DE4440914A1 - Substituted diazacyclohexanedi (thi) one - Google Patents

Abstract

The invention concerns novel diazacyclohexane di(thi)ons of general formula (I) in which R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, Q<1> and Q<2> have the meanings given in the description. The invention further concerns a process for their preparation and their use as herbicides.

Description

The invention relates to novel diazacyclohexanedi (thi) ones, a process for their preparation position and their use as herbicides.

It is known that certain diazacyclohexanedi (thi) ones have herbicidal properties have (see US 4927451 and JP 06092943). Those from the specified patent However, known compounds have no significant importance obtained.

There have now been the new diazacyclohexanedi (thi) one of the general formula (I) found,

in which
Q¹ is oxygen or sulfur,
Q² is oxygen or sulfur,
R¹ is hydrogen, cyano, nitro, halogen, alkyl or haloalkyl,
R 2 represents hydrogen, cyano, nitro, thiocarbamoyl, halogen or represents in each case optionally halogen-substituted alkyl or alkoxy,
R³ represents the following grouping,

-A A²-A³

wherein
A¹ represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the group -N-A⁴-, wherein A⁴ is hydrogen (in which case R² is not halogen), hydroxy, alkyl, alkoxy, aryl , Alkylcarbonyl, alkylsulfonyl or arylsulfonyl, or
A¹ furthermore represents in each case optionally substituted alkanediyl, alkynediyl, azaalkendiyl, alkynediyl, cycloalkanediyl, cycloalkendiyl or arendiyl,
A² represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen, hydroxy, alkyl, alkoxy, aryl, alkylcarbonyl, alkylsulfonyl or aryl sulfonyl,
A² furthermore represents optionally substituted alkanediyl, alkene diyl, azaalkendiyl, alkynediyl, cycloalkanediyl, cycloalkendiyl or arendiyl, and
A³ represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyano, thiocyanato, nitro, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, dialkoxy (thio ) phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkynyl, alkynyloxy, alkynylamino, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, aryl, aryloxy, arylalkyl, arylalkoxy, heterocyclyl, heterocyclylalkyl or heterocyclylalkoxy,
R⁴ is hydrogen, halogen, alkyl or haloalkyl,
R⁵ is alkyl or haloalkyl, and
R⁶ is hydrogen, amino, hydroxy or each optionally substituted alkyl or cycloalkyl.

The novel diazacyclohexanedi (thi) ones of the general formula (I) are obtained when uracils of the general formula (II)

in which
Q¹, Q², R¹, R², R³, R⁴, R⁵ and R⁶ have the meanings given above,
with a hydrogenating agent, if appropriate in the presence of a catalyst and optionally in the presence of a diluent.

The new Diazacyclohexandi (thi) one of the general formula (I) are distinguished by strong and selective herbicidal activity.

The invention preferably compounds of formula (I), in which
Q¹ is oxygen or sulfur,
Q² is oxygen or sulfur,
R¹ is hydrogen, cyano, nitro, fluorine, chlorine, bromine or optionally fluorine- and / or chlorine-substituted alkyl having 1 to 4 carbon atoms,
R² represents hydrogen, cyano, nitro, thiocarbamoyl, fluorine, chlorine, bromine or represents in each case optionally fluorine- and / or chlorine-substituted alkyl or alkoxy having in each case 1 to 4 carbon atoms,
R³ represents the following grouping,

-A A²-A³

in which
A¹ is a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen (in which case R² is not fluorine, chlorine or bromine), hydroxy, C₁ C₄-alkyl, C₁-C₄-alkoxy, phenyl, C₁-C₄-alkylsulfonyl or phenylsulfonyl,
A¹ further for each optionally substituted by fluorine, chlorine or bromine-substituted C₁-C₆ alkanediyl, C₂-C₆-alkenediyl, C₂-C₆ azaalkene diyl, C₂-C₆ alkynediyl, C₃-C₆ cycloalkanediyl, C₃-C₆ cycloalkendiyl or phenylene stands,
A² represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, in which A⁴ represents hydrogen, hydroxy, C₁-C₄-alkyl, C₁-C₄-alkoxy, phenyl, C₁- C₄-alkylsulfonyl or phenylsulfonyl,
A² further for each optionally substituted by fluorine, chlorine or bromine C₁-C₆-alkanediyl, C₂-C₆-alkenediyl, C₂-C₆-azaalkylene diyl, C₂-C₆-alkynediyl, C₃-C₆-cycloalkanediyl, C₃-C₆-cycloalkendiyl or phenylene stands,
A³ is hydrogen, hydroxy, amino, cyano, isocyano, thiocyanato, nitro, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen, in each case optionally substituted by halogen or C₁-C₄-alkoxy substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino , Dialkylamino, or dialkoxy (thio) phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkynyl, alkynyloxy or alkynylamino having in each case 2 to 6 carbon atoms in the alkenyl, Alkylidene or alkynyl groups, each optionally substituted by halogen, cyano, carboxy, C₁-C₄-alkyl and / or C₁-C₄-alkoxy-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy or cycloalkylideneamino each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or for each GE optionally by nit ro, cyano, carboxy, halogen C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkyloxy, C₁-C₄-haloalkyloxy and / or C₁-C₄alkoxycarbonyl-substituted phenyl, phenyloxy, phenyl-C₁-C₄ -alkyl or phenyl-C₁-C₄-alkoxy, (in each case if wholly or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, iso thiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl , Pyrazolyl-C₁-C₄-alkyl, furyl-C₁-C₄-alkyl, thienyl-C₁-C₄-alkyl, oxazolyl-C₁-C₄-alkyl, isoxazole-C₁-C₄-alkyl) thiazole-C₁-C₄-alkyl, pyridinyl C₁-C₄alkyl, pyrimidinyl-C₁-C₄alkyl, pyrazolylmethoxy, furylmethoxy, is perhydropyranylmethoxy or pyridyl methoxy,
R⁴ is hydrogen, halogen or optionally fluorine- and / or chlorine-substituted alkyl having 1 to 4 carbon atoms,
R⁵ is optionally substituted by fluorine and / or chlorine-substituted alkyl having 1 to 4 carbon atoms, and
R⁶ is hydrogen, amino, hydroxy, optionally substituted by fluorine and / or chlorine-substituted alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

In the definitions are the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl - also in conjunction with Heteroatoms, such as in alkoxy, alkylthio or alkylamino - in each case straight-chain or branched.

Halogen is generally fluorine, chlorine, bromine or iodine, preferably Fluorine, chlorine or bromine, in particular for fluorine or chlorine.

The invention relates in particular to compounds of the formula (I) in which
Q¹ is oxygen,
Q² is oxygen,
R¹ is hydrogen, fluorine or chlorine,
R² is cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl,
R³ represents the following grouping,

-A A²-A³

in which
A¹ represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen (in which case R² is not chlorine or bromine), hydroxy, methyl, ethyl , n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl or ethylsulfonyl,
A¹ furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2 -diyl, propene-1,2-diyl, propene-1,3-diyl, ethyne-1,2-diyl, propyne-1,2-diyl or propyne-1,3-diyl,
A² is a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n - or i-propoxy, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or phenylsulfonyl,
A² further for methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2 -diyl, propene-1,2-diyl, propene-1,3-diyl, ethyne-1,2-diyl, propyne-1,2-diyl or propyne-1,3-diyl,
A³ represents hydrogen, hydroxyl, amino, cyano, nitro, carbamoyl, sulfo, fluorine, chlorine, bromine, in each case optionally fluorine, chlorine, methoxy or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i- , s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n - or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, dimethoxyphosphoryl, diethoxy phosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, in each case optionally by fluorine or chlorine substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylideneamino, propynyl, butynyl, propynyloxy, butynyloxy, propynylamino, butynylamino, for each given optionally substituted by fluorine, chlorine, cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, Cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, or each optionally substituted by nitro, cyano, carboxy, fluoro, chloro, bromo, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy , n- or i-propoxy, di-fluoromethoxy, trifluoromethoxy, methoxycarbonyl and / or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, Oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylme methyl, thienylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolemethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy,
R⁴ represents hydrogen, fluorine, chlorine, bromine or represents in each case optionally fluorine- and / or chlorine-substituted methyl or ethyl,
R⁵ is in each case optionally substituted by fluorine and / or chlorine-substituted methyl or ethyl, and
R⁶ is hydrogen, amino, each optionally substituted by fluorine and / or chlorine, methyl or ethyl or cyclopropyl.

The general or preferred radicals given above Definitions apply to both the end products of the formula (I) and ent speaking for each required for the preparation starting materials or Intermediates. These remainders can be used with each other, so too between the specified ranges of preferred compounds, any kom be combined.  

For example, using 1- (2,4-dichloro-5-methoxy-phenyl) -3,6-dihydro-2,6- dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine and hydrogen in the presence of platinum as starting materials, the reaction sequence in the inventive according to the method are outlined by the following formula scheme:

The process of the invention for the preparation of the compounds of all of the general formula (I) as starting materials to be used uracils are by the Formula (II) generally defined. In the formula (II), Q¹, Q², R¹, R², R³, R⁴, R⁵ and R⁶ preferably or in particular those meanings that already above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for Q¹, Q², R¹, R², R³, R⁴, R⁵ and R⁶ were specified.

The starting materials of the formula (II) are known and / or may according to be Methods were known (see US 5084084, US 5127935, US 5,154,405, US 5169430, DE 43 27 743, DE 43 43 451, DE 44 14 326, Herstellungsbei games).

The process according to the invention for the preparation of the compounds of the formula (I) is carried out using a hydrogenating agent. They come customary for the hydrogenation of carbon-carbon double bonds ge suitable means. These include, for example, hydrogen (in counter a catalyst), lithium alanate (LiAlH₄), lithium borohydride (LiBH₄), Sodium boranate (NaBH₄) and potassium borohydride (KBH₄).

The inventive method is optionally - especially at Hydrogenation with hydrogen - carried out in the presence of a catalyst. It In this case, preferably the usual hydrogenation catalysts come into consideration.  

These include, for example, Raney nickel or Raney cobalt, platinum or Palladium (the latter optionally on a support material such as carbon).

As a diluent for carrying out the method according to the invention the usual organic solvents come into consideration. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as pentane, hexane, heptane, petroleum ether, Ligroin, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, Methylcyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as di ethyl ether, diisopropyl ether, t-butyl methyl ether, t-pentyl methyl ether, dioxane, Tetrahydrofuran, ethylene glycol dimethyl or diethyl ether, diethylene glycol dimethyl ether or diethyl ether; Ketones, such as acetone, butanone or methyl iso butyl ketone; Nitriles, such as acetonitrile, propionitrile, butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters like vinegar acid methyl ester, ethyl ester, n- or i-propyl ester, n-, i- or iso-butyl ester, Sulfoxides, such as dimethylsulfoxide; Alcohols, such as methanol, ethanol, n- or i-Pro panol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; their Mixtures with water or pure water.

The reaction temperatures can in carrying out the inventive Be varied in a wider range. In general works at temperatures between -20 ° C and + 100 ° C, preferably at tempera tures between -10 ° C and + 80 ° C.

The process according to the invention is generally carried out under atmospheric pressure guided. However, it is also possible under elevated or reduced pressure - generally between 0.1 bar and 100 bar - to work.

To carry out the method according to the invention are each required The starting materials are generally used in approximately equimolar amounts. However, it is also possible, one of the two components used in each case to use a larger excess. The reactions are in general in a suitable diluent, if appropriate in the presence of a  Catalyst carried out, and the reaction mixture is several hours at stirred the required temperature. The workup takes place at the Process according to the invention in each case by customary methods (cf. position examples).

The active compounds according to the invention can be used as defoliants, desiccants, cabbage killer and in particular be used as a weed killer. By weeds in the broadest sense are meant all plants in places grow up where they are unwanted. Whether the substances of the invention as a total or selective herbicides, depends essentially on the one used Amount off.

The active compounds according to the invention can, for. B. be used in the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means up these types are limited, but extend in the same way other plants.

The compounds are suitable depending on the concentration to total weed control z. B. on industrial and railway lines and on ways and Places with and without tree cover. Likewise, the connections to the Weed control in permanent crops, eg. Forest, ornamental, fruit, wine, Citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hops, on ornamental and sports turfs and grazing land and for selective Weed control in one-year crops.

The compounds of the formula (I) according to the invention are particularly suitable for selective control of dicotyledonous weeds in monocots and dicots Cultures both pre-emergence and post-emergence.

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

These formulations are prepared in a known manner, for. B. by Vermi rule the active ingredients with extenders, ie liquid solvents and / or fe carriers, optionally with the use of surfactants So, emulsifiers and / or dispersants and / or foam-producing Means.

In the case of using water as an extender z. B. also organic Solvent can be used as auxiliary solvent. As liquid solvents are essentially in question: aromatics, such as xylene, toluene, or alkylnaph Thaline, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chloroethylenes or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, for. B. petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and theirs  Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents, such as dimethylformamide and Dimethyl sulfoxide, as well as water.

Suitable solid carriers are:
z. As ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as finely divided silica, alumina and silicates, as solid carriers for granules are: z. Broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents are in question: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylarylpolyglykolether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; as Disper giermittel come into question: z. As lignin-sulphite liquors and methylcellulose.

In the formulations, adhesives such as carboxymethylcellulose, natural and synthetic powders, granules or latices used as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic ones Phospholipids. Other additives may be mineral and vegetable oils.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalo cyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, Cobalt, molybdenum and zinc are used.

The formulations generally contain between 0.1 and 95 Weight percent of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in theirs Formulations also in mixture with known herbicides for  Weedbekämpfung find use, where finished formulations or Tank mixes are possible.

For the mixtures known herbicides come into question, for example, anilides, such as Diflufenican and propanil; Arylcarboxylic acids, such as. B. Dichloro-picolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2.4D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, Haloxyfop-methyl and Quizalofop-ethyl; Azinones, such as B. Chloridazon and norflurazon; Carbamates, such as. B. Chlorpropham, Desmedipham, Phenmedipham and Prophet; Chloroacetanilides, such as. Alachlor, acetochlor, butachlor, Metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines, such as. B. Oryzalin, pendimethalin and trifluralin; Diphenyl ether, such as. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxyfluorfen; Urea, such as. Chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxylamines, such as. Alloxydim, clethodim, cyclo xydim, sethoxydim and tralkoxydim; Imidazolinones, such as Imazethapyr, Imazamethabenz, Imazapyr and Imazaquin; Nitriles, such as. Bromoxynil, Dichlobenil and ioxynil; Oxyacetamides, such as. B. mefenacet; sulfonylureas, such as Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, Cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates, such as Butylates, cycloates, dialkylates, EPTC, esprocarb, molinates, prosulfocarb, Thiobencarb and triallates; Triazines, such as. Atrazine, cyanazine, simazine, Simetryne, Terbutryne and Terbutylazine; Triazinones, such as. Hexazinone, Metamitron and metribuzin; Other, such as B. aminotriazole, benfuresates, Bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, Ethofumesates, fluorochloridones, glufosinates, glyphosates, isoxaben, pyridates, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.

Also a mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellents, plants nutrients and soil conditioners is possible.  

The active compounds can be used as such, in the form of their formulations or the resulting prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules applied become. The application is done in the usual way, for. B. by pouring, spraying, Spraying, sprinkling.

The active compounds according to the invention can be used both before and after Emergence of the plants are applied. You can also before sowing in the Ground to be incorporated.

The amount of active ingredient used can vary within a substantial range. you depends essentially on the nature of the desired effect. In general the application rates are between 10 g and 10 kg of active ingredient per hectare of soil surface, preferably between 50 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention starts the following examples.  

Preparation Examples Example 1

2.03 g (5 mmol) of 1- (4-cyano-2-fluoro-5-methylsulfonylphenyl) -3,6-dihydro-2,6- dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine and 300 mg palladium on carbon (10%) are presented in 30 ml of tetrahydrofuran. At 20 ° C becomes hydrogen pressed and the reaction mixture is then under the hydrogen Atmosphere stirred for 24 hours. It is then filtered, the filtrate in water concentrated by evaporation under vacuum and the residue was purified by column chromatography (silica gel, Chloroform / ethyl acetate, vol. 1: 1).

This gives 0.5 g (25% of theory) of 1- (4-cyano-2-fluoro-5-methylsulfonyl-phenyl) - hexahydro-2,6-dioxo-3-methyl-4-trifluoromethyl-pyrimidine. Melting point <250 ° C.

example 2

2.03 g (5 mmol) of 1- (4-cyano-2-fluoro-5-methylsulfonylphenyl) -3,6-dihydro-2,6- dioxo-3-methyl-4-trifluoromethyl-1 (2H) -pyrimidine are dissolved in 20 ml of tetrahydrofuran submitted and cooled to 0 ° C. At this temperature, 210 mg (5.5  mmol) of sodium borohydride (NaBH₄) is added thereto and the reaction mixture is then stirred at 0 ° C for 3 hours. Subsequently, 30 ml of 5% hydrochloric acid added to this and the mixture is reacted with 50 ml of ethyl acetate shakes. The organic phase is separated, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and the residue column chromatography (silica gel, chloroform / ethyl acetate, vol. 1: 1) worked up.

This gives 0.5 g (25% of theory) of 1- (4-cyano-2-fluoro-5-methylsulfonyl-phenyl) - hexahydro-2,6-dioxo-3-methyl-4-trifluoromethyl-pyrimidine. Melting point <250 ° C.

Analogously to Examples 1 and 2 and according to the general Description of the production process according to the invention can, for example example, the compounds listed in Table 1 below Formula (I) are produced.

Starting materials of the formula (II) Example (II-1)

1.8 g (10 mmol) of ethyl 3-amino-4,4,4-trifluoro-crotonsäure are dissolved in 30 ml of di submitted to methylformamide and 2 ml of toluene and at 0 ° C to 5 ° C with 0.3 g (10 mmol) of sodium hydride (80%). The mixture is at 0 ° C for 30 minutes stirred to 5 ° C. After cooling the mixture to -70 ° C., 0.9 g (5 mmol) 4-Cyano-2,5-difluoro-phenyl isocyanate - dissolved in 10 ml of toluene - added to and the mixture is stirred for 150 minutes at -60 ° C to -70 ° C. After removing the Cooling bath 2 ml of acetic acid are added. Then use water to about diluted twice the volume and extracted with ethyl acetate. The organic phase is concentrated and the residue with diisopropyl ether to Crystallization brought.

This gives 1.1 g (69% of theory) of 1- (4-cyano-2,5-difluoro-phenyl) -3,6-dihydro- 2,6-dioxo-4-trifluoromethyl-1 (2H) -pyrimidine of melting point 194 ° C.  

Example (II-2)

A mixture of 0.83 g (3 mmol) of 1- (4-cyano-2,5-difluorophenyl) -3,6-dihydro- 2,6-dioxo-3,4-dimethyl-1 (2H) -pyrimidine, 0.32 g (3 mmol) methanesulfonamide, 0.6 Potassium carbonate and 10 ml of dimethyl sulfoxide are heated at 120 ° C for 10 hours. After cooling, the mixture is poured onto ice-water and treated with 2N hydrochloric acid acidified. Then it is extracted with ethyl acetate, the organic phase washed with water, dried with sodium sulfate and filtered. From the filtrate will The solvent is carefully distilled off in a water-jet vacuum.

This gives 0.8 g (76% of theory) of 1- (4-cyano-2-fluoro-5-methylsulfonylamino) - 3,6-dihydro-2,6-dioxo-3,4-dimethyl-1 (2H) -pyrimidine as a crystalline residue (Melting point <250 ° C).  

applications example A Post-emergence test

Solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Part by weight of active ingredient with the stated amount of solvent, indicates the given amount of emulsifier and the concentrate is diluted with water on the desired concentration.

With the preparation of active compound injected test plants, which have a height of 5 15 cm have such that the respective desired amounts of active ingredient per unit area be applied. The concentration of the spray mixture is chosen so that in 2000 l of water / ha, the respective desired amounts of active ingredient are applied. After three weeks, the degree of damage to the plants is rated in% Damage compared to the development of the untreated control.

It means:

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

In this test, for example, show the compounds according to the manufacturing Examples 1 and 2 with good compatibility with crops, such. B. Wheat (10%) and an application rate of 500 g / ha strong effect against Weeds such as Amaranthus (95-100%), Ambrosia (90-100%), Polygonum (100%), viola (90-95%) and xanthium (95-100%).  

example B Pre-emergence test

Solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Part by weight of active compound with the stated amount of solvent, indicates the added amount of emulsifier and the concentrate is diluted with water on the desired concentration.

Seeds of the test plants are sown in normal soil and after 24 hours doused with the preparation of active ingredient. You keep the amount of water per Area unit expediently constant. The drug concentration in the Preparation does not matter, only the application rate is decisive Active ingredient per unit area. After three weeks, the degree of damage of the Plants scored in% damage compared to the development of untreated control. It means:

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

In this test, for example, show the compounds according to the manufacturing Examples 1 and 2 with good compatibility with crops, such. B. Corn (0%) and an application rate of 500 g / ha strong effect against Weeds such as Amaranthus (95-100%), Ambrosia (100%), Galinsoga (100%), Polygonum (90-100%) and Solanum (95-100%).

Claims (8)

1. diazacyclohexanedi (thi) one of the general formula (I) in which
Q¹ is oxygen or sulfur,
Q² is oxygen or sulfur,
R¹ is hydrogen, cyano, nitro, halogen, alkyl or haloalkyl,
R² represents hydrogen, cyano, nitro, thiocarbamoyl, halogen or represents in each case optionally halogen-substituted alkyl or alkoxy,
R³ is the following moiety, -A¹-A²-A³worin
A¹ represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen (in which case R² is not halogen), hydroxy, alkyl, alkoxy, aryl , Alkylcarbonyl, alkylsulfonyl or aryl sulfonyl, or
A¹ furthermore represents in each case optionally substituted alkanediyl, alkenediyl, azaalkendiyl, alkynediyl, cycloalkanediyl, cycloalkendiyl or arendiyl,
A² represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, in which A⁴ represents hydrogen, hydroxyl, alkyl, alkoxy, aryl, alkylcarbonyl, alkylsulfonyl or arylsulfonyl,
A² furthermore represents optionally substituted alkanediyl, alkenediyl, azaalkendiyl, alkynediyl, cycloalkanediyl, cycloalkendiyl or arendiyl, and
A³ represents hydrogen, hydroxyl, mercapto, amino, cyano, isocyano, thiocyanato, nitro, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, dialkoxy ( thio) phosphoryl, alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkynyl, alkynyl oxy, alkynylamino, cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino, aryl, aryloxy, arylalkyl, arylalkoxy, heterocyclyl, heterocyclylalkyl or heterocyclylalkoxy,
R⁴ is hydrogen, halogen, alkyl or haloalkyl,
R⁵ is alkyl or haloalkyl, and
R⁶ is hydrogen, amino, hydroxy or each optionally substituted alkyl or cycloalkyl. 2. Diazacyclohexandi (thi) one of the general formula (I) according to claim 1, characterized in that
Q¹ is oxygen or sulfur,
Q² is oxygen or sulfur,
R¹ is hydrogen, cyano, nitro, fluorine, chlorine, bromine or optionally substituted by fluorine and / or chlorine-substituted alkyl having 1 to 4 carbon atoms,
R² represents hydrogen, cyano, nitro, thiocarbamoyl, fluorine, chlorine, bromine or represents in each case optionally substituted by fluorine and / or chlorine-substituted alkyl or alkoxy having in each case 1 to 4 carbon atoms,
R³ is the following moiety, -A¹-A²-A³ in which
A¹ is a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen (in which case R² is not fluorine, chlorine or bromine), hydroxy, C₁ C₄-alkyl, C₁-C₄-alkoxy, phenyl, C₁-C₄-alkylsulfonyl or phenylsulfonyl,
A¹ furthermore represents in each case optionally substituted by fluorine, chlorine or bromine-substituted C₁-C₆-alkanediyl, C₂-C₆-alkenediyl, C₂-C₆- azaalkendiyl, C₂-C₆-alkinediyl, C₃-C₆-cycloalkanediyl, C₃-C₆- cycloalkendiyl or phenylene .
A² represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, in which A⁴ represents hydrogen, hydroxy, C₁-C₄-alkyl, C₁-C₄-alkoxy, phenyl, C₁- C₄-alkyl sulfonyl or phenylsulfonyl,
A² furthermore represents in each case optionally fluorine-, chlorine- or bromine-substituted C₁-C₆-alkanediyl, C₂-C₆-alkenediyl, C₂-C₆-azaalkendiyl, C₂-C₆-alkynediyl, C₃-C₆-cycloalkanediyl, C₃-C₆-cycloalkendiyl or phenylene .
A³ is hydrogen, hydroxyl, amino, cyano, isocyano, thio cyanato, nitro, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, halogen, in each case optionally halogen- or C₁-C₄alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, Alkylamino, dialkylamino, or dialkoxy (thio) phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally halogen-substituted alkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkynyl, alkynyloxy or alkynylamino having in each case 2 to 6 carbon atoms in the alkenyl Alkylidene or alkynyl groups, in each case optionally substituted by halogen, cyano, carboxy, C₁-C₄-alkyl and / or C₁-C₄alkoxycarbonyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy or cycloalkylideneamino having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or for each optionally by N itro, cyano, carboxy, halogen C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyloxy and / or C₁-C₄alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C₁- C₄ -alkyl or phenyl-C₁-C₄-alkoxy, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, Pyrazolyl-C₁-C₄-alkyl, furyl-C₁-C₄-alkyl, thienyl-C₁-C₄-alkyl, oxazolyl-C₁-C₄-alkyl, isoxazol-C₁-C₄-alkyl, thiazole-C₁-C₄-alkyl, pyridinyl C₁-C₄alkyl, pyrimidinyl-C₁-C₄alkyl, pyrazolylmethoxy, furylmethoxy, perhydropyranyl methoxy or pyridylmethoxy,
R⁴ is hydrogen, halogen or optionally fluorine- and / or chlorine-substituted alkyl having 1 to 4 carbon atoms,
R⁵ is optionally substituted by fluorine and / or chlorine-substituted alkyl having 1 to 4 carbon atoms, and
R⁶ is hydrogen, amino, hydroxy, optionally substituted by fluorine and / or chlorine-substituted alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms. 3. Diazacyclohexandi (thi) one of the general formula (I) according to claim 1, characterized in that
Q¹ is oxygen,
Q² is oxygen,
R¹ is hydrogen, fluorine or chlorine,
R² is cyano, thiocarbamoyl, chlorine, bromine, methyl or trifluoromethyl,
R³ is the following moiety, -A¹-A²-A³ in which
A¹ represents a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen (in which case R² is not chlorine or bromine), hydroxy, methyl, ethyl , n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl or ethylsulfonyl,
A¹ further for methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2 -diyl, propene-1,2-diyl, propene-1,3-diyl, ethyne-1,2-diyl, propyne-1,2-diyl or propyne-1,3-diyl,
A² is a single bond, oxygen, sulfur, -SO-, -SO₂- or the grouping -N-A⁴-, wherein A⁴ is hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n - or i-propoxy, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or phenylsulfonyl,
A² further for methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2 -diyl, propene-1,2-diyl, propene-1,3-diyl, ethyne-1,2-diyl, propyne-1,2-diyl or propyne-1,3-diyl,
A³ represents hydrogen, hydroxyl, amino, cyano, nitro, carbamoyl, sulfo, fluorine, chlorine, bromine, in each case optionally fluorine, chlorine, methoxy or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i- , s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, dimethoxyphosphoryl, diethoxy phosphoryl, dipropoxyphosphoryl or diisopropoxy phosphoryl, in each case optionally by fluorine or Chlorine-substituted propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylideneamino, butylidene amino, propynyl, butynyl, propynyloxy, butynyloxy, propynylamino, butynylamino, for each g optionally substituted by fluorine, chlorine, cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropyl methyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexyl methyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclo pentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino, cyclohexylideneamino, or each optionally substituted by nitro, cyano, carboxy, fluoro, chloro, bromo, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n - or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl and / or ethoxycarbonyl-substituted phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, (in each case optionally fully or partially hydrogenated) pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, Thiazolyl, iso-thiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furyl methyl, thienylmethyl, oxazolylmethyl, isoxazolmethyl, thiazolemethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy,
R⁴ represents hydrogen, fluorine, chlorine, bromine or represents in each case optionally fluorine- and / or chlorine-substituted methyl or ethyl,
R⁵ is in each case optionally substituted by fluorine and / or chlorine-substituted methyl or ethyl, and
R⁶ is hydrogen, amino, each optionally substituted by fluorine and / or chlorine, methyl or ethyl or cyclopropyl. 4. Process for the preparation of the diazacyclohexanedi (thi) ones of the general formula (I) in which
R¹, R², R³, R⁴, R⁵, R⁶, Q¹ and Q² have the meanings given in claim 1,
characterized in that uracils of the general formula (II) in which
Q¹, Q², R¹, R², R³, R⁴, R⁵ and R⁶ have the meanings given above,
with a hydrogenating agent, if appropriate in the presence of a catalyst and optionally in the presence of a diluent. 5. Herbicidal agents, characterized by a content of at least one substituted Diazacyclohexandi (thi) on the general formula (I) according to the claims 1 to 4. 6. A method for controlling unwanted plants characterized thereby characterized in that substituted diazacyclohexanedi (thi) one of the general Formula (I) according to claims 1 to 4 on undesirable plants and / or their habitat. 7. Use of substituted Diazacyclohexandi (thi) ones of the general Formula (I) according to claims 1 to 4 for controlling unwanted plants.   8. A process for the preparation of herbicidal compositions, characterized in that substituted diazacyclohexanedi (thi) ones of the general formula (I) according to claims 1 to 4 with extenders and / or surface-active Mixed substances.