Diphenylphosphinic azide

Diphenyl phosphorszldate can be replaced with diethyl phosphorazidate in the above procedure. Use of other azides such as p-toluenesulfonyl azide, p-methoxybenzyloxycarbonyl azide, diphenylphosphinic azide, or diphenylthio-phosphinic azide is less satisfactory. No reaction occurs when trimethylsilyl azide, dimethylthiophosphinic azide, or alkaline azides are used, while decomposition of formed trimethylsilyldiazomethane seems to occur when... 

Thus photolysis of diphenylphosphine azide leads unequivocally to the transient metaphosphonimidate 1 which, by head to tail dimerization, gives rise to the phosphaTJiazetidine 2 and to polymers. 

Diphenylphosphinous azide Dihydro pyrrole Ethyldiazoacetate Palladium Alanylalanine... 

Isocyanates. This reagent has similar properties to diphenylphosphinic azide. The reaction on conjugated acids produces isocyanates which can be used in cycloadditions. 

In the work just described, the formation of a species thought to be the metaphosphon-imidate intermediate was demonstrated by its entrapment with an alcohol, normally MeOH, although Harger and Stephen also used other alcohols and also r rr-butylamine. Other workers, in an examination of the photolytic breakdown of diphenylphosphinic azide, used a variety of agents to trap the intermediate (Scheme 7), but also observed its dimerization to give the l,3,2,4-diazadiphosph(V)etidine 70 accompanied by more extensive polymerization ... 

The initial 2-iodopropyolanilides are rather inaccessible compounds. Their preparation requires a three-stage synthesis with diphenylphosphinic acid azide as the starting material. 

Peptides. A new amide or peptide synthesis is based on the formation of iminophosphoranes, R N=PR3, from the reaction of azides with a tertiary phosphine. These phosphoranes react with carboxylic acids to form amides.1 Ethyl diphenylphosphinite is more useful than a triarylphosphine because the by-product is hydrolyzed to diphenylphosphinic acid, which can be readily removed. The iminophosphorane 2, derived from 1 and ethyl azidoacetate, reacts with CboGly-L-Phe-OH to give optically pure 3 in 70% yield.2... 

Phenyllead(IV) azides, synthesis 15 Tetraphosphorus hexamethylhexaimide, synthesis 16 Diphenyl phosphorochloridite, synthesis 17 Diphenylphosphinic acid, synthesis 18 (2,2-Dimethylhydrazino)diphenylphosphine, synthesis 19 Alkoxy- and aryloxycyclophosphazenes, synthesis 20 Mercapto derivatives of chlorocyclophosphazencs, synthesis 21 Dialkylsulfamoyl chlorides, synthesis 27 N- and J T,A1 -Substituted sulfamides, synthesis 28 Dialkylamides of (trichlorophosphoranylidene)sulfamic acid, synthesis 29... 

Diphenylpentadiynone, 248 Diphenylphosphine, 505 Diphenyl phosphite, 210 Diphenylphosphorochloridate, 210 Diphenylphosphoryl azide, 210-211... 

A one-flask procedure for the synthesis of methyl 6-azido-6-deoxy-a-D-hexopyranosides has been described, in which the corresponding glycoside is treated with triphenylphosphine and iV-bromosuccinimide in DMF followed by sodium azide to give the 6-azido-6-deoxy glycosides in 75% yield the work-up procedure was also simplified by using / -(dimethylaminophenyl)-diphenylphosphine in place of triphenylphosphine. ... 

Sugar azides can be reduced directly to the corresponding acetamido-sugars with a mixture of thiolacetic acid and its potassium salt. A heterogenized homogeneous catalyst, interlamellar montmorillonite diphenylphosphine palladium(II), has been reported (two carbohydrate examples) to reduce azides selectively to amines without affecting benzyl ether or alkene moieties. ... 

---