1-[2-Bromo-4-(tert-butyl-dimethyl-silanyloxy)-3,5,6-trimethyl-phenylsulfanyl]-2-methyl-propan-2-ol | 205182-89-4

• 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-[2-Bromo-4-(tert-butyl-dimethyl-silanyloxy)-3,5,6-trimethyl-phenylsulfanyl]-2-methyl-propan-2-ol
• 英文别名: 1-[2-Bromo-4-[tert-butyl(dimethyl)silyl]oxy-3,5,6-trimethylphenyl]sulfanyl-2-methylpropan-2-ol
• CAS: 205182-89-4
• 化学式: C₁₉H₃₃BrO₂SSi
• 分子量: 433.525
• InChiKey: HDYRWRJDZCGQRK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.62
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  54.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-[2-Bromo-4-(tert-butyl-dimethyl-silanyloxy)-3,5,6-trimethyl-phenylsulfanyl]-2-methyl-propan-2-ol 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以68%的产率得到[3-Bromo-2,5,6-trimethyl-4-(2-methyl-allylsulfanyl)-phenoxy]-tert-butyl-dimethyl-silane
  参考文献：
  名称：

  Novel Antioxidants:  Unexpected Rearrangements in the Radical Cyclization Approach to 2,3-Dihydrobenzo[b]thiophene-5-ol Derivatives

  摘要：

  The novel alpha-tocopherol analogue 3,3,4,6,7-pentamethyl-2,3-dihydrobenzo[b]thiophene-5-ol (4a) was prepared by cyclodehydration of the aryl 2-hydroxyalkyl sulfide 6 in concentrated sulfuric acid. Aromatic bromination and dehydration of alcohol 6 furnished the 2-bromoaryl methallyl sulfide 10a as the kinetic product and the 2-bromoaryl 2-methyl-2-propenyl sulfide 11a as the thermodynamic one. Radical cyclization of these compounds afforded the desired 2,3-dihydrobenzo[b]thiophene derivative 12 in addition to a rearranged isomer 13 thereof. It is proposed that the transformation of compound 10a to 13 occurs via 6-endo cyclization, beta-scission, and subsequent 5-exo cyclization. The radical cyclization of the 2-bromoaryl allyl sulfide 16, unsubstituted in the allylic moiety, furnished only 2,3-dihydrobenzo[b]thiophene-5-ol derivative 17.

  DOI：

  10.1021/jo972087l
• 作为产物：
  描述：

  [3-Bromo-4-(2-bromo-2-methyl-propylsulfanyl)-2,5,6-trimethyl-phenoxy]-tert-butyl-dimethyl-silane 在 三乙胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 2.5h， 生成 1-[2-Bromo-4-(tert-butyl-dimethyl-silanyloxy)-3,5,6-trimethyl-phenylsulfanyl]-2-methyl-propan-2-ol
  参考文献：
  名称：

  Novel Antioxidants:  Unexpected Rearrangements in the Radical Cyclization Approach to 2,3-Dihydrobenzo[b]thiophene-5-ol Derivatives

  摘要：

  The novel alpha-tocopherol analogue 3,3,4,6,7-pentamethyl-2,3-dihydrobenzo[b]thiophene-5-ol (4a) was prepared by cyclodehydration of the aryl 2-hydroxyalkyl sulfide 6 in concentrated sulfuric acid. Aromatic bromination and dehydration of alcohol 6 furnished the 2-bromoaryl methallyl sulfide 10a as the kinetic product and the 2-bromoaryl 2-methyl-2-propenyl sulfide 11a as the thermodynamic one. Radical cyclization of these compounds afforded the desired 2,3-dihydrobenzo[b]thiophene derivative 12 in addition to a rearranged isomer 13 thereof. It is proposed that the transformation of compound 10a to 13 occurs via 6-endo cyclization, beta-scission, and subsequent 5-exo cyclization. The radical cyclization of the 2-bromoaryl allyl sulfide 16, unsubstituted in the allylic moiety, furnished only 2,3-dihydrobenzo[b]thiophene-5-ol derivative 17.

  DOI：

  10.1021/jo972087l

文献信息

• Novel Antioxidants:  Unexpected Rearrangements in the Radical Cyclization Approach to 2,3-Dihydrobenzo[<i>b</i>]thiophene-5-ol Derivatives
  作者：Jonas Malmström、Vijay Gupta、Lars Engman

  DOI：10.1021/jo972087l

  日期：1998.5.1

  The novel alpha-tocopherol analogue 3,3,4,6,7-pentamethyl-2,3-dihydrobenzo[b]thiophene-5-ol (4a) was prepared by cyclodehydration of the aryl 2-hydroxyalkyl sulfide 6 in concentrated sulfuric acid. Aromatic bromination and dehydration of alcohol 6 furnished the 2-bromoaryl methallyl sulfide 10a as the kinetic product and the 2-bromoaryl 2-methyl-2-propenyl sulfide 11a as the thermodynamic one. Radical cyclization of these compounds afforded the desired 2,3-dihydrobenzo[b]thiophene derivative 12 in addition to a rearranged isomer 13 thereof. It is proposed that the transformation of compound 10a to 13 occurs via 6-endo cyclization, beta-scission, and subsequent 5-exo cyclization. The radical cyclization of the 2-bromoaryl allyl sulfide 16, unsubstituted in the allylic moiety, furnished only 2,3-dihydrobenzo[b]thiophene-5-ol derivative 17.