Trimethylsilyl amine

Tellurium nitride was first obtained by the reaction of TeBt4 with liquid ammonia more than 100 years ago. The empirical formula TeN was assigned to this yellow, highly insoluble and explosive substance. However, subsequent analytical data indicated the composition is Tc3N4 which, in contrast to 5.6a and 5.6b, would involve tetravalent tellurium. This conclusion is supported by the recent preparation and structural determination of Te6N8(TeCl4)4 from tellurium tetrachloride and tris(trimethylsilyl)amine (Eq. 5.5). The TceNs molecule (5.12), which is a dimer of Tc3N4, forms a rhombic dodecahedron in which the... 

The important reagent Mc3SiNSO is obtained by the reaction of thionyl chloride with tris(trimethylsilyl)amine at 70°C in the presence of AICI3 (Eq. 9.9). " It may also be prepared by the interaction of sulfur dioxide with HN(SiMc3)2. ... 

Bis(trimethylsilyl)amine is found to be not sufficiently nucleophilic for the synthesis of 3,3-di-(trimethylsilyl)-l-phenyltriazene. Therefore Wiberg and Pracht... 

A carbon-selenium bond can also be formed [106] by Diels-Alder reaction of the transient selenonitroso species 106 generated by phenylsulfinylselenylchlor-ide reacting with amines or trimethylsilylated amines. Selenonitroso compounds 106 were trapped with 2,3-dimethylbutadiene to afford 1,2-selenazine derivatives 107 (Scheme 2.44) in low yield. 1,2- Selenazines are interesting compounds which are quite unstable (2-3 h), except for the one having an... 

A closely related lithium amidinate with a pendant methyl(trimethylsilyl) amine functionality was prepared by the straightforward route outlined in Scheme 178 (55% yield)... 

By reaction of 2-alkyl-4,6-dichloro-l,3,5-trimethylborazines (alkyl = methyl, ethyl, i-propyl) with bis(trimethylsilyl)amine the tetrameric borazine ring systems 4-6 are produced (Fig. 2) they can be purified by several successive vacuum sublimations (yields 4-60%). If the borazines carry n-propyl and tert-butyl groups in the 2-position or if methylbis(trimethylsilyl)amine is used to bridge the borazine molecules, the macrocyclic ring formation is inhibited [17, 18]. 

An alternative method of synthesis of N3P3Cl6 has been developed recently, based on the reaction of tris (trimethylsilyl) amine and phosphorus pentachloride (40). This reaction either preferentially leads to the formation of N3P3C16 or to an N-silylated phosphoranimine intermediate C13P - NSiMe3, depending on the reaction conditions used. Thus the reaction between tris (trimethylsilylamine) and PC15 in methylene chloride at 40° C affords a mixture of cyclo and linear phosphazenes, which has been shown by an NMR analysis to contain up to 76% of N3P3C16 (Eq. 2). 

It is supposed that the nickel enolate intermediate 157 reacts with electrophiles rather than with protons. The successful use of trimethylsilyl-sub-stituted amines (Scheme 57) permits a new carbon-carbon bond to be formed between 157 and electrophiles such as benzaldehyde and ethyl acrylate. The adduct 158 is obtained stereoselectively only by mixing nickel tetracarbonyl, the gem-dibromocyclopropane 150, dimethyl (trimethylsilyl) amine, and an electrophile [82]. gem-Functionalization on a cyclopropane ring carbon atom is attained in this four-component coupling reaction. Phenyl trimethyl silylsulfide serves as an excellent nucleophile to yield the thiol ester, which is in sharp contrast to the formation of a complicated product mixture starting from thiols instead of the silylsulfide [81]. (Scheme 58)... 

With dimethyl(trimethylsilyl)amine, the nickel enolate 162 is capable of reacting with benzaldehyde to produce the condensation product 163 (Scheme 60). 

The a-arylamino nitriles 251, obtained from primary aromatic amines, trimethylsilyl cyanide and acetone in the presence of zinc chloride, react with methyllithium to give A-t-butylarylamines 252287. Af,Af-Bis(trimethylsilyl)amines 253 (R = allyl, benzyl, 3-phenylpropyl etc.) are formed in 50-88% yields by the action of chlorotrimethylsilane on primary amines in the presence of a catalytic amount of titanium(IV) chloride288. 

Tetrafluoroethane-l,2-disulfenyl dichloride (83) reacts readily with At,iV-bis(trimethylsilyl)amines to give A -substituted tetrafluoro-l,3,2-dithiazolidines (84) (Scheme 16) <85CB281l>. The same type of products are obtained by reaction with a combination of trimethylsilyl azide and alkylarenes <89CB1071>. At a low temperature (83) was reported to be cyclized by NHj to 4,4,5,5-tetrafluoro-1,3,2-dithiazolidine <93JPC9625>. 

Compound 26, likewise, undergoes a series of displacement reactions (Scheme 34). Whereas reaction with copper(I) cyanide replaces only one chlorine atom to yield 136, all are displaced by reactions with ammonia and isopropylamine, diethyl(trimethylsilyl)amine, water, and thiols to give, respectively, 137-140. Some additional transformations are also shown. 

Schistosoma japonicum. The carbobenzoxy (CBz) protected template 160 was initially converted to the a, p-dehydrolactone 161 via the phosphate ester, before undergoing cycloaddition to ylide 162, generated in situ by acidic treatment of A(-benzyl-A(-(methoxymethyl)trimethylsilyl amine. The resultant cycloadduct (163) was isolated in 94% yield as a single diastereoisomer. Destructive template removal, by catalytic hydrogenation, released (5)-( )-cucurbitine, after ion-exchange chromatography, as the free amino acid in 90% yield (Scheme 3.46). 

Zum Ersatz des Jod-Atoms in Aryl-jodiden durch die unsubstituierte Amino-Gruppe eig-net sieh auch die Reaktion mit Kupfer(I)-bis-[trimethylsilyl]-amid in siedendem Pyridin das auf diese Weise zunachst erhaltene Aryl-bis-[trimethylsilyl]-amin ergibt bei der Methanolyse das primare aromatische Amin, z. B. Anilin (60%), 4-Methoxy- (45%), 4-Me-thyl-anilin (50%), 2-Amino-thiophen (45%). Das Kupfer(I)-bis-[trimethylsilyl]-amid wird in situ aus Hexamethyldisilazane, Butyllithium und Kupfer(I)-jodid erzeugt4. 

We have found that the primary amine moiety can be protected from organolithium reagents and polymers by use of the N,N-bis(trimethylsilyl)amine, -N(TMS)p, protecting group. In turn, the N(TMS)2 substituted4 polymers can be converted to primary amine polymers by simple hydrolysis (Eqs. 12-14 (14.52). 

Alkylbis(trimethylsilyl)amines give alkyliminosulfur difluorides, e.g. 28, upon treatment with sulfur tetrafluoride at low temperature.226... 

Using an indirect approach, Olah et al.443 were able to diazotize ammonia [Eq. (4.134)], bis(trimethylsilyl)amine, and isocyanic acid with 15NO+BF4, resulting in the formation of 14N15N, which requires the intermediacy of the parent diazonium ion HN2+. 

---