TY - JOUR
T1 - The products and kinetics of hydrolysis of cyanopyridinium ions
AU - Kosower, E. M.
AU - Patton, J. W.
N1 - Funding Information:
1 Alfred P. Sloan Fellow 1960-1964. * Abstracted in part from the Ph.D. Thesis of J.W.P. submitted to the faculty of the University of Wisconsin, June 1961. a Support from the National Institutes of Health under Grant E-1608, from the Ohio Oil Company for a fellowship and from the Wisconsin Alumni Research Foundation is gratefully acknowledged. ’ It should be noted that substantial numbers of chemists are completely unable to detect HCN by odor. Cf. footnote 21, E. M. Kosower, J. A. Skorcz, Jr. and W. M. Schwartz, Jr., J. W. Patton, J. Amer. Chem.S ot. 82,2188 (1960). J R. I. Ellin, J. Amer. Chem.S ot. Mb,6588( 1958). a I. Enander, A. Sundwall and B. Sorbo, Biochem. Pharmacol.7 ,232 (1961). ‘I J. L. Way, School of Medicine, Marquette University, personal communication. a I. Enander, A. Sundwall and B. Sorbo, Bloc/rem. Pharmacol. 7,226 (1961). @H. L. Bradlow and C. A. Vanderwerf, J. Org. Chem.1 6, 1143 (1951).
PY - 1966
Y1 - 1966
N2 - The hydrolysis of 1-methyl-2-cyano, 4-cyano-, and 3-cyanopyridinium ions by aqueous base has been studied. The kinetics of the reaction of the 2- and 4-cyano derivatives were measured by polarographic analysis of cyanide ion formation, and the rate of reaction of the 3-cyano ion was followed spectroscopically at 3500 Å. The 2- and 4-cyano ions yielded the corresponding pyridones and carbamidopyridinium ions, while the 3-cyano ion formed 3-carbamidopyridinium ion and 4-cyano-5-methyl-amino-2, 4-pentadienal. The ratios of the products varied in each case with pH. The ratio of carbamidopyridinium ion formation rates for the three isomers was 50:5·7:1 (2-:4-:3-) with a second-order rate constant for the 3-isomer of 0·28 1 mol-1sec-1. The rate ratio for attack on the pyridinium ring was > 1100:43:1 (2-:4-:3-) with a rate constant for the 2-isomer of ∼76 1 mol-1 sec-1 at 25°.
AB - The hydrolysis of 1-methyl-2-cyano, 4-cyano-, and 3-cyanopyridinium ions by aqueous base has been studied. The kinetics of the reaction of the 2- and 4-cyano derivatives were measured by polarographic analysis of cyanide ion formation, and the rate of reaction of the 3-cyano ion was followed spectroscopically at 3500 Å. The 2- and 4-cyano ions yielded the corresponding pyridones and carbamidopyridinium ions, while the 3-cyano ion formed 3-carbamidopyridinium ion and 4-cyano-5-methyl-amino-2, 4-pentadienal. The ratios of the products varied in each case with pH. The ratio of carbamidopyridinium ion formation rates for the three isomers was 50:5·7:1 (2-:4-:3-) with a second-order rate constant for the 3-isomer of 0·28 1 mol-1sec-1. The rate ratio for attack on the pyridinium ring was > 1100:43:1 (2-:4-:3-) with a rate constant for the 2-isomer of ∼76 1 mol-1 sec-1 at 25°.
UR - http://www.scopus.com/inward/record.url?scp=0040056300&partnerID=8YFLogxK
U2 - 10.1016/S0040-4020(01)82128-1
DO - 10.1016/S0040-4020(01)82128-1
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AN - SCOPUS:0040056300
SN - 0040-4020
VL - 22
SP - 2081
EP - 2093
JO - Tetrahedron
JF - Tetrahedron
IS - 7
ER -