3-deuteriobicyclo<1.1.1>pentane-1-carboxylic acid | 156517-89-4

• 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: 3-deuteriobicyclo<1.1.1>pentane-1-carboxylic acid
• 英文别名: 3-deuterobicyclo<1.1.1>pentane-1-carboxylic acid；3-deuteriobicyclo[1.1.1]pentane-1-carboxylic acid
• CAS: 156517-89-4
• 化学式: C₆H₈O₂
• 分子量: 113.12
• InChiKey: ORCXPYPDHLVQFP-QYKNYGDISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.87
• 重原子数：
  8.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-deuteriobicyclo<1.1.1>pentane-1-carboxylic acid 在 1-溴-1-氯-2,2,2-三氟乙烷 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 1-bromo-3-deuteriobicyclo<1.1.1>pentane
  参考文献：
  名称：

  Bridgehead Carbocations: A Solvolytic Study of 1-Bromobicyclo[1.1.1]pentane and Its Bridgehead-Substituted Derivatives

  摘要：

  The rate constants (k) for solvolysis of a range of 3-X-substituted bicyclo[1.1.1]pentyl bromides in 80% aqueous ethanol have been measured and a linear relationship found to exist between log k and the inductive/field constant sigma(I). These observations, together with the results of isotope and solvent effect studies described below, have been interpreted as evidence for the formation of 1-bicyclo[1.1.1]pentyl cations in the ionization step in preference to mechanisms in which either ring-opening is concerted with ionization to give 3-methylenecyclobutyl cations or ionization is accompanied by ring-contraction to give bicyclo[1.1.0]butyl-1-carbinyl cations. The latter mechanisms would have been expected to show the effects of strong pi-donor substituent participation, a phenomenon which was not observed. A comparison of the rates of solvolysis of the parent bromide and its 3-deuterated analog is characterized by a large deuterium-isotope effect (k(H)/k(D) = 1.30) which, combined with the observation that 1-bromobicyclo[1.1.1]pentane solvolyses with enhanced rates in solvents which are strong hydrogen bonding accepters, lends support to the view that the 1-bicyclo[1.1.1]pentyl cation derives substantial stabilization from sigma-hyperconjugative interactions.

  DOI：

  10.1021/ja00093a014
• 作为产物：
  描述：

  2-thioxo-1,2-dihydropyridin-1-yl 3-(methoxycarbonyl)bicyclo<1.1.1>pentane-1-carboxylate 在 氘代三正丁基锡 作用下， 以 苯 为溶剂， 反应 1.0h， 以73%的产率得到3-deuteriobicyclo<1.1.1>pentane-1-carboxylic acid
  参考文献：
  名称：

  Bridgehead Carbocations: A Solvolytic Study of 1-Bromobicyclo[1.1.1]pentane and Its Bridgehead-Substituted Derivatives

  摘要：

  The rate constants (k) for solvolysis of a range of 3-X-substituted bicyclo[1.1.1]pentyl bromides in 80% aqueous ethanol have been measured and a linear relationship found to exist between log k and the inductive/field constant sigma(I). These observations, together with the results of isotope and solvent effect studies described below, have been interpreted as evidence for the formation of 1-bicyclo[1.1.1]pentyl cations in the ionization step in preference to mechanisms in which either ring-opening is concerted with ionization to give 3-methylenecyclobutyl cations or ionization is accompanied by ring-contraction to give bicyclo[1.1.0]butyl-1-carbinyl cations. The latter mechanisms would have been expected to show the effects of strong pi-donor substituent participation, a phenomenon which was not observed. A comparison of the rates of solvolysis of the parent bromide and its 3-deuterated analog is characterized by a large deuterium-isotope effect (k(H)/k(D) = 1.30) which, combined with the observation that 1-bromobicyclo[1.1.1]pentane solvolyses with enhanced rates in solvents which are strong hydrogen bonding accepters, lends support to the view that the 1-bicyclo[1.1.1]pentyl cation derives substantial stabilization from sigma-hyperconjugative interactions.

  DOI：

  10.1021/ja00093a014

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.