二(三甲基硅基)氨基钠

二(三甲基硅基)氨基钠
IUPAC名
Sodium bis(trimethylsilyl)amide
系统名
Sodiobis(trimethylsilyl)amine
别名 双(三甲基硅基)氨基钠
二(三甲基硅基)胺基钠
识别
缩写 NaHMDS
CAS号 1070-89-9  checkY
PubChem 2724254
ChemSpider 21169873
SMILES
 
  • C[Si](C)(C)N([Na])[Si](C)(C)C
InChI
 
  • 1/C6H18NSi2.Na/c1-8(2,3)7-9(4,5)6;/h1-6H3;/q-1;+1/rC6H18NNaSi2/c1-9(2,3)7(8)10(4,5)6/h1-6H3
InChIKey WRIKHQLVHPKCJU-JSJAVMDOAQ
Beilstein 3629917
UN编号 UN 3263
EINECS 213-983-8
性质
化学式 C6H18NNaSi2
摩尔质量 183.37 g/mol g·mol⁻¹
外观 灰白色固体
密度 0.9 g/cm3,固体
熔点 171-175 °C(444-448 K)
沸点 170 °C(443 K)(2 mmHg)
溶解性 与水反应
溶解性(其他溶剂) 四氢呋喃
甲苯
结构
分子构型 三角锥形
危险性
警示术语 R:R11 R15 R34
安全术语 S:S16 S24/25
主要危害 高度易燃,腐蚀性
相关物质
其他阳离子 二(三甲基硅基)氨基锂(LiHMDS),二(三甲基硅基)氨基钾
相关化学品 二异丙基氨基锂 (LDA),KH
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

二(三甲基硅基)氨基钠是一种具有分子式((CH3)3Si)2NNa的化学品。这类物质,通常称为NaHMDS(六甲基二硅烷重氮钠),是一种强,常用于反应中的去质子化或作为碱性反应中的催化剂。这种化合物的优势在于可以是固体试剂,且溶于广泛的非质子性溶剂中,如:四氢呋喃乙醚甲苯中,有非常强的碱性但亲核性差,这是由于分子内具有两个体积庞大且有亲脂性的三甲基硅基(TMS)基团影响了它参与亲核取代反应[1]

NaHMDS在水中会快速变质,形成氢氧化钠六甲基二硅氮烷

结构

通常有机金属试剂都是离子形态,而这类有机金属试剂却不是离子型的。结构式可以清晰的说明:钠原子通过共价键连接于氮原子上。在非溶剂化时,固态的该化合物以三聚体形态存在[2]

合成中的应用

NaHMDS被广泛的用于中和C-H型的酸。例如一些典型的例子:

  • 去质子化,得到其烯醇衍生物。
  • 通过将CH2X2(X = Br, I)去卤化氢反应,得到类似CHBr和CHI形式的卤代卡宾。这些卡宾化合物加成于烯烃上可以得到含取代基的环丙烷类化合物。
  • 通过对季鏻盐的去质子化,制备格奥尔格·维蒂希试剂。
  • 氰醇的去质子化。

NaHMDS还可以作为N-H型酸的中和碱。

NaHMDS与卤代烷烃反应得到胺的衍生物:

((CH3)3Si)2NNa + RBr → ((CH3)3Si)2NR + NaBr
((CH3)3Si)2NR + H2O → ((CH3)3Si)2O + RNH2

该法的已推广到使用如下试剂((CH3)3Si)2NCH2OMe,该试剂含有一个可置换的甲氧基。

参见

参考文献

  1. ^ Watson, B. T.; Lebel, H. "Sodium bis(trimethylsilyl)amide" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289X.rs071m.pub2
  2. ^ Driess, Matthias; Pritzkow, Hans; Skipinski, Markus; Winkler, Uwe. Synthesis and Solid State Structures of Sterically Congested Sodium and Cesium Silyl(fluorosilyl)phosphanide Aggregates and Structural Characterization of the Trimeric Sodium Bis(trimethylsilyl)amide. Organometallics. 1997, 16 (23): 5108–5112. doi:10.1021/om970444c. 

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