M. Venugopal, C. D. Reddy, M. F. S. Babu
2000
Citations
0
Influential Citations
3
Citations
Journal
Heterocyclic Communications
Abstract
Novel l,2-0-(l-methylethylidene)-3-0-(phenylmethyl)-a-D-glucofuranose cyclic phosphoramidate/phosphates/ phosphorothioate (3a-d) and 1,2-0-( 1 -methylethylidene)-a-D-xylofuranose cyclic bis(2-chloroethyl)phosphoramidate (5) have been synthesized from reactions of equimolar quantities of 3-0-benzyl-l,2-0-isopropylidene-a-D-glucofuranose (1) or 1,2isopropylidene-D-xylofuranose (4) with bis(2-chloroethyl)phosphoramidic dichloride (2a), O-2-chloroethyl phosphoryl dichloride (2b), trichloromethyl phosphonic dichloride (2c) and phenylphosphorothioic dichloride (2d) in the presence of triethylamine in dry tetrahydrofuran. The structures are characterized by IR, Ή , P NMR and mass spectral data. Introduction Phospha sugars are one kind of pseudo sugar derivatives having a phosphorus atom in the hemiacetal ring of the sugar'·. Like aza or thia sugars,whose hemiacetal rings has a nitrogen or a sulfur atom respectively, phospha sugars have been expected to exert biological activities by their affinity to organs. Therefore phospha sugars are of interest in the aspects related to not only syntheses but also structures and biological activities. They are mainly prepared from sugar starting materials with suitable protections, functional group interconversions, cyclisations and deprotections". N-Phosphorylated nitrogen mustard compounds are proven drugs in cancer chemotherapy". In view of this, the title compounds 3&5 were synthesized and characterized by elemental, IR, NMR ( Ή and "Ρ) and mass spectral data. Results and Discussion 3-0-Benzyl-l,2-0-isopropylidene-a-glucofiiranose (1) was prepared from D-glucose and reacted with members of 2 namely bis(2-chloroethyl)phosphoramidic dichToride (2a), O-2-chioroethyl phosphoryl dichloride (2b), trichloromethyl phosphonic dichloride (2c) and phenylphosphorothioic dichloride (2d) to obtain members of 3 (Scheme 1). 1,2-IsopropylideneD-xylofiiranose (4) was prepared from xylose'' and treated with 2a to get 5. Two equivalents of triethylamine served as the base with tetrahydrofuran as the solvent. Purification of members of 3&5 was achieved by filtering off the triethylamine hydrochloride, removing the solvent under reduced pressure and treating the residue obtained, with increasing gradients of hexane-ethylacetate mixture. The compounds 3&5 were obtained as liquids. Attempts to determine their boiling points even under reduced pressure failed due to their thermal sensitivity. Physical and spectral data for the products obtained are found in Tables 1-3.