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Diphenylphosphonic azide acts as a reagent for the synthesis of peptides and phosphoramidates by reacting with amines. It is also used in the preparation of oligosaccharides linked with carbamate and urea bonds utilizing modified Curtis rearrangement. It is involved in pseudohalogen replacement of the azido group by treatment with nucleophilic reagents, such as water, butanol, ammonia, and various amines. Further, it is used as a hydroazidation catalyst for preparation of organoazides.
Stable azide-transfer agent.
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 ɑß-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).
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).
Faigl, F.; Erdelyi, Z.; Nyerges, M.; Matravolgyi, B. Racemization-free synthesis of atropisomeric 1-phenylpyrrole based diamines using diphenylphosphoryl azide. Tetrahedron: Asymmetry 2015, 26 (14), 738-745.
Vothi, H.; Halm, S.; Nguyen, C.; Bae, I.; Kim, J. Thermal stabilities and flame retardancies of phloroglucinol-based organo phosphates when applied to polycarbonate. Fire Mater. 2014, 38 (1), 36-45.
Gefahrenhinweise (EU): H301-H311-H331-H315-H319-H335
Toxic if swallowed. Toxic in contact with skin. Toxic if inhaled. Causes skin irritation. Causes serious eye irritation. May cause respiratory irritation.
Avoid breathing dust/fume/gas/mist/vapours/spray. Wear protective gloves/protective clothing/eye protection/face protection. IF SWALLOWED: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. Store locked up. Dispose of contents/container in accordance with local/regional/national/international regulations.