iPr2NH*BH2SPh | 1387442-17-2

• 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: iPr2NH*BH2SPh
• 英文别名: [Di(propan-2-yl)azaniumyl]-phenylsulfanylboranuide
• CAS: 1387442-17-2
• 化学式: C₁₂H₂₂BNS
• 分子量: 223.19
• InChiKey: AVJQHEAIVRCDJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.48
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.7
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  iPr2NH*BH2SPh 以 甲苯 为溶剂， 反应 18.0h， 以59%的产率得到iPrN=BH(SPh)
  参考文献：
  名称：

  Synthesis and the Thermal and Catalytic Dehydrogenation Reactions of Amine-Thioboranes

  摘要：

  A series of trimethylamine-thioborane adducts, Me3N center dot BH2SR (R = tBu [2a], nBu [2b], iPr [2c], Ph [2d], C6F5 [2e]) have been prepared and characterized. Attempts to access secondary and primary amine adducts of thioboranes via amine-exchange reactions involving these species proved unsuccessful, with the thiolate moiety shown to be vulnerable to displacement by free amine. However, treatment of the arylthioboranes, [BH2-SPh](3) (9) and C6F5SBH2 center dot SMe2 (10) with Me2NH and iPr(2)NH successfully yielded the adducts Me2NH center dot BH2SR (R = Ph [11a], C6F5 [12a]) and iPr(2)NH center dot BH2SR (R = Ph [11b], C6F5 [12b]) in high yield. These adducts were also shown to be accessible via thermally induced hydrothiolation of the aminoboranes Me2N=BH2, derived from the cyclic dimer [Me2N-BH2](2) (13), and iPr(2)N=BH2 (14), respectively. Attempts to prepare the aliphatic thiolate substituted adducts R2NH center dot BH2SR' (R = Me, iPr; R' = tBu, nBu, iPr) via this method, however, proved unsuccessful, with the temperatures required to facilitate hydrothiolation also inducing thermal dehydrogenation of the amine-thioborane products to form aminothioboranes, R2N=BH(SR'). Thermal and catalytic dehydrogenation of the targeted amine-thioboranes, 11a/11b and 12a/12b were also investigated. Adducts 11b and 12b were cleanly dehydrogenated to yield iPr(2)N=BH(SPh) (22) and iPr(2)N=BH(SC6F5) (23), respectively, at 100 degrees C (18 h, toluene), with dehydrogenation also possible at 20 degrees C (42 h, toluene) with a 2 mol % loading of [Rh(mu-Cl)cod](2) in the case of the former species. Similar studies with adduct ha evidenced a competitive elimination of H-2 and HSPh upon thermolysis, and other complex reactivity under catalytic conditions, whereas the fluorinated analogue 12a was found to be resistant to dehydrogenation.

  DOI：

  10.1021/ic3008188
• 作为产物：
  描述：

  PhSBH2*THF 、 二异丙胺 生成 iPr2NH*BH2SPh
  参考文献：
  名称：

  Synthesis and the Thermal and Catalytic Dehydrogenation Reactions of Amine-Thioboranes

  摘要：

  A series of trimethylamine-thioborane adducts, Me3N center dot BH2SR (R = tBu [2a], nBu [2b], iPr [2c], Ph [2d], C6F5 [2e]) have been prepared and characterized. Attempts to access secondary and primary amine adducts of thioboranes via amine-exchange reactions involving these species proved unsuccessful, with the thiolate moiety shown to be vulnerable to displacement by free amine. However, treatment of the arylthioboranes, [BH2-SPh](3) (9) and C6F5SBH2 center dot SMe2 (10) with Me2NH and iPr(2)NH successfully yielded the adducts Me2NH center dot BH2SR (R = Ph [11a], C6F5 [12a]) and iPr(2)NH center dot BH2SR (R = Ph [11b], C6F5 [12b]) in high yield. These adducts were also shown to be accessible via thermally induced hydrothiolation of the aminoboranes Me2N=BH2, derived from the cyclic dimer [Me2N-BH2](2) (13), and iPr(2)N=BH2 (14), respectively. Attempts to prepare the aliphatic thiolate substituted adducts R2NH center dot BH2SR' (R = Me, iPr; R' = tBu, nBu, iPr) via this method, however, proved unsuccessful, with the temperatures required to facilitate hydrothiolation also inducing thermal dehydrogenation of the amine-thioborane products to form aminothioboranes, R2N=BH(SR'). Thermal and catalytic dehydrogenation of the targeted amine-thioboranes, 11a/11b and 12a/12b were also investigated. Adducts 11b and 12b were cleanly dehydrogenated to yield iPr(2)N=BH(SPh) (22) and iPr(2)N=BH(SC6F5) (23), respectively, at 100 degrees C (18 h, toluene), with dehydrogenation also possible at 20 degrees C (42 h, toluene) with a 2 mol % loading of [Rh(mu-Cl)cod](2) in the case of the former species. Similar studies with adduct ha evidenced a competitive elimination of H-2 and HSPh upon thermolysis, and other complex reactivity under catalytic conditions, whereas the fluorinated analogue 12a was found to be resistant to dehydrogenation.

  DOI：

  10.1021/ic3008188