Derivative 3(2h) - pyridazinone

 

(57) Abstract:

Usage: in agriculture and horticulture. The essence of the invention: derivatives of 3(2H)pyridazinone f-ly I specified in the text of the description, where the radicals and n have values exhibiting pesticidal activity. 22 table.

The invention relates to new 3[2H]-pyridazinone derived, as well as to receive them, containing their insecticidal acaricide, nematocide, fungicidal compositions for use in agriculture and horticulture; compositions for removing ticks from animals, where these compositions contain these derivatives as the active ingredient.

There are various 3[2H]-pyridazinone derivatives, which contain a thioester bond, as in the compounds of the invention. Known compounds and their physiological activity are listed in table. 1.

Physiological activity are all listed in the table. 1 compounds is limited bactericidal, fungicidal and suppressing the Central nervous system properties and/or herbicide properties. Still it was not reported that these compounds have excellent insecticidal, acaricidal and nematocidal actinobacterium and acaricidal activities in addition to antifungal activity. These activities attributed to the specific structure of the compounds of the invention. Namely, the proposed compounds are characterized in that they contain a branched or unbranched2-C6the alkyl group in the 2-position pyridazinones rings, and substituted menzilcioglu in the 5-position of the specified ring. In previously known literature was not disclosed compounds of the invention, and there is no indication of such activity of these compounds as insecticidal and acaricidal activity.

All of the compounds represented by the General formulas IV-VIII, clearly differ from the compounds of the invention of formula I, below, the fact that the former contain the phenyl group in position 2 is. On the other hand, compounds of General formula IX are also clearly different from that in position 2 first there is no substitute. Tirinya compounds and their salts of General formula X, as is reported to have fungicidal activity and are different from the compounds of the invention by the fact that the former have the Deputy menzilcioglu in the 5-position.

The inventors have made studies on preparation of new compounds of the present invention of formula I, below, and defining the île-combat ticks and insects in agriculture and horticulture, to prevent damage to plants, insect pests and for removing ticks from animals.

The aim of the invention is the creation of a new 3[2H]-pyridazinone derivatives, which possess insecticidal, acaricidal, bactericidal and fungicidal activities, creating a method of producing such derivatives 3[2H]-pyridazinone and creating bactericidal, insecticidal, acaricidal, nematocide compositions that contain derivatives 3[2H]-pyridazinone as the active ingredient.

3[2H] -pyridazinone derivatives of the invention have the following General formula I:

(I) where R is a branched or unbranched2-C6the alkyl, R1and R2each independently are hydrogen or lower alkyl, R4is a halogen, R3is a halogen; a branched or non-branched C1-C12the alkyl, cycloalkyl, substituted or unsubstituted lower alkyl; branched or unbranched1-C12alkoxy; lower haloalkyl; lower haloalkoxy; -CN; -NO2, -OCH-CH-O-S where X is a halogen, lower alkyl, cycloalkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy, -CN or-NO2and m is what iridological, which may be substituted by halogen and/or-CF3; hinoksalinovym, which may be substituted by halogen and/or-CF3; lower alkenylamine; lower alkylthiol; lower haloalkylthio; -Si(CH3)3; -OH; -N(CH3)2; -SCN; -COOCH3; or-OCH(CH3)COOC2H5, a n is an integer from 1 to 5, and these R3same or different when n is an integer from 2 to 5.

Compounds according to the method of the invention have a particularly high insecticidal and acaricidal activities and demonstrate the great immediate impact, and residual activity.

Description of the preferred variant of the invention.

"Lower alkyl, including lower alkyl fragments contained in such groups as "lower alkoxy", "lower haloalkyl", "lower haloalkoxy", "lower alkylthio" and "lower haloalkylthio" usually is a branched or non-branched alkyl containing from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, ISO-propyl, n-butyl, ISO-butyl, sec-butyl or tert-butyl.

"Lower alkenyl" contained in the lowest alkenylacyl, is usually LRG carbon such as ethylene, n-propenyl, n-PROPADIENE, ISO-propenyl, n-butenyl, 4-butadienyl, n-butadienyl, sec-butanol and sec-butadienyl.

The term "halogen" and "halogen" in the names of such groups as the "haloalkyl", "haloalkoxy and haloalkylthio" refer to fluorine atoms, chlorine, bromine, iodine, or their mixtures.

"Cycloalkyl as R3or Deputy X preferably contains from 5 to 6 carbon atoms.

R is preferably a branched or non-branched alkyl containing 2 to 4 carbon atoms, such as ethyl, n-propyl, ISO-propyl, n-butyl, ISO-butyl, sec-butyl or tert-butyl, and more preferably, tert-bootrom.

R1and R2each are preferably a hydrogen or a branched or unbranched lower alkyl containing from 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl or ISO-propyl, and more preferably hydrogen, stands or ethyl.

R3preferably is a branched or non-branched alkyl containing 3 to 8 carbon atoms such as isopropyl, tert-butyl, isobutyl, n-hexyl, n-heptyl, n-octyl)2-C8alkoxyl (such as ethoxy, n-propoxy, isopropoxy, n-pantoloc is B>-OCHF2cyclopropyl, cylohexane, allyloxy, 2-butenyloxy and-Si(CH3)3. Most preferably, R3was opt-bootrom, phenyl, cyclohexyl, and-OCF3The preferred position of the substituent R3is the 4-position preferably n is an integer from 1 to 3 and, more preferably, from 1 to 2, most preferably 1. R4preferably is chlorine or bromine, more preferably chlorine.

From the point of view of the pesticidal activity of the most important are the following compounds: 70. 2-tert-butyl-4-chloro-5-(4-tert-butyl-methylbenzyl)-3[2H] -pyridazinone, 81. 2-tert-butyl-4-chloro-5-(4-tert-butyl-benzylthio)-3[2H] -pyridazinone, 88. 2-tert-butyl-4-chloro-5-(4-cyclohexylbenzene)-3[2H]-pyridazinone, 95. 2-tert-butyl-4-chloro-5-(4-phenyl-benzylthio)-3[2H]-pyridazinone; 103. 2-tert-butyl-4-chloro-5-(4-isopropyl-methylbenzyl)-3[2H]-pyridazinone, 106. 2-tert-butyl-4-chloro-5-(4-cyclohexyl- -methylbenzyl)-3[2H]-pyridazinone, 109. 2-tert-butyl-4-chloro-5-(4-phenyl-methylbenzyl)-3[2H]-pyridazinone, 129. 2-tert-butyl-4-chloro-5-(4-alkyloxybenzoic)-3[2H] -pyridazinone, 133. 2-tert-butyl-4-chloro-5-(4-trimethylsilylethynyl)-3[2H] -pyridazinone, 138. 2-tert-butyl-4-chloro-5-(4-defermativnimy)-3[2H]-pyridazinone, 141. 2-tert-butyl-4-tert-butyl-4-chloro-5-(4-n-propoxybenzene)-3[2H] -pyridazinone, 155. 2-tert-butyl-4-chloro-5-(4-isobutyl-benzylthio)-3[2H] -pyridazinone, 157. 2-tert-butyl-4-chloro-5-(4-n-hexylbenzene)-3[2H] -pyridazinone, 158. 2-tert-butyl-4-chloro-5-(4-n-heptyl-benzylthio)-3[2H] -pyridazinone, 159. 2-tert-butyl-4-chloro-5-(4-n-octylbenzene)-3[2H] -pyridazinone, 163. 2-tert-butyl-4-chloro-5-(4-isopropoxy-benzylthio)-3[2H] -pyridazinone, 169. 2-tert-butyl-4-chloro-5-(4-n-pentyloxy-benzylthio)-3[2H] -pyridazinone, 170. 2-tert-butyl-4-chloro-5-(4-n-hexyloxy-benzylthio)-3[2H] -pyridazinone, 171. 2-tert-butyl-4-chloro-5-(4-n-heptyloxy-benzylthio)-3[2H] -pyridazinone, 180. 2-tert-butyl-4-chloro-5-(4-(2-butenyloxy)-benzylthio)-3[2H] -pyridazinone, 243. 2-tert-butyl-4-chloro-5-(4'-(4"-triptoreline)-benzylthio)-3-[(2H] -pyrid Azin 245. 2-tert-butyl-4-chloro-5-(4'-(4"-tert-butylphenoxy)--methylbenzyl)-3 [2H]-pyridazinone. Most preferred are compounds 70, 81, 88, 95, 106, 109 and 243.

The formulas of these compounds

70. 138. 81. 141.

88. 153.

95. 154.

103. 155.

106. 157.

109. 158.

133. 163.

169. 129.

170. 159.

171.

180.

243.

245.

The symbol "+" means tert-butyl Compounds of formula I can be obtained by interaction of compounds IIA:

(IIA) where R and R4have the same meanings as in formula I, V means-SH, halogen or-OR5(where R5t is to be placed, as in formula I, Z is halogen or-SH, provided that Z means a halogen when Y is-SH, and Z means a halogen-SH, if Y is halogen or-OR5.

Compounds of the invention can be obtained according to the following schemes of reactions 1, 2, or 3:

Reaction 1

+ hal-

The reaction of 2

+ HS-

Reaction 3

R - where R, R1, R2, R3, R4and n in the above reactions 1, 2 and 3 have the previously indicated meanings, hal means a halogen, and R5is lower alkyl.

The proposed connection can be obtained by interacting 3[2H] -pyridazinone derivatives of the formula II, XVIII or XV as the source material with a benzyl compound of the formula III or XIV as another starting compound in an appropriate solvent in the presence of the absorbing agent galoidovodorodov, or agent that removes the alcohol.

The solvent can be used lower alcohols such as methanol, ethanol; ketones such as acetone, methyl ethyl ketone; hydrocarbons such as benzene, toluene; ethers as isopropyl ether, tetrahydrofuran, 1,4-dioxane; amides such as N,N-dimethylformamide, hexamethylphosphorotriamide; and such halogenated hydrocarbons as dichloromethane is the future galoidovodorodov, can be used inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and such organic bases like triethylamine, pyridine. If necessary you can add to the reaction system such catalysts, as well as the salt of tetraamine (for example, triethylbenzene - ammoniate). The reaction temperature may vary from room temperature to the boiling point of the solvent used in the reaction. The relationship of the source materials can be chosen arbitrarily. However, the reaction is advantageously conducted, using equimolarly or nearly equimolar amounts of material.

The compounds of formula II can be obtained in accordance with the following reaction scheme:

where R, R4and Hal have the previously indicated meanings.

Receipt of the proposed compounds I are described in more detail by using examples that do not limit the invention.

Example of synthesis 1. Getting 2-tert-butyl-4-chloro-5-mercapto-3[2H]-pyridazinone.

To 560 ml of water is added to 66.3 g of 2-tert-butyl-4,5-dichloro-3[2H]-pyridazinone and 48.0 g of 70% sodium hydrosulfide. After stirring at 60aboutC for 4 h add activated carbon. Pay the pH is not reduced to 3 or below. The obtained solid product is filtered off, washed with water, dried, and then recrystallized from a mixture solvent benzene-n-hexane to obtain the target product as white acicular crystals. Melting point 112-113about(Yield Of 81.5%).

For the thus obtained compounds were removed spectra1H-NMR in deuterium chloroform (CDCl3):1H-NMR (CDCl3), (MD): 1,61 (N, s, 2-tert-butyl), Android 4.04 (1H, s, -SH), 7,56 (1H, s, 6N).

Example of synthesis 2. Getting 2-tert-butyl-4-bromo-5-mercapto-3[2H]-pyridazin Nona.

To 200 ml of water is added 31.0 g of 2-tert-butyl-4,5-dibromo-3[2H]-pyridazinone and 15.8 g of 70% sodium hydrosulfide. After stirring at 60aboutC for 4 h the mixture is allowed to cool down to room temperature and add about 8 ml of concentrated hydrochloric acid to reduce the pH of the mixture to a value of not more than 2. The obtained solid product is filtered off, washed with water, dried, and then recrystallized from a mixture of benzene-n-hexane to obtain 8.0 g of the desired product in the form of crystals with so pl. 107-110about(Output 30,4%). For the thus obtained compounds were removed spectra1H-NMR in deuterium chloroform (CDCl3):1H-NMR (CDCl3) (MD): 1,63 (N, s, 2-tert-is asinine (compound 77)

t-C4H9-

In 10 ml of N,N-dimethylformamide was dissolved 1.5 g of 2-tert-butyl-4-chloro-5-mercapto-3[2H] -pyridazinone, to this add 1.2 g of anhydrous potassium carbonate and 1.0 g-chloro-o-xylene. The resulting mixture was heated up to 80-110aboutWith stirring for 2 hours After mixture is allowed to cool to room temperature, to the mixture was added 100 ml of water and then stirred. Precipitated precipitated product is filtered off, washed with water, dried and recrystallized from ethanol to obtain acicular crystals in white with the following physical properties (exit 72,2%). So pl. 138-139,0aboutS.1H-NMR (CDCl3), (MD):

1,62 (N, s, 2-tert-butyl), is 2.40 (3H, s, 2'-CH3), is 4.21 (2H, s, -SH2-), 7,18 (4H, m, phenyl), to 7.61 (2H, s, 6-H).

Example of synthesis 4. Getting 2-tert-butyl-4-chloro-5-(4-tert-butylbenzyl)-3[2H]-pyridazinone (compound 81):

t-C4H9-

According to the method similar to the method of example 3, except that the use of 2.0 g of 2-tert-butyl-4-chloro-5-mercapto - 3[2H]-pyridazinone, 15 ml of N, N-dimethylformamide, 1,3 g of anhydrous sodium carbonate and 1.6 g of 4-tert-butylbenzylamine, get a white needle-like crystals having the following physical properties (yield 87.9 per cent): So pl. 111,0-112,0about

The synthesis example 5. Getting 2-tert-butyl-4-chloro-5-(4-tert-butyl-methylbenzyl thio)-3[2H]-pyridazinone (compound 70):

t-C4H9-

According to the method of example 3, except that use 1.5 g of 2-tert-butyl-4-chloro-5-mercapto-3[2H]-pyridazinone, 10 ml of N,N-dimethylformamide, 1.0 g of anhydrous sodium carbonate and 1.4 g of 4-tert-butyl-methylbenzylamine, get a white needle-like crystals having the following physical properties (exit 72,7%): So pl. 100-106,0aboutWITH1H-NMR (CDCl3) (MD): 1,29 (N, s, 4'-tert-butyl), 1,58 (N, C. 2-tert-butyl), to 1.70 (3H, d, J 7 Hz, -CH3), 4,58 (1H, kV-SCH ), 7,33 (4H, m, phenyl), 7,56 (1H, s, 6N).

Example of synthesis 6. Receive (+)2-tert-butyl-4-chloro-5-(4-tert-butyl--methyl-benzo, ylthio)-3[2H]-pyridazinone (compound 71).

In 300 ml of 0.2 M aqueous solution of dinatriumfosfaatti (pH 9,1) suspended 17.0 g (77.2 mmol) of para-tert-butyl-methylbenzylamine, and 1.00 g of acetone powder bovine liver add to the mixture. After stirring at room temperature for 77 hours, the reaction liquid is extracted twice with portions of 200 ml of ethyl acetate (insoluble portion removed by filtration on celite). An ethyl acetate layer is dried over anhydrous sodium sulfate and the solvent is distilled off to obtain 16,1 the PMC silica gel (eluent: benzene-ethyl acetate 20/1 volume/volume) until receipt of 3.60 g (+)-para-tert-butyl-methylbenzylamino alcohol in the form of colorless crystals with So pl. 85about(Output 26,2%); ()D25+ 47,8about(FROM 1.01,6H12), 98% of E. E.

Part of the product (3,49 g) is recrystallized from a 10.5 g of hexane to obtain a 3.06 g of crystals 100% E. E. ()D25+ 48,9about(1,03,6H12).

In addition, get 12,16 g (-)-para-tert-butyl-methyl-benzoylacetate in the form of almost colorless oil (yield 71.5% of the), ()D2536,9about(WITH 1.09, WITH6H12), with 35.6% E. E.

To 25 ml of ethyl ether is added 1.78 g of (+)-4-tert-butyl-methylbenzylamino alcohol 100% E. E. and 1.8 g of dry pyridine. The obtained mixed solution was kept at -25aboutWith and to it added dropwise a solution of 3.1 g trichromate phosphorus dissolved in 18 ml of ethyl ether (-15 to -25aboutC). After complete addition, the resulting mixture was stirred at -10aboutWith in an hour, and then left to stand at 5aboutWith in 2 days. Add ice water. The obtained organic layer is successively washed with saturated aqueous sodium bicarbonate and ice water, dried over anhydrous Glauber's salt and the solvent is distilled off under reduced pressure to obtain 1.6 g of 4-tert-butyl-methylbenzylamine.

0.96 g of the obtained ProductID and 0.25 g of anhydrous sodium carbonate at -20aboutC. the resulting mixture was left to stand for 2 days at room temperature. Then to the mixture is added 300 ml of benzene and washed twice with water. The resulting organic layer is dried over anhydrous Glauber's salt, the solvent is distilled off to obtain the crude product. This product was then purified using thin-layer chromatography (using a mixture of benzene-ethyl acetate 50/1, Pf of 0.5). To 1.1 g of the thus obtained product add hexane, resulting in a gain of 0.83 g of crystals. Thus obtained product was identical with the product of example 5 according to the1H-NMR. So pl. of 102.3-104,3aboutC. ()D25+ 0,96aboutWith(1,0, l3).

The synthesis example 7. Obtaining (-)2-tert-butyl-4-chloro-5-(4-tert-butyl-methylbenzyl)-3[2H]-pyridazinone (compound 72).

In 400 ml of 0.2 M aqueous solution of dinatriumfosfaatti suspended and 22.6 g of (-)-para-tert-butyl-methylbenzylamine ()D2536,9about(1, C6H12) and optical purity of 35.6% obtained in synthesis example 6, and of 1.33 g of acetone powder chicken liver add to this. The resulting mixture was left to react at 25aboutC for 67 hours, the Reaction liquid is extracted twice with 400 ml of ethyl acetate (insoluble part of valour is. The obtained pale-yellow oily residue is treated through column chromatography (200 g silica gel), and para-tert-butyl-methylbenzylamine elute with a mixture of benzene-ethyl acetate 50/1 (volume/volume), and then para-tert-butylperbenzoate alcohol elute with a mixture of benzene-ethyl acetate 10/1 (volume/volume), after which the solvent in each portion of the eluate is distilled off. So get 14,01 g (yield 62%) of (-)-para-tert-butyl-methylbenzylamine ()D2585,5about(WITH 1.07, WITH6H12), optical purity 82.6% of E. E. and 6.25 g (yield 34%) of (+)-para-tert-butyl-methylbenzylamino alcohol ()D25+ 23,1about(WITH 1.07, WITH6H12)optical purity 47.2% of E. E. 33.6 ml of methanol is dissolved 13,79 g (and 62.6 mmol) of (-)-para-tert-butyl-methylbenzylamine ()D2585,5about(WITH 1.07, WITH6H12), the optical purity of 82.6% E. E. thereafter, the resulting solution is stirred and cooled with ice, and then thereto are added dropwise to 21.7 g of 15% aqueous sodium hydroxide solution (sodium hydroxide at 81.4 mmol) over a time period of 5 minutes After the obtained mixture is allowed to cool to room temperature, it is stirred for one hour, and then add 100 ml of water and 100 ml of benzene for the extraction. The aqueous layer was extragere the solvent is distilled off resulting in a gain 10,86 g (yield 97%) of colorless (-)-para-tert-butyl-methylbenzylamino alcohol ()D2541,1 (1,03,6H12), 84,0% E. E.

Part (10.6 g ) the product is recrystallized from 31.8 g of hexane to obtain to 8.20 g (-)-para-tert-butyl-methylbenzylamino alcohol ()D2547,8about(1.00 M6H12), optical purity of 97.8% E. E. Then spend processing analogous to example 6. Reaction and cleaning is performed similarly, except that the use of 1.78 g of (-)-4-tert-butyl-methylbenzylamino alcohol (enantiomer product of example 6) with optical rotation (1), and an optical purity of 97.9% of E. that is, instead of 1.87 g (+) isomer, resulting in a gain of 0.62 g of crystals of the target compound. The compound was identical to the compound obtained in example 5 according to the1H-NMR. So pl. 102,2-106,7aboutC. ()D251,14about(1,0 l3).

Example 8 synthesis. Getting 2-tert-butyl-4-chloro-5-(4'-(4"-triptoreline) benzylthio)-3[2H]-pyridazinone (compound 243).

In 30 ml of N, N-dimethylformamide was dissolved 2.2 g (0.01 mol) of 2-tert-butyl-4-chloro-5-mercapto-3[2H] -pyridazinone and 3.5 g (0,0105 mol) of 4-(4'-triptoreline)benzylbromide, to this add 2.1 g (0.02 mol) of anhydrous sodium carbonate to perform the reaction at a temperature of from 85 to 90aboutC for 4 h After several washed with 5% aqueous solution of sodium hydroxide, and then water, dried over anhydrous sodium sulfate, and then the benzene is distilled off under reduced pressure. The oily residue is placed in n-hexane and precipitated precipitated crystals are filtered off to obtain white crystals (yield of 85.5%). So pl. to 152.0-155,5aboutS.1H-NMR (CDCl3) (MD): 1,60 (N, s, 2-tert-butyl), 4,22 (2H, s, -SCH2-), 6,92-7,60 (N, m, phenyl and 6-H).

Example 9 synthesis. Getting 2-tert-butyl-4-bromo-5-(4-tert-butylbenzyl)-3[2H] -pyridazinone (compound 139).

To a solution in dimethylformamide of 4.4 g of 2-tert-butyl-4-bromo-5-mercapto-3[2H] -PI-redazione and 4.7 g of 4-tert-butylbenzylamine add 3.5 g of sodium carbonate. The resulting reaction mixture was stirred at 80aboutC for 4 h, then allow it to cool to room temperature, add water and extracted with benzene. The benzene layer was washed with 3% aqueous solution of sodium hydroxide and then water, dried and distilled benzene, resulting in a gain yellowish-brown solid product. The hard part is recrystallized from a solvent mixture of benzene and n-hexane to obtain white crystals (yield 64%). So pl. 137,0-139,0aboutS.1H-NMR (CDCl3), (MD): 1,33 (N, C. 4'-tert-butyl), 1,62 (N, s, 2-tert-butyl), is 4.21 (2H, s, -SCH2-), 7,33 (4H, m, phenyl), 7a (compound N 81).

Conduct the reaction mixture of 1.5 g of 2-tert-butyl-4-chloro-5-mercapto-3[2H]-pyridazino-on, 200 ml of benzene, 1.5 g of anhydrous potassium carbonate and 1.4 g of 4-tert-butylbenzylamine at boiling under reflux for 6 hours Then carry out processing similar to that of example 5, to obtain white crystals (yield 60%).

The connection is similar to the compound obtained in example 4 according to the1H-NMR.

Example 11 synthesis. Getting 2-tert-butyl-4-chloro-5-(4-chlorobenzylthio)-3[2H]-pyridazinone (compound 175).

0.7 g of sodium hydroxide dissolved in 15 ml of water, to this add 100 ml of benzene, and 3.3 g of 2-tert-butyl-4,5-dichloro-3[2H]-pyridazinone and 0.15 g of triethylmethylammonium. To the resulting solution was added 2.4 g of 4-chlorobenzylidene at room temperature and then stirred for 15 hours After completion of the reaction of a mixture of only emit the organic layer, it was washed with 5% aqueous solution of sodium hydroxide and then with water and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure. To the resulting oily residue add hexane and get the crystals. The crystals are filtered to obtain 3.3 g of target compound (yield 64% ). So pl. 142).

Example 12 synthesis. Getting 2-tert-butyl-5-bromo-5-(4-tert-butyl-benzylthio)-3[2H]-pyridazinone (compound 139).

0,22 g of sodium hydroxide dissolved in 5 ml of water, to this add 10 ml dichloromethane, 1.55 g of 2-tert-butyl-4,5-dibromo-3[2H] -pyridazinone and 0.05 g of triethylmethylammonium. To the resulting solution was added 0,83 g of 4-tert-butyl-benzylmercaptan at room temperature and then stirred for 10 hours After completion of the reaction the solution was added about 50 ml of CH2CL2and from it produce organic layer was washed with 5% aqueous solution of sodium hydroxide and then with water, dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure and the resulting solid residue is recrystallized from a solvent mixture of benzene-n-hexane to obtain 1,32 g of target compound (yield 65%). So pl. 137,0-138,0aboutWITH 1H-NMR (CDCl3), (MD): 1,33 (N, s, tert-butyl), 1,62 (N, s, tert-butyl), is 4.21 (2H, s, -SCH2), 7,33 (4H, s, phenyl), 7,54 (1H, s 6-N).

Example of synthesis 13. Getting 2-tert-butyl-4-chloro-5-(4-tert-butyl-benzylthio)-3 [2H]-pyridazinone (compound 81).

0.7 g of sodium Hydroxide dissolved in 15 ml of water and add 30 ml of dichloromethane, and 3.3 g of 2-tert-butyl-4,5-dichloro-3[2H]-peridas at room temperature, and the resulting mixture is stirred for 15 hours After completion of the reaction allocate only the organic layer, it was washed with 5% aqueous solution of sodium hydroxide and then with water, dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure and the oily residue is supplemented with hexane to obtain crystals. These crystals are filtered to obtain 3.8 g of target compound (yield 70%).

The physical properties of the compound are identical to the properties of the compound obtained in example 4.

By methods similar to the above, there were obtained the following compounds are given in table.2.

When the proposed compounds are used as insecticidal, acaricidal and/or fungicidal agents for agriculture and horticulture or as agents for removing ticks parasitic on animals, they are usually mixed with appropriate carriers, such solid carriers such as clay, talc, bentonite or hard-shelled land, or with such liquid carriers such as water, alcohols (e.g. methanol or ethanol), aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons, ethers, ketones, inorganic salts of acids (e.g the ü emulsifiers, dispersing agents, suspendresume agents, agents promoting penetration and wetting, stabilizers and the like for ease of use them in practice in the form of liquid preparations, emulsifiable concentrates, wettable powders, Farrukh Dustov, granules, peresypaya powders, etc. moreover, the mixtures can be added to other herbicides, various insecticides, bactericides, plant growth regulators and/or synergy in the process of preparation and their application.

The number of compounds of the invention, which should be used as the active ingredient are usually in the range of 0.005 to 5 kg/ha, although these values vary greatly depending on location and season of application of the compounds, method of making, disease or pest of cultivated plants, which are subject to protection, etc.

The following are examples of fungicidal, insecticidal and acaricidal compositions, and compositions for removing ticks parasitic on animals, and these compositions contain the proposed connection as the active ingredient. These examples are only illustrative and do not limit the invention.

Example composition 2. Wettable powders, dry wt. including the Active ingredient 25

Siegreit PFP (trading

mark clay-based

kaolin, shotable-

by Siegreit Minig Industries Co. Ltd.), 69

Solpol 5039 (trade mark,

a mixture of non-ionic surface

surface-active agent and

anionic surfactants-

active agent manufacturing

by Toho Chemical Co. Ltd. Japan) 3

Carplex (trading

mark, inhibiting

coagulating agent,

the mixture of surface-active

tion agent and a white charcoal

made Shionogi Seiyaku K. K. Japan) 3

These components are homogeneous mixed together and pulverized to obtain a wettable powder. When using wettable who ha which corresponds to the dose of 12.5-5000 ppm, 400-1000 l/ha

Example of composition 3. Oil solutions, wt. including the Active ingredient 10 Methylcellosolve 90

These homogeneous components are mixed with each other to obtain an oil solution. When using the oil solution is applied in an amount of from 0.005 to 5 kg of active ingredient per hectare.

Example of composition 4. Dusty, wt. including the Active ingredient 3

Carplex (brand

the inhibitory agent

coagulation as indicated) 0.5 Clay 95 Diisopropylphenol 1,5

These components are homogeneous mixed together and pulverized to obtain dust. When using the dust is applied in the amount of 0.005 to 5 kg of active ingredient per hectare.

Example of composition 5. Granules, wt. including the Active ingredient 5 Bentonite 54 Talc 40 Ligninsulfonate calcium 1

These components are thoroughly mixed together and crushed, add a small amount of water and mix together. The resulting mixture granularit using an extrusion granulator and dried to obtain granules. When using them contribute in the amount of 0.005 to 5 kg/ha of active ingredient.

An example of the composition 6. Flowing powder, wt. including the Asset is R>
by Toho Chemicals, Co. Ltd. Japan) 10

lunox 1000C (trade mark,

anionic surfactants-

the active agent, izgotavlivaet-

by Toho Chemicals, Co. Ltd. Japan) 0,5

1% aqueous solution of the resin

xantam (natural, professional - molecular connection) 20 Water 44,5 These components except the active ingredient is thoroughly mixed with each other to obtain a solution, to it add the active ingredient. The resulting mixture was thoroughly mixed, crushed raw using a sand mill to impart flowability. When using it diluted down from 0.02 to 0,00005 water and put in the amount of 0.005 to 10 kg of active ingredient per hectare. Compounds of the present invention not only have excellent insecticidal activity against such hemipteran insects, such as green rice Cicada (Nephotettix cineficeps) and against such lepidopteran insects, such as the cabbage moth (Plutella xylostella) and against such insects as the ordinary mosquito (Culex pipiens), but is also suitable for the destruction of mites on fruit trees and vegetables, such as detachedly clasic spider mites (Tetranychus urtical), clasic spider mites (Tetranychus kanzawai), clasic red (Tetranychus cinnabarinus), clasic red citrus (Panonychus cirti) and the European ilus microplus), mite of cattle (Boophilus annulatus), galf coast tick (Ambluomma maculatum), brown ear tick (Rhipicephalus appendiculatus), and (Haemaphysalis longicornis). The main feature of the compounds of the invention is that these compounds are useful for preventing or combating diseases in fruit trees and vegetables such, which are called false or powdery mildew, etc. besides the fact that they have specified earlier insecticidal properties. Accordingly, the compounds of the invention are excellent products for use in agriculture, which provide a simultaneous struggle with insects and with fading (or disease). Moreover, they are ideal for removing ticks parasitic on animals, such as Pets (for example, cattle, horses, sheep and pigs), poultry and other animals, including dogs, cats, rabbits, etc.

Test example 1. Insecticidal test against domestic flies (Musca domestica) adult.

1 ml of an acetone solution containing 1000 hours at million offer of connection to be tested, is added dropwise in a laboratory flask with a diameter of 9 cm so that the solution could evenly, which corresponds to a dose of 1 mg to 64 cm2aboutC. Assessment activity produced after 48 h, counting the number of dead adult insects and calculate the percentage of mortality of insects at the following ratio:

Mortality (% ) 100 Each test was repeated twice for each compound. The results are shown in table. 3.

Test example 2. Insecticidal test against the ordinary mosquito (Culex pipiens), in the larval stage.

200 ml of an aqueous solution of concentration 10 am on million proposed connection is placed in a tall vessel with a diameter of 9 cm and a height of 6 cm, which corresponds to a dose of 2 mg / 64 cm2i.e. 3,125 kg/ha. Then 10 larvae of the last stage of development of a mosquito ordinary placed in the vessel. High vessel is placed in a thermostat at 25aboutAnd the number of dead larvae determined after 96 hours, the mortality rate is defined as in test example 1. The specified test was repeated twice for each compound. The results are shown in table. 3.

Test example 3. Contact insecticidal test on cabbage moth (Plutella xylastella).

A sheet of about 10, and then air-dried. The thus treated sheet is placed in a container, which released 10 of the larvae of the cabbage moth second stage of development. The vessel is covered with a lid, in which there are several holes and placed in a thermostat at 25aboutC. the Percent mortality determined after 96 h in the same manner as in test example 1. Each test was repeated twice for each compound. The results are shown in table. 3.

Test example 4. Contact insecticidal test on 28-spot beetle (Henosepilachna vigintioctopunctata).

The tomato leaf is dipped in water emulsion containing 1000 hours at million proposed connection and then air-dried. The thus treated sheet is placed in a laboratory vessel, which put 10 larvae 28-point bug in the second stage of development. The vessel is then covered with a lid, which made the hole, and then placed in a thermostat at 25aboutC. the Number of killed larvae counted after 96 h, the mortality rate is defined as in test example 1. This test was repeated twice for each compound. The results are shown in table. 3.

Test example 5. Acaricidal test Clasica spider (T. Kanzawai).

the oval paper in styrene Cup with a diameter of 7 cm, which corresponds to a dose of 2 cm340 cm2(500 l/10 acres), 5 kg/ha Each piece of sheet inoculant 10 nymphs of klasika ordinary. Half a day after insulinopenia, 2 ml water emulsion containing 1000 hours at million proposed connection diluted wetting agent is applied to each styrene Cup using a rotary sprayer. After 96 h to determine the number of dead nymphs, and the percentage mortality of the nymphs is defined as in test example 1. The test was repeated twice for each compound. The results are shown in table. 3.

Test example 6. Acaricidal test Clasica red citrus (Panonychus citri).

Sheet Mandarin cut into round pieces with a diameter of 1.5 cm, and then placed on moistened filter paper, put in styrene Cup with a diameter of 7 cm, which corresponds to the dose specified in example 5. Each piece of sheet inoculant 10 nymphs of klasika red citrus. Half a day after inoculation in each styrene Cup using a rotary sprayer put 2 ml water emulsion containing 1000 hours per million of the active substance with a wetting agent. The number of dead nymphs counted after 96 h, and the percentage of mortality apready test green rice Cicada (Nephotettix cineticeps).

The stems and leaves of rice is dipped in the emulsion containing 1000 hours at million proposed connection 10, and then the stems and leaves are immersed in a glass cylinder. Then 10 adults of green rice cycatki that are resistant to organophosphorus insecticides of the type produced in the cylinder, which is then covered with a lid and then placed in a thermostat at 25aboutC. After 96 h, the mortality rate is determined according to the method of example 1. The test was repeated twice for each compound. The results are shown in table. 3.

Test example 8. Nematocidal test root nematode (Meloidogyne spp.).

Soil infected with root nematode, placed in a styrene Cup diameter 8 see Prepare a liquid containing 1,000 hours per million of active ingredient, diluting the emulsifiable concentrate according to the method of the present invention with water, and then adding a wetting agent. Soil infected with nematodes and placed in a styrene Cup, impregnated with 50 ml of the fluid. After 48 h in the thus treated soil as an indicator of plant tomato seeds. 30 days after planting, the roots of tomato washed with water and the presence of root nematodes check resoluted nematodes 1. there are several nematodes 2. observed average number of nematodes 3. there is a lot of nematodes 4. there is significantly a lot nematodes.

Each test was repeated twice for each compound. The results are shown in table. 3.

Test example 9. Test to combat downy mildew on cucumbers.

Used cucumber (Cucumis sativus L. variety sagamihanjiro) grown for 2 weeks, after which they are sprayed with a solution of the emulsifiable concentrate of the proposed method, which is brought to the desired concentration (1000 hours per million ) in the amount of 20 million in the pot, which corresponds to a dose of 500 l/10 acre, i.e. 5 kg/ha After each pot is placed in the greenhouse at night, the spore suspension Pseudoperonospora cubeusis (concentration dispute this, that when observed through a microscope with magnification of 150 times can be observed 15 dispute) sprinkle the cucumbers on the subject of inoculation. Cucumbers, which are inoculated with spores (Pseudoperonospora cubensis), left for 24 hours in a room with temperature of 25aboutC and with a relative humidity of 100% and then transferred to the greenhouse for observation of the appearance of the disease. After 7 days of inoculation, the percentage of the disease are counted and evaluated according to the following scheme: 0. there is no visibility on 6-20% of inoculated leaves 3. -"- 21-50% -"- 4. -"- 51-90% -"- 5. the disease manifested itself not less than 90% of inoculated leaves

The results are shown in table. 4. Test example 10. Test against powdery mildew of cucumbers.

Used in example cucumbers (Cucumis sativus L. variety Sagamihanjiro) grown in pots about 2 weeks, sprayed with a solution of the emulsifiable concentrate of the proposed method, which is adjusted to a predetermined concentration, in the amount of 20 ml per pot. After each pot was placed overnight in a greenhouse, the spore suspension Sphaerothecu fuliginea (the concentration of spores in the suspension such that when observed through a microscope with a magnification of 150, you can see 25 dispute) sprayed on cucumber for insulinopenia. Cucumbers are placed in a greenhouse at a temperature of 25-30aboutFor observation of the appearance of the disease. 10 days after insulinopenia, the percentage manifestations of the disease define and evaluate in the same scale as in test example 9. The results are shown in table. 5.

The proposed connections on ticks parasitic on animals, is explained in the following test examples.

Test example 11. Acaricidal test Haemaphysalis longicornis.

PR is the new solution to control. Inside the glass cylinder (2.8 cm in diameter and 10.5 cm in height), which serves as a test vessel, placed in a cylindrical filter with the inner surface 142,9 cm2side surface to 130.6 cm2and the full surface of the bottom and top of 24.6 cm2and this filter before immersed in one of these solutions, and then dried sufficiently.

After this the vessel out 20 nymphs of the tick, the vessel lid with filter and a cotton plug. After a certain period of time the filter is removed from the vessel is irradiated with light using a microscope condenser in binocular stereo microscope and observe the movement of the body and movement of the legs of the tick. The life or death of the tick appreciate, considering that he's alive, if there are movements of his body or legs.

The test is carried out not blood on the nymphs of the tick, which were incubated person laying parthenogenetic female adult tick (Haemaphysalis longicornis) strain Okayama, which gave to nanosats blood of domestic rabbit. The results are shown in table. 6.

Additionally, in order to show the advantages of the claimed compounds before known compounds and methods specified in the test p is raimunda offer connections shown in the structure of agricultural compositions of different preparative forms emulsifiable concentrate, wettable powders and flowable powders.

An example of a form 1. Emulsifiable concentrates, wt. including the Active ingredient 20-25 Liquid media 67-76 (in Russian) Surface-active agent 5-8

The mentioned components are thoroughly mixed before the formation of the emulsifiable concentrates of the following structures. These components are listed in the table. 8.

The test example 1. Contact insecticidal test on the 28-point of God the cow (Henosepilachna oigintioctopunctata).

Each composition emulsifiable concentrates, specified in the table. 8, was diluted with water to obtain an aqueous emulsion of 100 ppm.

The sheet was dipped in tomato emulsion of water, and then dried in the air. The thus treated sheet was placed in a Petri Cup, which was also released 10 larvae 28-spot ladybirds in the second stage of development. Then the Cup was covered with a lid, provided with a long and placed in a thermostatic chamber in which is maintained a temperature of 25aboutC. the Number of dead larvae was counted after 96 h, and the percentage of their death was determined in accordance with the following equation:

Death (%) 100

This test was repeated twice for each emulsion. The results are shown in table. 9

Each composition emulsifiable concentrates are given in table. 8, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. The stems and leaves of rice was immersed in the emulsion for 10 s, and then the stems and leaves were placed in a glass cylinder. Then released 10 adults of green rice kobyluck that show resistance to insecticides of the type of organic phosphorus, and glass cylinder was covered with a lid, which has several long and was placed in a thermostatic chamber in which is maintained a temperature of 25aboutC. After 96 h mortality was determined in accordance with the procedure of test example 1. The test was repeated twice for each emulsion. The results are shown in table. 10.

The test example 3. A special test on Clasica the spider Cansave (So Kanzawa).

Each composition emulsifiable concentrates are given in table. 8, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. List of beans cut in round pieces with a diameter of 1.5 cm using a leaf punch, and then placed on moistened filter paper, printed on styrene Cup with a diameter of 7 cm On each piece of paper was placed 10 nymphs to roloway Cup using a rotary sprayer. The number of dead nymphs were counted after 96 h, and the percentage loss of nymphs was determined in accordance with test example 1. The test was repeated twice for each emulsion. The results are shown in table. 11.

The test example 4. A special test against citrus red mite (Panonychus citri).

Each composition emulsifiable concentrates are given in table. 8, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. Sheet Mandarin noble cut in round pieces with a diameter of 1.5 cm using a leaf punch, and then placed on moist filter paper contained in the styrene Cup with a diameter of 7 cm On each piece of leaf was inoculated 10 nymphs citrus red mite. After 12 h after the procedure, 2 ml of each aqueous emulsion used in each styrene Cup using a rotary sprayer. The number of dead nymphs were counted after 96 h, and the percentage of death was determined in accordance with test example 1. The test was repeated twice for each emulsion. The results are shown in table. 12.

An example of a form 2. Wettable powders, dry wt. including the Active ingredient 20-25 Solid media 72-77 Surface-active agent 3-5

The test example 5. Contact insecticidal test on the 28-point of God the cow (Henosepilachua oigintioctopunstata).

Each composition wettable powders are given in table. 13, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. The tomato leaf was immersed in water emulsion and dried in the air. The thus treated sheet was placed in a Petri Cup, which was released 10 larvae 28-spot ladybirds. Then the Cup was covered with a lid, provided with a long and placed in a thermostatic chamber in which is maintained a temperature of 25aboutC. Counting the number of dead larvae after 96 h, and the percentage of death was determined by the same formula that has been shown in test example 1. The test was repeated twice for each emulsion. The results obtained were placed in a table. 14.

The test example 6. Insecticidal test against green rice locusts (Nephotettix cineticeps).

Each composition wettable powders listed in table. 13, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. The stems and leaves of rice was immersed in the emulsion for 10 s, and then the stems and leaves were placed is of insecticidal type of organic phosphorus, produced in the glass cylinder was closed with a lid having a few long and was placed in a thermostatic chamber in which is maintained a temperature of 25aboutC. After 96 h was determined by the percentage of loss in accordance with test example 1. The test was repeated twice for each emulsion. The results are shown in table. 15.

The test example 7. A special test against Clasica the spider Cansave (So Kanzawa).

Each composition wettable powders are given in table. 13, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. List of beans cut in round pieces with a diameter of 1.5 cm using a leaf punch, and then placed on moist filter paper contained in the styrene Cup with a diameter of 7 cm On each piece of paper was placed 10 nymphs of klasika the spider Kansai. Within 12 hours after this procedure, 2 ml of each aqueous emulsion was applied to each styrene Cup using a rotary sprayer. The number of dead nymphs were counted after 96 h, but the death of a percentage determined in accordance with test example 1. The test was repeated twice for each emulsion. The results are shown in table. 16.

An example of a form 3. Flowing powders.

The active ingredient of 20-25 wt. including liquid media 44,5-52 wt. including surface-active agent 8-10,5 wt. including 1% xanthan gum 20 wt. including the above components, except the active ingredient, are thoroughly mixed together to obtain a solution, and it was added to the active ingredient. The resulting mixture was thoroughly mixed, crushed in a wet state by means of a sand mill to obtain fluid p is against 28-spot ladybirds (Menosepilachua oigintioctopunctata).

Each composition flowing powder, shown in table. 11, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. The sheet was dipped in tomato emulsion of water, and then dried in the air. The thus treated sheet was placed in a Petri Cup, which was released 10 larvae in the second stage 28-spot ladybirds. Then the Cup was closed with a lid, provided with a long and placed in a thermostatic chamber in which is maintained a temperature of 25aboutC. the Number of dead larvae was counted after 96 h, and the percentage of death was determined by the same procedure as in test example 1. The test was repeated twice for each emulsion.

The results are shown in table. 19. The test example 10. Insecticidal test against green rice kobylecki (Nephotettix cincticeps).

Each composition flowing powder that is specified in the table. 18, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. The stems and leaves of rice was immersed in the emulsion for 10 s, and then the stems and leaves were placed in a glass cylinder. Then 10 adults of green rice kobyluck that are resistant relative to insecticides of the type of organic phosphorus was released in STEMI maintained a temperature of 25aboutC. After 96 h, the percentage of death was determined in accordance with test example 1. This test was repeated twice for each emulsion. The results are given in table. 20.

The test example 11. A special test on Clasica the spider Cansave (So Kanzawa).

Each composition flowing powder, shown in table. 18, was diluted with water to obtain an aqueous emulsion with a concentration of 100 ppm. List of beans cut in round pieces with a diameter of 1.5 cm using a leaf punch, and then placed on moistened filter paper contained in the styrene Cup with a diameter of 7 cm On each piece of paper was placed 10 nymphs of klasika the spider Kansai. Within 12 hours after this procedure, 2 ml of each aqueous emulsion was applied to each styrene Cup using a rotary sprayer. The number of nymphs that died during the test were counted after 96 h, and the percentage of death was determined as in test example 1. This test was repeated for each emulsion. The test results are placed in table. 21.

The test example 12. A special test against citrus red mite (Panonychus citri). Each composition flowing powder found in Mandarin cut in round pieces with a diameter of 1.5 cm using a leaf punch, and then placed on moistened filter paper contained in the styrene Cup with a diameter of 7 cm On each piece of paper was placed 10 nymphs citrus red mite. Within 12 hours after this procedure, 2 ml of each aqueous emulsion was applied to each styrene Cup using a rotary sprayer. The number of dead nymphs were counted after 96 h, and the loss percentage was calculated in accordance with the description given in test example 1. This test was repeated twice for each emulsion. The results are shown in table. 22.

DERIVATIVE 3(2H) - PYRIDAZINONE General formula 1

< / BR>
where R is a branched or unbranched2- C6-alkyl;

R1and R2- independently from each other hydrogen or lower alkyl;

R4- halogen; R3- halogen, branched or unbranched1- C12-alkyl,C3-C6-monocyclohexyl,resetwndtranslucency1-C12-alkoxy, hydroxy, nitro, lower haloalkyl, lower haloalkoxy-, lower alkylthio, lower haloalkylthio-, lower alkenylacyl-, trimethylsilyl, thiocyanato-, dimethylamino -, and methoxycarbonyl, 1-ethoxycarbonylmethoxy, pyridyloxy, trifluoromethyl,

or a group of the formula

< / BR>
< / BR>
where X is halogen, lower alkyl, or lower haloalkyl;

m denotes 0 or an integer of 1 or 2;

n is an integer from 1 to 3, and X is the same or different when m is 2,

these R3are the same or different when n is an integer from 2 to 3 or, when R3- the group of formulas a - e, n-1.

Priority signs:

23.06.83 when R3is halogen, lower alkyl, C3- C6-monocyclohexyl, lower alkoxy, lower haloalkyl, lower haloalkoxy, the nitro group of the formulas a and b when these values of R, R1, R2and R4;

29.07.83 when R3- methoxycarbonyl group, the group of formulas d and e in the above mentioned values of R, R1, R3and R4.

 

Same patents:

The invention relates to new derivatives of 3(2H)-pyridazinone and to their pharmaceutically acceptable salts, possessing inhibitory activity against the aggregation of platelets, cardiotonic activity, vasodilating activity, anti-SRS-A activity, to processes for their preparation and to pharmaceutical compositions containing them as active ingredient

The invention relates to new compounds useful as herbicides, and to their use in weed control in the cultivation of fine-grained cereals

The invention relates to chemical means of protection of plants, particularly to herbicide compositions based on derivatives of sulfonylurea

The invention relates to new derivatives of 3(2H)-pyridazinone and to their pharmaceutically acceptable salts, possessing inhibitory activity against the aggregation of platelets, cardiotonic activity, vasodilating activity, anti-SRS-A activity, to processes for their preparation and to pharmaceutical compositions containing them as active ingredient

The invention relates to new biologically active compounds, namely, the derivative of 4-aminophenol of the formula I

XNROR1where R1represents a group WITH/ABOUT/УZ;

Y represents a single bond, 0, NR7or; Z represents hydrogen, pyridyl; phenyl which may be substituted with halogen, nitro, lower alkoxy or carboxy; lower alkyl which may be substituted by hydroxy, lower acyloxy, carboxy, lower alkoxycarbonyl, CONR8R9, phenyl/lower/ alkoxy, phenyl, halogen, cyano or NR10R11;

R2, R3, R5and R6that may be the same or different, represent hydrogen, lower alkyl or alkenyl, lower alkoxy or halogen;

R4and R7that may be the same or different, represent hydrogen or lower alkyl;

X 4.5-dihydropyrazolo or pyrazolyl, which may be substituted WITH3-C6-cycloalkyl or phenyl which can be substituted by trihalomethyl;

R8, R9, R10, R11which may be the same or different, represent hydrogen, lower alkyl or benzyloxycarbonyl, or their N-alkyl

The invention relates to the production of new proizvodnyh of thiazolidine that are used in pharmaceutical compositions

The invention relates to a method for obtaining complex diesters of alkyl substituted 4-hydroxy-piperidino connection of some complex organic esters, in particular to a method for producing a complex of diesters of alkyl-substituted 4-hydroxy-piperidino compounds of esters of dicarboxylic acids using a catalyst system containing the basic inorganic compound and a polar aprotic organic compound

The invention relates to the derivatives of pyrimidine, herbicide compositions and chemical method of weed control with their use

The invention relates to novel 3(2H)-pyridazinone derivatives and to a method of combating harmful insects and their use

The invention relates to novel 3(2H)-pyridazinone derivatives and to a method of combating harmful insects and their use

The invention relates to agriculture, namely, tobacco production, in particular to methods of inhibiting the growth of lateral shoots on verschwende tobacco plants as a result of application of chemicals
Up!