Diphenylphosphonic azide

• Catalog No.: A12124
• CAS Number: 26386-88-9
• M. F.: C12H10N3O3P
• M. W.: 275.199861
• Purity: 97%

SYNONYMS

• Title: 叠氮磷酸二苯酯
• IUPAC name: {[azido(phenoxy)phosphoryl]oxy}benzene
• IUPAC Traditional name: diphenylphosphoryl azide
• Synonyms: Diphenylphosphorazidate; Diphenylphosphoryl azide

DATABASE IDS

• CAS Number: 26386-88-9
• EC Number: 247-644-0
• MDL Number: MFCD00001987
• Beilstein Number: 2058967

PROPERTIES

• Purity: 97%
• Boiling Point: 161-162°C/0.5mm
• Density: 1.275
• Flash Point: >110°C(230°F)
• Refractive Index: 1.5520
• GHS Hazard statements: H301-H311-H331-H315-H319
• European Hazard Symbols: Toxic (T)
• GHS Precautionary statements: P280H-P305+P351+P338-P361-P309-P310
• Risk Statements: 23/24/25-32-36/38
• Safety Statements: 26-27-36/37/39-45
• TSCA Listed: 否
• Hazard Class: 6.1
• UN Number: UN3278
• Packing Group: III

REFERENCES

• Pyrrolidine enamines of cyclic ketones undergo 1,3-dipolar cycloaddition followed by rearrangement with loss of N₂ to the ring contracted N-phosphoryl amidine which can be base hydrolyzed (high temperature) to the corresponding acid: Tetrahedron Lett., 4749 (1976); (cyclododecanone to cycloundecanecarboxylic acid): Org. Synth. Coll., 7, 135 (1990).
• Li enolates unsubstituted at the ɑ-position can undergo diazo-transfer reactions to give the diazo carbonyl derivatives. With ɑ-alkyl amides, azide transfer occurs to give 3-amino-2H-azirines: Helv. Chim. Acta, 78, 1983 (1995). Enolates of ɑ-unsubstituted carboxamides, on treatment with the reagent, followed by di-t-butyl dicarbonate, give derivatives ɑ-amino acids: Helv. Chim. Acta, 79, 213 (1996):
  
• Enables decarbonylation reactions of aldehydes to be carried out at ambient temperature with a catalytic amount of Chlorotris(triphenylphosphine)rhodium(I), 10468, by regeneration of the catalyst from an inactive Rh carbonyl complex: J. Org. Chem., 57, 5075 (1992).
• In the presence of an amine, carboxylic acids are converted to acyl azides which undergo a modified Curtius reaction in the presence of an alcohol to give alkyl carbamates directly. With t-butanol, the resulting t-butyl carbamates can readily be converted to the free amines with mild acid. Malonic half-esters, e.g. Ethyl hydrogen malonate, A12627, give ɑ-amino acid derivatives: J. Am. Chem. Soc., 94, 6203 (1972); Chem. Pharm. Bull., 22, 1398 (1974); J. Org. Chem., 49, 185 (1984):
  
• Use of the hindered base 1,8-Bis(dimethylamino)naphthalene, L00313, enables the isocyanate intermediates to be isolated: Synth. Commun., 23, 335 (1993). Application to ɑ?-unsaturated acids provides a useful degradation to aldehydes with one C atom fewer by hydrolysis of the intermediate enamine. See, e.g.: Synth. Commun., 20, 589 (1990).
• N-protected amino acids are converted to acyl azides for use in a low racemization peptide coupling technique: J. Am. Chem. Soc., 94, 6203 (1972); Synthesis, 549 (1974); J. Org. Chem., 44, 3101 (1979); 52, 764 (1987). See Appendix 6. The method is also applicable to the coupling of carboxylic acids with thiols: J. Org. Chem., 39, 3302 (1974); Chem. Pharm. Bull., 25, 2423 (1977). Similarly, macrocyclic lactams have been prepared without high dilution by reaction of diacids with diamines: Tetrahedron Lett., 31, 6469 (1990).
• Under Mitsunobu conditions, converts alcohols directly to alkyl azides: Tetrahedron Lett., 1977 (1977). Alternatively, with 1,8-Diazabicyclo[5.4.0]undec-7-ene, A12449, activated (e.g. benzylic) chiral alcohols have been converted to the azides with inversion in high ee: J. Org. Chem., 58, 5886 (1993); for illustrative example, see: Org. Synth., 75, 31 (1997).
• Stable azide-transfer agent.