甲磺酸 | 62965-22-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机次磺酸及其衍生物
• 中文名称: 甲磺酸
• 英文名称: methanesulphenic acid
• 英文别名: methanesulfenic acid；methylsulfenic acid；methylsulfanol；methylthioalcohol；Methyl sulfensaeure；Methylsulfensaeure；hydroxysulfanylmethane
• CAS: 62965-22-4
• 化学式: CH₄OS
• 分子量: 64.1082
• InChiKey: VLGWYKOEXANHJT-UHFFFAOYSA-N

物化性质

• 沸点：
  125.1±23.0 °C(Predicted)
• 密度：
  1.134±0.06 g/cm3(Predicted)
• 保留指数：
  1005

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  45.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  氯甲烷 在 HOS^(1-) 作用下， 以 gas 为溶剂， 生成 甲磺酸
  参考文献：
  名称：

  羟基硫化物阴离子HOS-的气相化学和热化学

  摘要：

  The chemistry and thermochemistry of the hydroxysulfide anion, HOS-, has been studied in a tandem flowing afterglow-selected ion flow tube (FA-SIFT). The reactions of HOS- with O2, CO, CO2, CS2, SO2, H2S, (CH3)3CSH, CH3SH, CH3Cl, and (CH3)2CHCl have been examined and compared to the corresponding reactions of HOO-. The gas-phase basicity of HOS- has been established via the bracketing technique [DELTAG(acid)0(HOSH) = 347 +/- 3 kcal mol-1, DELTAH(acid)0(HOSH) = 354 +/- 3.5 kcal mol-1]. Ab initio calculations have been carried out on HOS-, HSO-, HOSH, and H2SO which demonstrate that HOS- and HOSH are the more stable isomers. At the MP4SDTQ(FC)/6-311++G**//MP2(Full)/6-311++G** level of theory, these calculations predict DELTAH(acid)0(HOSH) = 356.7 kcal mol-1, in agreement with the experimentally determined value. Measurement of the forward and reverse rate constants for the reaction generating HOS- yields DELTAH(f)0 (HOS-) = -38.7 +/- 2 kcal mol-1, which when combined with the experimental electron affinity of HOS, determines DELTAH(f)0(HOS) = -0.5 +/- 2 kcal mol-1; this value is in good agreement with a recent ab initio determination. The gas-phase basicity of HSS-, the major product ion in the reaction of HOS- and CS2, has also been determined via the bracketing technique [DELTAG(acid)0(HSSH) = 339 +/- 3 kcal mol-1, DELTAH(acid)0(HSSH) = 346 +/- 3.5 kcal mol-1]. Combination of our gas-phase acidity values for HOSH and HSSH as well as for CH3SSH reported in a previous paper, with known electron affinities for the corresponding radicals, allows determination of the S-H bond dissociation energies (D298): HOSH (79 +/- 3.5 kcal mol-1), HSSH (76 +/- 3.5 kcal mol-1), and CH3SSH (79 +/- 3.5 kcal mol-1).

  DOI：

  10.1021/j100132a026

文献信息

• Sulfenic Acids in the Gas Phase:  A Photoelectron Study
  作者：S. Lacombe、M. Loudet、E. Banchereau、M. Simon、G. Pfister-Guillouzo

  DOI：10.1021/ja9511331

  日期：1996.1.1

  methanethiosulfinate and methyl tert-butyl sulfoxide has been studied by photoelectron (PE) spectroscopy. The electronic structure of methanesulfenic acid (1) generated from both compounds has been determined, and the thermal stability of 1 was checked. 1 appears rather stable in the gas phase, giving rise to thioformaldehyde and water at high temperature. Thermolysis of vinyl tert-butyl sulfoxide gives rise to

  已通过光电子 (PE) 光谱研究了甲基硫代亚磺酸甲酯和甲基叔丁基亚砜的热解。确定了由两种化合物生成的甲磺酸 (1) 的电子结构，并检查了 1 的热稳定性。1 在气相中显得相当稳定，在高温下会生成硫代甲醛和水。乙烯基叔丁基亚砜的热解产生乙硫醚 S-氧化物 (6)。在热解开始时，在与鉴定为亚乙基次磺酸 (4) 的化合物的混合物中观察到亚磺酸 6。这些结果意味着 4 到 6 的容易异构化，与之前的理论评估一致，或者起始亚砜的替代热解途径，直接导致亚砜 6。
• Thermolysis of Alkyl Sulfoxides and Derivatives:  A Comparison of Experiment and Theory
  作者：Jerry W. Cubbage、Yushen Guo、Ryan D. McCulla、William S. Jenks

  DOI：10.1021/jo0160625

  日期：2001.12.1

  Gas-phase activation data were obtained for model sulfoxide elimination reactions. The activation enthalpy for methyl 3-phenylpropyl sulfoxide is 32.9 +/- 0.9 kcal/mol. Elimination by methyl vinyl sulfoxide to form acetylene has an enthalpic barrier of 41.6 +/- 0.8 kcal/mol and that of 3-phenylpropyl methanesulfinate to form hydrocinnamaldehyde is 34.6 +/- 0.6 kcal/mol. Calculations at the MP2/6-311+G(3df

  获得了用于模型亚砜消除反应的气相活化数据。3-甲基苯基丙亚砜的活化焓为32.9 +/- 0.9 kcal / mol。用甲基乙烯基亚砜消除形成乙炔的焓屏障为41.6 +/- 0.8kcal / mol，而3-亚苯基丙基甲亚磺酸盐形成氢肉桂醛的焓屏障为34.6 +/- 0.6kcal / mol。对于这些反应的简化模型，在MP2 / 6-311 + G（3df，2p）// MP2 / 6-31G（d，p）级别进行的计算分别提供了32.3、40.3和32.7 kcal / mol的势垒。通过计算检查了一系列其他化合物，结果表明，除通常确定的DeltaH ++外，如果有可用的DeltaH数据，则对亚砜消除反应的取代基影响要简单得多。
• A new synthesis of thioflavones
  作者：A.W. Taylor、D.K. Dean

  DOI：10.1016/s0040-4039(00)82060-2

  日期：1988.1
• Turecek, Frantisek; Brabec, Libor; Vondrak, Tomas, Collection of Czechoslovak Chemical Communications, 1988, vol. 53, # 9, p. 2140 - 2158
  作者：Turecek, Frantisek、Brabec, Libor、Vondrak, Tomas、Hanus, Vladimir、Hajicek, Josef、Havlas, Zdenek

  DOI：——

  日期：——
• Synthesis of sulfenic acids: Flash vacuum pyrolysis of aryl and alkyl t-butyl sulfoxides
  作者：Franklin A. Davis、Steven G. Yocklovich、G.Samuel Baker

  DOI：10.1016/s0040-4039(01)85053-x

  日期：——