KR19990084854A - How to convert (1S) -cis-permesrinic acid to (1R) -trans-permesrinic acid - Google Patents

How to convert (1S) -cis-permesrinic acid to (1R) -trans-permesrinic acid Download PDF

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KR19990084854A
KR19990084854A KR1019980016915A KR19980016915A KR19990084854A KR 19990084854 A KR19990084854 A KR 19990084854A KR 1019980016915 A KR1019980016915 A KR 1019980016915A KR 19980016915 A KR19980016915 A KR 19980016915A KR 19990084854 A KR19990084854 A KR 19990084854A
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acid
permesrinic
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KR100362728B1 (en
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이주영
조군호
서병우
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성재갑
주식회사 엘지화학
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Abstract

본 발명은 살충효과가 우수한 피레스로이드계 살충제의 유용한 중간단계 물질인 퍼메스린산에서 시스-퍼메스린산을 트란스-퍼메스린산으로 전환시키는 방법에 관한 것이다.The present invention relates to a method for converting cis-permesrinic acid to trans-permesrinic acid in permesrinic acid, which is a useful intermediate of pyrethroid insecticides having excellent insecticidal effect.

Description

(1Ｓ)-시스-퍼메스린산을 (1Ｒ)-트란스-퍼메스린산으로 전환시키는 방법Method of converting (1S) -cis-permesrinic acid to (1R) -trans-permesrinic acid

본 발명은 살충효과가 우수한 피레스로이드계 살충제의 유용한 중간단계 물질인 퍼메스린산에서 시스-퍼메스린산을 트란스-퍼메스린산으로 전환시키는 방법에 관한 것이다.The present invention relates to a method for converting cis-permesrinic acid to trans-permesrinic acid in permesrinic acid, which is a useful intermediate of pyrethroid insecticides having excellent insecticidal effect.

피레스로이드계 살충제는 대체로 2∼3개의 키랄 중심을 가지고 있는데 이들 각각의 이성체들은 그 활성정도 차이가 크다. 따라서 살충효과가 우수한 이성체를 선택적으로 합성하거나 분리하는 등의 방법을 통해 기존 제품보다 그 활성이 우수한 피레스로이드게 농약 제품이 개발되고 있다.Pyrethroid insecticides generally have two or three chiral centers, each of which isomers vary greatly in activity. Therefore, a pyrethroid crab pesticide product has been developed that has better activity than a conventional product by selectively synthesizing or separating isomers having excellent insecticidal effects.

퍼메스린산은 퍼메스린, 사이퍼메스린, 알파사이퍼메스린, 델타메스린 등을 합성하는 중간 물질로서 아주 유용하게 사용되고 있다. 그 중에서 (1S)-시스-퍼메스린산은 살충효과 없는 이성체인데 이를 본 발명을 이용하면 살충효과가 있는 (1R)-트란스-퍼메스린산으로 전환시킬 수 있다.Permesrinic acid is very usefully used as an intermediate for synthesizing permethrin, cyspermethrin, alphacypermethrin, deltamethrin and the like. Among them, (1S) -cis-permesrinic acid is an isomer having no pesticidal effect, and this can be converted to (1R) -trans-permesrinic acid having an insecticidal effect.

본 발명과 유사한 이성화에 관한 공시 기술이 스미토모(Sumitomo)에서 발표한 독일 공개공보 제 2,003,065 호에 공지되어 있는데, 여기에는 시스-크리산스민산 클로라이드를 140℃의 온도에서 85%의 수율로 트란스-크리산스민산 클로라이드로 전환시키거나, 트란스-크리산스민산 클로라이드가 68% 들어있는 시스-크리산스민산 클로라이드를 160℃에서 84%의 수율로 전환시키는 것이 기재되어 있다. 그러나 열에 의한 이성화 반응은 반응 조건이 고온이며, 반응 도중 열에 의해 시클로프로판 고리가 깨어지는 등의 현상이 일어날 수 있다.A disclosure technique for isomerization similar to the present invention is known from German Publication No. 2,003,065 published by Sumitomo, in which the cis-crysuccinic acid chloride is obtained in a trans- It is described to convert to chrysonic acid chloride or to convert cis-crixic acid chloride containing 68% of trans-crimic acid chloride into a yield of 84% at 160 ° C. However, heat isomerization reaction may be a phenomenon in which the reaction conditions are high temperature, and the cyclopropane ring is broken by heat during the reaction.

이에 본 발명자들은 보다 넓은 응용 범위를 가지고 있는 퍼메스린산에 대해서 이성화 반응기술을 개발하는 것이 중요하다고 판단하고 본 발명을 시작하였다. 따라서 본 발명의 목적은 생물학적 활성이 거의 없는 (1S)-시스-퍼메스린산을 활성이 높은 이성체인 (1R)-트란스-퍼메스린산으로 전환시키는 방법을 제공하는데 있다.Accordingly, the present inventors have determined that it is important to develop an isomerization reaction technology for permethic acid having a wider application range and started the present invention. It is therefore an object of the present invention to provide a method for converting (1S) -cis-permesrinic acid with little biological activity to (1R) -trans-permesrinic acid, which is a highly active isomer.

본 발명은 다음과 같이 반응식 1로 표시할 수 있다.The present invention can be represented by Scheme 1 as follows.

상기 방법 Ⅰ에서 화학식(1)의 (1S)-시스-퍼메스린산을 할로겐화제를 이용하여 (1S)-시스-퍼메스린산 클로라이드로 만들고, 여기에 염기를 가함으로써 열역학적으로 보다 안정한 화학식(2)의 (1R)-트란스-퍼메스린산으로 전환시킬 수 있다.In the above method I, (1S) -cis-permesrinic acid of formula (1) is converted into (1S) -cis-permesrinic acid chloride using a halogenating agent, and a base is added thereto to make thermodynamic stability more stable. Can be converted to (1R) -trans-permesrinic acid.

본 반응의 할로겐화제로서는 티오닐클로라이드를 사용하였으며, 염기는 피리딘, 1,8-디아자바이시클로[5,4,0]운데-7-엔 및 트리에틸아민으로 구성된 그룹중에서 선택된 1 종이상을 사용하였는데 그 사용량은 2.0∼4.0당량이며, 3.0당량에서 좋은 결과를 얻을 수 있다. 용매로는 에틸렌디클로라이드 및 톨루엔으로 구성된 그룹중에서 선택된 1 종이상이 사용될 수 있다.Thionyl chloride was used as the halogenating agent in this reaction, and the base was selected from the group consisting of pyridine, 1,8-diazabicyclo [5,4,0]-7-ene, and triethylamine. The amount used is 2.0 to 4.0 equivalents, and good results can be obtained at 3.0 equivalents. As the solvent, one paper phase selected from the group consisting of ethylenedichloride and toluene may be used.

한편 상기 방법Ⅱ에서 화학식(1)의 (1S)-시스-퍼메스린산을 할로겐화제를 사용하여 용매의 존재 또는 부재하에서 가열하여 열역학적으로 안정한 화학식(3)의 (1R)-트란스-퍼메스린산 클로라이드로 전환시키고, 이를 가수분해하여 목적하는 화학식(2)의 (1R)-트란스-퍼메스린산을 수득할 수 있다.Meanwhile, in the above method II, (1S) -cis-permesrinic acid of formula (1) is thermodynamically stable by heating (1S) -cis-permesrinic acid of formula (1) in the presence or absence of a solvent using a halogenating agent. Conversion to chloride and hydrolysis can yield the desired (1R) -trans-permesrinic acid of formula (2).

화학식 1Formula 1

화학식 2Formula 2

본 반응에서 할로겐화제로서는 티오닐클로라이드를 사용하였으며, 그 사용량은 1.0∼2.0 당량이며, 바람직하게는 1.1∼1.3 당량이다. 사용된 용매는 톨루엔 및 헵탄으로 구성된 그룹중에서 선택된 1 종이상이며, 이 반응은 용매 없이도 진행된다. 반응온도는 100℃ 내지 250℃이며, 바람직한 범위는 100℃∼150℃이다.Thionyl chloride was used as the halogenating agent in this reaction, and the amount thereof was 1.0 to 2.0 equivalents, preferably 1.1 to 1.3 equivalents. The solvent used is one species selected from the group consisting of toluene and heptane, and the reaction proceeds without solvent. Reaction temperature is 100 degreeC-250 degreeC, and a preferable range is 100 degreeC-150 degreeC.

본 반응의 분석은 기체크로마토그래피를 이용하고 분석 샘플은 (-)-2-옥탄올을 이용하여 퍼메스린산 옥틸에스터를 만들어서 분석한다.The analysis of this reaction is carried out using gas chromatography and the analytical sample is analyzed by making permethic acid octyl ester using (-)-2-octanol.

이하 실시예에서 발명의 내용을 보다 구체적으로 설명한다. 그러나 실시예는 본 발명의 설명을 돕기 위한 것이지 실시예로 본 발명의 내용을 국한하는 것은 아니다.Hereinafter, the content of the invention will be described in more detail. However, the examples are provided to assist in the description of the present invention, and are not intended to limit the scope of the present invention.

방법 ⅠMethod Ⅰ

실시예 1Example 1

시스-퍼메스린산 20.91g에 45g의 에틸렌디클로라이드를 녹이고 티오닐클로라이드 12.5g을 넣고 2시간 동안 환류 증류시킨 다음 질소를 불어 염산 개스 및 잔류 티오닐클로라이드를 제거한다. 온도를 상온으로 내리고 피리딘 23.73g을 30분간 적가하고 40 시간 동안 교반한 후 10% 황산 수용액으로 잔류 피리딘을 제거하여 96%의 수율로 시스/트란스 비가 10/90인 퍼메스린산 20.07g을 얻었다.Dissolve 45 g of ethylene dichloride in 20.91 g of cis-permethrinic acid, add 12.5 g of thionyl chloride, distillate under reflux for 2 hours, and blow nitrogen to remove gaseous hydrochloric acid and residual thionyl chloride. After the temperature was lowered to room temperature, 23.73 g of pyridine was added dropwise for 30 minutes, stirred for 40 hours, and residual pyridine was removed with an aqueous 10% sulfuric acid solution to obtain 20.07 g of permethrinic acid having a cis / trans ratio of 10/90 at a yield of 96%.

실시예 2Example 2

(1S)-시스-퍼메스린산 20.91g에 45g의 에틸렌디클로라이드를 녹이고 티오닐클로라이드 12.5g을 넣고 2시간 동안 환류 증류시킨 다음 질소를 불어 염산 개스 및 잔류 티오닐클로라이드를 제거한다. 온도를 상온으로 내리고 피리딘 23.73g을 30분간 적가하고 40시간 동안 교반한 후 10% 황산수용액으로 잔류 피리딘을 제거하여 94%의 수율로 (1S)-시스/(1R)-트란스비가 12/88인 (1R)-트란스-퍼메스린산 19.66g을 얻었다.Dissolve 45 g of ethylene dichloride in 20.91 g of (1S) -cis-permethrinic acid, add 12.5 g of thionyl chloride, and distillate under reflux for 2 hours, and then blow nitrogen to remove gaseous hydrochloric acid and residual thionyl chloride. Lower the temperature to room temperature, add 23.73 g of pyridine dropwise for 30 minutes, stir for 40 hours, remove residual pyridine with 10% aqueous sulfuric acid solution, and give (1S) -cis / (1R) -trans ratio of 12/88 in 94% yield. 19.66 g of (1R) -trans-permesrinic acid was obtained.

실시예 3Example 3

(1S)-시스-퍼메스린산 20.91g에 40g의 톨루엔을 녹이고 티오닐클로라이드 12.5g을 넣고 80℃로 가열하여 2 시간 교반한 후 질소를 불어 염산 개스 및 잔류 티오닐클로라이드를 제거한다. 온도를 상온으로 내리고 피리미딘 23.73g을 30분간 적가하고 40시간동안 교반한 후 10% 황산 수용액으로 잔류 피리미딘을 제거하여 89%의 수율로 (1S)-시스/(1R)-트란스 비가 15/85인 (1R)-트란스-퍼메스린산 18.61g을 얻었다.Dissolve 40 g of toluene in 20.91 g of (1S) -cis-permethrinic acid, add 12.5 g of thionyl chloride, heat to 80 ° C., stir for 2 hours, and blow nitrogen to remove gaseous hydrochloric acid and residual thionyl chloride. The temperature was lowered to room temperature, 23.73 g of pyrimidine was added dropwise for 30 minutes, stirred for 40 hours, and the residual pyrimidine was removed with an aqueous 10% sulfuric acid solution. 18.61 g of (1R) -trans-permesrinic acid was obtained as 85.

방법ⅡMethod II

실시예 4Example 4

시스-퍼메스린산 20.91g에 티오닐클로라이드 14.3g을 넣고 120℃로 가열하면서 4시간 동안 교반한다. 반응이 끝나면 감압 증류에 의해 염산 개스 및 잔류 티오닐클로라이드를 제거하고 가수분해하여 95%의 수율로 시스/트란스 비가 20/80인 퍼메스린산 19.86g을 얻었다.14.3 g of thionyl chloride was added to 20.91 g of cis-permesrinic acid, followed by stirring for 4 hours while heating to 120 ° C. After the reaction, hydrochloric acid gas and residual thionyl chloride were removed by hydrolysis and hydrolyzed to obtain 19.86 g of permethrinic acid having a cis / trans ratio of 20/80 in a yield of 95%.

실시예 5Example 5

(1S)-시스-퍼메스린산 20.91g에 티오닐클로라이드 14.3g을 넣고 140℃로 가열하면서 1 시간 동안 교반한다. 반응이 끝나면 감압 증류에 의해 염산 개스 및 잔류 티오닐클로라이드를 제거하고 가수분해하여 91%의 수율로 (1S)-시스/(1R)-트란스 비가 19/81인 (1R)-트란스-퍼메스린산 19.03g을 얻었다.14.3 g of thionyl chloride was added to 20.91 g of (1S) -cis-permesrinic acid and stirred for 1 hour while heating to 140 ° C. After completion of the reaction, hydrochloric acid gas and residual thionyl chloride were removed by hydrolysis and hydrolyzed to give (1S) -cis / (1R) -trans ratio of 19/81 (1R) -trans-permesrinic acid in 91% yield. 19.03 g was obtained.

실시예 6Example 6

(1S)-시스-퍼메스린산 20.91g에 티오닐클로라이드 14.3g을 넣고 120℃로 가열하면서 4 시간 동안 교반한다. 반응이 끝나면 감압증류에 의해 염산 개스 및 잔류 티오닐클로라이드를 제거하고 가수분해하여 94%의 수율로 (1S)-시스/(1R)-트란스 비가 17/83인 (1R)-트란스-퍼메스린산 19.65g을 얻었다.14.3 g of thionyl chloride was added to 20.91 g of (1S) -cis-permesrinic acid and stirred for 4 hours while heating to 120 ° C. After completion of the reaction, hydrochloric acid gas and residual thionyl chloride were removed by distillation under reduced pressure, and hydrolyzed to give (1S) -cis / (1R) -trans ratio of 17/83 in a yield of 94% (1R) -trans-permesrinic acid. 19.65 g was obtained.

실시예 7Example 7

(1S)-시스-퍼메스린산 20.91g 에 톨루엔 45g을 녹이고 티오닐클로라이드 14.3g을 넣고 환류 증류하면서 6시간 동안 교반한다. 반응이 끝나면 감압 증류에 의해 염산개스, 잔류 티오닐클로라이드 및 용매를 제거하고 가수분해하여 92%의 수율로 (1S)-시스/(1R)-트란스 비가 23/77인 (1R)-퍼메스린산 19.23g을 얻었다.Dissolve 45 g of toluene in 20.91 g of (1S) -cis-permesrinic acid, add 14.3 g of thionyl chloride, and stir at reflux for 6 hours. At the end of the reaction, gaseous hydrochloric acid, residual thionyl chloride and solvent were removed by distillation under reduced pressure, and hydrolyzed to give (1S) -cis / (1R) -trans ratio of 23/77 in 92% yield in (1R) -permesrinic acid. 19.23 g was obtained.

Claims (6)

하기 화학식 (1)의 (1S)-시스-퍼메스린산을 유기용매의 존재하에서 할로겐화제를 사용하여 (1S)-시스-퍼메스린산 클로라이드로 전환시키고, 이를 염기의 존재하에서 하기 화학식 (2)의 (1R)-트란스-퍼메스린산으로 전환시키는 방법:The (1S) -cis-permesrinic acid of formula (1) is converted to (1S) -cis-permesrinic acid chloride using a halogenating agent in the presence of an organic solvent, which is converted to the formula (2) To convert to (1R) -trans-permesrinic acid of: 화학식 1Formula 1 화학식 2Formula 2 제 1 항에 있어서, 용매가 에틸렌 디클로라이드 및 톨루엔으로 구성된 그룹중에서 선택된 1 종 이상인 것인 방법.The method of claim 1 wherein the solvent is at least one selected from the group consisting of ethylene dichloride and toluene. 제 1 항에 있어서, 염기가 피리딘, 1,8-디아자바이시클로[5,4,0]운데-7-엔 및 트리에틸아민으로 구성된 그룹중에서 선택된 1 종 이상인 것인 방법.The method of claim 1, wherein the base is at least one selected from the group consisting of pyridine, 1,8-diazabicyclo [5,4,0] unde-7-ene, and triethylamine. 제 3 항에 있어서, 염기가 2.0 내지 4.0 당량으로 사용되는 방법.4. The process of claim 3 wherein the base is used in 2.0 to 4.0 equivalents. 화학식 (1)의 (1S)-시스-퍼메스린산을 할로겐화제를 사용하여 (1S)-시스-퍼메스린산 클로라이드로 전환시키고, 이를 가열하여 화학식 (2)의 (1R)-트란스-퍼메스린산 클로라이드를 수득한 후, 가수분해하여 화학식 (3)의 (1R)-트란스-퍼메스린산으로 전환시키는 방법:(1S) -cis-permesrinic acid of formula (1) is converted to (1S) -cis-permesrinic chloride using a halogenating agent and heated to (1R) -trans-permes of formula (2) Obtaining chloric acid chloride, followed by hydrolysis to convert to (1R) -trans-permesrinic acid of formula (3): 화학식 1Formula 1 화학식 2Formula 2 화학식 3Formula 3 제 5 항에 있어서, 100 내지 250 ℃의 반응온도에서 수행되는 방법.The process according to claim 5, which is carried out at a reaction temperature of 100 to 250 ° C.
KR1019980016915A 1998-05-12 1998-05-12 Method for converting (1s)-cis-permethrin acid into (1r)-trans-permethrin acid KR100362728B1 (en)

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* Cited by examiner, † Cited by third party
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WO2003053905A1 (en) * 2001-12-20 2003-07-03 Syngenta Limited A process for the production of 1r pyrethroid esters

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