Novel 3-(4-cyanophenyl)uracils

Translation of description of equivalent WO 9624590 A1

New 3- (4-cyanophenyl) uracils

description

The present invention relates to novel 3- (4-cyanophenyl) uracils of the general formula I

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in which the variables have the following meanings:

A is hydrogen, methyl or amino;

Y is oxygen or sulfur;

R¹ Hydrogen or halogen;

R2 is hydrogen, halogen, Ci-Cβ-alkyl, -C-C₆Haloalkyl, Ci-Cβ-alkylthio, Ci-Cβ-alkylsulfenyl or Ci-Cε-alkylsulfonyl;

R³ Hydrogen, halogen or -C-C₆alkyl;

R⁴ Hydrogen, Ci-Cβ-haloalkyl, -C-C₆Alkyl, C₃-C_8thCycloalkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl, (Ci-Cβ-alkyl) carbonyl, (C₃-C₆Alkenyl) carbonyl, (C₃-C₆Alkynyl) carbonyl or alkylsulphonyl, each of the last 8 radicals gewünsc case scenario, can carry one to three substituents Substi¬, each selected from the group consisting of

Halogen, nitro, cyano, hydroxy, C.-Cβ cycloalkyl, Ci-Cβ alkoxy, C₃-Cβ-Cycloalkoxy, C₃-C₆Alkenyloxy, C₃-C₆Alkynyloxy, -C-C₆Alkoxy -C-C₆alkoxy, -C-C₆-alkylthio, -C-C₆Alkylsulfenyl, Ci-Cβ-alkylsulfonyl, -C-C₆~ A1 ky1idenaminoxy,

the phenyl, phenoxy or phenylsulfonyl group which may be unsubstituted or bear one to three substituents gene can, in each case selected from the group consisting of Halogen, nitro, cyano, C₆Alkyl, Ci-Cβ-alkoxy and Ci-Cβ-haloalkyl,

a 3- to 7-membered heterocyclyl or hetero- cyclyloxygruppe with one to three hetero atoms selected from the group consisting of two oxygen atoms, two sulfur atoms and 3 nitrogen atoms, where the heterocycle is saturated, partially or fully unsaturated or aromatic and, if desired, can carry one to three substituents each selected from the

Group consisting of halogen, nitro, cyano, C₆Alkyl, Ci-Cβ-alkoxy, -C-C₆Haloalkyl and (Cχ-C₆Alkyl) carbonyl,

- A group -CO-XR⁵, -OCO-XR⁵ or -N (R⁵) R⁶, in which

X is a chemical bond, oxygen, sulfur or -N (R⁶) -; R⁵ for are hydrogen, C₆Alkyl, C₃-C_8thCycloalkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl, -C-C₆Alkoxy -C-C₆alkyl, (-C-C₆Alkoxy) carbo- nyl-Ci-Cβ-alkyl, phenyl or phenyl-C -C-₆alkyl, where the phenyl group and the phenyl ring of phenylalkyl be unsubstituted or may carry one to three radicals, in each case selected from the group consisting of halogen,

Nitro, cyano, C₆-alkyl, C₆Haloalkyl, C_!-C₆Alkoxy and (Ci-Cβ-alkyl) carbonyl

or

X and R⁵ together for a nitrogen linked 3- to

7-membered heterocyclic ring with one to three hetero atoms, aus¬ selected from the group consisting of two oxygen atoms, carry two sulfur atoms and 3 nitrogen atoms, wherein the hetero th be cyclus saturated, partially or fully unsaturated or aromatic, and optionally one to three Substituen¬ may, each selected from the group consisting of halogen, nitro, cyano, Ci-Cε alkyl, -C-C₆Haloalkyl -C-C₆-alkoxy And (-C-C₆Alkyl) carbonyl;

and

R⁶ represents hydrogen, hydroxy, Ci-Cβ alkyl, C₃-Cβ-Cycloalkyl or Ci-Cβ-alkoxy

to stand, and the agriculturally useful salts of the compounds I where A is hydrogen.

The invention also relates

the use of the compounds I as herbicides and / or for the desiccation and / or defoliation of plants,

herbicidal compositions and compositions for the desiccation and / or defoliation of plants which comprise the compounds I as wirk¬ same substances,

A method for controlling undesirable vegetation and for the desiccation and / or defoliation of plants using the compounds I,

A process for the preparation of the compounds I and herbicidal compositions and compositions for the desiccation and / or defoliation of plants using the compounds I, and

novel intermediates of the formulas III and IV, from which the compounds I are obtainable.

Regarding the compounds I where A = hydrogen or methyl, EP-A 255 047 is of particular importance because are already writing in this Druck¬ general 3-aryluracils of the formula II

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where R^a hydrogen, alkyl Cι_, Cι_ -haloalkyl, formyl or C₂_₆alkanoyl,

R^b for Cι-₄Alkyl or Cι-₄Haloalkyl, R³'Is hydrogen, halogen or -C-C₄Alkyl, R^c for an ether group or a radical R-CO-O-, R-CS-O- or R-S0₂-0- and

R^d represent halogen or cyano, and the salts of the compounds II with R^a = Hydrogen, described as herbicides. Examples of 3-phenyluracils, in which the phenyl ring a cyano group in the para-position to uracil residue (R^d) Bears, and their herbicidal action are, however, not take ent this publication.

Certain l-amino-3-phenyluracils, but carry no cyano group on the phenyl ring are already taught in EP-A 517 181 and JP-A 05/025 143 as herbicides.

However, the herbicidal or desiccant / defoliants properties of be¬ knew compounds are not always completely satisfactory. Therefore, there were new this invention, in particular herbicidally active compounds an object which can be uner¬ wished plants better than previously targeted control.

The object also extends to the provision of new de- sikkant / defoliant action.

Accordingly, the 3- (4-cyanophenyl) were uracils of the formula I and their herbicidal action.

Further, have found herbicidal compositions which comprise the compounds I and have a very good herbicidal action. In addition, methods for preparing these compositions and methods for controlling undesirable vegetation using the compounds I were found.

Furthermore, it was found that the compounds I are also suitable for the defoliation and desiccation of parts of plants, whereby eligible for crops such as cotton, potato, rape, sunflower, soybean or field beans, in particular cotton, are suitable. This we have found compositions for the desiccation and / or defoliation of plants, processes for preparing these compositions and methods for the desiccation and / or defoliation of plants using the compounds I..

The compounds of formula I may vary depending on the substitution pattern, contain one or more centers of chirality and then exist as enantiomer or diastereomer mixtures. Subject of the invention are both the pure enantiomers or diastereomers and mixtures thereof.

If A is hydrogen, the 3- (4-cyanophenyl) uracils I be in the form of their agriculturally useful salts, whereby it does not depend on the type of salt generally. In general, the salts of those bases, in which the herbicidal action in comparison with the free compound I is not adversely affected.

As basic salts are particularly those of the alkali metals are metals, preferably sodium and potassium salts, the alkaline earth metals, preferably calcium and magnesium salts, the transition metals of Über¬, preferably zinc and iron salts, and ammonium salts, in which the ammonium if desired, one to three C -C-₄Alkyl, hydroxy-C -C-₄~ Alkyl substituent and / or may carry a phenyl or benzyl, preferably diisocyanate Propyla monium-, tetramethylammonium, tetrabutylammonium, tri- methylbenzylammonium- and trimethyl (2-hydroxyethyl) -ammonium¬ salts, furthermore phosphonium, sulfonium salts such as preferred wise tri (-C-C₄alkyl) sulfonium salts, and sulfoxonium as vorzugseise tri- (-C-C₄~ Alkyl) sulfoxonium.

The substituents for R¹ to R⁶ or genetically as radicals on phenyl rings or heterocycles make organic moieties mentioned - like the term halogen - collective terms for individual enumerations of the individual group members All carbon chains, ie all alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfenyl, alkylsulfonyl. -, alkylcarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkynyl, alkynyloxy, and Alkinylcarbonyl- Alkylidenaminoxy moieties can be straight or branched. Unless otherwise stated preferably carry one to five identical or different halogen atoms, halogenated substituents.

In Specific examples are:

Halogen: fluorine, chlorine, bromine or iodine;

C₁-C Alkyl and the alkyl portions of -C-C₆Alkoxy-Cχ-C₆alkyl and (-C-C₆Alkoxy) carbonyl-C -C₆alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl- propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethyl-propyl, 1-ethylpropyl, 1, 1-dimethylpropyl, 1,2-dimethyl- propyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-Dimethylb tyl, 1,3-Dimethylb tyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1, 2-tri- methylpropl, 1,2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl or l-ethyl-2-methylpropyl; Ci-Cβ-haloalkyl for: a Ci-C_ß-alkyl Radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chloro- difluoromethyl, 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, Petafluor- ethyl, 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl,

2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloro- propyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3, 3,3-trichloropropyl, 2,2, 3, 3, 3-pentafluoropropyl, Heptafluor¬ propyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluoro-butyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 5-fluoro pentyl, 5-chloropentyl, 5-bromopentyl, 5-Iodpentyl, Undecaflu- orpentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or Dodecafluorhexyl;

Phenyl-C_δ-alkyl: for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenyl-prop-1-yl, 1-phenylbut-l-yl , 2-phenylbut-l-yl, 3-phenyl-but-l-yl, 4-phenylbut-l-yl, l-phenylbut-2-yl, 2-phenyl-but-2-yl, 3-phenylbut-2 yl, 3-phenylbut-2-yl, 4-phenyl-but-2-yl, 1- (phenylmethyl) eth-l-yl, 1- (phenylethyl) -1- (methyl) eth-l -yl and 1- (phenylmethyl) prop-1-yl, preferably benzyl, 2-phenylethyl and 2-phenyl-hex-6-yl;

C₃-C₆Alkenyl and alkenyl parts of C₃-cg Alkenyloxy and (C₃-C₆Alkenyl) carbonyl for: prop-1-en-l-yl, prop-2-en-l-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n-butene 3-yl, 1-methyl-prop-l-en-l-yl, 2-methyl-prop-l-en-l-yl, 1-methyl-prop-2-en-l-yl or 2-methyl- prop-2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl-but-1- en-l-yl, 2-methyl-but-l-en-l-yl, 3-methyl-but-1-en-l-yl, l-methyl-but-2-en-l-yl, 2- methyl but-2-en-l-yl, 3-methyl-but-2-en-l-yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-ene l-yl, 3-methyl-but-3-en-l-yl, 1, l-dimethyl-prop-2-en-l-yl, 1,2-dimethyl-prop-1-en-l-yl, l, 2-dimethyl-prop-2-en-l-yl, 1-ethyl-prop-l-en-2-yl, l-ethyl-prop-2-en-l-yl, n-hex-1- en-l-yl, n-hex-2-en-l-yl, n-hex-3-en-l-yl, n-hex-4-en-l-yl, n-hex-5-ene l-yl, 1-methyl-pent-l-en-l-yl, 2-methyl-pent-1-en-l-yl, 3-methyl-pent-l-en-l-yl, 4-methyl- pent-1-en-l-yl, l-methyl-pent-2-en-l-yl, 2-methyl-pent-2-en-l-yl, 3-methyl-pent-2-en-l- yl, 4-methyl- pent-2-en-l-yl, l-methyl-pent-3-en-l-yl, 2-methyl-pent-3-en-l-yl, 3-methyl-pent-3-en-l- yl, 4-methyl pent-3-en-l-yl, l-methyl-pent-4-en-l-yl, 2-methyl-pent-4-en-l-yl, 3-methyl-pent- 4-en-l-yl, 4-methyl-pent-4-en-l-yl, 1, l-dimethyl-but-2-en-l-yl, 1, 1-dimethyl-put-3-en- l-yl, 1, 2-dimethyl-but-l-en-l-yl, 1,2-Dimetyl- put-2-en-l-yl, 1, 2-dimethyl-but-3-en-l- yl, 1,3-Dimetyl- put-1-en-l-yl, 1, 3-dimethyl-but-2-en-l-yl, 1,3-Dimetyl- put-3-en-l-yl, 2, 2-dimethyl-but-3-en-l-yl, 2,3-Dimetyl- put-1-en-l-yl, 2, 3-dimethyl-but-2-en-l-yl, 2, 3-Dimetyl- put-3-en-l-yl, 3, 3-dimethyl-but-l-en-l-yl, 3,3-Dimetyl- put-2-en-l-yl, 1-ethyl but-l-en-l-yl, l-ethyl-but-2-en-l-yl, l-ethyl-but-3-en-l-yl, 2-ethyl-but-l-en-l- yl, 2-ethyl-but-2-en-l-yl, 2-ethyl-but-3-en-l-yl, 1, 1, 2-trimethyl- prop-2-en-l-yl, l- ethyl-l-methyl-prop-2-en-l-yl, l-ethyl-2-methyl-prop-l-en-l-yl or l-ethyl-2-methyl-prop-2-en-l- yl;

C₃-C₆-alkynyl And the alkynyl moieties of C₃-C₆Alkynyloxy and (C₃-C₆-alkynyl) Carbonyl for: prop-1-in-l-yl, prop-2-in-l-yl,

But-1-in-l-yl, but-l-en-3-yl, but-l-yn-4-yl, but-2-in-l-yl, pent-1-yn-l-yl, n-pent-l-en-3-yl, n-pent-l-yn-4-yl, n-pent-l-in-5-yl, n-pent-2-in-l-yl, n- pent-2-yne-4-yl, n-pent-2-in-5-yl, 3-methyl-but-l-en-3-yl, 3-methyl-but-l-yn-4-yl, n-hex-1-yn-l-yl, n-hex-l-en-3-yl, n-

Hex-l-yn-4-yl, n-hex-l-in-5-yl, n-hex-l-in-6-yl, n-hex-2-in-l-yl, n-hex 2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in-l-yl, n-hex-3- in-2-yl, 3-methyl-pent-1-yn-l-yl, 3-methyl-pent-l-en-3-yl, 3-methyl-pent-l-yn-4-yl, 3- methyl-pent-l-in-5-yl, 4-methyl pent-1-yn-l-yl, 4-methyl-pent-2-yne-4-yl or 4-methyl-pent-2-in- 5-yl;

Ci-Cβ-alkoxy and the alkoxy parts of C_-C6-alk- oxy-Ci-Cβ-alkyl and (Ci-Cβ-alkoxy) carbonyl--C-C₆-alkyl: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, l-dimethylpropoxy, 1,2-Dime hylpropoxy, 2,2-dimethyl-propoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methyl- pentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1 dimethyl- butoxy, l, 2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethyl- butoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethyl- butoxy, 2-ethylbutoxy, 1,1 , 2-Trimethylpropoxy, 1,2,2-tri- methylpropoxy, 1-ethyl-l-methylpropoxy or 1-ethyl-2-methyl¬ propoxy; Ci-Cβ alkylthio of: methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methyl- propylthio, 1,1-dimethylethylthio, n-pentylthio, 1-methyl-butylthio, 2 -Methylbutylthio, 3-methylbutylthio, 2,2-Dimethylpropylthio, 1-Ethylpropylthio, n-hexylthio,

1, 1-Dimethylpropylthio, 1,2-Dimethylpropylthio, 1-methyl-pentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methyl-pentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1,3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2,3-dimethyl butylthio, 3,3-dimethylbutylthio, 1-ethylbutyl-thio, 2-ethyl-butylthio, 1, 1, 2-Trimethylpropylthio, 1,2,2-trimethylpropyl thio, 1-ethyl-l-methylpropylthio or l-ethyl-2-methylpropyl thio;

(Ci-Cβ-alkyl) carbonyl for: methylcarbonyl, ethylcarbonyl, n- propylcarbonyl, 1-Methylethylcarbonyl, n-butylcarbonyl, 1-Methylpropylcarbonyl, 2-Methylpropylcarbonyl, 1, 1-dimethyl-ethylcarbonyl, n-pentylcarbonyl, 1-Methylbutylcarbonyl, 2-Methylbutylcarbonyl, 3-Methylbutylcarbonyl, 1,1-dimethyl- propylcarbonyl, 1,2-Dimethylpropylcarbonyl, 2,2-dimethyl- propylcarbonyl, 1-Ethylpropylcarbonyl, hexylcarbonyl, 1-Methylpentylcarbonyl, 2-Methylpentylcarbonyl, 3-methyl-pentylcarbonyl, 4-Methylpentylcarbonyl, 1,1-dimethylbutyl carbonyl, 1,2-Dimethylbutylcarbonyl, 1, 3-dimethylbutyl carbonyl, 2,2-Dimethylbutylcarbonyl, 2, 3-dimethylbutyl carbonyl, 3,3-Dimethylbutylcarbonyl, l-Ethylbutylcarbonyl, 2-Ethylbutylcarbonyl, 1,1,2-Trimethylpropylcarbonyl, 1,2,2-Trimethylpropylcarbonyl, 1-ethyl-l-methylpropylcarbonyl or l-ethyl-2-methylpropylcarbonyl;

-C-C₄~ Alkylsulfenyl for: methylsulphenyl, ethylsulphenyl, n-pro- pylsulfenyl, 1-Methylethylsulfenyl, n-Butylsulfenyl, 1-Methylpropylsulfenyl, 2-Methylpropylsulfenyl, 1, 1-dimethyl-ethylsulphenyl, n-Pentylsulfenyl, 1-Methylbutylsulfenyl, 2-Me thylbutylsulfenyl, 3-Methylbutylsulfenyl, 2,2-dimethylpropyl sulfenyl, 1-Ethylpropylsulfenyl, 1, 1-Dimethylpropylsulfenyl, 1,2-Dimethylpropylsulfenyl, n-Hexylsulfenyl, 1-methylpentyl sulfenyl, 2-Methylpentylsulfenyl, 3-Methylpentylsulfenyl, 4- Methylpentylsulfenyl, 1,1-Dimethylbutylsulfenyl, 1,2-di- methylbutylsulfenyl, 1,3-Dimethylbutylsulfenyl, 2,2-dimethyl-butylsulfenyl, 2,3-Dimethylbutylsulfenyl, 3,3-dimethylbutyl sulfenyl, 1-Ethylbutylsulfenyl, 2- Ethylbutylsulfenyl, 1,1, 2-Trimethylproplsulfenyl, 1,2,2-Trimethylpropylsulfenyl, 1-ethyl-l-methylpropylsulfenyl or l-ethyl-2-methylpropyl sulfenyl; -C-C₄Alkylsulfonyl of: methylsulfonyl, ethylsulfonyl, n-pro- pylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-Methylpropylsulfonyl, 2-Methylpropylsulfonyl, 1, 1-dimethyl-ethylsulfonyl, n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethyl-propylsulfonyl, 1-Ethylpropylsulfonyl, 1, 1-dimethylpropyl sulfonyl, 1,2-Dimethylpropylsulfonyl, n-hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methyl-pentylsulfonyl, 4- methylpentylsulfonyl, 1,1-dimethylbutyl sulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-Dimethylbutyl¬ sulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-Dimethylbutyl¬ sulfonyl, 3,3-dimethylbutylsulfonyl, 1-Ethylbutylsulfonyl, 2- Ethylbutylsulfonyl, 1,1, 2-Trimethylproplsulfonyl, 1,2,2-Trimethylpropylsulfonyl, 1-ethyl-l-methylpropylsulfonyl or l-ethyl-2-methylpropylsulfonyl;

Ci-Cβ-Alkylidenaminoxy for: Acetylidena inoxy, 1-propylidene aminoxy, 2-Propylidenaminoxy, 1-Butylidenaminoxy, 2-Butylidenaminoxy or 2-Hexylidenaminoxy;

C₃-C_8thCycloalkyl of: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

Ca-Cβ-cycloalkoxy for: cyclopropyloxy, cyclobutyloxy, cyclo pentyloxy, cyclohexyloxy, and cycloheptyloxy Cyclooctyloxy.

Examples of 3- to 7-membered heterocycles are oxiranyl, aziridinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, dioxolanyl, such as 1,3-dioxolan-2-yl and 1,3- dioxolan-4-yl, 1,3-dioxan-2-yl, l, 3-dioxane-4-yl, 1, 3-dithian-2-yl, 1,2, -Oxadiazolidinyl, 1,3,4-oxadiazolidinyl , 1,2,4-Thiadiazolidinyl, 1,3,4-Thiadiazoli- dinyl, 1,2,4-Triazolidinyl, 1, 3,4-Triazolidinyl, 2,3-dihydro-furyl, 2,5-dihydrofuryl, 2 , 3-dihydrothienyl, 2,5-dihydrothienyl, 2, 3-pyrrolinyl, 2, 5-pyrrolinyl, 2,3-isoxazolinyl, 3, 4-Isoxazoli- nyl, 4,5-isoxazolinyl, 2,3-Isothiazolinyl, 3 , 4-Isothiazolinyl, 4, 5-Isothiazolinyl, 2, 3-dihydropyrazolyl, 3, -Dihydropyrazolyl, 4, 5-dihydropyrazolyl, 2,3-dihydrooxazolyl, 3,4-dihydrooxazolyl, thiazolyl, imidazolyl, 1,2,4- oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2,4-thiadiazolyl, 1, 3,4-thiadiazolyl, 1,2,4-triazolyl and 1,3,4-triazolyl, piperidinyl, tetrahydropyridazinyl, tetrahydro- pyrimidinyl, Tetrahydropyrazinyl, 1, 3, 5-Tetrahydrotriazinyl and 1,2,4-Tetrahydrotriazinyl, and the following heteroaromatic compounds: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-iso-thiazolyl, 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1-I idazolyl, 2-imidazolyl, 4-imidazolyl, 1 , 2, 4-oxadiazol-3-yl, 1,2, 4-oxadiazol-5-yl,

1,2-thiadiazole-3-yl, 1,2,4-thiadiazol-5-yl, 1,2, 4-triazol-l-yl, 1,2, 4-triazol-3-yl, 1,2 , 4-triazol-4-yl, 1, 3, 4-oxadiazol-2-yl, 1, 3, 4-thiadiazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4 -Pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5-triazine-2-yl and 1,2,4-tri- azin-3-yl, in particular pyridyl, pyri idyl , furanyl and thienyl.

All phenyl and heterocyclic rings are preferably unsubstituted or carry a halogen, methyl, methyl Trifluor¬ or methoxy substituent.

With regard to the use of the compounds of the formula I as herbicides and / or as a defoliant / desiccant effective compounds, the variables preferably have the meanings following Be¬, in each case on their own or in combination:

A is amino or methyl;

Y is oxygen;

R¹ Is hydrogen, fluorine or chlorine, particularly hydrogen or fluorine;

R² -C-C₆-alkyl, C₆Haloalkyl or -C-C₆Alkylsulfonyl, ins¬ special Cχ-C₄Haloalkyl, more preferably methyl Trifluor¬, chlorodifluoromethyl or pentafluoroethyl;

R³ Is hydrogen or halogen, in particular hydrogen, chlorine or bromine;

R⁴ Hydrogen, Ci-Cβ-haloalkyl, -C-C₆Alkyl, C₃-C_8th-cycloalkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl, (C] .- C₆Alkyl) carbonyl, (C₃-C₆Alkenyl) carbonyl or (C₃C6-alkynyl) carbonyl, wherein each of the last 8 radicals may bear optionally one or two substituents each selected from the group consisting of halogen, nitro, cyano, hydroxyl, C₃-Cβ -cycloalkyl, Ci-Cβ-alkoxy, C₃-Cβ-Cycloalkoxy, C₃-C₆Alkenyloxy, C₃C6-alkynyloxy, Ci-Cβ-alkoxy-Ci-Cβ-alkoxy, C_ßAlkylthio, -C-C₆Alkylsulfenyl, -C-C₆Alkylsulfonyl, Ci-Ce-Alkylidenaminoxy, -CO-XR⁵, -OCO-XR⁵ or -N (R⁵) R⁶, In particular are hydrogen, C alkyl, C3-C₆cycloalkyl, C₃-C₄Alkenyl, C₃-C₄Alkynyl, -C-C -Halogeιnalkyl, -C-C₄-alk- Oxy--C-C alkyl, (-C-C₄Alkyl) carbonyl, -CH₂CO-XR⁵, -CH (CH₃) -CO-XR⁵ or -C-C₄Cyanoalkyl such as cyanomethyl, 1-cyano Noeth-1-yl, 2-Cyanoeth-l-yl, 1-cyanoprop-l-yl, 2-cyano-prop-1-yl, 3-cyanoprop-l-yl, l -Cyanoprop-2-yl, 2-cyano- prop-2-yl, 1-Cyanobut-l-yl, 2-Cyanobut-l-yl, 3-Cyanobut-l-yl, 4-Cyanobut-l-yl, l -Cyanobut-2-yl, 2-cyano-but-2-yl, 1-cyano-but-3-yl, 2-Cyanobut-3-yl, l-cyano-2-methyl-prop-3-yl, 2 -cyano-2-methyl-prop-3-yl, 3-cyano-2-methyl-prop-3-yl and 2-cyano-methyl-prop-2-yl;

X is a chemical bond, oxygen or -N (R⁶) -;

R⁵ Hydrogen, Ci-Cβ-alkyl, C3-C_8thCycloalkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl, -C-C₆Alkoxy -C-C₆alkyl or (-C-C₆Alkoxy) carbene bonyl--C-C₆alkyl, in particular hydrogen, Cx-Cβ-alkyl, C₃-C_8thCycloalkyl, -C-C₆Alkoxy -C-C₆alkyl or (-C-C₆Alkoxy) carbonyl-C -C₆alkyl,

R⁶ Hydrogen, Ci-Cβ-alkyl or Ci-Cβ-alkoxy.

Very particularly preferred are the auf¬ in the following table 1 guided compounds Ia (= I where A = A ino, Y = oxygen, R¹ = Fluoro, R² = Trifluoromethyl, R³ = Hydrogen):

<img id="imgf000013_0001" he="30" wi="95" file="imgf000013_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

Table 1

<img id="imgf000013_0002" he="68" wi="163" file="imgf000013_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

<img id="imgf000014_0001" he="242" wi="156" file="imgf000014_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

<img id="imgf000015_0001" he="243" wi="157" file="imgf000015_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /><img id="imgf000016_0004" he="44" wi="156" file="imgf000016_0004.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

Further, the following 3- (4-cyanophenyl) uracils of the formula I For¬ particularly preferred:

the compounds Ib.01 - Ib.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R¹ Hydrogen:

<img id="imgf000016_0001" he="28" wi="93" file="imgf000016_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds Ic.01 - Ic.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R¹ Chlorine:

<img id="imgf000016_0002" he="28" wi="93" file="imgf000016_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds Id.01 - Id.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that A is methyl:

<img id="imgf000016_0003" he="28" wi="93" file="imgf000016_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> the compounds Ie.01 - Ie.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that A is hydrogen:

<img id="imgf000017_0001" he="28" wi="94" file="imgf000017_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds If.01 - If.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R¹ A hydrogen and methyl:

<img id="imgf000017_0002" he="28" wi="93" file="imgf000017_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds Ig.01 - Ig.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R¹ and A are hydrogen:

<img id="imgf000017_0003" he="28" wi="93" file="imgf000017_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds Ih.01 - Ih.94 that of the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R¹ Chlorine and A is methyl:

<img id="imgf000017_0004" he="28" wi="93" file="imgf000017_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> the compounds Ii.01 - Ii.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R¹ Chlorine and hydrogen A:

<img id="imgf000018_0001" he="28" wi="93" file="imgf000018_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds Ik.01 - Ik.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R³ Chlorine:

<img id="imgf000018_0002" he="28" wi="92" file="imgf000018_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds 11:01 - 11.94, which from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R³ Chlorine and A is methyl:

<img id="imgf000018_0003" he="29" wi="92" file="imgf000018_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> the compounds Im.01 - Im.94 that of the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R³ Chlorine and hydrogen A:

<img id="imgf000018_0004" he="28" wi="92" file="imgf000018_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> the compounds In.01 - In.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that R¹ and R³ Chlorine:

<img id="imgf000019_0001" he="29" wi="98" file="imgf000019_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds Io.Ol - Io.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that A is methyl, R¹ Is hydrogen and R³ Chlorine:

<img id="imgf000019_0002" he="28" wi="93" file="imgf000019_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

the compounds Ip.01 - Ip.94 that from the corresponding compounds Ia.01 itself - la.94 only in the unterschei¬ that A is methyl and R¹ and R³ Chlorine:

<img id="imgf000019_0003" he="28" wi="93" file="imgf000019_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

The 3- (4-cyanophenyl) uracils of the formula I are obtainable in various ways, reindeer, for example according to one of the following Verfah:

Method A):

Cyclization of a Enaminesters of formula III or an enamine carboxylate of the formula IV in the presence of a base: <img id="imgf000020_0001" he="81" wi="135" file="imgf000020_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

L¹ means lower alkyl, preferably C₁-C₄Alkyl, or phenyl.

As a rule, is cyclized in an inert organic Lösungs¬ or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic such as benzene and toluene or in a polar solvent such as dimethylformamide and dimethyl sulfoxide. Mixtures of polar solvent and a hydrocarbon such as n-hexane are also suitable. Depending on the starting compound, water may also be suitable as the diluent.

Suitable bases are preferably alkali metal alkoxides, particular ins¬ the sodium alcoholates, alkali metal hydroxides, ins¬ particular sodium hydroxide and potassium, alkali metal carbonates, especially sodium carbonate and potassium carbonate, and metal hydrides, particularly sodium hydride, are suitable. When using sodium hydride as base, it has proven to be advantageous to work in an aliphatic or cyclic ether, in dimethylformamide or in dimethyl sulfoxide.

Normally, 0.5- to 2-fold is the molar amount of base, be¬ coated on the amount of III or IV, for the reaction to succeed sufficient.

In general, the reaction temperature is from (-78) ° C to the boiling point of the respective Reakionsgemisches, especially at (-60) to 60 ° C. Means A in formula III or IV is hydrogen, the process product is obtained as a metal salt, the metal corresponding to the cation of the base used. The salt can be performed über¬ isolated on per se known manner and cleaned or, if desired, by means of acid into the free compound I where A = hydrogen.

Method B):

Methylation of a compound I, in which A represents hydrogen, in the presence of a base:

<img id="imgf000021_0001" he="40" wi="150" file="imgf000021_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

When methylation agents are, for example, methyl halides, preferably methyl chloride, iodide or bromide and dimethyl sulfate, methanesulfonate (methyl mesylate), methyl benzene sulfonate, methoxy (p-toluylsulfon) (methyl tosylate), p-Brombenzolsulfonyl- ethane (Methylbrosylat) Trifluormethansulfonylmethan (methyl triflate) and diazomethane into consideration.

Usually carried out in an inert organic Lösungs¬ medium or in an aprotic solvent, for example in an aliphatic or cyclic ether, preferably in 1,2-dimethoxyethane, tetrahydrofuran or dioxane, in an aliphatic ketone, preferably in acetone , in an amide, preferably in dimethylformamide, in a sulfoxide, preferably in dimethyl sulfoxide, in a urea such as tetramethylurea and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, in a Carbonsäure¬ ester such as ethyl acetate, or in a halogenated ali¬ phatic or aromatic hydrocarbon such as dichloromethane lind chlorobenzene.

Suitable bases are inorganic bases, for example carbonates such as Na riumcarbonat and potassium carbonate, hydrogencarbonates such as sodium and potassium bicarbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, and 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 methylating agent is preferably in each case 0.5- to 2-fold molar amount, based on the amount of starting compound.

In general, the reaction temperature is from 0 ° C to boiling temperature of the reaction mixture, in particular at 0 to 60 ° C.

A preferred process variant consists in that, from the cyclization of III (A = H) or IV (A = H) obtained according to method A) salt of I, without isolation from the reaction mixture, excess base, for example sodium hydride, sodium alcoholate or sodium carbonate may contain, to methylate.

Unless directly produced by the described method as a) cyclisation under basic conditions, can be obtained from the process products of method a) the salts of those compounds I in which A represents hydrogen, in manner known per se. To this end, it is mixed spielsweise the aqueous solution of an inorganic or organi¬'s base with the substituted 3- (4-cyanophenyl) uracil I wherein the A represents hydrogen. Salt formation normally occurs already at 20-25 ° C with sufficient speed.

to produce the sodium salt by dissolving the 3- (4-cyanophenyl) uracil of I (A = hydrogen) in aqueous sodium hydroxide at 20-25 ° C is particularly advantageous with about equivalents amounts of 3- (4-cyanophenyl) uracil and sodium hydroxide are placed ein¬. The salt of the 3- (4-cyanophenyl) uracil can then be isolated, for example by precipitation with a suitable inert solvent or by evaporation of the solvent.

Salts of 3- (4-cyanophenyl) uracils whose metal ion is no alkali metal ion can usually prepared by double decomposition of the relevant entspre¬ alkali metal salt in aqueous solution the wer¬. In this manner, 3- (4-CyanophenyDuracil-Me¬ metal salts prepared, for example, which are insoluble in water.

Method C):

Reacting a 3- (4-cyanophenyl) uracil of the formula I wherein A is hydrogen with an electrophilic A inierungsreagenz in the presence of a base: <img id="imgf000023_0001" he="40" wi="149" file="imgf000023_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

When aminating has been 2,4-dinitrophenoxyamine be¬ particularly useful, however, as well as hydroxylamine-O-sulfonic acid (HOSA) may be used, the nierungsreagenz from literature already considered amino is known (see. Eg, E. Hofer et al ., Synthesis 1983, 466; W. Friedrichsen et al, Heterocycles 20 (1983) 1271;. H. Hart et al, Tetrahedron Lett 25 (1984) 2073;.. B. Vercek et al, Chem Monatsh... 114 (1983) 789;. Sosnousky G. et al, Z. Na¬ turforsch 3_ £ (1983) 884;..... RS Atkinson et al, J. Chem Soc Perkin Trans, 1987, 2787).

The amination can be carried out in manner known per se the wer¬ (see for example T. Sheradsky, Tetrahedron Lett 1948, 1909;. MP Wentland et al, J. Med Chem 21 (1984) 1103 and in particular EP-A 240 194... , EP-A 476 697 and EP-A 517 181, where the amination of uracils is taught).

Normally, the reaction is carried out in a polar Lösungs¬ medium by, for example in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has so far been found suitable as beson¬ IDEM.

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

The amount of base and aminating agent is preferably in each case in the 0.5- to 2-fold molar amount, based on the amount of starting compound.

Depending on the meaning of R⁴ it may be necessary, this Substi¬ substituents prior to amination in a conventional manner to zen schüt¬. This is especially recommended if R⁴ is hydrogen. Method D):

Sulfurizing a 3- (4-cyanophenyl) uracil of the formula I with Y =

Oxygen:

<img id="imgf000024_0001" he="34" wi="143" file="imgf000024_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

The thionation is generally carried out in an inert solvent or diluent, for example in an aromatic Koh¬ lenwasserstoff such as toluene and the xylenes, in an ether such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine.

As sulphurization are particularly suitable phosphorus (V) sulfide and 2, 4-bis (4-methoxyphenyl) -1, 3, 2,4-dithiadi- phosphetan-2, 4-dithione ( "Lawesson's reagent").

Typically, the 1- to 5-fold molar amount, based on the starting compound to be sulfurized, enough for a largely constant voll¬ implementation.

The reaction temperature is normally 20 to 200 ° C, preferably at 40 ° C to the boiling temperature of the reaction mixture.

Method E): ether cleavage of a 3- (4-cyanophenyl) uracil of the formula I, wherein R⁴ an unsubstituted or substituted alkyl, cycloalkyl, alkenyl, alkynyl or benzyl:

<img id="imgf000024_0002" he="28" wi="142" file="imgf000024_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

I (R⁴ = Geg. Subst. alkyl,_{R4 = H \}

Cycloalkyl, alkenyl, alkynyl) ^{κ κ)}

The ether cleavage is usually carried out by means of acid, for example by means of hydrogen bromide, hydrogen iodide or pyridinium hydrochloride, by means of a Lewis acid such as aluminum trichloride, tribromide, -triiodid, boron tribromide, and -trifluorid Eisentri- Chloride, or by means of trimethylsilyl iodide. However, one also lithium salts such as lithium chloride or mixtures of one anorga¬ African iodide and trimethylsilyl chloride are useful to cleave the ether bond. In individual cases, for example, when R⁴ Benzyl, 5, the bonding material even under hydrogenation conditions using hydrogen peroxide solution in the presence of a hydrogenation catalyst such as platinum and palladium are cleaved on activated carbon.

Allyl (R⁴ = Allyl) can also be converted to this known per se manner 10 in the corresponding phenols, for example by isomerization in the presence of a crystallizer for Übergangsmetallkataly¬ Enolether and cleavage of the latter, preferably under slightly acidic conditions (see. Eg T. Greene u. PGM Wutz in "Protective Groups in Organic Synthesis", John Wiley &amp; 15. Sons, 2nd edition New York 1991, p 42ff.).

Usually carried out in an inert solvent or Dilution medium, z. B. in an aliphatic, cyclic or aroma¬ aromatic hydrocarbon such as n-pentane, petroleum ether, cyclohexane,

20, benzene, toluene or xylene, an aliphatic or cyclic ether such as diethyl ether, tert-butylmethyl ether, dimethoxyethane and tetrahydrofuran, an aliphatic or aromatic halogenated hydrocarbon such as dichloromethane, chloroform, Chorben¬ benzene, 1,2-dichloroethane and the dichlorobenzenes, an alcohol such as

25 methanol, ethanol and tert-butanol, an amide such as Dimethylform¬ amide and N-methylpyrrolidone, an amine such as ammonia, or a mixture of such solvents.

A reaction without a solvent may also be advantageous 30th

With respect to particularly preferred embodiments may be made to the comments in Houben-Weyl, "Methods of Organic Chemistry", Georg Thieme Verlag, 4th edition, Stuttgart 1979, Vol. 6 / la / l, p 35 309ff and in RC Larock, "Co prehensive Organic Transforma¬ tions ", VCH Publishers, Weinheim 1989, p 501ff and referenced cited therein.

Method F): 40 alkylation of 3- (4-cyanophenyl) racils of the formula I, wherein R⁴ is hydrogen, in the presence of a base:

45 <img id="imgf000026_0001" he="37" wi="140" file="imgf000026_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> I (R⁴ = Unsubst. o. subst. Alkyl, cycloalkyl, alkenyl o. Alkynyl)

The alkylation may for example with the halide, preferably the chloride or bromide, the sulfate, sulfonate, preferably the methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (tosylate), p-bromobenzenesulfonate (brosylate), the trifluoromethanesulfonate (triflate ) or the diazo compound alkyne be made an un- substituted or substituted alkane, cycloalkane, haloalkane, alkene or.

Is usually carried out in an inert organic medium Lösungs¬, wherein especially aprotic solvents such as aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aliphatic ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, ureas such as tetramethylurea and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone,

Carboxylic acid esters such as ethyl acetate, or halogenated ali¬ phatic or aromatic hydrocarbons such as dichloromethane and chlorobenzene, are also suitable.

Suitable bases are N-diethylaniline are both inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogencarbonates, such as sodium and potassium bicarbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, and organic bases, for example amines such as triethylamine, pyridine and N, or alkali metal such as sodium methanolate, ethanolate and potassium tert-butoxide.

The amount of base and alkylating agent is preferably 0.5- to 2-fold molar amount, based on the amount of I where R⁴ = Hydrogen.

In general, a reaction temperature of 0 ° C to the boiling temperature of the reaction mixture is recommended, in particular from 0 to 60 ° C. Possible regioselectivity problems starting compounds with A = hydrogen can be known per se (use of 2 equivalents of base, introduction of a protective group etc.) avoided in the.

Method G):

Acylating a 3- (4-cyanophenyl) uracil of the formula I, wherein R⁴

is hydrogen with an appropriate alkylating agent.

<img id="imgf000027_0001" he="31" wi="140" file="imgf000027_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

I (R = H) I (R⁴ = (Un) substituted. Alkyl, alkenyl, alkynylcarbonyl)

Suitable acylating agents are, for example the halides, ins¬ particular the acid chlorides, anhydrides, isocyanates or sulfonic fonylchloride alkane, cycloalkane, alkene, alkyne phenyl or Phenylalkancarbonsäuren. But there are also the free acids or their anhydrides, provided that is then worked xylcarbondiimid in the presence of a condensing agent such as carbonyldiimidazole and dicyclohexyl.

Usually carried out in an inert organic solvent or diluent which is preferably aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic ketone such as acetone, an amide such as dimethylformamide, a urea such as tetramethylurea and 1,3-Dimethyltetrahydro2 (1H) -pyrimidinone, a carboxylic acid ester such as ethyl acetate, or a aliphati¬ or aromatic halohydrocarbon such as dichloromethane and chlorobenzene.

Regarding suitable bases, the proportions and the reaction was tion temperature reported ver¬ to the comments under Method F). Method H):

Substitution of halide by cyanide:

<img id="imgf000028_0001" he="31" wi="140" file="imgf000028_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

V

Hal is halogen, preferably fluorine, bromine or iodine.

Suitable cyanides are especially metal cyanides, such as alkali limetallcyanide as lithium, sodium and cyanide Kaliu who expect dalkalimetallcyanide as magnesiu cyanide, or transition-tallcyanide as copper cyanide.

Is usually carried out in an ether such as tetrahydrofuran, dioxane and 1, 2-dimethoxyethane, or in an aprotic polar solvent, for example an alkyl nitrile such as acetonitrile, propionitrile and butyronitrile, an alkylurea such as N, N, N ', N' - tetramethylurea, a chain or cyclic dialkylamide as

Dimethylformamide, N-methyl-2-pyrrolidone, 1, 2-dimethyl-imidazolium din-2-one and 1, 2-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone, a dialkyl sulfoxide such as dimethyl sulfoxide, or hexamethyl triamide.

The evidence indicates that the presence of a catalyst can have an advantageous effect on the reaction course. Useful catalysts include transition metals and their complexes or salts, such as compounds of copper such as copper (I) chloride, iodide, cyanide, or the nickel as Nickei¬ bis-triphenylphosphine dibromide.

In starting compounds V where A = hydrogen, it is advisable to work in the presence of a base, especially weakly nucleophilic bases come into consideration, both anorgani¬ cal bases, eg Alkalimatellcarbonate as sodium and potassium carbonate, alkali metal such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, and organic bases, for example amines such as triethyl amine, pyridine and N, N-diethylaniline. The proportions are usually not critical. In all¬ common is about one to 10 times the amount of cyanide and of base, based on the amount of V sufficient.

The reaction temperature is usually from 50 to 250 ° C; for increasing the selectivity of the reaction it may however also be empfeh¬ mended, at lower temperatures, in particular at about 20 ° C to work.

With respect to various embodiments of this implementation is to Houben-Weyl, "Methods of Organic Chemistry", Georg Thieme Verlag, 4th edition, Stuttgart, 1985, Vol. E5, p 1444ff. and referred to the literature cited therein.

The method I):

Halogenation of a 3- (4-cyanophenyl) uracil of the formula I, wherein R³ is hydrogen

<img id="imgf000029_0001" he="40" wi="151" file="imgf000029_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

The halogenation is generally carried out in an inert organic solvent or diluent see. For chlorination and bromination for example, aliphatic carboxylic acids such as acetic acid, or chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, garb in Be¬. For the iodization low siedendende aliphatic carboxylic acids such as acetic acid are particularly preferred.

For chlorination and bromination are particularly elemen¬ tares chlorine or bromine, or sulfuryl chloride or sulfuryl bromide, at a reaction temperature of preferably 0 to 60 ° C, in particular 10 to 30 ° C.

If desired, can be carried out in the presence of an acid-binding agent, the chlorination and bromination, wherein sodium acetate and tertiary amines such as triethylamine, di ethyl Nilin described and pyridine are particularly preferred. As iodinating agent, elemental iodine is especially preferred, it being possible for in this case the reaction temperature at about 0 to 110 ° C, preferably at 10 to 30 ° C, is.

Particularly advantageously, the iodization is in the presence of a mineral acid such as fuming nitric acid.

The amount of halogenating agent is not critical; normaler¬ employed equimolar amounts of halogenating agent or an excess to about 200 mol%, based on the halo to enjoy Rende reactant.

Excess iodine can be removed, for example, after the reaction by means of saturated aqueous sodium bisulfite solution.

Method K):

Substitution of the nitro group of 3- (4-cyano-3-nitro-phenyl) uraci- len VI by a group -OR:

<img id="imgf000030_0001" he="30" wi="139" file="imgf000030_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

VI

The substitution of the nitro group is usually, by reacting VI with an alkoxide MOR⁴Wherein M is a metal atom, preferably lithium, sodium or potassium (see. For example, Org.Synth. Coll. Vol. III, 293).

As a rule, working either in the alcohol HOR⁴Whose alkoxide is used, or in an inert organic solvent or diluent, for example in an aromatic Koh¬ lenwasserstoff such as toluene and the xylenes, in an ether such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, or in a halogenated hydrocarbon such as dichloromethane and chlorobenzene.

The reaction temperature is generally from 0 to 150 ° C, preferably at room temperature (about 20 ° C) to the boiling temperature of the reaction mixture. The amount of alcoholate is usually not critical; disiloxane is given to approximately 1 to 3 equivalents of alkoxide per mole of VI.

The 3- (4-cyano-3-nitrophenyl) uracils V are themselves, for example uracils from 3- (4-halo-3-nitrophenyl) VII

<img id="imgf000031_0001" he="29" wi="92" file="imgf000031_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

obtainable by reacting the substituted halogen with cyano. The statements made in methods H&gt; apply here correspondingly.

The 3- (4-halo-3-nitrophenyl) uracils VII can in turn be uracils eg by nitration of 3- (4-halophenyl) VIII

<img id="imgf000031_0002" he="29" wi="94" file="imgf000031_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

with nitric acid, nitrating acid with an inorganic nitrate, such as sodium, potassium and ammonium or with an organic nitrate such as amyl see, manufacture.

Suitable solvents for the nitration are preferably an¬ organic acids such as nitric acid and sulfuric acid, organic acids such as acetic acid, or anhydrides such as acetic anhydride.

The reaction temperature is usually from (-20) to 50 ° C, preferably at from (-10) to 30 ° C.

The amount of nitrating agent is not critical; it is normally at the one- to 10-fold molar amount, based on the amount of VI. Method L):

Conversion of 3- (4-aminophenyl) uracils IX into compounds I by the method of Sandmeyer:

<img id="imgf000032_0001" he="32" wi="107" file="imgf000032_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

In this type of reaction, it is usual to provide that the amino group is converted in a known per se in the diazonium salt, and this then in the presence of a transition metal catalyst, in particular a copper (I) salt, expediently suitably copper (I) cyanide, with a metal, preferably with lithium, sodium or potassium cyanide, reacting.

Regarding the process conditions is, for example, to the statements in C. Ferri, "reactions of organic chemistry", Georg Thieme Verlag, Stuttgart 1978, p 319 and in Organic Syn- thesis Coll. Vol 1, S referenced 514 (1941).

The starting compounds IX are preferably prepared by reduction of corresponding nitro compounds with hydrogen in the presence of a metal catalyst consisting of Raney nickel, palladium or platinum, or with a reducing agent such as a tin-II-salt, or iron, to produce. Further information on these known reaction are, for example, DE-A 37 24 399 can be seen.

The compounds IX corresponding nitrided precursors are again expediently by nitration of compounds X Phenylver-

<img id="imgf000032_0002" he="28" wi="47" file="imgf000032_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

available. The respect of the nitration of 3- (4-halo phenyl) uracils VII in method K&gt; statements made shall apply mutatis mutandis for the nitration of phenyluracils X. Method M): Direct cyanidation of a phenyl compound X:

cyanation

The cyanation can be carried out without solvent or in an inert solvent or diluent, beispiels¬ example in an aliphatic, cyclic or aromatic hydro- carbon, such as n-pentane, petroleum ether and cyclohexane, an aliphatic or cyclic ether such as diethyl ether, tert-Bu - methyl ether, dimethoxyethane and tetrahydrofuran, a alipha¬ or aromatic halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane and the dichlorobenzenes, an alcohol such as ethanol, methanol and tert-butanol, an amide such as dimethylformamide and N-methylpyrrolidone , or an a in like ammonia. Mixtures of such solvents are also Be¬ costume.

As cyanide source to Alkylthiocyanate as Methylthiocya- nat {see suitable. eg Synth. Commun. 20, 71 (1990)}, chlorosulfonyl isocyanate (see. Eg, Org. Synth. Coll. Vol VI, p 465), cyanogen, cyanogen chloride and cyanogen bromide, further trichloroacetonitrile {see. this Gazz. Chim. Ital. 121, 283 (1992)}.

The temperature is usually at (-20) to 150 ° C, disiloxane given to at (-10) ° C to boiling point of the cal Reaktionsgemi¬.

The ratio cyanation agent to IX is not critical; it is normally from 1: 1 to 10: 1.

Modifications of this reaction include in Houben-Weyl, "Metho¬ to organic chemistry", Georg Thie e Verlag, Vol. E5, 4. Supervisory would, Stuttgart 1985, pp 1447 ff and described in the literature cited therein.

The starting compounds of formula VI, VII, VIII and IX are known or can be known per se (cf.,. For example, EP-A 255 047, EP-A 517 181 and JP-A 05/025 143).

The Ena in-esters of formula III are new. They may also be used as herbicides.

They can be prepared according to known methods, for example, according to one of following methods.: N)

<img id="imgf000034_0001" he="37" wi="145" file="imgf000034_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

Is preferably carried out under essentially anhydrous conditions in an in¬ Erten solvent or diluent, particularly preferably in Ge presence of an acidic or basic catalyst.

Suitable solvents or diluents are, in particular with Was¬ water azeotropically miscible organic solvents, for example aromatics such as benzene, toluene and o-, m- and p-xylene, halogenated hydrocarbons Koh¬ 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, in consideration.

Acid catalysts are preferably strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluene sulfonic acid, and acidic cation exchangers such as "Amberlyst 15" (Fluka).

The basic catalysts are, for example, metal hydrides such as sodium hydride and particularly preferably metal alcoholates such as sodium and ethanolate.

Expediently reacted XI and the ß-keto ester XII in about stoichiometry trical ratio, or operating with a slight excess of one or other component, to about 10 mol%.

Normally, an amount of catalyst is from 0.5 to 2 mol%, be¬ on the amount of a reactant sufficient.

In general, the reaction is preferably carried out at a temperature of 60 to 120 ° C, for rapid removal of water formed at the boiling temperature of the reaction mixture. O):

<img id="imgf000035_0001" he="37" wi="144" file="imgf000035_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

L² means -C-C₄-alkyl Or phenyl.

15 This reaction can, for example, in an inert, water-miscible organic solvent, for example a ali¬ phatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, especially ethanol, are performed, whereby the normal reaction temperature

20 mally at 50 to 100 ° C, preferably at the boiling temperature of the reaction mixture is.

However, the reaction can also be in an aromatic Verdünnungs¬ medium such as benzene, toluene and o-, m-, p-xylene be carried out

25 to, in which case the addition either of an acidic Kata¬ lysators as hydrochloric acid and p-toluenesulfonic acid or a base, eg an alkali metal alcoholate such as sodium methanolate and sodium ethanolate, is advisable. Also in this process variant, the reaction temperature is usually from 50 to

30 100 ° C, but preferably at 60 to 80 ° C.

Regarding the ratios for the information Me¬ method N) apply.

35 P):

<img id="imgf000035_0002" he="31" wi="134" file="imgf000035_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> XIV XV

45 The reaction takes place preferably in the presence of an in wesentli chen anhydrous aprotic organic solvent or Dilution medium, for example 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, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethyl formamide, hexamethylphosphoric triamide and Dimehylsulfoxid, or a mixture of the stated solvents.

If desired, a metal hydride base such as sodium and potassium hydride, or an organic tertiary base such as triethylamine and pyridine can also be carried out in the presence of, wherein the organic base may simultaneously serve as solvent.

Advantageously used, the starting materials in a stoichiometric ratio or working with a slight excess of one or other component to about 10 mol%. When working without solvent in the presence of an organic base, so this is in a larger excess.

The reaction temperature is preferably from (-80) to 50 ° C, in particular at (-60) to 30 ° C.

In a particularly preferred embodiment, the resulting enamine ester III is converted with excess base directly ( "in situ") in accordance with process A) into the corresponding desired product I.

Q⁾:

<img id="imgf000036_0001" he="31" wi="135" file="imgf000036_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

XIV XVI

L³ means -C-C₄Alkyl or phenyl.

This reaction is advantageously carried out in an aprotic polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously employed in the presence presence of a base, such as a metal or alkaline earth Akalimetall- limetallalkoholats, especially a Natriumalkanolates such as sodium, a Akalimetall- or Erdalkalimetallcarbo- nates, particularly sodium carbonate, or an alkali metal hydride such as lithium and sodium.

Normally, 1- to 2-times the molar amount of base, bezo¬ gene on the amount of XIV or XVI, is sufficient.

The reaction temperature is generally from 80 to 180 ° C, preferably at the boiling temperature of the reaction mixture.

Regarding the ratios of the starting compounds, the statements made for method N) apply.

In a particularly preferred embodiment, one uses a sodium alcoholate as a base and the resulting distilled over Reak¬ tion alcohol continuously. The thus prepared enamine ester III can without isolation from the mixture according to method A Re¬ action&gt; are cyclized I to a salt of the substituted th 3- (4-cyanophenyl) uracils.

R):

<img id="imgf000037_0001" he="30" wi="120" file="imgf000037_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

XVII XVIII

This reaction is advantageously carried out in a substantially anhydrous, aprotic organic solvent or Verdünnungs¬ means, for example, in the presence of an aliphatic or cy¬ clic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic carbons ¬ · hydrogen as n-hexane, benzene, toluene and o-, m- and p-xylene, a halogenated aliphatic hydrocarbon such as

Methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, tien polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of said Solvency. If desired, in presence of a metal such as sodium and potassium hydride, an alkali metal or alkaline earth metal such as sodium methoxide tallalkoholates, ethoxide and potassium tert-butoxide, or an organic nitrogen base such as tri- ethylamine and pyridine are worked, wherein the organic base can simultaneously serve as a solvent.

Is expedient to employ the reactants in stoichiometric amounts or to use one of the components in excess, up to about 20 mol%. When working without a solvent in the presence of a organi¬'s base, so is this advantageous present in an even larger excess.

The reaction temperature is generally from (-80) to 150 ° C, preferably at from (-30) ° C to the boiling point of the respective Reak¬ tion mixture.

The enamine carboxylates of the formula IV are also novel; also they can be prepared in manner known per se, for example from an aniline derivative of the formula VIII as follows Re¬ action schema:

(Gll)

<img id="imgf000038_0001" he="37" wi="154" file="imgf000038_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

XIX XVIII XX

(G12)

<img id="imgf000038_0002" he="34" wi="154" file="imgf000038_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> The reaction according to equation 1 is preferably carried out in an anhydrous inert aprotic solvent, beispiels¬ example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, -, p-xylene, or an aliphatic or cyclic ether such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.

The reaction of XIX with XVIII in accordance with equation (Gll) the reaction temperature is generally from about 70 to 140 ° C, especially at 100 to 120 ° C.

In the reaction according to reaction equation (G12) is an aminolysis which as a rule either without solvent [cf.. for example, J. Soc. Dyes Col. 12, 81 (1926), Ber. £ 4, 970 (1931). Org. Synth., Coll. Vol. IV, 80 (1943) and JACS 20_,, 2402 (1948)] or in an inert anhydrous solvent / diluents, for especially in an aprotic solvent, for example in an aromatic such as toluene and o-, m- and p-xylene, or a halogenated aromatics such as chlorobenzene halo¬ performed becomes.

Here, the work is recommended in the presence of a basic catalyst, for example a higher-boiling amine [see, for. Example Helv. Chim. Acta ü, 779 (1928) and US 2,416,738] or pyridine.

Preferably, the reaction temperature is about 130 to 160 ° C.

In both reactions {(Gll) and (G12)} is given to the starting compounds expediently in approximately stoichiometric amounts or to work with a slight excess of one or other component to about 10 mol. working in the presence of a basic catalyst, as is usually a catalytic amount of °, 5-2 mol%, based on the amount of one of the reactants is sufficient.

The subsequent reaction of the compounds prepared in the formula XX XXI with the amine advantageously results in an essentially anhydrous solvent / diluent at atmospheric pressure durchge, particularly preferably in the presence of an acidic Katalysa¬ sector.

To produce Enamincarboxylaten IV with A = amino, it is advisable compounds XXI with a protected amino group (for example as hydrazone) use. Suitable solvents / diluents are in particular water azeotropically miscible organic liquids, for example Aro¬ formats such as benzene, toluene and o-, m- and p-xylene, or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene, into consideration.

Suitable catalysts are in particular strong mineral 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).

In general, the reaction temperature is from about 70 to 150 ° C; for the rapid removal of the water of reaction is carried out, however, conveniently at the boiling temperature of the reaction mixture.

all processes described above are unless otherwise stated expediently performed at atmospheric pressure or under the inherent pressure of the reaction mixture.

Working up the reaction mixtures is usually done according to known methods, for example by removing the solvent, partitioning the residue in a mixture of water and a suitable organic solvent and Aufar¬ up the organic phase to afford the product.

The 3- (4-cyanophenyl) uracils of the formula I can contain one or more chiral centers and are usually obtained as enantiomer or diastereomer mixtures. The mixtures kön¬ NEN optionally by customary methods, for example by means of crystallization or chromatography on an optically ak¬ tive adsorbate, wer¬ separated into the largely pure isomers to. Pure optically active isomers can be, for example, from corresponding optically active starting materials herstel¬ len.

3- (4-cyanophenyl) uracils I, in which A is hydrogen, can be known per se into their salts, Preferably, in their alkali metal salts, convict (cf.. This also production method b)).

Salts of I whose metal ion is not an alkali metal, can be prepared by double decomposition of the corresponding alkali metal salt in a customary manner, just as ammonium, phosphonium, Sulfonium and sulfoxonium salts by means of ammonia, phosphonium, sulfonium or sulfoxonium.

The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of pure isomers - as herbicides. The herbicidal compositions comprising I control vegetation on non-crop areas very efficiently, especially at high rates of application. In crops such as wheat, rice, maize, soya and cotton, they act against weeds grasses and pollutants without damaging the crop. This effect occurs especially at low application rates.

Depending on the application method, the compounds I, or herbicidal compositions comprising them in a further number of crop plants for eliminating undesirable plants are used. In consideration to Example come example, the following cultures:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. 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), Cucumis sativus, Cynodon dactylon , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum,

(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp ., Nicotiana tabacum (N.ru- stica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense liu, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

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

Also suitable are the 3- (4-cyanophenyl) uracils I also suitable for the desiccation and / or defoliation of plants. As desiccants, they are particularly suitable for desiccating the aerial parts of crop plants such as potato, rape, sunflower and soybean. This allows completely mechanical harvesting of these important crop permits.

Of economic interest is to facilitate harvesting, which is made possible by the concentrated dropping or reduction of adhesion to the branches of citrus fruits, olives or other species and varieties of pomes, drupes and indehiscent fruit. The same mechanism, ie promotion of the formation of abscission tissue between fruit or leaf and shoot of the plants is also essential for the controlled defoliation of useful plants, in particular cotton.

Moreover, shortening of the time interval in which the individual cotton plants mature results in improved fiber quality to post-harvest.

The compounds I or the compositions comprising them can, for example, by in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, Oldisper¬ sions, pastes, dusts, broadcasting agents or granules spraying, atomizing, dusting, spreading or pouring displayed are used. The use forms depend training purposes by the Verwen¬; they should guarantee the finest possible distribution of the active compounds in each case.

Suitable inert auxiliaries for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are essentially: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons pyrrolidone, eg paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg amines such as N-methylpyrrolidone and water ,

Aqueous application forms can be prepared by adding water from emulsion concentrates, suspensions, pastes, wettable powders or water dispersible granules. To prepare emulsions, pastes or oil dispersions, the substances can as such or dissolved in an oil or solvent, can be homogenized by means of wetting agents, adhesives, dispersants or emulsifiers. It can also consist of active ingredient, Wetting agents, adhesives, dispersants or emulsifiers and possibly solvent or oil, and such concentrates are prepared, which are suitable for dilution with water.

Suitable surfactants (adjuvants) are the alkali metal, ammonium salts of aromatic sulfonic acids, eg ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and Alkylarylsulfona en, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl , Tributylphenylpolyglykolether, alkyl arylpolyetheralkohole, isotridecyl, Fettalkoholethylen- oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors or methylcellulose costume in loading.

Powders, dusts and dusts can be prepared by mixing or jointly grinding the active substances with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers are presents. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, Düngemit¬ tel, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell meal, cellulose powder or other solid carriers.

The concentrations of the active ingredients I in the anwendungsfer strength preparations can be varied within wide ranges. In general, the formulations contain from 0.001 to 98 wt .-%, preferably 0.01 to 95 wt .-% of active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% is used to 100% (according to NMR spectrum).

The following formulation examples illustrate the production of such preparations: I. 20 parts by weight of compound no. 1:01 are dissolved in a mixture of alkylated composed of 80 parts by weight of benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-mono- ethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Through the solution into 100 000 parts by weight of water pouring and finely distributing it therein gives an aqueous dispersion which comprises 0.02.% Of the active ingredient.

II. 20 parts by weight of compound no. 1:02 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of Anlagerungsproduk¬ of 40 mol of ethylene oxide consists of 1 mole of castor oil. Through the solution into 100 000 parts by weight of water and finely distributing Pouring% of the active ingredient gives an aqueous dispersion which comprises 0.02. Contains.

III. 20 parts by weight of compound no. 1:03 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mole of castor oil. Through the solution into 100 000 parts by weight of water and finely distributing Pouring% of the active ingredient gives an aqueous Disper¬ sion which comprises 0.02. Contains.

IV. 20 parts by weight of compound no. 1:04 to 3 parts by weight of sodium diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium well mixed salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1.% Of the drug contains.

V. 3 parts by weight of compound no. 1:05 with 97

Parts by weight of finely divided kaolin. This gives a dusting agent which contains 3.% Of the active ingredient. VI. 20 parts by weight of compound no. 1:06 is mixed with 2 parts by weight of calcium dodecylbenzenesulfonate,

8 parts of a fatty alcohol polyglycol ether, 2 Gewichts¬ divide sodium salt of a phenol-urea-formaldehyde condensate and 68 parts of a paraffinic

Mineral oil intimately mixed. This gives a stable oily dispersion.

VII. 1 part by weight of compound no. 1:07 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stabiiles emulsion concentrate.

VIII. 1 part by weight of compound no. 1:08 is used in an

Dissolved mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL¹' consists. This gives a stable emulsion concentrate.

The active ingredients I, or the herbicidal compositions can be applied pre- or postemergence. If the active ingredients by certain crop less compatible, application techniques may be used in which the herbicidal compositions are sprayed with the aid of the spray equipment such that the leaves of sensitive crop plants are not affected if possible, while the active compounds reach the leaves undesirable plants growing underneath or the bare soil surface (post-directed, lay-by).

The application rates of active ingredient I are depending on the control target, the season, the target plants and the growth stage 0.001 to 3.0, preferably 0.01 to 1 kg / ha of active ingredient (ai).

To widen the activity spectrum and to achieve synergistic effects, the 3- (4-cyanophenyl) uracils can I with numerous representatives of other herbicidal or growth-regulating active ingredients are mixed and applied together. For example, suitable mixture, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazole, anilides, aryloxy- / hetaryloxyalkanoic acids and their derivatives, benzoic acid and derivatives thereof, benzo thiadiazinones, 2- (hetaroyl / aroyl) -1,3-cyclohexanediones, hetero- aryl-aryl-ketones, Benzylisoxazolidinone, meta-CF₃-Phenylderivate, Carbamates, quinolinecarboxylic acid and its derivatives, anilides Chloracet-, cyclohexane-1,3-dione derivatives, diazines, Dichlorpropion- acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-one,

1) ethoxylated castor oil (caster-oil) Dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyl- uracils, imidazoles, imidazolinones, N-phenyl-3, 4, 5, 6-tetrahydro-phthalimide, oxadiazoles, oxiranes, phenols, aryloxy- and hetero- 5 aryloxyphenoxypropionsäureester, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils 10 into consideration.

It may also be useful to apply the compounds I, either alone or mixed in combination with other herbicides with other crop protection agents, together, for 15 example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutrient and trace element deficiencies. It is also possible Non-phytotoxic oils and oil concentrates.

20

preparation Examples

example 1

3- [4-cyano-3-methoxy-phenyl] -6-trifluoromethyl-1, 2,3, 4-tetrahydro-pyrimidin-2,4-dione 25 (comp. 1.01)

To a solution of 3- [4-Cyano-3-nitro-phenyl] -6-trifluoro methyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (2.4 g) in anhydrous methanol 50 ml was sodium methoxide (2.8 g of a

given 30 30 percent solution in methanol). Then heated the reaction mixture for 5 hours. At reflux. After cooling, first water (50ml) and then up to a pH of 3 -4 10% aqueous hydrochloric acid was added. Then the ge formed precipitate was separated, washed with water and petroleum ether

see 35 and dried. Yield: 1.1 g; Mp.&gt; 230 ° C.

Example 2 l-amino-3- [4-cyano-3-methoxy-phenyl] -6-me thyl-trif luor¬ 1, 2, 3, 4- tetrahydropyrimidine-2, 4-dione (verb .1. 02)

40

To a solution of 3- [4-cyano-3-methoxy-phenyl] -6-trifluoro-methyl-l, 2,3,4-tetrahydropyrimidine-2,4-dione (1.1 g) in 15 ml of ethyl acetate were added potassium carbonate (1.0 g) and 2,4-Dinitropheno- given xyamin (0.8 g). Then stirred 15 hrs. At 55-60

45 ° C, after which the solids fraction was separated and washed with 30 ml of ethyl acetate and diisopropylether. The verein¬ temperate filtrates were washed twice with 25 ml of water, about dried sodium sulfate and then concentrated. After crystallization with 10 ml diisopropyl ether gave 0.6 g desired product. Mp.&gt; 230 ° C.

Example 3 l-amino-3- [4-cyano-3-hydroxy-phenyl] -6-tr ifluor- methyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (Verb.1.07)

l-Amino-3- [-cyano-3-methoxy-phenyl] -6-trifluoro-methyl-l, 2,3,4-tetrahydropyrimidine-2,4-dione (2.0 g) and Pyridini¬ umhydrochlorid (2 , 1 g) were 2 hrs. stirring at 200-210 ° C. After cooling, the reaction mixture was dissolved in 100 ml of n-butanol and the solution was washed three times with 30 ml of water. The organic phase was dried over sodium sulfate and subsequently the solvent was evaporated. After crystallization with 10 ml diisopropylether and chromatographic purification of the crude product (eluent: dichloromethane / ethyl acetate = 9: 1 to 1: 1) gave 0.4 g desired product. Mp .:&gt; 230 ° C.

example 4

3- [3-allyloxy-4-cyano-phenyl] -l-methyl-6-trifluoro methyl-l, 2,3,4-tetrahydropyrimidine-2,4-dione (comp. 1:08)

To a solution of 3- [3-allyloxy-4-cyano-phenyl] -l-methyl-6-tri- fluoromethyl-l, 2,3,4-tetrahydropyrimidine-2,4-dione (10.1 g) in

130 ml of dimethylformamide were added potassium carbonate (4.6 g) and methyl iodide (2.1 ml, dissolved in 20 ml of dimethylformamide). After 20 hours of stirring at room temperature followed by admixing the Reakti¬ onsmischung with 150 ml water and the resulting precipitate collected, washed with water and petroleum ether and was ge dries. Yield: 2.5 g; Mp .: 158-160 ° C.

In the following Table 2 (4-cyanophenyl) in addition to the aforementioned another 3- listed uracils I, which were prepared in an analogous manner or can be prepared:

<img id="imgf000047_0001" he="29" wi="52" file="imgf000047_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

<img id="imgf000047_0002" he="19" wi="156" file="imgf000047_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /> 0 <img id="imgf000048_0001" he="53" wi="156" file="imgf000048_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

Preparation of the starting compounds:

Example 5 5 3- [4-Cyano-3-nitro-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydro-pyrimidin-2,4-dione

To a solution of 3- [4-fluoro-3-nitro-phenyl] -6-trifluoro methyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (31.9 g) in 250 ml anhydrous 0 N, N-dimethylformamide was added (7.8 g) potassium carbonate (16.6 g) and potassium cyanide. Then stirred the mixture Re¬ action 45 hrs. At 75-80 ° C, which, since the Reak¬ was tion not complete, twice Kaliumcyanaid (together 4.6 g) was added. For work-up yielded 5 cooling water (250 ml) into the reaction mixture. By Zu¬ issuance of 60 ml IN hydrochloric acid to a pH of 2-3 was then adjusted. Having to drive the exempted Blau¬ acid 4 hours. Nitrogen was bubbled through the suspension, the precipitate formed was separated, washed with water and petroleum ether and dried 0. Yield: 17.0 g; Mp .: 135 ° C.

example 6

3- [4-cyano-2-fluoro-5-nitro-phenyl] -l-methyl-6-trifluoro-5-methyl-l, 2,3,4-tetrahydropyrimidine-2,4-dione (comp. 8.2)

To a solution of 3- [2,4-difluoro-5-nitro-phenyl] -l-methyl-6-trifluoromethyl-1,2,3,4-tetrahydro-pyrimidin-2,4-dione (2, 5 g) in 50 ml of anhydrous dimethyl sulfoxide

40 potassium cyanide (0.5 g) was added. Followed by stirring the reaction mixture 10 h. At room temperature, and after 5 hrs. Further potassium cyanide (0.16 g) was added. For workup, the solvent is largely removed at 80 ° C under high vacuum. The residue was taken up in 150 ml of water, three times with

washed 45 30 ml of water, dried over sodium sulfate and concentrated einge¬. After chromatography on silica gel (dichloromethane as running medium) and crystallization with petroleum ether gave 1.2 g of the desired product; Mp .: 155-157 ° C.

In an analogous manner the following compounds of Table 3 were prepared:

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5

<img id="imgf000049_0002" he="24" wi="156" file="imgf000049_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /> n Application examples (herbicidal activity)

The herbicidal activity of 3- (4-cyanophenyl) uracils I was demonstrated by the following greenhouse experiments:

₅ The vessels employed were plastic flowerpots containing loamy sand with about 3.0% humus. The seeds of the test plants were sown separately for each species.

In Vorauf1aufbehandlung were suspended in water or _Q emulsified active ingredients applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants grown wa¬ reindeer. This cover caused uniform germination of the test 5 plants, unless this has been impaired by the chemicals ,

For the purpose of post-emergence Treatmen t the test plants were depending on growth form of 3 to 15 cm tightened 0 gen only up to a height and then suspended with or emulsified in water active ingredients which treats. The test plants were either sown directly and grown in the same containers, or they wur¬ the first as seedlings fed separately and transplanted some days before the treatment in the test vessels. The application rate₅ for the postemergence treatment was 0.0156 or 0.0078 kg / ha of as (active substance). The plants were kept species-specifically at temperatures of 10 to 25 ° C or 20 to 35 ° C. The test period extended over 2 to 4 weeks. During this time the plants were tended, and their reaction to the individual treatments was evaluated.

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

The plants used in the greenhouse experiments belonged to the following species:

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At an application rate of 0.0156 or 0.0078 kg / ha of active compound no. 1:02 postemergence showed a very good action against the abovementioned plants.

Examples (desikkative / defoliant activity)

The test plants used were young, 4-leaved (without seed leaves) cotton plants, which were grown under greenhouse conditions (relative humidity 50 to 70%;. Day / night temperature = 27/20 ° C).

The young cotton plants were dripping wet with aqueous preparations of the active ingredients Aufbe¬ (an addition of 0.15 wt of the fatty alcohol alkoxylate Plurafac LF 700, based on the spray mixture) leaf treated. The expelled assermenge was converted in 1000 1 / ha. After 13 days, the number of dropped Blät¬ ter and the degree of defoliation in% were determined.

In the untreated control plants, no leaf fall occurred.