α‐d‐Glucofuranose and α‐d‐allofuranose diacetonides and silyl ether of α‐d‐glucofuranose diacetonide in dithiophosphorylation reactions

Abstract

α‐d‐Glucofuranose and α‐d‐allofuranose diacetonides react with 2,4‐diorganyl 1,3,2,4‐dithiadiphosphetane‐2,4‐disulfides to form optically active dithiophosphonates in 78–81% yields, which are transformed into the corresponding ammonium salts in 90–97% yields by the treatment of n‐hexadecylamine. The S‐silyldithiophosphonate was prepared in 93% yield by the reaction of 2,4‐bis(butoxyphenyl) 1,3,2,4‐dithiadiphosphetane‐2,4‐disulfide with silyl ether of α‐d‐glucofuranose diacetonide. One of the salts obtained possesses antibacterial activity against Staphylococcus aureus ATCC 6538‐P.

Cinchona Alkaloids in the Synthesis of Chiral Salts of Phosphorus Dithioacids on the Basis of 1,2:3,4‐Di‐O‐isopropylidene‐α‐D‐galactopyranose

“…Protection of some hydroxyl groups of monosaccharides is required . We have earlier used diacetonide protection of four hydroxyl groups of α‐D‐glucofuranose and α‐D‐allofuranoseas well as D‐mannitol to obtain phosphorus dithioacids ,. One or two hydroxyl group respectively remained unprotected.…”

“…One or two hydroxyl group respectively remained unprotected. These free hydroxyl group can react with phosphorus sulfides ,. α‐D‐Glucofuranose and α‐D‐allofuranose diacetonides react with 2,4‐diorganyl 1,3,2,4‐dithiadiphosphetane‐2,4‐disulfides to form optically active dithiophosphonic acids transformed into the corresponding ammonium salts by the treatment of n ‐hexadecylamine .…”

“…These free hydroxyl group can react with phosphorus sulfides ,. α‐D‐Glucofuranose and α‐D‐allofuranose diacetonides react with 2,4‐diorganyl 1,3,2,4‐dithiadiphosphetane‐2,4‐disulfides to form optically active dithiophosphonic acids transformed into the corresponding ammonium salts by the treatment of n ‐hexadecylamine . The reaction of 2,4‐diaryl 1,3,2,4‐dithiadiphosphetane‐2,4‐disulfide with 1,2:5,6‐di‐ O ‐cyclohexylidene‐D‐mannitol results in optically active bisaryldithiophosphonic acids transformed into the bis( n ‐hexadecyldiammonium) salts .…”

“…The resonance is slightly shifted toward low field in comparison with the 31 Р{ 1 H} NMR data of linear dithiophosphoric acids (usually in the field of δ =86‐83 ppm) . The 31 P nucleus of 3 resonates in practically the same region ( δ =92.6‐87.4 ppm) as observed in dithiophosphonic acids bearing α‐D‐glucofuranosyl and α‐D‐allofuranosyl substituents . Compound 3 displays optical activity (see Supporting Information).…”

“…The weak band at 2222 cm –1 is assigned to the S‐H stretching vibrations in FTIR spectrum of 3 similarly . This bond is shifted toward low frequency range in comparison with the similar bond S–H (2394 cm –1 ) of dithiophosphonic acid with α‐D‐glucofuranosyl substituent . The 1 H NMR spectrum of 3 in CDCl 3 shows three intensive singlets ( δ =1.28, 1.40, and 1.49 ppm) of methyl groups (the fragments (C 11,12 H 3 ) 2 C and (C 9,10 H 3 ) 2 C) of acetonide cycles.…”