Trimethylsilylmethyl azide

Preparative Method obtained in high yield by reaction of sodium azide and (chloromethyl)trimethylsilane in DMF or HMPAi at 80 °C. 

Handling, Storage, and Precautions useful, safe substitute for methyl azide, bp 20 °C, which is explosive. Trimethylsilyl-methyl azide is stable to temperatures of at least 120 °C and can be stored in a refrigerator for more than 6 months. 

Amination. Trimethylsilylmethyl azide reacts with aryl Grignard reagents at room terr ierature to give aniline derivatives in 70-95% yield (eq 1). An intermediate of the reaction is probably a triazene, which is hydrolyzed by neutral water to yield an amine. Amination of Grignard reagent with other azides (sulfonyl azide and thiomethyl azide) is known, but relatively drastic conditions are required to decompose the intermediate. The azide also reacts with aryllithium compounds to afford amines (eq 2), but yields are generally lower.  

Azomethine Ylide Precursor. The azide is readily converted into a precursor of azomethine ylides (eq 3). Reactions of the ylides with carbon-carbon multiple bonds and carbonyl group are used in a synthesis of pyrroline and oxazole derivatives (eq 4).  

InChl = 1S/C4H1 lN3Si/cl-8(2,3)4-6-7-5/h4H2,l-3H3 InChlKey = HKBUFTCADGLKAS-UHFFFAOYSA-N 

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Trimethylsilylmethyl azide serves via its iminophosphorane derivative, as a source of... 

Trimethylsilylmethyl azide, (CH,),SiCH2N3 (1). B.p. 58-61°/80 mm. The azide is obtained in high yield by reaction of NaN, with (CHsljSiCHjCl in HMPT or DMF. It is a useful, safe substitute for methyl azide, b.p. 20°, which is explosive. 

AMINATION Azidomethyl phenyl sulfide. Trimethylsilylmethyl azide. 

Dimethylaniline (Preparation of Trimethylsilylmethyl Azide and Its Reaction with an Arylmagnesium Reagent to Give an Aniline). 264 A mixture of trimethylsilylmethyl chloride (0.2 mol), sodium azide (0.24 mol), and dry DMF was heated at 80° for 44 hours. Distillation gave trimethylsilylmethyl azide, bp 43° (43 mmHg) in 97% yield. XH NMR 8 2.75 (s, 2H), 0.12 (s, 9H). The product is stable and can be stored in a refrigerator for at least 6 months but like all azides it is potentially explosive and should be handled with care. 

Trimethylsilylmethyl azide (1.2 eq) was added dropwise at room temperature to a solution of 2,4-dimethylphenylmagnesium bromide (1 eq) in ether and the mixture was stirred at room temperature for 3 hours. After conventional workup the low-boiling substances were removed under reduced pressure, leaving the title product in 79% yield. It was identified by comparison of its properties with those of an authentic sample. 

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