Sodium-cytidine-5 -phosphate

Sodium uridine-5 -phosphate 224 is converted by HMDS 2/TCS 14 and pyrroh-dine at 145 °C, via the assumed persilylated intermediate 225, and after transsilyla-tion with boiling methanol and addition of NaOH, crystalline sodium-cytidine-5 -phosphate 226 in 69% yield [49] (Scheme 4.19). 

C9H11N307P-,Na+,2 H20 Sodium cytidine 2, 3 -cyclic phosphate, dihydrate (CYTCYP20)285... 

C9HUN307P- Na+ 2 H20 Cytidine (sodium 2, 3 -phosphate), dihydrate CYTCYP20 43 357... 

The structure shown was confirmed by the identification of cytidine 5 -phosphate and N-acetylneuraminic acid after mild acidic hydrolysis, and by the stability of the derivative on treatment with sodium borohydride. Comparison of the optical rotation of the starting derivative182 (44), the products of its hydrolysis,182 and the anomeric... 

Although the 2, 3 -cyclic phosphates of adenosine, cytidine, guano-sine, and uridine appear to be stable in aqueous solution between, approximately, pH 4 and 9, they are hydrolyzed under more-strenuous conditions (for example, 0.1M hydrochloric acid for 1 hour at room temperature or 0.5 M sodium hydroxide for 12 hours at 37°) to give a mixture of 2 - and 3 -phosphates287 in approximately equal amounts. An appreciation of this aspect of the chemistry of cyclic phosphates was of considerable importance in elucidating the mechanism of the chemical degradation of ribonucleic acid.288... 

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 Schmidt group utilized a sialyl phosphite in a very different synthesis strategy (Scheme 33) [39]. Upon treatment of sialyl donor 54 with cytidine phosphoric acid 103, a phosphite-phosphate exchange reaction occmred to give com-poimd 104 exclusively as the fi isomer. Deacylation by treatment with sodium meth-oxide followed by ester saponihcation through the addition of water provided CMP-NeuAc 88. This method circmnvented the need for an oxidation step or phosphorus deprotection. This method was also applied to the synthesis of another nat-lually occmring CMP-NeuAc derivative 105 [40]. 

Figure 21.12. Comparative TLC and PC separation of nucleotides. A Cellulose thin-layer chromatogram—development distance, 10 cm in 91 min. B Paper chromatogram run under identical conditions—development distance, 10 cm in 134 min paper Schleicher and Schull 20436. The solvent used for both was saturated ammonium sulfatejl M sodium acetate isopropanol (80 18 2). Each vertical column of spots corresponds to separate mixtures separated. Samples (1) 3 -AMP (2) 2 -AMP (3) 3 -GMP (4) I -GMP (5) 2 - and3 -GMP (6) 2 - and3 -UMP (7) 5 -AMP (8) 5 -ADP (9) 5 -ATP. (,A = adenosine, G = guanine, C = cytidine, M = mono-, D = di-, T = tri-, P = phosphate.) From K. Randerath, Biochem. Biophys. Res. Comm., 6, 452 (1961-62), by permission of Academic Press.

Nucleosides and their Analogues and Derivatives Thereof.- l-(3, 5 -Di-0-benzoyl-r-C-allyl-P-D-arabino-furanosyl)uraciI 69, 3-P-D-ribofuranosyl-6,7-dihydro-9H-thiazolo(3,2-a]purin-9-onc 70,and sodium 5-bromo-cytidine-5 -phosphate. The X-ray structure of 3-methyl-7-deazainosine (71) showed a conformation fixed anti about the glycosidic bond. 2 3 -Dideoxy-3 -methylamino-ribosylthymine (ddT(3 NHMe)), P-5-isopropyl-2 -deoxyuridine, 5-... 

Methylcytidine, 3-deazacytidine/ l-P-o-arabinofuranosylcytosine 2, 5 -phosphate/ cytidine 5 -diphosphocholine(sodium salt), thymidine 3, 5 -(dimethylphosphoramidate), 4-a-D-erythrofuranosyl-1 (4-tolyl)imidazo-... 

Prepare individual standards (Sigma) of adenosine-5 -phosphoric acid, cytidine 5 -phosphate (sodium salt), guanosine-5 -phosphate (sodium salt), and uridine-5 -phosphate (disodium salt) as l-pg/p. solutions in deionized water. Prepare each standard by dissolving 10 mg of the nucleotide in 10 ml of water. Prepare a mixed standard of the four nucleotides at 1 Ag/)il for each. To obtain the mixed standard, weigh 10 mg of each nucleotide and dissolve in 10 ml of water to achieve a concentration of 1 )ig/ J.l for each. 

The following separations (approximate values included) will be achieved for both individual nucleotides and the mixed standard guanosine-5 -phosphate (sodium salt), 0.34 adenosine-5 -phosphoric acid, 0.48 cytidine-5 -phosphate (sodium salt), 0.60 and uridine-5-phosphate (disodium salt), 0.74. The compounds will appear as dark spots against a bright fluorescent background at 254 nm. 

Nudeosides, Nudeotides, and their Derivatives.—Uridine, uridine 5 -(niethyl oxyacetate), 6-chloro-9-j8-D-ribofuranosylpurine, 6-methyl-9-j8-D-ribofurano-sylpurine, 5-acetyl-l-(3,5-0-isopropylidene-j8-D-xylofuranosyl)uracil, 2 -de-oxycytidine, the 1 1-complex of cytidine and iV-benzyloxycarbonylglutamic acid, l-(3-0-methyl-j8-D-arabinofuranosyl)cytosine, 2 -deoxyadenosine 5 -(sodium phosphate), 9-j8-D-arabinofuranosyladenine hydrochloride, 8-j8-D-ribofuranosyladenine, 8 - (2 - deoxy - oc - d - erythro - pentofuranosyl) - 6 -hydroxy-purine, l-methyl-4-jS-D-erythrofuranosyl-4-imida2oline-2-thione, and 4,6-di-0-acetyl-l,3 -anhydro-2,3-dideoxy-3-[3-hydroxy-5-methyl-(2if)-l,2,6-thiadiazin-2-yl l,l-dioxide]-a-D-n 6o-hexopyranose (455). ... 

---