Substituted benzoylpyrazoles and herbicide tool based on them

 

(57) Abstract:

Describes benzoylpyrazoles General formula (I)

where a means alkylene, R1- alkyl, R2is hydrogen, alkyl, R3is hydrogen, alkyl, halogen, alkylsulfonyl, alkoxy, R4- nitro, halogen, alkyl, Y is hydrogen, alkyl, alkylsulfonyl, alkenyl, phenylsulfonyl, phenylalkyl, Z - substituted 5-6-membered saturated or unsaturated heterocyclic group. Describes the herbicide agent based on the compound of formula (I). The proposed benzoylpyrazoles have a strong herbicide activity and a broad spectrum of activity both during cultivation and processing ground parts of plants. 2 s and 5 C.p. f-crystals, 10 PL.

The present invention relates to new benzoline compounds possessing biological activity, and more particularly to substituted benzoylpyrazoles and herbicide tool based on them.

It is already known that certain substituted benzoylpyrazoles have a weed-killing properties (see application EP No. 352543, international application WO 96/26206, WO 97/35850, WO 97/41105, WO 97/41116, WO 97/41117, WO 97/41118, WO 97/46530, WO 98/28981, WO 98/31681, WO 98/31682, WO 9907697).

Object of the invention is the expansion of the range to replace the Xia proposed substituted benzoylpyrazoles General formula (I)

where n is the number 0, 1,

A - alcander (alkylen),

R1- alkyl,

R2is hydrogen, alkyl,

R3is hydrogen, halogen, unsubstituted or substituted alkyl, alkoxy, alkylsulfonyl,

R4- nitro, halogen, substituted alkyl,

Y is hydrogen, unsubstituted or substituted alkyl, alkylsulfonyl, alkenyl, phenylsulfonyl, phenylalkyl, phenylcarbonylamino, and

Z - substituted 5-6-membered saturated or unsaturated heterocyclic group comprising 3 heteroatom (up to 2 nitrogen atoms and, if necessary - in addition to the sulfur atom) and includes advanced as a component of the heterocycle one oxoprop C=O,

including all possible salt.

In the first group of preferred substituted benzoylpyrazoles General formula (I) include compounds in which

n is the number 0, 1,

A - alkylen with 1-4 carbon atoms,

R1is alkyl with 1-6 carbon atoms,

R2is hydrogen, alkyl with 1-6 carbon atoms,

R3is hydrogen, halogen, alkyl, alkoxy, alkylsulfonyl, each with 1-4 carbon atoms in the alkyl groups, unsubstituted or substituted with halogen,

R

Z is one of the following heterocyclic groups

where is drawn in dashed line represent each simple bond or double bond,

Q is oxygen or sulphur,

R5is hydrogen, halogen, alkyl, alkoxyl, alkylthio, each with 1-6 carbon atoms in the alkyl groups, unsubstituted or substituted by residues from the group comprising halogen, alkoxy with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, dialkylamino with 1-6 carbon atoms in the alkyl groups, alkanity with 2-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, or in case two adjacent radicals R5and R5located on a double bond, R5together with the adjacent radical R5also means anthropo or 1,4-butandiol,

R6- alkyl, alkoxyl, each is built benzoylpropionic General formula (I) includes compounds have

n is the number 0 or 1,

A - methylene,

R1is methyl, ethyl tert.-butyl,

R2is hydrogen, methyl, ethyl,

R3is hydrogen, fluorine, chlorine, bromine, methyl, unsubstituted or substituted by fluorine, methoxy, methylsulphonyl,

R4- nitro, fluorine, chlorine, methyl, substituted by fluorine,

R5is hydrogen, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, triptoreline, methylthio, ethylthio, isopropylthio, Demetrio, property, cyclopropyl,

R6is methyl, ethoxy, cyclopropyl,

Y is hydrogen, methyl, ethyl, isopropyl, methylsulphonyl, propenyl, phenylsulfonyl, benzyl, phenylcarbonylamino, unsubstituted or substituted by residues from the group comprising nitro, cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl.

The most preferred substituted benzoylpyrazoles General formula (I) in which Z stands for a group

Q - mean oxygen

n means 0.

As the salt of the substituted benzoylpyrazoles General formula (I) are preferred salts of sodium, potassium, magnesium, calcium, ammonium, alkylamine with 1-4 carbon atoms in the alkyl part, dialkylamino with 1-4 carbon atoms in the alkyl part, trialkylphosphine with 1-4 carbon atoms in the alkyl part, cycloalkylation with 5 or 6 carbon atoms in cycloalkyl part and diallylmethylamine with 1-2 carbon atoms in the alkyl part.

As examples of compounds of formula (I) are compounds of the following groups.

Group 1

where R3, (R4)n, R5and R6are listed in table 1 values.

Group 2

where R3, (R4)n, R5and R6are listed in table 1 values.

Group 3

where R3, (R4)n, R5and R6are listed in table 1 values.

Group 4

where R3, (R4)n, R5and R6are listed in table 2 values.

Group 5

where R3, (R4)n, R5and R6are listed in table 2 values.

where R3, (R4)n, R5and R6are listed in table 2 values.

Group 7

where R3, (R4)n, R5and R6are listed in table 3 values.

Group 8

where R3

where R3, (R4)n, R5and R6are listed in table 3 values.

A Group Of 10

where R3, (R4)n, R5and R6are listed in table 4 values.

Group 11

where R3, (R4)n, R5and R6are listed in table 4 values.

Group 12

where R3, (R4)n, R5and R6are listed in table 4 values.

New substituted benzoylpyrazoles General formula (I) are due to the fact that

(a) pyrazoles total General formula (II)

where R1, R2and Y have the above values,

subjected to interaction with substituted benzoic acids of General formula (III)

where n, R3, R4and Z have the above values,

in the presence of means of dehydration, if necessary, in the presence of one or more auxiliaries and optionally in the presence of a diluent,

or

(b) pyrazoles of General formula (II)

where R1and R2have the above meanings and Y Osnach"ptx2">

where n, R3, R4and Z have the above meanings, and

X is cyano, halogen or alkoxyl,

- or the corresponding anhydrides of carboxylic acids

if necessary, in the presence of one or more auxiliaries and optionally in the presence of a diluent,

or

(C) substituted benzoylpyrazoles General formula (Ia)

where n, R1, R2, R3, R4and Z have the above values,

subjected to interaction with compounds of General formula (V)

where Y denotes unsubstituted or substituted alkyl, alkylsulfonyl, alkenyl, phenylsulfonyl, phenylalkyl, phenylcarbonylamino,

or, if necessary, with the appropriate isocyanate or isothioscyanates,

if necessary, in the presence of one or more auxiliaries and optionally in the presence of a diluent,

and then, if necessary, the thus obtained compounds of formula (I) can be subjected to standard electrophilic or nucleophilic reaction or oxidation reactions or restore or transfer in the usual way in salt.

5: l2H5, S3).

If as a parent compounds are used, for example, 3-chloro-5-hydroxy-1-methylpyrazole and 2-(3-carboxy-5-terbisil)-5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazole-3-one, the course of the reaction according to method (a) can be explained by the following scheme:

If as a parent compounds are used, for example, 3-cyano-5-hydroxy-1-aripirazole and 2-(3-methoxycarbonyl-5-terbisil)-4-ethyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazole-3-one, the course of the reaction according to method (b) can be explained by the following scheme:

If as a parent compounds are used, for example, 4-methyl-5-trifluoromethyl-2-[3-chloro-4-(1-ethyl-5-hydroxypyrazol-4-yl-carbonyl)-phenyl]-2,4-dihydro-3H-1,2,4-triazole-3-one and benzoyl chloride, the course of the reaction according to method (C) can be explained by the following scheme:

The initial compounds of General formula (II) are known and/or can be obtained by known his ways (see European patent application EP-240001).

The original substance of General formula (III) is not yet known from the literature, except 2-(5-carboxy-2,4-dichlorophenyl)-4-deformity-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one and 2,4-XI-2,4-dichlorophenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-one and 2,4-dichloro-5-(4,5-dihydro-3,4-dimethyl-5-oxo-1H-1,2,4-triazole-1-yl)-benzoic acid, respectively. However, they are subject application DE No. 19833360, published after the priority date of this application, 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-3-one (see application JP No. 58225070, cited in Chem. Abstracts 100:209881, application JP No. 02015069, cited in Chem. Abstracts 113:23929).

Substituted benzoic acid of General formula (III) are due to the fact that derivatives of benzoic acid of General formula (VI)

where n, R3, R4and Z have the above meanings, and

X1is cyano, carbarnoyl, halogencarbonic or alkoxycarbonyl,

subjected to contact with water, if necessary, in the presence of an auxiliary tool, such as, for example, sulfuric acid, at temperatures from 50C to 120C (see receipt).

The initial compounds of General formula (IV), as well as preliminary products of General formula (VI) are known and/or can be obtained by known methods (see application DE 3839480, DE 4239296, EP 597360, EP 609734, DE 4303676, EP 617026, DE 4405614, patent US 5378681).

The original substance of General formula (Ia) are new compounds according to the invention; and is known synthetic chemicals.

Method (a) obtaining new substituted benzoylpyrazoles General formula (I) is performed with the use of dehydration. Using conventional capable of binding water chemicals. As an example we can mention dicyclohexylcarbodiimide and carbonyl-bis-imidazole. As a particularly suitable means of dehydration can be called dicyclohexylcarbodiimide. Method (a) obtaining new substituted benzoylpyrazoles General formula (I) is carried out, if necessary, with the use of auxiliary tools. Examples are sodium cyanide, potassium cyanide, acetonecyanohydrin, 2-cyano-2-(trimethylsilyloxy)-propane and trimethylsilylacetamide. As a particularly suitable supporting means can be called trimethylsilylacetamide. Method (b) obtaining new substituted benzoylpyrazoles General formula (I) is carried out, if necessary, auxiliaries. Examples are (conc.) sulfuric acid, zinc chloride, aluminum chloride and boron fluoride.

The above methods of obtaining new substituted benzoylpyrazoles General formula (I) can be done with the use of further auxiliary means, such as, for example, trimethylamine, triethylamine, triprolidine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl - and 3,5-dimethylpyridine, 5-ethyl-2-methylpyridine, 4-dimethylaminopyridine, N-methylpiperidine, 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), (b) and (C) can be called first of all inert organic solvents. Preferably used aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride or 1,2-dichloroethane; ethers, such as, for example, a simple diethyl ether, simple, diisopropyl ether, dioxane, tetrahydrofuran or a simple etilenglikolevye ether or simple etilenglikolevye ether; ketones, such as acetone, butanone or methyl isobutyl ketone; NITRILES, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformamide, N is an organic or triamide hexamethylphosphoric KIS is ssnoi acid; the sulfoxidov, such as, for example, dimethyl sulfoxide.

When carrying out processes (a), (b) and (C) the reaction temperature can vary within wide limits. Typically operate at temperatures from 0C to 150C, preferably from 10C. to 120C.

Methods (a), (b) and (C) is usually carried out at atmospheric pressure. You can, however, also be operated at reduced or increased pressure. Typically operate at a pressure of from 0.1 to 10 bar.

When carrying out processes (a), (b) and (C) of the original substance is usually used in approximately equimolar quantities. However, you can use one of the components in excess. The reaction is usually carried out in an environment suitable diluent in the presence of means of dehydration, while the reaction mixture is typically stirred at the required temperature for several hours. The processing carried out by the usual methods (see receipt).

An additional object of the invention is a herbicide means that in addition to the usual fillers contains as active substance substituted benzoylpyrazoles the above formula (I).

The active principle according to the invention can be used as a defoliant, descale should be understood all plants, growing in places where they are unwanted. Activity proposed substances, i.e. their action or as herbicides full steps, or selective herbicides depends largely on the applied quantity.

According to the invention it is possible to treat all plants and plant parts. In this case, the plant should be understood all plants and plant populations such as desired and undesired wild plants or crop plants (including wild plants). Cultivated plants can be plants, pokasivaeya traditional culturing methods or optimization or biotechnological and gentechnologie methods, or a combination of these methods, including the transgenic plants and including hrajeme within the legislation for the storage of varieties or negraneau plants. Under parts of plants should understand all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower, root, and you can call, for example, leaves, needles, stems, flowers, fruit bodies, fruits and seeds and also roots, tubers and rhizomes. The parts of plants are also obtained when harvesting material and vegetative and generative sing plant active principles according to the invention is carried out by applying the active agent directly on plants or parts of plants or their environment, on their habitat or in the warehouse, that is, the location of their storage, when this treatment is carried out by conventional methods such as, for example, dipping, spraying, evaporating, dusting, scattering, smearing, and, in addition, when the material reproduction, in particular seed material, by applying one - or multi-layer coating in the form of a shell.

The active principle according to the invention can be applied, for example, in the struggle with the following plants:

Decotignie 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, Undernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Decotignie cultures of the genera: Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyle 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, Aegilops, Phalaris.

Monocotyle cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

However, the application of active principles according to the invention is not limited to these and the proposed connection is suitable for the complete eradication of weeds, available, for example, in the area of industrial plants or rail tracks, roads and squares with trees or no trees. Connections can also be used for combating weeds in perennial cultures, such as, for example, forestry, ornamental woody crops, fruit crops, vineyards, citrus and nut crops, banana, coffee, tea, rubber plantations, crops oil palm, cocoa plantations, soft fruit culture and hop-gardens; in addition, they can be used to control weeds in ornamental and sports derna and pasture ground, and for the selective combating of weeds in annual crops.

The proposed compounds of formula (I) have a strong herbicide activity and a broad spectrum of activity both during cultivation and processing ground parts of plants. They are to some extent also suitable for the selective combating monocotyle and decotignie weeds in monocationic and decotigny cultures by pre-emergence application, and by post-harvest application.

The active agent can be transferred in the usual formulation, for example p and, pellets, concentrates in the form of suspension and emulsion impregnated active beginning natural and synthetic substances, as well as nonconception in polymeric substances form.

These compounds get in a known manner, for example by mixing the active principle with extenders, i.e. liquid solvents and/or solid carriers, optionally with the use of surface-active agents, i.e. emulsifiers and/or dispersants and/or foam.

In the case of using water as a filler can also be used, for example, organic solvents as auxiliary means. As liquid solvents are mainly used aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, ethylene chloride or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, Vysokomol the x media use, for example, salts of Quaternary ammonium bases and grinding of natural rocks such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and the grinding of synthetic rocks, such as highly dispersed silicic acid, alumina and silicates. As solid carriers for granules are used crushed and fractionated natural rocks such as calcite, marble, pumice, thick, dolomite, and also synthetic granules of inorganic and organic grinding, and also granules of organic material such as sawdust, coconut husk, corn cobs and stalks of tobacco. As emulsifying and foaming means is used, for example, nonionic and anionic emulsifiers, such as esters of polyoxyethylene and fatty acids, ethers of polyoxyethylene and fatty alcohols, for example alkylarylsulphonates simple ether, alkyl sulphonates, alkyl sulphates, arylsulfonate and protein hydrolysates. As a dispersant is used, for example, ligninolytic liquor and methylcellulose.

The compositions can also be used binders, for example carboxymethylcellulose, natural and synthetic pioskolje natural phospholipids, for example Catalina and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

You can also use colorants such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanide blue, and organic dyestuffs, such as alizarin, azo and metallophthalocyanine dyes, and trace elements in the form of salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The compositions usually contain from 0.1 to 95 wt.% active principle, preferably from 0.5 to 90%.

Compounds according to the invention can be used in the fight against weeds as such or in the form of compounds in a mixture with known herbicides, may apply ready-to-use composition or preparation made in the tanks immediately before use.

As added to the mixture of substances used are known herbicides, such as acetochlor, acifluorfen (Sodi), klonipin, alachlor, aloxide (Sodi), ametryn, amithlon, amidosulfuron, anilofos, Azul, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), beforethat, encultured(-methyl), bentazon, benzefoam, benzoylperoxy(-ethyl), bialaphos, bifenox, b is dim, carbetamide, carfentrazone(-ethyl), gametocytes, chloramben, ozone chloride, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon(-ethyl), cinmetacin, chinaculture, clethodim, clodinafop-(propargyl), clomazone, clomipram, clopyralid, cloperastine(-methyl), karasulu(-methyl), cumyluron, cyanazine, cybotron, 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, timepart, 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), planrep-(-isopropyl-L), planrep(-methyl), flazasulfuron, fluazifop(-P-butyl), flatlet, flucarbazone, flufenacet, flumetsulam, flumiclorac (pencil), flumioxazin, flubiprofen, flumetsulam, fluometuron, verklaren, foreglimpse(-ethyl), flupoxam, flourophenyl, fluspirilene(-methyl-Sodi), flurenol(-butyl), fluridone, fluroxypyr(-methyl), flurried, flurtamone, fluthiacet(-methyl), flutamide, fomesafen Xasino, 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, (AUD)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinet, monolinuron, nitroanilide, napropamide, neburon, nicosulfuron, norflurazon, arrancars, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxacyclobutane, oxilorphan, paraquat, pelargonium acid, pendimethalin, phenoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), paradoxien, perbenzoic, perimutter, peridot, Perminova(-methyl), pyrithiobac (Sodi), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-R-tefuryl)rimsulfuron, sethoxydim, Simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tabulam, tebuthiuron, theproxy is, thiocarbonyl, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin, triflusulfuron and tritosulfuron.

It is also possible mixing with other known active principles, such as fungicides, insecticides, acaricides, nematicides, substances for the protection of birds, plant nutrients and a means to improve soil structure.

The active substance can be applied as such, in the form of their formulations or in the form prepared from them by further dilution of forms for applications, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granulates. The application in the normal way, for example by watering, spraying, spreading, spreading.

It is also possible to apply the proposed active substance before the shoot and after the shoot of the plants. They can also be incorporated into the soil before sowing.

The applied amount of active principle can vary in a wide interval. It mainly depends on the desired effect. The most commonly used number ranges from 1 g to 10 kg of active agent per hectare of soil surface, preferably from 5 g to 5 kg/ha

Obtaining compounds fo the Tyl-5-trifluoromethyl-2-(3-chloro-4-carboxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-one, of 0.62 g (5.5 mmol) of 1-ethyl-5-hydroxypyrazol and 40 ml of acetonitrile is added at room temperature (about 20C) under stirring 1.13 g (5.5 mmol) of dicyclohexylcarbodiimide, then the reaction mixture was stirred at room temperature for 16 hours. Then add 1.0 g (10 mmol) of triethylamine and 0.2 g (2 mmol) of trimethylsilylacetamide. The mixture is stirred at room temperature for 72 hours. Then add 60 ml of 2% aqueous sodium carbonate solution, whereupon the mixture is stirred at room temperature for 3 hours. Dropped dicyclohexylphosphino is separated by suction, the mother liquor is twice extracted by shaking with diethyl ether. The aqueous phase by the addition of concentrated hydrochloric acid with stirring alkalinized to a pH value of about 1. Released during this oily product extragere methylene chloride, the extract is dried over magnesium sulfate and filtered. From the filtrate carefully the solvent is distilled off in a water jet vacuum.

Receive 1.5 g (72% of theory) of 4-methyl-5-trifluoromethyl-2-[3-chloro-4-(1-ethyl-5-hydroxypyrazol-4-yl-carbonyl)-phenyl]-2,4-dihydro-3H-1,2,4-triazole-3-one as an amorphous product.

Is logr (pcati, for example, and are shown in table 5 compounds of General formula (I) or formula (IA), (IB) or (IB).

Analogously to example 1 and according to the shared data on the implementation of the methods (a), (b) and (C) can be obtained, for example, and are shown in table 6 compounds of General formula (I) or formula (IA).

Listed in tables 5 and 6 values logr defined according to EEC-Directive 79/831 Annex V. A8 by high-performance liquid chromatography on obetovannoi column (C18) at a temperature of 43C using as an eluent of 0.1% aqueous phosphoric acid and a linear gradient of acetonitrile (10% to 90%). Calibration was carried out linear alkane-2-areas (3-16 carbon atoms), is logr are known (determination of value Lohr on the basis of the retention times by linear interpolation between two subsequent one after another by alkenone).

Educt of the formula (III):

Example (III-1)

4.5 g (15 mmol) of 2-(3-chloro-4-cyanophenyl)-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-he served in 80 ml of 60% sulfuric acid, after which the mixture is heated under reflux for 6 hours. After cooling to room temperature the Boxing-4-chlorophenyl)-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-one with a melting point of 223C.

Example (III-2)

2 g (4.9 mmol) of 5-bromo-4-methyl-2-(2-etoxycarbonyl-5-trifloromethyl)-2,4-dihydro-3H-1,2,4-triazole-3-one (see example IV-1) in 30 ml of 10% aqueous solution of caustic potash dissolved and heated under reflux for 2 hours. The reaction mixture is condensed in a water-jet vacuum, then it is served in 20 ml of water and acidified with diluted hydrochloric acid.

Obtain 1.2 g (71% of theory) 5-ethoxy-4-methyl-2-(2-carboxy-5-trifloromethyl)-2,4-dihydro-3H-1,2,4-triazole-3-one as a solid product. Lohr:2,18.

Example (III-3)

To a 13.4 g (35 mmol) of 4-methyl-5-trifluoromethyl-2-(2,6-dichloro-3-methoxycarbonylbenzyl)-2,4-dihydro-3H-1,2,4-triazole-3-one in 60 ml of 1,4-dioxane is added slowly at room temperature a solution of 1.54 g (a 38.5 mmol) of sodium hydroxide in 20 ml of water. The reaction mixture was stirred at 60C for 150 minutes, and then concentrated in a water jet vacuum. The residue is dissolved in 100 ml of water by adding concentrated hydrochloric acid solution is alkalinized to pH values equal to 1. The resulting crystalline product produce by sucking.

Get 11.7 g (90% of theory) of 4-methyl-5-trifluoromethyl-2-(2,6-dichloro-3-carboxybenzoyl)-2,4-dihydro-3H-1,2,4-triennia in table 7 compounds of General formula (III)

Listed in table 7 values logr determined according to EEC-Directive 79/831, Annex V. A8 by high-performance liquid chromatography on obetovannoi column (18) at a temperature of 43C using as an eluent of 0.1% aqueous phosphoric acid and a linear gradient of acetonitrile (10% to 90%). Calibration was carried out linear alkane-2-areas (3-16 carbon atoms), is logr are known (determination of value Lohr on the basis of the retention times by linear interpolation between two subsequent one after another by alkenone).

Educt of the formula (IV):

Example (IV-1)

Stage 1

10 g (49 mmol) of 2-methyl-4-triftorperasin acid in 150 ml of ethanol is dissolved, the solution was added 1 ml of concentrated sulfuric acid.

After heating under reflux for 24 hours the solution is thickened, serve it in methylene chloride and extracted with a saturated aqueous solution of sodium bicarbonate. Phase methylene chloride is dried over sodium sulfate and concentrated in a water jet vacuum.

Get 9 g (80% of theory) of a compound ethyl ester of 2-methyl-4-triftorperasin acid is 2-methyl-4-triftorperasin acid in 200 ml of carbon tetrachloride is dissolved, to the solution was added 7 g (39 mmol) of N-bromosuccinimide and 0.1 g of dibenzoylperoxide. After heating under reflux for 6 hours exuded succinimide filtered, and the filtrate is concentrated in a water jet vacuum.

Get 12 g of amorphous residue, which in addition to complex ethyl ester 2-methyl bromide-4-triftorperasin acid contains 17% of complex ethyl ester of 2,2-dibromomethyl-4-triftorperasin acid and 12% of complex ethyl ester of 2-methyl-4-triftorperasin acid.

Stage 3

4 g complex ethyl ester 2-methyl bromide-4-triftorperasin acid (about 70%) and 2.28 g (12.8 mmol) of 5-bromo-4-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one in 150 ml of acetonitrile is dissolved, the solution was added to 5.3 g (38.4 mmol) of potassium carbonate and with vigorous stirring heated under reflux for 2 hours. The reaction mixture is poured into water and many times extracted with methylene chloride. Combined phase methylene chloride is dried over sodium sulfate, concentrated in a water jet vacuum and subjected to chromatography.

Get 2 g (38% of theory) of 5-bromo-4-methyl-2-(2-etoxycarbonyl-5-trifloromethyl)-2,4-dihydro-3H-1,2,4-triazole-3-one as an amorphous product is l) 4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-one in 150 ml of acetonitrile is added 11 g (80 mmol) of potassium carbonate. After heating the mixture to 50C was added dropwise with stirring a solution of 13.1 g (44 mmol) of a compound methyl ester 3-methyl bromide-2,4-dichlorobenzoyl acid in 20 ml of acetonitrile, and then the reaction mixture is heated with stirring under reflux for 15 hours. After that condense in water-jet vacuum, the residue is served in methylene chloride, washed with 1 N. hydrochloric acid, dried over sodium sulfate and filtered. The filtrate is concentrated under reduced pressure, the residue digeridoo using petroleum ether and the resulting crystalline product produce by sucking.

Obtain 14.9 g (97% of theory) of 4-methyl-2-5-trifloromethyl)-2-(2,6-dichloro-3-methoxycarbonylbenzyl)-2,4-dihydro-3H-1,2,4-triazole-3-one with a melting point of 109C.

Analogously to example (IV-1 and IV-2) can be obtained, for example, and are shown in table 8 compounds of General formula (IV)

Shown in table 8 values logr defined according to EEC-Directive 79/831, Annex V A8, by high-performance liquid chromatography on obetovannoi column (18) at a temperature of 43C using as an eluent of 0.1% aqueous phosphoric acid and a linear gradient of acetonitrile (10% to 90%). Calibration osushestvlya on the basis of the retention times by linear interpolation between two subsequent one after another by alkenone).

Experimental part

The biological activity of the proposed compounds of formula (I) are illustrated by the following examples.

Example

Pre-emergence experience

Solvent: 5 weight.h. of acetone.

Emulsifier: 1 weight.h. simple alkylarylsulphonates ether.

To obtain the appropriate preparation mix 1 weight.h. the active substance with the specified quantities of the solvent, add the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration.

The seeds of control plants are sown in normal soil. After 24 hours, the soil is sprayed with the preparation so that per unit of surface is applied the desired amount of the active substance. The concentration of the solution for spraying is chosen so that applies a desired amount of the active principle in 1000 l/ha

After three weeks determine the extent of damage in % in comparison with the development of the untreated control plants. Thus

0% = action not observed (corresponds to degree of action in untreated control plants),

100% = total destruction.

The active substance, nor the experience

Solvent: 5 weight.h. of acetone.

Emulsifier: 1 weight.h. simple alkylarylsulphonates ether.

To obtain the appropriate preparation mix 1 weight.h. the active substance with the specified quantities of the solvent, add the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration.

The plants have attained a height of from 5 to 15 cm are sprayed with the preparation so that the applied desired per unit surface area is the amount of the active substance. The concentration of the solution for spraying is chosen so that applies a desired amount of the active principle in 1000 l/ha

After three weeks determine the extent of damage in % in comparison with the development of the untreated control plants. Thus

0% = action not observed (corresponds to degree of action in untreated control plants),

100% = total destruction.

The active substance, the rate of consumption, plants and the results of the experiment are summarized in table B.

1. Substituted benzoylpyrazoles General formula (I)

where n is the number 0, 1;

A - alcander (alkylen);

R1- alkyl;

R2is hydrogen, alkyl;

R3is hydrogen, halogen, unsubstituted or substituted alkyl, alkoxy, alkylsulfonyl;

R4- nitro, halog sulfonyl, phenylalkyl, phenylcarbonylamino,

Z - substituted 5-6-membered saturated or unsaturated heterocyclic group comprising 3 heteroatom (up to 2 nitrogen atoms and, if necessary - in addition to the sulfur atom) and includes advanced as a component of the heterocycle one oxo group C=O, including all possible salt.

2. Substituted benzoylpyrazoles under item 1, in which n is the number 0, 1; a - alkylen with 1-4 carbon atoms; R1is alkyl with 1-6 carbon atoms; R2is hydrogen, alkyl with 1-6 carbon atoms; R3is hydrogen, halogen, alkyl, alkoxy, alkylsulfonyl, each with 1-4 carbon atoms, unsubstituted or substituted with halogen; R4- nitro, halogen, alkyl with 1-4 carbon atoms, substituted with halogen; Y is hydrogen, alkyl with 1-6 carbon atoms, alkylsulfonyl with 1 to 6 carbon atoms in the alkyl group, alkenyl with 2-6 carbon atoms, phenylsulfonyl, phenylalkyl with 1-4 carbon atoms in the alkyl part, phenylcarbonylamino with 1-4 carbon atoms in the alkyl part, unsubstituted or substituted by residues from the group comprising nitro, cyano, halogen, alkyl with 1-4 carbon atoms, halogenated with 1-4 carbon atoms; Z is one of the following heterocyclic groups

5is hydrogen, halogen, alkyl, alkoxyl, alkylthio, each with 1-6 carbon atoms, unsubstituted or substituted by residues from the group comprising halogen, alkoxy with 1-4 carbon atoms, alkylthio with 1-4 carbon atoms, dialkylamino with 1-6 carbon atoms in the alkyl groups, alkanity with 2-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, or in case two adjacent radicals R5and R5located on a double bond, R5together with the adjacent radical R5also means anthropo or 1,4-butandiol; R6- alkyl, alkoxyl, each with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms.

3. Substituted benzoylpyrazoles under item 1 or 2, in which n is the number 0 or 1; a is methylene; R1is methyl, ethyl, tert.-butyl; R2is hydrogen, methyl, ethyl; R3is hydrogen, fluorine, chlorine, bromine, methyl, unsubstituted or substituted by fluorine, methoxy, methylsulphonyl; R4- nitro, fluorine, chlorine, methyl, substituted by fluorine; R5is hydrogen, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, triptoreline, methylthio, ethylthio, isopropylthio, Demetrio, property, cyclopropyl; R6is methyl, ethoxy, cyclopropyl; Y is hydrogen, methyl, ethyl, isopropyl, methylsulphonyl, propenyl, FD, cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl.

4. Substituted benzoylpyrazoles on one of the PP.1-3, in which Z stands for a group

5. Substituted benzoylpyrazoles on one of the PP.1-4, in which Q means the oxygen.

6. Substituted benzoylpyrazoles on one of the PP.1-4, in which n is 0.

7. Herbicide agent, characterized in that it comprises connection at one PM.1-6 and the usual fillers.



 

Same patents:

The invention relates to novel polycyclic to dihydrothiazolo General formula (I), where Y is a simple bond; X is CH2; R1 is H, F, Cl, NO2, CN, COOH, (C1-C6)-alkyl, (C2-C6)-quinil, O-(C1-C6)-alkyl, and alkyl residues one, several or all of the hydrogen atoms may be replaced by fluorine; (CH2)n-phenyl, SO2-(C1-C6)-alkyl, and n = 0 and the phenyl residue up to twice may be substituted by F, Cl, CF3, OCF3, O-(C1-C6)-alkyl, (C1-C6)-alkyl; O-(CH2)n-phenyl, and n = 0 and phenyl cycle can be one - to twofold substituted by Cl, (C1-C6)-alkyl; 1 - or 2-naphthyl, 2 - or 3-thienyl; R1' is hydrogen; R2 is H, (C1-C6)-alkyl, R3 is hydrogen; R4 - (C1-C8)-alkyl, (C3-C7-cycloalkyl, (CH2)n-aryl, and n = 0-1, and aryl can be phenyl, 2-, 3 - or 4-pyridyl, 2 - or 3-thienyl, 2 - or 3-furyl, indol-3-yl, indol-5-yl, and aryl or heteroaryl residue up to twice may be substituted by F, Cl, HE, OCF3, O-(C1-C6)-alkyl, (C1-C6)-alkyl, 2-, 3-, 4-pyridium, pyrrol-1-yl, with peregrinae ring may be substituted CF3; and their physio is

The invention relates to a derivative of 1,2,4-thiadiazole, substituted in the 5-position of General formula I, in which X Is N; R1- C1-6alkyl; R2is hydrogen, R3, R4and R5each independently selected from hydrogen; trifloromethyl;is Ar2, Ar2CH2or Het2; AG2is phenyl; Het2is a monocyclic heterocycle selected from thiadiazolyl, pyridinyl, pyrimidinyl or pyrazinyl, their N-oxide forms, the pharmaceutically acceptable acid additive salts and stereochemical isomeric forms

The invention relates to new heterocyclic compounds of the formula (I), where R1represents a group of formula (II), R is 2,4-dioxothiazolidine-5-ylmethylene group and others, And represents C1-6alkylenes group, A represents an oxygen atom, R4represents a substituted phenyl or pyridyl which may have a Deputy, R6represents a hydrogen atom or a C1-6alkyl group, D represents an oxygen atom or sulfur, E is a CH group or a nitrogen atom, or their pharmacologically acceptable salts

The invention relates to new 1,4-benzothiazepine-1,1-dioxides of the formula (I), where R1is non-branched C1-6alkyl group, R2is non-branched C1-6alkyl group, R3is hydrogen, R4represents phenyl, R5R6and R8selected from hydrogen, R7represents a group of formula (Ia) and (IB), where the hydroxy-group may be substituted by acetyl, R16represents-COOH, -CH2-OH, -CH2-O-acetyl-Sooma, R9and R10the same or different and each represents hydrogen or C1-6alkyl group, X represents-O-, or its salt, solvate and physiologically acceptable derivative

The invention relates to novel potassium salts derived biphenylmethane - mono - or dicale 2-[[5-ethyl-3-[2'-(1H-tetrazol-5-yl)biphenyl-4-yl]methyl-1,3,4-thiadiazoline-2-ilidene] aminocarbonyl] -1-cyclopentanecarboxylate having anti-hypertensive activity

The invention relates to a derivative of a simple ester, application and intermediate compounds used for their production

The invention relates to new preparations of thiazolidinediones of the formula I, where A denotes a carbocyclic ring with 5 or 6 carbon atoms or a heterocyclic aromatic 5-or 6-membered ring containing an S atom or N; B is-CH=CH-; W represents O; X represents O; Y represents N; R represents pyridyl, thienyl or phenyl, in case you need one - or disubstituted C1-C3-alkyl, CF3, Cl or bromine; R1represents C1-C6-alkyl;n represents 2, and their tautomers, enantiomers, diastereomers or physiologically acceptable salts and medicinal product on the basis of their

The invention relates to organic chemistry and can find application in medicine

The invention relates to 4-(allumination)-2,4-dihydropyrazol-3-Onam General formula I, where R1denotes benzyl, alkoxybenzyl with 1-3 C-atoms in the alkyl part, unsubstituted or substituted once to three - fold amino, acyl, halogen, nitro, CN, AO, carboxyla, carbamoyl, N-allylcarbamate, N, N-dialkylammonium (with 1-6 C-atoms in the alkyl part), A-CO-NH-, AND-O-CO-NH-, AND-O-CO -, NA-, SO2NR4R5(R4and R5can denote H or alkyl with 1-6 C-atoms or NR4R5represents 5 - or 6-membered ring, optionally with other heteroatoms, like N, or O, which may be substituted),-CO-NH-SO2-, A-CO-NA-SO2- (AND-SO2-)2N-, tetrazolium phenyl; or pyridyl; R2denotes alkyl with 1-5 C-atoms, ethoxycarbonylmethyl, hydroxycarbonylmethyl; R3denotes unbranched or branched alkyl with 1-5 C-atoms, unbranched or branched alkoxy with 1-5 C-atoms or CF3And denotes unbranched or branched alkyl with 1-6 C-atoms or CF3and their salts

The invention relates to new 1-(biphenyl-4-yl)methyl-1H-1, 2,4-triazole compounds and 1-(biphenyl-4-yl)methyl-4H-1,2,4-triazole compounds, and each of them has as a substituent in the 2'-position (2,4-dioxopyrimidine-5-ilidene)methyl or (2,4-dioxotetrahydrofuran-5-ilidene)methyl, and their salts

The invention relates to new Amida condensed terracarbon acid of General formula I, where G is Q(C)k-W-(C)m-Z, Q is phenyl, 2-, 3-, 4-pyridyl, which may be substituted; T is halogen, hydrogen, hydroxyl, amino, C1-C6alkoxy; W is-O-, -N-, -S-, CR7R8where R7and R8the same or different and represent H, C1-C6alkyl; X is hydrogen; Z is hydroxyl, C1-C6alkoxy, C3-C7cycloalkylation, NH2and other, NR9COR10where R9and R10the same or different represent H, C1-C6alkyl, etc

The invention relates to new sulfonamide of General formula I, where R1-R8A and B have the meanings indicated in the formula, which are inhibitors of endothelin and can be used for the treatment of diseases associated with the activity of endothelin, such as high blood pressure, as well as to pharmaceutical compositions based on
Up!