[(Z)-2-(1,1,1,3,3,3-Hexamethyl-disilazan-2-yl)-3,3-dimethyl-but-1-enyl]-diphenyl-phosphane | 190847-69-9

• 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: [(Z)-2-(1,1,1,3,3,3-Hexamethyl-disilazan-2-yl)-3,3-dimethyl-but-1-enyl]-diphenyl-phosphane
• CAS: 190847-69-9
• 化学式: C₂₄H₃₈NPSi₂
• 分子量: 427.717
• InChiKey: HMXYHGCDVDBNNX-ATJXCDBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.98
• 重原子数：
  28.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [(Z)-2-(1,1,1,3,3,3-Hexamethyl-disilazan-2-yl)-3,3-dimethyl-but-1-enyl]-diphenyl-phosphane 以 氘代苯 为溶剂， 反应 1.5h， 生成 [(E)-2-(1,1,1,3,3,3-Hexamethyl-disilazan-2-yl)-3,3-dimethyl-but-1-enyl]-diphenyl-phosphane
  参考文献：
  名称：

  The role of lithium 1,3-bis(trimethylsilyl)-1-aza-allyls in phosphorus chemistry

  摘要：

  Treatment of the lithium 1-aza-allyl [Li{N(R)C(Bu-t)CHR}](2) 1, abbreviated as [<(Li(L)over bar>L')](2), with PCl3 gave in poor yields the trans-P,P'-dichlorodiazaphosphetidine C<(IPN(R')P(Cl)N)over bar>R' 3 (R=SiMe3, R'=C(Bu-t)=C(H)SiMe3). An improved route to 3 was based on [{Cu(mu-LL')}(2)] and PCl3; but the method of choice involved conversion of 1 into successively the imine RN=C(Bu-t)CHR2 4 (which upon heating gave the isomeric enamine 5) and Cl2PN=C(Bu-t)CHR2 6 and thermolysis of 6. The imine RN=C(Bu-t)CH(R)PPh2 7, obtained from [<(Li(L)over bar>L')](2) 1 and Ph2PCl, was isomerised into the Z-enamine R2NC(Bu-t)=C(H)PPh2 8, which upon irradiation gave a mixture of 8 and its E-isomer 9. Treatment of 7 with R '' PCl2 or PCl3 gave the cyclic phosphonium chlorides [Ph-2<(PP(R '')N(H)C(Bu-t)=C)over bar>H]Cl (10 R ''=Ph, or 11 R ''=Et) or [Ph-2<(PP(Cl)N(R)C(Bu-t)=C)over bar>H]Cl 12; 12 with AgOSO2CF3 or Na[BPh4] afforded [Ph-2<(PP(Cl)N(R)C((BU)-B-t)=C)over bar>H]A (13 A=CF3SO3, or 14 A=BPh4). The enamines RN=C(Bu-t)CH(X)R (15 X=Cl, or 16 X=I) were obtained from 1 and POCl3 or ICI respectively, and the enamine R2NC(Ph)=CR2 17 was obtained from the lithium 1-aza-allyl[Li(N(R)C(Ph)CR2)(THF)] and CF3SO3SiMe3. Compounds 3-17 were characterised by multinuclear NMR spectroscopy and (in most cases) MS; while single crystal X-ray diffraction data are provided for 3 and 10.

  DOI：

  10.1016/s0022-328x(96)06601-6
• 作为产物：
  描述：

  以 solid 为溶剂， 150.0 ℃ 、1.33 Pa 条件下， 以56%的产率得到[(Z)-2-(1,1,1,3,3,3-Hexamethyl-disilazan-2-yl)-3,3-dimethyl-but-1-enyl]-diphenyl-phosphane
  参考文献：
  名称：

  The role of lithium 1,3-bis(trimethylsilyl)-1-aza-allyls in phosphorus chemistry

  摘要：

  Treatment of the lithium 1-aza-allyl [Li{N(R)C(Bu-t)CHR}](2) 1, abbreviated as [<(Li(L)over bar>L')](2), with PCl3 gave in poor yields the trans-P,P'-dichlorodiazaphosphetidine C<(IPN(R')P(Cl)N)over bar>R' 3 (R=SiMe3, R'=C(Bu-t)=C(H)SiMe3). An improved route to 3 was based on [{Cu(mu-LL')}(2)] and PCl3; but the method of choice involved conversion of 1 into successively the imine RN=C(Bu-t)CHR2 4 (which upon heating gave the isomeric enamine 5) and Cl2PN=C(Bu-t)CHR2 6 and thermolysis of 6. The imine RN=C(Bu-t)CH(R)PPh2 7, obtained from [<(Li(L)over bar>L')](2) 1 and Ph2PCl, was isomerised into the Z-enamine R2NC(Bu-t)=C(H)PPh2 8, which upon irradiation gave a mixture of 8 and its E-isomer 9. Treatment of 7 with R '' PCl2 or PCl3 gave the cyclic phosphonium chlorides [Ph-2<(PP(R '')N(H)C(Bu-t)=C)over bar>H]Cl (10 R ''=Ph, or 11 R ''=Et) or [Ph-2<(PP(Cl)N(R)C(Bu-t)=C)over bar>H]Cl 12; 12 with AgOSO2CF3 or Na[BPh4] afforded [Ph-2<(PP(Cl)N(R)C((BU)-B-t)=C)over bar>H]A (13 A=CF3SO3, or 14 A=BPh4). The enamines RN=C(Bu-t)CH(X)R (15 X=Cl, or 16 X=I) were obtained from 1 and POCl3 or ICI respectively, and the enamine R2NC(Ph)=CR2 17 was obtained from the lithium 1-aza-allyl[Li(N(R)C(Ph)CR2)(THF)] and CF3SO3SiMe3. Compounds 3-17 were characterised by multinuclear NMR spectroscopy and (in most cases) MS; while single crystal X-ray diffraction data are provided for 3 and 10.

  DOI：

  10.1016/s0022-328x(96)06601-6

文献信息

• Hitchcock, Peter B.; Lappert, Michael F.; Layh, Marcus, Journal of Organometallic Chemistry, 1999, vol. 580, # 2, p. 386 - 398
  作者：Hitchcock, Peter B.、Lappert, Michael F.、Layh, Marcus

  DOI：——

  日期：——