Several decalin spiro-hydantoins and amino-acids have been prepared. Their configurations have been determined by deamination experiments, measurements of dissociation constants, and i.r. and n.m.r. spectra. The configurations are the opposite to those previously assigned to the alkyl amino-cyclohexane-carboxylic acids.
Diphenylphosphoryl azide, in contrast to N,N'-disubstituted phosphorodiamidic azides, undergoes nucleophilic displacement of the azido group by reaction with water, butanol, ammonia, and amines. Possible mechanisms for the conversion of diphenylphosphoryl azide into urethanes and amides are briefly discussed. Pyrolysis of N,N'-dicyclohexylphosphorodiamidic azide gave the phosphenimidic amide dimer. 0,O-Diphenylphosphoryl azide (1) has been obtained by reaction of the phosphorochloridate with sodium azide. This compound undergoes pseudohalogen replacement of the azido group by treatment with nucleophilic reagents, such as water, butanol, ammonia, and various amines. Thus with aniline, the corresponding N-phenylphosphoramidate (2; R = Ph) was formed in high yield:With strong bases, like ammonia and aliphatic amines, the reaction was rapid and exothermic at room temperature; but with weaker bases, like aniline, there was no apparent reaction at room temperature.The reactivity of the azide (1) towards nucleophiles resembled the behaviour of sulphonyl azides,' but differed markedly from that of N,Nf-disubstituted phosphorodiamidic azides which were very stable towards nucleophilic substitution at phosp h o r~~.~ However, efforts to obtain a phosphoryl nitrene insertion reaction, by heating the azide (1) with boiling o-xylene under similar conditions to those successfully used for the analogous reaction with sulphonyl azides,' were unsuccessful.The stability of the azide (1) towards heating was shown by its distillation at 157OY3 and by the fact that vigorous evolution of nitrogen was not observed until a temperature of 175" had been reached.
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