1,1-dimethylbenzyl p-tolyl sulfoxide | 187862-49-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,1-dimethylbenzyl p-tolyl sulfoxide
• 英文别名: 1-Methyl-4-(2-phenylpropan-2-ylsulfinyl)benzene
• CAS: 187862-49-3
• 化学式: C₁₆H₁₈OS
• 分子量: 258.384
• InChiKey: VFOQEZXULYNPSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,1-dimethylbenzyl p-tolyl sulfoxide 以 叔丁醇 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  Photolysis of Alkyl Aryl Sulfoxides:  α-Cleavage, Hydrogen Abstraction, and Racemization¹

  摘要：

  The photochemistry of a series of alkyl aryl sulfoxides is described. The initial event of the photolysis process is homolytic cleavage to form sulfinyl/alkyl radical pairs. The radical pair partitions between recombination to starting material, formation of sulfenic esters, disproportionation to an olefin and benzenesulfenic acid, and formation of typical radical escape products. The quantum yield for conversion depends on the structure or the reactivity of the alkyl radical, with the sequence benzyl > tertiary alkyl > secondary alkyl > primary alkyl > (di)aryl. The high racemization efficiency of some aryl primary-alkyl sulfoxides suggests that another nonradical pathway for the photoracemization process may exist. Product analysis does not support any hydrogen abstraction pathways.

  DOI：

  10.1021/jo961775m
• 作为产物：
  描述：

  (2-phenylpropan-2-yl)(p-tolyl)sulfane 在 尿素 作用下， 以87%的产率得到1,1-dimethylbenzyl p-tolyl sulfoxide
  参考文献：
  名称：

  Photolysis of Alkyl Aryl Sulfoxides:  α-Cleavage, Hydrogen Abstraction, and Racemization¹

  摘要：

  The photochemistry of a series of alkyl aryl sulfoxides is described. The initial event of the photolysis process is homolytic cleavage to form sulfinyl/alkyl radical pairs. The radical pair partitions between recombination to starting material, formation of sulfenic esters, disproportionation to an olefin and benzenesulfenic acid, and formation of typical radical escape products. The quantum yield for conversion depends on the structure or the reactivity of the alkyl radical, with the sequence benzyl > tertiary alkyl > secondary alkyl > primary alkyl > (di)aryl. The high racemization efficiency of some aryl primary-alkyl sulfoxides suggests that another nonradical pathway for the photoracemization process may exist. Product analysis does not support any hydrogen abstraction pathways.

  DOI：

  10.1021/jo961775m

文献信息

• Electron Transfer Mechanism in the Oxidation of Aryl 1-Methyl-1-phenylethyl Sulfides Promoted by Nonheme Iron(IV)–Oxo Complexes: The Rate of the Oxygen Rebound Process
  作者：Alessia Barbieri、Tiziana Del Giacco、Stefano Di Stefano、Osvaldo Lanzalunga、Andrea Lapi、Marco Mazzonna、Giorgio Olivo

  DOI：10.1021/acs.joc.6b02434

  日期：2016.12.16

  The oxidation of aryl 1-methyl-1-phenylethyl sulfides promoted by the nonheme iron(IV)–oxo complexes [(N4Py)FeIV═O]2+ and [(Bn-TPEN)FeIV═O]2+ occurs by an electron transfer–oxygen rebound (ET–OT) mechanism leading to aryl 1-methyl-1-phenylethyl sulfoxides accompanied by products derived from Cα–S fragmentation of sulfide radical cations (2-phenyl-2-propanol and diaryl disulfides). For the first time

  芳基1-甲基-1-苯乙基硫化物的由非血红素铁促进氧化（IV） -氧代配合物[（N4Py）的Fe IV = O] 2+和[（BN-TPEN）的Fe IV = O] 2+发生由电子转移-氧反弹（ET-OT）机理，导致芳基1-甲基-1-苯基乙基亚砜与硫化物自由基阳离子的Cα-S片段化衍生的产物（2-苯基-2-丙醇和二芳基二硫化物）伴随产生。氧回弹过程的速率常数（k OT）首次从自由基阳离子的裂解速率常数（<0.8×10 4到3.5×10 4 s –1）确定。k f）和S氧化/碎片产物的比率。