Gusakova G V, Denisov G S, Smolianskiĭ A L, Kuzovkov A D, Zhdanovich Iu V
Antibiot Khimioter. 1988 Feb;33(2):102-5.
IR spectra of rosamycin and its solutions in inert (CCl4 and C2Cl4), proton acceptor (tetrahydrofuran, hexametapol and diethylamine) and proton donor (CHCl3 and CH3OD) solvents were studied at various concentrations (0.1 to 0.001 mol/l) and temperatures (20 to 100 degrees C) in the region of the vC = O and vOH absorption bands (1600-1800 and 3200 3650 sm 1). It was found that the absorption bands at 3480 and 3560 sm-1 observed in the spectra of rosamycin diluted solutions in the inert solvents referred to variations of vOH...N of the aminosugar fragment and to vOH...O = C of the ester group of the macrocycle. Bands at 1697 and 1717 sm-1 referred to vC = O of the ketone and aldehyde carbonyl groups and band at 1728 sm-1 referred to vC = O of the ester group whose carbonyl was involved in the C = H...HO intramolecular hydrogen bond. Intensity of vC = O band (1745 sm-1) of the free ester group was nought. However, it increased with using the proton acceptor solvents. OH...N and OH...O = C intramolecular hydrogen bonds stabilized rosamycin molecule conformation. Mechanism of rosamycin interaction with the proton donor and acceptor molecules was elucidated. It was shown that tertiary nitrogen was the center of rosamycin molecule protonation.
在1600 - 1800 cm⁻¹和3200 - 3650 cm⁻¹的νC=O和νOH吸收带区域，研究了罗沙霉素及其在惰性（CCl₄和C₂Cl₄）、质子受体（四氢呋喃、六偏磷酸钠和二乙胺）和质子供体（CHCl₃和CH₃OD）溶剂中的溶液在不同浓度（0.1至0.001 mol/l）和温度（20至100℃）下的红外光谱。发现在惰性溶剂中稀释的罗沙霉素溶液光谱中观察到的3480和3560 cm⁻¹处的吸收带，是氨基糖片段的νOH...N和大环酯基的νOH...O = C的变化所致。1697和1717 cm⁻¹处的吸收带是酮和醛羰基的νC=O，1728 cm⁻¹处的吸收带是酯基的νC=O，其羰基参与了C = H...HO分子内氢键。游离酯基的νC=O带（1745 cm⁻¹）强度为零。然而，使用质子受体溶剂时其强度增加。OH...N和OH...O = C分子内氢键稳定了罗沙霉素分子构象。阐明了罗沙霉素与质子供体和受体分子的相互作用机制。结果表明叔氮是罗沙霉素分子质子化的中心。
