Uridine 3 -phosphate esters, alkaline

A recent example has been in an examination of the mechanism of alkaline cyclisations of uridine 3 -phosphate esters, Scheme 9.20 [51]. A plot of the logarithms of the second-order... 

The possibility that, during the alkaline hydrolysis of ribonucleic acid, tri-esters (18) - could be intermediates was ruled out on mechanistic groxmds."f > Furthermore, it was shown that the tri-ester, uridine 2 3 -(methyl phosphate) (18, R = CH3), synthesized by methylation of uridine 2 3 -cychc phosphate with diazomethane, is resistant to ribo-nuclease. f However, it has been observed that, when the benzyl ester of cytidylic acid 6 is partially hydrolyzed in acid, a significant proportion of the o isomer of this phosphoric diester is formed." ) In addition, the dinucleoside phosphates, such as adenylyl-(3 —>5 )-cytidine (14a), are also isomerized to the corresponding (2 - 5 )-dinucleoside phosphates by treatment with acid. " These studies suggest that cyclic triesters (or derivatives thereof) may be intermediates in isomerization of these phospho-diesters in acidic mediiun. 

When RNA is subjected to controlled alkaline hydrolysis eight nucleotides, two isomers each of AMP, GMP, cytosine monophosphate (CMP), and uridine monophosphate (UMP), are formed. These can be separated from one another on columns of anion exchange resins ISl), by paper chromatographic methods 1S2), and by fractional crystallization (iSS). The isomers are the 2 -phosphates ( a ) (XI) and 3 -phosphates ( b ) (XII) which arise from an intermediate cyclic 2, 3 -phosphate mononucleotide ester [Eq. (44)] (1S4-1S6). 

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