Acta Chimica 127. (1990)
1. szám - Hosztafi Sándor–Szilágyi László–Makleit Sándor–Tóth Géza: Morphine alkaloids, 107
10 HOSZTAFI et al.: MORPHINE ALKALOIDS, 107 studies [1], Hahn et al. [8, 9] described the preparation of some phenylhydrazones which are irreversibly linked to the opiate receptors. Literature data showed that hydrazone derivatives of several ketones with morphine skeleton had been described because the semicarbazones and phenylhydrazones can be readily crystallized and thus they can be conveniently analyzed. Known compounds are the hydrazones of 14-hydroxycodeinone and 14-hydroxydihydrocodeinone (la and lb) [10], the phenylhydrazones of dihydrocodeinone [11], 14-hydroxycodeinone and 14-hydroxydihydrocodeinone [12] (III2, b, c), and the semicarbazones of dihydrocodeinone [И], codeinone [13] and dihydrothebainone [14] (Vc, f, g). The dinitrophenylhydrazones of dihydrocodeinone [11] and codeinone [15] (IVc, f) have also been reported. These known compounds were also synthesized in our present work to investigate their nmr spectra and pharmacological properties. When the syntheses of the hydrazones of 14-hydroxycodeinone and 14-hydroxydihydrocodeinone (la, b), described by Speyer and Sarre [10], were performed in acetic acid, the ketazines Ila and lib were formed as shown by the XH nmr and mass spectra. Authentic hydrazones were prepared in ethanol or dimethylformamide. ХН nmr spectra of the crude products proved the presence of an E—Z isomeric mixture. Ketazines were synthesized by the interaction of the hydrazones and ketones. The phenylhydrazones (Ilia, b, c), 2,4-dinitrophenylhydrazones ((IVc, f) and semicarbazones (Vc, f, g) described in the literature proved homogeneous in tic and their structures were corroborated by JH nmr spectra. 16 17a R,= OH R2 = Me, Д. b R,= OH R2= Me c R,= H Rz= Me d R,= H R г = H Acta Chim. Hung. 127, 1990