sg

Chemistry

No. 2 (2025): FarDU ilmiy xabarlari jurnali (Tabiiy fanlar)

EFFECT OF CATALYSTS ON THE OXIDATION PROCESSES OF ACETYLENE ALCOHOLS

Submitted
February 21, 2025
Published
2025-04-25

Abstract

In the catalytic system Cu(OTf)2/TBHP/MeCN/C6H6O2, oxidation reactions of some acetylenic alcohols containing double and triple bonds in the molecules, including hexen-4-yn-1-ol-3, decen-2-yn-5-ol-4 and 1-phenylhexen-4-yn-1-ol-3, were carried out, and methods for synthesizing a new generation of unsaturated ketones were studied. The influence of reaction time, temperature, catalyst and nature of solvent on the oxidation of selected alcohols and the formation of ketones was systematically studied. The composition, purity and structure of the synthesized compounds were proven using modern physicochemical methods. The direction, stages and mechanisms of the oxidation process reaction are proposed.

References

  1. Silveira C.C., Mendes S.R., Wolf L., Martins G.M. Anhydrous CeCl3 catalyzed C3-selective propargylation of indoles with tertiary alcohols // Tetrahedron Letters, 2010, Volume 51, pp. 4560-4562.
  2. Raji Reddy C., Rani Valleti R., Dilipkumar U. One-pot sequential propargylation/cycloisomerization: A facile [4+2]- benzannulation approach to carbazoles // Chemistry European Journal, 2016, Volume 22, pp. 2501-2506.
  3. Gohain M., Marais C., Bezuidenhoudt B. An Al(OTf)3 catalyzed environmentally benign process for the propargylation of indoles // Tetrahedron Letters, 2012, Volume 53, pp. 4704-4707.
  4. Kumar G., Aridoss, G., Laali K. Condensation of propargylic alcohols with indoles and carbazole in [bmim][PF6]/Bi(NO3)3•5H2O // Tetrahedron Letters, 2012, Volume 53, pp. 3066-3069.
  5. Lim J.W., Kim S.H., Kim, J.; Kim N. Synthesis of benzo[a]carbazoles from 2-arylindoles via a sequential propargylation, propargyl-allenyl isomerization, and 6π-electrocyclization // Bulletin of the Korean Chemical Society, 2015, Volume 36, pp. 1351-1359.
  6. Das D., Pratihar S., Roy U.K., Mal D., Roy S. First example of a heterobimetallic “Pd–Sn” catalyst for direct activation of alcohol // Organic Biomolecular Chemistry, 2012, Volume 10, pp. 4537-4539.
  7. Ebitani K., Motokura K., Mori K., Mizugaki T., Kaneda K. Reconstructed Hydrotalcite as a Highly Active Heterogeneous Base Catalyst for Carbon−Carbon Bond Formations in the Presence of Water // The Journal of Organic Chemistry, 2006, Volume 71, Issue 15, pp. 5440-5447.
  8. Aridoss G., Sarca V.D., Ponder J.F., Crowe J., Laali K.K. Electrophilic chemistry of propargylic alcohols in imidazolium ionic liquids // Organic Biomolecular Chemistry, 2011, Volume 9, pp. 2518-2529.
  9. Cubbin J., Nassar C., Krokhin O. Waste-free catalytic propargylation /allenylation of aryl and heteroaryl nucleophiles and synthesis of naphthopyrans // Synthesis, 2011, Volume 19, pp. 3152-3160.
  10. McCubbin J.A., Krokhin O.V. Organocatalyzed Friedel-Crafts arylation of benzylic alcohols // Tetrahedron Letters, 2010, Volume 51, Issue 18, pp. 2447-2449.
  11. Reddy C. R., Srikanth B., Narsimha Rao N. Solid-supported acid-catalyzed C3-alkylation of 4-hydroxycoumarins with secondary benzyl alcohols // Tetrahedron, 2008, Volume 64, Issue 51, pp. 11666-11672.
  12. Kumar G.G., Laali K.K. Condensation of propargylic alcohols with N-methylcarbazole and carbazole in [Bmim]PF6 ionic liquid; synthesis of novel dipropargylic carbazoles using TfOH or Bi(NO3)3 5H2O as catalyst // Tetrahedron Letters, 2013, Volume 54, pp. 965-969.
  13. Lim J.W., Kim S.H., Kim J., Kim J.N. Synthesis of Benzo[a]carbazoles from 2-Arylindolesviaa Sequential Propargylation, Propargyl-Allenyl Isomerization, and 6π-Electrocyclization // Bulletin of the Korean Chemical Society, 2015, Volume 36, Issue 5, pp. 1351-1359.
  14. Nandi G.C., Laali K.K. Schmidt reaction in ionic liquids: highly efficient and selective conversion of aromatic and heteroaromatic aldehydes to nitriles with [BMIM(SO3H)][OTf] as catalyst and [BMIM][PF6] as solvent // Tetrahedron Letters, 2013, Volume 54, Issue 17, pp. 2177-2179.
  15. Lin M., Chen Q.Z., Zhu Y., Chen X.L., Cai J.J., Pan Y.M., Zhan Z.P. Copper (II)-catalyzed synthesis of pyrimidines from propargylic alcohols and amidine: A propargylation–cyclization–oxidation tandem reaction // Journal Synlett, 2011, Volume 20, Issue 11, pp. 1179-1183.
  16. Surabhi Mishra, Sumran Raikwar, Beeraiah Baire Synthesis of Functionalized Pyrimidines from Propargylic alcohols and their Derivatives // Chemical Asian Journal, 2023, Volume 17/18, Issue 14, pp. 230-236.
  17. Surabhi Mishra, Sindoori Nair, Beeraiah Baire Recent approaches for the synthesis of pyridines and (iso)quinolines using propargylic alcohols // Organic Biomolecular Chemistry, 2022, Volume 20, pp. 6037-6056.
  18. Kushan Weerasiri, Anne Gorden Oxidation of Propargylic Alcohols with a 2-Quinoxalinol Salen Copper(II) Complex and tert-Butyl Hydroperoxide // European Journal of Organic Chemistry, 2013, Volume 13, Issue 8, рр. 1546-1550.
  19. Qun Cao, Louise Hughes, Mark Muldoon Synthesis of 2-Alkynoates by Palladium(II)-Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols // European Journal of Organic Chemistry, 2016, Volume 22, Issue 34, рр. 11982-11985.
  20. Kushan Weerasiri, Anne Gorden Cu(II) 2-quinoxalinol salen catalyzed oxidation of propargylic, benzylic, and allylic alcohols using tert-butyl hydroperoxide in aqueous solutions // Tetrahedron, 2014, Volume 70, Issue 43, pp. 7962-7968.