Sodium bis(trimethylsilyl)amide

Summary

Sodium bis(trimethylsilyl)amide is the organosilicon compound with the formula NaN(Si(CH3)3)2. This species, usually called NaHMDS (sodium hexamethyldisilazide), is a strong base used for deprotonation reactions or base-catalyzed reactions. Its advantages are that it is commercially available as a solid and it is soluble not only in ethers, such as THF or diethyl ether, but also in aromatic solvents, like benzene and toluene by virtue of the lipophilic TMS groups.[1]

Sodium bis(trimethylsilyl)amide
Sodium bis(trimethylsilyl)amide.png
Cyclic Trimer of Sodium bis(trimethylsilyl)amide Structural formula V1.svg
Sodium bis(trimethylsilyl)amide trimer from crystal.png
Names
Preferred IUPAC name
Sodium 1,1,1-trimethyl-N-(trimethylsilyl)silanaminide
Other names
Sodium hexamethyldisilazide
Sodium hexamethyldisilazane
Identifiers
  • 1070-89-9 ☒N
3D model (JSmol)
  • Interactive image
Abbreviations NaHMDS
3629917
ChemSpider
  • 21169873 checkY
ECHA InfoCard 100.012.713 Edit this at Wikidata
EC Number
  • 213-983-8
  • 2724254
UN number 3263
  • DTXSID5061451 Edit this at Wikidata
  • InChI=1S/C6H18NSi2.Na/c1-8(2,3)7-
    9(4,5)6;/h1-6H3;/q-1;+1 ☒N
    Key: WRIKHQLVHPKCJU-UHFFFAOYSA-N checkY
  • 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
    Key: WRIKHQLVHPKCJU-JSJAVMDOAQ
  • InChI=1S/C6H18NSi2.Na/c1-8(2,3)7-9(4,5)6;/h1-6H3;/q-1;+1
    Key: WRIKHQLVHPKCJU-UHFFFAOYSA-N
  • C[Si](C)(C)N([Na])[Si](C)(C)C
Properties
NaN(Si(CH3)3)2
Molar mass 183.377 g·mol−1
Appearance off-white solid
Density 0.9 g/cm3, solid
Melting point 171 to 175 °C (340 to 347 °F; 444 to 448 K)
Boiling point 170 °C (338 °F; 443 K) 2 mmHg
Reacts with water
Solubility in other solvents THF, benzene
toluene
Structure
Triangular pyramidal
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Highly flammable, corrosive
GHS labelling:
GHS05: CorrosiveGHS07: Exclamation mark
Danger
H302, H312, H314, H332, H412
P260, P261, P264, P270, P271, P273, P280, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P310, P312, P321, P322, P330, P363, P405, P501
Related compounds
Other cations
Lithium bis(trimethylsilyl)amide
(LiHMDS)
Potassium bis(trimethylsilyl)amide
Related compounds
Lithium diisopropylamide (LDA)
Sodium hydride
Potassium hydride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)
Infobox references

NaHMDS is quickly destroyed by water to form sodium hydroxide and bis(trimethylsilyl)amine.

StructureEdit

Although the Na–N bond is polar covalent as a solid, when dissolved in nonpolar solvents this compound is trimeric, consisting of a central Na3N3 ring.[2]

Applications in synthesisEdit

NaHMDS is used as a strong base in organic synthesis. Typical reactions:

NaHMDS deprotonates compounds containing weakly acidic O–H, S–H, and N–H bonds. These include cyanohydrins and thiols.[5]

NaHMDS converts alkyl halides to amines in a two step process that begins with N-alkylation followed by hydrolysis of the N–Si bonds:

NaN(Si(CH3)3)2 + RX → RN(Si(CH3)3)2 + NaX
RN(Si(CH3)3)2 + H2O → O(Si(CH3)3)2 + RNH2

where X is a halogen and R is an alkyl.

This method has been extended to aminomethylation via the reagent CH3OCH2N(Si(CH3)3)2, which contains a displaceable methoxy group CH3O–.

See alsoEdit

ReferencesEdit

  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 (1997). "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. 16 (23): 5108–5112. doi:10.1021/om970444c.
  3. ^ Sergey A. Kozmin, Shuwen He, and Viresh H. Rawal. "Preparation of (E)-1-Dimethylamino-3-tert-Butyldimethylsiloxy-1,3-Butadiene". Organic Syntheses.{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 10, p. 301
  4. ^ Paul Binger, Petra Wedemann, and Udo H. Brinker. "Cyclopropene: A New Simple Synthesis and its Diels-Alder Reaction with Cyclopentadiene". Organic Syntheses.{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 10, p. 231
  5. ^ J. Christopher McWilliams, Fred J. Fleitz, Nan Zheng, and Joseph D. Armstrong, III. "Preparation of n-Butyl 4-Chlorophenyl Sulfide". Organic Syntheses.{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 10, p. 147