• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    There is provided a compound of formula <IMAGE> wherein R<1> and R<2> are each independently selected from chlorine, bromine and methyl, in the form of a 1:1 mixture of the 1RcisS- and 1ScisR- isomers substantially free of 1ScisS- and 1RcisR-isomers, processes for preparing such compounds, and their use as pesticides. Compounds according to the invention contain up to four times as much of the most active isomer of the compound of formula I as a compound containing equal amounts of all eight possible isomers, and they are readily prepared by routes which do not involve any stereospecific synthesis or optical resolution steps.
    公开号:SU1068036A3
    申请号:SU803007801
    申请日:1980-11-23
    公开日:1984-01-15
    发明作者:Джон Булл Майкл；Теренс Грэйсон Бэзил
    申请人:Шел Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

    sg
    00
    about
    00 SP) The invention relates to a process for the preparation of a novel crystalline mixture of 1K-cis-5- and IS cis-C-isomer derivatives of cyclopropanecarboxylic acids of general formula n 2 CN CH3 ;; t-CO-0-CH CH3; where R and R2 are chlorine, bromine, methyl, in an equimolar ratio, which can be used as pesticides. Ester derivatives of cyclo propancarboxylic acids of the general formula н 2 2 CN where R and R independently of each other represent chlorine, bromine, methyl are known as a racemate of 8 stereoisomers, which are chemically obtained by reacting cyclo propane carboxylic acid with alcohol or its reactive derivative Cl These compounds are pyrethroid insecticides. Compounds with the cis configuration relative to the cyclopropane ring and the S configuration of the alcohol (i.e., 1R cis 3 isomer) have the highest pesticidal activity. A known method for producing (S) ai cyano-3-phenoxybenzyl-2,2-dimethyl3R- (2,2-dichlorovinyl) -cyclopropane-1 carboxylate (1R cis S isomer of the structural formula I, where), is that isomer (R) (cyano-3-phenoxybenzyl 2,2-dimeti 3R- (2/2-dichlorovinyl) cyclopropan-1 carboxylate or a mixture of (R) and (S) isomers of oL cyano-3-phenoxybenzyl 2, 2-dimethyl-3R- (2,2-dichlorovinyl) cyclopropane-iR-carboxylate in an unequal ratio is subjected to interaction with the main agent selected from alkali metal hydroxides, tertiary amines, in a solvent — acetonitrile, alcohol, petr oleic ether, a mixture of alcohol and hydrocarbon 2 J. The purpose of the invention is to develop a method for producing a new crystalline mixture of lR-cis-S and IS cis-R isomers of compounds of formula (-1), in an equimolar ratio that has a higher Formula (1) in the form of a racemate of 8 stereoisomers and a racemate of 4 stereoisomers {1R cis-W-, IS cisR-, 1R cis-R and IS cis-S-). This goal is achieved in that according to the method for preparing a 1R cisG3 and IS cis-R crystal mixture of the ester derivatives of cyclopropanecarboxylic acids of structural formula (I) in an equimolar ratio, a mixture of 1R cis-S-, 18 cis-H-, 1R cis-R - and the IS cis-S-isomers of the derivatives of formula (g) are dissolved in isopropanol or petroleum ether and left at 0-10 ° C or 20 ° C for 1-5 days, followed by separation of the precipitated crystals of the target mixture from the mother liquor. Example 1. A 1: 1 mixture of 1R cis-8 and 13 cis R isomers of the oi-cyano-3-phenoxy-benzyl ester of 3- (2,2-dichlorovinyl) -2,2,2-dimethylcyclopropanecarboxylic acid (mixture C) is obtained by crystallization with using isopropanol. 5.0 g of a racemic mixture of cis-isomers of 3- {2,2-dichlorovinyl 3-{-2,2-dichlorovinyl 2-cyano-3-phenoxybenzyl ester (mixture B) is dissolved in 30 ml of isopropanol while being heated. The resulting solution is cooled to 10 ° C and left to stand at this temperature for 20 hours. The precipitation is separated by filtration, to obtain 1.4 g of a solid product in the form of colorless crystals, t. Pl. 77-81 ° C. Analysis by high performance liquid chromatography shows that the product is a 90% purity 1: 1 mixture of 1R cis S and 18 cis R isomers of the starting material. 3.2 g of solid product, recrystallized from pentane and obtain 2.0 g of a colorless crystalline solid and so on. 84-8bs. This product, according to high performance liquid chromatography, represents a 99% purity 1: 1 mixture of 1R cis S and IS cis R isomers of the starting material. At. measures 2. A 1: 1 mixture of 1R cis S and 18 cis H-isomers of the oC-cyano-3-phenoxy-benzyl ester of 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic acid is obtained by crystallization using petroleum ether with a bp. 40-60 ° C. 10 g of racemic mixture of cis-isomers of o-cyano-3-phenoxybenzyl
    3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane acetic acid ester (mixture B) is dissolved in 150 ml of petroleum ether with a boiling range of 40-60 ° C with gentle warming. The resulting solution is cooled to and allowed to stand at this temperature for 3 days. A colorless crystalline substance precipitates, which is separated by filtration. The yield is 3.3 g, m.p. 79-81 ° C; subject to high-resolution gas-liquid chromatography, the target product is more than 90% pure, a mixture of 1: 1 1R cis S and IS cis R isomers of the starting material. .
    Portions of the product obtained in the process described above are recaptured one, two, and three times from petroleum ether in b.p. 4060 s. Products are obtained which are colorless crystalline solids with colors of mp. 83-86, B4-86 and 86-87c, respectively. According to high-resolution high-performance liquid chromatography data, the solid products are 99, more than 99.9 and 100% pure samples (1: 1 mixture of formula (I) isomers) .
    Example 3. A 1: 1 mixture of 1R cis S and IS cis H-isomers of the 3-(2,2-dichlorovinyl) -2 -2,2-dimethylcyclopropanecarboxylic acid 3H-cyano-3-phenoxybenzyl ester is obtained by treating solid racemate with petroleum ether t. kip.40-60 0.
    10 g of the racemic mixture of cis-isomers of o-cyano-3-phenoxybenzyl ester of 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic acid (mixture B) is mixed with 75 mp with t. Bale. 40-60 ° C petroleum ether for 5 days at ambient temperature. 4.1 g of colorless crystals are filtered off with a mp. 81.5-83C, which, according to high resolution liquid chromatography data, is about 97% purity: a mixture of the R cis S and S cis R isomers of the starting material.
    Comparing with the products of examples -3, it should be noted that R cis S-oi-cyano-3-phenoxy-5-sil; The 3- (2,2-dichlorovinyl) -2,2-cyclopropanecarboxylate and the IS cis R-enantiomer both have mp. 53-54 ° C.
    Example p4. A 1: 1 mixture of the R cis 3- and IS cis R-isomers of the oC-cyano3-phenoxy-benzyl ester of 3- (2,2-dybromovinyl) -2,2-dimethylcyclopropanecarboxylic acid is obtained by a crystallization process with
    Using petroleum ether with. Kip. 60-80 ° C.
    10.0 g of the racemic mixture of ot-cyano-3-phenoxybenzyl ester of 3- (2,2-dibromvinyl) -2.2 of carboxylic acid cisomer ester is treated similarly to Examples 1 and 2 using Petroleum ether as a solvent in 6080 ° C of petroleum ether as solvent . 3.8 g of product are obtained which is colorless. crystals, so pl. 93-97 0, which, as a high-resolution liquid chromatography shows, is about 80% pure sample of this pair of isomers with a ratio of:. An additional two recrystallizations of this product give 3.15 g and 2.7 g of colorless crystals, respectively, mp. 99-100 ° C and 10010 ° C, which, according to high-resolution liquid chromatography data, contain more than 95 and 99%, respectively, of the desired pair of isomers.
    Example 5. A 1: 1 mixture of 1R cis S- and IS cis C-isomers of 3- (2-methylpropenyl) -2,2-dimethyl-cyclo-E-2-carboxylic acid ci-cyano-3-phenoxy-benzyl ester of 3- (2-methylpropylenyl) -2,2-dimethylcyclohexyane is obtained by crystallization using boil. 40-60 ° C.
    15.3 g of a racemic mixture of cis-isomers of o-cyano-3-phenoxybenzyl ester of 3- (2-methylpropenyl) 2, 2-dimethyl-benzlopropanecarboxylic acid (mixture B in the form of a colorless oil is processed in the same way as in examples 1 and 2 using petroleum ether with a boiling point. 40-60 0 as a solvent. 5.75 g of a colorless crystalline product are obtained with a mp of 60-66 ° C, HMR analysis data at 360 MHz show that the product is a 90% purity mixture of 1R cis S- and IS cis R-isomers of the original substance in the ratio of 1: 1. This initial product is recrystallized three ase from petroleum ether, 40-60 ° C, yielding 4.7 g, 4.3 g and 4.0 g, respectively, of a product having mp 65, 70, 69-72 and 70-72 ° C. According to HMR analysis data at 360 MHz, these products are 95, 98, and more than 99.5% pure: 1 mixture of the desired pairs of isomers.
    Example 6. A 1: 1 mixture of 1R cis S- and IS cis R-isomers of o (3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropanecarboxylic acid cyano-3-phenoxybenzyl ester 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic ester. 12 , 9 g of the starting racemic mixture of cis-isomers of ot-cyano-3-phenoc 3- {2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic acid sibenzyl ester is dissolved in 52 ml of isopropanol while 2.0 ml are added with stirring 88% ammonia solution in water. After stirring for 21 hours, the reaction mixture is cooled and stirred at 0-5 ° C for an additional 4 hours. The precipitate which precipitates is filtered off, washed with 5 ml of isopropanol, at 5-C and 15 ml. 60-80 0 petroleum ether. At the same time, 5.1 g of solid product are obtained in the form of colorless crystals with m.p. 77-81 ° C. High resolution liquid chromatography shows that the product is a 90% pure mixture of 1: 1 1R cis S and IS cis R isomers of the starting material. A similar analysis of the filtrate shows that the ratio of the concentrations of the IS cis S and 1R cis R isomers to the concentrations of the 1R cis S and IS cis R isomers is about 3: 2. The filtrate and washings from this process are concentrated, dissolved in 30 MP of isopropanol, and with stirring, 2.0 ml of a 83% solution of ammonia in water is added. Half an additional 2.1 g of colorless crystals with m: pl. 74-79 ° C, which according to high resolution liquid chromatography data are 85% pure 1: 1 mixture of 1R cis S and IS cis R-isomers of the starting material. A similar analysis of the filtrate shows the ratio of the concentrations of the IS cis S and 1R cis R-isomers and the concentrations of the 1R cis B- and IS cis R-isomers of about 4: 1. The conditions for analyzing the content of 1R cis S- and IS cis R-isomers in the mixture are carried out using a high-pressure liquid chromatograph: Column 0.25 m - 4.9 mm 1D stainless steel Steel Packing Partizil 5 mm for sycolone gel (1C 6.19) The liquid phase Hexane + acetonitrile (eluent) (99.75 + 0.25) at a flow rate of 3 ml / mi of a Lyap UV detector at a wavelength of 235 nm I Input quantities Calibration - 10 ml of an analytically prepared mixture of 1R cis S- and IS cis R isomers in amount from 0.5 to 2 mg / ml in ethyl acetate-hexane (2 + 98) Samples — 10 ml with concentration of 1 mg / ml in ethyl acetate / hexane (2 + 98). Calculations Peak area measurements were performed using an electronic integrator. The resulting mixture is tested for activity compared to: Compound A: a mixture of all 8 stereoisomers (i.e., cepermethrin itself) 1; Compound B is a mixture of all 4 stereoisomers with cyclopropane H atoms in the cis position, which is; THE ORIGINAL MATERIALS in the proposed method J These compounds are assessed for activity in the fight against the following pests. insect: Musca domestica (ME), Spodoptera ittorafris (S.e.) He iothis ZPa (H.Z) PguteEga xyCostePea P.X) Aphid fabae (A.f.) Tick:. Boophieus microptus The following are test methods applied to each species of Musca dpmectica (M.d.). An O, 4 wt.% Solution of the test compound in acetone is prepared and drawn into a lettered syringe. Adult female domestic flies (Musca domestica) at the age of two or. Three days are anesthetized with carbon dioxide and 1 ml of the test solution is injected into the abdominal part of the abdomen of each fly, 20 flies are tested. Treated flies are kept in glass, a vessel covered with paper tissue bound with elastic tape. Soaked with a diluted solution of sugar cotton wool pieces are placed on the upper side of the fabric as food. After 24 hours, the percentage of dead and dying flies is determined. . P. Spodoptera eettova “is (S.f.) Pairs of leaves of plants of forage beans on filter paper in plastic Petri dishes. The lower surface of the leaves is sprayed with an aqueous composition containing 20 wt.% Acetone, 0.05 wt.%. Triton X-100 (trade mark) as a wetting agent and 9.4 wt.% Of the test compound. After spraying, leaves are kept for 0.5-1 h, and then each pair of Leaves is infected with ten larvae (Spodoptera. MttopaEis). After 24 hours, the percentage of dead and larvae was determined. W. HeSio this Zia (HZ), Test compounds are introduced into aqueous solutions containing 20% by weight of acetone, 0.4% by weight of Atlox 1045A (AT1OX 1045A) (trade mark) and 0.2% by weight of the test compound. , more dilute solutions (to obtain dose-mortality curves) are obtained by diluting a 0.2% solution with an aqueous solution of 0.05 wt. Atlox 1045A. Feed bean plants are placed on the turntable. and sprayed with 4 ml of the solution being removed. Immediately after spraying, 5 larvae of cotton scoops (HeEiothis ZPa) are transferred to each plant- that was put into the water through a hole in the lid while maintaining an ambient temperature of 21 ° C and a relative humidity of 40-50%. After 44-46 h, mortality is determined. 1 W peuteeea xyeosteeea (rx.) Test pins were prepared as in the test with a fly. Moths of the cabbage moth (PEuteOSa Xyloste SSa at 3-4 age stages are immediately immersed in the solution of the test compound. 15-20 larvae are used and the percentage of mortality is determined 6 hours after dipping. In the tests, adults are used aphids (5-7 days old). Leaf leaf pairs are removed from the fodder bean plants and placed on filter paper in Petri thickets (mass formation) 9 cm in diameter. A group of 10-20 aphids are transferred onto filter paper into a Petri dish with a diameter 5 cm and covered with metal mesh covers. Both types of bowl Petri, containing leaves and aphids, are sprayed in parallel and left for 0.5-1 hours to dry, then each pair of leaves is infected with the appropriate group of sprayed aphids. After 24 hours, the number of dead and dying aphids on each pair of leaves is determined and calculated percent mortality. U1. BoophiEus micvopCus (Bm) A 0.1% by weight solution of the test active ingredient in acetone containing 10% by weight polyethylene glycol is prepared. Different concentrations are obtained by diluting this solution. 1 ml of the test solution is evenly applied on 11 cm of filter paper inside the Petri dish. When the paper is dry, it is folded in half and folded over the outer edge to form a bag. About 80-100 larvae of the ringed tick (BoophiEus micvopPus) at the age of 2-3 weeks are transferred into a bag, which is then sealed. The package is placed in an incubator at 27 ° C and a relative humidity of 80%. After 24 hours, the bag is opened and the percentage of dead and dying larvae is determined. In all cases, the tests are repeated in different concentrations of the evaluated compound in order to ensure that it is possible to determine the SDA. The activity of the compound is then presented as a toxicity index (P.P.), which is calculated according to the following formula: DM 50 of ethyl parathion (standard) P.T., X 100. of the test compound. The results obtained are presented in Table 1. Table 1
    520
    1200
    2500 For comparison, the activity of basic cypermethrin and the activity of the purified mixture of isomers;
    85
    380
    26 40 59
    180
    90
    1600
    390
    2300
    2800 60 cypermethrin, which is accepted as the standard (i.e., P. 100). ; The data obtained are given in table 2.
    It is clear from these data that a mixture of two 1: 1 isomers (compound C) exhibits a significantly higher level of activity.
    table 2
    in relation to all those who were tested on "11m" than the initial mixture of 2 of 4-cis-isomers (compound B).
    权利要求:
    Claims (1)
    [1]
    A method of obtaining a crystalline mixture of lR-cis-B- and 1S cis-B-isomers of cyclopropanecarboxylic acid derivatives of the general formula Ϊ
    CH = < Rl cn 3 / X- co-o- ^ n where R ^ h R 2 is chlorine, bromine, methyl, in an equimolar ratio, characterized in that the mixture is 1R cis-S—, 1S cis-R-, The 1R cis-R and 1S cis-B isomers of the derivatives of formula (I) are dissolved in isopropanol or petroleum ether and left at 0-10 or 20 ° C for 1-5 days, followed by separation of the precipitated crystals of the target mixture from the mother liquor.
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    同族专利:
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    引用文献:
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    US4152410A|1975-09-03|1979-05-01|Eisai Co., Ltd.|Diagnosis reagent for neoplasm and method for diagnosis of neoplasm|
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    US4261921A|1979-06-06|1981-04-14|Fmc Corporation|Process for preparation of a crystalline insecticidal pyrethroid enantiomer pair|CA1162560A|1980-04-23|1984-02-21|Ronald F. Mason|Process for preparing cyclopropane carboxylic acidester derivatives|
    DE3369128D1|1982-10-11|1987-02-19|Ici Plc|Insecticidal product and preparation thereof|
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    GB8418331D0|1984-07-18|1984-08-22|Ici Plc|Insecticidal ester|
    CA1275108A|1985-01-16|1990-10-09|Laszlo Pap|Insecticidal composition comprising more than oneactive ingredients|
    DE3522629A1|1985-06-25|1987-01-08|Bayer Ag|METHOD FOR PRODUCING SPECIFIC ENANTIOMER PAIRS OF PERMETHRINIC ACIDCYANO-3-PHENOXY-4-FLUOR-BENZYL ESTERS|
    US4997970A|1987-06-15|1991-03-05|Fmc Corporation|Conversion of pyrethroid isomers to move active species|
    CA1314559C|1987-06-15|1993-03-16|John Winfrid Ager|Conversion of pyrethroid isomers to more active species|
    CA2020356C|1989-01-17|2002-09-03|Agro-Chemie Novenyvedoszer Gyarto Ertekesito Es Forgalmazo Kft|Process for the preparation of cypermethrine isomers|
    US5128497A|1990-01-03|1992-07-07|Fmc Corporation|Conversion of pyrethroid isomers to more active species|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB7940857|1979-11-27|
    GB7940856|1979-11-27|
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