(2-(diphenylhydroxy)methyl-1,3-xylylene)-18-crown-5 | 156470-23-4

• 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: (2-(diphenylhydroxy)methyl-1,3-xylylene)-18-crown-5
• CAS: 156470-23-4
• 化学式: C₂₉H₃₄O₆
• 分子量: 478.585
• InChiKey: JCKGDWMAAIEHKC-UHFFFAOYSA-N

物化性质

• 沸点：
  646.0±50.0 °C(predicted)
• 密度：
  1.119±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  35.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  66.38
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2-(diphenylhydroxy)methyl-1,3-xylylene)-18-crown-5 、 碘甲烷 在 potassium hydride 作用下， 生成 (2-(1,1-diphenyl-2-oxapropyl)-1,3-xylylene)-18-crown-5
  参考文献：
  名称：

  Intra-annular reactions of the (1,3-xylylene)-18-crown-5 system: synthesis and crystal structure of [2-(bromomagnesio)-1,3-xylylene]-18-crown-5, [2-(bromomercurio)-1,3-xylylene]-18-crown-5 and bis[(1,3-xylylene-18-crown-5)-2-yl]mercury

  摘要：

  The Grignard compound [2-(bromomagnesio)-1,3-xylylene]-18-crown-5 (4) was prepared from the aryllithium compound (2-lithio-1,3-xylylene)-18-crown-5 (9) and magnesium bromide. The crystal structure of 4 shows that it crystallizes without solvent and is coordinatively saturated (distorted octahedral) by complexation of the magnesium with four of the five crown ether oxygens.The 1:1 reaction of 9 with HgBr2 yielded the corresponding organomercury compound [2-(bromomercurio)-1,3-xylylene]-18-crown-5 (10), which crystallizes without solvent. Its crystal structure reveals that intramolecular Hg-O coordination occurs with two of the five oxygens, and only weak interaction with a third crown ether oxygen. Reaction of 10 with metallic magnesium lead to the symmetric compound bis[(1,3-xylylene-18-crown-5)-2-yl]mercury (11). The centrosymmetric crystal structure of 11 shows that the mercury is intramolecularly coordinated with only four of the ten oxygens; the mercury atom is completely shielded by the crown ether rings. This shielding is probably the reason for the failure to bring about reaction of 11 with magnesium to give the corresponding diarylmagnesium compound.The crown ether Grignard 4 was treated with deuterium oxide, chlorotrimethylstannane, iodine and benzophenone to give the products (2-D-1,3-xylylene)-18-crown-5 (14a), (2-trimethylstannyl-1,3-xylylene)-18-crown-5) (15), (2-iodo-1,3-xylylene)-18-crown-5 (16) and 2-(diphenylhydroxy)methyl-1,3-xylylene)-18-crown-5 (17) (the latter being converted into its methyl ether (2-(1,1-diphenyl-2-oxapropyl)-1,3-xylylene)-18-crown-5 (17a) for identification), respectively. The lithium compound 9 was treated with benzophenone, chlorotrimethylgermane, chlorodiphenyrphosphine and 4,4'-dimethoxybenzophenone to give intra-annularly substituted crown ether derivatives 17, (2-trimethylgermyl-1,3-xylylene)-18-crown-5 (18), (2-diphenylphosphinyl-1,3-xylylene)-18-crown-5 (19) (the latter undergoing slow oxidation to (2-oxodiphenylphosphinyl-1,3-xylylene)-18-crown-5 (20)) and (2-(4,4'-dimethoxy-diphenylhydroxymethyl)-1,3-xylylene)-18-crown-5 (21) (which was converted under acidic conditions to (2-[(4-methoxyphenyl)(4'oxo-2',5'-cyclohexylidene)methyl]-1,3-xylylene)-18-crown-5 (22)), respectively.

  DOI：

  10.1016/0022-328x(93)83392-9
• 作为产物：
  描述：

  (2-lithio-1,3-xylylene)-18-crown-5 在 magnesium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 (2-(diphenylhydroxy)methyl-1,3-xylylene)-18-crown-5
  参考文献：
  名称：

  Intra-annular reactions of the (1,3-xylylene)-18-crown-5 system: synthesis and crystal structure of [2-(bromomagnesio)-1,3-xylylene]-18-crown-5, [2-(bromomercurio)-1,3-xylylene]-18-crown-5 and bis[(1,3-xylylene-18-crown-5)-2-yl]mercury

  摘要：

  The Grignard compound [2-(bromomagnesio)-1,3-xylylene]-18-crown-5 (4) was prepared from the aryllithium compound (2-lithio-1,3-xylylene)-18-crown-5 (9) and magnesium bromide. The crystal structure of 4 shows that it crystallizes without solvent and is coordinatively saturated (distorted octahedral) by complexation of the magnesium with four of the five crown ether oxygens.The 1:1 reaction of 9 with HgBr2 yielded the corresponding organomercury compound [2-(bromomercurio)-1,3-xylylene]-18-crown-5 (10), which crystallizes without solvent. Its crystal structure reveals that intramolecular Hg-O coordination occurs with two of the five oxygens, and only weak interaction with a third crown ether oxygen. Reaction of 10 with metallic magnesium lead to the symmetric compound bis[(1,3-xylylene-18-crown-5)-2-yl]mercury (11). The centrosymmetric crystal structure of 11 shows that the mercury is intramolecularly coordinated with only four of the ten oxygens; the mercury atom is completely shielded by the crown ether rings. This shielding is probably the reason for the failure to bring about reaction of 11 with magnesium to give the corresponding diarylmagnesium compound.The crown ether Grignard 4 was treated with deuterium oxide, chlorotrimethylstannane, iodine and benzophenone to give the products (2-D-1,3-xylylene)-18-crown-5 (14a), (2-trimethylstannyl-1,3-xylylene)-18-crown-5) (15), (2-iodo-1,3-xylylene)-18-crown-5 (16) and 2-(diphenylhydroxy)methyl-1,3-xylylene)-18-crown-5 (17) (the latter being converted into its methyl ether (2-(1,1-diphenyl-2-oxapropyl)-1,3-xylylene)-18-crown-5 (17a) for identification), respectively. The lithium compound 9 was treated with benzophenone, chlorotrimethylgermane, chlorodiphenyrphosphine and 4,4'-dimethoxybenzophenone to give intra-annularly substituted crown ether derivatives 17, (2-trimethylgermyl-1,3-xylylene)-18-crown-5 (18), (2-diphenylphosphinyl-1,3-xylylene)-18-crown-5 (19) (the latter undergoing slow oxidation to (2-oxodiphenylphosphinyl-1,3-xylylene)-18-crown-5 (20)) and (2-(4,4'-dimethoxy-diphenylhydroxymethyl)-1,3-xylylene)-18-crown-5 (21) (which was converted under acidic conditions to (2-[(4-methoxyphenyl)(4'oxo-2',5'-cyclohexylidene)methyl]-1,3-xylylene)-18-crown-5 (22)), respectively.

  DOI：

  10.1016/0022-328x(93)83392-9