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Conformations and inversion pathways leading to racemization of all the tautomers of gossypol, gossypolone, anhydrogossypol, and a diethylamine Schiff's base of gossypol were investigated with MM3(2000). All forms have hindered rotation because of clashes between the methyl carbon atom and oxygen-containing moieties ortho to the bond linking the two naphthalene rings. Inversion energies generally agree with available experimental data. Gossypol preferentially inverts in its dihemiacetal tautomeric form through the cis pathway (where similar groups clash). Gossypolone inverts more easily than gossypol, and preferentially through the trans pathway (where dissimilar groups clash) when one of its outer rings has an enol-keto group and the other has an aldehyde group. Anhydrogossypol racemizes through the cis pathway. The bridge bond and the ortho exo-cyclic bonds in all the structures bend from planarity, and the inner naphthalene rings pucker to accommodate the inversion. For gossypol, the transition is achieved through greater bending of the exo-cyclic bonds (up to 12°) and less distortion of the inner benzyl rings (q≤0.34 Å), (up to 12.7°) . For gossypolone the transition occurs with greater distortion of the inner benzyl rings (q≤0.63 Å) and less out-of-plane bending (up to 8.4°). By isolating individual clashes, their contribution to the overall barrier can be analyzed, as shown for the dialdehyde tautomer of gossypol. 相似文献
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Long Zhanga Xing Xin Caob Hai Xia Jiangb Biao Jiang Yu Xin Cui a State Key Laboratory of Natural Biomimetic Drugs School of Pharmaceutical Sciences Peking University Beijing China b 《中国化学快报》2009,20(6)
To investigate the structural form of gossypol and gossypolone Schiff's bases,seven relevant Schiff's bases were synthesized and the electrospray ionization-tandem mass spectrometry(ESI-MS/MS) with low-energy collision-induced dissociation was used to analyze their fragmentations.A common fragmentation pathway with the loss of RNH_2 from those schiff's bases quasi-molecular ions was observed and proposed on the basis of their MS/MS spectra data.This common pathway indicated that those Schiff's bases exis... 相似文献
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