Novel codeinone derivatives via Michael addition of barbituric acids

Two novel adducts of codeinone with barbituric and 2-thiobarbituric acids have been synthesized via Michael addition. The compounds were spectroscopically elucidated by means of IR-LD spectroscopy of oriented samples as a suspension in nematic liquid crystals, UV spectroscopy and 1H and 13C NMR spectroscopy. The 2-thiobarbituric adduct was characterized by X-ray crystallography. HPLC tandem mass spectrometry (HPLC ESI MS/MS) and thermal methods were also employed. Quantum chemical calculations have been performed with a view to obtaining the electronic structure and vibrational properties of the novel compounds.

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5-[10-Methoxy-4-methyl-14-oxo-12-oxa-4-azapentacyclo [9.6.1.01,1305,1707,18]octadeca-7(18),8,10-trien-16-yl] hexahydro-2,4,6-pyrimidine-trioneC22H23N3O6Ee = 88%[α]D20=-94.5 (c 0.25, C2H5OH)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

5-[10-Methoxy-4-methyl-14-oxo-12-oxa-4-azapentacyclo [9.6.1.01,1305,1707,18]octadeca-7(18),8,10-trien-16-yl] hexahydro-2,4,6-thiopyrimidine-trioneC22H23N3O5SEe = 81%[α]D20=-92.3 (c 0.25, C2H5OH)Source of chirality: asymmetric synthesisAbsolute configuration: (S)