1-methyl-5-alkylsulfonyl-,1-methyl-5-alkylsulfonyl - 1 - methyl-5-alkylthiophene pyrazolylborate and herbicide tool based on them

 

Describes 1-methyl-5-alkylsulfonyl-, 1-methyl-5-alkylsulfonyl - 1-methyl-5-alkylthiophene pyrazolylborate General formula (I)in which R1- Akil with 1-3 carbon atoms; R2- halogen, cyano; R3is cyano, nitro, thiocarbamoyl; R4- halogen, alkyl with 1-6 carbon atoms, possibly substituted by one halogen atom, or a group NR5R6, NR5COR7, XR8,-CH2-X-R8and
n = 0, 1, or 2,
and describes the herbicide agent containing at least one compound of General formula (I). The technical result consists in obtaining new compounds of General formula (I) exhibiting herbicide action in relation to a wide range of one - and dicotyledonous weeds. 2 S. and 6 C.p. f-crystals, 3 tables.

The invention relates to 1-methyl-5-alkylsulfonyl-, 1-methyl-5-alkylsulfonyl - 1-methyl-5-alkylthiomethyl pyrazolylborate and herbicide tool based on them.

Pyrazolylborate exhibiting herbicide activity, known from various the and, which have a 5-position hydrogen or in some cases replaced by halogen alkyl, alkylthio or alkoxy. In the German patent application 19623892.7 given pyrazolylborate that in the 5-position have the rest of the group alkyl, alkylthio, alkylsulfonyl, alkylsulfonyl, alkoxy, these remnants in some cases replaced respectively by halogen. In the International application WO 97/09313 presents pyrazolylborate that in the 5-position of the pyrazol ring, among other things, contain as a substituent in some cases replaced by a residue from the group of alkyl, alkoxy, alkylthio, and in the 4-position of another pyrazol ring - thiocarbamoyl group.

In these sources are not disclosed to the special properties of specifically substituted 1-methyl-5-alkylsulfonyl-, 1-methyl-5-alkylsulfonyl - 1-methyl-5-alkylthiophene of personalpersonal. In addition, herbicide action these compounds is not always sufficient or herbicide action in the cultivation of crops of useful plants face problems of selectivity.

The present invention consists in obtaining pyrazolylborate with improved biological properties.

The problem is solved pomi formula (I)

in which R1means alkyl with 1-3 carbon atoms;
R2means halogen or cyano;
R3means cyano, nitro or thiocarbamoyl;
R4means halogen, alkyl with 1-6 carbon atoms, possibly substituted by one halogen atom, or a group NR5R6, NR5COR7, XR8,



-CH2-X-R8

or

And means one of the groups

R5denotes hydrogen, alkyl with 1-6 carbon atoms;
R6means alkyl with 1-6 carbon atoms, cycloalkyl with 3-8 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 2-6 carbon atoms, and these residues in some cases substituted by one or more identical halogen atoms, or di(alkoxy)alkyl where the alkoxy with 1-4 carbon atoms, and alkyl with 1-3 carbon atoms, or a group

R7means alkyl with 1-4 carbon atoms;
R8means alkyl with 1-6 carbon atoms, the carbon chain in which in some cases p is, alkyl with 1-3 carbon atoms;
R11means hydrogen;
R12means alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by one heteroatom, oxygen;
R13means alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by one heteroatom, oxygen;
R14means alkyl with 1-6 carbon atoms;
R16, R17, R18, R19, R20and R21independently of one another denote hydrogen, alkyl with 1-6 carbon atoms, in some cases substituted by one or more identical halogen atoms, or two of these balance together form a bond;
X is oxygen or sulfur;
m means 0, 1 or 2;
n means 0, 1 or 2;
p denotes 0, 1 or 2 and
q is 1 or 2.

The name "halogen" includes fluorine, chlorine, bromine and iodine. Preferred are, if not stated otherwise, chlorine and fluorine.

The term "alkyl with 1-3 carbon atoms" should be understood methyl, ethyl, sawn and ISO-propyl residue. By "alkyl with 1-6 carbon atoms" should be understood unbranched or branched hydrocarbon residue with 1, 2, 3, 4, 5 or 6 carbon atoms, such as, for example, in addition to the above, 1-butyln the economic balance. Similarly, it should be understood alkyl residues with a different number of carbon atoms.

The name "cycloalkyl with 3-8 carbon atoms" includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl and cyclooctyl.

Names of alkenyl with 2-6 carbon atoms" and "quinil with 2-6 carbon atoms" means a linear or when possible branched hydrocarbon residue with 2, 3, 4, 5 or 6 carbon atoms, with the specified hydrocarbon residue includes at least one multiple bond, and it can be in any position of the corresponding unsaturated residue, preferably it is not the carbon atom, which is connected with the rest of the molecule of the compounds of General formula (I). "Alkenyl with 2-6 carbon atoms in accordance with this represents, for example, vinyl, allyl, 2-methyl-2-propenyloxy, 2-butenyloxy, pentanediol, 2-methylpentanediol and hexenyl group. "Quinil with 2-6 carbon atoms" represents, for example, etinilnoy, propargilovyh, 2-methyl-2-propenyloxy, 2-butenyloxy, 2-Punchinello and 2-hexenyl group. Similarly it should be understood alkeneamine and alkyline balances with other numeric area for carbon atoms.

If uglerodnom should not be located next to each other.

By "alkoxy with 1-4 carbon atoms" should be understood alkoxygroup, a hydrocarbon residue which inherently has the meaning specified in the definition of alkyl. In the same way, it should be understood alkyl residues in other compound names, such as" alkylamino with 1-4 carbon atoms". In the case of di(alkyl with 1-4 carbon atoms)amino" are both alkyl residue may be the same or different.

If the residue is repeatedly replaced, it should be understood that at least two and maximum of all the hydrogen atoms of this residue is substituted by an identical or various other remains. The possibility of a combination of different substituents of General formula (I) limited (construction joints) principles of the structure of chemical compounds that do not form compounds, which specialists know that they are chemically unstable or structure is not possible.

Compounds of General formula (I), depending on the type and connection of the substituents may be in the form of Stereolab. If, for example, in the molecule has one or more asymmetric carbon atoms, there may be enantiomers and diastereomers. Stereoisomers can be obtained from mixtures of generated prny also selectively using stereoselective reactions using optically active source or auxiliary substances. The invention also relates to all stereoisomers and their mixtures, which are covered by the General formula (I), but is not defined particularly.

Greater interest are the compounds of General formula (I), in which
R1means alkyl with 1-3 carbon atoms;
R2means bromine, chlorine, fluorine or cyano.

Of particular interest are compounds of General formula (I), in which
R1means alkyl with 1-3 carbon atoms;
R2means bromine, chlorine or cyano;
R5denotes hydrogen, alkyl with 1-6 carbon atoms;
R6means alkyl with 1-6 carbon atoms, cycloalkyl with 3-6 carbon atoms, alkenyl with 2-4 carbon atoms or quinil with 2-4 carbon atoms, and these residues in some cases substituted by one or more identical halogen atoms, or di(alkoxy)alkyl where the alkoxy with 1-4 carbon atoms, and alkyl with 1-3 carbon atoms, or a group

R7means alkyl with 1-4 carbon atoms;
R8means alkyl with 1-6 carbon atoms, the carbon chain in which in some cases interrupted by one heteroatom, oxygen;
R12means alkyl with 1-6 carbon atoms, the carbon chain of which in some cases peruga in some cases interrupted by one heteroatom, oxygen;
R14means alkyl with 1-6 carbon atoms;
n denotes 1 or 2.

Preferred are compounds of General formula (I), in which
R1means alkyl with 1-3 carbon atoms;
R8means alkyl with 1-6 carbon atoms, the carbon chain in which in some cases interrupted by an oxygen atom;
R12means alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by an oxygen atom;
R13means alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by an oxygen atom;
n means 2.

Particularly preferred are compounds of General formula (I), in which
R1means methyl, ethyl, propyl or ISO-propyl;
R3means cyano or nitro, and
R4means alkyl with 1-6 carbon atoms, possibly substituted by one halogen atom, or a group NR5R6, NR5COR7,


-CH2-X-R8

and

Obtaining the claimed compounds are known or may be implemented by combinations of known methods by analogy the lågen, NR5R6, NR5COR7, XR8or alkyl, possibly substituted by one halogen atom,
it is known from International application WO 94/08999.

In addition, obtaining the claimed compounds of General formula (I), in which
n means 0, and
R4means one of the groups



-CH2-X-R8

and

described in the International application WO 96/09303 and in the German patent application 19623892.7.

The inventive compounds of General formula (I) in which n represents 1 or 2, can be obtained from corresponding compounds of General formula (I) in which n represents 0, using the method known in the art, such as reaction with a suitable oxidizing agent. Suitable oxidants are, for example, hypochlorites, organic percolate, such as m-perchlorobenzene acid and peracetic acid, inorganic chemicals, such as ozone, chlorine, hydrogen peroxide, periodate sodium, perborate sodium, potassium permanganate and oxygen in the air.

The claimed compounds can be used in conventional compositions in fo the Subject of the invention is therefore also herbicide agent, which contains at least one compound of formula (I).

The compounds of formula (I) can be introduced into the compositions of various types, depending on which biological and/or physico-chemical parameters are provided. As possible type formulations may, for example, be considered sprayable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water" or "water in oil", solutions for spray, concentrated suspensions (CS), dispersions on an oil or water-based, mixed with oil solutions, suspensions for capsules (CS), funds in the form of dust (DP), etching tools, granules for spreading and deposition on soil, granules (GR) in the form of microgranules, granules spray, granules for Elevator and adsorption granules, dispersible in water and granules, water-soluble granules (WG), ULV formulations, microcapsules and compounds in the form of wax (mastic).

These separate types of trains in principle known and described, for example,, "Chemische Technologie", Band 7, C. Hauser Verlag, 4. Aufl. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N. Y. , 1973; K. Martens, "Spray Drying" Handbook, 3rd ed., 1 the crystals, surfactants, solvents and additional additives are also known and described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd ed., Darland Books, Caldwell N. J., H. V. Olphen, "Introduction to Clay Colloid Chemistry", 2nd ed., J. Willey & Sons, N. Y.; C. Marsden, "Solvents Guide", 2nd ed., Interscience, N. Y., 1963; McCutcheon''s "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N. J. ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N. Y., 1964;, "Grenzflachenaktive Athylenoxidaddukte", Wiss. Verlagsgesell. , Stuttgart, 1976; Winnacker-, "Chemische Technologie", Band 7, C. Hauser Verlag, 4. Aufl., 1986.

On the basis of these compounds may be obtained as a combination with other substances, active as pesticides, such as insecticides, acaricides, herbicides, fungicides, and also with protective equipment, mineral fertilizers and/or growth regulators, for example, in the form of a solid composition or in the form of commercial mixtures.

Powders for spraying are also dispersible in water preparations, which, along with the active component, in addition to diluents and inert substance, also contain surfactants of ionic and/or nonionic type (wetting and dispersing agents), for example, polyoxyethylene ALKYLPHENOLS, polyoxyethylenated residues of fatty polyhydric alcohols, alkanesulfonyl, alkylbenzenesulfonate, sodium salt ligninsulfonate acid, sodium salt of 2,2'- dynafilter-6,6'-disulfonate, sodium salt of dibutylaminoethanol or sodium salt oleoylethanolamide acid (taurine). To obtain a sprayable powder active ingredients (herbicides) finely pulverized, for example, in conventional apparatuses such as hammer mills, blower mills or air-jet mills, and simultaneously or after the above-mentioned process is mixed with part of assistive technology.

Emulsifiable concentrates are obtained by dissolving the active ingredients in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or high-boiling aromatic solvents or hydrocarbons or mixtures of organic solvents with addition of one or more surfactants of ionic and/or nonionic type (emulsifiers). As emulsifiers can be used, for example, calcium salt alkylarylsulfonates, such as qualitydetermination, or nonionic emulsifiers, such as polyglycolide esters of fatty acids, alkylaryl, alkalemia polyethers, esters sorbitan, such as esters sorbitan and fatty acids or polyoxyethylene esters sorbitan, for example polyoxyethylene esters sorbitan and fatty acids.

Fine powders (means in the form of dust) can be obtained by grinding the active ingredient with finely powdered solid substances, for example talc, natural clays such as kaolin, bentonite or pyrophyllites, or hard-shelled land.

The concentrated suspensions can be water or oil based. They can be obtained, for example, by wet grinding using conventional mills and in some cases with the addition of surface-active substances, such as already described above for other types of structures.

Emulsions, for example, emulsion oil in water (EW), can be obtained, for example, with agitators (mixers), colloid mills and/or static mixers using aqueous organic solvents and, in some cases, surface-active substances, such as, for example, has already been described above for other types of structures.

The granules can be obtained either by spraying the active components capable of adsorption, granulated inert material, or ipolyarray.h acids or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. Suitable active ingredients may also be granulomatosa usual to obtain a granular manner, optionally in a mixture with fertilizers.

Dispersible in water pellets, usually obtained by conventional technologies, such as spray drying, spray granulation in the vortex layer (flow), disk granulation, mixing in high-speed mixers and extrusion without solid inert material.

About getting disc granules fluidized granules, pellets made by extrusion and spray see, for example, the way in "Spray-Drying Handbook", 3rd ed., 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration", Chemical and Engineering 1967, Seiten 147 ff; "Perry's Chemical Engineer''s Handbook", 5th ed., McGraw-Hill, New York, 1973, s. 8-57.

Additional details regarding the composition of plant protection products see, for example, in G. C. Kingman, "Weed Control as a Science", John Wiley and Sons, Inc. , New York, 1961, Seiten 81-96 and J. D. Freyer, S. A. Evans, "Weed Control Handbook", 5th ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101-103.

Agrochemical compositions contain, as a rule, from 0.1 to 99 wt.%, in particular from 0.1 to 95 wt.%, the active substance of the formula (I).

In powders for spraying concentration act out of the ordinary ingredients of the composition. In the case of emulsifiable concentrates, the concentration of the active substance can be from 1 to 90 wt.%, preferably from 5 to 80 wt.%. Fine compositions contain from 1 to 30 weight. % of active substance, preferably mainly from 5 to 20 wt.% the active substance, spray solutions contain from about 0.05 to 80 weight. %, preferably from 2 to 50 wt.%, the active substance. In case dispersible in water and granules, the active substance depends partly on whether the active compound is liquid or solid and what granular auxiliary tool which fillers and so forth are used. For granules, dispersible in water, the active substance is, for example, between 1 and 95 wt.%, preferably between 10 and 80 weight. %.

Along with this, these compositions containing the active substance, in some cases, contain conventional current funds for adhesion, wetting, dispersing agents, emulsifiers, penetration means (penetrants, preservatives, antifreeze agents, solvents, fillers, carriers and colorants, defoamers, substances that prevent evaporation, and tools that affect the pH and viscosity.

The inventive compounds of General formula (I) exhibit excellent is s (weeds). On hard eradicates perennial weeds, which allowed shoots from rhizomes, roots or other long-lasting parts, also good are the active components. Still, information on whether the connection to the appropriate method before sowing, before germination or after germination. In particular, it should be called, for example, some representatives of one - and dicotyledonous weed flora, the growth of which can be controlled using the claimed compounds, although, based on the names, it is not necessary to impose restrictions on certain other types.

From among the monocotyledonous weed species action compounds are, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus (ground almonds) from the annual group, and from among the perennial species, Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species.

In dicotyledonous weed species, the spectrum of action extends, for example, on species of Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilion and Sida from the number of annual weeds, and nvolvulus, Cirsium, Rumex and Artemisia in perennial weeds.

When the specific conditions of cultivation of crops with weeds found in rice, such as Echinochloa, Sagittaria, Alisma, Eleocharis, S applied to the soil surface before germination, either the germination of embryos of completely suppressed weeds, or weeds only grow to the level of embryonic shoots, then comes their growth, and, in the end, they completely die within 3-4 weeks after germination.

When applying the active compounds in green parts of plants after germination sudden growth also comes very quickly after the treatment, and the weed stop at the stage of growth at which they were at the time of application, or die off after a certain time, and thus very early and permanently eliminates harmful to cultivated plants competition.

Despite the fact that the claimed compounds exhibit pronounced herbicide activity in relation to one - and dicotyledonous weeds, crop plants of economic important crops such as wheat, barley, rye, rice, maize, sugar beet, cotton and soya, are not significantly damaged or not damaged at all. For these reasons, the presented compounds are very well suited for the selective combating undesirable plant growth in the cultivation of useful agricultural crops and ornamental plants.

On the basis of their herbicide properties of the active substance can be and the ski modified plants still subject to development. Transgenic plants have, as a rule, are particularly useful properties, such as resistance to certain pesticides, especially to certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other distinguishing characteristics include, for example, fruits, namely, their quantity, quality, capacity for long-term storage, composition and special ingredients. So, for example, known transgenic plants with increased starch content or a changed amount of starch or plants with a different composition of fatty acids in the fruit.

Preferred is the use of the inventive compounds of the formula (I) in the cultivation of economically important transgenic crops of useful and ornamental plants, for example cereals such as wheat, barley, rye, oats, millet, rice, manioc and corn, or other crops of sugar beet, cotton, soybean, rapeseed, potato, tomato, peas and other vegetables.

Preferably, the inventive compounds of General formula (I) can be used as herbicides in Vostochnyi in santehnicheskie changes.

The traditional way of getting new plants which have modified properties compared to conventional plants, consists, for example, in the classical way of excretion and the production of mutants. Alternative new plants with modified properties can be generated using santehnichekogo method (see , for example, European patent application EP-A 0221044, EP-A 0131624). In some cases, are described, for example,
hentainiches changes of cultivated plants in order to modify synthesized in plants starch (for example, International application WO 92/11376, WO 92/14827, WO 91/19806),
transgenic crop plants which are resistant to certain herbicides of the type of glufosinate (see, for example, European patent application EP-A 0242236, EP-A 0242246) or glyphosate (international application WO 92/00377) or sulfonylureas (European patent application EP-A 0257993, U.S. patent US-A 5013659),
transgenic crop plants, for example cotton, with the ability to produce Bacillus Thuringian toxins (Bt toxins) which make the plants resistant to certain pests (European patent application EP-A 0142924, EP-A 0193259),
transgenic plants with modified of train is Yu, which can be obtained new transgenic plants with modified properties, in principle known (see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2. Aufl. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, or Winnacker "Gene und Klone", VCH Weinheim 2. Edition, 1996, or Christou, "Trends in Plant Science" 1 (1996), 423-431). For such santehnicheskie manipulation of the nucleic acid molecule can be introduced into plasmids which allow mutagenesis or changing sequences due to recombination of DNA sequences. Using the above standard methods can occur, for example, the exchange of reasons, to leave part of the sequences or to add natural or synthetic sequences. To link the DNA fragments to each other on the fragments can sit down adapters or links.

Obtaining plant cells with a reduced activity of geneproduct can be achieved, for example, using the expression of at least one corresponding antisense RNA (antisense-RNA), one sense RNA (sense-RNA) to achieve compressional effect or expression of at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned reproductiv. Besides can be used combined DNA molecules, which include the common code is likely DNA which include only part of the coded sequence, with the parts must be of sufficient length to cause the cells antisense (antisense) effect. You can also use sequences of DNA that have a high degree of gomologichnosti to coded sequences of geneproduct, but not identical.

When the expression of nucleic acid molecules in plants are synthesized protein can be localized in any compartment of plant cells. But in order to achieve localization in a particular compartment, it is possible, for example, to associate the encrypted region with DNA sequences which ensure localization in a particular compartment. Such sequences are known (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al. , Proc. Natl. Acad. Sci., USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).

Transgenic plant cells can be regenerated by known technologies in whole plants. In the case of transgenic plants fundamentally we can talk about plants of any kind, that is, as monocots and dicots. So can be obtained transgenic plants which exhibit modified properties due to overexpression, suppression or inhibition of homologous is Preferably the inventive compounds of General formula (I) can be used in transgenic crops, which are resistant to herbicides from the group including sulfonylureas, glufosinate ammonium or (and) picofast of Isopropylamine, and analogous active substances.

The use of the claimed active substances in transgenic crops, along with the action on the weeds observed in other cultures, there are also actions that are specific for use in the current transgenic crops, for example a modified or specifically the expected range (set) weeds which can be controlled, changed number, which can be used for application, preferably good ability in combination with herbicides, which is resistant transgenic crops and the impact on the growth and yield of transgenic crops.

Depending on external conditions such as temperature, humidity, the type of herbicide, among other things varies expenditure required amount of the inventive compounds of General formula (I). It can vary within wide limits, for example between 0.001 and 10.0 kg/ha of active substance or more, preferably it lies between 0.005 and 5 kg/ha

A. Examples of obtaining compositions
A1. Melkodispersnoe formula (I) with 90 weight. including talc as inert substance and then crushed in a hammer mill.

A2. Dispersible powder.

Easily dispersible in water, humidified powder is such that the mixing 25 weight.h. compounds of General formula (I), 64 weight.h. kalisoderjasimi quartz as inert substance, 10 weight.h. potassium salt of ligninsulfonate and 1 weight.h. sodium salt oleoylethanolamide acid as wetting and dispersing means and ground in a rod mill.

A3. The concentrate dispersion.

Easily dispersible in water concentrate dispersion receive so that mixing 20 weight.h. compounds of General formula (I), 6 weight.h. alkylphenol ether (@Triton X 207), 3 weight.h. isotridekanolethoxylate ether (8 EO) and 71 weight.h. paraffinic mineral oil (boiling, for example, from about 255 to 277oC) and milled in a ball mill to a fineness of less than 5 microns.

A4. Emulsifiable concentrate.

Emulsifiable concentrate is obtained from 15 weight.h. compounds of General formula (I), 75 weight.h. cyclohexanone as solvent and 10 weight.h. ethoxylated Nonylphenol as emulsifier.

A5. Dispersible in water granulate.

10 weight.h. the calcium salt of ligninsulfonate,
5 weight.h. acrylourethane,
3 weight.h. polyvinyl alcohol and
7 weight.h. kaolin
on the rod mill and the resulting powder was granularit in the vortex layer by spraying with water as the granulating fluid.

Dispersible in water, the granules also receive so that
25 weight.h. compounds of General formula (I),
5 weight.h. sodium salt of 2,2'-dynafilter-6,6'-disulfonate,
2 weight.h. sodium salt oleoylethanolamide acid,
1 weight.h. polyvinyl alcohol,
17 weight.h. calcium carbonate and
50 weight.h. water
homogenized in a colloid mill and then ground, then grind the bead mill, and the thus obtained suspension is sprayed into the scrubber and dry.

Dispersible in water granulate get so that mix
35 weight.h. connection 320,
40 weight.h. compounds 15,
10 weight.h. the calcium salt of ligninsulfonate,
5 weight.h. acrylourethane,
3 weight.h. polyvinyl alcohol and
7 weight.h. kaolin
on the rod mill and the resulting powder was granularit in the vortex layer by spraying with water as the granulating fluid.

C. Examples of obtaining wasestimated-1-(1-methyl-5-methylthio-3-pyrazolyl)of pyrazole in 50 ml of methylene chloride was stirred at -30oWith 0.9 g (6.5 mmol) of chloride Sulfuryl. Then the reaction mixture contribute with stirring into a solution of sodium bicarbonate, extracted with methylene chloride, dried over sodium sulfate and evaporated. Chromatography of the resulting product on silica gel with the eluent ethyl acetate/hexane gives the target of the above compound in the form of colorless crystals. The output of 1.80 g (81.3% of theory), melting point 129-132oC.

Getting the parent compounds (preliminary stage).

a) 3-Amino-1-methyl-4-cyano-5-methylmercaptopurine
9,63 g (a 56.6 mmol) of bis(methylmercapto)metromedical suspended in 50 ml of water and added to 3.7 ml (67,9 mmol) methylhydrazine. The mixture is heated 1 hour at boiling, cooled, the precipitate is sucked off and recrystallized from ethanol. Output 6,55 g (68,8% of theory), melting point of 120-121oC.

b) 3-Amino-1-methyl-5-methylmercaptopurine
5.5 g (33.0 mmol) of 3-amino-1-methyl-4-cyano-5-methylmercaptopurine heated with 50 ml of 32% caustic soda for 24 hours at boiling. The reaction mixture is cooled, acidified with a solution of nutregisterdevice to slightly acid reaction, is heated 8 hours at 50oC and then extracted with ethyl acetate. The organic layer is dried over sodium sulfate, UPT theory).

c) 3-Hydrazino-1-methyl-5-methylmercaptopurine
To 1.9 g (of 13.1 mmol) of 3-amino-1-methyl-5-methylmercaptopurine in 18 ml of concentrated hydrochloric acid at 0oWith added dropwise 1.1 g (15.8 mmol) of sodium nitrite in 4 ml of water and stirred for 2 hours at 0oC. Then, to the obtained solution at -30oWith added dropwise a solution of 7.4 ml (32,8 mmol) douglasthe tin in the form of a hydrate and stirred for 3 hours at the same temperature. After that, the mixture is alkalinized 32% solution of sodium alkaline to alkaline and extracted with methylene chloride. Dried (sodium sulfate) and after removal of the solvent obtain 2.0 g of product, which can be used without further purification.

d) 4-Cyano-5-diethoxylate-1-(1-methyl-5-methylthio-3-pyrazolyl)pyrazole
2.0 g (12.6 mmol) of 3-hydrazino-1-methyl-5-methylmercaptopurine and 2.86 g (12.6 mmol) of 2-cyano-4,4-diethoxy-1-(N,N-dimethylamino)-1-butene-3-one in 30 ml of ethanol is heated 5 hours at the boil under reflux. The solvent is then evaporated on the rotor and the remainder chromatographic on silica gel. Get 2.50 g (79%) of the desired intermediate substance in the form of a viscous oil.

B2. 4-Cyano-5-diethoxylate-1-(4-chloro-1-methyl-5-methylsulphonyl-3-pyrazolyl)pyrazole.

1.0 g (2.8 mmol) of 4-cyano-5-diethoxylate loretana stirred for 3 hours at 0oAnd then 12 hours at room temperature. The reaction mixture was washed with sodium thiosulfate solution and then with sodium bicarbonate solution and water, dried (sodium sulfate) and the solvent is distilled off. Column chromatography on silica gel (ethyl acetate/hexane) gives the desired product in the form of colorless flakes. Yield 0.87 g (80% of theory), melting point 129-132oC.

B3. 4-Cyano-5-(1,3-dioxolane-2-yl)-1-(4-chloro-1-methyl-5-methylsulphonyl-3-pyrazolyl)pyrazole.

0.6 g (1.5 mmol) 4-cyano-5-diethoxylate-1-(4-chloro-1-methyl-5-methylsulphonyl-3-pyrazolyl)pyrazole (example B2) and 0.5 ml of ethylene glycol are heated together with 10 mg of p-toluenesulfonic acid in 20 ml of toluene under reflux for 3 hours. The mixture is then shaken with sodium bicarbonate and water. Dried (sodium sulfate) and after concentrating on the rotor get the desired product in crystalline form, which can be then purified by recrystallization or column chromatography on silica gel. Yield 0.52 g (94% of theory), melting point 154-158oC.

B4. 4-Cyano-5-(1,3-dioxane-2-yl)-1-(4-chloro-1-methyl-5-methylsulphonyl-3-pyrazolyl)pyrazole.

1.0 g (3.2 mmol) of 4-cyano-5-formyl-1-(4-chloro-1-methyl-5-methylsulphonyl-3-pyrazolyl)pyrazole, 0.35 g (4.6 mmol) of 1,3-dihydroxypropane € target compound in the form of colorless crystals. Yield 0.96 g (82,4% of theory), melting point 210-214oC.

Getting the parent compounds (preliminary stage).

4-Cyano-5-formyl-1-(4-chloro-1-methyl-5-methylsulphonyl-3-pyrazolyl)pyrazole
1.10 g (3.5 mmol) of 4-cyano-5-diethoxylate-1-(4-chloro-1-methyl-5-methylsulphonyl-3-pyrazolyl)pyrazole was dissolved in 20 ml of dioxane and, after addition of 2 ml of 50% sulfuric acid is heated for 2 hours under reflux. After cooling, the solution of the volatile components distilled off, the residue is treated with dichloromethane and extracted with water and sodium bicarbonate solution. After drying with sodium sulfate and evaporation of the solvent on the rotor obtain 0.95 g (86%) of the desired aldehyde, which can be introduced into the reaction without additional purification.

The compounds listed in the table. 1, can be obtained analogously or by using similar methods.

C. Biological examples
C1. Predsjedava processing.

Seeds (embryos) or root processes of mono - and dicotyledonous harmful and useful plants were planted in pots with a diameter of 9 cm in sandy loam soil and covered the same ground. In addition, an alternative to the test on the rice sprouts rice, as well as the most harmful in these cultures weeds were cultivated in Presiden the ode, the amount which was taken from the calculation of 800 l/ha, in various dosages on the surface of bare soil or when testing on rice poured into the water for irrigation. Then the pots was kept for further cultivation of plants in the greenhouse under optimum conditions. Visual assessment of the damage to beneficial and harmful plants (weeds) were produced after shoots of these plants, that is, approximately 2-4 weeks after the start of the experiment.

When used in the amount of 330 g/ha compounds 13, 16, 23 and 26 have, for example, 90-100% effect on Stellaria viridis. When used in the same amounts of compounds 13, 16, 21 and 25 have, for example, 90-100% effect on Stellaria media.

When used in a quantity of 80 g/ha of compound 6 and 11 have, for example, 100% effect on Matricaria inodora, Chenopodium album and Veronica persica.

When using quantities of 80 g/ha compounds 6, 11 and 36 do not have, for example, any harmful effect on rice (in rice).

In addition, connections 7, 8, 9, 10, 11, 13, 38, 53, 54, 66, 68, 69, 95, 119, 120, 121, 126, 149, 169, 171, 185, 188, 202 and 254 when used in quantities less than 1000 g/ha have at least 90% effect on the number of one - and dicotyledonous harmful plants.

C2. Treatment after germination.

Useful plants and various saradhi germination 3-4 petals and then processed diluted with water, a composition of the claimed compounds the quantity of water was 300 l/ha, four weeks after treatment, the quality of the plants was estimated visually for each type of the harmful effects of active substances, when this was especially taken into account the amount of damage growth. Evaluation was performed on the percentage scale (0-100%) in comparison with the control group, not exposed to processing.

When used in the amount of 330 g/ha compounds 13, 16, 23 and 25 have, for example, 100% effect on Amaranthus retroflexus. When used the same amounts of compounds 13 and 25 have, for example, 100% effect on Setarria viridus.

When used in a quantity of 80 g/ha compounds 6, 11 and 42 have, for example, 100% effect on Galium aparine and Fallopia convolvulus. When used the same amounts of compounds 6, 11, 13, 23 and 36 have, for example, 100% action in Pharbitis purpurea.

When used in a quantity of 80 g/ha compound 37 and 41 do not have, for example, no harmful effects on corn. When the same quantities used do not have, for example, compounds 36 and 37 no harmful effects on the rice.

Moreover, connections 7, 8, 9, 10, 11, 13, 28, 38, 53, 54, 66, 79, 88, 90, 94, 97, 98, 102, 121, 162, 163, 174, 185, 186, 187 and 254 when used in quantities less than 1000 g/ha have, YTO receive the following data for the connection 257 (see table. 2).

All of the compounds falling within the above General formula (I) have similar herbicide activity.


Claims

1. 1-Methyl-5-alkylsulfonyl-, 1-methyl-5-alkylsulfonyl - 1-methyl-5-alkylthiophene pyrazolylborate General formula (I)

in which R1- alkyl with 1-3 carbon atoms;
R2halogen or cyano;
R3is cyano, nitro or thiocarbamoyl;
R4- halogen, alkyl with 1-6 carbon atoms, possibly substituted by one halogen atom, or a group NR5R6, NR5COR7, XR8,



-CH2-X-R8,

or

A - one group

or

R5is hydrogen, alkyl with 1-6 carbon atoms;
R6is alkyl with 1-6 carbon atoms, cycloalkyl with 3-8 carbon atoms, alkenyl with 2-6 carbon atoms or quinil with 2-6 carbon atoms, and these residues in some cases substituted by one or more identical atoms is r />
R7is alkyl with 1-4 carbon atoms;
R8is alkyl with 1-6 carbon atoms, the carbon chain in which in some cases interrupted by one heteroatom, oxygen;
R9is hydrogen, halogen;
R10is hydrogen, alkyl with 1-3 carbon atoms;
R11is hydrogen;
R12is alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by one heteroatom, oxygen;
R13is alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by one heteroatom, oxygen;
R14is alkyl with 1-6 carbon atoms;
R16-R21independently from each other hydrogen, alkyl with 1-6 carbon atoms, in some cases substituted by one or more identical halogen atoms, or two of these balance together form a bond;
X is oxygen or sulfur;
m= 0, 1, or 2;
n= 0, 1, or 2;
p= 0, 1, or 2;
q= 1 or 2.

2. Pyrazolylborate General formula (I) under item 1, where R1- alkyl with 1-3 carbon atoms; R2is bromine, chlorine, fluorine or cyano.

3. Pyrazolylborate General formula (I) under item 1 or 2, where R1- alkyl with 1-3 carbon atoms; R2is bromine, chlorine or cyano; R5is hydrogen, alkyl with 1-6 carbon atoms; R6 2-4 carbon atoms, moreover, these residues in some cases substituted by one or more identical atoms, halogen or di-(alkoxy)-alkyl where the alkoxy with 1-4 carbon atoms, and alkyl with 1-3 carbon atoms, or a group

R7is alkyl with 1-4 carbon atoms; R8is alkyl with 1-6 carbon atoms, the carbon chain in which in some cases interrupted by one heteroatom that is oxygen; R12is alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by one heteroatom, oxygen;13is alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by one heteroatom, oxygen;14is alkyl with 1-6 carbon atoms; n= 1 or 2.

4. Pyrazolylborate General formula (I) according to any one of paragraphs. 1-3, where R1- alkyl with 1-3 carbon atoms; R8is alkyl with 1-6 carbon atoms, the carbon chain in which in some cases interrupted by an oxygen atom; R12is alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by an oxygen atom; R13is alkyl with 1-6 carbon atoms, the carbon chain of which in some cases interrupted by an oxygen atom; n= 2.

5. Pyrazolylborate General formula (I) according to any one of paragraphs. 1-4,ode, possibly substituted by one halogen atom, or a group NR5R6, NR5COR7,


-CH2-X-R8,

and

6. Pyrazolylborate General formula (I) according to any one of paragraphs. 1-5, where R1is methyl; R2is bromine, chlorine or cyano; R4- one of the groups,


or

7. Herbicide tool which contains at least one compound of General formula (I) according to one of paragraphs. 1-6.

8. Herbicide product p. 7 in a mixture with an auxiliary means of composition.

 

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