Silylamines, reaction with

These derivatives undergo ready reactions with silylamines ... 

The reaction of silylamines 9 with cyanogen chloride in diethyl ether affords mono silyl carbodiimides 10. On standing only the t-butyl and the phenyl derivatives are stable, the other derivatives rearrange to give the cyanamide isomers 11. ... 

The method has been applied to one secondary amine, the benzyl allyl amine 4. In this case chlorodiphenylsilane was used as silylating agent, due to the stability of the derived silylamine. As with 1-3 (R1 = C6115 R2 =R3 = CH3), the reaction was highly stereoselective, giving amino alcohol 5 with a d.r. of >99 1. 

The chlorine atom of chlorocyclopropenylium ions can be replaced with other heteroatom substituents. Thus, the l,2-diamino-3-chlorocyclopropenyliumsalts 1 were converted to various derivatives of trisubstituted cyclopropenylium salts by the reaction with amines, silylamines, hydrazine,and triphenylphosphane. ... 

The sulphur-containing heterocycles (38) both undergo preferential reactions at the phosphorus atom with primary and secondary amines (including silylamines). It is interesting to note that the monoamino-derivatives were obtained on reaction with ammonia, whereas only diaraino-derivatives can be obtained from a similar reaction with NaPsCIg (c/. ref. 61). By contrast, (38 ... 

The silylamine thus produced is desilylated by methanol to the corresponding amine or is converted to the corresponding amide by the reaction with acyl chloride liberating chlorosilane, e.g. ... 

By comparison of these and other reactions with water and silylamines, it was shown that the reactivity to nucleophilic attack at a phosphazenyl phosphorus atom generally decreased in the order ... 

An extensive series of amino-, N3P3F5 NR R (R = H, R = Et Ri = R2 = Et, Pr , or Bu ), andhydrazino-derivatives, N3P3Fb NH NR R (R = R = H or Me R = H, R = Me) has been obtained by direct reactions of amines and hydrazines with N3P3F6. With derivatives of primary amines, reactions with silylamines occur at the amino-group rather than at the phosphorus atoms ... 

Reaction with silylamine 17, 15.2.9.2 C4H,3Cl2N3Zn ZnCl2(dien)... 

The corresponding reaction with (VAl-dimethylthioamides gives the enethiol tautomer of a thioacylsilane.4 a-Silylamines can also be made by addition of PhMe2SiLi to pyrazolium salts,4 and to iminium ions, created in situ from aldehydes and A-trimethylsilylamines. ... 

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