[3-chloro-4-(phenylthio)butyl]trimethylsilane | 105261-51-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: [3-chloro-4-(phenylthio)butyl]trimethylsilane
• 英文别名: (3-Chloro-4-phenylsulfanylbutyl)-trimethylsilane
• CAS: 105261-51-6
• 化学式: C₁₃H₂₁ClSSi
• 分子量: 272.914
• InChiKey: NKLXZVWYLSRVPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [3-chloro-4-(phenylthio)butyl]trimethylsilane 在 氢氧化钾 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 3.5h， 生成 trans-1-(phenylsulfonyl)-4-(trimethylsilyl)-1-butene
  参考文献：
  名称：

  (E)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene:  An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion

  摘要：

  The (E)-1-(arylsulfonyl)-4-(trimethylsilyl)-1-butenes 9, 25, and 26 are prepared by CuCl2-promoted and by photolytic additions of their precursor l-arylsulfonyl chlorides and bromides to 4-(trimethylsilyl)-1-butene (14) and then dehydrohalogenation of the resulting 1-(arylsulfonyl)-2-halo-4-(trimethylsilyl)butanes 15a, 15b, 23a, and 23b with KOH, LDA, or n-BuLi. Silylbutene 14 is obtained from reaction of [(trimethylsilyl)methyl]magnesium chloride (16, X = Cl) and allyl bromide (17) and better by protiodesilylations of (E)- and (Z)-1,4-bis(trimethylsilyl)-2-butenes (20) with sulfuric or trifluoroacetic acids. (Arylsulfonyl)(trimethylsilyl)-1-butenes 9, 25, and 26 are converted efficiently by LDA or n-BuLi at -78 degrees C to 1-(arylsulfonyl)-1-lithio-4-(trimethylsilyl)-1-butenes 10, 27a, and 27b, respectively. Reactions of 27a and 27b with deuterium oxide yield (E)-1-(4-chlorophenylsulfonyl)-1-deuterio-4-(trimethylsilyl)-1-butene (28a, 83%) and (E)-1-deuterio-1-(4-methylphenylsulfonyl)-4-(trimethylsilyl) 1-butene(28b, 89%), respectively. 1-Lithio derivatives 10, 27a, and 27b undergo benzylations by benzyl bromide in THF/HMPA with retention of the positions of their olefinic double bonds to give the (E)-2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-2-pentenes 29a, 29b, and 29c, respectively, in 84-90% yields. Of particular interest is that asa-care isomerized to their corresponding 2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-3-pentenes 30a-c, respectively, which then undergo conjugative eliminations df their arylsulfonyl and their trimethylsilyl groups to give (E)-5-phenyl-1,3-pentadiene (33) in 56-63% yields upon reactions with TBAF in THF at 25 degrees C. Further, 27b reacts with 1,3-dichloropropane to form 1-chloro-4-(4-methylphenylsulfonyl)-7-(trimethylsilyl)-4-heptene (35) which is cyclized by n-BuLi to 1-(4-methylphenylsulfonyl)-l-(3-(trimethylsilyl)-1-propenyl) (37, 67%). Elimination of 37 by TBAF then gives allylenecyclobutane (34, n = 3, 84%) simply. This study thus reveals that 8, 25, and 26 have outstanding potential as 1-(1,3-butadienyl) anion (7) and 1,1-(1,3-butadienyl) dianion (8) synthons.

  DOI：

  10.1021/jo970546c
• 作为产物：
  描述：

  (E)-2,2,7,7-四甲基-2,7-二硅杂辛-4-烯 在 硫酸 、 copper dichloride 作用下， 以 正戊烷 为溶剂， 反应 11.5h， 生成 [3-chloro-4-(phenylthio)butyl]trimethylsilane
  参考文献：
  名称：

  (E)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene:  An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion

  摘要：

  The (E)-1-(arylsulfonyl)-4-(trimethylsilyl)-1-butenes 9, 25, and 26 are prepared by CuCl2-promoted and by photolytic additions of their precursor l-arylsulfonyl chlorides and bromides to 4-(trimethylsilyl)-1-butene (14) and then dehydrohalogenation of the resulting 1-(arylsulfonyl)-2-halo-4-(trimethylsilyl)butanes 15a, 15b, 23a, and 23b with KOH, LDA, or n-BuLi. Silylbutene 14 is obtained from reaction of [(trimethylsilyl)methyl]magnesium chloride (16, X = Cl) and allyl bromide (17) and better by protiodesilylations of (E)- and (Z)-1,4-bis(trimethylsilyl)-2-butenes (20) with sulfuric or trifluoroacetic acids. (Arylsulfonyl)(trimethylsilyl)-1-butenes 9, 25, and 26 are converted efficiently by LDA or n-BuLi at -78 degrees C to 1-(arylsulfonyl)-1-lithio-4-(trimethylsilyl)-1-butenes 10, 27a, and 27b, respectively. Reactions of 27a and 27b with deuterium oxide yield (E)-1-(4-chlorophenylsulfonyl)-1-deuterio-4-(trimethylsilyl)-1-butene (28a, 83%) and (E)-1-deuterio-1-(4-methylphenylsulfonyl)-4-(trimethylsilyl) 1-butene(28b, 89%), respectively. 1-Lithio derivatives 10, 27a, and 27b undergo benzylations by benzyl bromide in THF/HMPA with retention of the positions of their olefinic double bonds to give the (E)-2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-2-pentenes 29a, 29b, and 29c, respectively, in 84-90% yields. Of particular interest is that asa-care isomerized to their corresponding 2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-3-pentenes 30a-c, respectively, which then undergo conjugative eliminations df their arylsulfonyl and their trimethylsilyl groups to give (E)-5-phenyl-1,3-pentadiene (33) in 56-63% yields upon reactions with TBAF in THF at 25 degrees C. Further, 27b reacts with 1,3-dichloropropane to form 1-chloro-4-(4-methylphenylsulfonyl)-7-(trimethylsilyl)-4-heptene (35) which is cyclized by n-BuLi to 1-(4-methylphenylsulfonyl)-l-(3-(trimethylsilyl)-1-propenyl) (37, 67%). Elimination of 37 by TBAF then gives allylenecyclobutane (34, n = 3, 84%) simply. This study thus reveals that 8, 25, and 26 have outstanding potential as 1-(1,3-butadienyl) anion (7) and 1,1-(1,3-butadienyl) dianion (8) synthons.

  DOI：

  10.1021/jo970546c

文献信息

• Kutyrev, G. A.; Kapura, A. A.; Cherkasov, R. A., Journal of general chemistry of the USSR, 1985, vol. 55, p. 1919 - 1930
  作者：Kutyrev, G. A.、Kapura, A. A.、Cherkasov, R. A.、Pudovik, A. N.

  DOI：——

  日期：——
• KUTYREV, G. A.;KAPURA, A. A.;CHERKASOV, R. A.;PUDOVIK, A. N., ZH. OBSHCH. XIMII, 1985, 55, N 10, 2162-2175
  作者：KUTYREV, G. A.、KAPURA, A. A.、CHERKASOV, R. A.、PUDOVIK, A. N.

  DOI：——

  日期：——
• (<i>E</i>)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene:  An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion
  作者：Timothy P. Meagher、Harold Shechter

  DOI：10.1021/jo970546c

  日期：1998.6.1

  The (E)-1-(arylsulfonyl)-4-(trimethylsilyl)-1-butenes 9, 25, and 26 are prepared by CuCl2-promoted and by photolytic additions of their precursor l-arylsulfonyl chlorides and bromides to 4-(trimethylsilyl)-1-butene (14) and then dehydrohalogenation of the resulting 1-(arylsulfonyl)-2-halo-4-(trimethylsilyl)butanes 15a, 15b, 23a, and 23b with KOH, LDA, or n-BuLi. Silylbutene 14 is obtained from reaction of [(trimethylsilyl)methyl]magnesium chloride (16, X = Cl) and allyl bromide (17) and better by protiodesilylations of (E)- and (Z)-1,4-bis(trimethylsilyl)-2-butenes (20) with sulfuric or trifluoroacetic acids. (Arylsulfonyl)(trimethylsilyl)-1-butenes 9, 25, and 26 are converted efficiently by LDA or n-BuLi at -78 degrees C to 1-(arylsulfonyl)-1-lithio-4-(trimethylsilyl)-1-butenes 10, 27a, and 27b, respectively. Reactions of 27a and 27b with deuterium oxide yield (E)-1-(4-chlorophenylsulfonyl)-1-deuterio-4-(trimethylsilyl)-1-butene (28a, 83%) and (E)-1-deuterio-1-(4-methylphenylsulfonyl)-4-(trimethylsilyl) 1-butene(28b, 89%), respectively. 1-Lithio derivatives 10, 27a, and 27b undergo benzylations by benzyl bromide in THF/HMPA with retention of the positions of their olefinic double bonds to give the (E)-2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-2-pentenes 29a, 29b, and 29c, respectively, in 84-90% yields. Of particular interest is that asa-care isomerized to their corresponding 2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-3-pentenes 30a-c, respectively, which then undergo conjugative eliminations df their arylsulfonyl and their trimethylsilyl groups to give (E)-5-phenyl-1,3-pentadiene (33) in 56-63% yields upon reactions with TBAF in THF at 25 degrees C. Further, 27b reacts with 1,3-dichloropropane to form 1-chloro-4-(4-methylphenylsulfonyl)-7-(trimethylsilyl)-4-heptene (35) which is cyclized by n-BuLi to 1-(4-methylphenylsulfonyl)-l-(3-(trimethylsilyl)-1-propenyl) (37, 67%). Elimination of 37 by TBAF then gives allylenecyclobutane (34, n = 3, 84%) simply. This study thus reveals that 8, 25, and 26 have outstanding potential as 1-(1,3-butadienyl) anion (7) and 1,1-(1,3-butadienyl) dianion (8) synthons.