Phosphate dibenzyl hydrogen

Dibenzyl esters of (X) are obtained by the action of keten on dibenzyl hydrogen phosphate.2... 

Dibenzyl hydrogen phosphate when warmed with oxalyl chloride evolves hydrogen chloride and gives bisdibenzyl-phosphoryl oxalate (XI), which when heated to its melting-point yields tetrabenzyl pyrophosphate, 4... 

Dibenzyl hydrogen phosphate and thionyl chloride give a small yield of the pyrophosphate. 

The same pyrophosphate5 can be prepared in high yield from dibenzyl hydrogen phosphate by reaction for a short time with tetraphenyl pyrophosphate at room temperature in an-... 

With acetic acid at room temperature, the Brigl anhydride rearranges, to give 1,3,4,6-tetra- 0-acetyl-/3-D-glucopyranose in high yield.213 With dibenzyl hydrogen phosphate, dibenzyl 3,4,6-tri-O-acetyl-/3-D-glucopyranosyl phosphate is formed.2,3a... 

Synthesis of Phosphoric Acids and their Derivatives.-New approaches to the preparation of dialkyl phosphorofluoridates include the treatment of a vinyl phosphate, e.g.,(l), or an irninophosphace, e.g.,(2), with triethylamine tris(hydrogen fluoride) when the alkyl group consists of a suitably protected nucleoside, the reaction between mono(crimethylsilyl) phosphite in pyridine and sulphuryl chloride fluoride at -30° has been successfully explored. Dibenzyl phosphorofluorldate, hitherto unreported, has been obtained from tecrabenzyl diphosphate and caesium fluoride, and also from the reaction between dibenzyl hydrogen phosphate and 2-fluoro-N-methylpyridinlum tosylate. ... 

An ethereal soln. of phenyldiazomethane added gradually during 20 min. to an ice-cold stirred ethereal soln. of phosphorous acid — dibenzyl phosphite. Y 84%.—An ethereal soln. of diphenyl-diazomethane added to a suspension of dibenzyl hydrogen phosphate until a pink coloration persists, then more dibenzyl hydrogen phosphate added until the coloration disappears —benzhydryl dibenzyl phosphate. Y almost 100 %.—This method is limited by the accessibility of the diazo compounds. (F. e. s. F. R. Atherton, H. T. Howard, and A. R. Todd, Soc. 1948, 1106.)... 

It has been known for some time that carbodi-imides react with carboxylic acids (a) giving acid anhydrides and ureas, or (b) iV -acylureas. Khorana and Todd have been successful in converting dibenzyl hydrogen phosphate into the pyrophosphate by the following reaction with dicyciohexylcarbodi-imide ... 

Two publications on the higher ketose mono- and bis-phosphates in rat-liver extracts have described their detection and estimation by colorimetry and enzymic assay,and the synthesis of octulose 1,8-bisphosphates using muscle aldolase. A stereospecific synthesis of adenosine 3, 5 -cyclic phosphothioate has appeared/ Standard condensation methods have been used to synthesize the 5 -O-(Taminoethane-phosphonyl) nucleosides (21) and (22). The compounds were shown to be inert to the action of alkaline phosphatase and are poor substrates for 5 -nucleotidase. The selenophosphates (23) and (24) have been prepared.Phosphorylation of nucleosides using dibenzyl hydrogen phosphate,... 

Diethyl azodicarboxylate in dry tetrahydrofuran added at room temp, to a mixture of thymidine, triphenylphosphine, and dibenzyl hydrogen phosphate in the same solvent, stirring continued 3 hrs., allowed to stand overnight at room temp., and the resulting intermediate hydrogenated with Pd in 75%-ethanol thymidine 5 -phosphate. Y 47% as the Ba-salt. - No isomeric 3 - or 2 -phosphates are formed. F. e. s. O. Mitsunobu, K. Kato, and J. Kimura, Am. Soc. 91, 6510 (1969) enzymatic phosphorylation with sodium p-nitrophenyl phosphate and cells of Pseudomonas trifolii s. S. Suzaki et al., Chem. Pharm. Bull. 18, 172 (1970). 

The phosphates (29) and (30) have been prepared by reaction of the corresponding peracetylated sugar 1,2-oxazoline derivative with dibenzyl hydrogen... 

Finally, bidentate bis(guanidinium) hosts like 26 reported by Anslyn et al. have recently been shown to bind phenyl phosphate anions in a bis(bidentate) fashion. Hydrogen-bonding N(H) -0 distances are in the range 2.658(7)-2.868(6) A, while solution studies in 15% HjO/DMSO give binding constants of ca. 500 M" with dibenzyl phosphate. ... 

Koga et al. complexed oxo acids like methyl phenylphosphonate with bis(resorcinol) quinoline derivative 57 [83], Anslyn and coworkers presented a more rigid polyazacleft containing hydrogen bond acceptor and donor sites in form of pyridine rings and amino groups, respectively. The formation of the 3 1 complex 58 with dibenzyl phosphate is assumed, in which the four components are spatially fixed by a net of H-bonds [84]. 

Thus, as shown below [Scheme 6], exposure of lactol 14 to dibenzyl-A,lV-diethylphosphoramidite and l//-tetrazole in dichloromethane followed by oxidation of the intermediate phosphite with 30% hydrogen peroxide provided the desired a-phosphate 11 (3Jhih2 = 3.4 Hz) in 86% yield as a single diastereomer. The stage was now set for introduction of the pentapeptide side chain. 

The reagent is used for phosphorylation of nucleosides. It reacts with a free primary or secondary hydroxyl group to form a dibenzyl phosphate. Hydrogenation... 

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