1-hydroxycyclobutanemethanol acetate | 148420-10-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-hydroxycyclobutanemethanol acetate
• 英文别名: (1-Hydroxycyclobutyl)methyl acetate
• CAS: 148420-10-4
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: KNYAMRQFYVINSN-UHFFFAOYSA-N

物化性质

• 沸点：
  201.5±13.0 °C(Predicted)
• 密度：
  1.163±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甲基磺酰氯 、 1-hydroxycyclobutanemethanol acetate 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 6.0h， 以27%的产率得到1-<(methylsulfonyl)oxy>cyclobutanemethanol acetate
  参考文献：
  名称：

  Thermolytic rearrangements of 1,1-cyclopropanedimethanol disulfonates: cyclopropylcarbinyl cations revisited

  摘要：

  1,1-Cyclopropanedimethanol dimethanesulfonate (1a) and the corresponding ditosylate lb underwent thermal rearrangement at 110-140-degrees-C after melting. Short reaction time resulted in the formation of mixtures containing 1-(sulfonyloxy)cyclobutanemethanol sulfonates 5a,b (major), starting material, and 2-methylene-1,4-butanediol disulfonates 6a,b. Longer reaction times afforded complete conversion to disulfonates 6a,b, isolated in 49 and 62 % yield, respectively. These reactions are postulated to proceed via initial carbocation formation, presumably interconverting bicylobutonium and cyclopropylcarbinyl cations, which exist as ion pairs in the melt. Crossover experiments with dimesylate la and ditosylate lb offer support for the presence of ion pairs in the melt: internal return competed with external trapping of the intermediate cations. Reaction of la and 2-methylene-1,4-butanediol ditosylate (6b) gave a mixture in which 2-methylene-1,4-butanediol 1-mesylate 4-tosylate (8) predominated over the isomeric 4-mesylate 1-tosylate 7 by a 5:1 ratio. Crossover experiments with 6a and 6b indicated that partial allylic substitution was occurring for the open-chain products under the thermolysis conditions. Reaction of la with excess tetrabutylammonium tosylate at 114-15-degrees-C afforded mixed 1-(sulfonyloxy)cyclobutanemethanol sulfonates and 2-methylene-1,4-butanediol disulfonates formed competitively by internal return and tosylate interception. Acetolysis of la at 42-43-degrees-C afforded predominately products of internal return early on the reaction profile. Longer reaction times afforded predominately monoacetates while reactions run at 108-10-degrees-C afforded substantial amounts of diacetates. Acetolysis of 1-acetoxycyclobutanemethanol mesylate (12a) resulted in the substitution of the mesyloxy group with substantial rearrangement.

  DOI：

  10.1021/jo00063a039
• 作为产物：
  描述：

  亚甲基环丁烷 在 吡啶 、 4-二甲氨基吡啶 、 甲酸 、 双氧水 作用下， 以 二氯甲烷 为溶剂， 反应 1.33h， 生成 1-hydroxycyclobutanemethanol acetate
  参考文献：
  名称：

  Thermolytic rearrangements of 1,1-cyclopropanedimethanol disulfonates: cyclopropylcarbinyl cations revisited

  摘要：

  1,1-Cyclopropanedimethanol dimethanesulfonate (1a) and the corresponding ditosylate lb underwent thermal rearrangement at 110-140-degrees-C after melting. Short reaction time resulted in the formation of mixtures containing 1-(sulfonyloxy)cyclobutanemethanol sulfonates 5a,b (major), starting material, and 2-methylene-1,4-butanediol disulfonates 6a,b. Longer reaction times afforded complete conversion to disulfonates 6a,b, isolated in 49 and 62 % yield, respectively. These reactions are postulated to proceed via initial carbocation formation, presumably interconverting bicylobutonium and cyclopropylcarbinyl cations, which exist as ion pairs in the melt. Crossover experiments with dimesylate la and ditosylate lb offer support for the presence of ion pairs in the melt: internal return competed with external trapping of the intermediate cations. Reaction of la and 2-methylene-1,4-butanediol ditosylate (6b) gave a mixture in which 2-methylene-1,4-butanediol 1-mesylate 4-tosylate (8) predominated over the isomeric 4-mesylate 1-tosylate 7 by a 5:1 ratio. Crossover experiments with 6a and 6b indicated that partial allylic substitution was occurring for the open-chain products under the thermolysis conditions. Reaction of la with excess tetrabutylammonium tosylate at 114-15-degrees-C afforded mixed 1-(sulfonyloxy)cyclobutanemethanol sulfonates and 2-methylene-1,4-butanediol disulfonates formed competitively by internal return and tosylate interception. Acetolysis of la at 42-43-degrees-C afforded predominately products of internal return early on the reaction profile. Longer reaction times afforded predominately monoacetates while reactions run at 108-10-degrees-C afforded substantial amounts of diacetates. Acetolysis of 1-acetoxycyclobutanemethanol mesylate (12a) resulted in the substitution of the mesyloxy group with substantial rearrangement.

  DOI：

  10.1021/jo00063a039

文献信息

• Wade Peter A., Kondracki Paul A., J. Org. Chem., 58 (1993) N 11, S 3140-3147
  作者：Wade Peter A., Kondracki Paul A.

  DOI：——

  日期：——
• Thermolytic rearrangements of 1,1-cyclopropanedimethanol disulfonates: cyclopropylcarbinyl cations revisited
  作者：Peter A. Wade、Paul A. Kondracki

  DOI：10.1021/jo00063a039

  日期：1993.5

  1,1-Cyclopropanedimethanol dimethanesulfonate (1a) and the corresponding ditosylate lb underwent thermal rearrangement at 110-140-degrees-C after melting. Short reaction time resulted in the formation of mixtures containing 1-(sulfonyloxy)cyclobutanemethanol sulfonates 5a,b (major), starting material, and 2-methylene-1,4-butanediol disulfonates 6a,b. Longer reaction times afforded complete conversion to disulfonates 6a,b, isolated in 49 and 62 % yield, respectively. These reactions are postulated to proceed via initial carbocation formation, presumably interconverting bicylobutonium and cyclopropylcarbinyl cations, which exist as ion pairs in the melt. Crossover experiments with dimesylate la and ditosylate lb offer support for the presence of ion pairs in the melt: internal return competed with external trapping of the intermediate cations. Reaction of la and 2-methylene-1,4-butanediol ditosylate (6b) gave a mixture in which 2-methylene-1,4-butanediol 1-mesylate 4-tosylate (8) predominated over the isomeric 4-mesylate 1-tosylate 7 by a 5:1 ratio. Crossover experiments with 6a and 6b indicated that partial allylic substitution was occurring for the open-chain products under the thermolysis conditions. Reaction of la with excess tetrabutylammonium tosylate at 114-15-degrees-C afforded mixed 1-(sulfonyloxy)cyclobutanemethanol sulfonates and 2-methylene-1,4-butanediol disulfonates formed competitively by internal return and tosylate interception. Acetolysis of la at 42-43-degrees-C afforded predominately products of internal return early on the reaction profile. Longer reaction times afforded predominately monoacetates while reactions run at 108-10-degrees-C afforded substantial amounts of diacetates. Acetolysis of 1-acetoxycyclobutanemethanol mesylate (12a) resulted in the substitution of the mesyloxy group with substantial rearrangement.