CN104311502A - 从茚虫威混合体中分离提纯s体茚虫威的方法 - Google Patents

从茚虫威混合体中分离提纯s体茚虫威的方法 Download PDF

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CN104311502A
CN104311502A CN201410465250.2A CN201410465250A CN104311502A CN 104311502 A CN104311502 A CN 104311502A CN 201410465250 A CN201410465250 A CN 201410465250A CN 104311502 A CN104311502 A CN 104311502A
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indoxacarb
mixture
isomer
solvent
purifying
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CN104311502B (zh
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仇耀康
刘建华
季美娟
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NANTONG SHI ZHUANG CHEMICAL Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

本发明公开了一种从茚虫威混合体中用溶剂重结晶分离提纯出S体茚虫威的方法，所用的有机溶剂为乙腈、醇类、烃类、醚类、酯类溶剂或他们任意比例的混合物，重结晶的温度为-10～10℃,制得最终产品S体茚虫威纯度大于98%，满足了市场对S体茚虫威的需求。

Description

从茚虫威混合体中分离提纯S体茚虫威的方法
技术领域
本发明涉及一种从茚虫威混合体中分离提纯S体茚虫威的方法。
背景技术
茚虫威[试验代号DPX-JW062、DPX-MP062、DPX-KNl27、DPX-KNl28，通用名称indoxacarb,商品名：Ammate(全垒打)、Avatar(安打)、Avaunt、Steward]是美国杜邦公司开发的新型噁二嗪类(oxadiazine)杀虫剂。已在美国、澳大利亚、中国等国作为“降低险产品”(reduced-riskproduct)登记注册
化学名称为(S)-7-氯-2,3,4a,5-四氢-2-[甲氧基羰基（4-三氟甲氧基苯基）氨基甲酰基]茚并[1,2-e][1,3,4-]噁二嗪-4a-羧酸甲酯。
英文化学名称为                                                      
methyl(S)-7-chloro-3,5-dihydro-2-[[methoxycarbony[(4-trifuoromethoxy)phenyl]amino]carbonyl]indeno[1,2-e-][1,3,4]oxadiazine-4a(3H)-carboxylate
化学结构式如下：
茚虫威结构中只有S异构体有活性，而R异构体没有活性。其中DPX-JW062：S异构体和R异构体的比例为l：l；DPX-MP062：的比例为3：l；DPX-KNl27：R异构体；DPX-KNl28：S异构体。有效成分以S异构体DPX-KNl28计。
因此提纯出S异构体茚虫威具有十分重要的意义，而目前文献上尚未有此方面的报道。
发明内容
本发明的目的是提出一种工艺简单成熟，成本低廉的从茚虫威混合体中，分离提纯出纯度＞98%的S体茚虫威的方法。
本发明是这样实现的，一种从茚虫威混合体中分离提纯S体茚虫威的方法，其采用溶剂重结晶的分离提纯方法，具体操作是：向含S体、R体的茚虫威混合体中加入与茚虫威混合体重量比为1～50：1的乙腈、醇类、烃类或酯类溶剂或他们任意比例的混合物，然后加热升温到50～100℃，待物料溶解后，将体系温度降至-10～10℃，并保持10～15小时，然后滤除结晶出的混合体茚虫威，收集滤液，浓缩溶剂，浓缩掉溶剂投料量的10～80%，然后再降温至-10～10℃，析出S体的茚虫威，经过滤干燥得到纯度＞98%的S体茚虫威。
进一步的，所用的茚虫威混合体中S体：R体为1～19：1，总含量≥95%。
本发明的优点是：方法简便易操作、产品品质高，生产成本低，生产过程环境污染小。
具体实施方式
实施例1：
取茚虫威混合体10g，总含量95%，S体：R体=2.5:1，加入乙腈10g，加热到70℃，物料全部溶解后将体系降温到0℃，并保持10小时，析出混合体结晶，滤除结晶物。滤液浓缩掉4g乙腈，再降温到0℃，析出结晶，过滤干燥得到S体茚虫威2.5g，手性柱分析S体98.3%，R体0.3%。
实施例2：
取茚虫威混合体10g，总含量95%，S体：R体=3:1，加入甲醇20g，加热到65℃，物料全部溶解后将体系降温到0℃，并保持10小时，析出混合体结晶，滤除结晶物。滤液浓缩掉10g甲醇，再降温到0℃，析出结晶，过滤干燥得到S体茚虫威3.8g，手性柱分析S体98.4%，R体0.2%。
实施例3
取茚虫威混合体10g，总含量95%，S体：R体=5:1，加入乙酸乙酯10g，环己烷20g，加热到75℃，物料全部溶解后将体系降温到-10℃，并保持10小时，析出混合体结晶，滤除结晶物。滤液浓缩掉8g乙酸乙酯与环己烷的混合溶剂，再降温到-10℃，析出结晶，过滤干燥得到S体茚虫威5g，手性柱分析S体98.6%，R体0.1%。
实施例4
取茚虫威混合体10g，总含量95%，S体：R体=10:1，加入乙腈10g，90-120#石油醚20g，加热到70℃，物料全部溶解后将体系降温到-10℃，并保持10小时，析出混合体结晶，滤除结晶物。滤液浓缩掉6g乙腈与90-120#石油醚的混合物，再降温到-10℃，析出结晶，过滤干燥得到S体茚虫威7.2g，手性柱分析S体98.7%，R体0.2%。
实施例5
取茚虫威混合体10g，总含量95%，S体：R体=19:1，加入甲醇10g，90-120#石油醚20g，加热到65℃，物料全部溶解后将体系降温到-10℃，并保持15小时，析出混合体结晶，滤除结晶物。滤液浓缩掉4g甲醇与90-120#石油醚的混合溶剂，再降温到-10℃，析出结晶，过滤干燥得到S体茚虫威8.1g，手性柱分析S体98.8%，R体0.1%。

Claims (2)

1.一种从茚虫威混合体中分离提纯S体茚虫威的方法，其特征在于：采用溶剂重结晶的分离提纯方法，具体操作是：向含S体、R体的茚虫威混合体中加入与茚虫威混合体重量比为1～50：1的乙腈、醇类、烃类或酯类溶剂或他们任意比例的混合物，然后加热升温到50～100℃，待物料溶解后，将体系温度降至-10～10℃，并保持10～15小时，然后滤除结晶出的混合体茚虫威，收集滤液，浓缩溶剂，浓缩掉溶剂投料量的10～80%，然后再降温至-10～10℃，析出S体的茚虫威，经过滤干燥得到纯度＞98%的S体茚虫威。
2.按照权利要求1所述的从茚虫威混合体中分离提纯S体茚虫威的方法，其特征在于：所用的茚虫威混合体中S体：R体为1～19：1，总含量≥95%。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105838772A (zh) * 2016-05-27 2016-08-10 苏州汉酶生物技术有限公司 (s)-5-氯-2,3-二氢-2-羟基-1-氧代-1h-茚-2-羧酸甲酯的生物制备方法
WO2018137387A1 (en) * 2017-01-27 2018-08-02 Jiangsu Rotam Chemistry Co., Ltd Crystalline form of indoxacarb, process for its preparation and use thereof
KR20190124809A (ko) * 2017-03-29 2019-11-05 아다마 마켓심 리미티드 인독사카브의 확장형 제조를 위한 새로운 촉매 시스템
WO2021005545A1 (en) * 2019-07-10 2021-01-14 Gharda Chemicals Limited A process for obtaining indoxacarb crystals with specific purity and enantiomeric ratio
CN116003342A (zh) * 2022-01-05 2023-04-25 山东京博农化科技股份有限公司 精茚虫威的获得方法及精茚虫威制剂
EP3996701A4 (en) * 2019-07-10 2023-07-05 Gharda Chemicals Limited METHOD OF ISOLATION OF S-ISOMER CRYSTALS OF INDOXACARB

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023131943A1 (en) * 2022-01-04 2023-07-13 Adama Makhteshim Ltd. Process of preparation of indoxacarb and its intermediates

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869657A (en) * 1994-04-20 1999-02-09 E. I. Du Pont De Nemours And Company Preparation of arthropodicidal oxadiazines
CN103694193A (zh) * 2013-10-11 2014-04-02 浙江大学 精茚虫威的晶型及其无定形形式
CN103889226A (zh) * 2011-10-25 2014-06-25 纳幕尔杜邦公司 1,3-二芳基取代的杂环杀虫剂

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869657A (en) * 1994-04-20 1999-02-09 E. I. Du Pont De Nemours And Company Preparation of arthropodicidal oxadiazines
CN103889226A (zh) * 2011-10-25 2014-06-25 纳幕尔杜邦公司 1,3-二芳基取代的杂环杀虫剂
CN103694193A (zh) * 2013-10-11 2014-04-02 浙江大学 精茚虫威的晶型及其无定形形式

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MOHAMMAD MAJID MOJTAHEDI ET AL.: "Chiral separation of three agrochemical toxins enantiomers by high-performance liquid chromatography on a vancomycin crystalline degradation products-chiral stationary phase", 《BIOMED. CHROMATOGR》, vol. 21, 17 January 2007 (2007-01-17), pages 234 - 240 *
YUPING ZHANG ET AL.: "Enantiomeric separation of indoxacarb on an amylose-based chiral stationary phase and its application in study of indoxacarb degradation in water", 《BIOMED. CHROMATOGR》, vol. 28, 31 March 2014 (2014-03-31), pages 1371 - 1377 *
刘一平 等: "茚虫威对映体分离及手性拆分热力学研究", 《分析测试学报》, vol. 29, no. 12, 25 December 2010 (2010-12-25), pages 1130 - 1134 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105838772A (zh) * 2016-05-27 2016-08-10 苏州汉酶生物技术有限公司 (s)-5-氯-2,3-二氢-2-羟基-1-氧代-1h-茚-2-羧酸甲酯的生物制备方法
WO2018137387A1 (en) * 2017-01-27 2018-08-02 Jiangsu Rotam Chemistry Co., Ltd Crystalline form of indoxacarb, process for its preparation and use thereof
CN109843859A (zh) * 2017-01-27 2019-06-04 江苏龙灯化学有限公司 茚虫威的晶型、其制备方法及其用途
CN109843859B (zh) * 2017-01-27 2022-04-19 江苏龙灯化学有限公司 茚虫威的晶型、其制备方法及其用途
CN110662739B (zh) * 2017-03-29 2023-10-27 安道麦马克西姆有限公司 可规模化制备茚虫威的催化系统
KR20190124809A (ko) * 2017-03-29 2019-11-05 아다마 마켓심 리미티드 인독사카브의 확장형 제조를 위한 새로운 촉매 시스템
CN110662739A (zh) * 2017-03-29 2020-01-07 阿达玛马克西姆有限公司 可规模化制备茚虫威的新的催化系统
KR102167608B1 (ko) * 2017-03-29 2020-10-20 아다마 마켓심 리미티드 인독사카브의 확장형 제조를 위한 새로운 촉매 시스템
US10961206B2 (en) 2017-03-29 2021-03-30 Adama Makhteshim Ltd. Catalytic system for scalable preparation of indoxacarb
WO2021005545A1 (en) * 2019-07-10 2021-01-14 Gharda Chemicals Limited A process for obtaining indoxacarb crystals with specific purity and enantiomeric ratio
EP3996701A4 (en) * 2019-07-10 2023-07-05 Gharda Chemicals Limited METHOD OF ISOLATION OF S-ISOMER CRYSTALS OF INDOXACARB
CN116003342A (zh) * 2022-01-05 2023-04-25 山东京博农化科技股份有限公司 精茚虫威的获得方法及精茚虫威制剂
CN116003342B (zh) * 2022-01-05 2024-04-05 山东京博农化科技股份有限公司 精茚虫威的获得方法及精茚虫威制剂

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