Acyl azide

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General chemical structure of an acyl azide Acyl azide.svg
General chemical structure of an acyl azide

Acyl azides are carboxylic acid derivatives with the general formula RCON3. These compounds, which are a subclass of organic azides, are generally colorless. [1]

Contents

Preparation

Diphenylphosphoryl azide DPPA-3D-balls.png
Diphenylphosphoryl azide

Typically acyl azides are generated under conditions where they rearrange to the isocyanate. [1]

Acid chlorides [2] [3] and anhydrides [4] react with sodium azide [5] or trimethylsilyl azide [6] to give acyl azides:

Preparation of acyl azides from acyl chlorides.png

In a Mitsunobu variant, triphenylphosphine and trichloroacetonitrile catalyze excellent yields from various carboxylic acids and sodium azide at mild conditions. [7]

The second major route to azides is from treating acylhydrazines with nitrous acid. [1] [8] Alternatively, the acyl azide can be formed by the direct reaction of a carboxylic acid with diphenylphosphoryl azide (DPPA). [9] [10]

Methods of forming acyl azides from carboxylic acids Acyl azide formation.png
Methods of forming acyl azides from carboxylic acids

Another route oxidizes aldehydes with iodine azide, formed from sodium azide and iodine monochloride in acetonitrile. [11]

Uses

On Curtius rearrangement, acyl azides yield isocyanates. [12] [13]

Curtius Rearrangement Scheme.png

Acyl azides are also formed in Darapsky degradation, [14] [15] [16]

Degradacion de Darapsky.png

Historical references

References

  1. 1 2 3 Lwowski, Walter (1971). "Acyl azides". In Saul Patai (ed.). The Azido Group. PATAI'S Chemistry of Functional Groups. pp. 849–907. doi:10.1002/9780470771266.ch9. ISBN   9780470771679.
  2. ↑ Allen, C. F. H.; Bell, Alan (1944). "Undecyl isocyanate". Organic Syntheses . 24: 94. doi:10.15227/orgsyn.024.0094 .
  3. ↑ Munch-Petersen, Jon (1953). "m-Nitrobenzazide (Benzoyl azide, m-nitro-)". Organic Syntheses . 33: 53. doi:10.15227/orgsyn.033.0053 .
  4. ↑ Weinstock, J (1961). "Modified Curtius reaction". J. Org. Chem. 26: 3511. doi:10.1021/jo01067a604.
  5. ↑ Carey, Francis A.; Sundberg, Richard J. (2007). Advanced Organic Chemistry: Part B: Reactions and Synthesis (5th ed.). New York: Springer. p. 948. ISBN   978-0387683546.
  6. ↑ Warren, J. D.; Press, J. B. (1980). "Formation and Curtius rearrangement of acyl azides from unreactive acid chlorides". Synth. Commun. 10: 107–110. doi:10.1080/00397918008061812.
  7. ↑ Jang, Doo; Kim, Joong-Gon (2008). "Direct Synthesis of Acyl Azides from Carboxylic Acids by the Combination of Trichloroacetonitrile, Triphenylphosphine and Sodium Azide". Synlett . 2008 (13): 2072–2074. doi:10.1055/s-2008-1077979.
  8. ↑ Pozsgay, V.; Jennings, H. J. (1987). "Azide synthesis with stable nitrosyl salts". Tetrahedron Lett. 28 (43): 5091–5092. doi:10.1016/s0040-4039(00)95598-9.
  9. ↑ Shioiri, T.; Ninomiya, K.; Yamada, S. (1972). "New convenient reagent for a modified Curtius reaction and for peptide synthesis". J. Am. Chem. Soc. 94 (17): 6203–6205. doi:10.1021/ja00772a052. PMID   5054412.
  10. ↑ Carey, Francis A.; Sundberg, Richard J. (2007). Advanced Organic Chemistry: Part B: Reactions and Synthesis (5th ed.). New York: Springer. p. 948. ISBN   978-0387683546.
  11. ↑ Marinescu, Lavinia; Thinggaard, Jacob; Thomsen, Ib B.; Bols, Mikael (2003). "Radical Azidonation of Aldehydes". J. Org. Chem. 68 (24): 9453–9455. doi:10.1021/jo035163v. PMID   14629171.
  12. ↑ Smith, Peter A. S. (1946). "The Curtius reaction". Org. React. 3: 337–449. doi:10.1002/0471264180.or003.09. ISBN   0471264180.{{cite journal}}: ISBN / Date incompatibility (help)
  13. ↑ Scriven, Eric F. V.; Turnbull, Kenneth (1988). "Azides: Their preparation and synthetic uses". Chem. Rev. 88 (2): 297–368. doi:10.1021/cr00084a001.
  14. ↑ Gagnon, Paul E.; Boivin, Paul A.; Craig, Hugh M. (1951). "Synthesis of Amino Acids from Substituted Cyanoacetic Esters". Can. J. Chem. 29 (1): 70–75. doi: 10.1139/v51-009 .
  15. ↑ E. H. Rodd (1965). Chemistry of Carbon Compounds (2nd ed.). New York. p. 1157.{{cite book}}: CS1 maint: location missing publisher (link)
  16. ↑ Gagnon, Paul E.; Nadeau, Guy; Côté, Raymond (1952). "Synthesis of α-Amino Acids from Ethyl Cyanoacetate". Can. J. Chem. 30 (8): 592–597. doi: 10.1139/v52-071 .
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