1-methoxybicyclo<2.2.2>oct-5-ene-2-carboxylic acid | 95782-22-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-methoxybicyclo<2.2.2>oct-5-ene-2-carboxylic acid
• 英文别名: 1-methoxybicyclo<2.2.2>oct-5-ene-2-endo-carboxylic acid；6-endo carboxy-1-methoxybicyclo<2.2.2>oct-2-ene；endo-1-Methoxy-bicyclo<2.2.2>oct-5-en-2-yl-carboxylsaeure；(1R,2S,4S)-1-methoxybicyclo[2.2.2]oct-5-ene-2-carboxylic acid
• CAS: 95782-22-2
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: TXQABGPMUJJVRM-XKSSXDPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.44
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-methoxybicyclo<2.2.2>oct-5-ene-2-carboxylic acid 在 对叔丁基邻苯二酚 、 氯甲酸乙酯 、 N,N-二异丙基乙胺 作用下， 以 丙酮 、 甲苯 为溶剂， 反应 22.17h， 生成 (1RS,3RS,6SR,7SR,10RS)-10-formyloxy-7-methoxy-4-azatricyclo[4.3.1.0^3,7]decane-4-carboxylic acid ethyl ester
  参考文献：
  名称：

  用于形成复杂三环胺的 Aza-Cope 重排-曼尼希环化：(±)-Gelsemine 的立体控制全合成

  摘要：

  描述了使用 aza-Cope 重排-Mannich 环化序列组装gelsemine 的氮杂三环[4.4.0.0(2,8)]癸烷核心的详细检查。衍生自内向取向的 1-甲氧基-或 1-羟基双环 [2.2.2] oct-5-烯胺的亚胺离子和 N-酰氧基亚胺离子不经历该序列的第一步，即阳离子氮杂-Cope 重排，形成顺式-氢异喹啉离子。然而，类似的碱促进的氧-氮杂-Cope 重排确实发生形成顺式-氢异喹诺酮类化合物，其含有允许在后续步骤中区域选择性地生成亚胺鎓离子或N-酰氧基亚胺鎓离子的官能团。以这种方式制备的顺式-氢异喹诺酮类化合物的曼尼希环化有效地组装了gelsemine的氮杂三环[4.4.0.0(2,8)]癸烷单元。

  DOI：

  10.1021/ja055710p
• 作为产物：
  描述：

  1-甲氧基-1,4-环己二烯 在 氢氧化钾 、 丁酰草胺 、 对苯二酚 作用下， 以 甲醇 、 水 为溶剂， 反应 54.0h， 生成 1-methoxybicyclo<2.2.2>oct-5-ene-2-carboxylic acid
  参考文献：
  名称：

  Synthesis based on cyclohexadienes: Part 10 synthesis of 5,5-dimethyl-7-methoxy-4-oxatricyclo[4.3.1.0]decan-2-ones.

  摘要：

  Synthesis of 5, 5-dimethyl- 7-methoxy-4 -oxatricyclo[4,3,1,0(3,7)]- decan-2-one 3a, a novel heterocyclic ring system present in morellin 1, and its 3-substituted derivatives 3b-e, is described from the Diels-Alder adducts 7, available from 1-methoxycyclohexa-1,4-dienes 4. Two routes, which involved the halocyclisation and the oxidative addition, were investigated for the conversion of the adducts 7 into 3. While the halocyclisation method resulted in mixtures, excellent yields of the target molecule were obtained by the second method. Solvolysis of the bromoether 9 resulted in a mixture of rearranged products 10, 13, 15 and 16.

  DOI：

  10.1016/s0040-4020(01)86976-3

文献信息

• Dihydroaromatic compounds in the Diels-Alder reaction—III
  作者：I. Alfaro、W. Ashton、L.D. McManus、R.C. Newstead、K.L. Rabone、N.A.J. Rogers、W. Kernick

  DOI：10.1016/0040-4020(70)85020-7

  日期：——

  isomerization and Diels-Alder reaction of 2,5-dihydroanisoles are presented. Some of the further chemistry of the products is detailed. The in situ generation, and further reactions of 2,3-dihydroanisoles by the pyrolysis of 2-methoxy-1,4-dihydrobenzoic acids is described. This technique constitutes a route to certain cyclohexadienes otherwise difficult of access. The in situ isomerization and Diels-Alder reaction

  给出了2，5-二氢茴香醚的原位异构化和Diels-Alder反应技术的合成实用性的其他实例。详细介绍了产品的一些其他化学性质。描述了通过2-甲氧基-1，4-二氢苯甲酸热解的2，3-二氢茴香醚的原位生成和进一步反应。该技术构成通往某些否则难以获得的环己二烯的途径。该原位异构化和2,5- dihydroanisoles Diels-Alder反应与乙炔二羧酸酯构成的取代的邻苯二甲酸酸的方便和有效的合成。
• ACAT inhibitors derived from hetero-Diels-Alder cycloadducts of thioaldehydes
  作者：Richard G. Wilde、Jeffrey T. Billheimer、Sandie J. Germain、Elizabeth A. Hausner、Paul C. Meunier、Deborah A. Munzer、Janet K. Stoltenborg、Peter J. Gillies、Deborah L. Burcham、Shiew-Mai Huang、John D. Klaczkiewicz、Soo S. Ko、Ruth R. Wexler

  DOI：10.1016/0968-0896(96)00143-5

  日期：1996.9

  Acyl-CoA:cholesterol acyltransferase (ACAT) is the enzyme largely responsible for intracellular cholesterol esterification. A systemic inhibitor of ACAT is believed to be able to slow or even reverse the atherosclerotic process. Towards that goal, a series of cyclic sulfides, derived from the hetero-Diels-Alder reaction of thioaldehydes with 1,3-dienes, and bearing carboxamide substituents, were prepared and evaluated for in vitro (in several tissues and species) and ex vivo ACAT inhibition. Minor changes in subsequent structure were found to have a significant effect in optimization of the biological activity of this series of compounds. Copyright (C) 1996 The DuPont Merck Pharmaceutical Company.
• Raghavan, Sadagopan; Rao, G. S. R. Subba, Heterocycles, 1994, vol. 37, # 1, p. 131 - 136
  作者：Raghavan, Sadagopan、Rao, G. S. R. Subba

  DOI：——

  日期：——
• Synthesis and absolute configuration of (R)- and (S)-ethyl 3-(4-oxocyclohex-2-enyl)propionate
  作者：Mark L. Elliott、Frank J. Urban、Jon Bordner

  DOI：10.1021/jo00210a037

  日期：1985.5