3-methylenecyclobutanone dimethyl ketal | 143923-57-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methylenecyclobutanone dimethyl ketal
• 英文别名: 3,3-dimethoxy-1-methylenecyclobutane；1,1-Dimethoxy-3-methylidenecyclobutane
• CAS: 143923-57-3
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: RCIACCWDIUFUAT-UHFFFAOYSA-N

物化性质

• 沸点：
  127.9±40.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  sodium methylate 、 1-iodo-3-methoxybicyclo<1.1.1>pentane 以 甲醇 为溶剂， 反应 6.0h， 以0.4 g的产率得到3-methylenecyclobutanone dimethyl ketal
  参考文献：
  名称：

  Nucleophilic substitution in 1-substituted 3-iodobicyclo[1.1.1]pentanes. A new synthetic route to functionalized bicyclo[1.1.1]pentane derivatives

  摘要：

  Nucleophilic substitution of the iodine in 1-substituted 3-iodobicyclo[1.1.1]pentanes [R = I (1), CF3 (2)] was investigated. The results of the reaction are strongly dependent on the nature of the nucleophile and the substituent. Whereas the trifluoromethyl derivative 2 is found to be inert in the reactions and gave substitution products only with organolithium reagents, the 1,3-diiodide 1 is much more reactive and affords normal substitution products with nitrogen bases and MeONa but gives [1.1.1]propellane with Grignard and organolithium reagents and with triaryl(alkyl)phosphines. Other synthesized 3-iodobicyclo[1.1.1]pentanes did not give substitution products. A general scheme for the transformations of 1 is also proposed.

  DOI：

  10.1021/jo00049a030

文献信息

• Experimental and theoretical study of substituent effects on3J(13C1-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
  作者：Ernest W. Della、Ian J. Lochert、N�lida M. Peruchena、Gustavo A. Aucar、Rub�n H. Contreras

  DOI：10.1002/(sici)1099-1395(199603)9:3<168::aid-poc766>3.0.co;2-v

  日期：1996.3

  A series of 23 bridgehead-substituted bicyclo[1,1,1]pentanes were synthesized and the (3)J(C1-H) coupling constants determined from their proton-coupled C-13 NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exerted by the halogens in particular. The IPPP-CLOPPA-INDO theoretical approach, which was employed to provide a measure of the extent of through-bond versus through-space transmission of coupling information, was found to give (3)J(C1-H) values in good agreement with experimental data. Empirical substituent parameter regressions were performed and found to be consistent with the CLOPPA description of the increase in both the through-bond and through-space contributions to the coupling. The substituent parameter regressional analyses also demonstrated that electronegativity effects play a predominant role in determining the magnitude of the couplings, particularly in those substrates in which the substituent is attached to the ring system by a second-row element.
• Nucleophilic substitution in 1-substituted 3-iodobicyclo[1.1.1]pentanes. A new synthetic route to functionalized bicyclo[1.1.1]pentane derivatives
  作者：James L. Adcock、Andrei A. Gakh

  DOI：10.1021/jo00049a030

  日期：1992.11

  Nucleophilic substitution of the iodine in 1-substituted 3-iodobicyclo[1.1.1]pentanes [R = I (1), CF3 (2)] was investigated. The results of the reaction are strongly dependent on the nature of the nucleophile and the substituent. Whereas the trifluoromethyl derivative 2 is found to be inert in the reactions and gave substitution products only with organolithium reagents, the 1,3-diiodide 1 is much more reactive and affords normal substitution products with nitrogen bases and MeONa but gives [1.1.1]propellane with Grignard and organolithium reagents and with triaryl(alkyl)phosphines. Other synthesized 3-iodobicyclo[1.1.1]pentanes did not give substitution products. A general scheme for the transformations of 1 is also proposed.