(E)-1-<(4-chlorophenyl)seleno>-1,3-butadiene | 137008-07-2

• 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: (E)-1-<(4-chlorophenyl)seleno>-1,3-butadiene
• 英文别名: 1-[(1E)-buta-1,3-dienyl]selanyl-4-chlorobenzene
• CAS: 137008-07-2
• 化学式: C₁₀H₉ClSe
• 分子量: 243.594
• InChiKey: SFWIMAOAKQIAEZ-FPYGCLRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.37
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  N-<(p-chlorophenyl)seleno>phthalimide 、 alkaline earth salt of/the/ methylsulfuric acid 以 甲苯 为溶剂， 反应 0.08h， 以88%的产率得到(E)-1-<(4-chlorophenyl)seleno>-1,3-butadiene
  参考文献：
  名称：

  Preparation and isomerization of 1-phenylseleno 1,3-dienes

  摘要：

  The preparation of a series of 1-phenylseleno 1,3-dienes is described starting from enyne derivatives via a hydrozirconation/transfer sequence. Hydrozirconation of a series of conjugated enynes having the general formula HC = CCR1 = CR2R3 (3a: R1 = R2 = R3 = H; 3b: R1 = R3 = H, R2 = OMe; 3c: R1 = R2 = H, R3 = OMe; 3d: R1 = R2 = -(CH2)4-, R3 = H) leads to the formation of zirconium dienyls of the formula (eta-5-C5H5)2Zr(Cl)-CH = CHCR1 = CR2R3, 4a-d, respectively; this reaction is both completely stereoselective and chemoselective. Use of the deuterium-substituted reagent (eta-5-C5H5)2Zr(D)Cl generates the corresponding isotopomers (eta-5-C5H5)2Zr(Cl)-CH = CDCR1 = CR2R3, 4a-d-d1. Addition of PhSeX (X = SePh, Cl, or N-phthalimido) to the zirconium dienyl derivatives 4a-d at low temperature (-20-degrees-C) and in the dark results in the formation of the 1-phenylseleno 1,3-dienes (PhSeCH = CHCR1 = CR2R3 (5a: R1 = R2 = R3 = H; 5b: R1 = R3 = H, R2 = OMe; 5c: R1 = R2 = H, R3 = OMe; 5d: R1 = R2 = -(CH2)4-, R3 = H). This transfer of the dienyl unit from zirconium to selenium proceeds with complete stereoselectivity and with retention of configuration at the 1-position as long as light is excluded and the reaction is carried out at low temperatures. In the presence of room light (fluorescent), mixtures of stereoisomers are obtained for the seleno dienes 5a-c; no apparent isomerization is observed for 5d; similar results are obtained upon thermolysis (80-degrees-C for 24-48 h). The mechanism of this isomerization process was determined to be intermolecular on the basis of crossover experiments; in addition, the use of radical traps established that the process was a radical chain mechanism, probably via addition of PhSe. to the seleno diene followed by single-bond rotation.

  DOI：

  10.1021/jo00026a006

文献信息

• Preparation and isomerization of 1-phenylseleno 1,3-dienes
  作者：Michael D. Fryzuk、Gordon S. Bates、Charles Stone

  DOI：10.1021/jo00026a006

  日期：1991.12

  The preparation of a series of 1-phenylseleno 1,3-dienes is described starting from enyne derivatives via a hydrozirconation/transfer sequence. Hydrozirconation of a series of conjugated enynes having the general formula HC = CCR1 = CR2R3 (3a: R1 = R2 = R3 = H; 3b: R1 = R3 = H, R2 = OMe; 3c: R1 = R2 = H, R3 = OMe; 3d: R1 = R2 = -(CH2)4-, R3 = H) leads to the formation of zirconium dienyls of the formula (eta-5-C5H5)2Zr(Cl)-CH = CHCR1 = CR2R3, 4a-d, respectively; this reaction is both completely stereoselective and chemoselective. Use of the deuterium-substituted reagent (eta-5-C5H5)2Zr(D)Cl generates the corresponding isotopomers (eta-5-C5H5)2Zr(Cl)-CH = CDCR1 = CR2R3, 4a-d-d1. Addition of PhSeX (X = SePh, Cl, or N-phthalimido) to the zirconium dienyl derivatives 4a-d at low temperature (-20-degrees-C) and in the dark results in the formation of the 1-phenylseleno 1,3-dienes (PhSeCH = CHCR1 = CR2R3 (5a: R1 = R2 = R3 = H; 5b: R1 = R3 = H, R2 = OMe; 5c: R1 = R2 = H, R3 = OMe; 5d: R1 = R2 = -(CH2)4-, R3 = H). This transfer of the dienyl unit from zirconium to selenium proceeds with complete stereoselectivity and with retention of configuration at the 1-position as long as light is excluded and the reaction is carried out at low temperatures. In the presence of room light (fluorescent), mixtures of stereoisomers are obtained for the seleno dienes 5a-c; no apparent isomerization is observed for 5d; similar results are obtained upon thermolysis (80-degrees-C for 24-48 h). The mechanism of this isomerization process was determined to be intermolecular on the basis of crossover experiments; in addition, the use of radical traps established that the process was a radical chain mechanism, probably via addition of PhSe. to the seleno diene followed by single-bond rotation.