Method of producing crystalline equimolecular mixture of pair of enanthiomers of (s)-alpha-cyano-(3-

专利摘要:
This invention relates to the preparation of cyclopropane carboxylic acid ester derivatives, which are useful as pesticides. There is provided a process for preparing a mixture of cis-isomers of a compound of formula <IMAGE> (I) wherein R1 and R2 are independently selected from chlorine, bromine and methyl, consisting predominantly of the 1R cis S- and 1S cis R- isomers, which process comprises dissolving a mixture of 1S cis S- and 1R cis R- isomers of the compound of formula I, alone or in the presence of 1R cis S- and 1S cis R-isomers, in an organic amine base containing from 5 to 7 carbon atoms and being a secondary amine containing two branched alkyl groups or a tertiary amine, crystallizing out from a resulting solution of cis- isomers of formula I in the organic amine base a 1:1 mixture of the 1R cis S- and 1S cis R- isomers, and evaporating off the organic amine base. The process of the invention yields a product which may contain up to twice as much of the most active isomer of the compound of formula I as a racemic mixture of all four cis-isomers, and is a readily effected process which does not involve any sterospecific synthesis or optical resolution steps.
公开号:SU1238729A3
申请号:SU813273758
申请日:1981-04-21
公开日:1986-06-15
发明作者:Джон Булл Майкл
申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В.(Фирма)；
IPC主号:

专利说明:

 one
This invention relates to a process for the preparation of a crystalline equimolecular mixture of a pair of enantiomers of (S) -c) 1C-cyano- (3-phenoxybenzyl) -1 R-cis-3- - (2,2-dichlorovinyl) -2,2-dimethylcyclo- propancarboxylate and (E) -ts b-cyano- (3- -phenoxybenzyl) -1S-cis-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, which finds use as insecticide 1 yes,
The purpose of the invention is to increase the yield of the target product.
The proposed citoQo6 is illustrated by the examples given.
P ROME a. J) 1. 10 g of a mixture of dis- isomers (5-cyano-3-feioxybenzyl-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, in which the weight ratio of 18-cis-8 - and 1R-cis-E-isomers to 1E-cis-8-1S-cis-E-isomers is 2: 1, dissolved in 20 ml of triethyl 1a (water content 0.1 wt.%) when heated to 70 C. The solution is allowed to cool to ambient temperature with stirring and several crystals of a mixture of 1K-cis-5- and 15-cis-E-isomers (1 g 1) of about-cyano-3-phenoxy-benzyl-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-carbonate silate, stirred at ambient temperature Triethylamine is distilled off for 40 hours and then at 20 ° C for 10 hours. 10 g of a dry solid is obtained with a melting point of 65-77 s, which according to GLC data is a pure 98.9% cis mixture - isomers of ob-cyano-3-phenoxybenzyl-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, and according to
Editor M, Kelemesh
Order 3311/61 Circulation 379,
VNIIPI USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
Production and printing company, Uzhgorod, st. Project, 4
38729. 2
High performance liquid chromatography contains 20 parts by weight. 15-cis-8-and 1E-cis-K-isomers and 80 weight.h. 1K-cis-8- and 15-dis-E-iso-5 isomers. The output of the product is 100%.
Example 2. 15g of a mixture of cis isomers of α-cyano-3-phenoxybenzyl-3- (2,2-dichlorovinyl) -2,2-dimethylcyc-. lopropanecarboxylate, in which the weight ratio of 18-cis-5- and 1K-cis-K-isomers to 1E-cis-8- and 18-cis-E-isomers is 1: 1, is dissolved in 30 ml of triethylamine with heating until. The solution is allowed to cool to ambient temperature with stirring and several crystals of a mixture of 1K-cis-3- and 18-cis-K- (111) ° C -Cyano-3-phenoxybenzyl-3- (2 , 2-dichlorovinyl) -2,2-di- 20 dimetypcyclopropanecarboxylate. After 42 hours of stirring at ambient temperature, sparse nitrogen through the solution slowly to add triethylamine. After 24 hours, the dry solid residue is transferred to a round bottom flask, washed with 20 ml of petroleum ether 60/80. Dry to 14.85 g.
square
thirty
dry solids with t.
78-81 C, which (according to high-performance liquid chromatography data) contains more than 90% by weight of a mixture of iR-dis-S- and 1S-cis -R-isomers (1: 1) v-cyano- 3-phenoxybenzyl 3- (2,2-d-chloro-vinyl) -2,2-dimethyldiclopropanecarboxylate. The yield of the target Product is 98%.
Thus, the proposed method allows to obtain the target product with a yield of 98-100%, against 28--56% in the known method.
Compiled by I. Zavarzin
Tehred I. Veres- Proofreader T. Kolb
Subscription

权利要求:
Claims (1)
[1]
METHOD FOR PRODUCING CRYSTALLINE EQUYULECULAR MIXTURE OF A (B) - (Xrcyano- (3-phenoxybenzyl) -1R-CYS-3- (2,2-dichloro-rvinyl-2-dimethylbenzyl-3-cycloalkyl) -cyclohexane Phenoxybenzyl) -1s-cis-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropaicarboxylate , 2-dimethylcyclopropanecarboxylate using triethyl amine and removing it from the reaction mixture, characterized in that, in order to increase the yield of the target product, a racemic mixture of four isomers of ci-cyano- (3-f noxybenzyl) -cis-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate taken in the molar ratio (1S-hhc-S- + + 1R-4hc-R ~) AND (IR-uhc-S- + IS-cis-R-), equal to 1: (1-2), dissolved in triethylamine at 60-70 ° C followed by exposure of the reaction mixture AND by evaporation of triethylamine from the reaction mixture at 15-25 ° C to obtain the target product in the residue after triethylamine removal.
about
SO C> cm

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

GB1413491A|1972-05-25|1975-11-12|Nat Res Dev|3-substituted-2,2-dimethyl-cyclopropane carboxylic acid esterstheir preparation and their use in pesticidal compositions|

---

US4024163A|1972-05-25|1977-05-17|National Research Development Corporation|Insecticides|

---

FR2348901B1|1976-04-23|1983-01-28|Roussel Uclaf|

---

FR2375161B1|1976-04-23|1979-04-13|Roussel Uclaf|

---

FR2383147B2|1977-03-09|1983-04-29|Roussel Uclaf|

---

US4176195A|1978-07-20|1979-11-27|Sumitomo Chemical Company, Limited|Pesticidal α-cyanobenzyl ester enantiomer pair|

---

US4261921A|1979-06-06|1981-04-14|Fmc Corporation|Process for preparation of a crystalline insecticidal pyrethroid enantiomer pair|

---

US4260633A|1980-04-21|1981-04-07|Zoecon Corporation|Pesticidal esters of amino acids|CA1206483A|1982-11-11|1986-06-24|Johannes Van Berkel|Process for preparing cyclopropane carboxylic acidester derivatives|

---

DE3401483A1|1984-01-18|1985-07-25|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING SPECIFIC ENANTIOMER PAIRS OF PERMETHRINIC ACID-CYANO-3-PHENOXY-4-FLUOR-BENZYL ESTERS|

---

CA1275108A|1985-01-16|1990-10-09|Laszlo Pap|Insecticidal composition comprising more than oneactive ingredients|

---

GB0229803D0|2002-12-20|2003-01-29|Syngenta Ltd|Chemical process|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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GB8013309|1980-04-23|

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