1-甲基丙-2-烯基亚磺酸 | 154318-12-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 亚磺酸及其衍生物
• 中文名称: 1-甲基丙-2-烯基亚磺酸
• 英文名称: 1-Methylprop-2-enylsulfinic acid
• 英文别名: α-Methylallylsulfinsaeure；But-3-ene-2-sulfinic acid
• CAS: 154318-12-4
• 化学式: C₄H₈O₂S
• 分子量: 120.172
• InChiKey: FGWNHHFXVNBHQJ-UHFFFAOYSA-N

物化性质

• 沸点：
  255.8±33.0 °C(predicted)
• 密度：
  1.238±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  56.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-甲基丙-2-烯基亚磺酸 在 三氟乙酸 作用下， 以 氯仿 为溶剂， 生成 2-丁烯
  参考文献：
  名称：

  烯丙基亚磺酸的热分解：逆向烯机理的确认

  摘要：

  三烷基锡烯丙基亚磺酸盐的酸解产生相应的亚磺酸，其经γ- syn取代进行一阶热分解，如对逆烯机理的预测。

  DOI：

  10.1039/c39930001797
• 作为产物：
  描述：

  丁-2-烯氯化镁 在 二氧化硫 作用下， 生成 1-甲基丙-2-烯基亚磺酸
  参考文献：
  名称：

  Organic reactions of sulfur dioxide. 4. A facile regiospecific hydrogen-deuterium exchange in olefins. Consequence of the intermediacy of allylic sulfinic acids in the ene reaction of sulfur dioxide with double bonds

  摘要：

  DOI：

  10.1021/ja00482a072

文献信息

• Desulfination of Allylic Sulfinic Acids: Characterization of a Retro-Ene Transition State
  作者：Stephen D. Hiscock、Neil S. Isaacs、Malcolm D. King、Rodney E. Sue、Rodney H. White、David J. Young

  DOI：10.1021/jo00127a022

  日期：1995.11

  Allylic sulfinic acids have been prepared by cleavage of trialkyltin allylic sulfinates with trifluoroacetic acid (TFA). Allylsulfinic acid prepared in this way could be trapped as the sodium salt or observed by NMR and UV spectroscopy to undergo spontaneous decomposition to propene and sulfur dioxide at ambient temperatures. The corresponding reaction of 1-methylprop-2-enylsulfinic acid was regiospecific, yielding (E)- and (Z)-2-butene (E:Z = 82:18). Acidolysis of E/Z mixtures of trimethyltin 5-methylcyclohex-2-enylsulfinate with [H-2]-TFA followed by desulfination indicated that the latter process proceeded with gamma-syn deuterium migration, consistent with a concerted, retro-ene mechanism. A detailed kinetic investigation of allylsulfinic acid desulfination supported this conclusion. This reaction obeyed a first order rate law (k(297K) = (5.5 +/- 0.1) x 10(-4) s(-1) in toluene) with a large, negative activation entropy (Delta S double dagger = -146 +/- 17 J K-1). The rate of desulfination was essentially independent of solvent. The volume profile (Delta V double dagger = -5.5 +/- 1.0 cm(3) mol(-1), Delta V = 15 +/- 5 cm(3) mol(-1)) is comparable to that of a retro Diels-Alder reaction and taken together with the above evidence and a relatively small deuterium kinetic isotope effect (k(H)/k(D) = 2.5 +/- 0.1) strongly supports a concerted desulfination, proceeding via a relatively compact, early transition state.
• Thermal decomposition of allylic sulfinic acids: confirmation of a retro-ene mechanism
  作者：Malcolm D. King、Rodney E. Sue、Rodney H. White、David J. Young

  DOI：10.1039/c39930001797

  日期：——

  The acidolysis of trialkyltin allylic sulfinates yields the corresponding sulfinic acids which undergo a first-order thermal decomposition with γ-syn substitution as predicted for a retro-ene mechanism.

  三烷基锡烯丙基亚磺酸盐的酸解产生相应的亚磺酸，其经γ- syn取代进行一阶热分解，如对逆烯机理的预测。
• Organic reactions of sulfur dioxide. 4. A facile regiospecific hydrogen-deuterium exchange in olefins. Consequence of the intermediacy of allylic sulfinic acids in the ene reaction of sulfur dioxide with double bonds
  作者：Divakar Masilamani、Milorad M. Rogic

  DOI：10.1021/ja00482a072

  日期：1978.7