Synthesis And Characterization Of 2, 3, 4, 6-Tetra-O-Acyl-β-D-Glucopyranosyl Isothiocyanate Phosphorus Derivatives

Glycosyl isothiocyanates as a kind of special sugar compound, not only has good physiological function, but also is the important intermediate of organic synthesis. As alkyl or aryl isothiocyanates, can happen nucleophilic and cycloaddition reactions etc. They have been widely used in synthesis of physiological activity and the potential of glycosyl glycosylthioureas, glycosylguanidins , heterocyclic compounds, as well as sugar derivatives of glycosyl amino acids, protein peptide and sugar-protein so on . As a small molecule compounds, organophosphate n-phosphoryl ester derivatives also has extensive biological activity, they participate the material transformation of the organism and plays an important role in the life process of material transformation. Most of the enzyme reactions were controlled by ways of phosphorus and phosphorus acylation acylation.The glucose which is inexpensive and easy to result in was used as material in this paper, the intermediate of the entire acylation glucopyranosyl isothiocyanate was synthesized through three steps of acylation and benzoylation, bromination and isothio- cyanic. And then make the whole acylation glucopyranosyl isothiocyanate and diethyl phosphite esters, diisopropyl phosphite esters, dibutyl phosphite esters and diisobutyl phosphite esters and so on four kinds of alkyl phosphate esters additive to be nucleophilic glycosyl phosphoryl esters; Results, a total of fourteen compounds were synthesized throughout the experiment. Among them, eight glucopyranosyl isothiocyanate phosphorylation compounds of 4a - 4d and 4'a - 4'd have not been reported in the literature. Specific synthetic route is as follows: 1.Synthesis of N-(dialkoxy phosphoryl) sulfo-formyl -2,3,4,6-Tetra-O-acetyl-β-D-Glucopyranosyl amine2.Synthesis of N-(dialkoxy phosphoryl) sulfo formyl-2,3,4,6-Tetra-O-benzoyl-β-D-Glucopyranosyl amineTheir structures of 4a-4dand4'a-4'd were characterized by infared spectroscopy (IR),nuclear magnetic resonance hydrogen spectrum(¹HNMR),phosphorus spectrum (³¹PNMR)and high-resolution mass spectrometry(MS). And their melting point were determined, besides these, The physiological activity of part of the target compounds are testing.Paper not only borrowed idieas from classic synthesis and separation methods, but also joined our innovation by times of fumble in the experimental process. First, When glucose were protected by benzoyl, because using the lively benzoyl chloride, more heat was released from the reaction process, reaction was too violent under the room-temperature condition,and easy to cause the reaction mixture black and curing, causing dif ficulty in the post-treatment,yield is extremely low; we keep the reaction system lower tempe rature with water-ice bath in the experimental process, so that the reaction can be occurred stea dily, simplify the post-processing, and make the yield increase.Second, The separation method was improved in products separation process of bro- minetion reaction, Directly with petroleum ether recrystallization, not only make the operating process simple and improving the yield, also avoid trival and waste solvent in the separation process of using column chromatography.Third, In synthesis of glucose glycosyl isothiocyanates, Using the molecular sieve of high temperature activation can make yield increase by 15% or so,and the effect using fourA molecular sieve powder is better than the granular. This may be because of the molecular sieve activated can be better in absorption of solvent water, reducing side reaction of glycosyl isothiocyanates NCS with water molecules;And the molecular sieve powder has bigger surface than the granular, so that the reaction can be fully carried out.