Methyl 2,2-dimethyl-4-methylidenecyclohexane-1-carboxylate | 122313-94-4

• 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: Methyl 2,2-dimethyl-4-methylidenecyclohexane-1-carboxylate
• CAS: 122313-94-4
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: UQHWUCOPIMVVSE-UHFFFAOYSA-N

物化性质

• 沸点：
  215.6±29.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯甲砜 、 Methyl 2,2-dimethyl-4-methylidenecyclohexane-1-carboxylate 在 正丁基锂 、 溶剂黄146 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.0h， 以55%的产率得到
  参考文献：
  名称：

  β-Pinene-6-one: a pivotal synthetic intermediate

  摘要：

  Submitting the title ketone to either acetoxymercuration or basic conditions resulted in the formation of the acid beta-5 and alpha-5, respectively, with an useful selectivity, related rearrangements being observed by using the corresponding alcohol and its epoxy derivative. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01399-9
• 作为产物：
  描述：

  6,6-dimethyl-4-hydroxybicyclo<2.2.2>octan-2-one 在 吡啶 、 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 5.3h， 生成 Methyl 2,2-dimethyl-4-methylidenecyclohexane-1-carboxylate
  参考文献：
  名称：

  Solvolyses of 3-oxo- and 3-methylenebicyclo[2.2.2]oct-1-yl triflates: through-bond interaction of a .beta.-carbonyl lone pair with a cationic p orbital

  摘要：

  The rates of solvolysis of 3,3-dimethyl-2-oxobicyclo[2.2.2]oct-1-yl triflate (1b), 2-methylenebicyclo[2.2.2]oct-1-yl-triflate (2b), 5,5-dimethyl-3-oxobicyclo[2.2.2]oct-1-yl triflate (3b), 3-oxobicyclo[2.2.2]oct-1-yl triflate (4b), 3-methylenebicyclo[2.2.2]oct-1-yl triflate (5b), 3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate (6b), and bicyclo[2.2.2]oct-1-yl triflate (7b) have been determined in 80% ethanol at 25-degrees-C. The O-18- and deuterium-labeling studies exclude both carbonyl addition and the enolization processes in the solvolyses of 3b and 4b. The rate ratios 1b/6b and 2b/7b are 10(-9.1) and 10(-3.9), respectively, indicating that the oxo substituent at the C(2) position is more electron withdrawing than the methylene substituent at the same position. In contrast, the rate ratios 3b/6b and 5b/7b, 10(-2.3) and 10(-2.2), respectively, are comparable with each other. Moreover, the rate ratio 4b/5b is 2.3, suggesting that the 3-oxo substituent is less electron withdrawing than the 3-methylene substituent with respect to the cationic center. Evaluation of the inductive effect of the oxo substituent at the C(3) position by means of the reported rates of solvolysis of various 2-or 3-substituted and unsubstituted bicyclo[2.2.2]oct-1-yl p-nitrobenzenesulfonates (14, 13, and 15, respectively) indicates a rate enhancement of 10(3)-10(4) for 3b and 4b. This marked enhancement is interpreted as evidence of the stabilization of the 3-oxo carbocation by a through-bond interaction between the beta-carbonyl lone pair and the cationic p orbital. The m Y relationships and the formation of fragmentation products 11 (9%) and 12 (20%) in the methanolyses of 3-oxo compounds 3b and 4b, respectively, support the through-bond interaction.

  DOI：

  10.1021/jo00061a036

文献信息

• Process for Conducting an Organic Reaction in Ionic Liquids
  申请人：Bourgeois Daniel Martin

  公开号：US20110152566A1

  公开（公告）日：2011-06-23

  The present disclosure describes processes for producing cyclohexenes using Lewis acidic ionic liquids comprising the steps of providing to a reactor an α,β-unsaturated carbonyl dienophile, providing to the reactor a 1,3-diene, providing a Lewis acidic ionic liquid to the reactor; and reacting the α,β-unsaturated carbonyl dienophile with 1,3-diene to form a substituted cyclohexene product. The α,β-unsaturated carbonyl dienophile can be mesityl oxide, the 1,3-diene can be piperylene; and the Lewis acidic ionic liquid can be AlCl 3 :[C 2 mim]Cl; AlCl 3 :[C 8 mim]Cl; or mixtures thereof.

  本公开描述了使用含有Lewis酸性离子液体的方法生产环己烯的过程，包括向反应器提供α，β-不饱和羰基二烯亲受体，向反应器提供1,3-二烯，向反应器提供Lewis酸性离子液体；并将α，β-不饱和羰基二烯亲受体与1,3-二烯反应以形成取代环己烯产物。α，β-不饱和羰基二烯亲受体可以是甲苯酮氧，1,3-二烯可以是戊二烯；Lewis酸性离子液体可以是AlCl3:[C2mim]Cl；AlCl3:[C8mim]Cl；或它们的混合物。
• Unexpectedly facile solvolysis of 3-oxobicyclo[2.2.2]oct-1-yl triflates: through-bond interaction of the .beta.-carbonyl lone pair with the cationic p orbital
  作者：Kenichi Takeuchi、Masayasu Yoshida

  DOI：10.1021/jo00277a006

  日期：1989.8
• TAKEUCHI, KENICHI;YOSHIDA, MASAYASU, J. ORG. CHEM., 54,(1989) N6, C. 3772-3773
  作者：TAKEUCHI, KENICHI、YOSHIDA, MASAYASU

  DOI：——

  日期：——
• US8067644B2
  申请人：——

  公开号：US8067644B2

  公开（公告）日：2011-11-29
• β-Pinene-6-one: a pivotal synthetic intermediate
  作者：D. Hébrault、D. Uguen

  DOI：10.1016/s0040-4039(98)01399-9

  日期：1998.9

  Submitting the title ketone to either acetoxymercuration or basic conditions resulted in the formation of the acid beta-5 and alpha-5, respectively, with an useful selectivity, related rearrangements being observed by using the corresponding alcohol and its epoxy derivative. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.