2,3,5,6-tetraphenyl-1,1,4,4-tetrakis(dimethylamino)-1,4-disila cyclohexa-2,5-diene | 261907-35-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,3,5,6-tetraphenyl-1,1,4,4-tetrakis(dimethylamino)-1,4-disila cyclohexa-2,5-diene
• 英文别名: 1-N,1-N,1-N',1-N',4-N,4-N,4-N',4-N'-octamethyl-2,3,5,6-tetraphenyl-1,4-disiline-1,1,4,4-tetramine
• CAS: 261907-35-1
• 化学式: C₃₆H₄₄N₄Si₂
• 分子量: 588.943
• InChiKey: RZCRNTOMAJNNCP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.51
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,3,5,6-tetraphenyl-1,1,4,4-tetrakis(dimethylamino)-1,4-disila cyclohexa-2,5-diene 在 溴化硅(IV) 作用下， 以 乙醚 为溶剂， 以95%的产率得到2,3,5,6-tetraphenyl-1,1,4,4-tetrabromo-1,4-disilacyclohexa-2,5-diene
  参考文献：
  名称：

  Synthesis of 1,4-disilacyclohexa-2,5-dienes

  摘要：

  Title Compounds of the type 2,3,5,6-tetraphenyl-1,4-di-X-1,4-di-Y-1,4-disilacyclohexa-2,5-diene wherein X = Y = NMe2 (4): X NMe2. Y = Cl (cis, trans-5) X = NMe2, Y = Me [(trans)-6] and X = t-Bu. Y = Cl (trans-8) were synthesized from Si-2(NMe2)(5)Cl, sym-Si-2(NMe2)(4)Cl-2, sym-Si-2(NMe2)(4)Me-2, and sym-Si2Cl4(t-Bu)2, respectively. in the presence of diphenylacetylene at 200 degreesC. Similarly the analogous title compound from the combination of 1-phenyl-1-propyne and Si-2(NMe2)(5)Cl [X = Y = NMe2 (cis and trans-7) was synthesized. In all cases where cis/trans diastereomers could arise from two different silicon substituents (5, 6 8) the trans isomer was the sole or dominant product. Evidence for the intermediacy of the silylene Si(NMe2)(2) in these reactions was gained from a trapping experiment. Compound 4 upon treatment with SiCl4 SiBr4 or PI3 provided the corresponding 1,1,4,4-tetrahalo derivatives 9a-c, respectively. Treatment of 4 with MeOH or PhOH gave the 1.1.4.4-tetramethoxy and tetraphenoxy analogues 9d and 9e, respectively. The tetrachloro derivative 9a upon LAH reduction led to the corresponding tetrahydro compound 10. while the reaction of 9a with H2O gave the tetrahydroxy derivative 11. Allowing (trans)-6 to react with SiCl4 provided a ca. 1:1 cis/trans ratio of the derivative 12 in which X = Cl. Y = Me. and possible pathways that rationalize this loss of stereochemistry are proposed. Synthesis of trans-13 in which X = t-Bu. Y = H was achieved by LAH reduction of 8. All of the title compounds except 8 experience free phenyl rotation at room temperature. At - 30 degreesC this rotation in 8 is essentially halted. The molecular structures of 4, 8. 9c, 9e, 10 and 13 were determined by X-ray crystallography. (C) 2002 Published by Elsevier Science B.V.

  DOI：

  10.1016/s0022-328x(02)01142-7
• 作为产物：
  描述：

  二苯基乙炔 、 pentakis(dimethylamino)chlorodisilane 反应 48.0h， 以45%的产率得到2,3,5,6-tetraphenyl-1,1,4,4-tetrakis(dimethylamino)-1,4-disila cyclohexa-2,5-diene
  参考文献：
  名称：

  Synthesis of 1,4-disilacyclohexa-2,5-dienes

  摘要：

  Title Compounds of the type 2,3,5,6-tetraphenyl-1,4-di-X-1,4-di-Y-1,4-disilacyclohexa-2,5-diene wherein X = Y = NMe2 (4): X NMe2. Y = Cl (cis, trans-5) X = NMe2, Y = Me [(trans)-6] and X = t-Bu. Y = Cl (trans-8) were synthesized from Si-2(NMe2)(5)Cl, sym-Si-2(NMe2)(4)Cl-2, sym-Si-2(NMe2)(4)Me-2, and sym-Si2Cl4(t-Bu)2, respectively. in the presence of diphenylacetylene at 200 degreesC. Similarly the analogous title compound from the combination of 1-phenyl-1-propyne and Si-2(NMe2)(5)Cl [X = Y = NMe2 (cis and trans-7) was synthesized. In all cases where cis/trans diastereomers could arise from two different silicon substituents (5, 6 8) the trans isomer was the sole or dominant product. Evidence for the intermediacy of the silylene Si(NMe2)(2) in these reactions was gained from a trapping experiment. Compound 4 upon treatment with SiCl4 SiBr4 or PI3 provided the corresponding 1,1,4,4-tetrahalo derivatives 9a-c, respectively. Treatment of 4 with MeOH or PhOH gave the 1.1.4.4-tetramethoxy and tetraphenoxy analogues 9d and 9e, respectively. The tetrachloro derivative 9a upon LAH reduction led to the corresponding tetrahydro compound 10. while the reaction of 9a with H2O gave the tetrahydroxy derivative 11. Allowing (trans)-6 to react with SiCl4 provided a ca. 1:1 cis/trans ratio of the derivative 12 in which X = Cl. Y = Me. and possible pathways that rationalize this loss of stereochemistry are proposed. Synthesis of trans-13 in which X = t-Bu. Y = H was achieved by LAH reduction of 8. All of the title compounds except 8 experience free phenyl rotation at room temperature. At - 30 degreesC this rotation in 8 is essentially halted. The molecular structures of 4, 8. 9c, 9e, 10 and 13 were determined by X-ray crystallography. (C) 2002 Published by Elsevier Science B.V.

  DOI：

  10.1016/s0022-328x(02)01142-7