Displacement techniques amide

An anionic technique by indirect grafting was proposed for N-metallation of Nylon by Yamaguchi (153-155), in which alcali metals dissolved in liquid ammonia displace the amidic hydrogen atoms. Nylon derivatives and graft copolymers can be synthetized from the N-metallated Nylon (153). For ethylene oxide as grafting monomer, the metallated fibers were soaked in a tetrahydro-furan solution of the monomer, at 60° C (154). Methyl methacrylate is grafted on Nylon with a conversion over 90% by this technique (155). Other procedures involve the use of sodium methoxide in methanol solution and subsequent anionic graft copolymerization of acrylonitrile in a tetrahydrofuran solution (156). 

Unfortunately, the hydrazino esters or amides required inconveniently high pressures for their hydrogenolysis (500 psi Schemes 8.25a and b). An improvement involved the direct azidation of the same enolates using arylazide derivatives, which were found to undergo reactions with enolate nucleophiles to provide a C-sulfonyltriazene intermediate which could be decomposed to the a-azido ester (Scheme 8.25c) [110]. Alternatively, azides may be obtained by enolate bromination followed by Sn2 azide displacement note that these techniques are stereochemically complementary. Similar chemistry has also been accomplished using 10-suIfonamidoisobomyl chiral auxiliaries (Scheme 8.25d) [111]. 

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