Substituted benzoylketones and herbicide agent based on thereof

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention relates to new substituted benzoylketones of the general formula (I): , all possible tautomeric forms and possible salts that can represent active substance as a component of herbicide agent. In the formula (I) A means (C1-C4)-alkyl; R1 means cyclo-(C3-C6)-alkyl; R2 means hydrogen atom (H), cyano-group (CN); R3 means hydrogen atom (H), halogen atom, CF3, (C1-C4)-alkylsulfonyl; R4 means halogen atom; X means groups: or wherein R5 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, (C1-C4)-alkylthio-group, di-(C1-C6-alkyl)-amino-group; R6 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, cyclo-(C3-C6)-alkyl; n = 0 or 1 including all possible tautomeric forms and possible salts. Compounds of the formula (I) elicit herbicide activity and can be used in herbicide composition.

EFFECT: valuable properties of compounds.

3 cl, 1 sch, 3 tbl, 13 ex

 

The present invention relates to new derivatives of benzoyl more specifically to new substituted benzoylacetone and herbicide tool based on them.

It is known that certain substituted benzoylacetone have a weed-killing properties (see European patent application EP-A-625505, EP-A-625508, U.S. patent US-A-5804532, US-A-5846906, international application WO-A-96/26193). However, the effectiveness of these compounds does not meet all necessary requirements.

The closest analogue of the invention are described in U.S. patent US 5846906 substituted benzoylacetone General formula (X)

where

L and M denote hydrogen, unsubstituted or substituted by halogen or alkoxygroup alkyl, alkenyl, quinil and alkoxy, halogen, cyano, nitro, a group -(Y)n-S(O)mR7or(Y)n-CO-R8where R7means alkyl, haloalkyl or a group NR9R10where R9means means hydrogen or alkyl, and R10means alkyl, R8means alkyl, haloalkyl, alkoxy or the group NR9R10where R9and R10have the above meaning, R1means tert-butyl, cyclopropyl, 1-methylcyclopropyl or 1-metaltitlepane or acceptable in agriculture salt.

Object of the invention is the expansion of the range of the substituted benzoylamino, possessing the x high herbicide activity.

The problem is solved proposed substituted benzoylacetonate General formula (I),

in which

And is alkylene with 1-4 carbon atoms;

R1is cycloalkyl with 3-6 carbon atoms;

R2is hydrogen or cyano group;

R3is hydrogen, halogen, trifluoromethyl, alkylsulfonyl with 1-4 carbon atoms;

R4is halogen;

Z is a heterocyclic group of the formula

where

R5is hydrogen, alkyl with 1-4 carbon atoms, alkoxygroup with 1-4 carbon atoms, alkylthiol with 1-4 carbon atoms, dialkylamino group having up to 6 carbon atoms in the alkyl groups;

R6is an alkyl with 1-4 carbon atoms, alkoxy group with 1-4 carbon atoms, cycloalkyl with 3-6 carbon atoms,

n is 0 or 1,

including all possible tautomeric forms and possible salt.

Preferred substituted benzoylacetonate General formula (I) are compounds in which

But is methylene;

R1is cyclopropyl;

R2is hydrogen, cyano group;

R3is fluorine, chlorine, bromine, trifluoromethyl, methylsulfonyl;

R4is chlorine;

Z is a heterocyclic gruppovogo

or

where

R5is stands, ethyl, methylthiourea, a methoxy group, ethoxypropane, dimethylamino;

R6is stands, ethoxypropane, cyclopropyl;

n is 0 or 1.

New substituted benzoylacetone General formula (I) have a high and selective herbicide activity and, therefore, a further object of the invention is the herbicide agent containing the compound of formula (I) and the usual diluents.

New substituted benzoylacetone General formula (I) can be obtained by interaction

(a) ketones of General formula (II)

in which

R1and R2have the above meaning,

with substituted benzoic acids of General formula (III),

in which

n, A, R3, R4and Z have the above meaning,

if necessary, in the presence of one or more auxiliary substances and, if necessary, in the presence of one or more diluents,

or

(b) benzoimidazole General formula (IV)

in which

n, A, R1, R2, R3, R4and Z have the above meaning,

isomerizing in the presence of one or more sub who's substances and if necessary, in the presence of one or more diluents,

and, if necessary, obtained by the method (a) or (b), the compound of formula (I) is transferred in the usual way into salt.

In principle, compounds of General formula (I) can also be synthesized, for example, as follows:

The interaction of ketones of General formula (II) (see above) with a reactive derivative of the substituted benzoic acids of General formula (III) (see above) preferably with the corresponding anhydrides of carboxylic acids, anhydrides of carboxylic acids, cyanides, carboxylic acid, a complex of methyl or ethyl esters of carboxylic acids and, if necessary, in the presence of auxiliary substances, such as triethylamine (and, if necessary, in addition to zinc chloride) and, if necessary, in the presence of a diluent, such as methylene chloride:

(X is, for example, CN, Cl).

If the starting compounds are used, for example, ethylmethanesulfonate-ketone and 2-(3-carboxy-5-fluoro-benzyl)-5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazole-3-one, the course of the reaction according to method (a) is as follows:

If the starting compounds are used, for example, (5-cyclopropyl-isoxazol-4-yl)-[2-(4-methyl-3-methylthio-5-the CSR-4,5-dihydro-[1,2,4]-triazole-1-yl-methyl)-4-trifluoromethyl-phenyl]-methanon, the course of the reaction according to method (b) takes place according to the following scheme 1:

The original substance of General formula (II) are known and/or can be obtained according to known methods (see receipt).

The original substance of General formula (III) is not yet known, except 2-(5-carboxy-2,4-dichloro-phenyl)-4-deformity-5-methyl-2,4-dihydro-2H-1,2,4-triazole-3-one, or 2,4-dichloro-5-(4-deformity-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole-1-yl)-benzoic acid (CAS-Rg. No. 90208-77-8), and 2-(5-carboxy-2,4-dichloro-phenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-one, or 2,4-dichloro-5-(4,5-dihydro-3,4-dimethyl-5-oxo-1H-1,2,4-triazole-1-yl)-benzoic acid (CAS Reg. No. 90208-76-7).

The original substance of General formula (III), except 2-(5-carboxy-2,4-dichlorophenyl)-4-deformity-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one and 2-(5-carboxy-2,4-dichlorophenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazole-H-he (see Japan patent JA-58225070 link in Chem. Abstracts 100:209881, Japanese patent application JPA 02015069 link in Chem. Abstracts 113:23929), are subject not yet published patent application DE-A 19833360.

New substituted benzoic acid of General formula (III) is produced by interaction of derivatives of benzoic acid of General formula (V),

in which

n, A, R3, R4and Z have the above meaning,

X1is cyano,carbamoyl, carbamoyl or alkoxycarbonyl, with water, if necessary, in the presence of auxiliary substances such as sulfuric acid, at temperatures between 50 and 120C (see receipt).

Derivatives of benzoic acid of General formula (V) are known and/or can be obtained according to known methods (see patents Germany DE-A-3839480, DE-A-4239296, European patent application EP-A-597360, EP-A-609734, German patent application DE-A-4303676, European patent application EP-A-617026, German patent application DE-A-4405614, U.S. patent US-A-5378681).

New substituted benzoic acid of General formula (III) is produced by interaction of the halogen(alkyl)benzoic acids of General formula (VI)

in which

n, A, R3and R4have the above meaning,

X is halogen (preferably chlorine or bromine),

with compounds of General formula (VII)

in which

Z has the abovementioned meaning,

if necessary, in the presence of auxiliary substances, such as triethylamine or potassium carbonate, and, if necessary, in the presence of a diluent, for example acetone, acetonitrile, N,N-dimethyl-formamide or N,N-dimethyl-ndimethylacetamide, at a temperature between 50 and 200C (see receipt).

Instead halogen(alkyl)benzoic acids of the General formula is (VI) it is also possible, similarly to the above-described methods, the interaction of the corresponding NITRILES,

amides and esters, preferably complex methyl or ethyl esters with compounds of General formula (VII). Subsequent hydrolysis by conventional methods, for example, by interaction with water-ethanol solution of potassium hydroxide, obtaining a corresponding substituted benzoic acids.

Halogen(alkyl)benekenii acid of General formula (VI) (or the corresponding NITRILES or esters) are known and/or can be obtained according to known methods (see European patent application EP-A-90369, EP-A-93488, EP-A-399732, EP-A-480641, EP-A-609798, EP-A-763524, German patent application DE-A-2126720, international application WO-A-93/03722, WO-A-97/38977, U.S. patent US-A-3978127, US-A-4837333).

Compounds of General formula (VII) are known and/or can be obtained according to known methods.

As auxiliary substances in carrying out process (a) can be called, for example, sodium cyanide, potassium cyanide, cyanhydrin acetone, triazole, diethyl ether complex cyanide of phosphoric acid, 2-cyano-2-(trimethylsilyloxy)-propane and trimethylsilylacetamide.

The most preferred auxiliary substances are complex diethyl ether cyanide phosphoric acid and trimethylsilylacetamide.

Methods (a) and (b) can be carried out in the presence of further ancillary the different substances, such as, for example, basic organic nitrogen compounds, such as trimethylamine, triethylamine, Tripropylamine, tributylamine, ethyl-Diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,4-dimethyl-pyridine, 2,6-dimethyl-pyridine, 3,4-dimethyl-pyridine and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane, 1,5-diazabicyclo[4,3,0]-non-5-ene or 1,8-diazabicyclo[5,4,0]-undec-7-ene.

As a diluent for carrying out the methods (a) and (b) first of all inert organic solvents, for example, preferably aliphatic, alicyclic or aromatic, if necessary, halogenated hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, chloroform, carbon tetrachloride or 1,2-dichloroethane; ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, simple etilenglikolevye or etilenglikolevye ether; ketones, such as acetone, butanone or methyl isobutylketone; NITRILES, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylated the Ministry of foreign Affairs, N-methyl-formanilide, N-methyl-pyrrolidone or triamide hexamethylphosphoric acid; esters, e.g. methyl ester of acetic acid or ethyl ester of acetic acid; sulfoxidov, for example, dimethyl sulfoxide.

When carrying out processes (a) and (b), the reaction temperatures can be varied within wide limits. It is usually between 0 and 150C., preferably between 10 and 120C.

Methods (a) and (b) is conducted usually under normal pressure. However, it is also possible to perform the methods (a) and (b) at elevated or reduced pressure (typically between 0.1 bar and 10 bar).

For carrying out the methods (a) and (b) the initial substance is usually used in approximately equimolar amounts. However, it is also possible to use one of the components in excess. The reaction is usually carried out in a suitable diluent in the presence of a dehydration agent, and the reaction mixture is stirred generally for several hours at the required temperature. The treatment is carried out by conventional methods (see receipt).

Compounds of the above General formula (I) can be used as defoliants, desiccants, agents inhibit the growth of grasses and preferably as agents for the destruction of weeds. Under the weeds understood all plants which grow in places where they are regulate the elegance. The action of the compounds according to the invention (hereinafter: the "active substance") as total or selective herbicides depends mainly on their consumption rates.

The active substance can be used in the following plants.

Dicotyledonous weed species: Sinapis (mustard), Lepidium (cress), Galium (bedstraw), Stellaria (starwort), Matricaria (Matricaria), Anthemis (Popovka), Galinsoga (galinsoga), Chenopodium (pigweed), Urtica (nettle), Senecio (Senecio), Amaranthus (amaranth), Portulaca (purslane), Xanthium (cocklebur), Convolvulus (bindweed), Ipomoea (morning glory), Polygonum (knotweed), Sesbania (sesbania), Ambrosia (ragweed), Cirsium (Thistle), Carduus (Thistle), Sonchus (oten), Solanum (nightshade), Rorippa, Rotala, Lindemia, Lamium (dead-nettle), Veronica (Veronica), Abutilon (abutilon), Emex, Datura (Datura), Viola (violet), Galeopsis, Paraver (IAC), Centaurea (cornflower), Trifolium (clover), Ranunculus (Buttercup), Taraxacum (dandelion).

Dicotyledonous cultivated plants species: cotton, soybeans, beets, carrots, beans, peas, nightshade, flax, morning glory, Vic, tobacco, tomato, peanuts, cabbage, lettuce, cucumber, pumpkin.

Monocotyledonous weeds species: Echinochloa (barnyard grass), Setaria (spickle), Panicum (millet), Digitaria (weed), Phleum (Timothy grass), PoA (bluegrass), Festuca (fescue), Eleusine (Eleusis), Brachiaria, Lofium (the chaff), Bromus (brome), Avena (oats), Cyperus (Cyperus), Sorghum (sorghum), Agropyron (Wheatgrass), Cynodon (cynodon), Monochoria, Fimbristylis, Sagittaria (arrowhead), Eleocharis (bolotnitsa), Scirpus (bulrush), Paspalum (buckwheat), Ischaemum, Sphenoclea, Dactyloctenium, Agrostis (bentgrass), Alopecurus (Alopecurus), area Aegilops (Aegilops), Phalaris (Canary grass).

Dicotyledonous cultivated plants species: rice, tea, wheat, barley, oats, rye, sorghum, millet, sugarcane, pineapple, asparagus, onions.

The use of active substances is in no way limited to these species, and also equally apply to other plants.

Depending on the concentration of the active substances are suitable for the complete destruction of weeds, for example, industrial equipment and rail tracks, roads and squares with or without tree growth. You can also use active substances for combating weeds in perennial cultures, for example, when planting the tree, ornamental, fruit, wine, citrus, walnut, banana, coffee, tea, rubber, oil-palm, cocoa, fruit and hop crops, ornamental lawns and sports fields, pastures, and for the selective combating of weeds in annual crops.

The active substances have a strong herbicide activity and a wide range of soil and green parts of plants above the ground surface. Also they are most suitable for the selective combating of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, processing as before the shoot and after the shoot of the plants.

The active substance can p is levaditi in the usual formulation, for example solutions, emulsions, wettable powders, suspensions, powders, pollinating agents, pastes, soluble powders, granules, concentrates, emulsions and suspensions, natural and synthetic substances impregnated with active ingredient, as well as by microencapsulation in polymeric substances.

These preparative form get in a known manner, for example by mixing the active substances with solvents, for example, liquid solvents and/or solid fillers, if necessary, using surfactants, such as emulsifiers and/or dispersants and/or foam.

If the diluent is water, as an auxiliary solvent may also be used, for example, of an organic solvent. Liquid solvents are: aromatic hydrocarbons, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene, or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their simple and complex spiry, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, very polarimetrie, for example dimethylformamide and dimethylsulfoxide, and water.

As particulate fillers are used, for example, ammonium salts and natural mineral powder-like substances, such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral powder-like substances, such as highly dispersed silicic acid, alumina and silicates; as fillers granules are used: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, thick, dolomite, and also synthetic granules of inorganic and organic powder, and granules of organic material such as wood sawdust, coconut kernel, corn cobs and stalks of tobacco; as emulsifiers and foaming agents are used: for example nonionic and anionic emulsifiers, such as ester of polyoxyethylene and fatty acids, simple ether and polyoxyethylene fatty alcohol, for example a simple alkylarylsulphonates ether, acelaltroca, alkyl sulphates, arylsulfonate, and also protein hydrolysates; as dispersant use: for example lignin-sulphite lye and methylcellulose.

Preparative form may contain adhesive agents, e.g. the carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latexes, such as gum Arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as Catalina and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyes, for example, alizarin dyes, azo dyes and metallophthalocyanine dyes and coloring nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Preparative forms usually contain 0.1 to 95 wt. -%, preferably 0.5 to 90 wt%. the active substance.

The active substance can be used in its preparative form or can be mixed with known herbicides for pest control, and it is possible to use the finished formulation or mixing in the tank.

For mixing use a known herbicides, such as acetochlor, alfthan(-sodium), klonipin, alachlor, aloxide(-sodium), ametrine, amithlon, amidosulfuron, anilofos, Azul, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benvenisty, encultured(-methyl), bentazon, benzefoam, benzoylperoxy(-ethyl), bialaphos, b is Fenox, bispyribac(-sodium), bromobutyl, bromophenoxy, bromoxynil, butachlor, butoxide, butylate, catastropy, galaxidi, carbetamide, carfentrazone(-ethyl), chlorethoxyfos, chloramben, ozone chloride, chlorimuron(-ethyl), pernitrate, chlorsulfuron, chlortoluron, cinidon(-ethyl), cinmetacin, kinokultura, clethodim, clodinafop(-propargyl), clomazone, clomipram, clopyralid, cloperastine(-methyl), karasulu(-methyl), cumyluron, cyanazine, cybutryne, cycloate, cycloaliphatic, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), dicloflam, diacetyl(-ethyl), difenzoquat, diflufenican, diflubenzuron, dimefuron, gameparty, dimethachlor, deltamethrin, dimethenamid, Dimexidum, dinitramine, diphenamid, Diquat, dithiopyr, Diuron, damron, apoprotein, ARTS, asbroker, ethalfluralin, atomiculture(-methyl), ethofumesate, idoxifene, ethoxysulfuron, etamesonic, fenoxaprop(-P-ethyl), planrep(-isopropyl), femprep(-isopropyl-1), planrep(-methyl), flazasulfuron, fluazifop(-P-butyl), plazoleta, flucarbazone, flufenacet, flumetsulam, flumiclorac(pencil), flumioxazin, flubiprofen, flumetsulam, fluometuron, verkleiden, foreglimpse(-ethyl), flupoxam, flypaper, flupyrsulfuron(-methyl-sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurried, flurtamone, fluthiacet(methyl), flutamide, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), galasoft, haloxyfop(-ethoxyethyl), haloxyfop(P-methyl), hexazinone, imazamethabenz(-methyl), imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, ioxynil, isopropylene, Isoproturon, Sauron, isoxaben, isoxaflutole, isoxaflutole, isocaporate, lactofen, lenacil, linuron, MSRA, MSR, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metaventure, metobromuron, (alpha)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, nitroanilide, napropamide, neburon, nicosulfuron, norflurazon, arrancars, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxacyclobutane, oxilorphan, paraquat, pelargonia acid, pendimethalin, phenoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), procarbazine, prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), paradoxien, perbenzoic, peribuccal pyridate, Perminova(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-R-tefuryl), rimsulfuron, sethoxydim, Simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-(ethyl), sulfosate, sulfosulfuron, tabulam, tebuthiuron, tepraloxydim, terbutylazine, terbutryn, tanishlar, leflunamide, thiazopyr, thidiazuron, thifensulfuron(-methyl), thiobencarb, thiocarbonyl, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin, triflusulfuron and tritosulfuron.

Also is it possible mixing with other active ingredients, such as fungicides, insecticides, acaricides, nematicides, protective substances from damage by birds, nutrients and agents for improving soil structure.

The active substance can be used in its preparative form or with the addition of a diluent, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granulates. The introduction of active substances is carried out in the usual way, e.g. through spraying, spraying, watering, litter.

Proposed in accordance with the present invention the active substance can be entered both before and after germination of the plants. Also the active substances can be introduced into the soil before sowing.

Used the consumption rate of the active substance may vary within wide limits, it basically depends on the desired effect. The consumption rate is usually 1 g - 10 kg of active substance per hectare of land area is, preferably 5 g to 5 kg per hectare

Obtaining compounds of formula (I) is illustrated by the following examples.

Example 1

of 2.38 g (6.4 mmol) of 4-cyclopropyl-5-ethoxy-2-(2-carboxy-5-trifluoromethyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-it is placed in 20 ml of N,N-dimethyl-formamide and under stirring successively added 0.7 g (6.4 mmol) cyanomethyl-cyclopropyl-ketone, and 2.7 ml (19 mmol) of triethylamine and 1.04 g (6.4 mmol) diethyl ether complex cyanide of phosphoric acid at room temperature (about 20C). The reaction mixture is stirred for 2 days at room temperature, add about double the amount of water, acidified with 2N-hydrochloric acid and shaken with methylene chloride. The organic phase is separated, washed with 2N-hydrochloric acid, dried over sodium sulfate and filtered. The filtrate is concentrated and the residue purified column chromatography (silica gel, hexane/complex ethyl ester acetic acid, Rev.: 4/1).

Obtain 1.18 g (40% of theory) 3-cyclopropyl-2-{2-[4-(cyclopropyl-3-ethoxy-5-oxo-4,5-dihydro-1H-1,2,4-triazole-1-yl)-methyl]-4-trifluoromethyl-benzoyl}-3-oxopropanenitrile in the form of an amorphous product.

logP1)3,35.

Similarly receive the connection formula

Analogously to example 1, and in accordance with the above General method in Sogno obtaining compounds of formula (IA), shown in table 1.

Table 1
Example No.R3R5R6Physical data (log1))
2CF3S32,92
3CF3OS2H5CH33,03
4CF3With2H5OS2H53,19
5BrS3CH32,83
6BrOS2H5CH32,94
7FN(CH3)2CH32,28
8FOch32,56
9SO2CH3S3CH31,74
10CF3CH3CH3 2,35
1)Determination of the logP values are conducted according to EEC-Directive 78/831 Annex V.A8 using high-performance liquid chromatography (HPLC) on a column with treatment phases (18). Temperature: 43C. as solvents used a 0.1% aqueous solution of phosphoric acid, acetonitrile; linear gradient from 10% to 90% acetonitrile.

Examinations carried out using unbranched Alkan-2-ones (with 3 to 16 carbon atoms), in which the logP values are known (determination of the logP values spend some time by means of linear interpolation between two successive alkanoate).

Educt of the formula (II):

Example (II-1)

100 ml of a 1.6 molar solution of utility in hexane is added to 30 ml of tetrahydrofuran at a temperature of -60C. Then the mixture successively added 6.6 g (0.16 mol) of acetonitrile and 14.6 grams (0.15 mol) of a compound methyl ester cyclopropanecarbonyl acid at a temperature of -60C. Then the ice bath is removed and the temperature was adjusted to room, to the resulting white suspension add about the same number of 2N-hydrochloric acid and then extracted three times with methylene chloride. Organic extracting solutions combine, dried over sodium sulfate and filter the Ute. From the filtrate carefully the solvent is distilled off in a water jet vacuum and the residue distil under strongly reduced pressure.

Get 7.5 g (46% of theory) cyanomethyl-cyclopropyl-ketone having a boiling point of 56C (0.8 mbar).

Educt of the formula III

Example (III-1)

2 g (4.9 mmol) of 5-bromo-4-methyl-2-(2-etoxycarbonyl-5-trifluoromethyl-benzyl)-2,4-dihydro-3H-1,2,4-triazole-3-one (see example IV-1) dissolved in 30 ml of 10%potassium hydroxide solution with ethanol and heated for 2 hours in the presence of phlegmy. The reaction mixture was concentrated in a water jet vacuum, absorbed in 20 ml of water and acidified with diluted hydrochloric acid.

Precipitated solid is filtered and dried.

Obtain 1.2 g (71% of theory) 5-ethoxy-4-methyl-2-(2-carboxy-5-trifluoromethyl-benzyl)-2,4-dihydro-ZN-1,2,4-triazole-W-it is in the form of a solid product.

logP: 2,18 (definition described above).

Educt of the formula (IV):

Example (IV-1)

A solution of 1.20 g (33%, that is, 2.8 mmol) complex methyl ester 4-(3-methyl bromide-5-trifloromethyl)-5-cyclopropyl-isoxazol-3-carboxylic acid in 10 ml of N,N-dimethylformamide are added dropwise with stirring, a mixture of 0.44 g (2.8 mmol) of 4-ethoxy-5-ethyl-2,4-dihydro-3H-1,2,4-triazole-3-one, 84 mg (2.8 mmol) of sodium hydride (75%) and 20 ml of N N-dimetilformamida at room temperature (about 20C.) and the reaction mixture is stirred for 30 minutes at room temperature. The mixture is then diluted with saturated aqueous sodium chloride up to about double the volume and twice extracted with complex ethyl ester of acetic acid. The combined organic extracting solution is dried over sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum and the residue purified column chromatography (silica gel, hexane/complex ethyl ester acetic acid, volume: 7/3).

Obtain 0.45 g (96% of theory, relative to 33% selected substances) (5-cyclopropyl-3-methoxycarbonyl-isoxazol-4-yl)-[2-(4-ethoxy-3-ethyl-5-oxo-4,5-dihydro-[1,2,4]-triazole-1-yl-methyl)-4-trifluoromethyl-phenyl]-methanone in the form of an amorphous product.

logP (definition described above) of 3.56.

Herbicide activity of the compounds of formula (I) is illustrated by the following examples.

Example

Pre-emergence treatment plants in the greenhouse

1% of the mass. specified in table 2 of the active substance is 5% of the mass. acetone as a solvent, was added 1% of the mass. simple alkylarylsulphonates ether as an emulsifier, and the resulting concentrate is diluted with water to the desired concentration.

The seeds of the studied plants are sown in normal soil. After about 24 hours, the soil is sprayed preparative form of the active substance so that 250-500 g of the active substance had per hectare. Concentration is the situation of the structure define so to the specified amount of active substance was in 1000 litres of water per hectare.

Three weeks later analyze the degree of plant damage in % damage in comparison with the growth of the untreated control plants.

0% = result not available (untreated control samples)

100% = total destruction of weeds.

Plants, of the active substance, their consumption rate and the experimental results are summarized in table 2.

Table 2
The analyzed compound of example no.Consumption rate, g active substance/haCornAbutilonAmaranthusSinapis
15000100100100
2500010010080
350010100100-
425010959595
55000100100100
65000100100100

An example of the

Post-harvest processing plants in the greenhouse

1% of the mass. the active substance is mixed with 5% of the mass. acetone in kachestve solvent, add 1% of the mass. simple alkylarylsulphonates ether as an emulsifier, and the resulting concentrate is diluted with water to the desired concentration.

The investigated plants with a height of 5-15 cm are sprayed with the preparative form of the active substance so that 250-500 g of the active substance had per hectare. The concentration of the composition is determined so that the specified amount of active substance was in 1000 litres of water per hectare.

Three weeks later analyze the degree of plant damage in % damage in comparison with the growth of the untreated control plants.

0% = result not available (untreated control samples)

100% = total destruction of weeds

Plants, of the active substance, their consumption rate and the experimental results are summarized in table 3.

250
Table 3
The analyzed compound of example no.Consumption rate, g active substance/haAmaranthusSinapis
1500100100
250010095
395100
425010095
5500100100
6500100100

1. Substituted benzoylacetone General formula (I)

in which

And is alkylene with 1-4 carbon atoms;

R1is cycloalkyl with 3-6 carbon atoms;

R2is hydrogen or cyano;

R3is hydrogen, halogen, trifluoromethyl, alkylsulfonyl with 1-4 carbon atoms;

R4is halogen;

Z is a heterocyclic group of the formula

where

R5is hydrogen, alkyl with 1-4 carbon atoms, alkoxygroup with 1-4 carbon atoms, alkylthiol with 1-4 carbon atoms, dialkylamino having up to 6 carbon atoms in the alkyl groups;

R6is an alkyl with 1-4 carbon atoms, alkoxygroup with 1-4 carbon atoms, cycloalkyl with 3-6 carbon atoms,

n is 0 or 1,

including all possible tautomeric forms and possible salt.

2. Substituted benzoylacetone General formula (I) according to claim 1, in which

And that is what I methylene;

R1is cyclopropyl;

R2is hydrogen, cyano;

R3is fluorine, chlorine, bromine, trifluoromethyl, methylsulfonyl;

R4is chlorine;

Z is a heterocyclic group of the formula

where

R5is stands, ethyl, methylthiourea, a methoxy group, ethoxypropane, dimethylamino;

R6is stands, ethoxypropane, cyclopropyl;

n is 0 or 1.

3. Herbicide agent, characterized in that it contains a compound according to claim 1 or 2, and the usual diluents.



 

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