CZ20002105A3 - Herbicidal 3-(benzazol-4-yl)pyrimidinedione derivatives, their use, herbicidal composition, process of its preparation and intermediates - Google Patents

Abstract

The present invention relates to 3- (benzazol-4-yl) pyrimidinedione derivatives of formula I and their salts, wherein R 1 = H, NH 2, C 1 -C 6 -alkyl, C 1 -C 6 haloalkyl; R 2 = H, halogen atom, C 1 -C 6 -alkyl, C 1-6 -alkyl; C6-haloalkyl, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6- alkylsulfonyl; R 3 = H, halogen atom, C 1 -C 6 -alkyl; R "= H, a halogen atom; R5 = CN, halogen, C1-C6-alkyl, C1-C6- haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy; the group = N-N (R 6) -, = C (ZR 7) -N (R 6) -, = C (ZR 7) -O-, = C (ZR 7) - WITH-; X = O or S; and the other substituents have specific meanings. Herbicidal compositions containing these substances, the method of their preparation and the method of restriction undesirable vegetation.

Description

Herbicidal 3- (benzazol-4-yl) pyrimidinedione derivatives, their use, herbicidal composition, process for its preparation and intermediates

Technical field

The invention relates to 3- (benzazol-4-yl) pyrimidinedione derivatives, their use, a herbicidal composition, a process for its preparation and intermediates.

BACKGROUND OF THE INVENTION

WO 97/08170 discloses certain 3- (benzox / benzothiazol-7-yl) 6- (trifluoromethyl) uracil as herbicides. Next

3- (benzothiazol-7-yl) uracil and their use as herbicides and for desiccation / defoliation of plants are disclosed in WO 97/08171. WO 97/12886 relates inter alia

3-Benzisoxazol-7-yl-2,4- (1H, 3H) pyrimidinediones, which are described as having herbicidal and desiccant action.

It is an object of the present invention to provide novel herbicidally active uracil compounds which allow better targeted control of unwanted plants than was possible with known compounds.

SUMMARY OF THE INVENTION

The present invention relates to novel 3- (benzazol-4-yl) pyrimidinedione derivatives of the general formula I

wherein the substituents have the following meanings:

X represents an oxygen atom or a sulfur atom;

R ¹ represents a hydrogen atom, amino, C 1 -C 8 -alkyl or

C 1 -C ₆ -haloalkyl;

R ² is hydrogen, halogen, Cl-C6-alkyl,

_Ci-C6 haloalkyl, _Ci-C6 alkylthio, _Ci-C6 alkylsulfinyl or Cl-C6-alkylsulfonyl;

R ³ represents a hydrogen atom, a halogen atom or a halogen atom;

C 1 -C 8 -alkyl;

R ⁴ represents a hydrogen atom or a halogen atom;

R ⁵ represents cyano, halogen, C 1 -C 8 -alkyl,

C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;

represents a group = NN (R ⁶⁾ -, = C (ZR ⁷⁾ -N (R ⁶⁾ -, = C (ZR ⁷⁾ 0-, or = C (ZR ⁷⁾ -S-;

= Y- 3 · · · Y Y Y

R ⁶ represents C 1 -C ₆ -alkyl, C 1 -C ₄ -haloalkyl,

C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₁ -C ₆ -alkylsulfonyl, (C 1 -C 6 -alkyl) carbonyl, (C 1 -C ₆ -haloalkyl) carbonyl, ( C 1 -C ₆ -alkyl) thiocarbonyl, (C 1 -C 6 -alkoxy) carbonyl, (C 1 -C 6 -alkoxy) thiocarbonyl or C 1 -C 6 -alkyl optionally substituted by cyano, C 1 -C ₆ -alkoxy, C 1 -C ₆ - alkylthio, (C 1 -C ₆ -alkoxy) carbonyl, (C 1 -C ₆ -alkylamino) carbonyl, di (C 1 -C ₆ -alkyl) aminocarbonyl or (C 1 -C 6 -alkyl) carbonyloxy;

Z is a chemical bond, oxygen, sulfur, -S (0) -, -S (0) ₂ - <-NH- or -N (R ⁸⁾ -;

R ⁷ and R ⁸ independently represent one of the following groups

Cl-C6-alkyl, Cl-C6-haloalkyl, _{hydroxy-Ci-C4-alkyl, cyano-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4} -haloalkoxy -C 1 -C ₄ -alkyl, C ₃ -C ₄ -alkenyloxyC 1 -C ₄ -alkyl, C ₃ -C ₄ -alkyloxy-C 1 -C ₄ -alkyl,

C ₃ -C 8 cycloalkoxy-C ₄ alkyl, _{amino-Ci-C4-alkyl, Ci-C4-alkylamino-Ci-C4-alkyl,} di (Ci-C ₄ -alkyl) amino-C _C4 alkyl, _Ci-C4 -alkylthioCi -C ₄ -alkyl, C ₄ -haloalkylthio-C ₄ -alkyl, C ₃ -C ₄ -alkenylthio-C ₄ -alkyl, C ₃ -C _4- alkynylthioC 1 -C ₄ -alkyl, C 1 -C ₄ -alkylsulfinyl-C 1 -C ₄ -alkyl, C 1 -C ₄ -haloalkylsulfinyl-C 1 -C ₄ -alkyl,

C ₃ -C ₄ -alkenyl sulfinyl-C 1 -C ₄ -alkyl,

C ₃ -C ₄ -alkynylsulfinyl-C 1 -C ₄ -alkyl, C 1 -C ₄ -alkylsulfonyl-

• ·

C 1 -C ₄ -alkyl, C 1 -C ₄ -haloalkylsulfonyl-C 1 -C ₄ -alkyl, C ₃ -C ₄ -alkenylsulfonyl-C 1 -C ₄ -alkyl,

C ₃ -C ₄ -alkylsulfonyl-C 1 -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, cyanoC ₃ -C ₆ -alkenyl, C ₃ -C ₆ -haloalkenyl, C ₃ -C ₆ -alkynyl, cyano-C C ₃ -C ₆ -alkynyl, C ₃ -C ₆ -haloalkynyl, hydroxycarbonyl-C 1 -C ₄ -alkyl, (C 1 -C ₄ -alkoxy) carbonylC 1 -C ₄ -alkyl, (C 1 -C ₄ -alkylthio) carbonyl-C 1 -C ₄ -alkyl, aminocarbonyl-C 1 -C ₄ -alkyl, (C 1 -C ₄ -alkylamino) carbonylC 1 -C ₄ -alkyl, di (C 1 -C ₄ -alkyl) aminocarbonyl-C 1 -C ₄ -alkyl, di ( Ci-C ₄ -alkyl) phosphonyl-C ₄ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₈ -cycloalkyl-C ₄ -alkyl, phenyl, _phenyl-Ci-C4 alkyl, 3- to 7-membered heterocyclyl or heterocyclylC 1 -C ₄ -alkyl, wherein each heterocyclic ring may contain a carbonyl or thiocarbonyl ring as a member, and each cycloalkyl, phenyl and heterocyclic ring may be optionally substituted with one to four substituents in each of these is selected from the group consisting of cyano, nitro, amino, hydroxy, carboxy, halogen, C 1 -C ₄ -al alkyl, _Ci-C4 haloalkyl, _Ci-C4 alkoxy, _Ci-C4 haloalkoxy, _Ci-C4 alkyl -al alkylthio, _Ci-C4 alkyl thio -halogenal,

_Ci-C4 alkylsulfonyl, _Ci-C4 -halogenalkylsulfonyl, _(Ci-C4 alkoxy) carbonyl, _(Ci-C4 alkyl) carbonyl, _(Ci-C4 haloalkyl) carbonyl, (Ci-C ₄ - alkyl) carbonyloxy, (C ₁ -C ₄ -haloalkyl) carbonyloxy and di (C 1 -C ₄ -alkyl) amino, or, when Z represents a chemical bond, R ⁷ represents, if desired, also a hydrogen atom, a hydroxy group , cyano, mercapto, amino, halo, -CH (OH) -CH ₂ -R ⁹ -CH (halogen) ^-CH2-R9, -CH2-CH (halogen) ^-R9, -CH = CH-R ⁹ or -CH = C (halogen) -R ⁹ , wherein

R ⁹ represents hydroxycarbonyl, (C 1 -C ₄ -alkoxy) carbonyl, (C 1 -C ₄ -alkylthio) carbonyl, aminocarbonyl, (C 1 -C ₄ -alkylamino) carbonyl; or di (C ₁ -C ₄ -alkyl) aminocarbonyl, or R ⁷ and R ⁸ together represent a 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain, which in each case may be optionally substituted by one to four C 1 -C ₄ -alkyl groups or one or two (C 1 -C ₄ -alkoxy) carbonyl groups;

and agriculturally useful salts of the compounds of formula I.

The present invention further relates to

- use of the compounds of formula I as herbicides,

- herbicidal compositions containing compounds of formula I as active ingredients, processes for preparing compounds of formula I and herbicidal compositions containing compounds of formula I,

methods for controlling undesirable vegetation by the compounds of the formulas I, and

- intermediates of formulas III, IV and V for the preparation of compounds of formula I.

It is an object of the present invention to provide novel herbicidally active uracil compounds which allow for better targeted containment

99 · undesirable plants than was possible with known compounds. It has been found that this can be achieved by using 3- (benzazol-4-yl) pyrimidinedione derivatives of the general formula

AND.

It has further been found that the herbicidal compositions of the compound of formula (I) have a very potent action. In addition, methods of compositions and methods of reducing unwanted compounds of Formula I have been found.

which contain good herbicidal preparation of these vegetation using

Depending on the substitution method, the compounds of formula I may have one or more chiral centers, in which case they may exist as enantiomers or mixtures of diastereomers. In each of these cases, compounds of Formula I having at least one olefinic residue may have E / Z isomers. The present invention relates to both pure enantiomers or diastereomers as well as mixtures thereof.

Formula I represents only one of the possible variants for some of the compounds of the present invention. For example, those compounds of formula I wherein R ⁷ = hydroxyl may also be described as tautomers of formula 1 '[-N = C (OH) - <-> - NH-CO-];

• 4 • ··

4 <

4 4

Particularly suitable as agriculturally useful salts are those such that their cations or, for acid addition salts, their cations or anions do not adversely affect the herbicidal activity of the compounds I. Thus, suitable cations are in particular alkali metal ions, preferably lithium, sodium and potassium ions, ions alkaline earth metals, preferably calcium and magnesium, and transition metals, preferably manganese, copper, zinc and iron and ammonium, which may, if desired, carry one to four C 1 -C ₄ -alkyl substituents and / or one phenyl or benzyl substituent , preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, and furthermore phosphonium ions, and sulfonium ions, preferably tri _{(Ci-C4-alkyl)} sulfonium and sulfoxonium ions, preferably tri _(Ci-C4 alkyl) sulfoxonium.

The anions of the useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulphate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and anions of C 1 -C ₄ -alkanoic acids, preferably propionate, butyrate. They may be formed by reacting the compounds of formula I with an acid with a corresponding anion, preferably with an acid

• φφ »* φ *» 4

· Hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The organic moieties of the molecules, such as the halogen atom, which are mentioned in the definitions of the substituents R ¹ to R ³ and R ⁵ to R ⁹ or as radicals formed by cycloalkyl rings, phenyl or heterocyclic systems are collective terms for the individual members of the corresponding groups. All carbon chains, i.e. all alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, phenylalkyl, heterocyclylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkynyl, haloalkynyl, cyanoalkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl and alkynylsulfonyl may be straight or branched. Halogenated substituents preferably have one to five identical or different halogen atoms bound to each other. The meaning of the halogen atom is in all cases a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Other possible meanings are:

- C 1 -C ₄ -alkyl: CH ₃ , C ₂ H ₅ , CH ₂ -C ₂ H ₅ , CH (CH ₃ ) ₂ , n-butyl, CH (CH ₃ ) C ₂ H ₅ , CH ₂ -CH ( CH ₃ ) ₂ or C (CH ₃ ) ₃ ;

- _{Ci-C4-haloalkyl:} Ci-C ₄ -alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, for example CH ₂ F, CHF _2, CF ₃ , CH ₂ C1, CH (Ci) _2z C (Ci) ₃ ,, * * * * * * * * «« «« «« «« « Chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,

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,

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, CH2-C2F5, CF2-C2F5, 1- (fluoromethyl) -2-fluoroethyl,

1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl,

4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;

C 1 -C ₆ -alkyl: a C 1 -C 4 -alkyl radical as mentioned above or, 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-methylpentyl, 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-1-methylpropyl or 1-ethyl2-methylpropyl, preferably CH ₃ , C ₂ H ₅ , CH ₂ -C ₂ H ₅ , CH (CH ₃ ) ₂ , n-butyl, C (CH ₃ ) ₃ , n-pentyl or n-hexyl;

- _{Ci-C6-haloalkyl:} Cj-Cg-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, i.e., one of the radicals mentioned as _Ci-C4 - haloalkyl 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-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-10 «« Φφφφ · · · ·

1-hexyl, 6,6, β-trichloro-1-hexyl or dodecafluorohexyl;

- cyano-C ₁ -C ₄ -alkyl: CH ₂ CN, 1-cyanoethyl, 2-cyanoethyl,

1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl,

1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl,

3-cyanobut-2-yl, 4-cyanobut-2-yl, 1- (CH ₂ CN) eth-1-yl,

1- (CH ₂ CN) -1- (CH ₃ ) -eth-1-yl or 1- (CH ₂ CN) prop-1-yl;

- hydroxy-C 1 -C ₄ -alkyl: CH ₂ OH, 1-hydroxyethyl, 2-hydroxyethyl,

1-hydroxyprop-1-yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl,

1-hydroxybut-1-yl, 2-hydroxybut-1-yl, 3-hydroxybut-1-yl,

4-hydroxybut-1-yl, 1-hydroxybut-2-yl, 2-hydroxybut-2-yl,

3- hydroxybut-2-yl, 4-hydroxy-2-yl, 1- _(CH2 OH) eth-l-yl,

1- (CH ₂ OH) -1- (CH ₃ ) -eth-1-yl or 1- (CH ₂ OH) prop-1-yl;

- amino-C 1 -C ₄ -alkyl: CH ₂ NH ₂ , 1-aminoethyl, 2-aminoethyl,

1-Aminoprop-1-yl, 2-Aminoprop-1-yl, 3-Aminoprop-1-yl,

1-amino-but-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl,

4-aminobut-1-yl, 1-aminobut-2-yl, 2-aminobut-2-yl,

3-aminobut-2-yl, 4-aminobut-2-yl, 1- _{(CH2 NH2)} eth-l-yl,

1- (CH ₂ NH ₂ ) -1- (CH ₃ ) -eth-1-yl or 1- (CH ₂ NH ₂ ) prop-1-yl;

- hydroxycarbonyl-C 1 -C ₄ -alkyl: CH ₂ COOH, 1- (COOH) ethyl,

2- (COOH) -ethyl, 1- (COOH) -prop-1-yl, 2- (COOH) -prop-1-yl,

3- (COOH) prop-1-yl, 1- (COOH) but-1-yl, 2- (COOH) but-1-yl,

3- (COOH) but-1-yl, 4- (COOH) but-1-yl, 1- (COOH) but-2-yl,

2- (COOH) but-2-yl, 3- (COOH) but-2-yl, 4- (COOH) but-2-yl,

1- (CH ₂ COOH) eth-1-yl, 1- (CH ₂ COOH) -1- (CH ₃ ) -eth-1-yl, or

1- _(CH2 COOH) prop-l-yl;

- aminocarbonyl-C 1 -C ₄ -alkyl: CH ₂ CONH ₂ , 1- (CONH ₂ ) ethyl,

2- _(CONH2) ethyl, 1- _(CONH2) prop-l-yl, 2- _(CONH2) prop-l-yl,

3- (CONH ₂ ) prop-1-yl, 1- (CONH ₂ ) but-1-yl, 2- (CONH ₂ ) but-1-yl,

3- (CONH ₂ ) but-1-yl, 4- (CONH ₂ ) but-1-yl, 1- (CONH ₂ ) but-2-yl,

2- _(CONH2) but-2-yl, 3- _(CONH2) but-2-yl, 4- _(CONH2) but-2-yl,

1- (CH ₂ CONH ₂ ) eth-1-yl, 1- (CH ₂ CONH ₂ ) -1- (CH ₃ ) -eth-1-yl, or

1- (CH 2 CONH 2) prop-1-yl

- phenyl-C ₁ -C ₄ alkyl: benzyl, 1-phenylethyl, 2-phenylethyl,

1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl,

1-phenyl-but-1-yl, 2-phenyl-but-1-yl, 3-phenyl-but-1-yl,

4-phenyl-but-1-yl, 1-phenyl-but-2-yl, 2-phenyl-but-2-yl,

3-phenylbut-2-yl, 4-phenylbut-2-yl, 1- (benzyl) eth-1-yl,

1- (benzyl) -1- (methyl) eth-1-yl or 1- (benzyl) prop-1-yl, preferably benzyl or 2-phenylethyl;

- heterocyclyl-C 1 -C ₄ -alkyl: heterocyclylmethyl,

1-heterocyclylethyl, 2-heterocyclylethyl,

1-heterocyclylprop-1-yl, 2-heterocyclylprop-1-yl,

3-heterocyclylprop-1-yl, 1-heterocyclylbut-1-yl,

2-heterocyclylbut-1-yl, 3-heterocyclylbut-1-yl,

4-heterocyclylbut-1-yl, 1-heterocyclylbut-2-yl,

2-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl,

3-heterocyclyl-but-2-yl, 4-heterocyclyl-but-2-yl,

1- (heterocyclylmethyl) eth-1-yl, 1- (heterocyclylmethyl) 1- (methyl) eth-1-yl or 1- (heterocyclylmethyl) prop-1-yl, preferably heterocyclylmethyl or 2-heterocyclylethyl;

- C 1 -C ₄ -alkoxy: 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 or C (CH ₃ ) ₃ , preferably OCH ₃ , OC ₂ H ₅ or OCH (CH ₃ ) ₂ ;

«· · ♦ ·· · · · ·

Β · ··

- _Ci-C4 -haloalkoxy: a _C-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, for example OCH ₂ F, OCHF _2, OCF ₃ , OCH ₂ C1, OCH (Ci) ₂ , OC (C1) ₃ , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy,

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 ₂ 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 , OCF ₂ -C ₂ F ₅ , 1- (CH ₂ F) 2-fluoroethoxy, 1- (CH ₂ Cl) -2-chloroethoxy, 1- ( CH ₂ Br) 2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably OCHF ₂ , OCF ₃ , dichlorofluoromethoxy, chlorodifluoromethoxy or

2.2.2-trifluoroethoxy;

- _{Ci-C6-alkoxy: Cl-C4-alkoxy} radical as mentioned above or, for example n-pentoxy, 1-methylbutoxy, 2-methylbutoxy,

3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,

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-1-methylpropoxy or 1-ethyl-2-methylpropoxy, preferably OCH ₃ ,

OC ₂ H _5, OCH ₂ -C ₂ Hs, OCH _{(CH3) 2,} n-butoxy, OC (CH3) _3, n-pentoxy or n-hexoxy;

- Ci-C6-haloalkoxy: Ci-Cg-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, i.e., one of the radicals mentioned as Ci-C ₄ - haloalkoxy or

5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1-pentoxy,

5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, β-bromo-1-hexoxy, 6-iodo- 1-hexoxy, 6,6,6-trichloro-1-hexoxy or dodecafluorohexoxy;

- C 1 -C ₄ -alkylthio: 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 or SC (CH ₃ ) ₃ , preferably SCH ₃ or SC ₂ H ₅ ;

- _Ci-C4 -haloalkylthio: Ci -C ₄ -alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, for example _SCH2 F, SCHF _2, SCF ₃ , SCH ₂ Cl, SCH (Cl) ₂ , SC (Cl) ₃ , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio,

2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio,

2.2.2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,

2.2.2- trichloroethylthio, SC ₂ F ₅ , 2-fluoropropylthio,

3-fluoropropylthio, 2,2-difluoropropylthio,

2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio,

2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio,

3.3.3-trifluoropropylthio, 3,3,3-trichloropropylthio,

SCH ₂ -C ₂ F ₅ , SCF ₂ -C ₂ F ₅ , 1- (CH ₂ F) -2-fluoroethylthio, 1- (CH ₂ Ci) 14 • • 9 99

99

2-chloroethylthio, 1- (CH ₂ Br) -2-bromoethylthio,

4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or SCF ₂ -CF ₂ -C ₂ F ₅ , preferably SCHF ₂ , SCF ₃ , dichlorofluoromethylthio, chlorodifluoromethylthio or 2,2,2-trifluoroethylthio;

- Ci-Cg-alkylthio: radical _Ci-C4 -alkylthio, as mentioned above, or for example, 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-ethylbutylthio, 2-ethylbutylthio,

1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio,

1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio, preferably SCH ₃ , SC ₂ H ₅ , SCH ₂ -C ₂ H ₅ , SCH (CH ₃ ) ₂ , n-butylthio, SC (CH ₃ ) ₃ , n-pentylthio or n-hexylthio;

C 1 -C ₄ -alkoxy-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl which is substituted by C 1 -C ₄ -alkoxy as mentioned above, for example CH ₂ -OCH ₃ , CH ₂ -OC ₂ H ₅ , 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) propyl,

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- (1-methylethoxy) propyl, 3- (n-butoxy) propyl,

3- (1-methylpropoxy) propyl, 3- (2-methylpropoxy) propyl,

3- (1,1-dimethylethoxy) propyl, 2- (methoxy) butyl,

2- (ethoxy) butyl, 2- (n-propoxy) butyl,

2- (1-methylethoxy) 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- (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, preferably CH 2 OCH 3, CH ₂ -OC ₂ H _5,

2- (OCH 3) ethyl or 2- (OC ₂ H ₅ ) ethyl;

- C ₁ -C ₄ -haloalkoxy-C ₄ -alkyl: C-Cy-alkyl, kter7 is substituted _Ci-C4 -haloalkoxy as mentioned above, for example 2- _(OCHF2) ethyl, 2- (OCF 3) ethyl or

2- (OC ₂ F ₅ ) ethyl;

C 1 -C ₄ -alkylthio-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl which is substituted by C 1 -C ₄ -alkylthio as mentioned above, for example CH ₂ -SCH ₃ , CH ₂ -SC ₂ H ₅ , n-propylthiomethyl,

CH ₂ -SCH (CH ₃ ) 2 / n-butylthiomethyl, (1-methylpropylthio) methyl, (2-methylpropylthio) methyl, CH ₂ -SC (CH 3) 3,

2- (methylthio) ethyl, 2- (ethylthio) ethyl, 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, 2- (ethylthio) propyl, 2- (n-propylthio) propyl, 2- (1-methylethylthio) propyl, 2- (n-butylthio) propyl, 2- (1-methylpropylthio) propyl,

2- (2-methylpropylthio) propyl,

2- (1,1-dimethylethylthio) propyl, 3- (methylthio) propyl,

3- (ethylthio) propyl, 3- (n-propylthio) propyl,

3- (1-methylethylthio) propyl, 3- (n-butylthio) propyl,

3- (1-methylpropylthio) propyl, 3- (2-methylpropylthio) propyl,

3- (1,1-dimethylethylthio) propyl, 2- (methylthio) butyl,

2- (ethylthio) butyl, 2- (n-propylthio) butyl,

2- (1-methylethylthio) butyl, 2- (n-butylthio) butyl,

2- (1-methylpropylthio) butyl, 2- (2-methylpropylthio) butyl,

2- (1,1-dimethylethylthio) butyl, 3- (methylthio) butyl,

3- (ethylthio) butyl, 3- (n-propylthio) butyl,

3- (1-methylethylthio) butyl, 3- (n-butylthio) butyl,

3- (1-methylpropylthio) butyl, 3- (2-methylpropylthio) butyl,

3- (1,1-dimethylethylthio) butyl, 4- (methylthio) butyl,

4- (ethylthio) butyl, 4- (n-propylthio) butyl,

4- (1-methylethylthio) butyl, 4- (n-butylthio) butyl,

4- (1-methylpropylthio) butyl, 4- (2-methylpropylthio) butyl or 4- (1,1-dimethylethylthio) butyl, preferably CH ₂ -SCH ₃ , CH ₂ -SC ₂ H ₅ , 2- (SCH ₃ ) ethyl or 2- (SC ₂ H ₅ ) ethyl;

- _{Ci-C4 -haloalkylthio-Ci-C4-alkyl: Ci-C4-alkyl} which is substituted by Ci-C ₄ -haloalkylthio as mentioned above, for example 2- ₍₂ SCHF) ethyl, 2- ( SCF ₃ ) ethyl or 2- (SC ₂ F ₅ ) ethyl;

• 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 4 4 9

94445 49 94 94 49

- (C 1 -C ₄ -alkyl) carbonyl: CO-CH ₃ , CO-C ₂ H ₅ , CO-CH ₂ -C ₂ H ₅ , COCH (CH ₃ ) ₂ , n-butyl carbonyl, CO-CH (CH ₃ ) -C ₂ H ₅ , CO-CH ₂ -CH (CH ₃ ) ₂ or CO-C (CH ₃ ) ₃ , preferably CO-CH ₃ or CO-C ₂ H ₅ ;

- (C 1 -C ₄ -haloalkyl) carbonyl: (C 1 -C ₄ -alkyl) carbonyl radical as mentioned above which is partially or fully substituted by a fluorine atom, a chlorine atom, a bromine atom and / or an iodine atom, for example CO- CH ₂ F, CO-CHF ₂ , CO-CF ₃ , COCH ₂ Cl, CO-CH (Cl) ₂ , CO-C (Cl) ₃ , chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl,

2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl,

2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl,

2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2-fluoroethylcarbonyl,

2,2,2 trichlorethylkarbonyl CO-C ₂ F _5, 2-fluoropropylcarbonyl,

3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl,

2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl,

3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl,

2-bromopropylcarbonyl, 3-bromopropylcarbonyl,

3.3.3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO-CH ₂ -C ₂ F ₅ , CO-CF ₂ -C ₂ F ₅ , 1- (CH ₂ F) -2-fluoroethylcarbonyl,

1- (C1 _CH2) -2-chlorethylkarbonyl, 1- _(CH2 Br) 2 bromethylkarbonyl 4-fluorbutylkarbonyl,

4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF ₃ , CO-CH ₂ Cl or

2,2,2-trifluoroethylcarbonyl;

- (C 1 -C 6 -alkyl) carbonyl: one of the above-mentioned (C 1 -C ₄ -alkyl) carbonyl or, for example, n-pentyl-CO,

1-methylbutyl-CO, 2-methylbutyl-CO, 3-methylbutyl-CO, φ φ 9 9 9 9 9 9 9 9 9 9 9

9 · 9 9 9 9 9 9 9

99 99 · ·· 99

2.2-dimethylpropyl-CO, 1-ethylpropyl-CO, n-hexyl-CO,

1,1-dimethylpropyl-CO, 1,2-dimethylpropyl-CO,

1-methylpentyl-CO, 2-methylpentyl-CO, 3-methylpentyl-CO,

4-methylpentyl-CO, 1,1-dimethylbutyl-CO, 1,2-dimethylbutylCO, 1,3-dimethylbutyl-CO, 2,2-dimethylbutyl-CO,

2,3-dimethylbutyl-CO, 3,3-dimethylbutyl-CO, 1-ethylbutyl-CO,

2-ethylbutyl-CO, 1,1,2-trimethylpropyl-CO,

1,2,2-trimethylpropyl-CO, 1-ethyl-1-methylpropyl-CO or 1-ethyl-2-methylpropyl-CO, preferably CO-CH ₃ , CO-C2 H ₅ , COCH ₂ -C ₂ H ₅ , CO- CH (CH ₃ ) ₂ , n-butyl-CO, CO-C (CH ₃ ) ₃ , CO- (nC ₅ H _n ) or CO- (n-C ₆ H ₁₃ );

- (C 1 -C 6 -haloalkyl) carbonyl: (C 1 -C ₆ -alkyl) carbonyl radical as mentioned above which is partially or fully substituted by a fluorine atom, a chlorine atom, a bromine atom and / or an iodine atom, for example CO-CH ₂ F, CO-CHF ₂ , CO-CF ₃ , COCH ₂ Cl, CO-CH (Cl) ₂ , CO-C (Cl) ₃ , chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl,

2-fluoroethylcarbonyl, 2-chloroethylcarbonyl,

2-bromoethylcarbonyl, 2-iodoethylcarbonyl,

2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl,

2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2-fluoroethylcarbonyl,

2,2,2 trichlorethylkarbonyl CO-C ₂ F _5, 2-fluoropropylcarbonyl,

3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl,

2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl,

3-chloropropylpropylcarbonyl, 2,3-dichloropropylpropylcarbonyl,

2-bromopropylcarbonyl, 3-bromopropylcarbonyl,

Trifluorpropylkarbonyl 3,3,3, 3,3,3-trichlorpropylkarbonyl, CO-CH ₂ -C ₂ F _5, CO-CF2-C2F5, 1- (CH ₂ F) -2-fluorethylkarbonyl,

1- (CH ₂ Cl) -2-chloroethylcarbonyl, 1- (CH ₂ Br) • ·

2-bromoethylcarbonyl, 4-fluorobutylcarbonyl,

4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF 3, CO-CH ₂ Cl or

2,2,2-trifluoroethylcarbonyl;

- (C 1 -C ₄ -alkyl) carbonyloxy: O-CO-CH 3, O-CO-C ₂ H ₅ , O-CO-CH ₂ -C ₂ H ₅ , O-CO-CH (CH ₃ ) 2, O -CO-CH ₂ -CH ₂ -C ₂ H ₅ , O-CO-CH (CH ₃ ) -C ₂ H ₅ , O-COCH ₂ -CH (CH ₃ ) ₂ or O-CO-C (CH ₃ ) 3, preferably O-CO-CH 3 or O-COC ₂ H ₅ ;

- (C 1 -C ₄ -haloalkyl) carbonyloxy: (C 1 -C ₄ -alkyl) carbonyl radical as mentioned above which is partially or fully substituted by a fluorine atom, a chlorine atom, a bromine atom and / or an iodine atom, for example O- CO-CH ₂ F, O-CO-CHF ₂ , O-CO-CF ₃ , O-CO-CH 2 Cl, O-CO-CH (Cl) ₂ , O-CO-C (C 1) 3, chlorofluoromethylcarbonyloxy, dichlorfluoromethylcarbonyloxy, chlordifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy,

2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy,

2-iodoethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy,

2.2.2-trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2-difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 2,2,2-trichloroethylcarbonyloxy, OCO-C2F5, 2-fluoropropylcarbonyloxy, 3-fluoropropylcarbonyloxy,

2,2-difluoropropylcarbonyloxy, 2,3-difluoropropylcarbonyloxy,

2-chloropropylcarbonyloxy, 3-chloropropylcarbonyloxy,

2,3-dichloropropylcarbonyloxy, 2-bromopropylpropylcarbonyloxy,

3-bromopropylcarbonyloxy, 3,3,3-trifluoropropylcarbonyloxy,

3,3,3 trichlorpropylkarbonyloxy, O-CO-CH ₂ -C ₂ F _5, O-CO-CF ₂ -C ₂ F _5,

1- (CH ₂ F) -2-fluoroethylcarbonyloxy, 1- (CH ₂ Cl) 2-chloroethylcarbonyloxy, 1- (CH ₂ Br) -2-bromoethylcarbonyloxy,

4-fluorobutylcarbonyloxy, 4-chlorobutylcarbonyloxy,

4-bromobutylcarbonyloxy or nonafluorobutylcarbonyloxy, preferably O-CO-CF ₃ , O-CO-CH 2 Cl 2 or

2.2.2-trifluoroethylcarbonyloxy;

- (C 1 -C 6 -alkyl) carbonyloxy: one of the above-mentioned (C 1 -C ₄ -alkyl) carbonyloxy or, for example, n-pentyl-COO,

1-methylbutyl-COO, 2-methylbutyl-COO, 3-methylbutyl-C00,

2.2-dimethylpropyl-C00, 1-ethylpropyl-COO, n-hexyl-COO,

1,1-dimethylpropyl-COO, 1,2-dimethylpropyl-COO,

1-methylpentyl-COO, 2-methylpentyl-C00, 3-methylpentyl-C00,

4-methylpentyl-C00, 1,1-dimethylbutyl-COO,

1,2-dimethylbutyl-COO, 1,3-dimethylbutyl-COO,

2,2-dimethylbutyl-COO, 2,3-dimethylbutyl-COO,

3.3-dimethylbutyl-C00, 1-ethylbutyl-COO, 2-ethylbutyl-COO,

1,1,2-trimethylpropyl-C00, 1,2,2-trimethylpropyl-COO,

1-ethyl-1-methylpropyl-COO or 1-ethyl-2-methylpropyl-COO, preferably O-CO-CH 3, O-CO-C ₂ H ₅ , O-CO-CH ₂ -C ₂ H ₅ , O- CO-CH (CH ₃ ) ₂ , n-butyl-COO, O-CO-C (CH ₃ ) 3, O-CO- (nC ₅ Hn) or O-CO- (nC ₆ H ₃ );

- (C 1 -C ₆ -alkyl) thiocarbonyl: CS-CH ₃ , CS-C ₂ H ₅ , CS-CH ₂ -C ₂ H ₅ , CSCH (CH ₃ ) ₂ , CS- (nC ₄ Hg), CS- CH (CH ₃ ) -C ₂ H ₅ , CS-CH ₂ -CH (CH ₃ ) ₂ , CSC (CH ₃ ) ₃ , CS- (n-CsHu), CS-CH (CH ₃ ) -CH ₂ -C ₂ H ₅ , CS-CH ₂ -CH (CH ₃ ) -C ₂ H ₅ , CS-CH ₂ CH ₂ -CH (CH ₃ ) ₂ , CS-C (CH ₃ ) ₂ -C ₂ H ₅ , CS- CH (CH ₃₎ -CH (CH _{3) 2,} CSCH ₂ -C (CH3) _3, CS-CH (C ₂ H ₅₎ -C ₂ H ₅ S- (nC ₆ H _13), CS-CH (CH ₃ ) - (nC 4 H 9), en-ch ₂ -ch (ch ₃ ) -ch ₂ -c ₂ h ₅ , en-ch ₂ ch ₂ -ch (ch ₃ ) -c ₂ h ₅ , enCH ₂ CH ₂ CH ₂ -CH (CH ₃ ) ₂ , CS-C (CH ₃ ) ₂ -CH ₂ -CH ₂ , CS-CH (CH ₃ ) -ch (CH ₃ ) -C ₂ H ₅ , CS-CH (CH ₃ ) -CH ₂ - CH (CH ₃ ) ₂ , CS-CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , CS-CH ₂ -CH (CH ₃ ) CH (CH ₃ ) ₂ , CS-CH ₂ CH ₂ -C ( CH ₃ ) ₃ , CS-CH (C ₂ H ₅ ) -ch ₂ -c ₂ h ₅ , csCH ₂ -CH (C ₂ H ₅ ) -C ₂ H ₅ , CS-C (CH ₃ ) ₂ -CH (CH ₃ ) ₂ , CS-CH (CH ₃ ) -C (CH ₃ 3, c (CH ₃ ) (C ₂ H ₅ ) -C ₂ H ₅ or CS-CH (C ₂ H ₅ ) -CH (CH ₃ ) ₂ , preferably CS-CH3,

CS-C2H5, CS-CH ₂ -C ₂ H _5, CS-CH _{(CH3) 2,} or S- (nC ₄ H _9);

- (C 1 -C ₄ -alkoxy) carbonyl: CO-OCH ₃ , CO-OC ₂ H ₅ , CO-OCH ₂ -C ₂ H ₅ , COOCH (CH ₃ ) ₂ , n-butoxy carbonyl, CO-OCH (CH ₃ ) -C ₂ H ₅ , CO-OCH ₂ -CH (CH ₃ ) ₂ or CO-OC (CH ₃ ) ₃ , preferably CO-OCH ₃ or CO-OC ₂ H;

- (C 1 -C 6 -alkoxy) carbonyl: one of the above-mentioned (C 1 -C 6 -alkoxy) carbonyl or, for example, n-pentoxy-CO,

1-methylbutoxy-CO, 2-methylbutoxy-CO, 3-methylbutoxy-CO,

2,2-dimethylpropoxy-CO, 1-ethylpropoxy-CO, n-hexoxy-CO,

1,1-dimethylpropoxy-CO, 1,2-dimethylpropoxy-CO,

1-methylpentoxy-CO, 2-methylpentoxy-CO, 3-methylpentoxy-CO,

4-methylpentoxy-CO, 1,1-dimethylbutoxy-CO,

1,2-dimethylbutoxy-CO, 1,3-dimethylbutoxy-CO,

2,2-dimethylbutoxy-CO, 2,3-dimethylbutoxy-CO,

3.3-dimethylbutoxy-CO, 1-ethylbutoxy-CO, 2-ethylbutoxy-CO,

1,1,2-trimethylpropoxy-CO, 1,2,2-trimethylpropoxy-CO,

1-ethyl-1-methylpropoxy-CO or 1-ethyl-2-methylpropoxy-CO, preferably CO-OCH 3, CO-OC ₂ H ₅ , CO-OCH ₂ -C ₂ H ₅ , CO-OCH (CH ₃ ) ₂ , n-butoxy-CO, CO-OC (CH3) _3, n-pentoxy or n-CO-CO-hexoxy;

- (C 1 -C ₄ -alkoxy) carbonyl-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl which is substituted by a (C 1 -C ₄ -alkoxy) carbonyl group - as mentioned above, for example CH ₂ -CO -OCH ₃ , CH ₂ -CO-OC ₂ H ₅ , CH ₂ -COOCH ₂ -C ₂ H ₅ , CH ₂ -CO-OCH (CH ₃ ) ₂ , n-butoxycarbonylmethyl, CH ₂ -COOCH (CH ₃ ) -C ₂ H ₅ , CH ₂ -CO-OCH ₂ -CH (CH ₃ ) 2, CH ₂ -CO-OC (CH ₃ ) ₃ , 1- (COOCH ₃ ) ethyl, 1- (CO-OC ₂ H ₅ ) ethyl, 1- (CO-OCH ₂ -C ₂ H ₅ ) ethyl,

1- [CH _{(CH3) 2]} ethyl, 1- (n-butoxycarbonyl) ethyl,

1- [1-methylpropoxycarbonyl] ethyl

1- [2-methylpropoxycarbonyl] ethyl, 2- (CO-OCH 3) ethyl, 2- (COOC ₂ H ₅ ) ethyl, 2- (CO-OCH ₂ -C ₂ H ₅ ) ethyl, 2- [CO-OCH (CH ₃ ) ₂ ] ethyl, 9 * 9

9 9

9 9

9 9 9

99

999 • «• <

9 9 9 9

99

2- (n-butoxycarbonyl) ethyl, 2- [1-methylpropoxycarbonyl] ethyl,

2- [2-methylpropoxycarbonyl] ethyl, 2- [CO-OC (CH3) _3] ethyl,

2- (CO-OCH 3) propyl, 2- (CO-OC 2 H 5) propyl, 2- (CO-OCH 2 -C 2 H 5) propyl,

2- [CO-OCH _{(CH3) 2]} propyl, 2- (n-butoxycarbonyl) propyl,

2- [1-methylpropoxycarbonyl] propyl,

2- [2-methylpropoxycarbonyl] propyl, 2- [CO-OC (CH3) _3] propyl,

3- (CO-OCH ₃ ) propyl, 3- (CO-OC ₂ H ₅ ) propyl, 3- (CO-OCH ₂ -C ₂ H ₅ ) propyl,

3- [CO-OCH _{(CH3) 2]} propyl, 3- (n-butoxycarbonyl) propyl,

3- [1-methylpropoxycarbonyl] propyl,

3- [2-methylpropoxycarbonyl] propyl, 3- [CO-OC (CH3) _3] propyl,

2- (CO-OCH ₂ ) butyl, 2- (CO-OC ₂ H ₅ ) butyl, 2- (CO-OCH ₂ -C ₂ H ₅ ) butyl,

2- [CO-OCH _{(CH3) 2]} butyl, 2- (n-butoxycarbonyl) butyl,

2- [1-methylpropoxycarbonyl] butyl,

2- [2-methylpropoxycarbonyl] butyl, 2- [CO-OC (CH3) _3] butyl,

3- (CO-OCH 3) butyl, 3- (CO-OC ₂ H ₅ ) butyl, 3- (CO-OCH ₂ -C ₂ H ₅ ) butyl,

3- [CO-OCH _{(CH3) 2]} butyl, 3- (n-butoxycarbonyl) butyl,

3- [1-methylpropoxycarbonyl] butyl,

3- [2-methylpropoxycarbonyl] butyl, 3- [CO-OC (CH3) _3] butyl,

4- (CO-OCH 3) butyl, 4- (CO-OC ₂ H ₅ ) butyl, 4- (CO-OCH ₂ -C ₂ H ₅ ) butyl,

4- [CO-OCH _{(CH3) 2]} butyl, 4- (n-butoxycarbonyl) butyl,

4- [1-methylpropoxycarbonyl] butyl,

4- [2-methylpropoxycarbonyl] butyl or 4- [CO-OC (CH ₃ ) 3] butyl, preferably CH ₂ -CO-OCH ₃ , CH ₂ -CO-OC ₂ H ₅ , 1- (CO-OCH 3) ethyl or

1- (CO-OC ₂ H ₅ ) ethyl;

- _(Ci-C6 alkoxy) thiocarbonyl: for example, CS-OCH 3, CS-OC ₂ H _5z CSOCH ₂ -C ₂ H _5, CSOCH _(CH3) 2, CS-O (nC ₄ H _9), CS -OCH (CH ₃ ) -C ₂ H ₅ , CSOCH ₂ -CH (CH ₃ ) ₂ , CS-OC (CH ₃ ) ₃ , CS-O (n-CsHn), CS-OCH (CH ₃ ) -CH ₂ -C ₂ H ₅ , CS-OCH ₂ -CH (CH ₃ ) -C ₂ H ₅ , CS-OCH ₂ CH ₂ -CH (CH ₃ ) ₂ , CO-OCH ₂ -C (CH ₃ ) 3, CSOCH ( C2H5) -C ₂ H _5, CS-O (nC ₆ H _13), CS-OC _{(CH3) 2} ^_ C ₂ H _5, CS-OCH _(CH3) CH _{(CH3) 2,} CS-OCH ( CH ₃ ) - (nC ₄ Hg), CS-OCH ₂ -CH (CH ₃ ) -CH ₂ -C ₂ H ₅ , CS »» ···

OCH ₂ CH ₂ -CH (CH ₃ ) -c ₂ h ₅ , CS-OCH ₂ CH ₂ CH ₂ -CH (CH ₃ ) ₂ , CSOC (CH ₃ ) 2 -CH ₂ -C ₂ H 5, CS-OCH (CH ₃₎ ) -CH (CH ₃ ) -C ₂ H ₅ , CS-OCH (CH ₃ ) CH ₂ -CH (CH ₃ ) 2r CS-OCH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , CS-OCH ₂ -CH (CH ₃ ) -CH (CH ₃ ) ₂ , en-o ₂ ch ₂ -c (CH ₃ ) 3, en-oc (C ₂ H ₅ ) -ch ₂ -c ₂ h ₅ , CS-OCH 2 - CH (C ₂ H ₅ ) -c ₂ h ₅ , CS-OC (CH ₃ ) ₂ -CH (CH ₃ ) ₂ , CS-OCH (CH ₃ ) -C (CH ₃ ) ₃ , CS-OC (CH ₃₎ ) (C ₂ H _s) -C ₂ H ₅ or CS-OCH (C ₂ H ₅₎ CH (CH _{3) 2,} preferably CS-CS-OCH 3 or OC ₂ H _5;

- (C 1 -C ₄ -alkylthio) carbonyl: CO-SCH 3, CO-SC ₂ H ₅ , CO-SCH ₂ -C ₂ H ₅ , CO-SCH (CH ₃ ) ₂ , CO-SCH ₂ CH ₂ -C ₂ H ₅ , co-sch (ch ₃ ) -c ₂ h ₅ , coSCH ₂ -CH (CH ₃ ) 2 or CO-SC (CH ₃ ) ₃ , preferably CO-SCH 3 or CO-SC ₂ H ₅ ;

- (Ci -C ₄ -alkylthio) _{carbonyl-Ci-C4-alkyl: Ci-C4-alkyl} which is substituted with _(Ci-C4 -alkylthio) carbonyl as mentioned above, i.e. CH ₂ -CO- SCH ₃ , CH ₂ -CO-SC ₂ H ₅ , CH ₂ -COSCH ₂ -C ₂ H ₅ , CH ₂ -CO-SCH (CH ₃ ) ₂ , CH ₂ -CO-SCH ₂ CH 2 -C ₂ H ₅ , ch _2- COSCH (CH ₃ ) -c ₂ h ₅ , CH ₂ -CO-SCH ₂ -CH (CH ₃ ) ₂ , CH ₂ -CO-SC (CH ₃ ) 3, 1- (COSCH ₃ ) ethyl, 1- (CO-SC ₂ H ₅ ) ethyl, 1- (CO-SCH ₂ -C ₂ H ₅ ) ethyl, 1- [COSCH (CH ₃ ) ₂ ] ethyl, 1- (CO-SCH ₂ CH ₂ -C ₂ H) ₅ ) ethyl, 1- [CO-SCH (CH ₃ ) ₂ H ₅ ] ethyl, 1- [CO-SCH ₂ -CH (CH ₃ ) 2] ethyl, 1- [CO-SC (CH ₃ ) ₃ ] ethyl,

2- _(CO-SCH3) ethyl, 2- (CO-SC ₂ H ₅₎ ethyl, 2- (CO-SCH ₂ C ₂ H _5), ethyl

2- [CO-SCH (CH ₃ ) ₂ ] ethyl, 2- (CO-SCH ₂ CH ₂ -C ₂ H ₅ ) ethyl, 2- [COSCH (CH ₃ ) -C ₂ H ₅ ] ethyl, 2- [ CO-SCH ₂ -CH (CH ₃ ) ₂ ] ethyl, 2- [COSC (CH ₃ ) ₃ ] ethyl, 2- (CO-SCH 3) propyl, 2- (CO-SC ₂ H ₅ ) propyl, 2- ( COSCH ₂ -C ₂ H ₅ ) propyl, 2- [CO-SCH (CH ₃ ) ₂ ] propyl, 2- (COSCH ₂ CH ₂ -C ₂ H ₅ ) propyl, 2- [CO-SCH (CH ₃ ) - C ₂ H ₅ ] propyl, 2- [COSCH ₂ -CH (CH ₃ ) ₂ ] propyl, 2- [CO-SC (CH ₃ ) 3] propyl, 3- (COSCH ₃ ) propyl, 3- (CO-SC ₂ H ₅ ) propyl, 3- (CO-SCH ₂ -C ₂ H ₅ ) propyl,

3- [CO-SCH (CH ₃ ) ₂ ] propyl, 3- (CO-SCH ₂ CH ₂ -C ₂ H ₅ ) propyl, 3- [COSCH (CH ₃ ) -C ₂ H ₅ ] propyl, 3- [ CO-SCH ₂ -CH (CH ₃ ) ₂ ] propyl, 3- [COSC (CH ₃ ) ₃ ] propyl, 2- (CO-SCH 3) butyl, 2- (CO-SC ₂ H ₅ ) butyl, 2- ( COSCH ₂ -C ₂ H ₅ ) butyl, 2- [CO-SCH (CH ₃ ) ₂ ] butyl, 2- (CO99 · 9 · 9 ·

9 9 9

9 9 9 9 9

99 * ·· · · # · # · # · 99 · 99

9

SCH2CH2-C2H5) butyl, 2- [COSCH (CH ₃₎ -C ₂ H _5] butyl, 2- [COSCH ₂ CH (CH _{3) 2]} butyl, 2- [CO-SC (CH3) ₃ Butyl, 3- (CO-SCH3) butyl,

3- (CO-SC ₂ H ₅ ) butyl, 3- (CO-SCH ₂ -C ₂ H ₅ ) butyl, 3- [COSCH (CH ₃ ) ₂ ] butyl, 3- (CO-SCH ₂ CH ₂ -C) ₂ H ₅ ) butyl, 3- [CO-SCH (CH ₃ ) C ₂ H ₅ ] butyl, 3- [CO-SCH ₂ -CH (CH ₃ ) ₂ ] butyl, 3- [CO-SC (CH ₃ ) ₃ ] butyl,

4- _(CO-SCH3) butyl, 4- (CO-SC ₂ H ₅₎ butyl, 4- (CO-SCH ₂ C ₂ H ₅₎ butyl,

4- [CO-SCH (CH ₃ ) ₂ ] butyl, 4- (CO-SCH ₂ CH ₂ -C ₂ H ₅ ) butyl, 4- [COSCH (CH ₃ ) -C ₂ H ₅ ] butyl, 4- [CO-SCH ₂ -CH (CH ₃ ) ₂ ] butyl or 4- [COSC (CH ₃ ) ₃ ] butyl, preferably CH ₂ -CO-SCH ₃ , CH ₂ -CO-SC ₂ H ₅ , 1- (COSCH ₃ ) ethyl or 1- (CO-SC ₂ H ₅₎ ethyl;

C 1 -C 8 -alkylsulfinyl: a C 1 -C ₄ -alkylsulfinyl radical such as SO-CH ₃ , SO-C ₂ H ₅ , SO-CH ₂ -C ₂ H ₅ , SO-CH (CH ₃ ) ₂ , SO- (nC ₄ H ₉ ), SOCH (CH ₃ ) -C ₂ H ₅ , SO-CH 2 -CH (CH ₃ ) 2 or SO-C (CH ₃ ) ₃ , or, for example, SO- (n C ₅ H ₁₁ ), 1- methylbutyl-SO, 2-methylbutyl-SO,

3-methylbutyl-SO, 2,2-dimethylpropyl-SO, 1-ethylpropyl-SO, n-hexyl-SO, 1,1-dimethylpropyl-SO, 1,2-dimethylpropyl-SO,

1-methylpentyl-SO, 2-methylpentyl-SO, 3-methylpentyl-SO,

4-methylpentyl-SO, 1,1-dimethylbutyl-SO, 1,2-dimethylbutylSO, 1,3-dimethylbutyl-SO, 2,2-dimethylbutyl-SO,

2,3-dimethylbutyl-SO, 3,3-dimethylbutyl-SO, 1-ethylbutyl-SO,

2-ethylbutyl-SO, 1,1,2-trimethylpropyl-SO,

1,2,2-trimethylpropyl-SO, 1-ethyl-1-methylpropyl-SO or 1-ethyl-2-methylpropyl-SO, preferably SO-CH ₃ , SO-C ₂ H ₅ , SOCH ₂ -C ₂ H ₅ , SO-CH _{(CH3) 2,} SO- (nC ₄ H _9), SO-C (CH3) _3, -SO- (nC ₅ H _u) or SO- (n-CgHi, _3);

- _{Ci-C4-alkylsulfinyl} C ₁ -C ₄ alkyl: _Ci-C4-alkyl which is substituted by _Ci-C4 alkylsulfinyl, as mentioned above, for example, CH ₂ SOCH _3, CH ₂ SOC ₂ H ₅ , n-propylsulfinylmethyl, CH ₂ SOCH (CH ₃ ) ₂ , n-butylsulfinylmethyl, (1-methylpropylsulfinyl) methyl, (2-methylpropylsulfinyl) methyl, (1,1-dimethylethylsulfinyl) methyl, 2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2- (n-propylsulfinyl) ethyl, 2- (1-methylethylsulfinyl) ethyl, 2- (n-butylsulfinyl) ethyl, 2- (1-methylpropylsulfinyl) ethyl,

2- (2-methylpropylsulfinyl) ethyl,

2- (1,1-dimethylethylsulfinyl) ethyl, 2- ₍₃ SOC) propyl,

3- (SOCH 3) propyl, 2- (SOC ₂ H ₅ ) propyl, 3- (SOC ₂ H ₅ ) propyl,

3- (propylsulfinyl) propyl, 3- (butylsulfinyl) propyl,

4- (SOCH 3) butyl, 4- (SOC ₂ H 5) butyl, 4- (n-propylsulfinyl) butyl or 4- (n-butylsulfinyl) butyl, especially 2- (SOCH ₃ ) ethyl;

- _{Ci-C4 -halogenalkylsulfinyl-Ci-C4-alkyl: Ci-C4-alkyl} which is substituted by _Ci-C4 -halogenalkylsulfinyl, as mentioned above, e.g.

2- (2,2,2-trifluoroethylsulfinyl) ethyl;

- C 1 -C ₄ -alkylsulfonyl: SO ₂ -CH ₃ , SO ₂ -C ₂ H ₅ , SO ₂ -CH ₂ -C ₂ H 5,

SO ₂ -CH (CH ₃ ) ₂ , n-butylsulfonyl, SO ₂ -CH (CH ₃ ) -C ₂ H ₅ ,

SO ₂ -CH ₂ -CH (CH ₃ ) 2 or SO ₂ -C (CH ₃ ) ₃ , preferably SO ₂ -CH ₃ or SO ₂ -C ₂ H ₅ ;

C 1 -C ₄ -haloalkylsulfonyl: a C 1 -C ₄ -alkylsulfonyl radical as mentioned above which is partially or fully substituted by a fluorine atom, a chlorine atom, a bromine atom and / or an iodine atom, for example SO ₂ -CH ₂ F, SO ₂ -CHF ₂ , SO ₂ -CF ₃ , SO ₂ -CH ₂ Cl, SO ₂ -CH (C 1) 2, SO ₂ -C (C 1) ₃ , chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl,

2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl,

2,2-difluoroethylsulfonyl; 2,2,2-trifluoroethylsulfonyl;

φφφ Φ 4

4 »· ·» 4

4 · * φ Φ · *

4 4 9 4

4 4 4

4

¢ ¢ 4

4 4

4 4 • Φ Φ

2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl,

2.2.2- trichloroethylsulfonyl, SO ₂ -C ₂ F ₅ , 2-fluoropropylsulfonyl,

3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl,

2,3-difluoropropylsulfonyl, 2-chloropropylsulfonyl,

3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl,

2-bromopropylsulfonyl, 3-bromopropylsulfonyl,

3.3.3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, SO ₂ -CH ₂ -C ₂ F ₅ , SO ₂ -CF ₂ -C ₂ F ₅ , 1- (fluoromethyl) 2-fluoroethylsulfonyl, 1- (chloromethyl) -2-chloroethylsulfonyl,

1- (bromomethyl) -2-bromoethylsulfonyl, 4-fluorobutylsulfonyl,

4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl, preferably SO ₂ -CH ₂ Cl, SO ₂ -CF ₃ or

2,2,2-trifluoroethylsulfonyl;

- C 1 -C 6 -alkylsulfonyl: a C 1 -C ₄ -alkylsulfonyl radical as mentioned above or, for example, SO ₂ - (nC ₅ H _n ), 1-methylbutyl-SO ₂ ,

2-methylbutyl-SO ₂ , 3-methylbutyl-SO ₂ , 2,2-dimethylpropyl-SO ₂ , 1-ethylpropyl-SO ₂ , n-hexyl-SO ₂ , 1,1-dimethylpropyl-SO ₂ ,

1,2- dimethylpropyl-S0 ₂ L _{methylpentylSO-2,} 2-methylpentylSO _2, 3 _{methylpentylSO-2,} 4-methylpentylSO ₂

1 dimethylbutyl-SO ₂ 1,2-dimethylbutyl-S0 _2,

1,3- dimethylbutyl-SO ₂ 2,2-dimethylbutyl-SO _2,

2,3- dimethylbutyl-SO ₂ 3,3-dimethylbutyl-SO ₂ ethylbutylS0 _L-2, 2-ethylbutyl-SO _2, 1,1,2-trimethylpropyl-S0 _2,

1,2,2-trimethylpropyl-SO ₂ , 1-ethyl-1-methylpropyl-SO ₂ or 1-ethyl-2-methylpropyl-SO ₂ , preferably SO ₂ -CH ₃ , SO ₂ -C ₂ H ₅ , SO ₂ -CH ₂ -C ₂ H ₅ , SO ₂ -CH (CH ₃ ) ₂ r SO ₂ - (nC ₄ H ₉ ), SO ₂ -C (CH ₃ ) ₃ , SO ₂ - (nC ₅ H ₁₁ ) or SO ₂ - ( nC ₆ H _I3);

- C 1 -C ₄ -alkylsulfonyl-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl which is C ₁ -C ₄ -alkyl, which is C ₁ -C ₄ -alkyl, which is C ₁ -C ₄ -alkyl; * ♦ ♦ ♦ 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4

4 4 ·

9) 4

Φ «substituted by C 1 -C ₄ -alkylsulfonyl as mentioned above, for example CH ₂ SO ₂ -CH ₃ , CH ₂ SO ₂ -C 2 H 5, CH ₂ SO ₂ -CH ₂ -C 2 H 5, CH ₂ SO ₂ -CH (CH ₃ ) ₂ , CH ₂ SO ₂ -CH ₂ CH ₂ -C ₂ H ₅ , (1-methylpropylsulfonyl) methyl, (2-methylpropylsulfonyl) methyl, CH ₂ SO ₂ -C (CH ₃ ) ₃ ,

CH (CH ₃₎ SO ₂ CH _3, CH (CH ₃₎ SO ₂ -C ₂ H _5, CH ₂ CH ₂ SO ₂ -CH _3, CH2CH2SO2-C2H5, CH ₂ CH ₂ SO ₂ -CH 2 -C ₂ H 5 CH ₂ CH ₂ SO ₂ -CH (CH _{3) 2,} CH ₂ CH ₂ -SO ₂ -CH ₂ -CH ₂ -C ₂ H _5,

2- (1-methylpropylsulfonyl) ethyl,

2- (2-methylpropylsulfonyl) ethyl, CH ₂ CH ₂ SO ₂ -C (CH ₃ ) ₃ ,

2- (SO ₂ -CH ₃ ) propyl, 2- (SO ₂ -C ₂ H 5) propyl, 2- (SO ₂ -CH ₂ -C ₂ H ₅ ) propyl, 2- [SO ₂ -CH (CH ₃ ) ₂ ] propyl , 2- (SO ₂ -CH ₂ CH ₂ -C ₂ H ₅ ) propyl,

2- (1-methylpropylsulfonyl) propyl,

2- (2-methylpropylsulfonyl) propyl, 2- [SO ₂ -C (CH ₃ ) 3] propyl,

3- _{(SO2 --CH3)} propyl, 3- _{(SO2 C2} H5) propyl, 3- (SO ₂ -CH ₂ -C ₂ H ₅₎ propyl, 3- _[SO2 --CH _{(CH3) 2} ] propyl, 3- (SO ₂ -CH ₂ CH ₂ -C ₂ H ₅ ) propyl,

3- (1-Methylpropylsulfonyl) propyl

3- (2-methylpropylsulfonyl) propyl, 3- [SO ₂ -C (CH ₃ ) 3] propyl,

2- (SO ₂ -CH ₂ ) butyl, 2- (SO ₂ -C ₂ H ₅ ) butyl, 2- (SO ₂ -CH ₂ -C ₂ H ₅ ) butyl,

2- [SO ₂ -CH (CH ₃ ) ₂ ] butyl, 2- (SO ₂ -CH ₂ CH ₂ -C ₂ H ₅ ) butyl,

2- (1-methylpropylsulfonyl) butyl,

2- (2-methylpropylsulfonyl) butyl, 2- [SO ₂ -C (CH ₃ ) ₃ ] butyl,

3- (SO ₂ -CH ₃ ) butyl, 3- (SO ₂ -C ₂ H 5) butyl, 3- (SO ₂ -CH ₂ -C ₂ H 5) butyl,

3- [SO ₂ -CH (CH ₃ ) ₂ ] butyl, 3- (SO ₂ -CH ₂ CH ₂ -C ₂ H ₅ ) butyl,

3- (1-methylpropylsulfonyl) butyl,

3- (2-methylpropylsulfonyl) butyl, 3- [SO ₂ -C (CH ₃ ) ₃ ] butyl,

4- (SO ₂ -CH ₂ ) butyl, 4- (SO ₂ -C ₂ H ₅ ) butyl, 4- (SO ₂ -CH ₂ -C ₂ H ₅ ) butyl,

4- [SO ₂ -CH (CH ₃ ) ₂ ] butyl, 4- (SO ₂ -CH ₂ CH ₂ -C ₂ H ₅ ) butyl,

4- (1-methylpropylsulfonyl) butyl,

4- (2-methylpropylsulfonyl) butyl or 4- [SO ₂ -C (CH ₃ ) ₃ ] butyl, especially CH ₂ CH ₂ SO ₂ -CH ₃ or CH ₂ CH ₂ SO ₂ -C ₂ H ₅ ;

- _{Ci-C4 -halogenalkylsulfonyl-Ci-C4-alkyl: Ci-C4-alkyl} which is substituted by _Ci-C4 -halogenalkylsulfonyl, as mentioned above, e.g.

2- (2,2,2-trifluoroethylsulfonyl) ethyl;

C 1 -C ₄ -alkylamino-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl substituted with C 1 -C ₄ -alkylamino such as H ₃ C-NH-, HSC ₂ -NH-, n-propyl-NH -, 1-methylethyl-ΝΗ-, n-butyl-NH-, 1-methylpropyl-ΝΗ-, 2-methylpropyl-NH- and 1,1-dimethylethyl NH-, preferably H 3 C-NH- or HSC ₂ -NH-, i.e. is, for example, CH ₂ CH ₂ -NH-CH 3, CH ₂ CH ₂ -N (CH ₃ ) ₂ , CH ₂ CH ₂ -NH-C ₂ H ₅ or CH ₂ CH ₂ -N (C ₂ H ₅ ) ₂ ;

- (C 1 -C ₄ -alkylamino) carbonyl: CO-NH-CH 3, CO-NH-C2 H 5, n-propylamino, CO-NH-CH (CH ₃ ) ₂ , CO-NH-CH ₂ CH ₂ -C ₂ H ₅ , CO-NH-CH (CH ₃ ) ₂ H ₅ , CO-NH-CH ₂ -CH (CH ₃ ) ₂ or CO-NH-C (CH ₃ ) ₃ , preferably CO-NH-CH ₃ or CO-NH -C ₂ H _5;

- (C 1 -C ₆ -alkylamino) carbonyl: one of the (C 1 -C ₄ -alkylamino) carbonyl radicals mentioned above or, for example, CONH- (nC ₅ Hn), 1-methylbutyl-NHCO-, 2-methylbutyl-NHCO-,

3-methylbutyl-NHCO-, 2,2-dimethylpropyl-NHCO-,

1-ethyl-propyl-NHCO-, CO-NH- (nC ₆ H ₁₃ ), 1,1-dimethylpropyl-NHCO-, 1,2-dimethylpropyl-NHCO-, 1-methylpentyl-NHCO-,

2-methylpentyl-NHCO-, 3-methylpentyl-NHCO-, 4-methylpentyl-NHCO-, 1,1-dimethylbutyl-NHCO-, 1,2-dimethylbutyl-NHCO-,

1,3-dimethylbutyl-NHCO-, 2,2-dimethylbutyl-NHCO-,

2,3-dimethylbutyl-NHCO-, 3,3-dimethylbutyl-NHCO-,

1-ethylbutyl-NHCO-, 2-ethylbutyl-NHCO-,

1,1,2-trimethylpropyl-NHCO-, 1,2,2-trimethylpropyl-NHCO-, 1-ethyl-1-methylpropyl-NHCO- or 1-ethyl-2-methylpropyl29 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

NHCO-, preferably CO-NH-CH 3, CO-NH-C ₂ H ₅ , CO-NH-CH ₂ -C ₂ H ₅ , CO-NHCH (CH ₃ ) 2, CO-NH- (nC ₄ H ₉ ) CO-NH-C (CH _{3) 3} CO-NH- (nC ₅ H _n), or -CO-NH- (n C ₆ Hi _3);

- (C 1 -C ₄ -alkylamino) carbonyl-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl which is substituted with a (C 1 -C ₄ -alkylamino) carbonyl group as mentioned above, preferably CO-NH- CH ₃ or CO-NH-C ₂ H ₅ , such as CH ₂ -CO-NH-CH ₃ , CH ₂ -CO-NH-C ₂ H ₅ , CH ₂ -CO-NHCH ₂ -C ₂ H ₅ , CH _2- CO-NH-CH (CH ₃ ) ₂ , ch ₂ -co-nh-ch ₂ ch ₂ -c ₂ h ₅ , ch ₂ -co-nhCH (CH ₃ ) -C ₂ H ₅ , CH ₂ -CO -NH-CH ₂ -CH (CH ₃ ) ₂ , CH ₂ -CO-NH-C (CH ₃ ) ₃ ,

CH _(CH3) -CO-NH-CH3, CH _(CH3) -CO-NH-C2H5, 2- (C0-NH-CH3) ethyl,

2- (CO-NH-C ₂ H ₅ ) ethyl, 2- (CO-NH-CH ₂ -C ₂ H ₅ ) ethyl, 2- [CH ₂ -CO-NHCH (CH ₃ ) ₂ ] ethyl, 2- (CO-NH-CH ₂ CH ₂ -C ₂ H ₅ ) ethyl, 2- [CO-NH-CH (CH ₃ ) C ₂ H ₅ ] ethyl, 2- [CO-NH-CH ₂ -CH (CH ₃₎ ) ₂ ] ethyl, 2- [CO-NHC (CH ₃ ) ₃ ] ethyl, 2- (CO-NH-CH 3) propyl, 2- (CO-NH-C ₂ H ₅ ) propyl,

2- (CO-NH-CH ₂ -C ₂ H ₅ ) propyl, 2- [CH ₂ -CO-NH-CH (CH ₃ ) ₂ ] propyl, 2- (CONH-CH ₂ CH ₂ -C ₂ H ₅₎ propyl, 2- [CO-NH-CH (CH ₃ ) -C ₂ H ₅ ] propyl, 2- [CO-NHCH ₂ -CH (CH ₃ ) 2] propyl, 2- [CO-NH-C (CH) ₃ ) ₃ ] propyl, 3- (CO-NHCH ₃ ) propyl, 3- (CO-NH-C ₂ H ₅ ) propyl, 3- (CO-NH-CH ₂ -C ₂ H ₅ ) propyl,

3- [CH ₂ -CO-NH-CH (CH ₃ ) ₂ ] propyl, 3- (CO-NH-CH ₂ CH ₂ -C ₂ H ₅ ) propyl,

3- [CO-NH-CH (CH ₃ ) -C ₂ H ₅ ] propyl, 3- [CO-NH-CH ₂ -CH (CH ₃ ) ₂ ] propyl,

3- [CO-NH-C (CH ₃ ) 3] propyl, 2- (CO-NH-CH 3) butyl, 2- (CO-NHC ₂ H ₅ ) butyl, 2- (CO-NH-CH ₂ -C) ₂ H ₅ ) butyl, 2- [CH ₂ -CO-NHCH (CH ₃ ) ₂ ] butyl, 2- (CO-NH-CH ₂ CH ₂ -C ₂ H ₅ ) butyl, 2- [CO-NH-CH (CH ₃ ) C ₂ H ₅ ] butyl, 2- [CO-NH-CH ₂ -CH (CH ₃ ) ₂ ] butyl, 2- [CO-NHC (CH ₃ ) ₃ ] butyl, 3- (CO-NH -CH ₃ ) butyl, 3- (CO-NH-C ₂ H ₅ ) butyl, 3- (CONH-CH ₂ -C ₂ H ₅ ) butyl, 3- [CH ₂ -CO-NH-CH (CH ₃ ) ₂ ] butyl, 3- (CO-NHCH ₂ CH ₂ -C ₂ H ₅ ) butyl, 3- [CO-NH-CH (CH ₃ ) -C ₂ H ₅ ] butyl, 3- [CO-NHCH ₂ -CH (CH ₃ ) ₂ ] butyl, 3- [CO-NH-C (CH ₃ ) 3] butyl, 4- (CO-NHCH ₃ ) butyl, 4- (CO-NH-C ₂ H ₅ ) butyl, 4- (CO-NH-CH ₂ -C ₂ H ₅₎ butyl,

4- [CH ₂ -CO-NH-CH (CH ₃ ) ₂ ] butyl, 4- (CO-NH-CH ₂ CH ₂ -C ₂ H ₅ ) butyl,

4- [CO-NH-CH (CH ₃ ) -C ₂ H ₅ ] butyl, 4- [CO-NH-CH ₂ -CH (CH ₃ ) ₂ ] butyl or

4- [CO-NH-C (CH3) _3] butyl, preferably CH ₂ -CO-NH-CH _3, CH ₂ -CO-NH-C ₂ H _5, CH (CH ₃₎ -CO-NH-CH3 or CH (CH ₃ ) -CO-NH-C ₂ H ₅ ;

di (C 1 -C ₄ -alkyl) amino: N (CH ₃ ) ₂ , N (C ₂ H ₅ ) ₂ , N, N-dipropylamino, N, N-di (1-methylethyl) amino, N, N- dibutylamino,

N, N-di (1-methylpropyl) amino, N, N-di (2-methylpropyl) amino, N, N-di (1,1-dimethylethyl) amino, N-ethyl-N-methylamino, N-methyl- N-propylamino, N-methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) amino, N-methyl-N- (2-methylpropyl) amino , N- (1,1-dimethylethyl) N-methylamino, N-ethyl-N-propylamino, N-ethyl N- (1-methylethyl) amino, N-butyl-N-ethylamino, N-ethyl N- (1-methylpropyl) amino, N-ethyl-N- (2-methylpropyl) amino, N-ethyl-N- (1,1-dimethylethyl) amino, N- (1-methylethyl) N-propylamino, N-butyl-N-propylamino, N - (1-methylpropyl) N-propylamino, N- (2-methylpropyl) -N-propylamino,

N- (1,1-dimethylethyl) -N-propylamino, N-butyl N- (1-methylethyl) amino, N- (1-methylethyl) N- (1-methylpropyl) amino, N- (1-methylethyl) N- (2-methylpropyl) amino, N- (1,1-dimethylethyl) N- (1-methylethyl) amino, N-butyl-N- (1-methylpropyl) amino, N-butyl-N- (2-methylpropyl) amino , N-butyl N- (1,1-dimethylethyl) amino, N- (1-methylpropyl) N- (2-methylpropyl) amino, N- (1,1-dimethylethyl) N- (1-methylpropyl) amino or N- (1,1-dimethylethyl) N- (2-methylpropyl) amino, preferably N (CH ₃ ) 2 or N (C ₂ H ₅ ) ₂ ;

di (C 1 -C ₄ -alkyl) amino-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl which is substituted by a di (C 1 -C ₄ -alkyl) amino group as mentioned above, for example CH ₂ N (CH ₃ ) ₂ , CH ₂ N (C ₂ H ₅ ) ₂ , • · ··

N, N-dipropylaminomethyl, Ν, N-di [CH (CH ₃ ) ₂ ] aminomethyl,

N, N-dibutylaminomethyl, N, N-di- (1-methylpropyl) aminomethyl, N, N-di (2-methylpropyl) aminomethyl,

N, N-di [C (CH3) _3] aminomethyl, N-ethyl-N-methylaminomethyl, N-methyl-N-propylaminomethyl, N-methyl-N- [CH _{(CH3) 2]} aminomethyl, N-butyl-N -methylaminomethyl, N-methyl-N- (1-methylpropyl) aminomethyl, N-methyl N- (2-methylpropyl) aminomethyl,

N- [C (CH3) ₃ lN-methylaminomethyl, N-ethyl-N-propylaminomethyl,

N-ethyl-N- [CH _{(CH3) 2]} aminomethyl, N-butyl-N-ethylaminomethyl, N-ethyl-N- (1-methylpropyl) aminomethyl, N-ethylN- (2-methylpropyl) aminomethyl, N- ethyl-N- [C (CH ₃ ) ₃ ] aminomethyl, N- [CH (CH ₃ ) ₂ ] -N-propylaminomethyl, N-butyl-N-propylaminomethyl, N- (1-methylpropyl) -N-propylaminomethyl, N- ( 2-methylpropyl) -N-propylaminomethyl, N- [C (CH3) _3] -N-propylaminomethyl, N-butyl-N- (1-methylethyl) aminomethyl, N- [CH _{(CH3) 2]} -N- (1-methylpropyl) aminomethyl, N- [CH _{(CH3) 2]} -N- (2-methylpropyl) aminomethyl, N- [C (CH3) _3] -N- [CH _{(CH3) 2]} aminomethyl, N- butyl-N- (1-methylpropyl) aminomethyl, N-butyl-N- (2-methylpropyl) aminomethyl, N-butyl-N- [C (CH3) _3] aminomethyl, N- (1-methylpropyl) -N- ( 2-methylpropyl) aminomethyl, N- [C (CH3) _3] -N- (1-methylpropyl) aminomethyl, N- [C (CH3) _3] -N- (2-methylpropyl) aminomethyl, N, N-dimethylaminoethyl, Ν, Ν-diethylaminoethyl, N, N-di (n-propyl) aminoethyl,

N, N-di [CH _{(CH3) 2]} aminoethyl, N, N-dibutylaminoethyl,

N, N-di (1-methylpropyl) aminoethyl,

N, N-di (2-methylpropyl) aminoethyl, N, N-di [C (CH3) _3] aminoethyl, N-ethyl-N-methylaminoethyl, N-methyl-N-propylaminoethyl, N-methyl-N- [ CH (CH ₃ ) ₂ ] aminoethyl, N-butyl-N-methylaminoethyl, N-methyl-N- (1-methylpropyl) aminoethyl, N-methyl 32 ··· · · · 4 · ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

N- (2-methylpropyl) aminoethyl, N- [C (CH3) _3] -N-methylaminoethyl, N-ethyl-N-propylaminoethyl, N-ethyl-N- [CH _{(CH3) 2]} aminoethyl, N- butyl-N-ethylaminoethyl, N-ethylN- (1-methylpropyl) aminoethyl, N-ethylN- (2-methylpropyl) aminoethyl, N-ethyl-N- [C (CH3) _3] aminoethyl, N- [CH (CH ₃ ) ₂ ] -N-propylaminoethyl, N-butyl-N-propylaminoethyl, N- (1-methylpropyl) -N-propylaminoethyl, N- (2-methylpropyl) N-propylaminoethyl, N- [C (CH ₃ ) ₃ ] -N-propylaminoethyl, N-butyl-N- [CH _{(CH3) 2]} aminoethyl, N- [CH _{(CH3) 2]} -N- (1-methylpropyl) aminoethyl, N- [CH _{(CH3) 2]} ~

N- (2-methylpropyl) aminoethyl, N- [C (CH3) _3] -N- [CH _{(CH3) 2]} aminoethyl, N-butyl-N- (1-methylpropyl) aminoethyl, N-butyl-N- (2-methylpropyl) aminoethyl, N-butyl-N- [C (CH3) _3] aminoethyl, N- (1-methylpropyl) -N- (2-methylpropyl) aminoethyl, N- [C (CH3) _3] -N- (1-methylpropyl) aminoethyl or N- [C (CH3) _3] -N- (2-methylpropyl) aminoethyl, in particular

N, N-dimethylaminoethyl or N, N-diethylaminoethyl;

- di _(Ci-C4 alkyl) aminocarbonyl CON (CH _{3) 2,} CON _(C2 H5), -CON (CH ₂ -C ₂ H ₅₎ 2, CON (CH [CH _{3 12} ] 2, N, N-dibutylaminocarbonyl, CON [CH (CH ₃ ) -C ₂ H ₅ ] 2, CO-N [CH ₂ -CH (CH ₃ ) ₂ ] 2 CO-N [C (CH ₃ ) 3] 2, N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N- [CH (CH ₃ ) ₂ ] aminocarbonyl, N-butyl N-methylaminocarbonyl, N-methyl N- (1-methylpropyl) aminocarbonyl N-methyl-N- (2-methylpropyl) aminocarbonyl, N- [C (CH3) _3] -N-methylaminocarbonyl, N-ethyl-N-propylaminocarbonyl, N-ethyl-N- [CH _{(CH3) 2]} aminocarbonyl, N-butyl N-ethylaminocarbonyl, N-ethyl N- (1-methylpropyl) aminocarbonyl, N-ethyl N- (2-methylpropyl) aminocarbonyl, N-ethyl 33 ·· <44 ·· ♦ 4 4 4 · · · 4 · 4 4 4 4 4 4 4

4,444 44,444 44 4

444 4445 44 4 4

444 44 44 44 44 44

N- [C (CH ₃ ) ₃ ] aminocarbonyl, N- [CH (CH ₃ ) ₂ ] -N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N- (1-methylpropyl) N-propylaminocarbonyl, N- (2 methylpropyl) N-propylaminocarbonyl, N- [C (CH3) _3] -N-propylaminocarbonyl, N-butyl-N- [CH _{(CH3) 2]} aminocarbonyl, N- [CH _{(CH3) 2]} -N- (1-methylpropyl) aminocarbonyl, N- [CH _{(CH3) 2]} -N- (2-methylpropyl) aminocarbonyl, N- [C (CH3) _3] -N- [CH _{(CH3) 2]} aminocarbonyl, N- -butyl N (1-methylpropyl) aminocarbonyl, N-butyl-N- (2-methylpropyl) aminocarbonyl, N-butyl-N- [C (CH3) _3] aminocarbonyl, N- (1-methylpropyl) -N- (2-methylpropyl) aminocarbonyl, N- [C (CH ₃ ) ₃ ] N- (1-methylpropyl) aminocarbonyl or N- [C (CH ₃ ) ₃ ] N- (2-methylpropyl) aminocarbonyl, preferably CO-N (CH ₃ ) ₂ or C0N (C ₂ H _{5) 2;}

di (C 1 -C 6 -alkyl) aminocarbonyl: one of the above di (C 1 -C ₄ -alkyl) aminocarbonyl or, for example, N (CH ₃ ) - (nC ₅ Hu), N (C ₂ H ₅ ) - (nC ₅ H ₁₁ ), N (CH ₂ -C ₂ H ₅ ) - (n-C ₅ H ₁₁ ), N (n C ₄ H ₉ ) - (n C ₅ H ₁₁ ),

N (n-CSHN) - (n-CSHN) Ν (η-ΟβΗη) - (n-CsHu), N (CH ₃₎ - (n-CgHi _3), N (C ₂ H ₅₎ - (nC ₆ H ₁₃₎ N (CH ₂ -C ₂ H ₅₎ - (nC ₁₃ H _$), -N (nC ₄ H ₉₎ - (nC ₆ Hi _3), N (n C ₅ H _n) - (n C ₆ H ₁₃ ) or N (nC ₆ H ₁₃ ) ₂ ;

di (C 1 -C ₄ -alkyl) aminocarbonyl-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl, which is substituted with di (C 1 -C ₄ -alkyl) aminocarbonyl as mentioned above, preferably CO- N (CH ₃ ) ₂ or CO-N (C ₂ H ₅ ) ₂ , for example CH ₂ -CO-N (CH ₃ ) ₂ , CH ₂ -CO-N (C ₂ H ₅ ) ₂ , CH (CH ₃ ) -CNN (CH ₃ ) ₂ or CH (CH ₃ ) -CO-N (C ₂ H ₅ ) ₂ , preferably CH ₂ -CO-N (CH ₃ ) ₂ or CH (CH ₃ ) -CO-N (CH ₃₎ ) ₂ ;

di (C 1 -C ₄ -alkyl) phosphonyl-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl which is substituted by a di (C 1 -C ₄ -alkyl) phosphonyl group such as ΡΟ (ΟΟΗ ₃ ) ₂ , - ΡΟ (ΟΟ ₂ Η ₅ ) ₂ , N, N-dipropylphosphonyl,

N, N-di (1-methylethyl) phosphonyl, N, N-dibutylphosphonyl,

N, N-di (1-methylpropyl) phosphonyl,

N, N-di (2-methylpropyl) phosphonyl,

N, N-di (1,1-dimethylethyl) phosphonyl, N-ethyl-N-methylphosphonyl,

N-methyl-N-propylphosphonyl, N-methyl-N- (1-methylethyl) phosphonyl, N-butyl-N-methylphosphonyl,

N-methyl-N- (1-methylpropyl) phosphonyl, N-methyl N- (2-methylpropyl) phosphonyl, N- (1,1-dimethylethyl) N-methylphosphonyl, N-ethyl-N-propylphosphonyl, N-ethylN- (1-methylethyl) phosphonyl, N-butyl-N-ethylphosphonyl, N-ethyl N- (1-methylpropyl) phosphonyl, N-ethyl N- (2-methylpropyl) phosphonyl, N-ethyl N- (1,1-dimethylethyl) phosphonyl, N- (1-methylethyl) N-propylphosphonyl, N-butyl-N-propylphosphonyl,

N- (1-methylpropyl) -N-propylphosphonyl, N- (2-methylpropyl) N-propylphosphonyl, N- (1,1-dimethylethyl) -N-propylphosphonyl, N-butyl-N- (1-methylethyl) phosphonyl, N- (1-methylethyl) N- (1-methylpropyl) phosphonyl, N- (1-methylethyl) N- (2-methylpropyl) phosphonyl, N- (1,1-dimethylethyl) N- (1-methylethyl) phosphonyl, N-butyl N- (1-methylpropyl) phosphonyl, N-butyl N- (2-methylpropyl) phosphonyl, N-butyl N- (1,1-dimethylethyl) phosphonyl, N- (1-methylpropyl) N- (2-methylpropyl) phosphonyl , N- (1,1-dimethylethyl) N- (1-methylpropyl) phosphonyl or N- (1,1-dimethylethyl) N- (2-methylpropyl) phosphonyl, preferably -PO (OCH ₃ ) ₂ or PO (OC) ₂ H ₅ ) ₂ , for example CH ₂ -PO (OCH ₃ ) ₂ , CH ₂ -PO (OC ₂ H ₅ ) ₂ , CH (CH ₃ ) PO (OCH ₃ ) ₂ or CH (CH ₃ ) -PO (OC ₂ H ₅ ) ₂ ;

- C3- _C6- alkenyl: prop-1-en-1-yl, allyl, 1-methylethenyl,

1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2-buten-1-yl,

1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, n- penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl,

1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut- 2-en-1-yl

3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1- dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop- 2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en1- yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4- methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent- 2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3- en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl,

3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl,

1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,

1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl

1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl

1,3-dimethyl-but-2-en-1-yl, 1,3-dimethyl-but-3-en-1-yl,

2,2-dimethyl-but-3-en-1-yl, 2,3-dimethyl-but-1-en-1-yl,

2,3-dimethyl-but-2-en-1-yl, 2,3-dimethyl-but-3-en-1-yl,

3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl

1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut- 2-en-1-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, 1-ethyl-2- methylprop-1-en99 99

9 9 9

9 9 9

9 9 9

9 9 9 • 99 · 99 · * • 9 · «* • ·· ♦ 9 9 99

9 9

999 99 99 99

1-yl or 1-ethyl-2-methylprop-2-en-1-yl;

C ₃ -C ₆ -haloalkenyl: C ₃ -C ₆ -alkenyl as mentioned above which is partially or fully substituted by a fluorine atom, a chlorine atom, a bromine atom and / or an iodine atom, for example

2-chlorallyl, 3-chlorallyl, 2,3-dichlorallyl, 3,

3-dichlorallyl, 2,3,3-trichlorallyl, 2,3-dichlorobut-2-enyl, 2-bromallyl, 3-bromallyl, 2,3-dibromallyl,

3,3-dibromallyl, 2,3,3-tribromallyl or 2,3-dibromobut-2-enyl;

- cyano-C ₃ -C ₆ -alkenyl: for example 2-cyanoallyl, 3-cyanoallyl,

4-cyanobut-2-enyl, 4-cyanobut-3-enyl or 5-cyanopent-4-enyl;

- C ₃ -C ₆ -alkynyl: prop-l-yn-l-yl, prop-2-yn-l-yl, n-but-in1-yl, n-but-l-yn-3-yl , n-but-1-yn-4-yl, n-but-2-yn-1-yl, npent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent 1-in-4-yl, n-pentl-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n-pent-2-in5 - yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl, n-hex-1-yn-3-yl, n -hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2 -in-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl,

3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl,

4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl a

4-methylpent-2-yn-5-yl, preferably prop-2-yn-1-yl;

- C ₃ -Cg-haloalkynyl, C ₃ -Cg-alkynyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, for example φ

* φ

ΦΦΦ Φ Φ φ φ φ φ · · · · · φ φ φ • φ φ φ φ φ φ φ φ φ φ φ φ

1,1-difluoroprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 5-fluoropent-3-yn-1-yl or 6-fluorohex-4-yn-1-yl;

- _cyano-C3 -Cg-alkynyl: for example 3-cyanopropargyl,

4-cyanobut-2-yn-1-yl, 5-cyanopent-3-yn-1-yl and 6-cyanohex-4-yn-1-yl;

C ₃ -C ₄ -alkenyloxy-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl, which is substituted by a C ₃ -C ₄ -alkenyloxy group such as allyloxy, butl-en-3-yloxy, but-1- en-4-yloxy, but-2-en-1-yloxy, 1-methylprop-2-enyloxy or 2-methylprop-2-enyloxy, e.g. allyloxymethyl, 2-allyloxyethyl or but-1-en-4-yloxymethyl, in particular 2-allyloxyethyl;

- C ₃ -C _{4 -alkinyloxy-Ci-C4-alkyl: Ci-C4-alkyl} which is substituted by C ₃ -C ₄ -alkinyloxy such as propargyloxy, but-l-yn-3-yloxy, -but 1-yn-4-yloxy, but-2-yn-1-yloxy,

1-methylprop-2-ynyloxy or 2-methylprop-2-ynyloxy, preferably propargyloxy, e.g. propargyloxymethyl or

2-propargyloxyethyl, especially 2-propargyloxyethyl;

C ₃ -C ₄ -alkenylthio-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl substituted with C ₃ -C ₄ -alkenylthio such as allylthio, but-1-en-3-ylthio, but- 1-en-4-ylthio, but-2-en-1-ylthio, 1-methylprop-2-enylthio or 2-methylprop-2-enylthio, e.g., allylthiomethyl, 2-allylthioethyl or butl-en-4-ylthiomethyl especially 2- (allylthio) ethyl;

- C ₃ -C ₄ -alkynylthio-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl, which is substituted by a C ₃ -C ₄ -alkynylthio group such as 44-4-94 49

494 4999 9 * 94

4499 44 44 444 · ·· 4 · · 44 4 · 4 · 4 9

444 4944 4494

444 44 4494 44 44 Propargylthio, but-1-yn-3-ylthio, but-1-yn-4-ylthio, but-2-yn-1-ylthio, 1-methylprop-2-ynylthio or 2-methylprop2-ynylthio, preferably propargylthio, i.e. propargylthiomethyl or 2-propargylthioethyl, in particular

2- (propargylthio) ethyl;

C ₃ -C ₄ -alkenylsulfinyl-C 1 -C ₄ -alkyl: C ₁ -C ₄ -alkyl substituted with C ₃ -C ₄ -alkenylsulfinyl such as allylsulfinyl, but-1-en-3-ylsulfinyl , but-1-en-4-ylsulfinyl, but-2-en-1-ylsulfinyl, 1-methylprop-2-enylsulfinyl, or

2-methylprop-2-enylsulfinyl, e.g. allylsulfinylmethyl, 2-allylsulfinylethyl or but-1-en-4-ylsulfinylmethyl, especially 2- (allylsulfinyl) ethyl;

- C ₃ -C ₄ -alkylsulphinyl-C ₁ -C ₄ -alkyl: C 1 -C ₄ -alkyl which is substituted by C ₃ -C ₄ -alkylsulphinyl such as propargylsulphinyl, but-1-in-3-ylsulphinyl, but-1-in-4-ylsulfinyl, but-2-in-1-ylsulfinyl, 1-methylprop-2-ynylsulfinyl or 2-methylprop-2-ynylsulfinyl, preferably propargylsulfinyl, e.g. propargylsulfinylmethyl or 2-propargylsulfinylethyl, especially

2- (propargylsulfinyl) ethyl;

C ₃ -C ₄ -alkenylsulfonyl-C 1 -C ₄ -alkyl: C 1 -C ₄ -alkyl substituted with C ₃ -C ₄ -alkenylsulfonyl such as allylsulfonyl, but-1-en-3-ylsulfonyl, but 1-en-4-ylsulfonyl, but-2-en-1-ylsulfonyl, 1-methylprop-2-enylsulfonyl or

2-methylprop-2-enylsulfonyl, e.g. allylsulfonylmethyl, 2-allylsulfonylethyl or but-1-en-4-ylsulfonylmethyl, especially 2- (allylsulfonyl) ethyl;

99

44 44 44 •

4 43 4 4 4 4

4 4 4 4 4 5

50 99 44

C ₃ -C ₄ -alkylsulfonyl-C ₁ -C ₄ -alkyl: C 1 -C ₄ -alkyl substituted with C ₃ -C ₄ -alkylsulfonyl such as propargylsulfonyl, but-1-in-3-ylsulfonyl, but 1-in-4-ylsulfonyl, but-2-yn-1-ylsulfonyl, 1-methylprop-2-ynylsulfonyl or 2-methylprop-2-ynylsulfonyl, preferably propargylsulfonyl, e.g. propargylsulfonylmethyl or 2-propargylsulfonylethyl, especially

2- (propargylsulfonyl) ethyl;

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

- C ₃ -C 8 -cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;

- _{C3-C8-cycloalkyl-Cl-C6-alkyl:} for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 2- (cyclopropyl) ethyl,

2- (cyclobutyl) ethyl, 2- (cyclopentyl) ethyl,

2- (cyclohexyl) ethyl, 2- (cycloheptyl) ethyl,

2- (cyclooctyl) ethyl, 3- (cyclopropyl) propyl,

3- (cyclobutyl) propyl, 3- (cyclopentyl) propyl,

3- (cyclohexyl) propyl, 3- (cycloheptyl) propyl,

3- (cyclooctyl) propyl, 4- (cyclopropyl) butyl,

4- (cyclobutyl) butyl, 4- (cyclopentyl) butyl,

4- (cyclohexyl) butyl, 4- (cycloheptyl) butyl,

4- (cyclooctyl) butyl, 5- (cyclopropyl) pentyl,

5- (cyclobutyl) pentyl, 5- (cyclopentyl) pentyl,

5- (cyclohexyl) pentyl, 5- (cycloheptyl) pentyl,

5- (cyclooctyl) pentyl, 6- (cyclopropyl) hexyl,

6- (cyclobutyl) hexyl, .6- (cyclopentyl) hexyl, • φφφ φ φ φφφφφ φφφφφφ φφφφφφφφφφφφ * · · ·φφφφ cyk cyk cyk cyk cyk (((· () β- (cycloheptyl) hexyl or

6- (cyclooctyl) hexyl;

- C ₃ -C 8 cycloalkyloxy-C-C4-alkyl: cyclopropyloxymethyl,

1-cyclopropyloxyethyl, 2-cyclopropyloxyethyl,

1-cyclopropyloxyprop-1-yl, 2-cyclopropyloxyprop-1-yl,

3-cyclopropyloxyprop-1-yl, 1-cyclopropyloxybut-1-yl,

2-cyclopropyloxybut-1-yl, 3-cyclopropyloxybut-1-yl,

4-cyclopropyloxybut-1-yl, 1-cyclopropyloxybut-2-yl,

2-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl,

3-cyclopropyloxybut-2-yl, 4-cyclopropyloxybut-2-yl,

1- (Cyclopropyloxymethyl) eth-1-yl, 1- (Cyclopropyloxymethyl)

1- (CH ₃ ) eth-1-yl, 1- (cyclopropylmethyloxy) prop-1-yl, cyclobutyloxymethyl, 1-cyclobutyloxyethyl,

2-cyclobutyloxyethyl, 1-cyclobutyloxyprop-1-yl,

2-cyclobutyloxyprop-1-yl, 3-cyclobutyloxyprop-1-yl,

1-cyclobutyloxybut-1-yl, 2-cyclobutyloxybut-1-yl,

3-cyclobutyloxybut-1-yl, 4-cyclobutyloxybut-1-yl, 1-cyclobutyloxybut-2-yl, 2-cyclobutyloxybut-2-yl,

3-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl,

4-cyclobutyloxybut-2-yl, 1- (cyclobutyloxymethyl) eth-1-yl,

1- (cyklobutyloxymethyl) -1- _(CH3) eth-l-yl,

1- (cyclobutyloxymethyl) prop-1-yl, cyclopentyloxymethyl,

1-cyclopentyloxyethyl, 2-cyclopentyloxyethyl,

1-cyclopentyloxyprop-1-yl, 2-cyclopentyloxyprop-1-yl,

3-cyclopentyloxy-prop-1-yl, 1-cyclopentyloxy-but-1-yl,

2-cyclopentyloxybut-1-yl, 3-cyclopentyloxybut-1-yl,

4-cyclopentyloxy-but-1-yl, 1-cyclopentyloxy-but-2-yl,

2-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl,

3-cyclopentyloxy-but-2-yl, 4-cyclopentyloxy-but-2-yl,

1- (cyclopentyloxymethyl) eth-1-yl, 1- (cyclopentyloxymethyl)

1- _(CH3) eth-l-yl, 1- (cyklopentyloxymethyl) prop-l-yl, cyclohexyloxymethyl, 1-cyklohexyloxyethyl,

2-cyclohexyloxyethyl, 1-cyclohexyloxyprop-1-yl,

2-cyclohexyloxyprop-1-yl, 3-cyclohexyloxyprop-1-yl,

1-cyclohexyloxybut-1-yl, 2-cyclohexyloxybut-1-yl,

3-cyclohexyloxybut-1-yl, 4-cyclohexyloxybut-1-yl, 1-cyclohexyloxybut-2-yl, 2-cyclohexyloxybut-2-yl,

3-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl,

4-cyclohexyloxybut-2-yl, 1- (cyclohexyloxymethyl) eth-1-yl,

1- (cyclohexyloxymethyl) -1- _(CH3) eth-l-yl,

1- (cyclohexyloxymethyl) prop-1-yl, cycloheptyloxymethyl,

1-cycloheptyloxyethyl, 2-cycloheptyloxyethyl,

1-cycloheptyloxyprop-1-yl, 2-cycloheptyloxyprop-1-yl,

3-cycloheptyloxy-prop-1-yl, 1-cycloheptyloxy-but-1-yl,

2-cycloheptyloxybut-1-yl, 3-cycloheptyloxybut-1-yl,

4-cycloheptyloxybut-1-yl, 1-cycloheptyloxybut-2-yl,

2-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl,

3-cycloheptyloxybut-2-yl, 4-cycloheptyloxybut-2-yl,

1- (cykloheptyloxymethyl) eth-l-yl, 1- (cykloheptyloxymethyl) -1- _(CH3) eth-l-yl, 1- (cykloheptyloxymethyl) prop-l-yl, cyklooktyloxymethyl, 1-cyklooktyloxyethyl,

2-cyclooctyloxyethyl, 1-cyclooctyloxyprop-1-yl,

2-cyclooctyloxyprop-1-yl, 3-cyclooctyloxyprop-1-yl,

1-cyclooctyloxybut-1-yl, 2-cyclooctyloxybut-1-yl,

3-cyclooctyloxybut-1-yl, 4-cyclooctyloxybut-1-yl, 1-cyclooctyloxybut-2-yl, 2-cyclooctyloxybut-2-yl,

3-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl,

4-cyclooctyloxybut-2-yl, 1- (cyclooctyloxymethyl) eth-1-yl,

1- (cyklooktyloxymethyl) -1- _(CH3) eth-l-yl or

1- (cyclooctyloxymethyl) prop-1-yl, especially

C ₃ -C 6 -cycloalkoxymethyl or 2- (C ₃ -C 6 -cycloalkoxy) ethyl.

φ 9 · * · «I I · * * * ·

995 4 4 94 4 4 4 4

9 4 4 4 4 9 9

4 4 4 4 4 9 4 4 4 5

444 44 44 49

3- to 7-membered heterocyclyl means a heterocycle which may be not only saturated or partially or fully unsaturated, but also aromatic, and contains one to three heteroatoms selected from the group consisting of:

- one to three nitrogen atoms,

one or two oxygen atoms, and

- one or two sulfur atoms.

Examples of saturated heterocycles that may contain a carbonyl or thiocarbonyl ring are:

oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxethan-2-yl, oxethan-3-yl, thietan-2-yl, thietan-3- yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin- 2-yl, pyrrolidin-3-yl, 1,3-dioxolane-2-yl,

1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl,

1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl, 1,3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin-5-yl,

1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl,

1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-5-yl, tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydropyran- 3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl;

9,999 9 · · ·

999 »9 99 9

999-99-99 99 · · piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4 -Dioxan-2-yl, 1,3-oxathian-2-yl

1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl,

1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyridazin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazine- 4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, hexahydro-1,3,5- triazin-1-yl, hexahydro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan-3-yl, oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, thiepan- 4-yl, 1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl,

1,3-dioxepan-5-yl, 1,3-dioxepan-6-yl, 1,3-dithiepan-2-yl,

1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl,

1,4-dioxepan-2-yl, 1,4-dioxepan-7-yl, hexahydroazepin-1-yl, hexahydroazepin-2-yl, hexahydroazepin-3-yl, hexahydroazepin-4-yl, hexahydro-1,3-diazepin-1- yl, hexahydro-1,3-diazepin-2-yl, hexahydro-1,3-diazepin-4-yl, hexahydro-1,4-diazepin-1-yl and hexahydro-1,4-diazepin-2-yl.

Examples of unsaturated heterocycles that may contain a carbonyl or thiocarbonyl ring are: dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazolin-5-yl,

1,3-oxazolin-2-yl;

Preferred heteroaromatic ring systems contain 5- and β-membered rings, for example furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and

3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 999 # 9 9 9 • 9 9 9 9 ··> · 99 99 99 9 9 99 9 9 9 · · · ·

9

9 9 • 9 99

5-isoxazolyl, isothiazolyl such as 3-isothiazolyl,

4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as

3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as

2-oxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl such as

2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl such as

2-imidazolyl and 4-imidazolyl, oxadiazolyl such as

1 _r 2 _r 4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and

1,3,4-oxadiazol-2-yl, thiadiazolyl such as 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and 1,3,4-thiadiazol-2-yl, triazolyl such as 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl a

1,2,4-triazol-4-yl, pyridinyl such as 2-pyridinyl,

3-pyridinyl and 4-pyridinyl, pyridazinyl such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl such as 2-pyrimidinyl,

4-pyrimidinyl and 5-pyrimidinyl; 2-pyrazinyl;

1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl, especially pyridyl, pyrimidyl, furanyl and thienyl.

All phenyl, carbocyclic and heterocyclic rings are preferably unsubstituted.

Preferred for use of the 3- (benzazol-4-yl) pyrimidinedione derivatives of formula I as herbicides are those compounds of formula I wherein the substituents have the following meanings, either singly or in combinations:

X represents an oxygen atom;

R ¹ represents a hydrogen atom, amino or C 1 -C ₆ -alkyl, in particular hydrogen or C 1 -C ₄ -alkyl, particularly preferably hydrogen or methyl;

• ·

R ² represents a hydrogen atom, a halogen atom, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or C 1 -C ₆ -alkylsulfonyl, in particular trifluoromethyl;

R ³ represents a hydrogen atom;

R ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom;

R ⁵ represents a cyano group or a halogen atom, in particular a chlorine atom;

= Y- represents = NN (R ⁶ ) - or = C (ZR ⁷ ) -5-, especially = NN (R ⁶ ) -;

R ⁶ represents C ₁ -C ₆ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C 1 -C ₆ -alkylsulfonyl, (C 1 -C ₆ -alkyl) carbonyl, (C 1 -C ₆ -alkyl) thiocarbonyl, _(Ci-Ce alkoxy) carbonyl, or

C 1 -C 6 -alkyl optionally substituted by cyano, (C 1 -C ₆ -alkoxy) carbonyl, di (C 1 -C ₆ -alkyl) aminocarbonyl or (C 1 -C ₆ -alkyl) carbonyloxy, in particular C 1 -C 6 -alkyl,

C ₃ -C 6 alkynyl, Ci-Cg-alkylsulfonyl, or (Ci-C ₆ -alkoxy) carbonyl.

Particularly preferred are 3- (benzazol-4-yl) pyrimidinedione derivatives of the formula Ia {i.e., formula I, wherein X - represents O, R ¹ = methyl, R ² = trifluoromethyl, R ³ = H, R ⁴ = fluorine atom, R ⁵ = chlorine atom and = Y- = C (ZR ⁷ ) -N (CH ₃ ) -}

:::::

:. ::· :::: ·: :::

in particular the following compounds of formula Ia.1 to Ia.272:

Table 1

C. -ZR ^z Ia.l -H Ia.2 -ch ₃ Ia.3 -C3H7 la. 4 -nC ₃ H ₇ la. 5 -CH (CH _{3) 2} la. 6 -nC ₄ H ₉ Ia.7 -CH ₂ -CH (CH ₃ ) ₂ la. 8 -CH (CH ₃ ) -c ₂ h ₅ la. 9 -C (CH ₃ ) ₃ la. 10 -ch ₂ -ch = ch ₂ la. 11 -ch ₂ -ch = ch-ch ₃ la. 12 -ch ₂ -ch ₂ -ch = ch ₂ la. 13 -CH ₂ -CsCH la. 14 -ch ₂ -och ₃ la. 15 Dec -ch ₂ -ch ₂ -och ₃ la. 16 -ch ₂ -cn

Ia.17 -CH ₂ -CH ₂ F la. 18 -CH 2 -CF 3 la. 19 Dec -CH 2 -CH 2 Cl 2 Ia.20 -CH 2 -CO-OCH 3 Ia.21 -CH 2 -CO-OC 2 H 5 la. 22nd -CH ₂ -CO-N (CH ₃ ) ₃ Ia.23 -cyclobutyl Ia.24 -cyclopentyl la. 25 -cyclohexyl Ia.26 -phenyl Ia.27 -CH ₂ -cyclobutyl Ia.28 -CH ₂ -cyclopentyl la. 29 -CH ₂ -cyclohexyl la. 30 -CH ₂ -phenyl la. 31 -no ₂ la. 32 -CN la. 33 -F la. 34 -Cl la. 35 -Br la. 36 -och ₃ la. 37 -oc ₂ h ₅ la. 38 -O (nC ₃ H ₇ ) la. 39 -OCH _{(CH3) 2} la. 40 -0 (nC ₄ H ₉ ) la. 41 -OCH ₂ -CH (CH ₃ ) ₂ la. 42 -OCH (CH ₃ ) -C ₂ H ₅ la. 43 -OC (CH3) ₃ la. 44 -och ₂ -ch = ch ₂ la. 45 -OCH 2 -CH-CH-CH 3 la. 46 -och ₂ -ch ₂ -ch = ch ₂

• ·

Ia.47 -OCH (CH ₃ ) -CH = CH ₂ Ia.48 -och ₂ -c = ch Ia. 49 -OCH (CH ₃ ) -C ₅ CH Ia.50 -OCH 2 -OCH 3 Ia.51 -OCH ₂ -CH ₂ -OCH ₃ Ia.52 -OCH2-CN Ia. 53 -OCH ₂ -CH ₂ F Ia.54 -och ₂ -cf ₃ Ia. 55 -och ₂ -co-och ₃ Ia. 56 -och ₂ -co-oc ₂ h ₅ Ia.57 -OCH 2 -CO-N (CH ₃ ) 2 Ia. 58 -O-cyclobutyl Ia.59 -O-cyclopentyl Ia. 60 -O-cyclohexyl Ia. 61 -O-phenyl Ia. 62 -OCH ₂ -cyclobutyl Ia. 63 -OCH ₂ -cyclopentyl Ia. 64 -OCH ₂ -cyclohexyl Ia. 65 -OCH ₂ -phenyl Ia. 66 -CH 2 -OH Ia. 67 -ch ₂ -och ₃ Ia. 68 -nh ₂ Ia. 69 -NH-CH3 Ia.70 -N (CH ₃ ) ₂ Ia. 71 -NH-C2H5 Ia. 72 -N (C ₃ H ₅ ) ₂ Ia.73 -NH- (nC ₃ H ₇ ) Ia.74 -N (nC ₃ H ₇ ) ₂ Ia. 75 -NH- (nC ₄ H ₉ ) Ia.76 -N (nC ₄ H ₉ ) ₂

• 4

4 4

4

4 44

44 • 4 4 4 • 4 4 4 • 4 4

4 4 4 ·· 44

Ia.77 -NH-CH _(CH3) 2 la. 78 -N [CH _{(CH3) 2] 2} Ia.79 -NH-CH ₂ -CH (CH ₃ ) ₂ la. 80 -N (CH ₂ -CH (CH ₃ ) ₂ ) ₂ Ia.81 -NH-CH ₂ -CH = CH ₂ la. 82 -N (CH ₂ -CH = CH ₂ ) ₂ la. 83 -NH-CH ₂ -O ₅ CH Ia.84 -N (CH ₂ -C =CH) ₂ la. 85 -CH ₂ -N (CH ₃ ) ₂ la. 86 -SH la. 87 -sch ₃ la. 88 -sc ₂ h ₅ Ia.89 -S- (nC ₃ H ₇ ) la. 90 -S- (nC ₄ H ₉ ) la. 91 -SCH (CH3) ₃ la. 92 -SCH ₂ -CH (CH ₃ ) ₂ la. 93 -SCH (CH ₃ ) -c ₂ h ₅ la. 94 -SC (CH3) ₃ la. 95 -sch ₂ -ch = ch ₂ la. 96 -sch ₂ -ch = ch-ch ₃ la. 97 -sch ₂ -ch ₂ -ch = ch ₂ la. 98 -SCH _(CH3) -CH = CH ₂ la. 99 -SCH ₂ -CsCH la.100 -SCH _(CH3) -CsCH la.101 -sch ₂ -och ₃ la.102 -sch ₂ -ch ₂ -och ₃ la.103 -sch ₂ -cn la.104 -sch ₂ -ch ₂ f la.105 -sch ₂ -cf ₃

• 9 9 • 9 9 • 9 9 9

9 9

9 «·

Ia.106 -sch ₂ -ch ₂ ci la.107 -sch ₂ -co-och ₃ la.108 -sch ₂ -co-oc ₂ h ₅ la.109 -SCH ₂ -CO-N (CH ₃ ) ₂ Ia.110 -S-cyclobutyl la.111 -S-cyclopentyl la.112 -S-cyclohexyl la.113 -S-phenyl la.114 -SCH ₂ -cyclobutyl la.115 -SCH ₂ -cyclopentyl la.116 -SCH ₂ -cyclohexyl Ia.117 -SCH ₂ -phenyl la.118 -CH ₂ -SCH ₃ la.119 -so-ch ₃ la.120 -so-c ₂ hours ₅ Ia.121 -SO- (nC ₃ H ₇₎ la.122 -SO- (nC ₄ H ₉ ) la.123 -SO-CH _(CH3) 2 la.124 -SO-CH ₂ -CH (CH ₃ ) ₂ la.125 -SO-CH (CH ₃₎ -C ₂ H ₅ la.126 -SO-C (CH3) ₃ Ia.127 —So — ch ₂ —ch — ch ₂ la.128 -so-ch ₂ -ch = ch-ch ₃ la.129 -SO-CH ₂ -CH ₂ -CH = CH 2 Ia.130 -SO-CH _(CH3) -CH = CH ₂ la.131 -SO-CH ₂ -C ₅ CH la.132 -SO-CH (CH ₃ ) -C ₅ CH Ia.133 -so-ch ₂ -och ₃ la.134 —SO — ch ₂ —ch ₂ —och ₃ la.135 -so-ch ₂ -cn

• · · · · · · · · · φ · · · · · • · • ·

Ia.136 -SO-CH ₂ -CH ₂ F la.137 -so-ch ₂ -cf ₃ la.138 - so-ch ₂ —ch ₂ or la.139 -so-ch ₂ -co-och ₃ la.140 -SO-CH 2 -CO-OC 2 H 5 la.141 -SO-CH 2 -CO-N (CH ₃ ) 2 la.142 -SO-cyclobutyl Ia.143 -SO-cyclopentyl Ia.144 -SO-cyclohexyl Ia.145 -SO-phenyl la.146 _{-SO-CH2-cyclobutyl} Ia.147 -SO-CH ₂ -cyclopentyl la.148 -SO-CH ₂ -cyclohexyl Ia.149 -SO ₂ -phenyl-CH Ia.150 -CH ₂ -SO-CH ₃ la.151 -so ₂ -ch ₃ la.152 -SO ₂ -C ₂ H ₅ la.153 -SO ₂ - (nC ₃ H ₇ ) la.154 -SO 2 - (nC ₄ H ₉ ) la.155 -SO ₂ -CH (CH ₃ ) 2 la.156 -SO ₂ -CH ₂ -CH (CH ₃ ) ₂ Ia.157 -SO 2 -CH (CH ₃ ) -C ₂ H ₅ Ia.158 -SO ₂ -C (CH ₃ ) 3 Ia.159 -so ₂ -ch ₂ -ch = ch ₂ la.160 -so ₂ -ch ₂ -ch = ch-ch ₃ Ia.161 -SO ₂ -CH ₂ -CH ₂ -CH = CH ₂ la.162 -so ₂ -ch (CH ₃ ) -ch = ch ₂ la.163 -SO ₂ -CH ₂ -CsCH Ia.164 -SO 2 -CH (CH ₃ ) -c = ch la.165 -so ₂ -ch ₂ -och ₃

• ·

99 _λ »9 9 * t 9 9 9 9

la.166 -SO 2 -CH 2 -CH 2 -OCH 3 la.167 -SO2-CH2-CN la.168 -SO 2 -CH 2 -CH 2 F la.169 -SO2-CH2-CF3 la.170 -SO ₂ -CH ₂ -CH ₂ Cl la.171 -SO 2 -CH 2 -CO-OCH 3 la.172 -SO ₂ -CH ₂ -CO-OC ₂ H ₅ la.173 -SO ₂ -CH ₂ -CO-N (CH ₃ ) 2 la.174 -SO ₂ -cyclobutyl la.175 -SO ₂ -cyclopentyl la.176 - SO _{2 -} cyclohexyl Ia.177 -SO ₂ -phenyl la.178 -SO ₂ -CH ₂ -cyclobutyl la.179 - SO ₂ —CH ₂ - cyclopentyl la.180 -SO ₂ -CH ₂ -cyclohexyl la.181 -SO ₂ -CH ₂ -phenyl la.182 -CH ₂ -SO ₂ -CH ₃ la.183 -CH ₂ -CH (Cl) -CO-OH Ia.184 -CH ₂ -CH (Cl) -CO-OCH 3 Ia.185 -CH ₂ -CH (Cl) -CO-OC ₂ H ₅ la.186 -CH ₂ -CH (Cl) -CO-O (nC ₃ H ₇ ) Ia.187 -CH ₂ -CH (Cl) -CO-O (nC ₄ H ₉ ) la.188 _-CH2-CH (C1) -CO-OCH _{(CH3) 2} la.189 -CH ₂ -CH (Cl) -CO-OCH ₂ -CH (CH ₃ ) 2 la.190 -CH ₂ -CH (Cl) -CO-OCH (CH ₃₎ -C ₂ H ₅ la.191 -CH 2 -CH (Cl) -CO-OC (CH ₃ ) 3 la.192 -CH 2 -CH (Br) -CO-OH la.193 -CH ₂ -CH (Br) -CO-OCH 3 la.194 -CH ₂ -CH (Br) -CO-OC ₂ H ₅ la.195 -CH ₂ -CH (Br) -C0-0 (nC ₃ H ₇₎

* «9

4 * 9 9 * 4 4 ·· • 4 4 • • 4 4 9 · 4 4 • 4 4 4 · 4

la.196 -CH ₂ -CH (Br) -CO-O (nC ₄ H ₉ ) - la.197 -CH ₂ -CH (Br) -CO-OCH (CH ₃ ) ₂ la.198 -CH ₂ -CH (Br) -CO-OCH ₂ -CH (CH ₃ ) ₂ la.199 -CH ₂ -CH (Br) -CO-OCH (CH ₃ ) -C ₂ H ₅ Ia.2OO -CH ₂ -CH (Br) -CO-OC (CH ₃ ) ₃ Ia.201 -CH = CH-CO-OH Ia.2O2 -CH = CH-CO-OCH ₃ Ia.203 -CH = CH-CO-O-C ₂ H ₅ Ia.204 -CH = CH-CO-0 (nC ₃ H ₇ ) la.205 -CH = CH-CO-0 (nC ₄ H ₉ ) la.206 -CH = CH-CO-OCH _{(CH3) 2} Ia.207 -CH = CH-CO-OCH ₂ -CH (CH _{3) 2} Ia.208 -CH = CH-CO-OCH (CH ₃ ) -C ₂ H ₅ Ia.209 -CH = CH-CO-OC (CH ₃ ) ₃ Ia.210 -CH = C (Cl) -CO-OH Ia.211 -CH = C (Cl) -CO-OCH 3 la.212 -CH = C (Cl) -CO-OC ₂ H ₅ Ia.213 -CH = C (Cl) -CO-O (nC ₃ H ₇ ) Ia.214 -CH = C (Cl) -CO-O (nC ₄ H ₉ ) Ia.215 -CH = C (Cl) -CO-OCH _{(CH3) 2} Ia.216 -CH = C (Cl) -CO-OCH ₂ -CH (CH ₃ ) ₂ Ia.217 -CH = C (Cl) -CO-OCH (CH ₃ ) -C ₂ H ₅ Ia.218 -CH = C (Cl) -CO-OC (CH ₃ ) ₃ Ia.219 -CH = C (Br) -CO-OH Ta.220 -CH = C (Br) -CO-OCH ₃ Ia.221 -CH = C (Br) -CO-OC 2 H 5 la.222 -CH = C (Br) -CO-O (nC ₃ H ₇ ) la.223 -CH = C (Br) -CO-O (nC ₄ H ₉ ) la.224 -CH = C (Br) -CO-OCH _{(CH3) 2} Ia.225 -CH = C (Br) -CO-OCH ₂ -CH (CH ₃ ) 2

9 φ • * 9t • Φ Φ

ΦΦΦ ΦΦ

ΦΦ • ♦ Φ

Φ ΦΦ

Φ Φ Φ Φ • • • •

Φ · Φ

ΦΦ ΦΦ

Ia.226 -CH = C (Br) -CO-OCH (CH ₃ ) -C ₂ H ₅ Ia.227 -CH = C (Br) -CO-OC (CH ₃ ) ₃ Ia.228 -CH ₂ -CH (Cl) -co-nh ₂ Ia.229 —Ch ₂ —CH (Cl) -co-nh-ch ₃ Ia.230 -ch ₂ -ch (Cl) -CO-N (CH ₃ ) 2 Ia.231 -CH ₂ -CH (Cl) -CO-NH-C ₂ H ₅ Ia.232 -CH ₂ -CH (Cl) -CO-N (C ₂ H ₅₎ 2 Ia.233 -CH ₂ -CH (Cl) -CO-NH- (nC ₃ H ₇ ) Ia.234 -CH 2 -CH (Cl) -CO-N (nC ₃ H ₇ ) 2 Ia.235 -CH ₂ -CH (Cl) -CO-NH- (nC ₄ H ₉ ) Ia.23 β -CH ₂ -CH (Cl) -CO-N (nC ₄ H ₉ ) ₂ Ia.237 -CH ₂ -CH (Br) -CO-NH ₂ Ia.238 -CH ₂ —CH (Br) -CO-NH-CH 3 Ia.239 -CH ₂ -CH (Br) -CO-N (CH ₃ ) ₂ Ia.240 -CH ₂ -CH (Br) -CO-NH-C ₂ H ₅ Ia.241 -CH ₂ -CH (Br) -CO-N (C ₂ H ₅ ) ₂ Ia.242 -CH ₂ -CH (Br) -CO-NH- (nC ₃ H ₇ ) Ia.243 -CH ₂ -CH (Br) -CO-N (nC ₃ H ₇ ) ₂ Ia.244 -CH ₂ -CH (Br) -CO-NH- (nC ₄ H ₉ ) Ia.245 -CH ₂ -CH (Br) -CO-N (nC ₄ H ₉ ) ₂ Ia.246 -CH = CH-CO-NH ₂ Ia.247 -ch = ch-co-nh-ch ₂ Ia.248 -CH = CH-CO-N (CH ₃ ) 2 Ia.249 -CH = CH-CO-NH-C ₂ H ₅ Ia.25O -CH = CH-CO-N (C ₂ H ₅ ) 2 Ia.251 -CH = CH-CO-NH- (nC ₃ H ₇ ) Ia.252 -CH = CH-CO-N (nC ₃ H ₇ ) 2 Ia.253 -CH = CH-CO-NH- (nC ₄ H ₉ ) Ia.254 -CH = CH-CO-N (nC ₄ H ₉ ) ₂ Ia.255 -CH = C (Cl) -CO-NH 2

• φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ ·

Ia.256 -CH = C (Cl) -CO-NH-CH 3 Ia.257 -CH = C (Cl) -CO-N (CH ₃ ) 2 Ia.258 -CH = C (Cl) -CO-NH-C2H5 Ia.259 -CH = C (Cl) -CO-N (C ₂ H ₅ ) 2 Ia.260 -CH = C (Cl) -CO-NH- (nC ₃ H ₇ ) la.261 -CH = C (Cl) -CO-N (nC ₃ H ₇ ) 2 Ia.262 -CH = C (Cl) -CO-NH- (nC ₄ H ₉ ) Ia.263 -CH = C (Cl) -CO-N (nC ₄ H ₉ ) ₂ Ia.264 -CH = C (Br) -CO-NH 2 Ia.2 65 -CH = C (Br) -CO-NH-CH 3 Ia.266 -CH = C (Br) -CO-NH (CH ₃ ) 2 Ia.267 -CH = C (Br) -CO-NH-C ₂ H ₅ Ia.268 -CH = C (Br) -CO-N (C ₂ H ₅ ) 2 Ia.269 -CH = C (Br) -CO-NH- (nC ₃ H ₇ ) la.270 -CH = C (Br) -CO-N (nC ₃ H ₇ ) ₂ Ia.271 -CH = C (Br) -CO-NH- (nC ₄ H ₉ ) Ia.272 -CH = C (Br) -CO-N (nC ₄ H ₉ ) ₂

Furthermore, 3- (benzazol-4-yl) pyrimidinedione derivatives of formulas 1b to V are particularly preferred, in particular compounds of formulas Ib.1-Ib.272 which differ from the corresponding compounds of formulas Ia. 1aa.272 only by the fact that R ⁴ represents a hydrogen atom:

4

4 4 4

4 4

4 4

4 compounds of the formulas Ic.l-Ic.272 which differ from the corresponding compounds of the formulas Ia.1-Ia.272 only in that R @ ¹ represents a hydrogen atom:

compounds of formulas Id.1 - Id.272 which differ from the corresponding compounds of formulas Ia.1 - Ia.272 only in that R @ ¹ and R @ ⁴ represent a hydrogen atom:

Φ

Φ · · · • «« «« · · · · · ·

Compounds of formulas Ie.l - Ie.272 which differ from the corresponding compounds of the formulas Ia.l - Ia.272 only in that Y is = C (ZR ⁷⁾ -N (SO ₂ CH ₃₎ -;

ZR ⁷ compounds of formulas If.1 - If.272, which differ from the corresponding compounds of formulas Ia.1 - Ia.272 only in that R ⁴ represents a hydrogen atom and Y represents = C (ZR ⁷ ) -N (SO) ₂ CH ₃₎ -;

4 · 4

9t • 4 4 4

4 4 4 • »4 4 • 9 4 4 ·· 44 hrs ₃ c

F ₃ C Ν — σ υ ^C1

If

SO ₂ - CH ₃

ZR ⁷ compounds of formulas Ig.1-Ig.272 which differ from the corresponding compounds of formulas Ia.1-Ia.272 only in that R ¹ represents a hydrogen atom and Y represents = C (ZR ⁷ ) -N (SO 2 CH ³ ) ) -:

ig compounds of formulas Ih.1-Ih.272 which differ from the corresponding compounds of formulas Ia.1-Ia.272 only in that R ¹ and R ⁴ represent a hydrogen atom and Y represents = C (ZR ⁷ ) -N (SO ₂ CH ₃ ) -:

1 1 1 1 1 1 1 1 2 3 4 5 6 7 8 9

compounds of formulas Ii.1-I.272 that differ from the corresponding compounds of formulas Ia.1-Ia.272 only in that = Y- represents = C (ZR ⁷ ) -O-:

compounds of formulas Ik.1-Ik.272 which differ from the corresponding compounds of formulas Ia.1-Ia.272 only in that: = Y- represents = C (ZR ⁷ ) -O- and R ⁴ represents a hydrogen atom:

44

4 4 4 9 4 9 9 4 4 4 4

44

Compounds of formulas Im.l - Im.272, which differ from the corresponding compounds of the formulas Ia.l - Ia.272 only in that Y is = C (ZR ⁷⁾ -O-, and R ¹ is hydrogen:

the compounds of formulas Vl - V.272, which differ from the corresponding compounds of the formulas Ia.l - Ia.272 only in that Y is = C (ZR ⁷⁾ -O-, and R ¹ and R ⁴ represent hydrogen:

In

9 9 9 9 9 9 9

9

9 «

9 ·

9 9 • 9 9

9 9

The 3- (benzazol-4-yl) pyrimidinedione derivatives of formula (I) may be obtained by various methods, for example by one of the following methods:

Process A) Reaction of a 3- (benzazol-4-yl) pyrimidinedione derivative of formula I wherein R ¹ is hydrogen with a compound of formula II in a manner known per se:

I (R ¹ = Η) II I (R H, NH)

L 1 represents a conventional leaving group such as a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, (halogen) alkylsulfonyloxy, trifluoromethylsulfonyloxy, toluenesulfonyloxy and preferably methylsulfonyloxy or arylsulfonyloxy, preferably alkoxysulfonyloxy, preferably methoxysulfonyloxy or ethoxysulfonyloxy.

«Ί

Φ

Φ w

Φ Φ »Φ

Φ Φ φ

Φ φ

φ • φ · · φ φ φ • • • • • • • • • • • • • • • • •

ΦΦ

The process is normally carried out in an inert organic solvent, for example a protic solvent such as lower alcohols, preferably methanol or ethanol, if desired in the form of a mixture with water, or an aprotic solvent, for example an aliphatic or cyclic ether such as methyl -tert-butyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aliphatic ketone such as acetone, diethylketone and ethylmethylketone, in an amide such as dimethylformamide and N-methylpyrrolidone, in a sulfoxide such as dimethylsulfoxide, in a urea such as tetramethylurea and

1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, in a carboxylic acid ester such as ethyl acetate or in a halogenated aliphatic or aromatic hydrocarbon such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzenes.

If desired, the process can be carried out in the presence of a base, with suitable bases being inorganic bases such as carbonates such as sodium carbonate and carbonate, bicarbonates such as sodium bicarbonate and potassium bicarbonate or alkali metal hydrides such as sodium hydride and potassium hydride; also organic bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.

The amount of base and alkylating agent of formula (II) is preferably in each case 0.5 times to twice the molar amount, based on the amount of the starting compound of formula (I) (in which R ¹ = hydrogen).

• · · · · · · · · · · · · · · · · · · · ·

The reaction temperature is generally in the range from 0 ° C to the boiling point of the reaction mixture, in particular from 0 to 60 ° C.

A preferred embodiment of the production method consists in alkylating a salt of formula (I) obtained by cyclizing a compound of formula (IV) wherein R ¹ = H or V, wherein R ¹ = H according to Method D without isolating it from the reaction mixture which contain an excess of a base such as sodium hydride, sodium alkoxide or sodium carbonate.

If salts of these compounds of formula I in which R ¹ represents a hydrogen atom cannot be prepared directly by cyclization under basic conditions described as process D), they can also be obtained by a process known per se from the procedures given as C ) to F). For this, for example, the preparation can be treated with an inorganic aqueous solution of 3- (benzazolv

4-yl) pyrimidindionovým derivative of an organic base where R ¹ represents a hydrogen atom. In such a case, the salt formation is normally fast enough at 20-25 ° C.

It is particularly preferred to prepare the sodium salts by dissolution

Of a 3- (benzazol-4-yl) pyrimidinedione derivative of the Formula I wherein R ¹ = hydrogen in aqueous sodium hydroxide solution at 20 to 25 ° C, using approximately equal amounts of 3- (benzazol-4-yl) pyrimidinedione a compound of formula I (wherein R ¹ = H) and sodium hydroxide. The corresponding salt of the 3- (benzazol-4-yl) pyrimidinedione derivative of formula (I) may then be isolated, for example, by precipitation with a suitable inert solvent or by evaporation of the solvent.

Salts of 3- (benzazol-4-yl) pyrimidinedione derivatives of the general formula I in which the metal ion is other than the alkali metal ion can usually be prepared by double decomposition of the corresponding alkali metal salt in aqueous solution, and the ammonium, phosphonium, sulfonium and sulfoxonium salts via ammonium or phosphonium, sulfonium or sulfoxonium hydroxides.

Method B)

Reaction of a 3- (benzazol-4-yl) pyrimidinedione derivative of the Formula I wherein R ¹ represents a hydrogen atom with an electrophilic amination reagent in the presence of a base:

aminační reagent

RS -► bases

The amination reagent which has proved to be particularly advantageous is

2,4-dinitrophenoxyamine, but it is also possible to use, for example, hydroxylamine-O-sulfonic acid (HOSA), which is already known from the literature as an amination reagent (see, for example, E. Hofer et al., Synthesis 1983, 466; kol.,

Heterocycles 20 (1983) 1271; H. Hart et al., Tetrahedron

Lett. 2 (1984) 2073; B. Vercek et al., Monatsh. Chem. 114 (1983) 789; G. Sosnousky et al., Z. Naturforsch. 22 (1983) · 1983 1983 «« 1983 1983 1983 1983 1983 1983 1983 1983 1983 1983 1983 1983 1983 1983 1983

884; R.S. Atkinson et al., J. Chem. Soc. Perkin Trans. 1987, 2787).

The amination may be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1968, 1909; MP Wentland et al., J. Med. Chem. 27 (1984) 1103, and in particular EP-A 240 194 , EP-A 476 697 and EP-A 517 181, which disclose the amination of uracils).

The reaction is normally carried out in a polar solvent, for example dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or ethyl acetate, which has proven to be particularly suitable.

Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide, or alkali metal hydrides such as sodium hydride.

The amount of base and amine reagent is preferably 0.5 to 2 molar amounts based on the amount of the starting compound.

Method C)

Sulfurization of a 3- (benzazol-4-yl) pyrimidinedione derivative of the Formula I wherein X is O:

Sulfurization is generally carried out in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and xylenes, in an ether such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine.

Particularly suitable sulfurizing reagents are phosphorus pentasulfide and 2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphethane-2,4-dithione (Lawesson's reagent).

Normally, one to five times the molar amount, based on the amount of the starting compound to be sulfurized, is sufficient to substantially complete the reaction.

The reaction temperature is normally in the range from 20 to 200 ° C, preferably from 40 ° C to the boiling point of the reaction mixture.

Method D)

Cyclization of an aryl urea of formula III or an arylanilide of formula IV in the presence of a base:

I (X = O)

L ₂ represents lower alkyl, preferably C 1 -C ₄ -alkyl, or phenyl.

The cyclization is usually carried out in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as

1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic solvent such as benzene or toluene, or in a polar solvent such as dimethylformamide or dimethylsulfoxide. A mixture of polar solvents and hydrocarbons such as n-hexane is also suitable. Depending on the starting compound, water may also be suitable as a diluent.

Suitable bases are preferably alkali metal alkoxides, in particular sodium alkoxide, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali metal carbonates, especially sodium carbonate and carbonate, 9 ··· 9, 9, 9, 9, 9, 9, 9, 9, 9, 9, 9, 9, 99, 9, 99, 9, and potassium, and metal hydrides, especially sodium hydride. When sodium hydride is used as the base, it has proven advantageous to carry out the process in an aliphatic or cyclic ether, in dimethylformamide or in dimethylsulfoxide.

Normally 0.5 to 2 times the molar amount of the base relative to the amount of formula (IV) or (V) is sufficient to carry out the reaction successfully.

The reaction temperature is generally in the range of -78 ° C to the boiling point of the reaction mixture under consideration, in particular -60 to 60 ° C.

When R ¹ in formula III or IV is hydrogen and the process product is obtained as a metal salt, then the corresponding metal base cation. The salt can be isolated and purified in a manner known per se or, if desired, converted with an acid to the free compound of formula I wherein R ¹ = hydrogen.

Method E)

Treatment of substituted 2-aminoaniline Va with nitrous acid

44 • 4 4 4 4 4 • • 4 · 4 · 4 · 4

44

The cyclization reaction can be carried out by methods known per se (see, for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. E8d, 1st edition 1994, pp. 409-415) .

The reaction is preferably carried out in an acidic aqueous medium, but lower carboxylic acids such as acetic acid are also suitable diluents. Suitable acidic aqueous solvents are in particular dilute inorganic acids, for example 10% hydrochloric acid.

Nitrous acid is preferably prepared in situ by adding alkali metal nitrite - directly or in aqueous solution to a reaction mixture consisting of diaminobenzene in an acidic aqueous solution or in a carboxylic acid.

A suitable reaction temperature is in particular in the range from 0 to 20 ° C, most preferably about 5 ° C.

The starting materials are immediately used in approximately stoichiometric amounts or the process is carried out with an excess of the theoretically expected amount of nitrous acid of not more than 10 mole percent.

The following intermediate may be cyclized in a similar manner:

• 4 ·· 44 ·· • ♦ · 4 4 4 4 4

44 44 4 * 4 *

44 444 44 4 • 44 4 4 44

4 «· · 44

Method F)

Condensation of substituted 2-aminophenol, 2-aminothiophenol or 2-aminoaniline (V) with carbonic acid or carboxylic acid derivatives:

I (Z = chemical bond, O, NH, R7 = H, optionally substituted alkyl, alkenyl or aryl)

The condensation reaction of the bifunctional benzenes of the formula V with carbonic acid or carboxylic acid derivatives is carried out in a manner known per se (see, for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. E8c). , 1st edition 1994, pp. 247-284, Vol. E8b, 1st edition 1994, pp. 881-901, Vol. E8a, 1st edition 1993, p.

• 9 9 99 • • 9 9 9 9 9 9 999 • 9 9 · 9 9 9 • 9 9 · 9 9 · · 99

1032-1078). Preferred carbonic acid derivatives or carboxylic acid derivatives are the corresponding anhydrides, acid chlorides, orthoesters, diimides, nitriles, trichloromethylsubstituted compounds, isocyanates and thio analogues thereof.

Suitable solvents / diluents are especially organic solvents, for example aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane, tetrahydrofuran and dioxane, carboxylic acid esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and dimethylsulfoxide.

If desired, the reaction can be accelerated by adding a catalytic amount of acid. Suitable acids are, in particular, inorganic acids such as hydrochloric acid or sulfonic acids such as ptoluenesulfonic acid. The amount of acid is preferably 0.1 to 5 mole percent based on the amount of V.

The reaction temperatures are preferably in the range from 20 ° C to the reflux temperature of the reaction mixture under consideration, in particular from 60 ° C to the reflux temperature.

The carbonic acid derivative or carboxylic acid derivative is used either in an approximately stoichiometric amount or in excess. If appropriate, a very large excess may also be used or the process may be carried out without solvent. An approximate stoichiometric amount of &lt; RTI ID = 0.0 &gt; 9,999 &lt; / RTI &gt;

Substituted 2-aminophenols, -thiophenols and -anilines (V) are immediately obtained by reduction of the corresponding 2-nitrophenols, thiophenols or -anilines of the general formula VIII (see, for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag) Stuttgart, Vol. XI / 1, 4, edition 1957, p. 431 et seq.):

Suitable reducing agents are in particular,

- metallic elements such as iron, tin and zinc,

hydrogen in the presence of suitable catalysts such as palladium or platinum on activated carbon or Raney nickel, or

hydride complexes such as LiAlH ₄ and NaBH ₄ , in the presence or absence of catalysts.

Depending on the reducing agent, suitable solvents are normally carboxylic acids such as acetic acid or propionic acid, alcohols such as methanol and ethanol, ethers such as diethyl ether, methyl tert-butyl ether,

• · * Tt tttt • tt • tt ♦ tt · Ttt tt tt tt « tt • ··· tt tt tttt • • tt « * tt ·· · ·· tttt • tt • • ·

tetrahydrofuran and dioxane; aromatic compounds such as benzene and toluene; and mixtures thereof.

The reaction may be carried out at a temperature of from -100 ° C to the boiling point of the reaction mixture under consideration.

The starting compounds are normally used in approximately stoichiometric amounts; however, in particular cases it may be advantageous to use an excess of one or the other component up to about 10 mole percent.

The 2-nitrophenols, -thiophenols, and -anilines of formula VIII can be obtained as free compounds from the corresponding protected nitro compounds of formula IX:

agent

IX

R ⁶

Protection = conventional protecting group that protects phenols or thiophenols as ethers or amino groups as amide.

Protecting groups may be removed by methods known per se (see, for example, Greene / Wuts: Protective Groups in Organic Synthesis, John Wiley & Sons, Inc., 2nd Edition 1991, pp. 145 et seq. And pp. 279 et seq.) .

• · · 00 00 00 00 • 0 0 • 0 0 t 0 0 • 0 • ··· 0 0 00 0 0 0 « * · 0 0 0 0 0 0 0 0 0 ··· ·· • · • 0 00 00

Suitable elimination reagents are especially:

for alkylphenols: trimethylsilyl iodide, boron tribromide, boron tribromide, aluminum chloride, lithium chloride or bromohydride; for unsubstituted or substituted benzylphenols or thiophenols: boron trifluoride, hydrofluoric acid or hydrogen / catalyst, preferably noble metal catalysts such as palladium or platinum.

The solvent / diluent is preferably selected in such a way that it is inert with respect to the elimination reagent under consideration. When halides such as trimethylsilyl iodide, boron tribromide, boron trichloride or aluminum chloride are used, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane are particularly preferred. The bromide is preferably used in an aqueous solution, particularly preferably as a 48% solution; lithium chloride is preferably used in polar solvents such as lower alcohols, dimethylsulfoxide and dimethylformamide; The hydrogenolytic processes are preferably carried out in lower alcohols or carboxylic acids, with or without the addition of a hydrogen transfer agent such as cyclohexene and cyclohexadiene.

The temperature for the elimination reactions is preferably from 0 ° C to the boiling point of the contemplated reaction mixture.

The elimination reagent is preferably used in approximately stoichiomeric amounts or in excess. The excess is particularly preferably in the range between one and ten molar equivalents, based on the amount of the compound of the general formula

Φ · · · · · · φ φ φ φ · · · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ · ·

IX

Finally, protected nitro compounds of the formulas IX can be obtained in a manner known per se using nitrated (protected) phenols, thiophenols or anilines of the formula X (see, for example, Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol. 10/1, 1971, pp. 479 et seq.):

Suitable nitrating reagents are in particular nitric acid, in admixture with sulfuric acid or acetic anhydride or nitronium salts, in particular nitronium tetrafluoroborate. The mixture consisting of nitric acid and sulfuric acid may consist of any desired ratios of the two components; mixtures are preferred in which the sulfuric acid is highly predominant or acts as a solvent. The same applies to a mixture of nitric acid and acetic anhydride. Nitronium tetrafluoroborate is preferably used in aprotic polar solvents, for example acetonitrile or nitromethane.

The reaction temperature is generally in the range from -80 to 80 ° C, in particular from -20 ° C to 30 ° C.

φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

When the nitric acid reagent is used in nitration reactions, the process is preferably carried out with an approximately equimolar amount or particularly preferably with an excess of the nitration reagent. The excess may be a multiple amount of a compound of formula (X). Nitronium tetrafluoroboram is preferably used in an equimolar amount with respect to the substrate or in a small excess between 1.1 and 1.5 molar equivalents.

The following intermediates may also be nitrated in a similar manner:

XI

XII

3- (Benzazol-4-yl) pyrimidinedione derivatives of formula I with one or more chiral centers are normally obtained as enantiomeric or diastereomeric mixtures which, if desired, can be resolved into the substantially pure isomers by methods commonly used for this purpose. , for example by crystallization or chromatography on an optically active adsorbate. Pure optically active isomers may be prepared preferably from the corresponding optically active starting materials.

The 3- (benzazol-4-yl) pyrimidinedione derivatives of the general formula I, in which R ¹ represents a hydrogen atom, may be: - (-) - - - - - converted into their salts in a manner known per se (see, in this context, what has been said for process A)).

The aryl ureas of formula III are novel. They may be prepared by methods known per se, for example in one of the following ways:

Method G)

Reaction of the β-keto ester of the carboxylic acid of the formula XIII with the urea of the formula XIV:

XIII

XIV

L ₂ represents lower alkyl, preferably C 1 -C ₄ -alkyl, or phenyl.

The process is preferably carried out under substantially anhydrous conditions in an inert solvent or diluent, particularly preferably in a solvent

• · « * · ·· • · ·· »· · • • • · «♦ • * • ··· • • ·· • · • · • · · • • • · • · • · ··· ·· • • ·· ♦ « ··

presence of an acidic or basic catalyst.

Suitable solvents or diluents are especially organic solvents that are miscible with water to form azeotropic mixtures, for example aromatic solvents such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as

1,2-dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol.

Suitable acid catalysts are preferably strong inorganic acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid, and acidic cation exchangers such as Amberlyst 15 (Fluka).

Examples of suitable base catalysts are alkali metal hydrides such as sodium hydride and particularly preferably alkali metal alkoxides such as sodium methoxide and sodium ethoxide.

The compounds of formula XIV and the β-keto esters of carboxylic acids of formula XIII are used in approximately stoichiometric amounts, or the process is also carried out with a small excess of one or the other component up to about 10 mole percent.

The amount of 0.5 to 2 mole percent of catalyst, based on the amount of one of the starting compounds, is normally • ♦ <44 4

444

4 · 44 · 4 · · 4 44 · * · 4 44 · 4 * 4 44 · 4 4 · 4 4 · 4 4 ·

4 4 ·

4 4 4

44 sufficient.

The reaction is generally carried out at a temperature in the range of from 60 to 120 ° C so as to rapidly eliminate the water that is formed, preferably at the boiling point of the reaction mixture.

Method H)

Reaction of the enol ether of formula XV with urea of formula XVI:

R3

L ₂ and L ₃ represent lower alkyl, preferably C 1 -C 4 -alkyl, or phenyl.

The reaction with the aliphatic solvent is preferably carried out in an inert organic which is miscible with water, for example in or a cyclic ether such as

· »» 4

44

4 99

4 9

99

1,2-dimethoxyethane, tetrahydrofuran and dioxane, or in a lower alcohol, especially ethanol, the reaction temperature is normally in the range from 50 to 100 ° C, preferably the boiling point of the reaction mixture.

However, the reaction may also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case it is recommended to add either an acid catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base such as an alkali alkoxide. metal such as sodium methoxide and sodium ethoxide. In this embodiment of the method of manufacture, ° C, but preferably what has been said is the reaction temperature normally from 50 to 100 from 60 to 80 ° C.

With respect to weight ratios, the same applies to process G).

Method J)

Reactions of the enamino ester of formula XVII of formula XVIII:

with isocyanate

R4

N- Y

XVII XVIII xn

L ₂ represents lower alkyl, preferably C 1 -C ₄ -alkyl, or phenyl.

The reaction is carried out in the presence of a substantially anhydrous aprotic organic solvent or diluent, for example.

4 4 4 4 4 4 4 4 4 4 4 4 4 4 44 444 4 4 4

444 · 4 4 4444

44444 44 44 44 44 aliphatic or cyclic ether such as diethyl ether,

1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride,

1,2-dichloroethane and chlorobenzene, an aprotic polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethylsulfoxide, or mixtures thereof.

If desired, the process can also be carried out in the presence of a metal hydride base such as sodium hydride and potassium hydride or an organic tertiary base such as triethylamine and pyridine, while allowing the organic base to act simultaneously as a solvent.

The starting materials are used in stoichiometric amounts or the process is also carried out with a small excess of either component up to about 10 mole percent. If the process is carried out in the absence of a solvent and in the presence of an organic base, the base is used in a larger excess.

The reaction temperature is preferably in the range from -80 to 50 ° C, in particular from -60 to 30 ° C.

In a particularly preferred embodiment, the resulting enamine ester of formula III is converted directly (i.e. in situ) with an excess of the base according to method D) to give the corresponding product of formula I.

9 *

9 9 9

9 9 9

9 9 9

9 9 9

99 • 9 »

999

99

9 9 9

9 99

9 9

999 99

9 9 9

9 99

Method Κ)

Reactions of the enamino ester of formula XVII of formula XIX:

with urethane

L ₂ and L ₄ independently represent one of the following groups lower alkyl, preferably C 1 -C ₄ -alkyl, or phenyl.

This reaction is conveniently carried out in an aprotic polar solvent or diluent such as dimethylformamide,

2-butanone, dimethylsulfoxide and acetonitrile, preferably in the presence of a base, for example an alkali metal or alkaline earth metal alkoxide, especially in sodium alkoxide such as sodium methoxide, alkali metal carbonate or alkaline earth metal carbonate, especially sodium carbonate or alkali metal hydride such as lithium hydride and sodium hydride.

One or twice the molar amount of the base, relative to the amount of the compound of formula XVII or XIX, is normally sufficient.

The reaction temperature is generally in the range from 80 to 180 ° C, preferably

• · « «· ·· ·· »♦ ·· · c · · · • · • « Φ ·· * • ♦ · » «· • 1 ·· «* · • c · * »*

to the boiling point of the reaction mixture.

With respect to the weight ratios of the starting compounds, what was stated with respect to method G) applies.

In a particularly preferred embodiment, the base is sodium alkoxide and the alcohol formed during the reaction is continuously distilled off. The resulting enaminoesters of formula IV may be cyclized according to method D) without being isolated from the reaction mixture to give substituted benzothiazoles of formula I (wherein R ¹ = H).

The urethanes of the formula XIX can in turn be prepared, for example, from carbonyl chlorides of the formula XX and anilines of the formula XXI:

To avoid excess aniline, it is usually necessary to add an additional base such as triethylamine, pyridine or alkali metal carbonates to scavenge the hydrochloride formed during the reaction. Pyridine is particularly suitable as it can be used simultaneously as a solvent.

tf · t · tf tf 9 9 9 9 9 9 9 9 9

499 99 49

Suitable solvents / diluents other than pyridine are especially aromatic hydrocarbons such as benzene, toluene and o-, m-, p -ylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane , tetrahydrofuran and dioxane, carboxylic acid esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and dimethylsulfoxide.

The reaction temperature is generally in the range of 0 ° C to the reflux temperature of the reaction mixture under consideration.

The starting materials are used in approximately stoichiometric amounts or also in an excess of carbonyl chloride of not more than 10 mole percent.

The auxiliary base is normally used in an approximately equimolar amount - based on the amount of the compound of formula XX or XXI - or in excess of up to about twice the molar amount. If pyridine is used as an auxiliary base, an even greater excess is recommended; in this case, the process can be carried out without additional solvent.

Method L)

Reaction of an isocyanate of formula XXII with an aniline derivative of formula XXI:

XXII XXI III (R ¹ = Η)

L ₂ represents lower alkyl, preferably C 1 -C ₄ -alkyl, or phenyl.

This reaction is carried out in a substantially anhydrous aprotic organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o. m, p-xylene and a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, in an aprotic polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethylsulfoxide, or mixtures thereof.

If desired, the process may be carried out in the presence of a base represented by a metal hydride such as sodium hydride and potassium hydride, an alkali metal or alkaline earth metal alkoxide such as sodium methoxide, sodium ethoxide and potassium tert-butoxide or in an organic nitrogen base such as is triethylamine and pyridine, it being possible for the organic base to act simultaneously as a solvent.

The starting materials are used in approximately stoichiometric amounts or also one component is used in excess up to about 20 mole percent. If the process is carried out in the absence of a solvent in the presence of an organic base, the base is preferably used in an even greater excess.

The reaction temperature is generally in the range of -80 to 150 ° C, preferably -30 ° C to the boiling point of the reaction mixture under consideration.

The arylanilides of the formula IV are also novel and can also be prepared in a manner known per se, for example by reacting an amide of the formula XXIII with a urethane of the formula XXIV according to method M):

L ₂ represents lower alkyl, preferably C 1 -C ₄ -alkyl, or phenyl.

The reaction is preferably carried out in a substantially anhydrous solvent / diluent at atmospheric pressure, particularly preferably in the presence of an acid catalyst.

For the preparation of enamine carboxylates of the formula IV in which R ¹ = amino, it is recommended to use compounds of the formula XXIV with an amine-protected group (for example, as an amine-protected compound of formula XXIV). • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •

Suitable solvents / diluents are especially organic liquids which are miscible with water to obtain an azeotropic mixture, for example aromatic compounds such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.

Suitable catalysts are particularly strong inorganic acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as Amberlyst 15 (Fluka).

A sufficient reaction temperature is generally in the range of about 70 to 150 ° C; however, for rapid removal of the water resulting from the reaction, it is advantageous to carry out the reaction mixture at the boiling point.

Compounds XXIII and XXIV are normally used in approximately stoichiometric amounts; preferably, the compound of formula XXIV is used in a small excess up to about 20 mole percent.

The amide of formula XXIII can be prepared as follows (Method N)):

• 4 · · 4 4 4 4 44 4 ···· 4 4 44 4 4 4 4

4,444 44,444 44 4

444 4444 4444

44444 44 44 44 44

-A // oy— ch ₃ h ₃ c

XXV

XXI

The reaction is preferably carried out in

R ⁵

XXIX X (R ³ - H) anhydrous inert aprotic solvent, for example, in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, pxylene or in an aliphatic or cyclic solvent ether such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.

The reaction temperature is generally in the range of about 70 to 140 ° C, in particular 100 to 120 ° C.

The compound of formula XXV and the compound of formula XXI are normally used in approximately stoichiometric amounts or also one of the components is used in excess of up to about 10 mole percent.

Isocyanates of formula (XVIII) may be obtained, for example, from aniline derivatives of formula (XXI) according to method O):

0 0000 00 00 0 0 0 0 0 000 000 000 000 000 000 000 000

0000 00 00 00 00

XXI

XVIII

The process may be carried out in an inert and substantially anhydrous solvent or diluent or in the absence of solvents, the aniline derivatives of formula XXI are preferably reacted with phosgene and a phosgene equivalent such as diphosphine, triphosgene and carbonyldiimidazole or with trichloromethyl chloroformate.

Suitable solvents or diluents are particularly aprotic organic solvents, for example dimethylformamide or aromatic compounds such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform,

1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane or esters such as ethyl acetate and mixtures thereof.

The starting materials are suitably used in approximately stoichiometric amounts, or one of the components is also used in excess of up to about 200 mole percent.

Depending on the aniline derivative of formula (XXI) used, it may be advantageous to add a base such as triethylamine, for example in half to twice the molar amount, based on the amount of compound of formula (XXI).

• · · φ · * · * · * · * · * · · · · · · · · · · · · · · φφ

The reaction temperature is generally in the range of -20 ° C to the reflux temperature of the solvent or reaction mixture under consideration.

The aniline derivatives of the formula XXI can in turn be obtained in a manner known per se (see, for example, Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Vol. XI / 1,

4th edition 1957, p. 431 et seq.) By reduction of the corresponding nitro derivatives of formula XXVI:

With respect to the reducing agent, solvents, reaction temperatures and weight ratios, reference is made to the above data relating to method F).

Compounds of formula XXVIII and formula XXI may also contain one or more chiral centers, in which case they are normally obtained as mixtures of enantiomers or diastereomers. If desired, the compositions can be resolved into substantially pure isomers by methods commonly used for this purpose, for example, by crystallization or chromatography by optically active adsorbate. Pure optically active isomers can also be prepared, for example, from the corresponding optically active starting materials.

·············································

Unless otherwise specified, all of the processes described above are preferably carried out at atmospheric pressure or at the actual pressure of the reaction mixture under consideration. Generally, the reactants are used in a molar ratio of 0.95: 1 to 5: 1.

Typically, the reaction mixtures are worked up by methods known per se, for example by diluting the reaction solution with water and then recovering the product by filtration, crystallization or solvent extraction or solvent removal, partitioning the residue in a mixture of water and a suitable organic solvent and treating the organic phase to yield the product.

The compounds of the formulas I and their agriculturally useful salts are suitable as herbicides both in the form of a mixture of isomers and as pure isomers.

The herbicidal compositions containing the compounds of formula I allow very good vegetation control in areas where crop plants are not grown, especially at high application rates. For crops such as wheat, rice, maize, soybeans and cotton, they act against broadleaf weeds and grasses without causing substantial damage to the crops.

This effect is mainly observed at low application rates.

Depending on the application method used. may be compounds of formula I or herbicidal compositions,

They are further used in many other useful plants to eliminate unwanted plants. Examples of suitable crops are as follows:

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 liberica); arboreum (Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Medus spec. Nicotiana tabacum (N.rustica), Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, , Solanum tuberosum, Sorghum bicolor (s. Vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

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

• ·· φ ♦ φ · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

The compounds of the formula I or the herbicidal compositions containing them can be used, for example, in the form of aqueous spray solutions, powders, suspensions, as well as highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, powders, spreading or granules and applied by spraying, spreading or pouring.

The forms used depend on the intended use; in any case, it must ensure the finest possible distribution of the active ingredient according to the present invention.

Suitable inert additives are, in particular: mineral oil fractions of medium to high boiling point, such as kerosene or naphtha, other coal tar oils and vegetable and animal oils, aliphatic, cyclic and aromatic hydrocarbons such as paraffins, naphthalene, alkylated naphthalenes; their alkylated benzenes or derivatives thereof, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, for example amines such as N-methylpyrrolidone, or water.

tetrahydro derivatives and

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders, or water dispersible granules by adding water. To prepare emulsions, pastes, or oil dispersions, the substrates, either as such or dissolved in an oil or solvent, can be homogenized in water by wetting agents, tackifiers, dispersing agents or emulsifying agents. Alternatively, it is possible to prepare concentrates consisting of the active ingredient, wetting agents.

tackifiers, dispersants or emulsifiers and, if desired, solvent or oil, the concentrates suitable for dilution with water.

Suitable surfactants (adjuvants) are alkali metal salts, alkaline earth metal salts, and ammonium salts of aromatic sulfonic acids, for example ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid and fatty acids, alkyl- and alkylarylsulfonates, alkylsulfates, lauryl ethers and fatty acids. alcohols and salts of sulfated hexa-, hepta- and octadecanols and glycol ethers of fatty alcohols, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylenoctylphenol ether, ethoxylated isooctyl, polyphenylolylphenyl, octyl, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulphite waste methylcellulose.

Powders, spray materials and powder formulations can be prepared by mixing or crushing the active ingredient together with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, may be prepared by binding the active ingredient to solid carriers. Solid carriers are mineral soils such as

4 · 4 4 4 44 44 • · • • • 4 4 4 4 • 3 4 « • • 44 4 • 4 44 44 • »4 • 4 4 • 4 4 4 4 4 4

silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, red earth clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, basic synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate , ammonium nitrate, urea, and substances of plant origin, such as cereal flour, tree bark flour, wood flour and nutshell flour, cellulose powders or other solid carriers.

The concentrations of the active compounds of the formula I in ready-to-use preparations vary within wide limits. In general, the composition comprises, for example, from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight. at least one active ingredient. The active compounds are employed in a purity of from about 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

The following formulation examples illustrate the preparation of such formulations:

I. 20 parts by weight of compound 1 were dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of adduct 40. moles of ethylene oxide with 1 mole of castor oil. The solution was poured into 100,000 parts by weight of water and finely dispersed therein, giving an aqueous dispersion containing 0.02% by weight. active ingredient.

II parts by weight of Compound # 2 were dissolved

4 V * ·· ► 9 • • * · • · • * • · ·· • • 4 • S $ • • · « • « • · • * • 0 ·· • · r « 4 ·

in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil. The solution was poured into 100,000 parts by weight of water and finely dispersed to give an aqueous dispersion containing 0.02% by weight. active ingredient.

III. 20 parts by weight of the active ingredient No. 4 were dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point of 210-280 ° C and 10 parts by weight of an adduct of 40 moles ethylene oxide and 1 mole castor oil. The solution was poured into 100,000 parts by weight of water and finely dispersed to give an aqueous dispersion containing 0.02% by weight. active ingredient.

IV. 20 parts by weight of the active ingredient No. 6 were intimately mixed with 3 parts by weight of sodium diisobutyl-naphthalene-sulfonate, 17 parts by weight of lignosulfonic acid sodium salt from the sulphide effluent and 60 parts by weight of pulverized silica and milled in a hammer mill. Fine dispersion of the mixture in 20,000 parts by weight of water gave a spray mixture containing 0.1% by weight. active ingredient.

V. 3 parts by weight of the active ingredient No. 8 were mixed with 97 parts by weight of finely divided kaolin. This gave a powder which contained 3 wt. active ingredient.

VI. 20 parts by weight of the active ingredient No. 12 were intimately mixed with 2 parts by weight of calcium dodecylbenzene sulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium phenol / urea / formaldehyde condensate and 68 parts by weight of paraffin mineral oil. This gave a stable oil dispersion.

was dissolved in parts by weight of ethoxylated parts

VII. 1 part by weight of the active ingredient mixture consisting of 70 cyclohexanone, 20 parts by weight of isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gave a stable emulsion concentrate.

VIII. 1 part by weight of the active ingredient No. 19 was 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). This gave a stable emulsion concentrate.

The herbicidal compositions or active ingredients of formula I may be applied before or after germination of the plant. If the active ingredients are less well tolerated by certain useful plants, application techniques may be used in which the herbicidal compositions are sprayed by spraying devices in such a way that they come in as little or no contact with the leaves of the sensitive useful plants as the active ingredients hit. tt tttt • · · tt 4

4 undesirable plants that grow beneath them or the surface of the earth.

Depending on the intended use, the season, the target plants and their growth phase, the application rates of the active ingredients of the formula I are in the range of 0.001 to 3.0, preferably 0.01 to 1.0, kg of active ingredient per hectare.

mixed together with the active groups

In order to broaden the spectrum of action and to achieve a synergistic effect, the heteroaroyl derivatives of the general formula I can be present in a large number of other agents having a herbicidal action or affecting the growth rate. Suitable components for the mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, (hetero) aryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones , 2- (hetero) aroyl-1,3-cyclohexanediones, heteroarylaryl ketones, benzylisoxazolidinones, meta-CF ₃ -phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitrophenols, diphenyl ethers, dipyridyls, acids and their derivatives, imidazoles, imidazolinones, phthalimides, oxadiazoles, oxiranes, phenols, aryloxy- or heteroaryloxyphenoxypropionic esters and its phenylacetic acids, phenylacetic acids phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, dinitr oanilines, halocarboxylic 3-phenyluracils, ureas,

N-Phenyl-3,4,5,6-tetrahydro-99- • N-phenyl-3,4,5,6-tetrahydro-99-

sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

Furthermore, it may be advantageous to use the compounds of the formula I alone or in combination with other herbicides, also in admixture with other plant protection agents, for example pesticides or agents acting on phytopathogenic fungi or bacteria. Also interesting is the possibility of mixing with inorganic salt solutions which are used in the absence of nutrients and trace elements. Non-phytotoxic oils and oil concentrates may also be used.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

3- [7-Chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl] -1-methyl-6-trifluoromethyl-2,4 (η, 3H) -pyrimidinedione (Compound 2)

0.12 g of methyl iodide was added dropwise at 20 ° C to a mixture of 0.25 g of 3- [7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl] -6-trifluoromethyl-2,4 ( ΙΗ, 3H) -pyrimidinedione, 0.12 g of potassium carbonate and 20 ml of absolute dimethylformamide. The reaction mixture was then stirred for an additional 18 hours, then treated with 50 mL of water. Then the mixture was extracted three times each using 20 ml of ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. The crude product was purified by silica gel chromatography (eluent: cyclohexane / ethyl acetate = 1: 1).

Yield: 0.07 g;

^τ Η NMR (270 MHz, in CDCl ₃ ): δ [ppm] =

7.45 (d, 1H); 6.45 • »

- 100 (s, 1H), 4.55 (s, 3H), 3.60 (s, 3H).

Example 2

3- [7-Chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (Compound 1)

0.43 g of ethyl 3-amino-4,4,4-trifluorobut-2-enoate in 3 ml of dimethylformamide was added at 0 ° C over 15 minutes under a nitrogen atmosphere to 0.13 g of sodium methoxide in 7 ml of absolute. dimethylformamide. The mixture was first stirred for one and a half hours at 10 ° C, then a solution of 0.57 g of ethyl-7-chloro-5-fluoro-1-methyl-1H-benzotriazole-4- was added dropwise to the reaction mixture over 15 minutes. ylcarbamate in 20 ml of dimethylformamide. The mixture was then heated to 20 ° C and stirring was continued for 5 minutes. The mixture was then heated to 60 ° C and 0.35 g of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was added. Finally, stirring was continued for 4 hours at 120 ° C and for 18 hours at 20 ° C.

For the final treatment, the mixture was poured into 100 ml of 10 wt. aqueous potassium carbonate solution. The desired product was extracted with diethyl ether (2 x 50 mL) and after adjusting the pH of the aqueous phase remaining to 1 with hydrochloric acid, it was extracted with ethyl acetate (3 x 30 mL).

The combined organic phases were then washed with approximately 20 mL of saturated aqueous sodium chloride solution and 30 mL of 10 wt. aqueous lithium chloride solution, then dried over sodium sulfate and finally concentrated.

• ··

101

φ · · φ φ φ φ φ φ φ φ

Yield: 0.25 g;

^{Χ Η} NMR (250 MHz, in CDC1 _3): δ [ppm] = 10.25 (br, IH), 7.45 (d, IH), 6.30 (s, IH), 4.60 (s, 3H).

Step 2.1 2-Chloro-4-fluoro-N-trifluoroacetylaniline

144.3 g of trifluoroacetanhydride in 150 ml of diethyl ether were added dropwise at 0 ° C to 100 g of 2-chloro-4-fluoroaniline in 800 ml of absolute diethyl ether. After heating the mixture to 20 ° C, 500 mL of water was added. The organic phase was separated and washed three times with water, then dried over sodium sulfate and finally concentrated. Yield: 151.5 g;

^{Χ Η} NMR (270 MHz, in CDC1 _3): δ [ppm] = 8.35 (br, IH), 8.25 (dd, IH), 7.20 (dd, IH), 7.05 (dt, 1H).

Step 2.2

3-Chloro-5-fluoro-2N-trifluoroacetylaminonitrobenzene

375 ml of 98% nitric acid was slowly added dropwise at -5 ° C to 75 g of 2-chloro-4-fluoro-N-trifluoroacetylaniline in 753 ml of acetic anhydride. The mixture was then stirred for one hour at -5 ° C and then heated to 20 ° C. The progress of the reaction was monitored by high pressure liquid chromatography on an Rp-18 column (reverse phase, silica gel; elution solvent: acetonitrile / water = 7: 3). Once the starting material ceased to be detectable, the reaction solution of sodium chloride. The solid product sought was then separated, washed with water and dried for several hours in a drying oven under reduced pressure at 20 ° C.

102 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Yield: 62.3 g;

¹ H NMR (270 MHz, in CDCl ₃ ): δ [ppm] = 8.50 (br, 1H), 7.80 (dd, 1H), 7.60 (dd, 1H).

Step 2.3

3-Chloro-5-fluoro-2- (N-methyl-N-trifluoroacetylamino) nitrobenzene

12.0 g of methyl iodide was added to a mixture of 16.1 g of 3-chloro-5-fluoro-2N-trifluoroacetylaminonitrobenzene, 11.6 g of potassium carbonate and 100 ml of absolute dimethylformamide. The reaction mixture was then stirred for 18 hours at 20 ° C, then 500 mL of water was added.

Then the mixture was extracted three times with 100 ml of ethyl acetate. The combined organic phases were dried over sodium sulfate and finally concentrated.

Yield: 16.3 g;

¹ H NMR (270 MHz, in CDCl ₃ ): δ [ppm] = 7.80 (m, 1H), 7.60 (m, 1H), 3.40 (s, 3H).

Step 2.4

3-Chloro-5-fluoro-2-methylaminonitrobenzene

173 ml of 1 N sodium hydroxide solution was added to a solution of 16.3 g of 3-chloro-5-fluoro-2- (N-methyl-N-trifluoroacetylamino) nitrobenzene in 173 ml of ethanol. The mixture was then stirred for 1 hour, then diluted with 500 mL of water. Then the mixture was extracted three times with 80 ml of ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated.

Yield: 10.1 g;

103 ·· ·· · · · «· φ · · · ·

Φ Φ 9 Φ ·

Φ · * 4 9 9 Φ • ΦΦΦ ΦΦΦΦ ·· ·· ΦΦ Φ * ^{Χ Η} NMR (270 MHz, in CDC1 _3); δ [ppm] = 7.70 (dd, 1H), 7.35 (dd, 1H), 6.70-6.50 (br, 1H), 3.10 (d, 3H).

Step 2.5

2-Amino-6-chloro-4-fluoro-N-methylaniline

55.94 g of stannous chloride dihydrate was added to 10.1 g

Of 3-chloro-5-fluoro-2-methylaminonitrobenzene in 207 ml of absolute ethanol. The mixture was then heated at 50 ° C and 0.94 g of sodium borate in 55 ml of absolute ethanol was added dropwise such that the temperature of the mixture did not exceed 60 ° C. For final treatment, the mixture was poured into 1 L of ice-water, then the pH was raised to 14 with sodium hydroxide solution. Then the mixture was extracted three times with 100 ml of tert-butyl methyl ether. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated.

Yield: 7.5 g;

^{Τ Η} NMR (270 MHz, in CDC1 _3): 6 [ppm] = 6.50 (dd, IH), 6.35 (dd, IH), 3.90-3.60 (br, 3H), 2, 65 (s, 3 H).

Step 2.6

7-Chloro-5-fluoro-1-methylbenzotriazole

A solution of 3.25 g of sodium nitrite in 19 ml of water was added at 5 ° C to 7.5 g of 2-amino-6-chloro-4-fluoro-N-methylaniline in 117 ml of 10% hydrochloric acid. After stirring the reaction mixture for 1 hour at 5 ° C, the mixture was diluted with 200 mL of water. The solids were then separated, the mixture was washed with 3x50 mL of water and dried in a vacuum oven at 20 ° C.

Φ tt · * • φ · ·

104 φ · φ • · · φ

Yield: 7.2 g;

^{Χ Η} NMR (270 MHz, in CDC1 _3): δ [ppm] = 7.60 (dd, IH), 7.30 (dd, IH), 4.55 (s, 3H).

Step 2.7

7-Chloro-5-fluoro-1-methyl-4-nitrobenzotriazole

0.65 ml of 98% nitric acid was slowly added dropwise at -20 ° C to 1.5 g of 7-chloro-5-fluoro-1-methylbenzotriazole in 28 ml of concentrated sulfuric acid. Then the mixture was stirred for one hour at 0 ° C and then heated to 20 ° C. Stirring was then continued for 18 hours and the reaction mixture was then poured into 500 mL of ice-water. The solids were separated, washed with water and dried in a vacuum oven at 20 ° C.

Yield: 1.66 g;

¹ H NMR (270 MHz, in CDCl ₃ ): δ [ppm] = 7.50 (d, 1H), 4.65 (s, 3H).

Step 2.8

4-Amino-7-chloro-5-fluoro-1-methylbenzotriazole

1.66 g of 7-chloro-5-fluoro-1-methyl-4-nitrobenzotriazole was reduced with stannous chloride / sodium borate in a manner similar to that described in step 2.5.

Yield: 1.27 g;

¹ H NMR (250 MHz, v (CD 3) ₂ SO): δ [ppm] = 7.45 (d, 1H), 6.25 (br, 2H), 4.45 (s, 3H), 4.30 (q, 2H), 1.35 (t, 3H).

Step 2.9

105

4 • 44 4 «3 · 4 4 4 4 • · · • 4 4 4 44 44 4 4

Ethyl 1- 7-chloro-5-fluoro-1-methyl-ΙΗ-benzotriazol-4-ylcarbamate

2.28 g of ethyl chloroformate was slowly added dropwise to 13 ml of absolute pyridine at 0 ° C, then the mixture was stirred at this temperature for 15 minutes. Then, 1.27 g of 4-amino-7-chloro-5-fluoro-1-methylbenzotriazole in 20 ml of pyridine was added dropwise at 0 ° C.

Stirring was then continued, first for 30 minutes at 0 ° C, and the mixture was then heated at 20 ° C and stirred again for 18 hours. Finally, the reaction mixture was poured into 100 ml of 10% hydrochloric acid. Then the mixture was extracted three times with 50 ml of tert-butyl methyl ether. The combined organic phases were washed with 100 mL of water and then concentrated.

ml of diethyl ether was added to the residue. The undissolved ingredients were separated and washed with 3x30 ml diethyl ether. The combined ether phases were concentrated.

Yield: 0.37 g;

^{Χ Η} NMR (250 MHz, in CDC1 _3): δ [ppm] = 7.35 (d, IH), 6.90 (br, 1H), 4.55 (s, 3H).

Example 3

3- [7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -1-methyl-6-trifluoromethyl-2,4 (ΙΗ, 3H) pyrimidinedione (Compound 1.5)

2.46 g of 3- [7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -6-trifluoromethyl-2,4 (δ, 3H) pyrimidinedione was alkylated with methyl iodide in the manner described above. similar to that described in Example 1. Crude · 4 4 · 4 9

4 4 ·

4 4 4

44 • 4

106

product was purified by chromatography on Silica gel (elution) solvent: : cyclohexane / ethyl acetate = 2: 1). Yield: 1.4 G; ¹ H NMR (250 MHz, in CDC1 _3): δ [ppm] = 7.35 (d, 1H), 6.40 (S, 1 H), 4.30 (s, 3H), 3.55 (s, 3H). Example 4

3- [7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -1-amino-6-trifluoromethyl-2,4 (1H, 3H) pyrimidinedione (Compound 6)

0.25 g of 2,4-dinitro-O-aminophenol was added to the mixture of 0.5 g

3- [7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -6-trifluoromethyl-2,4 (1H, 3H) pyrimidinedione, 2.35 g of potassium carbonate and 5 ml of ethyl acetate . After stirring at 20 ° C for 18 hours, the mixture was diluted with 50 mL of ethyl acetate. The resulting mixture was washed with 3x30 mL of water, dried over sodium sulfate and finally concentrated. The crude product was purified by medium pressure liquid chromatography (MPLC; eluting solvent: cyclohexane / ethyl acetate = 2: 1). Yield: 0.4 g;

¹ H NMR (250 MHz, in CDCl ₃ ): δ [ppm] = 7.35 (d, 1H), 6.30 (s, 1H), 4.65 (s, 2H), 4.25 (s, 3H).

Example 5

3- [7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (Compound 4)

4.31 g ethyl 3-amino-4,4,4-trifluorobut-2-enoate in 20 ml • 4 ♦ · • 44

4 • 4

4

107 dimethylformamide was added dropwise at 0-5 ° C to 0.82 g of sodium hydride in 50 ml of absolute dimethylformamide. The mixture was then stirred for one hour at the same temperature and then added at -30 ° C

7-chloro-5-fluoro-4-isocyanato-1-methyl-2-trifluoromethylbenzimidazole (from step 5.4) in 40 mL of dimethylformamide. Stirring was then continued for one hour at -30 ° C and for an additional one hour at 20 ° C.

For the final work-up, the reaction mixture was carefully poured into 200 ml of ice-water. Acidification with 10% hydrochloric acid gave a solid which was filtered off, washed with water and dried in a vacuum oven at 20 ° C. After purification by flash chromatography (eluting solvent: cyclohexane / ethyl acetate = 2: 1), 5.08 g of the desired product was obtained.

After separation of the solids, the desired product remaining in the filtrate (2.46 g) was isolated by extracting the filtrate three times with 200 ml of tert-butyl methyl ether, washing the combined ether phases, drying them over sodium sulfate and concentrating.

Total yield: 7.54 g;

NMR (250 MHz, in CDCl ₃ ): δ [ppm] = 7.40 (d, 1H), 6.30 (s, 1H), 4.30 (s, 3H).

Step 5.1

7-Chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole

- 108

9 9 9 9

999 9 9 99 9 9 9 9

9 9 9 9 9 9 9 9

999 9999

999 99 99 99

15.5 g of 3-chloro-5-fluoro-2- (N-methyl-N-trifluoroacetylamino) nitrobenzene (step 2,3) was reduced with stannous chloride / sodium borate without isolation of the intermediate in a manner similar to that described in step 2.5 to obtain the corresponding amino compound, which then underwent spontaneous cyclization with elimination of water to produce the desired product.

Yield: 9.32 g;

NMR (250 MHz in CDCl ₃ ): δ [ppm] = 7.45 (d, 1H), 7.20 (d, 1H), 4.25 (s, 3H).

Step 5.2

7-Chloro-5-fluoro-1-methyl-4-nitro-2-trifluoromethylbenzimidazole

46.3 ml of 98% nitric acid was slowly added dropwise at 0 ° C to 9.65 g of 7-chloro-5-fluoro-1-methyl-12-trifluoromethyl-benzimidazole in 96.5 ml of acetic anhydride. After stirring the mixture for 1 hour at 0 ° C, it was carefully heated to 20 ° C. (In case an exothermic reaction would start, the temperature was kept below 25 ° C by means of an ice bath). The reaction mixture was subsequently stirred for another two hours at 20 ° C and then poured into ice-cold saturated aqueous sodium chloride solution. The solids formed were separated, washed with water and dried at 20 ° C in a vacuum drying oven.

Yield: 8.5 g;

¹ H NMR (400 MHz, in CDC1 _3): δ [ppm] = 7.40 (d, IH), 4.35 (s, 3H).

> 0 ·

0 · · · · ·

0 0

000

109 *

00

Step 5.3

4-Amino-7-chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole

8.71 g of 7-chloro-5-fluoro-1-methyl-4-nitro-2-trifluoromethylbenzimidazole was reduced via stannous chloride / sodium borate in a manner similar to that described in step 2.5.

Yield: 6.3 g;

^{Χ Η} NMR (270 MHz, in CDC1 _3): δ [ppm] - 7.05 (d, IH), 4.45 (br, 2H), 4.20 (s, 3H).

Step 5.4

7-Chloro-5-fluoro-4-isocyanato-1-methyl-2-trifluoromethylbenzimidazole

23.32 g of diphosgene was added to 6.3 g of 4-amino-7-chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole in 100 ml of absolute toluene. The mixture was then heated to reflux for 6 hours. After stirring the reaction mixture for an additional 18 hours at 20 ° C, this was concentrated. The crude product obtained was reacted directly without purification to give the final product of formula 1.4.

Example 6

3- [7-Chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl] -1-methyl-6-trifluoromethyl-2,4 (δ, 3H) -pyrimidinedione (Compound 8)

0.33 g of 3- [7-chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl] -6-trifluoromethyl-2,4 (ΙΗ, 3H) -pyrimidinedione were ► 4 ♦ <

• · tttt which was similar

110 is alkylated with methyl iodide by the method of Example 1.

Yield: 0.04 G; ¹ H NMR (250 MHz, in CDCl3): δ [ppm] = 7.10 (d, 1H), 6.40 (s, 1H), 4.00 (s, 3H), 3.55 (s, 3H), 2.55 (s, 3 H). Example 7

3- [7-Chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (Compound 7)

The 7-chloro-1,2-dimethyl-5-fluoro-4-isocyanatobenzimidazole from step 7.4 was reacted with ethyl 3-amino-4,4,4-trifluorobut-2-enoate in a manner similar to that described in the example 5. The crude product was purified by medium pressure liquid chromatography (elution solvent / ethyl acetate / methanol = 15: 1).

Yield: 0.7 g;

¹ H NMR (270 MHz, in CDCl ₃ ): δ [ppm] = 7.15 (d, 1H), 6.20 (S, 1H), 4.05 (s, 3H), 2.55 (s, 3H).

Step 7.1

7-Chloro-1,2-dimethyl-5-fluorobenzimidazole

100 ml of 10% hydrochloric acid was added to 6.96 g

2-amino-6-chloro-4-fluoro-N-methylaniline (from step 2.5) in 4.1 g of acetic anhydride. The mixture was then heated to reflux for 4 hours. After cooling, the mixture was taken up in ice-water. It was then carefully neutralized with aqueous sodium carbonate solution. The solid crude product that formed was separated, washed with water and dried in a vacuum oven at 20 ° C.

··

111

Yield: 7.92 g;

1 H NMR (270 MHz, in CDCl 3): δ [ppm] = 7.25 (dd, 1H), 6.95 (dd, 1H), 4.00 (s, 3H), 2.55 (s, 3H) .

Step 7.2

7-Chloro-1,2-dimethyl-5-fluoro-4-nitrobenzimidazole

98% nitric acid was added dropwise at a temperature of 5 to no more than 0 ° C to 7.92 g of 7-chloro-1,2-dimethyl-5-fluorobenzimidazole in 139 ml of concentrated sulfuric acid, during which the progress of the reaction was monitored by means of high performance liquid chromatography (HPLC) on a RP-18 column (elution solvent: acetonitrile / water = 1: 1). Once the starting material ceased to be detectable, the reaction mixture was poured into ice-water, and then the pH was raised to 14 with sodium hydroxide solution. The solids were separated, washed with water and dried at 20 ° C in a vacuum drying oven. The two regioisomeric nitro compounds that formed were separated by flash chromatography on silica gel (eluent: ethyl acetate; the product eluting first was the desired regioisomer). Yield: 5.6 g.

¹ H NMR (400 MHz in CDCl ₃ ): δ [ppm] = 7.05 (d, 1H), 4.10 (s, 3H), 2.65 (s, 3H).

Step 7.3

4-Amino-7-chloro-1,2-dimethyl-5-fluorobenzimidazole

5.6 g of 7-chloro-1,2-dimethyl-5-fluoro-4-nitrobenzimidazole was reduced by means of a tin (II) chloride / borate mixture.

φφφ

112 φ φ φ · · φ φ φ · · · · · · · · · · · · * · · · · · · · · · · · způsobem způsobem způsobem the method of step

2.5. The crude product obtained was used directly, without purification, in step 7.4.

Yield: 4.1 g.

Step 7.4

7-Chloro-1,2-dimethyl-5-fluoro-4-isocyanatobenzimidazole

4.1 g of 4-amino-7-chloro-1,2-dimethyl-5-fluorobenzimidazole were reacted with diphosgene in a manner similar to that described in step 5.4. The crude product obtained was used directly, again without purification, to obtain the end product of formula (1.7).

Example 8

3- [7-Chloro-2-dimethylamino-5-fluoro-benzoxazol-4-yl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione (Compound 19)

1.0 g of 3- [2-amino-4-chloro-6-fluoro-3-hydroxyphenyl] -1-methyl-3-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione and 0.5 g of dichloromethylenammonium chloride were mixed in 100 ml

1,2-dichloroethane, then the mixture was placed in a glass pressure container and heated for 5 hours at 120 ° C in a sealed pressure container. During this procedure, the internal pressure in the container increased to approximately 5 bar. The container was then cooled. The clear product solution was washed with dilute aqueous potassium carbonate solution.

Organic phase concentrated. dried over sodium sulfate by chromatography. The crude product was purified using a short column and finally a flash column (eluting with water).

113 solvent: cyclohexane / tert-butyl methyl ether = 8: 2). Yield: 0.5 g;

¹ H NMR (270 MHz, in CDC1 _3): δ [ppm] = 6.85 (d, lH), 6.4 (s, lH), 3. 6 (s, 3H), 3.25 (s, 6H).

Step 8.1

3- [4-Chloro-6-fluoro-3-methoxy-2-nitrophenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione

Nitrating acid, composed of 20.4 ml concentrated sulfuric acid and 25.5 ml 98% nitric acid, was slowly added dropwise with cooling to -20 ° C to 51.0 g.

Of 3- [4-chloro-6-fluoro-3-methoxyphenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione of VI concentrated sulfuric acid. After the addition was complete, stirring was continued for 30 minutes at -20 ° C. The reaction mixture was then stirred with 1 N ice / water. The solids formed were separated, washed with water and dried in a vacuum oven at 20 ° C.

Yield: 57.0 g;

¹ H NMR (270 MHz, in CDCl ₃ ): δ [ppm] = 7.55 (d, 1H), 6.35 (S, 1H), 4.05 (s, 3H), 3.55 (s, 3H).

Step 8.2

3- [4-Chloro-6-fluoro-3-hydroxy-2-nitrophenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione

19.0 g of lithium chloride was added to 57.0 g of 3- [4-chloro-6-fluoro-3-methoxy-2-nitrophenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione in approximately 500 ml of absolute dimethylformamide. The mixture was then stirred for 3 hours.

ΦΦ ·· • ♦ · φ φ «·

114

φ φφφφ

ΦΦ Μ at 80-90 ° C. After cooling, 1 L of water was added to the reaction mixture. The product sought was extracted with 3x200 ml of methyl tert-butyl ether. The ether phase was washed repeatedly with water and then dried and finally concentrated. Yield: 46.1 g;

¹ H NMR (250 MHz, in CDCl ₃ ): δ [ppm] = 7.65 (d, 1H), 6.35 (s, 1H), 3.60 (s, 3H).

Step 8.3

3- [2-Amino-4-chloro-6-fluoro-3-hydroxyphenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione g powder was added in portions to 65 ° C. 46.0 g of 3- [4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) pyrimidinedione in 423 ml of water and 36.8 ml of concentrated hydrochloric acid. The mixture was then heated to reflux for 3 hours. After cooling, the mixture was shaken with 500 mL of ethyl acetate. The organic phase was separated from the remaining inorganic material by filtration on Celite® (Manville Corporation). The filtrate was dried over sodium sulfate and finally concentrated. Yield: 37.5 g, ^X H NMR (270 MHz, in CDC1 _3): δ [ppm] = 6.65 (d, IH), 6.40 (s, IH), 3.60 (s, 3H) .

Example 9

3- [7-Chloro-5-fluorobenzoxazol-4-yl] -1-methyl-3-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione (Compound 12)

0.5 g of trimethyl orthoformate was added to the solution of 0.5 g

115 • ··

3- [2-amino-4-chloro-6-fluoro-3-hydroxyphenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione (from step 8.3) in 30 mL of absolute methanol. The mixture was then heated to reflux for 20 hours. The solvent and excess orthoester were then removed under reduced pressure. The residue was dissolved in ethyl acetate. The organic phase was washed with water and then dried over sodium sulfate and finally concentrated. The crude product was purified by flash chromatography (eluent: cyclohexane / tert-butyl methyl ether = 3: 1).

Yield: 0.26 G; ^{Χ Η} NMR (250 MHz, h CDCl 3): δ [ppm] = 8.20 (s, 1H), 7.40 (d, 1H), 6.40 (whitefish), 3.60 (s, 3H). Example 10

3- [7-Chloro-5-fluoro-2-methoxybenzoxazol-4-yl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione (Compound 14)

1.0 g of 3- [2-amino-4-chloro-6-fluoro-3-hydroxyphenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione (from step 8.3) was reacted with tetramethyl orthocarbonate in a manner similar to that described in Example 9. Yield: 0.7 g;

¹ H NMR (250 MHz, in CDCl ₃ ): δ [ppm] = 7.10 (d, 1H), 6.40 (S, 1H), 4.20 (s, 3H), 3.60 (s, 3H).

In addition to the 3- (benzazol-4-yl) pyrimidinedione derivatives of formula I described above, other compounds that have been or could be prepared in a similar manner are listed in Table 2 below:

116 »« • 3 4 »

4 ♦♦

4 4 ·

4 4 4

I 4 5 «» 4 5 «

I 4 4 * 4 4 ·

44

Table 2

Rl OR ⁴

I {X = O; R ² = CF _3; R ³ = H; ^R5 = C1}

R ¹ r ’ = Y- OF R ' Temp. thaw [° C] 1 H F = N-N (CH 3) - - - 2 ch ₃ F = NN (CH ₃₎ - - - oil 3 nh ₂ F = NN (CH ₃₎ - - 4 H F = C (ZR ') - N (CH ₃₎ - custody cf ₃ 122-124 5 CH ₃ F = C (ZR ') - N (CH ₃₎ - custody cf ₃ 68-70 6 nh ₂ F = C (ZR ') - N (CH ₃₎ - custody cf ₃ 110 7 H F = C (ZR ') - N (CH ₃₎ - custody ch ₃ oil 8 ch ₃ F = C (ZR ') - N (CH ₃₎ - custody ch ₃ 130-132 9 nh ₂ F = C (ZR ') - N (CH ₃₎ - custody ch ₃ 10 ch ₃ Cl = C (ZR ') -O- custody ch ₃ 67-69 11 ch ₃ F = C (ZR ') -O- custody ch ₃ 65-67 12 ch ₃ F = C (ZR ') -O- custody H 135-136 13 ch ₃ F = C (ZR ') -O- custody ch ₂ ci oil 14 ch ₃ F = C (ZR ') -O- 0 ch ₃ 110-112 15 Dec ch ₃ F = C (ZR ') -O- custody nC ₃ H ₇ ole j 16 ch ₃ F = C (ZR ') -O- custody n-C ^Hg ole j 17 ch ₃ F = C (ZR ') -O- custody phenyl 145-146 18 ch ₃ F = C (ZR ') -O- custody C2H5 ole j 19 Dec ch ₃ F = C (ZR ') -O- -N (CH ₃₎ - ch ₃ 110-112 20 May ch ₃ F = C (ZR ') -O- -NH- cyclohexyl 105-107 21 ch ₃ F = C (ZR ') -O- custody CH = CH-COOC ₂ H ₅ ole j 22nd ch ₃ F = C (ZR ') -O- custody CH (OH) -CH ₂ -CO-OC ₂ H ₅ ole j

• · • · Φ

Φ Φ Φ

Φ · Φ Φ Φ

Φ Φ φ φ · · · · · · ·

ΦΦΦ • e · · * φφ

Φ

117

9

Φ ·

9 • 9

Λ •

Φ *

23 ch ₃ F => C (ZR ') - O- custody CH ₂ P (O) (OC ₂ H _{s) 2} 102-103 24 ch ₃ F = C (ZR ') -O- custody (CH ₂ ) ₂ CH ₂ Br 25 CH ₃ F = C (ZR ') -O- 0 C2H5 oil 26 ch ₃ F = C (ZR ') -O- WITH CH ₃ oil 27 Mar: ch ₃ F = C (ZR ') -O- custody SH oil 28 ch ₃ Cl = C (ZR ') - S- custody CH ₃ 29 H Cl = C (ZR ') - S- custody ch ₃ 30 nh ₂ Cl = C (ZR ') - S- custody ch ₃ 31 H F = NN (SO ₂ CH ₃ ) - - 32 ch ₃ F = NN (SO ₂ CH ₃ ) - - 33 ch ₃ F = NN (SO ₂ CH ₃ ) - - 34 ch ₃ F = C (ZR ') -O- custody OH 230 35 ch ₃ F = C (ZR ⁷ ) -N (CH ₂ -C ₅ CH) - custody CF ₃ 80 36 ch ₃ F = C (ZR ') -O- custody CH ₂ CH ₂ -OC ₂ H 5 oil 37 ch ₃ F = C (ZR ') -O- custody (CH ₂ ) ₃ -OCH ₃ oil 38 H F = C (ZR ') -O- WITH C ₂ Hs oil 39 H F = C (ZR ') -O- custody nC ₃ H ₇ oil 40 H F = C (ZR ') -O- custody t-C -Hs oil 41 ch ₃ F = C (ZR ') -O- custody nh ₂ oil 42 ch ₃ F = C (ZR ') -O- NH phenyl 160

Examples of use

The herbicidal effect of the 3- (benzazol-4-yl) pyrimidinedione derivatives of formula I has been demonstrated by the following greenhouse experiments:

Plastic pots containing aluminum sand with about 3.0% humus as substrate were used as culture vessels. The seeds of the test plants were sown separately for each species.

In the case of pre-germination treatment, the active substances which were suspended or emulsified in water were applied directly

- 118 after sowing using finely divided nozzles. The containers were lightly irrigated to promote germination and growth, and were then subsequently covered with translucent plastic lids until the plants had grown. These enclosures ensure uniform germination of the test plants unless adversely affected by the active ingredients.

In the case of germination treatment, the test plants were first grown to a height of 3-15 cm depending on the habitat of the plant and then treated with a composition of the present invention which was suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same pots or they were first grown separately as seedlings and then transplanted into the test pots a few days before treatment. The active ingredients were applied in an amount of 15.6 or 7.8 kg of active ingredient per hectare.

The plants were maintained at 10-25 ° C or 20-35 ° C depending on the species. The testing period was 2 to 4 weeks. During this time, the plants were treated and their response to individual treatments evaluated.

The evaluation was carried out using a scale of 0 to 100. "100 meant that the plant did not appear at all, or at least its airborne part was completely destroyed, while" 0 meant that no damage or noxal growth occurred.

Plants used in greenhouse experiments belonged to the following species:

• · • ·

- 119 -

Scientific name English name German name Czech name Amaranthus redroot zurUckgekriimmter merlík retroflexus pigweed Fuchsshwanz red Chenopodium lambsquarters weisser merlík album (goosefoot) Gansefuss White Galium aparine catchweed bedstraw Klettenlabkraut he had a trouble přítula Solanum black schwarzer eggplant nigrům nightshade Nachtschatten black Veronica species speedwell species Ehrenpreisarten second rozrazilu

At application rates of 15.6 or 7.8 g / ha, compound 18, after germination, had a very good effect against the above weeds.

Claims (9)

A 3- (benzazol-4-yl) pyrimidinedione derivative of the Formula I wherein the substituents have the following meanings: X represents an oxygen atom or a sulfur atom; R ¹ represents a hydrogen atom, amino, C 1 -C 8 -alkyl or C 1 -C 8 -haloalkyl; R ² represents a hydrogen atom, a halogen atom, C 1 -C ₆ -alkyl, Ci-Cg-haloalkyl, _Ci-C6 alkylthio, _Ci-C6 alkylsulfinyl or Ci-Cg-alkylsulfonyl; R ³ represents a hydrogen atom, a halogen atom or a halogen atom; C 1 -C 8 -alkyl; R ⁴ represents a hydrogen atom or a halogen atom; R ⁵ represents cyano, halogen, C 1 -C 8 -alkyl, C 1 -C 8 -haloalkyl, C 1 -C 8 -alkoxy or C 1 -C 8 -haloalkoxy; • · · 121 = Y represents a group = NN (R ⁵⁾ -, = C (ZR ⁷⁾ -N (R ⁶⁾ -, = C (ZR ⁷⁾ 0-, or = C (ZR ⁷⁾ -S-; R ⁶ represents C 1 -C ₆ -alkyl, C 1 -C ₄ -haloalkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C 1 -C ₆ -alkylsulfonyl, (C 1 -C ₆ -alkyl) carbonyl, (C 1 -C ₆ -haloalkyl) carbonyl , (C 1 -C ₆ -alkyl) thiocarbonyl, (C 1 -C ₆ -alkoxy) carbonyl, (C 1 -C ₆ -alkoxy) thiocarbonyl or C 1 -C ₆ -alkyl optionally substituted by cyano, C 1 -C 6 -alkoxy, C x -Cg-alkylthio, (Ci-Cg-alkoxy) carbonyl, (Ci-C ₆ -alkylamino) carbonyl, di _(Ci-C6 alkyl) aminocarbonyl, or (Cj-Cg-alkyl) carbonyloxy; Z represents a chemical bond, an oxygen atom, a sulfur atom, -S (O) -, -S (O) ₂ -, -NH- or -N (R ⁸ ) -; R ⁷ and R ⁸ independently represent one of the following groups _Ci-C6 alkyl, _Cx-C6 haloalkyl, _{hydroxy-Ci-C4-alkyl, cyano-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4} -haloalkoxy-C ₄ -alkyl, C ₃ -C ₄ -alkenyloxyCx-CU-alkyl, C ₃ -C _{4 -alkinyloxy-Cx-C4} alkyl, _{C3-C8-cycloalkoxy-C} x -C ₄ -alkyl , amino-C 1 -C ₄ -alkyl, C 1 -C ₄ -alkylamino-C 1 -C ₄ -alkyl, di (C 1 -C ₄ -alkyl) amino-C 1 -C ₄ -alkyl, C 1 -C ₄ -alkylthioC 1 -C ₄ -alkyl ₄ -alkyl, C -C ₄ -haloalkylthio-C x -C ₄ -alkyl, C ₃ -C ₄ -alkenylthio-C x -C ₄ -alkyl, C ₃ -C ₄ -alkinylthioCx -C ₄ -alkyl, C ₄ -C -alkylsulfinyl-C 1 -C ₄ -alkyl; 122 _Ci-C4 -halogenalkylsulf ynyl-C ₄ -alkyl, C ₃ -C ₄ -alkenylsulfinyl-C 1 -C ₄ -alkyl, C ₃ -C ₄ -alkynylsulfinyl-C ₄ -alkyl, Ci-C ₄ -alkylsulfonylCi -C ₄ -alkyl, C ₄ -C -halogenalkylsulfonyl -C ₄ -alkyl, C ₃ -C ₄ -alkenylsulfonyl-C -C ₄ -alkyl, C ₃ -C ₄ -alkylsulfonyl-C 1 -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, cyanoC ₃ -C ₆ -alkenyl, C ₃ -C ₆ -haloalkenyl, C ₃ -C ₆ -alkynyl, cyano-C C ₃ -C ₆ -alkynyl, C ₃ -C 6 -haloalkynyl, hydroxycarbonyl-C 1 -C ₄ -alkyl, (C 1 -C ₄ -alkoxy) carbonylC 1 -C ₄ -alkyl, (C 1 -C ₄ -alkylthio) carbonyl-C 1 -C ₄ -alkyl C ₄ -alkyl, aminocarbonyl-C 1 -C ₄ -alkyl, (C 1 -C ₄ -alkylamino) carbonylC 1 -C ₄ -alkyl, di (C 1 -C ₄ -alkyl) aminocarbonyl-C 1 -C ₄ -alkyl, di (C 1 -C ₄ -alkyl) -C ₄ -alkyl) phosphonyl-C 1 -C ₄ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₈ -cycloalkyl-C ₄ -alkyl, phenyl, _{phenyl-Ci-C4-alkyl,} 3- to 7-membered heterocyclyl or _{heterocyclyl-Ci-C4-alkyl} wherein each heterocyclic ring may contain a carbonyl or thiocarbonyl member, and each cycloalkyl, phenyl and heterocyclyl may be unsubstituted or substituted with one to four substituents selected from the group consisting of cyano, nitro, amino, hydroxy, carboxy, halogen, C 1-6 -C ₄ -alkyl, _Ci-C4 haloalkyl, _Ci-C4 alkoxy, _C3.-C4 haloalkoxy, _Ci-C4 -alkylthio, Ci-C ₄ -haloalkylthio, C 1 -C ₄ -alkylsulfonyl, C 1 -C ₄ -haloalkylsulfonyl, (C 1 -C ₄ -alkoxy) carbonyl, (C 1 -C ₄ -alkyl) carbonyl, (C 1 -C ₄ -haloalkyl) carbonyl, (C 1 -C ₄ -haloalkyl) carbonyl, C ₄ -alkyl) carbonyloxy, _(Ci-C4 haloalkyl) carbonyloxy and di _(Ci-C4 alkyl) amino, or when Z represents a chemical bond, R ⁷ is, if desired, also hydrogen, 123 hydroxy, cyano, mercapto, amino, halogen, -CH (OH) -CH 2 -R ⁹ , -CH (halogen) -CH ₂ -R ⁹ , CH 3 -CH (halogen) -R ⁹ , -CH = CH -R ⁹ or -CH = C (halogen) -R ⁹ , wherein R ⁹ represents hydroxycarbonyl, (C 1 -C ₄ -alkoxy) carbonyl, (C 1 -C ₄ -alkylthio) carbonyl, aminocarbonyl, (C 1 -C ₄ -alkylamino) carbonyl or di (C 1 -C ₄ -alkyl) aminocarbonyl, or R ⁷ and R ⁸ together represent a 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain, which in each case may be optionally unsubstituted or have one to four C 1 -C ₄ -alkyl groups or one or two (C 1 -C ₄ -alkyl) ( _4- alkoxy) carbonyl groups; or an agriculturally useful salt of a compound of formula I. A 3- (benzazol-4-yl) pyrimidinedione derivative of the Formula I according to claim 1, wherein: X represents an oxygen atom, R ¹ represents a hydrogen atom, amino or C 1 -C ₆ -alkyl, R ² is hydrogen, halogen, Cl-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkylsulfonyl, R ³ represents hydrogen, R ⁴ represents hydrogen, fluorine or chlorine, 124 • φ »Φ Φ φ φ φ φ φ φ φ ΦΦ ΦΦ R ⁵ represents cyano or a halogen atom and R ⁶ represents C 1 -C ₆ -alkyl, C ₃ -C ₆ -alkynyl, C 1 -C ₆ -alkylsulfonyl or (C 1 -C ₆ -alkoxy) carbonyl. Use of a 3- (benzazol-4-yl) pyrimidinedione derivative of the formula I or an agriculturally useful salt thereof according to claim 1 as a herbicide. A herbicidal composition comprising a herbicidally effective amount of at least one 3- (benzazol-4-yl) pyrimidinedione derivative of formula I or a salt of a compound of formula I according to claim 1 and at least one liquid and / or solid carrier and optionally at least one surface. active agent. 5. A process for preparing herbicidally active compositions comprising mixing a herbicidally effective amount of at least one 3- (benzazol-4-yl) pyrimidinedione derivative of formula I or a salt of a compound of formula I according to claim 1 and at least one inert liquid and / or or a solid carrier and optionally at least one surfactant. 6. A method for controlling undesirable vegetation comprising treating the plants, their surroundings or their seeds with a herbicidally effective amount of at least one 3- (benzazol-4-yl) pyrimidinedione derivative of the formula I or a salt of the compound of the formula I according to claim 1. . 125 An aryl urea of formula III wherein L ₂ is C 1 -C ₄ -alkyl or phenyl and R ¹ -R ⁵ and Y are as defined in claim 1. An arylanilide of formula IV wherein L ₂ is C 1 -C ₄ -alkyl or phenyl and R ¹ -R ⁵ and Y have the meanings set forth in claim 1. Substituted 2-aminophenol, -thiophenol or -aniline of general formula V - 126 0 0 0 00 00 00 00 * 0000 0000 000 0 000 0 00 0 000 000 000 000 0 00 0000 0000 000 00 00 00 00 wherein claim 1.