二环[2.2.1]庚-5-烯-2-甲醇,1,4,5,6,7,7-六氯-,内- | 1080-25-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 中文名称: 二环[2.2.1]庚-5-烯-2-甲醇,1,4,5,6,7,7-六氯-,内-
• 英文名称: rac-((1R,2S,4S)-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-en-2-yl)methanol
• 英文别名: (+/-)-2-endo-hydroxymethyl-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene；endo-2-hydroxymethyl-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-2-ene；(+/-)-(1,4,5,6,7,7-hexachloro-norborn-5-ene-2endo-yl)-methanol；(+/-)-(1,4,5,6,7,7-Hexachlor-norborn-5-en-2endo-yl)-methanol；(+/-)-1,4,5,6,7,7-Hexachlor-2endo-hydroxymethyl-norbornen-(5)；1,2,3,4,7,7-Hexachlor-5-hydroxymethyl-bicyclo<2.2.1>hepten-(2)；[(1S,2R,4R)-1,4,5,6,7,7-hexachloro-2-bicyclo[2.2.1]hept-5-enyl]methanol
• CAS: 1080-25-7；17280-40-9；64577-08-8
• 化学式: C₈H₆Cl₆O
• 分子量: 330.853
• InChiKey: JFSYHGUBAXUJEV-NRYKZSQYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  二环[2.2.1]庚-5-烯-2-甲醇,1,4,5,6,7,7-六氯-,内- 在 吡啶 、 horse liver acetone 作用下， 以 phosphate buffer 、 二氯甲烷 为溶剂， 反应 37.0h， 生成 (1S,2R,4R)-(-)-2-endo-acetoxymethyl-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  Enzymatic resolution of (±)-2-endo-hydroxymethyl and acetoxymethyl substituted hexachloronorbornene derivatives

  摘要：

  (±)-2-endo-羟甲基-1,4,5,6,7,7-六氯双环[2.2.1]庚-5-烯及其(±)-2-endo-乙酰氧甲基衍生物通过使用各种水解酶进行分解，得到光学纯度高达94%-98%的对映体富集产物。绝对构型通过将2-endo-乙酰氧甲基-1,4,5,6,7,7-六氯双环[2.2.1]庚-5-烯转化为已知绝对构型的2-endo-羟甲基双环[2.2.1]庚-5-烯来确定。© 2005 Elsevier Ltd. 保留所有权利。

  DOI：

  10.1016/j.tetasy.2005.06.014
• 作为产物：
  描述：

  二环[2.2.1]庚-5-烯-2-羧酸,1,4,5,6,7,7-六氯-,甲基酯,(1S,2R,4R)- 在 lithium aluminium tetrahydride 作用下， 以92%的产率得到二环[2.2.1]庚-5-烯-2-甲醇,1,4,5,6,7,7-六氯-,内-
  参考文献：
  名称：

  Diels中的六氯环戊二烯-不对称反应

  摘要：

  使用六氯环戊二烯（HCC）与手性亲二烯体丙烯酸1-薄荷酯和1-薄荷烯丙基醚进行不对称热Diels-Alder反应，得到高达150％ee的环加合物。通过使用路易斯酸催化实现的较温和的反应条件使光学收率提高了2.8倍。使用丙烯酸1-薄荷基酯的催化和未催化反应导致形成具有相反构型的加合物。产物也已经通过非对映异构体形成拆分为纯对映异构体。

  DOI：

  10.1016/s0040-4020(01)85072-9

文献信息

• The cyclic acetals from 1,4,5,6,7,7-hexachloronorborn-5-en-2-endo-ylalkanols
  作者：David I. Davies、Adrian L. B. Gale

  DOI：10.1039/p19760002581

  日期：——

  ethoxide to afford the cyclic acetal 5-endo,6,7,7,8-pentachloro-4-exo-ethoxy-3-oxatricyclo[4.2.1.04,8]nonane is found to involve the intermediacy of 1,4,5,7,7-pentachloro-6-ethoxynorborn-5-en-2-endo-ylmethanol and 4-exo, 5-endo, 6,7,7,8-hexachloro-3-oxatricyclo[4.2.1.04,8]nonane. 6-endo,7,8,8,9-Pentachloro-5-exo-ethoxy- and methoxy-4-oxatricyclo[5.2.1.05,9]decane are formed from the reactions of 1,4

  的反应1,4,5,6,7,7- hexachloronorborn -5-烯-2-内-ylmethanol与乙醇钠，得到环状缩醛5-内，6,7,7,8五氯-4-发现exo -ethoxy-3-oxatricyclo [4.2.1.0 4,8 ]壬烷涉及1,4,5,7,7-五氯-6-乙氧基norborn-5-en-2-内基甲醇和4的中间体-外，5-内，6,7,7,8六氯-3-氧杂三环[4.2.1.0 4,8 ]壬烷。6-内，7,8,8,9五氯-5-外-乙氧基和甲氧基-4-氧杂三环[5.2.1.0 5,9 ]癸烷从1,4,5,6,7反应形成，7-hexachloronorborn-5-en-2-内乙醇分别与乙醇钠和甲醇钠混合。Nmr研究表明，在这些产物的环状缩醛中，吡喃环的构象趋向于船形而不是椅子形。
• Halogenated bicycl oheptenyl sulfite derivatives
  申请人：VELSICOL CHEMICAL CORP

  公开号：US02867564A1

  公开（公告）日：1959-01-06
• Stereoselective synthesis of γ-lactone fused cyclopentanoids
  作者：Ayşegül Gümüş、Cihangir Tanyeli

  DOI：10.1016/j.tetasy.2012.09.010

  日期：2012.10

  The stereoselective synthesis of gamma-lactone fused cyclopentanoids applying chemoenzymatic methods is described. rac-2-Hydroxymethyl-1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-ene and rac-2-hydroxymethyl-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene were successfully resolved by Candida rugosa lipase (CRL), to afford enantiomerically enriched products with an ee of 94 and 97%, respectively. The enantiomerically enriched acetates were then subjected to ruthenium and/or cerium catalyzed oxidation to afford alpha-diketones and subsequent alkaline H2O2 mediated oxidative cleavage reaction of alpha-diketones, followed by CH2N2 esterification, gave enantiomerically enriched gamma-lactone fused cyclopentanoids with known absolute configurations. (C) 2012 Elsevier Ltd. All rights reserved.
• Synthesis of hexachlorobicyclo[2.2.1]hept-5-enylmethyl haloacetates
  作者：E. G. Mamedbeili (Mamedov)、T. G. Kyazimova、Kh. I. Gasanov、O. B. Abdiev、I. M. Mamedova

  DOI：10.1134/s1070427209020220

  日期：2009.2

  The possibility of preparing hexachlorobicyclo[2.2.1]hept-5-enylmethyl haloacetates by reactions of hexachlorocyclopentadiene with allyl haloacetates was examined. The optimal conditions for preparing the esters were found. The structures of the compounds prepared were proved by IR and H-1 NMR spectroscopy.
• Zur Chemie von Polyhalocyclopentadienen und verwandten Verbindungen, 18. Mitt.: Hexachlorcyclopentadien und Allylglykoläther
  作者：R. Riemschneider、H. J. Kötzsch

  DOI：10.1007/bf00903168

  日期：1960.1