5-hydroxypyrazol-4-ylcarbamate derivatives of saccharin with herbicide action and herbicide tool

 

(57) Abstract:

The invention relates to new 5-hydroxypyrazol-4-incorporatedin saccharin derivative of formula I

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in which the substituents have the following meaning: L, M means hydrogen, C1-C4alkyl, chlorine, Z denotes hydrogen, C1-C4alkyl, C3-C8alkenyl, C3-C5quinil, phenyl, Q means the radical CO-J; J means connected to position 4 of the benzene ring 5-hydroxypyrazoles ring of formula II

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in which R1means C1-C4alkyl, and R2means hydrogen or methyl, and is usually used in agriculture salts of compounds (I). Herbicide agent, derivative containing saccharin of formula I and conventional inert additives used to control undesirable vegetation. 2 S. and 2 C.p. f-crystals, 3 tables.

The object of the present invention are 5-hydroxypyrazol-4-ylcarbamate derivatives of saccharin of formula I

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in which the substituents have the following meanings:

L, M means hydrogen, C1-C4alkyl, chlorine,

Z denotes hydrogen, C1-C4alkyl, C3-C6alkenyl, C3-C5quinil, phenyl;

Q RA means the

R1means C1-C4alkyl and

R2means hydrogen or methyl,

as well as typically used in agriculture salts of the compounds I.

The subject invention are further herbicide preparations containing the compounds of formula I and a method of controlling undesirable vegetation using the derivatives of saccharin I. Derivatives of saccharin with herbicide action, in the prior art to date has not been described. As for the unsubstituted saccharin (amide o-sulfobenzoic acids, i.e. L, M, Q and Z in formula I mean H), it is known from ancient times as synthetic sweeteners. As such sweeteners known next 4-hydroxycoumarin (see laid out the proposal of Germany DE-OS 3607343). It is also known the use of saccharin derivatives as fungicides to combat agricultural pests (see, for example, publication of Japanese 72/00419 and 73/35457) and pharmaceuticals (see, for example, European patent application EP-A 594257 and provides it as reference patents).

Heterocyclic compounds with ring containing sulfonamidnuyu group became known as herbicides, a typical representative for new herbicides with unknown up to the present time for this display, the main structure. In accordance with this task were obtained the compounds of formula I above composition. The compounds of formula I get due to the fact that 5-hydroxypyrazol formula II acelerou the acid chloride of the acid of formula IV and the resulting phrasology ether to regroup saccharin derivatives of the formula I. 1.

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In the above formulas, L, M and Z have the above meaning. The first stage of a sequential reaction, i.e., acylation, are carried out by generally known methods, for example, by adding a carboxylic acid of formula IV to a solution or suspension of 5-hydroxypyrazol II in the presence of an auxiliary base. Reagents and auxiliary basis it is reasonable to use approximately equimolar amounts. A slight excess of the auxiliary base, for example, 1.2 to 1.5 mol. equivalent in terms of the number of compounds II, under certain circumstances, may be preferred.

As auxiliary bases are suitable, for example, tertiary bonds alkylamines, pyridine or carbonates of alkali metals, and solvents can be used, for example, methylene chloride, diethyl ether, toluene or ethyl ether cooled to 0 to 10oC, then mix it at an elevated temperature, for example, in the range from 25 to 50oC, until the completion of the exchange reaction. The processing carried out by the usual methods, for example, the reaction mixture is poured into water and the desired product is extracted with, for example, methylene chloride. After drying the organic phase and removal of the solvent the crude 5-hydroxypyrazolo ether can without subsequent treatment to use to rearrange. The examples of the preparation of esters of benzoic acid 5-hydroxypyrazolo can be found, for example, in European application EP-A 282944 or in U.S. patent 4643757.

The rearrangement of 5-hydroxypyrazolo esters to compounds of formula I. 1 expediently carried out at temperatures in the range from 20 to 40oC in a solvent and in the presence of an auxiliary base, and using cyanocobalamine acting as a catalyst.

As solvents can be used, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl ester acetic acid or toluene. The preferred solvent is acetonitrile. As auxiliary bases are suitable tertiary bonds alkylamines, pyridine or carbonates of alkali metals, which are used preference what Finance is triethylamine in double quantity.

As catalysts acceptable amongst zianidnye compounds such as potassium cyanide or acetonecyanohydrin, preferably in an amount of from 1 to 50 mol.%, first of all, from 5 to 20 mol.% in terms of 5-hydroxypyrazolo ether. It is advisable to apply acetonecyanohydrin, for example, in amounts of 10 mol.%.

Examples of rearrangement benzoylacetate esters of 5-hydroxypyrazolo can be found, for example, in European application EP-A 282944 or in U.S. patent 4643757, but as a catalyst in these publications apply only potassium carbonate or sodium carbonate in dioxane. The use of cyanide of potassium or acetonecyanohydrin in connection with carrying out a similar rearrangement of enol esters of cyclohexane-1,3-diones although it is known (see U.S. patent 4695673), however in the literature there are no examples showing that zianidnye compounds are particularly suitable for implementation rearrangements Fris O-acyl derivatives of 5-hydroxypyrazol.

The processing carried out by well-known methods. For example, the reaction mixture is acidified with dilute mineral acids, such as 5% hydrochloric acid or sulfuric acid, and extracted with, for example, methylene chloride or ethyl is metal, and the final product is transferred to the aqueous phase. Acidification of an aqueous solution of the product of formula I are precipitated or re-extracted with methylene chloride, dried and then removed from the solvent.

Used as starting material 5-hydroxypyrazol formula II are known and can be obtained by known methods (cf. the European application EP-A 240001 and Journ. Prakt. Chem. 315, 382 (1973)). 1,3-dimethyl-5-hydroxypyrazol is commercially available connection.

Educt of the formula IV get by well-known methods interaction shinkareva acid of formula III with thionyl chloride.

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Shrinkable acid III partially known (4-COOH: Zincke, Liebigs Ann. 427. 231 (1922), 5-COOH: Jacobsen, Chem. Ber. 13, 1554 (1980), 6-COOH: Weber, Chem. Ber. 25, 1740 (1982)). Further, in lined with the application of Germany DE-OS 3607343 described getting 4-hariharan-5-carboxylic acid.

The possibility of obtaining shinkareva acids also lies in the fact that the corresponding bromo - or izlesene derivatives of saccharin of formula A1

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in which L, M and Z have the above meaning, or, if Z does not imply H, the compounds of formula A2

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in the presence of a catalyst based on a transition metal from the group vkluchaya is responsible with C1-C6alcohol at an elevated pressure.

Itchina already known from the literature, in particular 6-itchin: see De Roode, Amer. Chem. Journal 13, 231 (1981). You can get them either permanganate oxidation izlesene 2-methylbenzenesulfonamide, or by the reaction of Sandmeier of aminosaccharides. Aminocoumarin get by well-known methods by restoring nitrosoureas, which in turn are either known (see Kastle, Amer. Chem. Journal 11, 184 (1989) or DRP 551423 (1930)), or can be synthesized by known methods publications from the corresponding derivatives of nitrobenzene (see Liebigs Ann. 669, 85 (1963)) or nitrobenzenesulfonamide.

If, for example, L is methyl, and M and Z denote hydrogen, the sequence of the reaction can be represented in the following form:

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Nickel, cobalt, rhodium and especially palladium catalysts can be represented in the metallic form or in the form of the usual salts, such as halogen compounds, for example, PdCl2, RhCl3H2O, acetates, for example, Pd(OAc)2, cyanide, and so on, with some degree of valence. Then can be represented by the complexes with tertiary phosphines, alkylcarboxylic metals, Carboni for example, (PPh3)2Ni(CO)2or salts of transition metals that form complexes with tertiary phosphines. This latter implementation is particularly preferred in the case of a palladium catalyst. When this type phosphine ligands can vary within wide limits. They can be represented, for example, in the form of the following formula:

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or

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where n means the number 1, 2, 3 or 4 and the radicals R3-R6represent low-molecular alkyl, for example, C1-C6alkyl, aryl, C1-C4alkylaryl, for example, benzyl or phenethyl, or aryloxy. Aryl is, for example, naphthyl, antril and preferably optionally substituted phenyl, and about deputies should consider only their inertness to reaction carboxylation, otherwise they can be varied in a wide range and they include all inert C-organic radicals, such as C1-C6alkyl radicals, e.g. methyl, carboxyl radicals, such as COOH, COOM (M represents, for example, salts of alkali, alkaline earth metal or ammonium salt), or C-organic radicals linked through oxygen, such as C1-C6alkoxy.

the above publications. So, for example, originate from a conventional, commercially available metal salts, such as PdCl2or Pd(OCOCH3)2and add a phosphine, for example, P(C6H5)3P(n-C4H9)3, PCH3(C6H5)2, 1,2-bis(diphenylphosphino)ethane.

The amount of phosphine relative to the transition metal is typically 0-20, especially 0.1 to 10 mol. equivalents, particularly preferably 1-5 mol.equivalents.

The amount of transition metal is not the decisive factor. Of course, that for reasons of economy I prefer to use a small amount, for example, from 0.1 to 10 mol.%, first of all, from 1 to 5 mol% in terms of the initial connection A1, A2 respectively.

To obtain shinkareva acids of the formula III interact with carbon monoxide and at least equimolar quantities of water in terms of starting compound A1, A2 respectively. The reaction component water can also serve solvent, in other words, it is the maximum number does not play a decisive role.

Depending on the type of starting compounds and the used catalyst may also be added is, or use as a solvent base, which is used for carboxylation.

As inert solvents are acceptable such, usually used for carboxylation reactions, in particular hydrocarbons such as toluene, xylene, hexane, pentane, cyclohexane, ethers such as methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides, such as dimethylformamide, peremeshenie urea, such as Tetra-C1-C4alkylation, or NITRILES, such as benzonitrile or acetonitrile.

In one of the preferred embodiments of the method of one of the reaction components, the base is used in excess, thus eliminating the necessity of dopolnitelnom solvent.

Suitable for implementing the method bases are bases that can bind released during the reaction of hydrogen iodide, respectively, hydrogen bromide. As examples can be mentioned in this connection tertiary amines, such as triethylamine, cyclic amines such as N-methylpiperidine or N,N'-dimethylpiperazine, pyridine, hydroxides, carbonates or bicarbonates of alkali or alkaline earth metal, or tetraalkylammonium p the/P> The amount of base is not the decisive factor is usually applied from 1 to 10, especially from 1 to 5 moles. While using the base as a solvent, its amount is chosen so that the components of the reaction were dissolved, and for reasons of practicality avoid unnecessarily large excess in order to save money, but also for the ability to use a small reaction vessels and the conditions for maximum contact between the reaction components.

During the reaction the pressure of carbon monoxide is set to provide a constant excess CO in relation to the compounds A1, A2 respectively. Preferably the pressure of carbon monoxide at room temperature is from 1 to 250 bar, particularly from 5 to 150 bar CO.

Carbonylation is conducted usually at temperatures in the range from 20 to 250oC, especially from 30 to 150, continuous or semi-continuous mechanism. When running in periodic mode to maintain a constant pressure suitable carbon monoxide continuously feeding to the reaction mixture.

The resulting reaction mixture can be selected pesta formulas A1, accordingly A2 is known or can be obtained by known methods, for example, as described in the above prior art. In addition, you can get similar recommendations in examples 1-12.

Based on the target application of such preferred derivatives of saccharin of formula I in which the radicals L, M respectively denote hydrogen, methyl, methoxy, methylthio, chloro, cyano, methylsulphonyl, nitro or trifluoromethyl. The preferred values of L, M respectively are further hydrogen, C1-C4alkyl and chlorine. To a preferred further include such compounds of formula I, where L and M denote hydrogen or one of the radicals L, respectively, M denotes hydrogen and the other represents methyl or chlorine.

The radical R1in the formula I is preferably methyl, a R2means preferably hydrogen or methyl.

The radical Z is particularly preferably one of the above organic radicals, especially methyl, ethyl, propargyl, acetyl or phenyl.

The most preferred active substances are presented in table 1. Listed in table 1 for one of the Deputy group are, in addition, sledge preferred values corresponding to the Deputy.

The compounds of formula I can be represented in the form acceptable for use in agriculture salts, and it is in principle not dependent on the type of salt. Commonly used salts of these bases, which do not adversely affect herbicide efficacy of the compounds I.

As basic salts suitable especially those of alkali metals, preferably sodium and potassium salts, alkaline earth metals, preferably calcium salts, magnesium and barium, and of the transition metals, preferably salts of manganese, copper, zinc and iron, and also ammonium salts which may carry from one to three C1-C4alkyl, hydroxy-C1-C4alkyl substituents and/or one phenyl or benzyl Deputy, preferably salts of Diisopropylamine, Tetramethylammonium, tetrabutylammonium, trimethylantimony and trimethyl(2-hydroxy-ethyl)ammonium salt of a phosphonium salt of sulfone, preferably three salt(C1-C4)alkylsulfonyl, and salt sulfoxide, preferably three(C1-C4)alkylsulfonate.

The compounds of formula I containing these compounds herbicide drugs, as well as their environmentally acceptable salt, for example the s preparations can high performance be used to control weeds and unwanted plants in these cultures, as wheat, rice, maize, soybean and cotton, almost without damaging the plants. This effect reaches primarily at low application rates.

Considering the diversity of processing methods of the compounds of formula I, respectively containing drugs can be used for controlling undesirable vegetation in a number of other useful plants. Among them are the following crops: Allium CEPA, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima. Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium country, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum L., Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba L., Vitis vinifera and Zea mays.

In addition, the compounds of formula I can also be used in crops which methods to seidam.

Active substances, respectively herbicide preparations can be used in the methods as predsjedava and post-harvest processing. If the active substances have insufficient compatibility with some cultivated plants, it is recommended to apply the technology of processing, in which herbicide preparations should be sprayed using a sprayer so that they do not fall on the leaves of sensitive crops, and were aimed at the leaves growing among them undesirable plants or the open areas of soil (way directional spraying, fashion belt spraying).

The compounds of formula I, respectively containing herbicide preparations can be used, for example, in the form intended for direct spray aqueous solutions, powders, suspensions, including concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, products for dusting, preparations for powder or granules, which can be used for processing a variety of methods, such as spraying, treatment in the form of mists, dusting, dusting or watering. Meth is maksimalno thin and uniform distribution of the active substances according to the invention.

As the inert auxiliary agents for the preparation intended for direct spraying of solutions, emulsions, pastes or oil dispersions can be considered mainly as follows: fraction of oil fuel having a boiling range from medium to high, such as kerosene and diesel oil, further coal oil, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffins, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. amines such as N-organic, or water.

Aquatic forms of application can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or dispersible in water granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates as such or after dilution in the oil or solvent using wetting, adhesives, dispersants or emulsifiers homogenized in dateline solvents or oils to obtain concentrates, suitable for dilution with water.

As surface-active substances can be used salts of alkali and alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin-, phenol-, naphthalene - and dibutylaminoethanol, as well as salts of fatty acids, alkyl - and alkylarylsulfonates, alkyl sulphates, sulphates lauric ester and fatty alcohols, and salts of sulfated hexa-, hepta - and octadecanol, as well as glycol ethers of fatty alcohols, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene, respectively naphthalenesulfonic with phenol and formaldehyde, polyoxyethyleneglycol ether, ethoxylated isooctyl-, octyl - or Nonylphenol, polyglycolide esters of alkylphenol and tributylamine, alkylsilane polyether alcohols, isotridecyl alcohol, condensates of ethylene oxide and fatty alcohols, ethoxylated castor oil, polyoxyethylene or polyoxypropylene esters, acetate ester of lauric alcohol and polyglycols, esters of sorbitol, exhaust ligninolytic liquor or methylcellulose.

Powder preparations, preparations for dusting and dusting mo what polytelis.

Granulates, for example, the pellets in the shell, impregnated granulates and homogeneous granulates can be obtained by binding of active substances with solid fillers. As such can serve as mineral lands, in particular silicic acid, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as grain flour, flour from tree bark, wood flour and flour from a nutshell, cellulose powders or other solid fillers.

The concentration of active ingredients in the compositions can vary widely, generally from 0.01 to 95 wt.%, preferably from 0.5 to 90 wt.%. Active substances applied with the same degree of purity from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

Compounds of formula Ia, respectively Ia' according to the invention can be used, for example, for the preparation of the following songs:

I. 20 wt.parts connection N 1.08 dissolved in a mixture, costeau N-monoethanolamide oleic acid, 5 wt. parts of the calcium salt of dodecylbenzenesulfonate and 5 wt.parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. After desantirovaniya and a thin uniform distribution of the solution in 100000 wt.the parts of water to obtain an aqueous dispersion containing 0.02 wt.% the active substance.

II. 20 wt.parts connection N 1.08 dissolved in a mixture consisting of 40 wt.parts of cyclohexanone, 30 wt.parts of Isobutanol, 20 wt.parts of the product of the joining of 7 moles of ethylene oxide to 1 pray isooctylphenol and 10 wt.parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. After desantirovaniya and a thin uniform distribution of the solution in 100000 wt. the parts of water to obtain an aqueous dispersion containing 0.02 wt.% the active substance.

III. 20 wt. parts of the active substance N 1.08 dissolved in a mixture consisting of 25 wt. parts of cyclohexanone, 65 wt.parts obtained by the distillation of petroleum fractions of fuel oil with a boiling point 210-280oC and 10 wt. parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil. After desantirovaniya and a thin uniform distribution of the solution in 100000 wt.the parts of water to obtain the aqueous dispersion, soteriades 3 wt. parts of the sodium salt of Diisobutylene- -sulfonic acids, 17 wt. parts of the sodium salt of ligninsulfonate from spent sulfite liquor and 60 wt.parts of powdered silica gel, and then pulverized in a hammer mill. After a fine and uniform distribution of the mixture in 20000 wt.the parts of water to obtain a solution for spraying, containing 0.1 wt.% the active substance.

V. 3 wt.part of the active substance N 1.08 mixed with 97 wt.parts of fine kaolin. In this way receive the drug for dusting containing 3 wt.% the active substance.

VI. 20 wt.parts of the active substance N 1.08 thoroughly mixed with 2 wt.parts of the calcium salt of dodecylbenzenesulfonate, 8 mass.parts polyglycolic ether fatty alcohol, 2 wt.parts of the sodium salt of a condensate of formatively and formaldehyde and 68 wt. parts of a paraffinic mineral oil. In this way get a stable oil dispersion.

To broaden the spectrum of action and to achieve synergistic effect derived shinkareva acid can be mixed with numerous representatives of other groups of active substances with herbicide and will rastraguru the processing can serve for example, diazine, derivatives of 4H-3,1-benzoxazine, benzothiadiazine, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamate, halogenecarbonate acid, triazine, amides, urea, diphenyl ethers, triazinones, orally, derivatives benzofuran, derivatives, cyclohexane-1,3-dione, bearing in position 2, for example, carboxy - or carbiener, derivatives of quinoline-carboxylic acid, imidazolinones, sulfonamides, sulfonylureas, aryloxy and heterooligomerization acid, and their salts, esters and amides, and others.

In addition, it may be useful and appropriate compounds of formula I, individually or in combination with other herbicides also be used in mixtures together with a variety of other plant protection products, for example, with the means of combating pests or phytopathogenic fungi, bacteria, respectively. The interest is then the possibility of mixing with solutions of mineral salts used to compensate the lack of nutrients and trace elements. You can also enter additives revitalising oils and oil concentrates.

The rates of consumption of active substances depending on the purpose of treatment, time of year, the treated plants>/P>Examples of making

1. 2-methyl-6-acetamidobenzoic acid

To a solution of 24.8 g (of 0.62 mol) of NaOH in 500 ml of water, add 90,6 g (0,6 mol) 6-methylanthranilic acid and then added dropwise and 63.4 g (of 0.62 mol) of acetanhydride. After stirring for 1 h, acidified under cooling with concentrated HCl to pH 3, drop down the precipitate is filtered off, washed with water and with 50oC dried under vacuum.

Output: 107 g (of 0.55 mol) = 92% of theory, tPL189-190oC.

2. 2-methyl-3-nitro-6-acetamidobenzoic acid

When -5oC load 271 ml of 98% nitric acid and then added in several portions 106 g (with 0.55 mol) obtained in example 1 2-methyl-6-acetamidobenzoic acid. After stirring for 1 h the reaction mixture at 10oC is poured into a mixture of 540 g of ice and 270 ml of water. The precipitation is filtered off, washed with water and dried at 50oC under vacuum.

Output: 75,6 g (MX 0.317 mol) = 58% of theory, tPL190-191oC.

From the filtrate after prolonged exposure is allocated nitrified in position 3 isomer.

Output: 21,3 g (0,089 mol) = 16% of theory, tPL180-182oC.

3. 2-methyl-3-nitro-6-aminobenzoic acid

Pre-load 450 ml ewout to 95oC and left at this temperature for 1 h for mixing. After cooling to 10oC acidifying additives 425 ml of 2N HCl, the precipitation is filtered off, washed with water and dried at 50oC under vacuum.

Output: 50,7 g (0,258 mol) = 82% of theory, tPL183-184oC.

4. Methyl ester of 2-methyl-3-nitro-6-aminobenzoic acid

49,7 g (0,253 mole) of 2-methyl-3-nitro-6-aminobenzoic acid are dissolved in 380 ml of acetone and added 43 g (of 0.51 mol) of sodium bicarbonate. Then heated to boiling until the completion of the allocation of CO2. To the thus obtained suspension of sodium salt of 2-methyl-3-nitro-6-aminobenzoic acid are added dropwise at the boiling point of acetone for 2 h to 35.3 g (0,28 mol) dimethylsulfate, then continue for another 3 h of heating under reflux, and then allowed to cool. After draining the reaction mixture in 1.8 l of water is extracted with methylene chloride. After drying the organic phase is concentrated. The obtained solid substance has a sufficient degree of purity (according to NMR) for use in subsequent reactions.

Yield: 50 g (0,238 mol) = 94% of theory, tPL92-94oC.

5. The acid chloride 2-methoxycarbonyl-3-methyl-4-nitrobenzylamine in 280 ml of ice-cold vinegar and this solution for 15-20oC merge in 85 ml of concentrated HCl. Then in 5-10oC added dropwise a solution of 19.3 g (0,28 mol) of sodium nitrite in 60 ml of water and leave for 30 minutes with 5oC for mixing. Further, the diazonium salt solution is added dropwise into a solution of 374 g SO2750 ml of ice-cold vinegar, containing 14 g of CuCl2(dissolved in 30 ml of water). After nitrogen excretion continue to stir for another 15 min, then poured into 1.4 l of ice water. The sulfonic acid chloride is separated by extraction with 1.2 l of methylene chloride. After drying and concentrating the organic phase receive 73 g (0.25 mol) (= 90% of theory) of oil, representing according NMR (CDCl3) net acid chloride 2-methoxycarbonyl-3-methyl-4-nitrobenzenesulfonic acid.

6. 4-methyl-5-nitrofuran

After loading 104 ml of 25% ammonia solution was added 100 ml of water and then with 10oC added dropwise a solution of 48.7 g (0,166 mol) of acid chloride of 2-methoxycarbonyl-3-methyl-4-nitrobenzenesulfonic acid in 70 ml of tetrahydrofuran. After 3 hours stirring at 25oC concentrated using a rotary evaporator to remove water and THF. The resulting residue is thoroughly stirred with acetic E. the AI is solid white with tPL312oC (decomposition).

7. 2,4-dimethyl-5-nitrofuran

This substance can be obtained by subsequent methylation obtained in example 6 saccharin by dimethylsulfate in the presence of NaOH.

8. 3-methyl-4-nitro-2-(N'-methyl)carboxamido-N-methylbenzenesulfonamide

50 ml of water is poured into 50 ml of 40% aqueous solution of methylamine and 10oC added dropwise a solution of 24.3 g (83 mmole) of the acid chloride of 2-methoxycarbonyl-3-methyl-4-nitrobenzenesulfonic acid in 35 ml of THF. After stirring for 1 h at 25oC all volatile components are removed using a rotary evaporator. The residue is extracted with acetic ether, the organic phase is washed with water, dried and concentrated. The resulting residue crystallizes after a long settling.

Yield: 10.3 g (40 mmol = 48% of theory), tPL125-126oC, after recrystallization from acetic ester tPL144-145oC.

9. 4-methyl-5-aminocoumarin

33.6 g (0,13 mol) of 4-methyl-5-nitrosourea dissolve when heated to 45oC 1.2 l of water and add 5 g of Pd/C (10% on charcoal). Then with vigorous stirring into the solution serves gaseous hydrogen (hydrogenation without pressure). For 4, the aqueous evaporator concentrate to a volume of 200 ml and then acidified to pH 1. The precipitation is filtered off, washed with water and with 50oC dried under vacuum. In this way gain of 23.4 g (of 0.11 mol = 85% of theory) of a solid white color with tPL272-273oC.

10. 4-methyl-5-itchin

Preloads a mixture of 205 ml of acetic ether, 160 ml of water and 40 ml of concentrated HCl and added with stirring to 23.4 g (of 0.11 mol) of 4-methyl-5-aminocoumarin at 15-20oC. To the resulting suspension at 5-10oC added dropwise 7.9 g (0,115 mole) of sodium nitrite and leave for 30 minutes with 5oC for mixing. Then formed in the form of suspension of the diazonium salt portions is added dropwise in a preheated 50oC solution of 19.1 g (0,115 mole) of potassium iodide in 170 ml of water and nitrogen is formed. After cooling to room temperature, precipitated in the sludge product produce by filtration, washed with water and with 50oC dried under vacuum. In this way gain of 32.5 g (0.1 mol = 91% of theory) of a solid substance with tPL257-258oC. combustion Analysis showed that the iodine content of 38.5% (theoretical calculation 39,3%).

The degree of purity of the product is sufficient for use in subsequent reactions.

11. 4-metalshark-5-carboxylic acid

6.4 g (0,002 m is lostin)palladium and the mixture is heated in an autoclave of 300 ml to 100oC and stirred for 36 h at a pressure of carbon monoxide 100 bar.

For further processing filter and water tetramethylrhodamine removed by distillation under high vacuum. The residue is dissolved in methyl tert-butyl ether (MTBE), extracted with a solution of NaHCO3and after acidification with HCl re-extracted with MTBE. After concentrating obtain 2.8 g of 4-metalshark-5-carboxylic acid (58% of theory).

1H-NMR (DMSO), 400.1 MHz): 2,85 (3H, s); with 8.05 (1H, d); or 8.2 (1H, d);

13C-NMR (DMSO, to 100.6 MHz): 167,4 (CO); 161,3 (CO); 141,6 (fourth. C) 139,7 (fourth. C); 138, 7mm (fourth. C) 135,6 (CH); and 125.4 (fourth. C) TO 118.5 (CH); 15,4 (CH3).

12. 2,4-dimethylfuran-5-carboxylic acid

of 7.3 g (0,02 mol) 3-methyl-4-iodine-2-(N'-methyl)carboxamido-N - methylbenzenesulfonamide together with 0,69 g chloride bis(triphenylphosphine)palladium, 30 ml of water and 70 ml of tetramethylrhodamine loaded into the autoclave of 300 ml, after which the mixture is heated to 100oC for 36 h and stirred at a pressure of carbon monoxide 100 bar.

After processing, similar to that described in example 12, to obtain 4.1 g specified in the connection header (of 0.014 mol = 72% of theory).

1H-NMR (DMSO, 400.1 MHz): 2,9 (3H, s); 3.15 in (3H, s); 8,2 (2H, 2d); 14,0 (1H, s)

13C-NMR (IS>; 15,6 (CH3).

13. 4-amino-3-methyl-2-(N'-methyl)carboxamido-N-methylbenzenesulfonamide

Similar to that described in example 9 method was first made without pressure obtained in example 8 3-methyl-4-nitro-2-(N'-methyl)carboxamido - N-methylbenzenesulfonamide. In this way received from 93% yield aniline derivative patterns

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with tPL217-218oC.

14. 3-methyl-4-iodine-2-(N'-methyl)carboxamido-N-methylbenzenesulfonamide

As described in example 10 method was diazotisable connection from the previous example and interaction with potassium iodide transformed into derived odensala the following structure

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Output: 95% of theory, tPL60-62oC.

15. The acid chloride 2,4-dimethylfuran-5-carboxylic acid

3.8 g (14.9 mmol) of 2,4-dimethylfuran-5-carboxylic acid are suspended in 100 ml of toluene, heated to 80oC and added dropwise to 3.5 g (29.8 mmol) of thionyl chloride. After heating for 2 h under reflux decanted while hot and the reaction mixture is concentrated using a rotary evaporator. The resulting product (3 g, 74% of theory) has tPLL149-150oC.

16. A General method of preparing compounds of the formula I

16.1 AC is 10 mmol) 5-hydroxy-1,3-dimethylpyrazole in 70 ml of methylene chloride added 1.01 g (11 mmol) of triethylamine. Then, when the 25oC added dropwise a solution or a suspension of 10 mmol of the carboxylic acid of formula IV in 30 ml of methylene chloride and then heated for 5 h to 45oC. After cooling to 25oC, the reaction mixture was mixed with 60 ml of water, poured into a separating funnel and the organic phase is separated. After extracting the aqueous phase with 50 ml of methylene chloride the combined organic phases are dried over sodium sulfate. After filtration and removal of the methylene chloride is formed an oil, which without further purification used in the rearrangement reaction.

16.2 Rearrangement obtained in example 16.1 pirazolonove ether

Received 16.1 O-acyl ester shinkareva acid 5-hydroxy-1,3-dimethylpyrazole (approximately 10 mmol) are placed in 80 ml of acetonitrile and mixed first with 2.7 ml (2.2 g = 20 mmol) of triethylamine and then with 0.2 g (2.3 mmole) of acetonecyanohydrin and stirred for 16 h at 25oC. Then the reaction mixture is poured 30 g of 5% HCl and extracted with methylene chloride. After that, the organic phase is extracted with 5% potassium carbonate solution, the organic phase is separated and the alkaline aqueous phase is added dropwise acidified with concentrated HCl to pH 1, and the product is sodium sulfate and concentrated. After trituration with diethyl ether-petroleum ether, the residue crystallizes.

A similar technique can be obtained the compounds shown in table 1.

In table. 2 and 3 shows selective herbicide activity during post-harvest processing greenhouses.

Examples for the application

Herbicide action saccharin derivatives of the formula I were confirmed in the course of carrying out the following experiments in the greenhouse.

As pots served plastic flower pots with sandy loam content of approximately 3% of humus as a substrate. The seeds of the experimental plants were sown separately.

Redshadow processing suspended or emulsified in water active ingredients was carried out directly after sowing by means of suitable nozzles, providing atomized spray. The vessels were subjected to a light sprinkling in order to promote germination and growth, after which the vessels were covered with transparent plastic covers until the plants started to grow. Such covers provide uniform germination of the experimental plants, not yet experiencing the impact of active substances.

On the mi the height of from 3 to 15 cm, and only then was treated with suspended or emulsified in water active ingredients. With this purpose, pilot plants or directly sown and grown in the same containers, or they were first grown separately as embryonic plants, and a few days before treatments were transplanted into containers for experiments.

Plant species kept at temperatures of 10-25oC, respectively 20-35oC. the Experiments were conducted within 2-4 weeks. During this period of time the plants were thorough care and determine their response to each of the implemented treatments.

The evaluation was made on a scale with gradations from 0 to 100. Where 100 meant that the plants do not sprout, respectively, that there is a total loss at least their aerial parts and a score of 0 meant that the plants are not damaged or observed their normal growth.

1. 5-Hydroxypyrazol-4-ylcarbamate derivatives of saccharin of formula I

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in which the substituents have the following meaning: L, M denote hydrogen, C1-C4alkyl, chlorine;

Z represents hydrogen, C1-C4alkyl, C3-C5-quinil, C3-C8alkenyl, phenyl;

Q denotes a radical CO-J;

J denotes attached to position 4 of the benzene ring 5-guide the 2 denotes hydrogen or methyl,

as well as typically used in agriculture salts of compounds of formula I.

2. Derivatives of saccharin of formula I under item 1, in which the radicals L, M denote hydrogen, C1-C4alkyl.

3. Derivatives of saccharin of formula I under item 1, in which the radicals L, M denote hydrogen, methyl, chlorine.

4. Herbicide agent, derivative containing saccharin of formula (I) under item 1 and conventional inert additives.

 

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FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

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