SU1579454A3 - Method of obtaining isomeric mixture - Google Patents

Abstract

The procceding of obtaining the isomer mixture of synthetic pyrotroizi (piretroizi)The use: in agriculture, because it manifests insecticide activity. The summary: the method of obtaining the new isomer mixture of synthetic pyrotroizi with the general formula:X2C =CH - COOCH(CN) - C6H4OC6H5where X1 chlorine, bromine that contains at least 95% mass of the enantiomeric pairs IR cis S, IS cis R (a), IR trans S and IS trans R (b) into a mass report from 55:45 till 25:75.The efficiency constitues 70-80% of the product.The melting temperature of the product, the mass report of the isomer 1a:1b is 55:45, 50:50, 40:60, 30:70, 25:75, is equal with 61,5 - 64, 60,5-62, 63,5-65, 65-68, 67-71,5°C. In the melted mass or in the saturated solution of mixter of the enantiomeric pairs IR cis S, IS cis R (1a) and IR trans S, IS trans R (ab) and IR cis R, IS cis S (1c), IR trans R, IS trans S (1b) in primary alcohol or a mixture of haloid hydrocarbon saturated and primary and with primary alkylek ether so as oil-bearing ether or hexane. For initiation crystals are added and the crystallization is made at the temperature from (+) 30 till (-) 10°C with the further separation at the indicated temperature of the pair enantiomerik crystals that contain 1a and 1b.

Description

the seed in the form of seed crystals of 215 mg of white crystals of the mixture of isomers Ib, stirred at 20 ° C for a day and cooled to 0-5 ° C. The suspension is filtered, the product is washed with cold isopropanol, and then with cold petroleum ether and dried. Obtain 8 g of a white crystalline isomeric pair Ib (1: 1), so pl. 78-79 ° C, purity 93% (analysis data by gas chromatography). The product is recrystallized from 75 ml of hexane. The result is 7.5 g of a white crystalline product with an Ib isomer content (1: 1) of 98%, and so on. 80-8GS.

chesky product, so pl. 80-81 ° C, the active content is 99%.

Example 25. 16.7 g of crystalline trans-cypermethrin (containing 5Q 51% isomers 1R trans-S and IS trans-R and 46% isomers 1R trans-R and 1S trans-S) are dissolved in 83 ml of dry methanol at 45 ° WITH.

0.05 g is added to this solution.

its 2,6-di-tert-butyl-4-methylphenol. After filtration, the seed mixture is seeded at 30 ° C in the form of seed crystals consisting of a 1: 1 mixture of Ib isomers, and stirred at

chesky product, so pl. 80-81 ° C, the active content is 99%.

Example 25. 16.7 g of crystalline trans-cypermethrin (containing 51% trans 1R trans-S and IS trans-R isomers and 46% trans 1R and 1S trans-S isomers) are dissolved in 83 ml of dry methanol at 45 ° C .

0.05 g is added to this solution.

2,6-di-tert-butyl-4-methylphenol. After filtration, the filtrate is seeded at 30 ° C in the form of seed crystals consisting of a 1: 1 mixture of Ib isomers, and stirred at

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round, after which the solution is filtered with 92% of it (according to the results of gas crystallized as crystallized, as described in example), from the mother liquor

2. Get 8 g of white crystal-get as a second collection

of the 1b liter of isomeric mixture, t „pl.1.5 g of white crystalline products 79-80, 5аС. Yield 80%, purity 97%. 5 ta, so pl. 78-79 ° C. The composition of the product

Example5. The south of the crystalline-second collection is identical to the composition of the Kris trans-cypermethrin (composed of first-generation galls. Total

of 52% of the isomers of 1R trans-R and IS output 75%.

trans-S and 47% of the isomeric pair Ib) rast-Q. Example 10. 10 g of trans-cypervorous in 15 ml of the tri-n-propylamine parametric (containing 54% of isomers

50 ° C. The solution is filtered, cooled with 1R trans-S and 1S trans-R and 45% isomedo 30 ° C and seeded by Id) is dissolved in 100 ml of petroleum injection of a seed crystal, soy ester (mp. 60-80 ° C) after a mixture of 1: 1 mixture of isomers Ib. 1 ml of a 0.5 M solution is added to the mixture. The mixture is left to crystallize sodium bonate and a mixture (1: 1) of water with

for 48 h “Obtain 8.2 g of white methanol containing 10 weight / volume

crystalline product, so pl. 78-tetrabutylammonium bromide. Into the solution

80 ° C. Purity of 95% (according to the result - make a seed in the form of seed

There gas chromatography analysis) .20 crystal, as described in example 2,

A yield of 82% was crystallized for 4 days,

Example The process is conducted as filtered, washed with petroleum ether as described in Example 5, except for and dried. 6.8 g beige are obtained.

of the fact that, as the base of an exemplary crystalline isomeric peer

15 ml of tributylamine. Receive 25 1b, mp. 78-80 ° С, purity 95% (gas.

7.5 g of pure white crystalline iso-chromatographic analysis). Output

dimensional pair Ib, so pl. 77-79 ° C, pure 68%.

that 93%. 75% yield. Example 11. South crystalline Example. The process is performed by whom trans-cypermethrin (containing

as described in example 5, except for -30 52% of the isomers of 1R trans-S and IS trans-R

The fact that as a base and 47% of 1R trans-R and 1S isomers

 15 ml of triisopropylamine is used. P-trans-S) is dissolved in 100 ml of petrol and 7.5 g of white crystalline ether at 50-60 ° C. To the solution of the isomeric pair Ib, so pl. 78-80 ° C, 0.02 g of 2,6-ditertbutylpurity 95.5% is added to the py. Yield 75%., -4-methylphenol. After filtering into

Try on The process is carried out, the filtrate at 30 ° C is seeded into

as described in example 5, with the exception of the form of seed crystals,

This is due to the fact that, as a base, those obtained from a mixture (1: 1) of isomers Ib. 15 ml of diisopropylamine are added. Semi-tallization is carried out similarly

8.0 g of pure white crystal-40 is described. 3.8 g of snow-white isomeric Ib pair are obtained, m.p. 78-80 C, Noah crystalline isomeric pair Ib

purity 95.5%. Yield 80%. (1: 1), m.p. 77-79 ° C, purity 93%.

Example 9. South trans-cypermeth-After recrystallization from petroleum (containing 48% isomers of 1R ether), the melting point of polyvinyl-S and 1S trans-R and 49% of isomers is up to 80.5 ° C.

Id boilers are dissolved in 50 ml of isproproducting epimerization on a separate

panola with stirring and heating, stage. The purity after recrystallization followed by the addition of 2 ml of a water solution of 99%.

ammonium hydroxide target (sp. weight) Example 12. South crystalline, 880 g / ml. To the solution, trans-cypermethrin (50% in the form of seed crystals from iso-go,%: 45% of isomers of 1R trans-S and IS

measured mixture of Ib, stirred at 20 Strans-R and 53% isomers of 1R trans-R and

within 24 hours, cooled to 0-5 ° C1S trans-S) is dissolved in 75 ml of isoia and stirring is continued with this propanol at 50-60 ° C. Reverse temperature solution. The suspension is filtered, it is processed in the same way as described in the premedicon, washed with isopropanol and petro-11. 3.6 g of snow-white are obtained.

ether and dry. A crystalline isomeric pair of Ib is obtained,

6 g white crystalline isomeric output 36% Purity of the mixture 1: 1 Reaches Ib (1: 1), so pl. C, pure 94% (according to the gauchramatdrafichesky dashshm analysis), so pl. 80 ° C. Additional crystallization is carried out as described in Example 2. A product is obtained with an active ingredient content of more than 99%. The mother liquor is subjected to epimerization in a separate stage.

Example 13. The mother liquor prepared according to Example 11 (solution enriched with Id isomer) and 1 g of Dowex basic ion exchange resin Toure 2x4 mesh (serva) are introduced into the apparatus equipped with a stirrer. Heterogeneous

charcoal, filtered in a warm state, and the filtrate is seeded at 30 ° C in the form of a seed crystal consisting of a 1: 1 mixture of Ib isomers. The mixture was allowed to crystallize at 10 ° C for 24 hours, at 0 ° C for 48 hours and finally at -5 ° C for 24 hours (crystallization was completed so as to avoid the appearance of an oily product). The crystals are filtered off in a cold state, washed with isopropanol and dried at room temperature.

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the suspension is stirred at 40 ° C at a te-jc temperature. 2.6 g are obtained by refluxing for 12 h, filtered, washed with a double crystalline isomeric pair.

Ib (1: 1), so pl. 78-80 ° C, purity 95%. After recrystallization from hexane, 2.3 g of a pure white crystalline product are obtained, mp. 80-81 ° C, the content of the active ingredient 99%. Total yield 23%.

Example 17. South of crystalline trans-cypermethrin (containing 52% trans isomers 1R trans-S and 1S trans-R and 47% isomers of trans 1R trans and R and 1S trans-S) in 150 ml of hexane at 50 dy (2 ml each) with isopropanol. According to gas chromatographic analysis, the solution contains 41% of the Ib isomeric pair and 46% of the Id isomer. The solution is evaporated and crystallized as described in example 1-1.

Example 14. The process is carried out analogously to example 13, except that petroleum ether is used as a solvent. According to gas chromatographic analysis, the solution contains 39% Ib isomers and 56% trans-R and IS trans-S isomers.

Example 15. In the South, colorless oily cypermethrin (containing Ib 30; Id 31; la 18; Ic 21) were seeded as seed crystals of a 1: 1 mixture of isomers Ib and allowed to crystallize at 7 ° C for a week. The resulting viscous crystalline oil is cooled to -15 ° C, suspended in 10 ml of a 1: 1 mixture, and it is dissolved.

60 ° C. 0.02 g is added to the solution.

thirty

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2,6-di-tert-butyl-4-methylphenol. After filtration, the filtrate is seeded at 30 ° C with seed crystals consisting of a 1: 1 mixture of Ib isomers and crystallized at 25 ° C for 10 hours. The crystals are filtered, washed with cold hexane and dried. Obtain 3.6 g of white crystalline isomeric pair Ib with so pl. 77-79 C and purity 92%. When recrystallization from 36 ml of ethanol so pl. rises to 80.5 ° C and the active ingredient content is 98.5%.

panol and diisopropyl ether, cooled to a temperature of -15 ° C, and filtered in a cold state. The crystals obtained are washed with 5 ml of ice-cold isopropanol and dried at room temperature. 2.5 g of white crystalline product Ib are obtained, m.p. 78-80 ° C, purity 96% (gas chromatography). After recrystallization from 13 ml of hexane, 2.25 g of a crystalline white product are obtained, m.p. 80-81 ° C, the content of the active ingredient is 99%. Overall yield of 22.5%.

Example 16. The south of cypermethrin (containing,%: Ib 30; Id 31; la 18; Ic 21) is dissolved in 100 ml of warm isoprpranol, then 0.02 g of 2,5-di-tert-butyl-4- is added methylphenol. The solution is clarified with 0.02 g of active

Example 17. The south of crystalline trans-cypermethrin (containing 52% isomers of 1R trans-S and 1S tra and 47% of isomers 1R trans-R and 1S tra in 150 ml of hexane at

dissolve

60 ° C. 0.02 g is added to the solution.

2,6-di-tert-butyl-4-methylphenol. After filtration, the filtrate is seeded at 30 ° C with seed crystals consisting of a 1: 1 mixture of Ib isomers and crystallized at 25 ° C for 10 hours. The crystals are filtered, washed with cold hexane and dried. Obtain 3.6 g of white crystalline isomeric pair Ib with so pl. 77-79 C and purity 92%. When recrystallization from 36 ml of ethanol so pl. rises to 80.5 ° C and the active ingredient content is 98.5%.

Example 18. The procedure of example 17 is repeated, except that 150 ml of heptane is used as the solvent. The result is 3.7 g of white crystalline. Mp.

five

isomeric Ib pair with 77-79 ° C, 92% purity.

Example 19. Example 18 is repeated, except cyclohexane is used as the solvent. Obtain 3.6 g of white crystalline isomeric pair Ib with so pl. 77-79.5 ° C and a purity of 93%.

Example 20. The south of crystalline trans-cypermethrin (containing 48% of 1R trans-S and 1S trans-R isomers and 49% of 1R trans-R and 1S isomers of trans-S) is dissolved in the rastlins forming the cells, and then susceptibility is assessed.

Processing: tested products and control (water treatment).

Replicates: at least 3. Method: 1 cell.

Use parasites age 24 hours

Concentrations of 5-1 parts per million of products are used for each of the glass plates.

10 females of A. matricariae are introduced into each cell; honey is given as food. The number of females that survived exposure was determined after 1.5 hours and 24 hours in independent experiments. The total number of surviving individuals is calculated for each cell. The results are presented in Table 4.

PRI me R 31. Test for direct contact on the pupae of A. matricariae.

Mature pupae of A. matricariae on pepper leaves in Petri dishes are exposed to direct spraying of the active ingredients.

Two or three days before the sprouting of the leaves of the pepper, parasitic pupae are introduced. Leaves are placed on filter paper in plastic Petri dishes. Filter paper is moistened.

The processing according to example 30.

The pieces of the sheet are transferred after processing to the bottom of clean petri dishes. These pallets are stored in a climate chamber at 20 ° C, a relative humidity of 70% and a light-to-light cycle of darkness of 16-8 hours. The surviving pupae will vyvot dt after 2-3 days. Estimate the number of excreted and dead pupae. The results are presented in Table. five.

EXAMPLE 32. The active ingredients are dissolved in 2-ethoxyethanol and 0.3 μl drops of solutions are applied to the abdominal portion of an adult potato beetle (Leptinotarsa decemlineata). The treatment was carried out in two parallel experiments using 10 insects for each dose. After treatment, the insects are placed in Petri dishes and the lesion is assessed after 48 hours. The results are presented in Table 6.

PRI me R 33. Adults individuals T. confusum (mealworm) ob5

ten

five

0

five

0

five

0

five

0

five

The procedure is as described in Example 20 and the lesion is determined after 24 hours. The dose of piperonyl butoxide (PBO) is 0.5 mg / disk. The results are presented in Table. 7. As follows from the data table. 7, enantiomers on pair Ib may exhibit synergism at a higher level than isomeric pair 1a.

EXAMPLE 34. The active ingredients are dissolved in 2-ethoxyethanol and the solutions are applied in the form of droplets with a volume of -0.2 µl onto the back of an American white butterfly (Hyphantria cunea) at the stage of development of L.r-Lg larva. The treated specimens are placed on the leaves of the soil in petri dishes. The test was performed using 5 doses. 2 parallel experiments were conducted and 10 insects were used for each dose. Lesions of the individuals are assessed after 24 hours.

The results are presented in table. eight,

PRI me R 35. On the composition of the 5 EU, including (kg / kg) isomeric pair of Ib, cyclohexanol, Atlox 3386v, Atlox. 3400B, mineral oil, respectively, 0.105, 0.290.0.020.0.045, 0.540, emulsions are prepared, diluted 50-, 100-, 200-, 400-, 800- and 1600-fold with water. 0.5 ml of the emulsions are sprayed onto glass plates, then dried and 10 Colorado beetles (L.decemlineata) are placed on each glass plate, adults, and insects are closed. The tests are carried out using 6 doses, 3 parallel experiments are performed for each dose. Insect damage is assessed after 48 hours and the extent of the damage is calculated.

The results are presented in table.9.

EXAMPLE 36. An insecticidal effect is tested on adults of bean kernels (Acanthoscelides obtectus). Affected insects are determined after 24 hours and the extent of the damage is calculated.

The results are presented in table 10.

Claims (2)

1. A method for producing an isomeric mixture of cypermethrin containing in an equimolar ratio an enantiomeric pair of 1R trans-S- and 1S trans-I-isomers of structural formula I COO-CHI CN from a mixture containing eight isomers or only trans isomers, characterized in that the starting mixture consisting of 8 isomers is dissolved in isopropanol or diisopropyl ether in the presence of an antioxidant or the starting mixture consisting of transisomers is dissolved; in the presence of antioxidant in isopropanol, petroleum ether, hexane, heptane, cyclohexane, methanol, ethanol, hexane mixed with carbon tetrachloride, or in isopropanol and petroleum ether in the presence of antioxidant 73.6 1291.8 51.9 139.3 2.68 50 and a base, such as 2-amino-benzimidaeol, a basic ion exchange resin, or in isopropanol and petroleum ether in the presence of a base, such as diazobicyclo 4,3,03-en-5, ammonia, sodium carbonate, ammonium hydroxide, or tert-C-C-alkylamine, di-C, -C4-alkylamine at 15-60 ° C and seed the mixture consisting of an enantiomeric 1R trans-S and 1S trans-R pair into the resulting solution or directly into the initial mixture, cooled to a temperature of from +30 to -30 ° C, the precipitated crystals are separated, followed by evaporation of the mother liquor. 2. A method according to claim 1, characterized in that 2,6-di-tert-butyl-4-methylphenol in isopropanol or hexane is used as an antioxidant. Table 1 table 2 TabaZa 13.4 HI, 9 12.8 24.5 1.92 17 4579454 13 Table nineteen Stereoisomers Defeat,%, at dose, μg / cypermethrin dose, 24 hours 0.023 0.047 | 0.094 0.188 0.375 Ib10 15 30 70 80 Cypermethrin OO 25 50 75 Table9 Composition Damage,%, upon dilution 1600x 800x 400x | 200x South 50x Cypermethrin 017 33 50 67 83 Ib013 37 57 87 100 Table 10 Composition Damage,%, upon dilution 1600x 800x 400x 200x South 50x Cypermethrin O 3 10 20 43 60 Ib3 10 20 37 53 67 1579454-20 Table 8