L-Ribitol 1-phosphate

Show that L-ribitol 1-phosphate is identical with D-ribitol 5-phosphate. 

The action of ammonia on cytidine ribitol pyrophosphate (III) gave a cyclic phosphate IX which was oxidized by periodate and bromine to yield X, the cyclic 2,3-0-phosphate of glyceronic acid. This substance was purified by paper chromatography, and hydrolyzed with acid to the 2-phos-phate (XI) and 3-phosphate (XII) of D-glyceronic acid. These substances were utilized by a multi-enzyme system from rabbit muscle which degrades carbohydrates by way of the Embden-Meyerhof pathway. The ribitol phosphate (VII) is therefore L-ribitol 1-phosphate (o-ribitol 5-phosphate). ... 

Acid hydrolysis of cytidine ribitol pyrophosphate led to a series of products, depending on the conditions of hydrolysis. L-Ribitol 1-phosphate (n-ribitol 5-phosphate), isomeric ribitol phosphates formed by acid-catalyzed migration of the phosphate group from the terminal position, and 1,4-anhydro-DL-ribitol were isolated. 

An interesting counterpart of the above reaction has been found by Baddiley and associates in the hydrolysis of L-ribitol 1-phosphate (which is the same as n-ribitol 5-phosphate) which, under acid conditions N hydrochloric acid), results in the formation of 1,4-anhydro-DL-ribitol. 

In another example, the formation89 of racemic 1,4-anhydroribitol by the action of dilute hydrochloric acid for 20 hours at 100° on D-ribitol 1-phosphate has likewise been assumed to take place by protonation of the oxygen atom of the ester function, followed by an intramolecular substitution by the hydroxyl group on C-4. Formation of this protonated phosphoric ester likewise explains the ra-cemization observed, caused by partial migration of the ester group at C-l to C-5. 

Refractive indexes, of dextrans, 353 Rhamnose, 2,4-di-O-methyl-, 297 —, 2-0-methyl-, 297 —, 2-0-methyl-L-, 298, 304, 316 Ribitol, 1-phosphate, 218 L form, 215 2-phosphate, 218 5-phosphate, 215... 

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... 

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. ... 

A quantitative determination with carob in anti-Pn XXVIII (homologous antibody N, 735 pg/ml) gave 40 pg. In an equine anti-XXIX, albizzia, carob, ghatti, okra showed + + +,-f--l-,+ + +, + reactions, respectively. Pn S XXIX contains D-galactofuranose, D-galactopyranose, N-acetyl-D-galactosamine, ribitol and phosphate (2 1 1 1 1) linked as shown in (24). The structure of S XXVIII is not known. 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

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... 

Ribitol phosphate has been identified as a component of the lipopolysaccharide from Proteus mirabilis D52. Acidic hydrolysis of the lipopolysaccharides from several strains of P. mirabilis from serogroups 016 and 033 liberated 1,4-anhydro-ribitol, which was identified by g.l.c.-m.s. of the peracetylated derivative. Ribitol has a role in the serological specificities exhibited by these lipopolysaccharides. 

Reactions (2) and (3) would be similar to those leading to the formation and transformation of cytosine diphosphate-choline 106) or uridine diphosphate 107). It is conceivable, of course, that the reduction of the pento l group to ribityl does not occur with the free pentose phosphate as pictured [reaction (1)], but by a mechanism involving the conversion of a cystosine diphosphate-pentose to cytorine diphosphate-ribitol. This type of reaction would be distantly related to reactions such as the oxidation of uridine diphosphate-glucose to uridine diphosphate-glucuronic acid 108,109). 

---