(triisopropylsilyl)diazomethane | 122093-27-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (triisopropylsilyl)diazomethane
• 英文别名: Silane, (diazomethyl)tris(1-methylethyl)-；diazomethyl-tri(propan-2-yl)silane
• CAS: 122093-27-0
• 化学式: C₁₀H₂₂N₂Si
• 分子量: 198.384
• InChiKey: OXGOSGFTIVOBLV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (triisopropylsilyl)diazomethane 在 二苯并-18-冠醚-6 、 正丁基锂 作用下， 以 苯 为溶剂， 生成 Methyl 1,3-bis[tri(propan-2-yl)silyl]pyrazole-4-carboxylate
  参考文献：
  名称：

  Synthesis and reactivity of stable silyl-substituted nitrilimines

  摘要：

  The reaction of chlorophosphanes and chlorosilanes with the lithium salts of the (bis(diisopropylamino)-thiophosphoranyl)-, bis(diisopropylamino)phosphanyl)-, (trimethylsilyl)-, and (triisopropylsilyl)diazomethane (1, 4, 5, 6) has been studied. Four isolable nitrilimines XCNNY (X = (iPr2N)2P(S), Y = SiiPr3, 10a; X = (iPr2N)2P, Y = SiPh3, 14a; X = (iPr2N)2P, Y = SiiPr3, 15a; X = Y = SiiPr3, 18a) and three observable nitrilimines (X = (iPr2N)2P(S), Y = SiMe3, 8a; X = (iPr2N)2P(S), Y = SiPh3, 9a; X = (iPr2N)2P, Y = SiMe3, 13a) have been obtained. The factors influencing the stability of nitrilimines are analyzed. Several examples of thermal nitrilimine-diazo rearrangements and photochemical nitrilimine-carbodiimide rearrangements are described. The regioselectivity of the reaction of the observable nitrilimines with methyl acrylate and methyl propiolate is compared to that reported for transient nitrilimines. An example of 1,3-addition of butyllithium to a nitrilimine is given.

  DOI：

  10.1021/jo00005a026
• 作为产物：
  描述：

  formyltriisopropylsilane tosylhydrazone 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以96%的产率得到(triisopropylsilyl)diazomethane
  参考文献：
  名称：

  Triisopropylsilyldiazomethane: A new stable reagent for esterification

  摘要：

  Triisopropylsilyldiazomethane (3), easily prepared in 96% yield from formyltriisopropylsilane tosythydrazone (2), undergoes smooth reaction with representative carboxylic acids to produce excellent yields of the corresponding silylmethyl esters (4).

  DOI：

  10.1016/s0040-4039(00)74042-1

文献信息

• Formation of nitrilimines and diazo compounds from lithiated and stannyl diazo derivatives: scope and mechanism
  作者：Regis Reau、Guilaine Veneziani、Guy Bertrand

  DOI：10.1021/ja00041a025

  日期：1992.7

  ophosphane (8) leading to a mixture of nitrilimine 9 and diazo derivative 10, in a 21/4 ratio. The reaction of [bis-(diisopropylamino)thioxophosphoranyl](triethylstannyl)diazomethane (11) with bis(diisopropylamino)chloroborane (12) gives C-[bis(diisopropylamino)thioxophosphoranyl]-N-[bis(diisopropylamino)boryl]nitrilimine (13), in 60% yield

  [双(二环己基氨基)膦基]重氮甲烷(7)的锂盐与双(二环己基氨基)氯膦(8)反应，生成腈亚胺9和重氮衍生物10的21/4比例的混合物。[双-(二异丙基氨基)硫代正膦基](三乙基甲锡烷基)重氮甲烷(11)与双(二异丙基氨基)氯硼烷(12)反应得到C-[双(二异丙基氨基)硫代正膦基]-N-[双(二异丙基氨基)硼基]腈亚胺(13) )，60% 的产率
• Castan, Florence; Baceiredo, Antoine; Bertrand, Guy, Angewandte Chemie, 1989, vol. 101, # 9, p. 1253 - 1254
  作者：Castan, Florence、Baceiredo, Antoine、Bertrand, Guy

  DOI：——

  日期：——
• Synthesis of stable boryl-substituted diazomethane and nitrilimines
  作者：Marie Pierre Arthur、Helen P. Goodwin、Antoine Baceiredo、Keith B. Dillon、Guy Bertrand

  DOI：10.1021/om00055a043

  日期：1991.9

  Addition of bis(diisopropylamino)chloroborane to the lithium salt of (triisopropylsilyl)-, [bis(diisopropylamino)phosphino]-, and [bis(diisopropylamino)thioxophosphoranyl]diazomethane led to the corresponding stable N-borylnitrilimines 6-8 in 80, 90, and 95% yield, respectively. Addition of sulfur to C-phosphinonitrilimine 7 gave the thioxophosphoranyl analogue 8. The chloroborane reacted with the lithium salt of diazomethane, leading to a mixture of [bis(diisopropylamino)boryl]diazomethane (11) (54% yield) and bis[bis(diisopropylamino)boryl]nitrilimine (9) (20% yield). Compound 9 can be obtained in good yield by reacting the lithium salt of [bis(diisopropylamino]boryl]diazomethane with chloroborane. Photolysis of nitrilimines 6-9 afforded the corresponding carbodiimides 12-15. The regioselectivity and stereoselectivity of the 2 + 3 cycloaddition reactions of 6-8 with olefins were studied.
• CASTAN, FLORENCE;BACEIREDO, ANTOINE;BERTRAND, GUY, ANGEW. CHEM., 101,(1989) N, C. 1253-1255
  作者：CASTAN, FLORENCE、BACEIREDO, ANTOINE、BERTRAND, GUY

  DOI：——

  日期：——
• GILLETTE, GREGORY R.;BACEIREDO, ANTOINE;BERTRAND, GUY, ANGEW. CHEM., 102,(1990) N2, C. 1486-1488
  作者：GILLETTE, GREGORY R.、BACEIREDO, ANTOINE、BERTRAND, GUY

  DOI：——

  日期：——