New spiro (thio) barbiturates based on cyclohexanone and bicyclo [3.1.1]heptan-6-one by nonconcerted [1+5] cycloaddition reaction and their conformational structures

  • N. N. Pesyan
  • S. Noori
  • S. Poorhassan
  • E. Şahin
Keywords: Crossed-aldol condensation, Michael addition, [1 5] Cycloaddition, Barbituric acid, Conformation, Spiro barbiturate

Abstract

Crossed-aldol condensation reaction of aromatic aldehydes with ketones such as; acetone and cyclohexanone leads to the efficient formation of cross conjugated α,β-unsaturated ketones in excellent yield. The intermolecular and then intramolecular Michael addition reaction of α,β-unsaturated ketones derived from acetone and cyclohexanone with (thio)barbituric acids lead to synthesis new type of 7,11-diaryl-2,4-diazaspiro[5.5]undecane-1,3,5,9-tetraone and 2,4-diaryl-1'H-spiro[bicyclo[3.3.1]nonane-3,5'-pyrimidine]-2',4',6',9(3'H)-tetraone, respectively in good yield. Structure elucidation is carried out by 1H NMR, 13C NMR, FT-IR, UV-Visible, mass spectroscopy and X-ray crystallography techniques. A possible mechanism of the formation is discussed. The structural conformation also demonstrated by coupling constants derived from dihedral angles between vicinal and geminal protons. The 1H NMR spectra of NH protons of spiro compounds derived from barbituric acid show a broad singlet peak instead, these protons in the spiro compounds derived from thiobarbituric acid show two distinct peaks.

 

KEY WORDS: Crossed-aldol condensation, Michael addition, [1+5] Cycloaddition, Barbituric acid, Conformation, Spiro barbiturate

 

Bull. Chem. Soc. Ethiop. 2014, 28(3), 423-440.

DOI: http://dx.doi.org/10.4314/bcse.v28i3.12

Published
2014-09-22
Section
Articles

Journal Identifiers


eISSN: 1726-801X
print ISSN: 1011-3924