Synthesis, Characterization Of N-(O, O-dialkyl Phosphryl)-D-glucosamine And Relative Quantum Chemistry Research

In this paper, the recent progress on the chemical modifications of chitosan and glucosamine, phosphorylated chitosan and glucosamine derivatives and phosphorus derivatives of natural products were reviewed in detail. Based on the reference survey, the structure parameters of glucosamine, the activity of-OH and-NH2 of reactant have been predicted by quantum chemistry calculation. A series of N-(O,O-dialkyl phosphoryl)-D-glucosamine were synthesized, and the problems about the structure characterization of N-(O,-dialkyl phosphoryl)-D-glucosamine also have been studied.1. The quantum chemistry research of glucosamineUsing a-D-glucosamine as model, after geometry optimization, the structure parameters of bond length and charge distribution have been calculated using DFT at the B3LYP/6-31G(d, p) level to get relative properties of a-D-glucosamine. The activities of-OH and-NH2 have been compared by Frontier Orbital Theory and Fukui Function, and this provide theoretical guidance for concrete experiments.2. Synthesis and characterization of N-(O,O-dialkyl phosphoryl)-D-glucosamineUsing D-glucosamine hydrochloride as the starting material, N-(O,O-dialkyl phosphoryl)-D-glucosamine were synthesized without protection of hydroxyl by Atherton-Todd reaction(Scheme 1), and the optimum reaction conditions were established by many experiments. The structure of N-(O,O-dialkyl phosphoryl)-D-glucosamine was determined by HR MS, FT-IR,1H NMR,13C NMR, 31P NMR and ESI-MS/MS. This concise and convenient synthetic pathway provides a new approach for the preparation of N-phosphoryl glucose derivatives.3. The research on the configurational transition of N-(O, O-dialkyl phosphoryl)-D-glucosamine By dynamic NMR and 2D NMR, it is confirmed that there's multirotation of N-(O,O-dialkyl phosphoryl)-D-glucosamine in H2O solution, that means the configuration has shifted. The relative structure parameters and energy calculation about a configuration andβconfiguration of two compounds of N-(O, O-dibutyl phosphoryl)-D-glucosamine and N-(O, O-diisobutyl phosphoryl)-D-glucosamine also prove that there's configurational transition of N-(O, O-dialkyl phosphoryl)-D-glucosamine in H2O.