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Diphenylphosphoryl azide

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Diphenylphosphoryl azide
Names
IUPAC name Diphenyl phosphorazidate
Other names Diphenylphosphonic azide
Diphenyl azidophosphate
Phosphoric acid diphenyl ester azide
Identifiers
CAS Number
3D model (JSmol)
Abbreviations DPPA
ChemSpider
ECHA InfoCard 100.043.298 Edit this at Wikidata
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C12H10N3OP/c13-14-15-17(16,11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10HKey: MKRTXPORKIRPDG-UHFFFAOYSA-N
  • InChI=1/C12H10N3OP/c13-14-15-17(16,11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10HKey: MKRTXPORKIRPDG-UHFFFAOYAD
SMILES
  • O=P(N==)(c1ccccc1)c2ccccc2
Properties
Chemical formula C12H10N3O3P
Molar mass 275.20 g/mol
Appearance Colourless or faintly yellow liquid
Density 1.277 g/cm
Boiling point 157 °C (0.2 mmHg)
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4 1 0
Flash point 112 °C
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Diphenylphosphoryl azide (DPPA; IUPAC name: Diphenyl phosphorazidate) is an organic compound. It is widely used in synthesis of other organic compounds.

Synthesis

Diphenylphosphoryl azide has been obtained by reaction of the phosphorochloridate with sodium azide. The stability of the azide towards heating was shown by its distillation at 157 °C and by the fact that vigorous evolution of nitrogen was not observed until a temperature of 175 °C had been reached.

Uses

This compound undergoes pseudohalogen replacement of the azido group by treatment with nucleophilic reagents, such as water, butanol, ammonia, and various amines.

This compound is used as a reagent for the synthesis of peptides by virtue of its reactions with carboxylic acids leading to either the urethane or the amide. The formation of the urethane is particularly valuable since it works with carboxylic acids which fail to undergo the Schmidt reaction, and is believed to involve transfer of the azido group to the carboxylic acid.

It is now suggested that this reaction proceeds through the intermediate mixed anhydride, resulting from attack by the nucleophilic carboxylate anion on the phosphorus atom, with expulsion of the azide ion. The latter then attacks the carbonyl carbon atom, to give the acyl azide and loss of the diphenyl phosphate anion, known to be a good leaving group. Finally, the acyl azide reacts in the normal manner to give the urethane.

The present studies show that diphenylphosphoryl azide reacts with amines giving the corresponding phosphoramidates; it therefore appears that formation of the amide similarly involves the intermediate anhydride, followed by nucleophilic substitution by the amine.

References

  1. Some Reactions of O,O-Diphenylphosporyl Azide, Australian Journal of Chemistry, 1973, 26, 1591-3.
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