cis-(3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate | 51134-88-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: cis-(3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate
• 英文别名: (1RS)-cis-Phenothrin；cis-Phenonthrin；cis-phenothrin；(-)-cis-Phenothrin；(3-phenoxyphenyl)methyl (1S,3R)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate
• CAS: 51134-88-4
• 化学式: C₂₃H₂₆O₃
• 分子量: 350.458
• InChiKey: SBNFWQZLDJGRLK-NHCUHLMSSA-N

物化性质

• 沸点：
  437.0±45.0 °C(Predicted)
• 密度：
  1.120±0.06 g/cm3(Predicted)
• 物理描述：
  PALE YELLOW-TO-YELLOW-BROWN LIQUID.
• 溶解度：
  Solubility in water: none
• 蒸汽压力：
  Vapor pressure, Pa at 20 °C:

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-(3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate 在 4,4'-二氨基二苯乙烯-2,2'-二磺酸 作用下， 以11%的产率得到(1RS)-cis-10,10-Difluorophenothrin
  参考文献：
  名称：

  Insecticidal activity of new fluorinated pyrethroids and their stability toward chemical oxidation and photoreaction

  摘要：

  AbstractThe insecticidal activity of several new fluorinated pyrethroids was measured using houseflies untreated and treated with piperonyl butoxide (PB). 10, 10‐Difluorophenothrin and 10, 10‐difluoroallethrin, which include fluorine atoms at a position most easily attacked by mixed function oxidases (mfo) in the acid moiety, showed smaller topical LD50 values on the PB‐untreated flies than the parent insecticides but rather large values on the PB‐treated flies, suggesting that the introduction of fluorine prevents metabolic oxidation, although it has a negative effect on the interaction with a target site. Monofluorinated analogues of phenothrin, in which the structure of chrysanthemic acid was rearranged, still had moderate insecticidal activity, but flies were scarcely killed by 7 fluoroallethrin into which fluorine was introduced at a position most easily oxidized by mfo in the alcohol moiety.Competitive oxidation of the fluorinated derivatives and the parent compounds showed that fluorine at both the 10‐ and 7′‐positions stabilizes the alkenyl side‐chains of the pyrethroids against selenium dioxide and m‐chloroperoxybenzoic acid. Photochemical studies with 10, 10‐difluorophenothrin indicated that the photo‐instability of the cyclopropanecarboxylic part could not be improved by this modification.

  DOI：

  10.1002/ps.2780400409
• 作为产物：
  描述：

  在 吡啶 、 C₂₉H₃₅Br₂CoN₃ 、 zinc dibromide 、 锌 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 24.25h， 生成 右旋苯醚菊酯 、 cis-(3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate
  参考文献：
  名称：

  钴催化的1,3-二烯的还原性二甲基环丙烷化

  摘要：

  二甲基环丙烷是有价值的合成靶标，使用锌类胡萝卜素试剂难以获得高收率。在本文中，我们描述了席梦思-史密斯反应的钴催化变体，该变体使用Me 2 CCl 2 / Zn试剂混合物能够有效地进行1,3-二烯的二甲基环丙烷化。根据1,3-二烯的取代模式，反应具有很高的区域选择性。产品是乙烯基环丙烷，可作为过渡金属催化的开环反应的底物，包括1,3重排和[5 + 2]环加成反应。初步研究表明，在钴催化条件下，中等活化度的单烯烃也适用于二甲基环丙烷化。

  DOI：

  10.1002/anie.201807542

文献信息

• Practical, Stereocontrolled Synthesis of Polyfluorinated Artificial Pyrethroids
  作者：Makoto Fujita、Kiyosi Kondo、Tamejiro Hiyama

  DOI：10.1246/bcsj.60.4385

  日期：1987.12

  Practical and stereocontrolled approaches to polyfluorinated synthetic pyrethroids based on aldehyde addition of CF3CCl2ZnCl are described. The zinc reagent was allowed to react with 3-formyl-2,2-dimethylcyclopropanecarboxylates (6) to give the corresponding adducts. These were acetylated and then reduced again with zinc to afford (1R*, 3S*)-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates (12). The (1R*, 3R*)-isomer was derived from 2,2-dichloro-1,1,1-trifluoro-5-methyl-4-hexen-3-ol by diazoacetylation, Cu(II)-catalyzed intramolecular carbene addition, and finally by the zinc reduction. An alternative access to 12 and its halogen homologues of the (Z)-pyrethroids involves addition of 1-halo-2,2-difluoroethenyl group across the CHO group of 6 and subsequent regio- and stereoselective halogenation.

  本文介绍了基于 CF3CCl2ZnCl 的醛加成法制备多氟合成拟除虫菊酯的实用立体控制方法。锌试剂可与 3-甲酰基-2,2-二甲基环丙烷羧酸盐 (6) 反应，生成相应的加合物。这些加合物经乙酰化后再次用锌还原，得到 (1R*，3S*)-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基环丙烷羧酸盐 (12)。(1R*, 3R*)异构体是由 2,2-二氯-1,1,1-三氟-5-甲基-4-己烯-3-醇通过重氮乙酰化、Cu(II)催化的分子内碳烯加成，最后通过锌还原得到的。获得 12 及其 (Z)- 吡咯烷卤素同系物的另一种方法是在 6 的 CHO 基上添加 1-卤代-2,2-二氟乙烯基，然后进行区域和立体选择性卤化。
• Muramatsu, Shigeki; Nakada, Yasuo; Endo, Rokuro, Agricultural and Biological Chemistry, 1984, vol. 48, # 3, p. 585 - 596
  作者：Muramatsu, Shigeki、Nakada, Yasuo、Endo, Rokuro、Kuwano, Harumitsu、Ide, Junya

  DOI：——

  日期：——
• Cobalt‐Catalyzed Reductive Dimethylcyclopropanation of 1,3‐Dienes
  作者：Jacob Werth、Christopher Uyeda

  DOI：10.1002/anie.201807542

  日期：2018.10.15

  variant of the Simmons–Smith reaction that enables the efficient dimethylcyclopropanation of 1,3‐dienes using a Me2CCl2/Zn reagent mixture. The reactions proceed with high regioselectivity based on the substitution pattern of the 1,3‐diene. The products are vinylcyclopropanes, which serve as substrates for transition‐metal‐catalyzed ring‐opening reactions, including 1,3‐rearrangement and [5+2] cycloaddition

  二甲基环丙烷是有价值的合成靶标，使用锌类胡萝卜素试剂难以获得高收率。在本文中，我们描述了席梦思-史密斯反应的钴催化变体，该变体使用Me 2 CCl 2 / Zn试剂混合物能够有效地进行1,3-二烯的二甲基环丙烷化。根据1,3-二烯的取代模式，反应具有很高的区域选择性。产品是乙烯基环丙烷，可作为过渡金属催化的开环反应的底物，包括1,3重排和[5 + 2]环加成反应。初步研究表明，在钴催化条件下，中等活化度的单烯烃也适用于二甲基环丙烷化。
• Insecticidal activity of new fluorinated pyrethroids and their stability toward chemical oxidation and photoreaction
  作者：Tetsu Ando、Nozomu Koseki、Isamu Yasuhara、Kie Kasuga、Noritada Matsuo、Takao Ishiwatari

  DOI：10.1002/ps.2780400409

  日期：1994.4

  AbstractThe insecticidal activity of several new fluorinated pyrethroids was measured using houseflies untreated and treated with piperonyl butoxide (PB). 10, 10‐Difluorophenothrin and 10, 10‐difluoroallethrin, which include fluorine atoms at a position most easily attacked by mixed function oxidases (mfo) in the acid moiety, showed smaller topical LD50 values on the PB‐untreated flies than the parent insecticides but rather large values on the PB‐treated flies, suggesting that the introduction of fluorine prevents metabolic oxidation, although it has a negative effect on the interaction with a target site. Monofluorinated analogues of phenothrin, in which the structure of chrysanthemic acid was rearranged, still had moderate insecticidal activity, but flies were scarcely killed by 7 fluoroallethrin into which fluorine was introduced at a position most easily oxidized by mfo in the alcohol moiety.Competitive oxidation of the fluorinated derivatives and the parent compounds showed that fluorine at both the 10‐ and 7′‐positions stabilizes the alkenyl side‐chains of the pyrethroids against selenium dioxide and m‐chloroperoxybenzoic acid. Photochemical studies with 10, 10‐difluorophenothrin indicated that the photo‐instability of the cyclopropanecarboxylic part could not be improved by this modification.