3-羟基-1-亚甲基环丁烷 | 68423-20-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 3-羟基-1-亚甲基环丁烷
• 英文名称: 3-Methylencyclobutanol
• 英文别名: 3-Methylidenecyclobutan-1-ol
• CAS: 68423-20-1
• 化学式: C₅H₈O
• 分子量: 84.1179
• InChiKey: WFOPSFJXXFOZCD-UHFFFAOYSA-N

物化性质

• 沸点：
  57-58 °C(Press: 20 Torr)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-羟基-1-亚甲基环丁烷 、 3,5-二硝基苯甲酰氯 以 吡啶 、 四氯化碳 、 乙醚 为溶剂， 生成 3.5-Dinitro-benzoesaeure-(4-methyl-cyclobutylester)
  参考文献：
  名称：

  Chemistry of Spiropentane. III. The Synthesis and Deamination of Spiropentylamine

  摘要：

  DOI：

  10.1021/ja01509a049
• 作为产物：
  描述：

  1-bromobicyclo<3.1.1>heptane 在 乙醇 作用下， 生成 3-羟基-1-亚甲基环丁烷
  参考文献：
  名称：

  Della, Ernest W.; Taylor, Dennis K., Australian Journal of Chemistry, 1990, vol. 43, # 5, p. 945 - 948

  摘要：

  DOI：

文献信息

• Inductive charge dispersal in the solvolysis of 3-substituted bicyclo[1.1.1] pentyl bromides
  作者：Cyril A. Grob、Cheng Xi Yang、Ernest W. Della、Dennis K. Taylor

  DOI：10.1016/s0040-4039(00)79433-0

  日期：1991.10

  Solvolysis rates and products of 3-substituted bicyclo[1.1.1]pentyl bromides indicate extremely strong inductive charge dispersal in the ionization to bicyclo[1.1.1]pentyl-1-cations, the precursors of 3-methylenecyclobutanols.

  3-取代的双环[1.1.1]戊基溴化物的溶剂分解速率和产物表明，在离子化为双环[1.1.1]戊基-1-阳离子（3-亚甲基环丁醇的前体）的过程中，极强的感应电荷分散。
• <b>Small-Ring Compounds. XXXVI. 3-Methylenecyclobutyl Bromide and 1-Methylcyclobut-2-enyl Bromide</b>
  作者：Edgar F. Kiefer、John D. Roberts

  DOI：10.1021/ja00864a021

  日期：1962.3

  3-Methylenecyclobutyl bromide and 1-methylcyclobut-2-enyl bromide have been synthesized from the cycloaddition products of allene with acrylonitrile and vinyl benzoate. The rate constants for solvolysis of the two bromides in aqueous ethanol have been determined and correlated with the solvolysis rates of a series of analogous bromides. 1-Methylcyclobut-2-enyl bromide appears to exhibit some rate enhancement

  由丙二烯与丙烯腈和苯甲酸乙烯酯的环加成产物合成了3-亚甲基环丁基溴和1-甲基环丁-2-烯基溴。两种溴化物在乙醇水溶液中的溶剂分解速率常数已经确定，并与一系列类似溴化物的溶剂分解速率相关联。1-甲基环丁-2-烯基溴化物似乎表现出一定的速率增强，这是由于电子形式上以3-位为中心的交叉环s型相互作用与过渡态中缺电子的1-位。
• Solvolysis of allenylcarbinyl chloride and its cyclopropanated homologs
  作者：A.T. Bottini、J.E. Christensen

  DOI：10.1016/s0040-4020(01)97012-7

  日期：1974.1

  Allenylcarbinyl, cyclopropylideneethyl, methylenecyclopropylcarbinyl, and spiropentylcarbinyl chloride were prepared and their solvolysis reactions in aqueous ethanol or aqueous dioxane or both were studied. Consideration of the solvolytic reactivity of these compounds and their products in aqueous dioxane indicate that all react, at least in part, via positive charge-delocalized transition states

  制备了烯丙基羰基，环亚丙基乙基，亚甲基环丙基羰基和螺戊基羰基氯，并研究了它们在乙醇水溶液或二恶烷水溶液或两者中的溶剂分解反应。对这些化合物及其产物在二恶烷水溶液中的溶剂分解反应性的考虑表明，它们全部至少部分地通过正电荷离域的过渡态反应。
• Stereochemistry of the Deamination of Spiropentylamine
  作者：Kenneth B. Wiberg、Carmen Österle

  DOI：10.1021/jo990654u

  日期：1999.10.1

  The stereochemistry of the deamination of (-)-spiropentylamine in acetic acid has been studied, and it was found that one of the major products, (-)-spiropentyl acetate, was formed with essentially complete inversion of configuration. This suggests that it is formed via an S(N)2 displacement on the spiropentyldiazonium ion. The stereochemistry was established by the conversion of(-)-spiropentanecarboxylic acid to (-)-spiropentylamine via a Curtius rearrangement that proceeds with retention of configuration. The (-) acid also was converted to spiropentyl methyl ketone with methyllithium and then to (+)-spiropentyl acetate via the Baeyer-Villiger reaction that also results in retention of configuration. The deamination of N-nitroso-N-spiropentyl urea was studied in methanol, and spiropentyl methyl ether was a major product. Similarly, the reaction in water led to spiropentanol. The latter reactions also lead to 2-methoxymethyl- or 2-hydroxymethyl-1,3-butadiene, respectively, corresponding to the alternative mode of reaction via a cyclopropyl cation-allyl cation rearrangement.
• Bridgehead Carbocations: A Solvolytic Study of 1-Bromobicyclo[1.1.1]pentane and Its Bridgehead-Substituted Derivatives
  作者：Ernest W. Della、Cyril A. Grob、Dennis K. Taylor

  DOI：10.1021/ja00093a014

  日期：1994.7

  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.