8-bromo-1-(p-chlorophenylselanyl)naphthalene | 399509-40-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 8-bromo-1-(p-chlorophenylselanyl)naphthalene
• 英文别名: Naphthalene, 1-bromo-8-[(4-chlorophenyl)seleno]-；1-bromo-8-(4-chlorophenyl)selanylnaphthalene
• CAS: 399509-40-1
• 化学式: C₁₆H₁₀BrClSe
• 分子量: 396.572
• InChiKey: BIAZDEDAOSVYMN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• 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：

  1,2-bis(4-bromophenyl)diselenide 在 magnesium 作用下， 以 乙醚 为溶剂， 生成 8-bromo-1-(p-chlorophenylselanyl)naphthalene
  参考文献：
  名称：

  Structure of 1-(Arylselanyl)naphthalenes. 2. G Dependence in 8-G-1-(p-YC₆H₄Se)C₁₀H₆

  摘要：

  The structures of 8-G-1-(p-YC6H4Se)C10H6 (1 (G = Cl) and 2 (G = Br): Y = H (a), OMe (b), Me (c), Cl (d), Br (e), COOEt (f), and NO2 (9)) were investigated by X-ray crystallographic analysis, NMR spectroscopy, and ab initio MO calculations. The structures of all members in I and 2 are concluded to be type B, which is in striking contrast to the type A structure for 4d-g (4 (g(n)), where G = H). The Se-C-i bond of the p-YC6H4Se group in 8-G-1-(P-YC6H4Se)C10H6 is almost perpendicular to the naphthyl plane in type A, and it is located on the plane in type B. The chlorine and bromine substitution at the 8-position in I and 2 dramatically changes the type A structure of 4 (g(n)) to type B. The nonbonded G---Se-C 3c-4e type interaction must contribute to stabilize the type B structure. The type B structure in 1 and 2 should also be more stabilized than the same structure in 4 by the 3c-4e type interaction: The structure of 4b is type B in the crystals and type B would be more stable for 4c and might be for 4a in solutions. Ab initio MO calculations are performed on 8-G-1-(p-YC6H4Se)C10H6, 8-G-C10H6SeH-1, and models HG---SeH2, where G = Cl, Br, and F, to clarify the reason for the dramatic change in the structures. The type B structure is optimized to be more stable than the type A for all species examined, which supports the observations. The energy differences between type B and type A are larger for the models than for the naphthalenes. While the superiority of the type B for the former is Br > Cl much greater than F, that of the latter is Br approximate to Cl greater than or equal to F. These results show that the main factor of the structural change from type A to type B is the nonbonded G---Se-C 3c-4e interaction. The electronic effect of halogens through the naphthalene pi-framework would also contribute to some extent, although the direct comparison of the evaluated values between the naphthalene systems and the models is not so easy. Factors to stabilize the two structures of 1, 2, 4, and 8-(MeSe)-1-(P-YC6H4Se)C10H6 are reexamined from a viewpoint of the nonbonded G---Se-C 3c-4e interaction (G dependence), together with the electronic effect of Y (Y dependence).

  DOI：

  10.1021/jo010380m

文献信息

• Structure of 1-(Arylselanyl)naphthalenes. 2. G Dependence in 8-G-1-(<i>p</i>-YC₆H₄Se)C₁₀H₆
  作者：Warô Nakanishi、Satoko Hayashi

  DOI：10.1021/jo010380m

  日期：2002.1.1

  The structures of 8-G-1-(p-YC6H4Se)C10H6 (1 (G = Cl) and 2 (G = Br): Y = H (a), OMe (b), Me (c), Cl (d), Br (e), COOEt (f), and NO2 (9)) were investigated by X-ray crystallographic analysis, NMR spectroscopy, and ab initio MO calculations. The structures of all members in I and 2 are concluded to be type B, which is in striking contrast to the type A structure for 4d-g (4 (g(n)), where G = H). The Se-C-i bond of the p-YC6H4Se group in 8-G-1-(P-YC6H4Se)C10H6 is almost perpendicular to the naphthyl plane in type A, and it is located on the plane in type B. The chlorine and bromine substitution at the 8-position in I and 2 dramatically changes the type A structure of 4 (g(n)) to type B. The nonbonded G---Se-C 3c-4e type interaction must contribute to stabilize the type B structure. The type B structure in 1 and 2 should also be more stabilized than the same structure in 4 by the 3c-4e type interaction: The structure of 4b is type B in the crystals and type B would be more stable for 4c and might be for 4a in solutions. Ab initio MO calculations are performed on 8-G-1-(p-YC6H4Se)C10H6, 8-G-C10H6SeH-1, and models HG---SeH2, where G = Cl, Br, and F, to clarify the reason for the dramatic change in the structures. The type B structure is optimized to be more stable than the type A for all species examined, which supports the observations. The energy differences between type B and type A are larger for the models than for the naphthalenes. While the superiority of the type B for the former is Br > Cl much greater than F, that of the latter is Br approximate to Cl greater than or equal to F. These results show that the main factor of the structural change from type A to type B is the nonbonded G---Se-C 3c-4e interaction. The electronic effect of halogens through the naphthalene pi-framework would also contribute to some extent, although the direct comparison of the evaluated values between the naphthalene systems and the models is not so easy. Factors to stabilize the two structures of 1, 2, 4, and 8-(MeSe)-1-(P-YC6H4Se)C10H6 are reexamined from a viewpoint of the nonbonded G---Se-C 3c-4e interaction (G dependence), together with the electronic effect of Y (Y dependence).