Acyl azide

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A general acyl azide

Acyl azides are carboxylic acid derivatives with the general formula RCON3.

Preparation[edit]

Alkyl or aryl acyl chlorides react with sodium azide to give acyl azides.[1][2]

Preparation of acyl azides from acyl chlorides.png

They can also be synthesized from various carboxylic acids and sodium azide in presence of triphenylphosphine and trichloroacetonitrile catalysts in excellent yields at mild conditions.[3] Another route starts with aliphatic and aromatic aldehydes reacting with iodine azide which is formed from sodium azide and iodine monochloride in acetonitrile.[4]

Uses[edit]

Acyl azides are used as chemical reagents. On Curtius rearrangement acyl azides yield isocyanates.[5][6][7][8]

Curtius Rearrangement Scheme.png

Acyl azides are also formed in Darapsky degradation,[9][10][11][12][13]

Darapsky degradation

References[edit]

  1. ^ C. F. H. Allen and Alan Bell. "Undecyl isocyanate". Org. Synth. ; Coll. Vol. 3, p. 846 
  2. ^ Jon Munch-Petersen (1963). "m-Nitrobenzazide". Org. Synth. ; Coll. Vol. 4, p. 715 
  3. ^ Jang, Doo; Kim, Joong-Gon (2008). "Direct Synthesis of Acyl Azides from Carboxylic Acids by the Combination of Trichloroacetonitrile, Triphenylphosphine and Sodium Azide". Synlett. doi:10.1055/s-2008-1077979. 
  4. ^ Marinescu, Lavinia; Thinggaard, Jacob; Thomsen, Ib B.; Bols, Mikael (2003). "Radical Azidonation of Aldehydes". The Journal of Organic Chemistry 68 (24): 9453–5. doi:10.1021/jo035163v. PMID 14629171. 
  5. ^ Curtius, T. (1890). Ber. 23: 3023. 
  6. ^ Curtius, Th. (1894). "20. Hydrazide und Azide organischer Säuren I. Abhandlung". Journal für Praktische Chemie 50: 275. doi:10.1002/prac.18940500125. 
  7. ^ Smith, P. A. S. (1946). Org. React. 3: 337–449. 
  8. ^ Scriven, Eric F. V.; Turnbull, Kenneth (1988). "Azides: Their preparation and synthetic uses". Chemical Reviews 88 (2): 297. doi:10.1021/cr00084a001. 
  9. ^ A. Darapsky (1936). "Darstellung von ?-Aminosäuren aus Alkyl-cyanessigsäuren". J. Prakt. Chem. 146 (8–12): 250. doi:10.1002/prac.19361460806. 
  10. ^ A. Darapsky; D. Hillers (1915). "Über das Hydrazid der Cyanessigsäure, Isonitrosocyanessigsäure und Nitrocyanessigsäure". J. Prakt. Chem. 92: 297. doi:10.1002/prac.19150920117. 
  11. ^ P. E. Gagnon; P. A. Boivin; H. M. Craig (1951). "Synthesis of Amino Acids from Substituted Cyanoacetic Esters". Can. J. Chem. 29: 70. doi:10.1139/v51-009. 
  12. ^ E. H. Rodd (1965). "Chemistry of Carbon Compounds" (2nd ed.). New York. p. 1157. 
  13. ^ Gagnon, Paul E.; Nadeau, Guy; Côté, Raymond (1952). "Synthesis of α-Amino Acids from Ethyl Cyanoacetate". Can. J. Chem. 30 (8): 592. doi:10.1139/v52-071.