Access count of this item: 145
|Title:||The effect of pressure on the rate of the benzidine rearrangement VI : 2-methoxy-2'-methylhydrazobenzene|
|Publisher:||The Physico-Chemical Society of Japan|
|Journal title:||The Review of Physical Chemistry of Japan|
|Abstract:||The effect of pressure on the rate of the acid-catalyzed rearrangement of 2-methoxy-2'methylhydrazobenzene in an aqueous ethanolic solution of 85 vol % was studied under the condition of 15～30℃ and 1～1, 500kg/cm^2. It was observed that the rearrangement was of first order with respect to the concentration of hydrogen ion and was accelerated by pressure. Comparing the activation parameters obtained, i.e. E≠=15.1kcal/mole, ΔS≠=-9.4 e.u., ΔV≠=-8.5 cm^3/mole for one-proton mechanism, with those previously obtained, it was concluded that the transition state of one-proton mechanism was strongly solvated, polar and compact. For this one-proton mechanism, by correcting the pK_a values for the steric effect of ortho-substituents, a good linear free energy relationship between the rate constants and pK_a of ortho-substituted anilinium ions was obtained.|
|Appears in Collections:||Vol.41 No.1 & 2|
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