l-en-l -yl, 2-methylbut-1-en-l-yl, 3-methylbut-l-en-l-yl, 1-methylbut-2-en-l-yl, 2-methylbut-2-en-l-yl , 3-methylbut-2-en-l-yl, l-methylbut-3-en-l-yl, 2-methylbut-3-en-l-yl, 3-methylbut-3-en-l-yl , 1, 1-dimethyl-prop-2-en-1-yl, 1, 2-dimethyl-prop-1-en-1-yl, 1, 2-dimethyl-prop-2-en-1-yl, 1 -Ethylprop- l-en-2-yl, l-Ethylprop-2-en-l-yl, n-Hex-1-en-l-yl, n-Hex-

2-en-l-yl, n-hex-3-en-l-yl, n-hex-4-en-l-yl, n-hex-5-en-l-yl, 1-methylpent-l- en-l-yl, 2-methylpent-l-en-l-yl, 3-methyl-pent-1-en-l-yl, 4-methylpent-l-en-l-yl, l-methylpent-2- en-l-yl, 2-methylpent-2-en-l-yl, 3-methylpent-2-en-l-yl, 4-methylpent-2-en-l-yl, l-methylpent-3-en- l-yl, 2-methylpent-3-en-l-yl, 3-methylpent-3-en-l-yl, 4-methylpent-3-en-l-yl, l-methylpent-4-en- l-yl, 2-methylpent-4-en-l-yl, 3-methylpent-4-en-l-yl, 4-methylpent-4-en-l-yl, 1, 1-dimethylbut-2- en-l-yl, 1, 1-dimethyl-but-3-en-l-yl, 1, 2-dimethyl-but-1-en-l-yl, 1, 2-dimethyl-but-2-en- l-yl, 1,2-dimethyl-but-3-en-l-yl, 1,3-dimethyl-but-l-en-l-yl, 1,3-dimethyl-but-2-en-1- yl, l, 3-dimethyl-but-3-en-l-yl, 2, 2-dimethyl-but-3-en-l-yl, 2, 3-dimethyl-but-l-en-l-yl, 2, 3-dimethyl-but-2-en-l-yl, 2, 3-dimethyl-but-3-en-l-yl, 3, 3-dimethyl-but-l-en-l-yl, 3, 3-dimethyl-but-2-en-l-yl, 1-ethylbut-l-en-l-yl, 1-ethyl-but-2-en-l-yl, l-ethylbut-3-en-l- yl, 2-ethylbut-l-en-l-yl, 2-ethylbut-2-en-l-yl, 2-ethylbut-3-en- l-yl, 1, 1, 2-trimethyl prop-2-en-l-yl, l-ethyl-l-methyl-prop-2-en-l-yl, l-ethyl-2-methyl-prop-1-en-l-yl or l-ethyl 2-methyl-prop-2-en-l-yl, especially for allyl or 2-buten-1-yl;

C ₂ -Cg alkenyl for: ethenyl or one of the radicals mentioned under C ₃ -Cg alkenyl, in particular for ethenyl or prop-2-en-1-yl;

C ₃ -Cg haloalkenyl for: C ₃ ~ Cg alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for 2-chloro-allyl, 3-chloroallyl, 2, 3-dichlorallyl, 3, 3-dichlorallyl, 2,3,3-trichlorallyl, 2, 3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2, 3-dibromoallyl, 3, 3-dibromoallyl, 2, 3, 3-tribromo-allyl or 2, 3-dibromobut-2-enyl, in particular for 2-chloro-allyl, 3-chloroallyl or 3, 3-dichloroallyl;

C ₃ -C ₆ alkenyloxy for: for example prop-1-en-l-yloxy, prop-2-en-l-yl-oxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2- yloxy, n-butene-3-yloxy, 1-methyl-prop-l-en-l-yloxy, 2-methyl-prop-1-en-l-yloxy, l-methyl-prop-2-en-l- 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-yloxy, 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- 1-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-1-en-l-yl-oxy, l-methyl-pent-2-en-l-yloxy, 2-methyl-pent-2-en-l- yloxy , 3-methyl-pent-2-en-1-yloxy, 4-methyl-pent-2-en-1-yloxy, 1-methyl-pent-3-en-1-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-ene -l-yloxy, l, 2-dimethyl-but-3-en-l-yloxy, 1, 3-dimethyl-but-l-en-l-yloxy, l, 3-dimethyl-but-2-en-l -yloxy, 1, 3-dimethyl-but-3-en-1-yloxy, 2, 2-dimethyl-but-3-en-1-yloxy, 2, 3-dimethyl-but-1-en-1-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, l-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 ₄ alkenyloxy for: ethenyloxy, prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2 -yloxy, n-buten-3-yloxy, 1-methyl-prop-1-en-1-yloxy, 2-methyl-prop-1-en-1-yloxy, 1-methyl-prop-2-en-1 -yloxy or 2-methyl-prop-2-en-1-yloxy, especially for prop-2-en-1-yloxy;

C ₃ -C ₆ alkenylthio for: for example prop-1-en-1-ylthio, prop-2-en-1-ylthio, 1-methylethenylthio, n-buten-1-ylthio, n-buten-2- ylthio, n-butene-3-ylthio, 1-methyl-prop-l-en-l-ylthio, 2-methyl-prop-l-en-l-ylthio, l-methyl-prop-2-en-l- ylthio, 2-methyl-prop-2-en-l-ylthio, n-penten-1-ylthio, n-pentene-2-ylthio, n-penten-3-ylthio, n-penten-4-ylthio, 1-methyl-but-l-en-1-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, l-dimethyl-prop-2-en-l-ylthio, 1, 2-dimethyl-prop-

1-en-l-ylthio, 1, 2-dimethyl-prop-2-en-l-ylthio, 1-ethyl-prop-l-en-2-ylthio, l-ethyl-prop-2-en-l- ylthio, n-hex-l-en-1-ylthio, n-hex-2-en-l-ylthio, n-hex-3-en-l-ylthio, n-hex-4-en-1-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, 4-methyl-pent-2-en-l-ylthio, l-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, l-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, 1-dimethyl-but-2-en-l- ylthio, l, l-dimethyl-but-3-en-l-ylthio, 1, 2-dimethyl-but-l-en-1-ylthio, l, 2-dimethyl-but-2-en-l-ylthio, 1, 2-dimethyl-but-3-en-1-ylthio, 1, 3-dimethyl-but-1-en-1-ylthio, 1, 3-dimethyl-but-2-en-1-ylthio, 1, 3-dimethyl-but-3-en-l-ylthio, 2,2-dimethyl-but-3-en-l-ylthio, 2,3-dimethyl-but-l-en- l-yl hio, 2,3-dimethyl-but-2-en-l-ylthio, 2, 3-dimethyl-but-3-en-l-ylthio, 3,3-dimethyl-but-l-en-l -ylthio, 3,3-dimethyl-but-2-en-1-ylthio, 1-ethyl-but-l-en-l-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, l, 2-trimethyl-prop-2-en-l-ylthio, 1-ethyl-l-methyl-prop-2-en-l-yl hio, l-ethyl-2-methyl-prop-l-ene -l-ylthio or l-ethyl-2-methyl-prop-2-en-l-ylthio, in particular for prop - 2 - en - 1 - y 1 thio;

C ₃ ~ Cg alkynyl for: e.g. B. Prop-1-in-l-yl, propargyl, n-but-1-in-l-yl, n-but-l-in-3-yl, n-but-l-in-4-yl, n- But-2-in-1-yl, n-pent-1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent l-in-5-yl, n-pent-2-in-l-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-l-in-3-yl, n-hex-l-in-4-yl, n-hex-l-in-5-yl, n-hex-l- in-6-yl, n-hex-2-in-l-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in- 6-yl, n-hex-3-in-l-yl, n-hex-3-in-2-yl, 3-methyl-pent-l-in-l-yl, 3-methyl-pent-l- 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-yn-4-yl or 4-methyl-pent-2-yn-5-yl, especially for propargyl;

C ₃ ~ Cg-alkynyloxy for: for example prop-1-in-l-yloxy, prop-2-in-l-yl-oxy, 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-l-yloxy, n-pent-l-in -3-yloxy, n-pent-1-in-4-yloxy, n-pent-1-in-5-yl-oxy, n-pent-2-in-1-yloxy, n-pent-2-in -4-yloxy, n-pent-2-yn-5-yloxy, 3-methyl-but-l-yn-3-yloxy, 3-methyl-but-l-yn-4-yloxy, n-hex-1 -in-l-yloxy, n-hex-l-in-3-yloxy, n-hex-l-in-4-yloxy, n-hex-l-in-5-yloxy, n-hex-l-in -6-yloxy, n-hex-2-in-1-yloxy, n-hex-2-in-4-yloxy, n-hex-2-in-5-yloxy, n-hex-2-in-6 -yloxy, n-hex-3-in-l-yloxy, n-hex-3-in-2-yloxy, 3-methylpent-l-in-l-yloxy, 3-methyl-pent-l-in-3 -yloxy, 3-methyl-pent-1-in-4-yloxy, 3-methyl-pent-1-in-5-yloxy, 4-methyl-pent-1-in-1-yloxy, 4-methyl -pent-2-in-4-yloxy or 4-methyl-pent-2-in-5-yloxy, especially for prop-2-in-1-yloxy;

C ₂ -C ₄ alkynyloxy for: ethynyloxy, prop-1-in-1-yloxy or prop-2-in-1-yloxy, in particular for Prσp-2-in-1-yloxy;

C ₃ ~ Cg-alkynylthio for: prop-1-in-l-ylthio, prop-2-in-l-ylthio, n-but-1-in-l-ylthio, n-but-l-in-3- ylthio, n-but-l-in-4-ylthio, n-but-2-in-l-ylthio, n-pent-1-in-l-ylthio, n-pent-l-in-3-ylthio, n-pent-l-in-4-ylthio, n-pent-l-in-5-ylthio, n-pent-2-in-l-ylthio, n-pent-2-in-4-ylthio, n- Pent-2-in-5-ylthio, 3-methyl-but-l-in-3-ylthio, 3-methylbut-l-in-4-ylthio, n-Hex-1-in-l-ylthio, n- Hex-l-in-3-ylthio, n-hex-1-in-4-ylthio, n-hex-l-in-5-ylthio, n-hex-l-in-6-ylthio, n-hex 2-in-l-ylthio, n-hex-2-in-4-ylthio, n-hex-2-in-5-ylthio, n-hex-2-in-6-ylthio, n-hex-3- in-l-ylthio, n-hex-3-in-2-ylthio, 3-methylpent-l-in-l-ylthio, 3-methyl-pent-l-in- 3-yl hio, 3-methyl-pent-l-in-4-ylthio, 3-methylpent-l-in-5-ylthio, 4-methyl-pent-l-in-l-ylthio, 4-methyl-pent -2-in-4-ylthio or 4-methyl-pent-2-in-5-ylthio, especially for prop-2-in-1-ylthio;

Ci-Cg alkylene for: e.g. Methylene, 1,1-ethylene, 1,2-ethylene, 1, 3-propylene, 2, 2-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene, especially for methylene, 1, 1-ethylene or 2,2-propylene.

With regard to the use of the substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3,4, 5-tetrahydro-l, 2, 4-triazines I as herbicides and / or as desiccant / defoliantly effective Compounds preferably have the following meanings, each individually or in combination:

X oxygen;

R ¹ Ci-Cg-alkyl, especially methyl;

R ² amino or Ci-Cg-alkyl, especially amino or methyl;

Ar Ar ¹ , Ar ² or Ar ³ ;

R ³ halogen, especially fluorine or chlorine;

R ⁴ halogen, especially chlorine;

R ⁵ on the one hand hydrogen, nitro, amino, Ci-Cg-alkyl, Ci-Cg-haloalkyl, formyl, -CH = N-OR ⁹ ,

-CH (OR ¹⁰ ), R ^U , R ¹² , -CO-Cl, -CO-OR ¹³ , -CO-ORKI-CO-OR ¹³ , -CO- jRiSj-Rlδ o er -N (R ²⁰ ) -R ¹⁹ ,

on the other hand hydrogen, -CO-OR ¹³ , -0CH (CH ₃ ) -C00H, -0CH (CH ₃ ) -COOCH ₃ or -N (R ²⁰ ) -R ¹⁹ ;

R ^{6 is} hydrogen, hydroxy, Ci-Cg-alkyl, Ci-Cg-alkoxy, C ₃ -Cg -alkenyl or C ₃ -Cg-alkynyl, in particular C ₃ ~ Cg-alkynyl;

R ^{7 is} hydrogen;

R ^{8 is} hydrogen, Ci-Cg-alkyl or (Ci-Cg-alkoxy) carbonyl-Ci-Cg-alkyl; n 1;

Y oxygen;

Z oxygen or sulfur, especially oxygen;

R ⁹ Ci-Cg-alkyl;

R ¹⁰ , R ^{1: L} , R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ independently of one another are hydrogen or Ci-Cg-alkyl;

R ^{14 is} methylene or 1,1-ethylene;

R2Ö hydrogen.

The substituted 6-aryl-3-thi-0x0-5-0x0-2, 3,4,5-tetrahydro-1,2,4-triazines of the formula Ia {ö I with X = oxygen; R ^ R ² = methyl; Ar = Ar ¹ ; R ³ = fluorine and R ⁴ = chlorine}, in particular the compounds Ia.l to Ia.523 listed in Table 1 below:

Table 1

Furthermore, the following substituted 6-aryl-3-thioxo-5-oxo-2, 3, 4, 5-tetrahydro-l, 2, 4-triazines of the formulas Ib to Im are particularly preferred, in particular

the compounds Ib.l to Ib.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{3 is} chlorine:

the compounds Ic.l to Ic.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{3 is} hydrogen:

the compounds Id.l to Id.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{4 is} cyano:

the compounds Ie.l to Ie.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{3 is} chlorine and R ^{4 is} cyano:

the compounds If .1 to If .248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{3 is} hydrogen and R ^{4 is} cyano:

the compounds Ig.l to Ig.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{2 is} amino:

the compounds Ih.l to Ih.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{2 is} amino and R ^{3 is} chlorine:

the compounds Ii.l to Ii.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{2 is} amino and R ^{3 is} hydrogen:

the compounds Ik.l to Ik.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{2 is} amino and R ^{4 is} cyano:

the compounds Im.l to Im.248, which differ from the corresponding compounds la.l to Ia.248 only in that R ^{2 is} amino, R ^{3 is} hydrogen and R ^{4 is} cyano:

The compounds Ia-166, Ia.167, Ib.166, Ib.167, Ic.166, Ic.167, Id.166, Id.167, Ie.166, Ie.167, If.166 are very particularly preferred. If.167, Ig.166, Ig.167, Ih.166, Ih.167, Ik.166, Ik.167, Im.166 and Im.167.

In addition, the substituted 6-aryl-3-thioxo-5-oxo-2, 3, 4, 5-tetrahydro-1,2, 4-triazines of the formula In {= I with Ar = Ar ² ; n = 1; X, Y = oxygen; R ^ R ² = methyl; R ³ = fluorine; R ⁷ = hydrogen} is particularly preferred, in particular the compounds In.l to In.80 listed in Table 2 below:

99/59983

29

Table 2

Furthermore, the following substituted 6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-1,2,4-triazines of the formulas lo to Is are very particularly preferred, in particular

the compounds Io.l to Io.80, which differ from the corresponding compounds In.l to In.80 only in that R ^{3 is} chlorine:

the compounds Ip.l to Ip.80, which differ from the corresponding compounds In.l to In.80 only in that R ^{3 is} hydrogen:

the connections Iq.l to Iq.80, which differ from the corresponding connections In.l to In.80 only in that n stands for zero:

the compounds Ir.l to lr.80, which differ from the corresponding compounds In.l to In.80 only in that n is zero and R ^{3 is} chlorine:

the compounds Is.l to Is.80, which differ from the corresponding compounds In.l to In.80 only in that n is zero and R ^{3 is} hydrogen:

In addition, the substituted 6-aryl-3-thioxo-5-oxo-2,3,4,5-tetrahydro-l, 2,4-triazines of the formulas It {= I with

X = oxygen; R ^ R ² = methyl; Ar = Ar ³ ; R ³ = fluorine and R ⁴ = chlorine} are particularly preferred, in particular the compounds It.l to It.310 listed in Table 3 below: Table 3

Furthermore, the substituted 6-aryl-3-thioxo-5-oxo-2, 3, 4, 5-tetrahydro-l, 2, 4-triazines of the formulas lu to ly are very particularly preferred, in particular

the compounds Iu.l to Iu.310, which differ from the corresponding compounds It.l to It.310 only in that R ^{3 is} chlorine:

- The compounds Iv.l to Iv.310, which differ from the corresponding compounds It.l to It.310 only in that R ^{3 is} hydrogen:

the compounds Iw.l to Iw.310, which differ from the corresponding compounds It.l to It.310 only in that Ar stands for Ar ⁴ :

the compounds Ix.l to Ix.310, which differ from the corresponding compounds It.l to It.310 only in that Ar is Ar ⁴ and R ^{3 is} chlorine:

the compounds Iy.l to Iy.310, which differ from the corresponding compounds It.l to It.310 only in that Ar is Ar ⁴ and R ^{3 is} hydrogen:

The substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetrahydro-1,2, 4-triazines of the formula I can be obtained in various ways, in particular by one of the following processes:

A) Cyclocondensation of a 2,4-disubstituted thiosemicarbazide or 2-substituted thiocarboxyhydrazide IV with an arylglyoxylic acid or its Ci-Cg-alkyl ester (V):

I {X = 0} R ²⁵ represents hydrogen or Ci-Cg-alkyl.

Usually one works in an inert solvent / diluent, e.g. in acetic acid, a lower alcohol such as methanol, ethanol, n-propanol and isopropanol, an ether such as tert. -Butyl methyl ether, tetrahydrofuran, dioxane and 1, 2-diethoxyethane, an aprotic solvent such as dimethyl formamide, dimethyl sulfoxide and pyridine. With the exception of tert. -Butyl methyl ethers are also suitable as mixtures of the solvents / diluents mentioned with water.

The reaction is generally carried out at 20 ° C. to the boiling point of the respective reaction mixture.

The condensation of IV with V is generally catalyzed by acids, in particular carboxylic acids such as formic acid and acetic acid, sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid or mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid.

The ring closure reaction from IV to I is usually catalyzed by bases. Suitable for this are e.g. Alkali metal carbonates such as sodium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and alkali metal hydroxides such as sodium hydroxide, but also nitrogen bases such as triethylamine, dicyclohexylethylamine, pyridine and 4-dimethylaminopyridine.

Reactions of this type are generally known, for example from

• H. Neunhoeffer in A.R. Katritzky, Comprehensive Heterocyclic Chemistry, Vol. 3, p. 430 ff. And literature cited there;

• J. Gut and M. Prystas, Coll. Czech. Chem. Commun. 24, 2986 (1959);

• M. Tisler and Z. Vrbaski, J. Org. Chem. 2_ϊ, 770

(1960);

• V.J. Ram and M. Nath, Ind. J. Chem. Vol. 34B, pp. 423-426 (1995);

• WO 94/03454. The arylglyoxylic acids and their alkyl esters (V) are known or can be prepared in a manner known per se (see, for example, JS Nimitz & HS Mosher, J. Org. Chem. 46. (1981), 211-213; WMP Johnson & G. Holan, Aust. J. Chem. 34 (1981), 2363 and X. Creary, J. Org. Chem. J52. (1987), 5026).

With regard to the particularly preferred active ingredients I with A = Ar ¹ , the compounds are Va

R5

of particular interest, especially those with

R ⁴ = chlorine and R ⁵ = OR ¹⁸ ', where R ¹⁸ ' represents hydrogen, methyl, or -CH (CH ₃ ) -COOCH ₃ .

B) Alkylation of a 6-aryltriazine derivative VII with an alkyl halide or dialkyl sulfate R ¹ -L:

VII VIII (by-product)

L stands for chloride, bromide, iodide or 0-S0 ₂ -OR ¹ .

Suitable solvents / diluents are especially aprotic solvents such as N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, acetone, tetrahydrofuran, dioxane and 1,2-diethoxyethane.

In general, the Reaktiosführung is carried out at 0 ° C to boiling ^¬ temperature of the reaction mixture.

Such alkylations are well known, e.g. out:

• M. Prystas and J. Gut, Coll. Czech. Chem. Commun. 27, 1898 (1962); • J. Daunis et al. , Bull. Soc. Chim. Fri _10th , 3658

(1971) and Bull. Soc. Chim. Fr. 11, 1511 (1972);

• A.K. Mansour and Y.A. Ibrahim, Journal f. Practical Chemistry 315, 221 (1973).

The 6-aryltriazine derivatives VII can advantageously be prepared by condensation of thiocarboxyhydrazides (R ² = NH ₂ ) or thiosemicarbazides IX monosubstituted in the 4-position with V analogously to process A):

IX V

Most of the thiosemicarbazides and thiocarboxylhydrazides IV and IX are known, but can also be prepared in a manner known per se (see, for example, KA Jensen et al., Acta Che ica Scandinavica 22 (1968), 1 and C.-J. Krö- ger et al., Liebigs Ann. Chem. 643 (1961), 121).

Thiolation of a 6-aryl-3-thioxo-5-oxo-2, 3, 4, 5-tetra-hydro-1, 2, 4-triazine {cf. e.g. M. Prystas & J. Gut, Coll. Czech. Chem. Commun. 27 (1962), 1898; J. Jonas & J. Gut, Coll. Czech. Chem. Commun. 27 (1962), 1886; C. Tzeng et al., J. Org. Chem. 48 (1983), 1271}:

_{τ r} - _r ._ sulfurization

I IX - 0} ^ j {= s}

The sulfurization is usually carried out in an inert solvent / diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes or in an organic amine such as pyridine.

Phosphorus (V) sulfide and 2,4-bis (4-methoxyphenyl) -1, 3-di-thia-2,4,4-diphosphetane-2,4-disulfide ("Lawesson reagent") are particularly suitable as the sulfurization reagent. . Usually 1 to 5 times the molar amount of sulfurization reagent, based on the starting compound I {X = 0} to be sulfurized, is sufficient for a largely complete reaction.

The reaction temperature is usually from 20 ° C to the boiling point of the reaction mixture.

Unless otherwise stated, all of the processes described above are expediently carried out at atmospheric pressure or under the autogenous pressure of the respective reaction mixture.

The substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetrahydro-1,2,4-triazines I can normally be prepared by one of the synthesis processes mentioned above. For economic or procedural reasons, however, it may be more convenient to use some compounds I from similar 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetrahydro-l, 2, 4-triazines differ, however, in particular in the meaning of one of the residues on Ar, to be produced, in a manner known per se, for example through nitration, sulfonation, chlorosulfonation, halogenation, alkylation, acylation, acetal hydrolysis, acetalization, amidation, ester hydrolysis, condensation reaction, oxidation, Peterson olefination, reduction, etherification, esterification, Wittig reaction or Meerwein reaction.

The starting compounds specified for the individual processes are either known or are obtainable in a manner known per se or in analogy to one of the processes described.

The 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 one organic solvents and working up the organic phase towards the product.

The substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetra-hydro-1, 2, 4-triazines I can be obtained in the preparation as isomer mixtures, which, however, if desired, according to the usual methods such as crystallization or chromatography, also on an optically active adsorbate, into which largely pure isomers can be separated. Leave pure optically active isomers can advantageously be produced from corresponding optically active starting products.

Salts of the compounds I which can be used commercially 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, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.

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

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoealumisisumisum , Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus pers , Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, 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 compositions comprising them can be sprayed, atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, sprays or granules. Dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The following are essentially considered as inert auxiliaries: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore 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 made from emulsion concentrates,

Suspensions, pastes, wettable powders or water-dispersible granules can be prepared by adding water. To prepare emulsions, pastes or old dispersions, the substrates 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 surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives 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, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

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

The following formulation examples illustrate the preparation of such preparations:

I. 20 parts by weight of compound No. Parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. II. 20 parts by weight of compound no. Icl are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone,

30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 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 comprises 0.02% by weight of the active ingredient.

III. 20 parts by weight of active ingredient No. Ia.167 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

IV. 20 parts by weight of active ingredient No. Ic.154 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 in a hammer mill marry. 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. Ig.167 are with

97 parts by weight of finely divided kaolin mixed. Obtained in this way, a dusting agent which contains 3 wt .-% of the active substance ^¬.

VI. 20 parts by weight of active ingredient no. Ic.172 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. A stable oily dispersion is obtained.

VII. 1 part by weight of active ingredient No. Ig.167 is in a

Dissolved 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 active ingredient No. Ic.2 is dissolved in a mixture of 80 rush weight of cyclohexanone and 20 parts by weight of Wettol ^® EM 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG) consists. 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 as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (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.

To broaden the spectrum of activity and to achieve synergistic effects, the substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetrahydro-l, 2, 4-triazines I with numerous representatives other herbicidal or growth-regulating active ingredient groups are mixed 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, benzothidadiazinones, 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 dichloropropane acid and its 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, oxadiazoles, oxiranes, phenols, aryloxy and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinca rbonic acid and its derivatives, pyrimidyl ether, sulfonamides, sulfonylureas, Triazines, Triazinones, Triazolinones, Triazolcarboxamides and Uracile.

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

1. Phenylglyoxylic acid derivatives

example 1

2- (4-Chloro-2-fluoro-5-methoxyphenyl) -2-oxoacetic acid ethyl ester

All work operations were carried out under anhydrous conditions and N ₂ protective gas.

To a solution of 95.8 g (0.4 mol) of 5-bromo-2-chloro-4-fluoro-anisole in 350 ml of tetrahydrofuran was added 200 ml of a 2-molar isopropylmagnesium chloride solution at 20-25 ° C (0, 4 mol) added dropwise in tetrahydrofuran. After the addition was complete, stirring was continued for a maximum of 20 minutes. This solution was then added dropwise at (-50) ° C. to a solution of 64.2 g (0.44 mol) of diethyl oxalate in 300 ml of tetrahydrofuran. The cold bath was removed and the suspension obtained was stirred further overnight. 200 ml of water and 200 ml of 10% hydrochloric acid were then added dropwise in succession while cooling with an ice bath. After saturating the aqueous phase with sodium chloride, the organic phase was separated off, dried over sodium sulfate and concentrated. The crude product is purified by means of chromatography (mobile phase cyclohexane / methyl tert-butyl ether = 100: 5) on silica gel. Yield: 66.2 g (white crystals); Mp: 42-45 ° C.

Example 2

2- (4-chloro-2-fluoro-5-methoxyphenyl) -2-oxoacetic acid

75.9 g (0.291 mol) of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -2-oxoacetic acid ethyl ester were heated under reflux in 1.0 1 47% aqueous HBr solution for seven hours. After cooling, the reaction mixture was poured into 3 l of ice water. Then extracted three times with 300 ml of methyl tert. -butyl ether. The combined organic phases were washed twice with a little water, dried over sodium sulfate and then concentrated. Yield: 63.1 g (white crystals); Mp: 134-137 ° C.

Example 3

2- (4-chloro-2-fluoro-5-hydroxyphenyl) -2-oxoacetic acid

63.1 g of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -2-oxo-acetic acid were heated to reflux temperature in 1.0 1 47% aqueous HBr solution for eight hours, after which a further 3 days Room temperature stirred. Then the mixture was poured into 3 liters of ice water. The resulting product of value was extracted with. three times 300 ml of ethyl acetate. The combined organic phases were washed twice with a little water, dried over sodium sulfate and concentrated. Yield: 53.5 g (white crystals); Mp: 137-139 ° C.

Example 4 (R) -2- [4-Chloro-2-fluoro-5- [(1-methoxycarbonyl) ethoxy] phenyl] -2-oxoacetic acid

1.8 g of an 80% suspension of sodium hydride in mineral oil were freed from the mineral oil by washing with dirnethylformamide, suspended in 20 ml of dirnethylformamide and added dropwise at 5-10 ° C. with a solution of 6.0 g

2- (4-Chloro-2-fluoro-5-hydroxyphenyl) -2-oxo-acetic acid in 30 ml Dirnethylformamid added. After stirring for 15 minutes, 4.0 g of (S) -2-chloropropionate were added dropwise. Then the mixture was stirred at 65 ° C. for seven hours and at 20 ° C. for twelve hours. The mixture was then poured into 200 ml of ice water, acidified with dilute hydrochloric acid and extracted three times with 50 ml of ethyl acetate. The combined organic phases were washed twice with 20 ml of water, dried over sodium sulfate and concentrated. Yield: 7.4 g of a light yellow oil; ⁱ H-NMR (270 MHz, (CD ₃ ) ₂ SO): δ [ppm] = 1.59 (d, 3H), 3.72 (s, 3H), 5.27 (q, lH), 7.43 (d, 1H), 7.78 (d, 1H).

Example 5

2- (4-Chloro-3-methylphenyl) -2-oxoacetic acid ethyl ester

Using 2-chloro-5-iodotoluene, the desired product of value was obtained analogously to Example 1. iH-NMR (270 MHz, CDC1 ₃ ): δ [ppm] = 1.42 (t, 3H), 2.44 (s, 3H), 4.46 (q, 2H), 7.48 (d, 1H) ), 7.80 (dd.lH), 7.90 (d, lH). Example 6

2- (4-chloro-3-methylphenyl) -2-oxoacetic acid

A solution of 10 g (44 mmol) of 2 - (4-chloro-3-methylphenyl) -2-oxoacetic acid ethyl ester in 390 ml of acetic acid and 98 ml of 2 M hydrochloric acid was heated at 80 ° C. for 4 hours. Then you narrowed down. Water was added to the residue, followed by extraction with ethyl acetate. The combined extracts were washed with water, dried over sodium sulfate and finally concentrated. Yield: 7.5 g; M.p .: 85-86 ° C.

Example 7

2- (4-chloro-2-fluorophenyl) -2-oxoacetic acid

Using ethyl 2- (4-chloro-2-fluorophenyl) -2-oxoacetate, the desired product of value was obtained analogously to Example 2. ⁱ H-NMR (270 MHz, CDC1 ₃ ): δ [ppm] = 6.48 (s, lH), 7.20-7.35 (m, 2H), 8.02 (t, lH).

Example 8

2- (4-Chloro-3-nitrophenyl) -2-oxoacetic acid ethyl ester

To a solution of 131.3 g (0.62 mol) cooled to 0 ° C

2 - (4-Chlorophenyl) -2-oxoacetic acid ethyl ester in 350 ml conc. Sulfuric acid was dropped with 38.9 g (0.62 mol) of nitric acid, followed by stirring for 5 hours. The solution was then poured onto ice water. Then the product of value was extracted with methyl - butyl ether. The combined extracts were washed with water, out via magnesium sulfate ^'dried and finally concentrated. Yield: 148.6 g; MS (m / z): 258 [M + H] ⁺ .

Example 9

2- (4-methoxy-3-nitrophenyl) -2-oxoacetic acid

A solution of 75 g (0.29 mol) of 2 - (4-chloro-3-nitrophenyl) -2-oxoacetic acid ethyl ester in 150 was added to a solution of 35 g (0.87 mol) of sodium hydroxide in 250 ml of methanol while cooling with ice added ml of methanol. The mixture was then stirred for 16 hours, after which the reaction mixture was acidified with dilute hydrochloric acid. The low-boiling fractions were then largely distilled off. Water was added to the residue. The product of value was extracted from the aqueous phase obtained with ethyl acetate. The organic phase was washed with water, dried over sodium sulfate and finally narrowed down. Yield: 69.5 g; MS [m / z]: 226 (M + H) ⁺ .

2. Thiosemicarbazide

Example 10

2, 4-dimethylthiosemicarbazide

To a solution of 15.0 g of methyl isothiocyanate in 200 ml of anhydrous tert. Butyl methyl ether, 9.5 g of methylhydrazine were added dropwise at room temperature. After stirring overnight, the solvent was removed and the residue was recrystallized from ethanol / water (2: 1). Yield: 21.5 g (white crystals); Mp: 139-140 ° C. ⁱ H-NM (270 MHz, in (CD ₃ ) ₂ SO): δ [ppm] = 2.87 (d, 3H), 3.43 (s, 3H), 4.80 (s, 2H), 8.13 (br., lH) .

Example 11

2- (4-chlorophenyl) -4-methylthiosemicarbazide

A solution of 2.08 g (29 mmol) of methyl isothiocyanate in 20 ml of methyl tert was added to a solution of 4.08 g (29 mmol) of 4-chlorophenylhydrazine in 60 ml of acetic acid. -butyl ether. After stirring for 16 hours, the mixture was concentrated. The residue was mixed with water. The product of value was extracted from the aqueous phase with dichloromethane. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. The crude product was purified by means of silica gel chromatography (eluent: cyclohexane / ethyl acetate). Yield: after a first fraction of 0.6 g of 1- (4-chlorophenyl) -4-methylthiosemicarbazide, 2.5 g of the desired product were obtained. M.p .: 114-115 ° C.

3. 1,2,4-triazines

Example 12

6- (4-chloro-2-fluoro-5-hydroxypheny1) -2,4 -dimethyl-5-oxo-

3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine

A solution of 19.7 g (90 mmol) of 2 - (4-chloro-2-fluoro-5-hydroxyphenyl) -2-oxoacetic acid and 10.7 g (90 mmol) of 2,4-dimethylthiosemicarbazide in 50 ml of acetic acid was heated to 85-90 ° C for 7 hours. The reaction mixture was then diluted with water, after which the solid product of value formed was separated off, washed with water and dried. Yield: 15.4 g; M.p .: 166-167 ° C. Example 13

(R) -2- [2-chloro-4-fluoro-5- (2,4-dimethyl -5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine 6 -yl) phenoxy] propionic acid methyl ester (No. Ia.167)

A suspension of 15 g (50 mmol) 6 - (4-chloro-2-fluoro-5-hydroxyphenyl) -2,4-dimethyl-5-oxo - 3-thioxo -2,3,4,5-tetrahydro-1 , 2, 4-triazine and 17.2 g (124 mmol) of potassium carbonate in 100 ml of dimethylformamide were mixed with 6.7 g (55 mmol) of (S) -2-chloropropionic acid methyl ester. After heating at 60-65 ° C for 4 hours, the solution was poured onto water. The resulting solid product of value was washed with water and petroleum ether and then dried. Yield: 18.8 g; M.p .: 123-124 ° C.

Example 14

(R) -2 - (5 - (4 -Amino -5 -oxo -3 -thioxo -2, 3,4,5 - tetrahydro-1, 2, 4-triazin-6 -yl) -2-chlorine -4 -fluorophenoxy) propionic acid methyl ester

6.9 g (23 mmol) of (R) -2 - (4-chloro-2-fluoro-5 - [(1-methoxycarbonyl) ethoxy] phenyl) -2-oxoacetic acid and 2.4 g (23 mmol) of thio- carbohydrazide was stirred at 85 ° C for 6 hours. Then it was narrowed. A little ether was added to the residue, after which the resulting solid product of value was filtered off and then recrystallized from toluene. Yield: 3.9 g; M.p .: 176-178 ° C.

Example 15

(R) -2- [5- (4-Amino-2-methyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl) -2-chlorine -4-fluorophenoxy] methyl propionate (No.Ig.167)

A suspension of 3.4 g (11 mmol) 6.9 g

(R) -2- [5- (4-Amino-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl) -2-chloro -4 -fluorophenoxy] methyl propionate and 2.2 g (16 mmol) of potassium carbonate in 50 ml of tetrahydrofuran were mixed with 1.5 g (11 mmol) of methyl iodide, after which the mixture was stirred for 3 days. Then the reaction mixture was concentrated. The residue was mixed with ethyl acetate. The organic phase obtained was washed with water, dried over sodium sulfate and finally concentrated. The crude product was purified by means of silica gel chromatography (eluent: cyclohexane / ethyl acetate = 1: 1). Yield: 0.6 g of the desired product were initially obtained (mp: 89-91 ° C.) and 2.3 g of (R) -2 - [5 - (4 -amino-3-methylt- hio-5-oxo -4, 5 -dihydro-1, 2, 4 -triazin-6 -yl) -2-chloro-4-fluorophenoxy] methyl propionate.

Example 16 6- (4-Chloro-2-fluoro-5-hydroxyphenyl) -4-methyl -5 -oxo -2 -phenyl - 3 - thioxo -2,3,4,5-tetrahydro -1,2,4- triazine

Using 2 - (4-chloro-2-fluoro-5-hydroxyphenyl) -2-oxoacetic acid and 4-methyl-2-phenylthiosemicarbazide, the desired product of value was obtained analogously to Example 12. mp: 168-169 ° C.

Example 17

6- (4 -Chlor -2 -fluor -5 -hydroxyphenyl) -2- (4-chlorophenyl) -4-methyl - 5 -oxo - 3 - thioxo -2,3,4,5- etrahydro -1, 2,4-triazine

Using 2 - (4-chloro-2-fluoro-5-hydroxyphenyl) -2-oxoacetic acid and 2- (4-chlorophenyl) -4-methylthiosemicarbazide, the desired product of value was obtained analogously to Example 12. 215-216 ° C.

Example 18

(R) -2- (2-chloro-4-fluoro-5- (4 -methyl- 5 -oxo -2 -phenyl -3 - thioxo -2, 3,4,5 - tetrahydro - 1, 2, 4 - triazin-6 -yl) phenoxy) propionic acid methyl ester

Using 6 - (4-chloro-2-fluoro-5-hydroxyphenyl) - 4 -methyl - 5 -oxo - 2 -phenyl - 3 - thioxo-2,3,4,5-tetrahydro-1, 2, 4 - triazine gave the desired product of value analogously to Example 13. MS [m / z]: 449 (M) ⁺ .

Example 19

(R) -2- (2-chloro-5- [2- (4-chlorophenyl) -4-methyl - 5-oxo-3 - thioxo -2,3,4,5-tetrahydro -1,2,4- triazine-6-yl] - 4-fluorophenoxy-methyl propionate

Using 6 - (4-chloro-2-fluoro-5-hydroxyphenyl) -2- (4-chlorophenyl) -4-methyl - 5 -oxo -3 - thioxo -2, 3, 4, 5 - tetrahydro- 1 , 2, 4-triazine gave the desired product of value analogously to Example 13. mp: 80-84 ° C.

Example 20

4-amino- 6- (4-chlorophenyl) -5 -oxo -3 - thioxo -2, 3, 4, 5 -tetrahydro -1,2, 4 -triazine Using 2 - (4-chlorophenyl) -2-oxoacetic acid, the desired product of value was obtained analogously to Example 14. mp: 273-274 ° C.

Example 21

4-amino-6- (4-chlorophenyl) -2-methyl -5-oxo-3-thioxo-2, 3, 4, 5 - tetrahydro-1, 2, 4 - triazine (No.Ii.l)

Using 4-amino-6 - (4-chlorophenyl) -5-oxo-3-thioxo-2, 3, 4, 5 - tetrahydro-1, 2, 4-triazine, the desired product of value was obtained analogously to Example 15. mp .: 157-158 ° C.

Example 22

6 - (4-chlorophenyl) -2,4-dimethyl-5-oxo - 3-thioxo -2,3,4,5-tetra-hydro-1,2,4-triazine (No. Icl)

A solution of 89.4 g (0.42 mol) of 2 - (4-chlorophenyl) -2-oxoacetate, 50.1 g (0.42 mol) of 2, 4-dimethylthiosemicarbazide and 17.6 g ( 0.44 mol) sodium hydroxide in 300 ml ethanol and 800 ml water was heated to reflux temperature for 7 hours. The mixture was then acidified with dilute hydrochloric acid, after which the resulting solid crude product was filtered off and purified by means of silica gel chromatography (eluent: cyclohexane / ethyl acetate = 9: 1). Yield: 21.1 g; M.p .: 130-131 ° C.

Example 23

6 - (4 - chloro-3-nitrophenyl) -2,4-dimethyl - 5-oxo - 3 - thioxo-

2, 3, 4, 5 -tetrahydro -1,2,4 -triazine (No.Ic.168)

Using 6 - (4-chlorophenyl) -2, 4 -di - methyl -5-oxo -3 - thioxo-2, 3,4,5 - tetrahydro-1, 2,4-he riazinetrione ^¬ held to obtain the desired Product of value analogous to Example 8. mp: 184-185 ° C.

Example 24

6- (3-Amino-4-chlorophenyl) -2, 4 -dimethyl -5 -oxo-3 - thoxo-2, 3, 4, 5 - tetrahydro -1,2, 4 -triazine (No. Ic.170)

A suspension of 39.7 g (0.71 mol) of iron powder in 200 ml of methanol and 870 ml of acetic acid was heated to reflux temperature and in portions with 55.5 g (0.18 mol) of 6- (4-chloro-3 -nitrophenyl) ) -2, 4 -dimethyl -5 -oxo -3 - thioxo - 2, 3, 4, 5 -tetrahydro -1, 2, 4 -triazine added. The mixture was then stirred for 3 hours, after which the solids were filtered off. The filtrate was restricted. The residue thus obtained was mixed with water. Extra from the aqueous phase then the valuable product was treated with ethyl acetate. The organic phase was dried over sodium sulfate and finally concentrated. The crude product was purified by means of silica gel chromatography (eluent: cyclohexane / ethyl acetate = 2: 1). Yield: 12.8 g; MS [m / z]: 282 (M) ⁺ .

Example 25

2 -Chlor- 3- [2 -chloro- 5- (2, 4 -dimethyl - 5 -oxo -3 - thioxo -2, 3, 4, 5 - tetrahydro- 1, 2, 4 -triazin-6 -yl) phenyl] ropionic acid methyl ester (No. Ic.154)

A solution of 2.3 g (22 mmol) tert. -Butyl nitrite in 50 ml acetonitrile was treated with 12.8 g (0.15 mol) methyl acrylate, 2.5 g (19 mmol) copper (II) chloride and 4.2 g (15 mmol) 6- (3-amino - 4-chlorophenyl) -2, 4 -dimethyl -5 -oxo -3 - thioxo -

2, 3, 4, 5 -tetrahydro -1,2,4 -triazine added. After stirring for 16 hours, the mixture was concentrated. The crude product obtained was purified by means of silica gel chromatography (eluent: cyclohexane / ethyl acetate = 10: 1). Yield: 0.6 g; MS [m / z]: 387 (M) ⁺ .

Example 26

6 - [3 -Di (methylsulfonyl) amino-4-chlorophenyl] -2,4 -dimethyl -5 -oxo -3 - thioxo- 2, 3,4, 5-tetrahydro-1, 2, 4 -triazine (No. Ic.180)

A solution of 4.3 g (15 mmol) of 6 - (3-amino-4-chlorophenyl) -2,4-dimethyl - 5-oxo - 3 - hioxo -2,3,4,5-tetrahydro-1 , 2, 4 - triazine in 100 ml dichloromethane was mixed with 3.4 g (35 mmol) triethylamine and 3.6 g (32 mmol) methanesulfonic acid chloride, after which the mixture was stirred for 4 hours. The reaction mixture was then washed with water, dried over sodium sulfate and then concentrated. Yield: quantitative; M.p .: 225-235 ° C.

Example 27

2,4-Dimethyl-6- [3- (methylsulfonyl) amino-4-chlorophenyl] - 5 - oxo - 3 - thioxo -2,3,4,5-tetrahydro -1,2,4-triazine (No. Ic .172)

To a solution of 4.5 g (10 mmol) of 6 - [3 -di (methylsulfonyl) amino -4-chlorophenyl] -2,4 -dimethyl -5 -oxo -3 - thioxo - 2, 3, 4, 5-tetrahydro -1,2,4 -triazine in 200 ml of methanol was given a catalytic amount of sodium methylate. After stirring for 3 hours, the mixture was concentrated. The remaining residue was mixed with water. The product of value was extracted from the aqueous phase obtained with ethyl acetate. The organic phase was washed with water and washed over sodium sulfate. dries and finally concentrated. The cleaning of the Rohpro ^¬ domestic product was carried out by recrystallization from dichloromethane. Yield: 1.7 g; MS [m / z]: 360 (M) ⁺ .

Example 28

6- (4 -Chlor -3 -methylphenyl) -2, 4 -dimethyl - 5 -oxo- 3 - thioxo - 2, 3, 4, 5 -tetrahydro -1,2, 4 -triazine (No. Ic.2)

Using 2 - (4-chloro-3-methylphenyl) -2-oxoacetic acid, the desired product of value was obtained analogously to Example 12. mp: 133-135 ° C.

Example 29

6- (4-Hydroxyphenyl) -2, 4 -dimethyl -5 -oxo- 3 - thioxo -2, 3, 4, 5 - tetrahydro-1, 2, 4 - triazine

Using 2 - (4-hydroxyphenyl) -2-oxoacetic acid he ^¬ obtained the desired product of value analogously to Example 12. mp: 214-215 ° C.

Example 30

2,4-dimethyl -5-oxo-3-thioxo- 6- [4- (4-trifluoromethoxybenzyloxy) phenyl] -2,3,4,5-tetrahydro-1,2,4-triazine

A suspension of 0.62 g (18 mmol) of 60% sodium hydride in dimethylformamide was mixed with a solution of 4 g (16 mmol) of 6 - (4-hydroxyphenyl) -2,4-dimethyl - 5 - oxo - 3 - thioxo - 2,3,4,5-tetrahydro-1, 2, 4 -triazine in 20 ml of dirnethylformamide. After stirring for 10 minutes, 4.5 g (18 mmol) of 4-trifluoromethoxybenzyl bromide were added to the reaction mixture. The mixture was then stirred for 3 days. Then the mixture obtained was mixed with ice water. The solid crude product thus obtained was filtered off and purified by means of silica gel chromatography (eluent: cyclohexane / ethyl acetate = 3: 1). Yield: 5.1 g; M.p .: 134-135 ° C.

Example 31

6- [4- (4-Chlorobenzyloxy) phenyl] -2,4-dimethyl -5-oxo-3-thioxo -2,3,4,5-tetrahydro -1,2,4-triazine

Using 4-chlorobenzyl bromide, the desired product of value was obtained analogously to Example 30. mp .: 162-164 ° C.

Example 32 6- (3-Chloro-4-hydroxyphenyl) -2, 4-dimethyl-5-oxo-3-thioxo - 2,3,4,5-tetrahydro -1,2,4-triazine Using 2 - (3-chloro-4-hydroxyphenyl) -2-oxoacetic acid, the desired product of value was obtained analogously to Example 12. iH-NMR (270 MHz; in SO (CD ₃ ) ₂ ): δ [ppm] = 3, 60 (s, 3H), £ 3.9

(s, 3H), 7.06 (d, 1H), 7.85 (dd, 1H), 8.03 (d, 1H), 10.84 (Ξ, 1H).

Example 33

(R) -2- [3-chloro-4- (2, 4-dimethyl -5-oxo-3 - thioxo-2, 3, 4, 5 - tetrahydro-1, 2, 4 -triazine-6-yDphenoxy] methyl propionate

Using 6- (3-chloro-4-hydroxyphenyl) -2, 4-dimethyl -5-oxo -3-thioxo-2, 3,4,5 - tetrahydro-1,2,4-triazine gave the desired Product of value analogous to example 13. mp: 67 ° C.

Example 34

6 - (3-Chloro-4-propargyloxypheny1) -2,4-dimethyl-5-oxo-3-thioxo -2,3,4,5-tetrahydro -1,2,4-riazine

Using 6 - (3-chloro-4-hydroxyphenyl) - 2,4-dimethyl - 5 - oxo - 3 - thioxo -2,3,4,5-tetrahydro -1,2,4-triazine and propargyl bromide were obtained the desired product of value analogous to Example 13. mp: 172 ° C.

Example 35 6- [3-Chloro -4- (2-propen-1-yloxy) henyl] -2, 4 -dimethyl-5-oxo-3-thioxo -2,3,4,5-tetrahydro -1,2 , 4-triazine

Using 6- (3-chloro-4-hydroxyphenyl) -2, 4 -dimethyl -5 -oxo-3 - thioxo-2, 3, 4, 5 -tetrahydro-1, 2, 4 -triazine and Al - lylbromide the desired product of value was obtained analogously to example 13. mp: 175 ° C.

Example 36

6 - (3 -Chlor- 4 - isopropoxyphenyl) - 2, 4 -dimethyl -5 -oxo -3 - thioxo -2, 3, 4, 5 - tetrahydro - 1, 2, 4 -triazine

Using 6 - (3-chloro-4-hydroxyphenyl) -2, 4-dimethyl -5-oxo-3-thioxo -2, 3,4, 5-tetrahydro-1,2,4-riazine and isopropyl iodide were obtained the desired product of value analogous to example 13. mp. 81 ° C.

Example 37

6 - (4-methoxy-3-nitropheny1) -2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro -1,2,4-riazine Using 2 - (4-methoxy-3-nitrophenyl) -2-oxoacetic acid, the desired product of value was obtained analogously to Example 12. mp: 218-219 ° C.

Example 38

6 - (4-Hydroxy-3-nitrophenyl) -2,4-dimethyl - 5 - oxo - 3 - thioxo -2,3,4,5-tetrahydro -1,2,4-triazine

A solution of 53 g (0.17 mol) of 6 - (4-methoxy-3-nitrophenyl) -2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-

1,2,4-triazine and 21.9 g (0.51 mol) of lithium chloride in 610 ml of dimethylformamide were heated to the reflux temperature for 7 hours. Then poured onto ice water. After acidification with dilute hydrochloric acid, the solid product of value formed was filtered off, then washed with water and ethyl acetate and finally dried. Yield: 45.5 g; M.p .: 219-221 ° C.

Example 39

6 - (3-Amino - 4-hydroxyphenyl) - 2, 4 -dimethyl -5 -oxo -3 -thioxo -2, 3,4,5-tetrahydro-1, 2,4-triazine

Using 6 - (4-hydroxy-3-nitrophenyl) -2, 4-dimethyl - 5-oxo - 3 - thioxo -2,3,4,5-tetrahydro -

1, 2, 4 -triazine gave the desired product of value analogously to Example 24. mp: 202-208 ° C.

Example 40

6 - (2,4-dimethyl - 5 - oxo - 3 - thioxo -2,3,4,5- tetrahydro -1,2,4- riazine-6 -yl) -2H- 1,4 -benzoxazin-3 ( 4H) -on (No. Ip.l)

A suspension of 8.2 g (31 mmol) of 6 - (3-amino-4-hydroxyphenyl) -2,4-dimethyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2 , 4 triazine, 4.6 g (40 mmol) of chloroacetyl chloride and 6.5 g (47 mmol) of potassium carbonate in 70 ml of dimethylformamide were first stirred at room temperature for 2.5 hours and then at 85 ° C. for 3 hours. The reaction mixture was then mixed with ice water. The resulting solid crude product was filtered off and purified by means of silica gel chromatography (eluent: cyclohexane / ethyl acetate = 2: 1). Yield: 4 g. ⁱ H-NMR (400 MHz; in SO (CD ₃ ) ₂ ): δ [ppm] = 3.60 (s, 3H), 3.95 (s, 3H), 4.65 (s, 2H), 7 , 03 (d, lH), 7.60 (dd, 1H), 7.64 (d, lH), 10.86 (s, lH). Example 41

6 - (2,4-Dimethyl - 5 - oxo - 3 - thioxo -2,3,4,5-etrahydro -1,2,4-triazine -6 -yl) -4- (2-propen-l-yl ) -2H-1, 4 -benzoxazin-3 (4H) -one (No. Ip.10)

Using 6 - (4-hydroxy-3-nitrophenyl) -2, 4-dimethyl -5-oxo -3 - thioxo -2, 3, 4, 5 - tetrahydro-1, 2, 4 - triazine and allyl bromide the desired product of value was obtained analogously to Example 30. mp .: 169-170 ° C.

Example 42

5 - (2,4-Dimethyl - 5-oxo -3 - thioxo -2,3,4,5-tetrahydro -1,2,4-triazine-6 -yl) -2 (3H) -benzoxazolone (No.Is .l)

A solution of 8.2 g (31 mmol) of 6 - (3-amino-4-hydroxyphenyl) -2,4-dimethyl -5-oxo -3 - thioxo -2,3,4,5-tetrahydro-1,2 , 4-triazine and 7.6 g (46 mmol) of carbonyldiimidazole in 70 ml of tetrahydrofuran were heated at reflux temperature for 4 hours. Then it was narrowed. The residue was stirred with dilute hydrochloric acid, after which the solid crude product was filtered off. Yield: 5.6 g; M.p .: 242 ° C.

Example 43

5 - (2,4-dimethyl - 5-oxo-3 - thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-6-yl) -3-propargyl-2 (3H) -benzoxazolone (No. Is.17)

Using 5 - (2, 4-dimethyl-5-oxo-3 - thioxo- 2,3,4,5-tetrahydro-1, 2,4-triazine-6-yl) -2 (3H) -benzoxazolone and Propargyl bromide gave the desired product of value analogous to Example 30. ^ H NMR (400 MHz; in SO (CD ₃ ) ₂ ): δ [ppm] - 3.50

(t, lH), 3.63 (s, 3H), 4.01 (s, 3H), 4.78 (d, 2H), 7.51 (d, 1H), 7.88 (dd.lH) , 7.93 (d, 1H).

Example 44 (R) -2- [5- (2,4-dimethyl -5-oxo-3-thioxo -2, 3,4,5 -tetrahydro-1,2,4-triazine-6 -yl) -2 (3H) -benzoxazolon-3 -yl] propionic acid methyl ester (No. Is.64)

Using 5- (2, 4-dimethyl-5-oxo -3 - thioxo - 2,3,4,5 - tetrahydro-1, 2,4-triazine-6 -yl) -2 (3H) -benzoxazolone and (S) -2-Chloropropionic acid methyl ester gave the desired product of value analogous to Example 30. mp .: 149-150 ° C. Examples of use

The herbicidal activity of the substituted 6-aryl-3-thioxo-5- (thi) oxo-2, 3, 4, 5-tetrahydro-1,2,4-triazines I was demonstrated by the following greenhouse experiments:

Plastic flower pots with loamy sand with about 3.0% humus 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, provided that this has not been impaired 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 application rate for post-emergence treatment was 31.2, 15.6, 7.8 and 3.9 g / ha a.S. (active substance).

The plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C. 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:

At application rates of 31.2 and 15.6 g / ha a.S. Compound No. Ig.167 was very effective against Galium aparine, Polygonum persicaria, Setaria faberii and Veronica species.

With application rates of only 7.8 and 3.9 g / ha a.S. Compound No. Ia.167 showed a very selective herbicidal activity against Abutilon theophrasti, Echinochloa crus-galli and Setaria faberii in the culture of summer wheat. The comparison compound A known from JP-A 10 / 053.508 and tested with the same application rates

r. 29 in JP-A 10 / 053.508)

was not selective.

Examples of use (desiccative / defolian effectiveness)

Young, 4-leafed (without cotyledons) cotton plants served as test plants, which were grown under greenhouse conditions (relative humidity 50 to 70%; day / night temperature 27/20 ° C.). The young cotton plants were dripping wet ( ', based on the spray addition of 0.15 wt .-% of the fatty alcohol alkoxylate Plurafac LF 700 ^® ¹ - broth) with aqueous preparations of the active compounds I treated leaf. The amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

No leaf infestation occurred in the untreated control plants,

U is a low-foam, non-ionic surfactant from BASF AG