Ribitol phosphate, preparation

Traces of an optically active anhydroribitol and its phosphates are produced when some teichoic acids are hydrolyzed with alkali.66 67 No anhydroribitol is formed by similar treatment of ribitol, its 1-, 2-, or 3-phosphates, or ribitol 1,5-diphosphate.68 However, small proportions of anhydroribitol and its phosphates are produced by the action of alkali on a synthetic poly (ribitol phosphate) prepared by the action of diphenyl phosphoro-chloridate oil 3,4-O-isopropylideneribitol l-phosphate and 2-phosphate.68 This observation suggests that 1,4-anhydroribitol (13) or its derivatives (15) are produced by fission of a phosphodiester, for example (14), in the manner indicated in Fig. 3, and that this reaction occurs together... 

Poly(ribitol phosphate) synthetase has been found in particulate fractions from Staphylococcus aureus H, and Lactobacillus plantatrum.lt ll-m The bulk of the activity in Lactobacillus plantarum was in crude, cell-wall preparations, and the enzyme is apparently located in the membrane, although intimate association with the wall itself has been suggested. Unlike the natural teichoic acid, the enzymically synthesized ribitol phosphate polymer was readily extracted with phenol hydrolysis by acid and by alkali gave the expected products, and oxidation with periodate indicated a chain length of 5-9 units, a value which compares well with that of 8 units for the natural polymer in the walls of this organism. 

Synthetic ribitol phosphate polymer, unlike teichoic acid in a wall, is readily extracted from the particulate enzyme or membrane preparation by treatment with phenol.18 Similarly, teichoic acid synthesized by intact cells in the presence of penicillin is only loosely attached to the wall,111 and it may be significant that, in each case, synthesis of teichoic acid has occurred without the simultaneous synthesis of glycosaminopeptide. It is now known that, in the normal wall, teichoic acid and glycosaminopeptide are attached to each other, and it has been suggested that the low activity of cell-free synthetase is due to the absence of suitable acceptor molecules of glycosaminopeptide. This possibility could account for the ease of removal of teichoic acid formed when simultaneous synthesis of glycosaminopeptide was not possible. 

The simplest parent compound, poly(glycerol phosphate) (R=H in (10.53a)) has been prepared by laboratory methods. Poly(ribitol phosphate) (R=R =H in Equation 10.53b) has been made by scheme (10.54). 

Synthetic cytidine ribitol pyrophosphate was prepared by condensing cytidine 5-phosphate and D-ribose 5-phosphate in the presence of dicyclohexylcarbodiimide, followed by the reduction of the cytidine D-ribose pyrophosphate with sodium borohydride. 

The synthetic material, like natural teichoic acid, is a (1 — 3)-linked polymer of glycerol phosphate. A similar preparation from Lactobacillus plantarum (ATCC 8014) catalyzes the synthesis of poly(ribitol... 

The value of — 22.6 0.6 kj mor obtained is similar to that of other hemi-acetal phosphoric esters. Treatment of 4-( -acetyl-2,3-< -carbonyl-a-L-rhamno-pyranosyl bromide with dibenzyl phosphate-triethylamine, followed by deprotection, yielded j3-L-rhamnopyranosyl phosphate. The same paper contains a synthesis of thymidine 5 H/ L fhamnopyranosyl)pyrophosphatc. Long-chain (C10-C16) alkyl 0-D-glucopyranosyl phosphates have been prepared via the orthoester method and described as novel anionic detergents. The MacDonald procedure (anhydrous phosphoric acid in vacuo at 56-60 for 2 h) has been used to convert di- and tri-saccharides into their a-glycosyl phosphates. The syntheses and n.m.r. of 2-acetamido-2-deoxy-D-glucose 1-, 3-, 4-, and 6-phosphates have been published. The chemical shifts were studied with respect to the position of the phosphate group D-Ribofuranosyl ribitol... 

The allyl glucosylrhamnoside derivative (46), which is an antigenic determinant specific for Mycobacterium leprae. was synthesised and copolymerized with polyacrylamide for use as a diagnostic for leprosy, and the repeating units of Haemophilus influenzae. 2-Q-)9-D-glucopyranosyl-L-ribitol 4 - and 1-phosphate, have also been prepared synthetically. ... 

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