Diacetonamine

Diacetonamine
Names
Other names
4-Amino-4-methylpentan-2-one
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.009.888 Edit this at Wikidata
EC Number
  • 210-876-8
UNII
  • InChI=1S/C6H13NO/c1-5(8)4-6(2,3)7/h4,7H2,1-3H3
    Key: CQTRUFMMCCOKTA-UHFFFAOYSA-N
  • CC(=O)CC(C)(C)N
Properties
C6H13NO
Molar mass 115.17 g/mol
Density g/cm3 (20°C)
Boiling point 163 °C (325 °F; 436 K) at 12 mm Hg
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Diacetonamine is a useful precursor in organic synthesis.

Diacetonamine and triacetonamine are formed in plant extracts:

Diacetonamine contains an acetyl group, a primary amine, and two methyl groups.

Applications

It is known to have application in the synthesis of eucaine & alpha-eucaine.

Additionally it was used in the synthesis of [2104-81-6], an agent discovered by C. Robin Ganellin. This compound has central nervous system activity as a combination of a stimulant and a depressant. A narcotic pharmacophore was associated with the structure in an earlier work.

Another place that diacetonamine is used is in the synthesis of Eucatropine (euphtalmin) [100-91-4]. The synthesis route is via the precursor 2,2,6-trimethylpiperidin-4-one [3311-23-7]. This is the same chemical as was used in the synthesis of beta-eucaine (see above).

Synthesis

It is formed by the conjugate addition of ammonia to mesityl oxide. Mesityl oxide itself is formed from the dehydration of diacetone alcohol. However, it can also be prepared directly from acetone without isolating the intermediate alcohol.

Diacetonamine synthesis.svg
Diacetonamine synthesis.svg

It is claimed that diacetonamine can also be prepared by the direct reaction between ammonia and acetone. However, closer inspection of the literature reveals that different products are obtained from this reaction.

References

  1. ↑ Stewart, I., Wheaton, T. A. (November 1967). "Formation of diacetonamine and triacetonamine in plant extracts". Phytochemistry. 6 (11): 1587–1588. Bibcode:1967PChem...6.1587S. doi:10.1016/S0031-9422(00)82956-8.
  2. 1 2 Lednicer, D., Mitscher, L. A. (1977). The organic chemistry of drug synthesis. 1. Wiley. ISBN 9780471521419.
  3. ↑ Ganellin, C. R., Spickett, R. G. W. (September 1965). "Compounds Affecting the Central Nervous System. I. 4-Piperidones and Related Compounds". Journal of Medicinal Chemistry. 8 (5): 619–625. doi:10.1021/jm00329a015. PMID 5867943.
  4. ↑ Ganellin Charon Robin & Spickett Robert Geoffr William, U.S. patent 3,067,204 (1962 to Smith Kline and French Laboratories Ltd).
  5. ↑ Anker, R. M., Cook, A. H., Heilbron, I. M. (1945). "240. Experiments in the piperidine series. Part II". Journal of the Chemical Society (Resumed): 917. doi:10.1039/jr9450000917.
  6. ↑ Kipping, F. S. (1923). "CCCLXVIII.—Some derivatives of the vinyldiacetonalkamines". J. Chem. Soc., Trans. 123: 3115–3119. doi:10.1039/CT9232303115.
  7. ↑ Organic medical chemicals, by M. Barrowliff, 98, 1921.
  8. ↑ Haeseler, P. R. (April 1925). "Preparation of Diacetonamine". Journal of the American Chemical Society. 47 (4): 1195–1196. Bibcode:1925JAChS..47.1195H. doi:10.1021/ja01681a504.
  9. ↑ Everest, A. E. (1919). "XLVIII.—The preparation of diacetonamine". J. Chem. Soc., Trans. 115: 588–592. doi:10.1039/CT9191500588.
  10. 1 2 "Diacetonamine Hydrogen Oxalate". Organic Syntheses. 6: 28. 1926. doi:10.15227/orgsyn.006.0028.
  11. 1 2 (Experiment 8 & 12) A Class-Book of Organic Chemistry, by J. B. Cohen, 12, 1919.
  12. ↑ Sokoloff, N., Latschinoff, P. (July 1874). "Ueber die Einwirkung des Ammoniaks auf Aceton". Berichte der Deutschen Chemischen Gesellschaft. 7 (2): 1384–1387. doi:10.1002/cber.187400702137.
  13. ↑ Ôeda, H. (1 June 1936). "ACTION OF LIQUID AMMONIA UPON ACETOONE COMPOUNDS OF α-HYDROXY-ACIDS". Bulletin of the Chemical Society of Japan. 11 (6): 385–389. doi:10.1246/bcsj.11.385.
  14. ↑ Heintz, W. (January 1876). "Rückverwandlung des Triacetonamins in Diacetonamin und eine fünfte Acetonbasis". Justus Liebigs Annalen der Chemie. 181 (1): 70–89. doi:10.1002/jlac.18761810107.
  15. ↑ Son, P.-N., Lai, J. T. (January 1981). "Synthesis of hexahydro-3,3,5,5,7-pentaalkyl-2H-1,4-diazepin-2-ones from 1,3-diamines and ketones". The Journal of Organic Chemistry. 46 (2): 323–327. doi:10.1021/jo00315a020.
  16. ↑ "MESITYL OXIDE". Organic Syntheses. 1: 53. 1921. doi:10.15227/orgsyn.001.0053.
  17. ↑ Patterson, T. S., McMillan, A. (1921). "XXXIII.—The action of ammonia on acetone". J. Chem. Soc., Trans. 119: 269–271. doi:10.1039/CT9211900269.
  18. ↑ Bradbury, R. B., Hancox, N. C., Hatt, H. H. (1947). "261. The reaction between acetone and ammonia : the formation of pyrimidine compounds analogous to the aldoxans of späth". J. Chem. Soc. 0: 1394–1399. doi:10.1039/JR9470001394.