Derivatives of saccharin and herbicide drug

 

(57) Abstract:

The invention relates to new derivatives of saccharin of formula I

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in which the substituents have the following meanings: L, M denote hydrogen, alkyl, alkyloxy, alkylthio, chlorine, cyano, methylsulphonyl, nitro or trifluoromethyl, J denotes hydrogen, alkyl, cycloalkyl, alkenyl, quinil, acyl, phenyl, optionally substituted with halogen or alkyl, benzyl, means connected in position 2 optional substituted cyclohexane-1,3-diNovo ring of formula II

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in which R1- R6mean hydrogen or methyl, or, if R1, R2, R3, R5and R6mean hydrogen, R4mean 2-ethylthiophen, tetrahydrothiopyran-3 or metaltitlepane, or R1, R4, R5mean hydrogen, and R6means methyl, R2and R3form a three-membered ring, which is formed connected in position 2 bicyclo-(4.1.0)heptane ring of formula III

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and they are usually used in agriculture salt. Herbicide product containing derivative of saccharin of formula I and conventional inert additives, for weed control. The technical result - the creation of a new herbicide. 2 c. and 2 C.p. f-crystals, 14 PL.


L, M means hydrogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, chlorine, cyano, methylsulphonyl, nitro or trifluoromethyl;

Z denotes hydrogen, C1-C4alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C5quinil, C1-C4acyl, benzyl or phenyl, and phenyl rings, respectively optionally substituted with halogen or C1-C4by alkyl;

Q denotes a radical CO-J;

J means connected in position 2 cyclohexane-1,3-diNovo ring of formula II

II

in which

or R1-R6mean hydrogen or methyl, or, if R1, R2, R3, R5and R6mean hydrogen, R4mean 2 - ethylthiophen, tetrahydropyranyl-3, tetrahydropyranyl 4 tetrahydrothiopyran-3 or 1-metaltitlepane,

or, if R1, R4, R5mean hydrogen, a R6means methyl, R2and R3form a three-membered ring, which is formed connected in position 2 bicyclo [4.1.0] heptane ring of formula III,

III

as well as typically used in agriculture salts of compounds 1.

The subject invention are further herbicide preparations safarina 1. In addition, the invention also includes intermediates to the final products of formula I according to the invention and the method of obtaining the products 1 on the basis of the new intermediates of the formulae IV and V

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where are the rest of the radicals L, M and Z have the above meaning.

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 therein references).

Have a weed-killing effect 2-aroylcyclopropane are the subject of old Germany application P 4403670. In this publication, among other things, mentions the combination with saccharin and N-alkylamino without specifying putaruru, gained fame as herbicides, a typical representative of which should be mentioned in this connection bentazon formula

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The basis of the invention was based on the task of creating 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 and intermediates of the formulae IV and V. Intermediate products IV and receipt of them are subject to the simultaneously filed application in Germany DE-A 4427996.

The compounds of formula I get due to the fact that the compounds of formula II, respectively, of formula III acelerou the acid chloride of the acid of formula V and regroup with getting saccharin derivatives of the formula I. 1.

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In the above formulas, L and M have the above significance, a, Z represents hydrogen, C1-C4alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C5quinil, C1-C4acyl or optionally substituted by halogen or C1-C4the alkyl benzyl or phenyl.

The first stage of a sequential reaction, i.e., acylation, carried out by known methods, e.g. the tvii auxiliary base. Reagents and auxiliary basis, that should be used in equimolar amounts. A slight excess of the auxiliary base, for example, 1.2 to 1.5 mol.EQ. in terms of the number of compounds II, III respectively, under certain circumstances, may be preferred.

As auxiliary bases are suitable tertiary bonds alkylamines, pyridine or carbonates of alkali metals. As solvents can be used, for example, methylene chloride, diethyl ether, toluene or ethyl ester of acetic acid.

With the introduction of additives to the carboxylic acid, the reaction mixture is preferably cooled to 0-10oC, followed by stirring it at a temperature in the range from 20 to 100oC, especially 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 enol ether without further purification used for the rearrangement. Examples get benzylaniline esters of cyclohexane-1,3-diones can be found, for example, in European application carried out at different temperatures in the interval 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 preferably used in equimolar amounts or with an excess of up to fourfold relative to benzoyleneurea ether. Preferred auxiliary base is triethylamine in double quantity.

As catalysts acceptable amongst the cyanide of potassium or acetonecyanohydrin, preferably in an amount of from 1 to 50 mol.% in terms of enol ether. It is advisable to add acetonecyanohydrin, for example, in amounts of from 5 to 15, mainly in the amount of 10 mol.%. Examples catalyzed by cyanide rearrangement of enol esters of cyclohexane-1,3-diones can be found in particular in European patent application EP-A 186118 or in U.S. patent 4780127.

The processing carried out by well-known methods. For example, reacts the slot, and extracted with an organic solvent, such as methylene chloride or ethyl ester of acetic acid. For purification of the extract is extracted with cold 5-10% solution of carbonate of alkali 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 1,3-diketones of formula II and III are known and can be obtained by known methods (cf. the European application EP-A 71707, EP-A 142741, EP-A 243313, U.S. patent 4249937 and international application WO 92/13821). Cyclohexadien - 1,3 and dimedone are commercially available compounds.

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

Shrinkable acid IV 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 IV also lies in the fact that the corresponding bromo - Lily, 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 comprising palladium, Nickel, cobalt or rhodium, and the base is subjected to interaction with carbon monoxide and water at elevated pressures.

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, in particular in the form of halogen compounds, such as, for example PdCI2, 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, CARBONYLS of metals, such as CO2(CO)8, Ni(CO)4, metallacarborane complexes with tertiary phosphines, 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. The type f is oral:

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where n means the number 1, 2, 3 or 4 and the radicals R7-R13represent low-molecular alkyl, for example C1-C6alkyl, aryl, C1-C4alkylaryl, for example, benzyl, 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, for example 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.

Getting phosphine complexes can be carried out by known techniques, e.g. as described in 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(C6H5is usually made 0-20, first of 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 IV 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 used catalysts may also be appropriate to use instead of the above-mentioned reaction component, any other inert solvent or to use as a solvent base, which is used for carboxylation.

As inert solvents are acceptable such, usually used for carbonylation reactions, in particular hydrocarbons, apreature, dioxane, dimethoxyethane, substituted amides, such as dimethylformamide, perezapisannaya 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 need for additional solvent.

Suitable for implementing the method bases are all inert base, is able to bind released during the reaction of hydrogen iodide, respectively, hydrogen bromide. As examples can be mentioned in this connection tertiary amines, such as tert-alkylamines followed, for example, trialkylamine, such as triethylamine, cyclic amines such as N-methylpiperidine or N,N'-dimethylpiperazine, pyridine, carbonates or bicarbonates of alkali metals or tetraalkylammonium derivatives of urea, such as Tetra-C1-C4alkylation, for example, tetramethylrhodamine.

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 Foundation as a dissolve reasons of feasibility avoid unnecessarily large excess in order to save money, and 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 150oC, continuous or semi-continuous mechanism. When working in semi-continuous mode to maintain a constant pressure suitable carbon monoxide continuously feeding to the reaction mixture.

The resulting reaktsionnoi mixture of products produce by conventional techniques, e.g. by distillation.

Required for reaction of the starting compound A1, A2 respectively, are known or can be obtained by well-known methods. You can get them either permanganate oxidation izlesene 2-methylbenzenesulfonamide, or by the reaction of Sandmeyer from aminosaccharides. Aminocoumarin get well-known technique is 1423 (1930)), or can be synthesized by known methods publications from the corresponding derivatives of nitrobenzene (see Liebigs Ann. 669. 85 (1963)) or benzosulfimide.

In addition, you can get similar recommendations on obtaining described in examples 1-12.

With regard to their target destination preferred such derivative sacharine formula I in which the radicals L, M respectively represent hydrogen, methyl, methoxy, methylthio, chloro, cyano, methylsulphonyl, nitro or trifluoromethyl. To preferred saccharin derivative of formula I are further those, in which one of the radicals L or M or both of the radicals L and M are not simultaneously hydrogen.

In formula I the radicals R1-R6either all means hydrogen or one, two or three of them represent methyl, and the remaining radicals are hydrogen. The combination of the radicals R3+R4=CH3and R1, R2, R5, R6= H along with unsubstituted cycle (where R1-R6mean (H) is particularly preferred.

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

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-hydroxyethyl)ammonium salt, 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 preparations, as well as their environmentally acceptable salts such as alkali and alkaline earth metals or ammonia and amines, respectively containing these salts herbicide PR the 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 volatile 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.

The granules such as 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).

The compounds of formula I according to the invention can be used, for example, for the preparation of the following songs:

I. 20 wt.parts connection N 2.08 dissolved in a mixture consisting of 80 wt. parts is 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. This solution is poured into 100000 wt. parts of water and after homogeneous mixing receive water dispersion containing 0.02 wt.% the active substance.

II. 20 wt.parts connection N 2.08 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. This solution is poured into 100000 wt.parts of water and after homogeneous mixing receive water dispersion containing 0.02 wt.% the active substance.

III. 20 wt. parts of the active substance N 2.08 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. This solution is poured into 100000 wt.parts of water and after homogeneous mixing receive water dispersion containing 0.02 wt% of active ingredient.

IV. 20 wt.frequent is facility, 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 2.08 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 2.08 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 of substituted derivatives of saccharin can be mixed with numerous representatives of other groups of active substances with herbicide and astragaloside properties, and performing the processing in conjunction with them. As sasina, 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 and bacteria. 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 and the growth stage are from 0.001 to 3.0, preferably from 0.0 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 2H NaOH and then add to 75.6 g (MX 0.317 at this temperature for 1 h for mixing. After cooling to 10oC acidifying additives 425 ml 2H 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.

When you try to detach this acetyl residue in acidic conditions would occur decarboxylation.

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. PI is ethyl-3-nitro-6-aminobenzoic acid are dissolved while heating 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 if possible, completely remove the water and THF and the resulting residue is thoroughly stirred with acetic ether, filtered and about color 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. 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). Within 4.5 hours absorbed 9 l H2. After about 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.

II. 4-amino-3-methyl-2-(N'-methyl)carboxamido-N-methylbenzol the Tyl-4-nitro-2-(N'-methyl)carboxamido-N - methylbenzenesulfonamide. In this way receive specified in the header of the connection with tPL217-218oC and 93%.

12. 3-methyl-4-iodine-2-(N'-methyl)carboxamido-N-methylbenzenesulfonamide

As described in example 10 method diasterous specified in the previous example, the connection and interaction with potassium iodide transform in the connection specified in the header.

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

B) Obtaining an intermediate product of the formula IV

13. 4-metalshark-5-carboxylic acid

6.4 g (0,002 mol) of 4-methyl-5-itchina dissolved in 70 ml of tetramethylrhodamine and 30 ml of water, mixed with 0.7 g of chloride bis(triphenylphosphine)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 S WHO).

14. 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 (as described in example 13) are obtained 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 (DMSO, to 100.6 MHz): 167,3 (CO); 158,6 (CO) 139,7 (fourth. C); 139,1 (fourth. C) 138,9 (fourth. C) 135,5 (CH); 124,6 (fourth. C); 119,0 (CH); 22,9 (CH3); 15,6 (CH3).

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 was concentrated.

Yield: 74% of theory, tPL149-150oC.

A similar technique can be obtained from the acid chlorides of shrinkable to have a weed-killing effect of the end products of the formula I

16. Acylation of cyclohexandione

< / BR>
To a suspension of 1.23 g (10.9 mmol) of cyclohexadiene-1,3 in 50 ml of methylene chloride is drained to 1.21 g (12 mmol) of triethylamine, and then at 25oC added dropwise a solution of 3 g (10.9 mmol) of the acid chloride 2,4-dimethylfuran-5-carboxylic acid in 60 ml of methylene chloride. Then for 7 h stirred at 40oC. After cooling, add 60 ml of water, methylenchloride phase is separated in a separating funnel and dried over magnesium sulfate. Formed after removal of the solvent amorphous residue (2.5 g) is an enol ether, which without further purification regroup at a later stage.

17. Regrouping with the final product of formula I

< / BR>
2.5 g (7.2 mmol) of enol ether from the previous example is dissolved in 80 ml of acetonitrile, mix in series with 3.5 ml of triethylamine and 0.33 g (4 mmole) of acetonecyanohydrin and stirred for 16 hours Then added 24.5 g of 5% HCl and the reaction mixture is extracted with 100 ml of methylene chloride. Next, the organic phase is extracted with 5% potassium carbonate solution, during this process, the product is transferred to the aqueous phase. Acidification of alkaline-aqueous solution of concentrated HCl seatallan. After washing with petroleum ether then dried under vacuum.

Yield: 0.88 g (35% of theory).

A similar technique get below the connection.

Listed in tables 1-8 for one substituent groups are, in addition, by themselves (regardless of their special combination with other substituents, in which they are presented) is particularly preferred values corresponding to the Deputy.

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 light sprinkling, in order to promote germination and growth, after which the vessels were covered with transparent plastic covers until the plants are not paste active substances.

For post-harvest processing pilot plant, depending on exterior raised first before they reach a 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. Norms of consumption in post-harvest processing was 0.5, respectively, 0.25 kg of active substance per hectare.

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, which 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.

As an experienced plant in the above-described abode compound from example 2.08 at the rate of 0.5, accordingly 0.25 kg/ha of active substance showed a high effectiveness against undesirable plants.

According to the methods described in the examples on the application, with a number of claimed compounds were tested in the greenhouse.

Data tables 9-12, below, clearly indicate a high herbicide activity of the claimed compounds and high selectivity against spring wheat, cotton, corn and soybeans.

Plants used in the experiment included the species are presented in table. B.

1. Derivatives of saccharin of formula I

< / BR>
in which the substituents have the following meanings:

L, M means hydrogen, C1- C4alkyl, C1- C4alkoxy, C1- C4alkylthio, chlorine, cyano, methylsulphonyl, nitro or trifluoromethyl;

Z denotes hydrogen, C1- C4alkyl, C3- C8cycloalkyl,3- C6alkenyl,3- C5quinil,1- C4acyl, benzyl or phenyl, and phenyl rings, respectively optionally substituted with halogen or1- C4by alkyl;

Q denotes a radical CO-J;

J means connected in position 2 collagen is if R1, R2, R3, R5and R6mean hydrogen, R4mean 2-ethylthiophen, tetrahydropyranyl-3, tetrahydropyranyl-4-tetrahydrothiopyran-3 or 1-methylthio-cyclopropyl,

or, if R1, R4, R5mean hydrogen, and R6means methyl, R2and R3form a three-membered ring, which is formed connected in position 2 bicyclo[4.1.0]heptane ring of formula III

< / BR>
as well as typically used in agriculture salts of compounds 1.

2. Derivatives of saccharin of formula I under item 1, in which L denotes a1- C4alkyl, C1- C4alkoxy,-Alkylthio, chlorine, cyano, methylsulphonyl, nitro or trifluoromethyl, and M stands for hydrogen, C1- C4alkyl, C1- C4alkoxy, C1- C4alkylthio, chlorine, cyano, nitro or trifluoromethyl, methylsulphonyl.

3. Derivatives of saccharin of formula I on PP.1 and 2, in which the radicals L, M means hydrogen, methyl, methoxy, methylthio, chloro, cyano, methylsulphonyl, nitro or trifluoromethyl.

4. Herbicide product containing at least one derivative of saccharin of formula I under item 1 and conventional inert additives.

 

Same patents:

The invention relates to new derivatives shinkareva acid of General formula I, in which L, M denote hydrogen, alkyl with 1-4 carbon atoms, alkoxy with 1-4 carbon atoms, alkylthiols with 1-4 carbon atoms, chlorine, methylsulphonyl, Z denotes hydrogen, alkyl with 1-4 carbon atoms, benzyl or phenyl, R is hydrogen, alkyl with 1-6 carbon atoms, provided that Z does not mean methyl, phenyl or hydrogen and 5-carboxy-7-metalshark and 5-carboxy-4-hariharan excluded

The invention relates to the derivatives of saccharin General formula 1, where L denotes 0 or N; when L is 0, R1- 2,6-dichloro-3-[2-(4-morpholinyl)ethoxy] benzoyl, when L is N, then L together with R1represents a 4,5-di(tert-butylsulfonyl)-1,2,3-triazole-1-yl, R2primary or secondary alkyl of 2-4 carbon atoms, R3- lower alkoxy at any of the 5-, 6 - or 7-positions, or their pharmaceutically acceptable additive salts of acids or bases, which inhibit the activity of proteolytic enzymes

The invention relates to the chemistry of heterocyclic compounds exhibiting inhibitory activity against elastase

The invention relates to 2-sharonlee - 4,5,6,7 - tetrahydro-2-sharinaletisha-phosphonates and-Phosphinates, inhibiting enzymatic activity; to compositions containing these compounds, their use and the treatment of disruptive disorders, and to methods for their preparation

The invention relates to new 2-sharonlee heterocyclic carboxylates, inhibiting the enzymatic activity of proteolytic enzymes, containing compositions, to a method of their use for the treatment of diseases associated with degeneration of the tissues, and to a method of production thereof

The invention relates to the production of heterocyclic compounds containing two cyclic selftimer grouping in a single aromatic nucleus such as diimide 4,6-Desulfovibrio acid (dithio-m-bisharin), formulas

HNNH,

which can be used as a monomer for the synthesis of new geterotsiklicheskikh heat-resistant polymers, new polymers with a system of conjugate relations, as well as new reactive oligomers

The invention relates to herbicide compositions containing herbicide derived sulfonylureas and at least one serviced, choose from a wide range of serviceof

The invention relates to new herbicide compositions containing a mixture of compounds

The invention relates to new derivatives shinkareva acid of General formula I, in which L, M denote hydrogen, alkyl with 1-4 carbon atoms, alkoxy with 1-4 carbon atoms, alkylthiols with 1-4 carbon atoms, chlorine, methylsulphonyl, Z denotes hydrogen, alkyl with 1-4 carbon atoms, benzyl or phenyl, R is hydrogen, alkyl with 1-6 carbon atoms, provided that Z does not mean methyl, phenyl or hydrogen and 5-carboxy-7-metalshark and 5-carboxy-4-hariharan excluded

The invention relates to new compositions containing herbicide on the basis of N-isopropylacetanilide and its derivative 4-benzoimidazole, and to their use as herbicides

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The invention relates to a new above-mentioned compounds, method of their production and the means of containing this compound, useful for combating fungi and insect pests

The invention relates to new isoxazol derivative, compositions containing them, methods of obtaining and use as herbicides

The invention relates to cyclic Amida substituted in-the position of different aryl groups, agricultural suitable salts and their mixtures, and their use as fungicides systemic or selective action

The invention relates to new derivatives of 4-benzoimidazole formula I where R is hydrogen or-CO2R4; R1- C3-6-cycloalkyl; R2- halogen, n-alkyl, possibly substituted by one or more halogen atoms, or5, -S(O)pR6; R3IS-S(O)qR7; X IS -(CR9R10)t-; n = 0, 1, and 2; when n is greater than 1, the groups R2may be the same or different; R4, R5and R6-n-alkyl; R7-n-alkyl, possibly substituted by one or more atoms of hydrogen, C3-C6alkenyl straight chain or phenyl; R9and R10is hydrogen or C1-C6-alkyl straight chain; p and q = 0, 1, or 2; t is an integer from 1 to 4, when t > 1, group-CR9R10may be the same or different; or acceptable for agriculture salt

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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