ACTION OF HYDROGEN FLUORIDE ON NUCLEOTIDES AND OTHER ESTERS OF PHOSPHORUS(V) ACIDS

The action of hydrogen fluoride, both liquid and aqueous, on a number of mono- and diesters of orthophos phoric acid, two cyclic phosphates, mono and diesters of polyphosphates, phosphorofluoridate esters, and inorganic phosphates was investigated. The particular reactions which take place are found to be a function of temperature (- 50 to +25°;), time (0.04-28 hr), and acid concentration. A comparison of the acid-catalyzed reactions of phosphate esters in aqueous solution with the behavior of such compounds toward 60% hydrofluoric acid brings out several interesting contrasts. First, the reactions in 60% hydrofluoric acid which are described here are fast compared with reactions observed with ordinary aqueous acids. Second, in the reactions with 60% hydrofluoric acid all of the evidence points toward the conclusion that phosphorus-oxygen, rather than carbon-oxygen, bond cleavage takes place exclusively. Third, this acid is a highly specific dephosphorylating agent compared with ordinary aqueous acid. These three features of the chemical properties of hydrogen fluoride in relation to phosphorus (V) esters are correlated with information concerning the characteristics of hydrogen fluoride both as an anhydrous liquid and in concentrated aqueous solution. Since extended exposure to 60% hydrofluoric acid causes no deamination of adenine, guanine, or cytosine, a method was devised for the base analysis of ribonucleic acid (RNA) by degradation with this reagent. © 1969, American Chemical Society. All rights reserved.