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There is evidence that ideas put forward by Curtin and Hammett pertaining to Scheme 1 were in fact published earlier in 1907 by Solomon Acree (Acree, S. F. Am. Chem. J. 1907, 38, 1). Acree studied the oxygen and nitrogen alkylations of tautomeric mixtures of 1-phenyl urazoles with diazomethane in ether solution. He correctly concluded that "such reactions do not give us decisive evidence in regard to the relative amounts of the enol and keto forms in any given amide group in which the change from one tautomeric form to the other is very rapid in comparison with the reactions between the two forms and the alkylating reagents." Furthermore, he derived an expression, identical in form to the Winstein-Holness equation, for the observed second-order rate constant for the appearance of total product as a function of the relative populations of the urazole enol and keto forms. The work by Acree was cited neither in the works of Curtin, Hammett, or Winstein on this subject nor in the review by Seeman (see ref 7b).
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The analytical solution given in eqs 1a-d have been verified using the symbolic logic program Mathematica (Wolfram Research).
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