methyl 2-methylpropane-1-sulfinate | 56909-12-7

• 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
• 英文名称: methyl 2-methylpropane-1-sulfinate
• 英文别名: 2-Methyl-1-propanesulfinic acid methyl ester
• CAS: 56909-12-7
• 化学式: C₅H₁₂O₂S
• 分子量: 136.215
• InChiKey: CXACAGZBDYTWAR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  8
• 可旋转键数：
  3
• 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：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-methylpropane-1-sulfinate 、 N,N-二乙基苯胺 在 aluminum (III) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 37.0h， 以63%的产率得到N,N-diethyl-4-(isobutylsulfinyl)aniline
  参考文献：
  名称：

  Methyl Sulfinates as Electrophiles in Friedel–Crafts Reactions. Synthesis of Aryl Sulfoxides

  摘要：

  The Friedel-Crafts reaction of methyl alkyl-and arylsulfinates with aromatic systems, activated by one or more electron-donating substituents (OH, OMe, NFIR, NR2), provides alkyl aryl and diaryl sulfoxides under mild conditions and in moderate to good yields. The very high regioselectivity usually observed in these sulfinylation reactions is rationalized on the basis of a Wheland intermediate having a trigonal bypyramidal structure in which steric and electronic interactions are significant factors strongly destabilizing the attack to the ortho positions.

  DOI：

  10.1021/jo2006335
• 作为产物：
  描述：

  甲醇 、 异丁硫醇 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以88%的产率得到methyl 2-methylpropane-1-sulfinate
  参考文献：
  名称：

  烷基亚磺酸盐：用于合成 TosMIC 类似物的正式亲核试剂

  摘要：

  烷基亚磺酸盐在曼尼希型反应中用作正式的亲核试剂，生成磺酰甲酰胺，后者很容易脱水成相应的磺酰甲基异腈。高效的两步合成为从容易获得的亚磺酸甲酯或硫醇制备磺酰甲基异腈提供了一条通用途径。机理分析表明，烷基亚磺酸盐的异常亲核性源于亚磺酸的原位释放。

  DOI：

  10.1002/ejoc.201403615

文献信息

• Mild and General Method for the Synthesis of Sulfonamides
  作者：José García Ruano、Francisco Yuste、Alejandro Parra、Virginia Mastranzo

  DOI：10.1055/s-2007-1000850

  日期：2008.1

  lowed by 3-chloroperoxybenzoic acid oxidation of the resulting sul- finamides provides primary, secondary, and tertiary alkane-, arene- and heteroarenesulfonamides in high yields. This constitutes a mild and facile experimental protocol that avoids the use of hazardous, unstable, or volatile reagents and does not affect the configurational stability of the amines

  亚磺酸甲酯与氨基化锂反应，然后对生成的亚磺酰胺进行 3-氯过氧苯甲酸氧化，以高收率提供伯、仲和叔烷烃、芳烃和杂芳烃磺酰胺。这构成了一个温和而简便的实验方案，避免使用危险、不稳定或易挥发的试剂，并且不影响胺的构型稳定性
• Oxidation of organic sulphides—XV
  作者：R. Curci、G. Modena

  DOI：10.1016/s0040-4020(01)99414-1

  日期：1966.1

  The oxidation of highly branched penyl-alkyl and di-alkyl sulphoxides shows that in the alkaline oxidation steric hindrance has a more pronounced influence than in acidic oxidation, even if the steric effects are not very large. On the basis of these and previous results some suggestions on the geometry of the transition state of the alkaline oxidation are advanced.

  高度支化的戊基亚烷基和二烷基亚砜的氧化表明，在碱性氧化中，即使位阻作用不是很大，位阻也比在酸性氧化中具有更显着的影响。基于这些和先前的结果，提出了关于碱性氧化的过渡态的几何构型的一些建议。
• Methyl Sulfinates as Electrophiles in Friedel–Crafts Reactions. Synthesis of Aryl Sulfoxides
  作者：Francisco Yuste、Angélica Hernández Linares、Virginia M. Mastranzo、Benjamín Ortiz、Rubén Sánchez-Obregón、Alberto Fraile、José Luis García Ruano

  DOI：10.1021/jo2006335

  日期：2011.6.3

  The Friedel-Crafts reaction of methyl alkyl-and arylsulfinates with aromatic systems, activated by one or more electron-donating substituents (OH, OMe, NFIR, NR2), provides alkyl aryl and diaryl sulfoxides under mild conditions and in moderate to good yields. The very high regioselectivity usually observed in these sulfinylation reactions is rationalized on the basis of a Wheland intermediate having a trigonal bypyramidal structure in which steric and electronic interactions are significant factors strongly destabilizing the attack to the ortho positions.
• Alkyl Sulfinates: Formal Nucleophiles for Synthesizing TosMIC Analogs
  作者：J. Armando Lujan-Montelongo、Angel Ojeda Estevez、Fraser F. Fleming

  DOI：10.1002/ejoc.201403615

  日期：2015.3

  Alkyl sulfinates function as formal nucleophiles in Mannich-type reactions to give sulfonyl formamides, which are readily dehydrated to the corresponding sulfonylmethyl isonitriles. The efficient, two-step synthesis provides a general route to sulfonylmethyl isonitriles from readily available methyl sulfinates or thiols. Mechanistic analysis reveals that the unusual nucleophlicity of the alkyl sulfinates

  烷基亚磺酸盐在曼尼希型反应中用作正式的亲核试剂，生成磺酰甲酰胺，后者很容易脱水成相应的磺酰甲基异腈。高效的两步合成为从容易获得的亚磺酸甲酯或硫醇制备磺酰甲基异腈提供了一条通用途径。机理分析表明，烷基亚磺酸盐的异常亲核性源于亚磺酸的原位释放。