Azide, trimethylsilyl

Subsequently it was found that trimethylsilyl azide in triflic acid is a more efficient and improved reagent for aminations (169). Amination of toluene in the presence of trichloramine—A1 CL proceeds predominantly at the / -position. 

The Cunius degradation of acyl azides prepared either by treatment of acyl halides with sodium azide or trimethylsilyl azide [47] or by treatment of acyl hydrazides with nitrous acid [f J yields pnmarily alkyl isocyanates, which can be isolated when the reaction is earned out in aptotic solvents If alcohols are used as solvents, urethanes are formed Hydrolysis of the isocyanates and the urethanes yields primary amines. 

MesSiNs yields (SN)x as a black solid. By contrast, the explosive and insoluble black compound SesNaCla, which probably contains the [SesNaCl]" cation, is prepared by the treatment of SeaCla with trimethylsilyl azide in CH2CI2 (Eq. 2.13). ... 

The cyclocondensation of trimethylsilyl azide with a bis(sulfenyl chloride) is an efficient synthesis of dithiazolium cations (Section 11.3.5) (Eq. 2.15). ... 

In a similar fashion [Mc4N][TeF5] reacts with trimethylsilyl azide to produce [Mc4N][Te(N3)5] (Eq. 5.7), which has been stmcturally characterized in the solid state. The pentaazidotellurite anion is a distorted pseudo-octahedron with Te-N bond lengths in the range 2.07-2.26 A. 

N3S3F2][MF6] can be isolated from the reaction of 8.12b with MF5 (M = As, Sb), but they decompose to give the bicyclic cation [S4N5] (Section 5.3.8). Treatment of 8.12a with trimethylsilyl azide generates the polymer presumably via the intermediate formation of... 

Me4N]N3, lose SO2 to give the corresponding [SO2N3] salts.The [SO3N3] anion is prepared by the reaction of Cs[S03Cl] with trimethylsilyl azide (Eq. 9.4). 

The primary route to 1,3,2-dithiazolium salts involves the cyclocondensation of l,2-bis(sulfenyl chlorides) with trimethylsilyl azide, which is illustrated for benzo-fused derivatives in Eq. 11.11. ° This method can be extended to the synthesis of bis( 1,3,2-dithiazolylium) salts. 

In order to prepare thin fdms of (SN) on plastic or metal surfaces, several processing techniques have been investigated, e.g., the electroreduction of [SsNs]" salts. Powdered (SN) is prepared by the reaction of (NSC1)3 with trimethylsilyl azide in acetonitrile/ The sublimation of (SN) at 135°C and at pressure of 3 x 10 Torr. produces a gas-phase species, probably the cyclic [SsNs] radical, that reforms the polymer as epitaxial fibres upon condensation/... 

Mercury phthalocyanine (PcHg) is prepared by lithium-metal exchange between Li2Pc and mercury(II) chloride.59 A different kind of phthalocyanine, bis(methylmercury) phthalocyanine [Pc(HgX)2], can be obtained by the reaction of phthalocyanine and methylmercury bis(trimethylsilyl)azide in benzene293 or by heating phthalocyanine with methylmercury(II)... 

S,3S)-(+)-Aziridine-2,3-dicarboxylic acid (234 Scheme 3.86), an example of a naturally occurring aziridinecarboxylic acid, is a metabolite of Streptomyces MD398-A1. This aziridine was prepared by treatment of diethyl (2i ,3K)-(-)-oxir-ane-2,3-dicarboxylate (231) with trimethylsilyl azide in EtOH/DMF to produced azido alcohol 232 [137], and treatment of this alcohol with triphenylphosphine afforded the aziridine dicarboxylate 233 in 71 % yield. Hydrolysis of 233 afforded the natural product 234 in 69% yield. 

The analogous chromium complex was used in the asymmetric ring opening of meso epoxides with trimethylsilyl azide [15] (Scheme 4). In this case a strong dependence on the anion of the ionic hquid was observed. Anions leading to hydrophobic ionic hquids, such as PFe" and SbFe", led to high... 

Method B was also used in the preparation of occluded (salen)Cr complexes. ligands Ih and li were prepared within the pores of Cr -exchanged EMT and Y zeolites, respectively [25]. These complexes were tested as catalysts in the ring opening of meso-epoxides with trimethylsilyl azide (Scheme 4). The occluded complexes showed a dramatic decrease in catalytic... 

Reactions of Heterocyclic N-Oxides with Trimethylsilyl Cyanide, Trimethylsilyl Azide, Trimethylsilyl Isothiocyanate, and Trimethylsilyl Halides... 

Reductions with Trimethylsilyl Iodide, Trimethylsilyl Azide, and Trimethylsilyl Cyanide... 

Reaction of N,N-dimethylaniline with 1-cyanobenziodoxol 1783 to afford N-methyl-N-cyanomethylaniline 1784 in 97% yield has been discussed in Section 12.1 [31]. Analogously, oxidation of dimethylaniline with iodosobenzene and trimethylsilyl azide 19 at 0°C in CDCI3 gives the azido compound 2040 in 95% yield, iodobenzene, and HMDSO 7 [194, 195] (Scheme 12.56). Likewise, the nucleophilic catalyst 4-dimethylaminopyridine (DMAP) is oxidized, in 95% yield, to the azide 2041, which is too sensitive toward hydrolysis to 4-N-methylaminopyri-dine to enable isolation [194, 195]. Amides such as 2042, in combination with tri-... 

The first biradicaloid, l,3-diaza-2,4-digermacyclobutane-l,3-diyl, 53, was simply prepared by the reaction of the digermyne ArGeGeAr with trimethylsilyl azide in hexane (Scheme 2.40). ... 

With hydrazoic acid or (better) trimethylsilyl azide and ImCSIm, 5-(l-imidazolyl)-1,2,3,4-thiatriazole is obtained 11301 11321... 

Addition of thiophosgene to the reaction mixture of ImCSIm and trimethylsilylazide causes the yield to become quantitative.11301,11323 In the conversion with trimethylsilyl azide the required ImCSIm could also be made in situ from trimethylsilylimidazole and thiophosgene, giving the thiatriazoles in 70—80% yield.11321... 

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