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In a number of kinetic runs (not reported in Table 1) carried out at benzenethiol concentrations on the order of 0.5 M, the third-order specific rates turned out to be higher by some 15-20% than those measured at lower concentrations. This finding might indicate the existence of a modest second-order contribution in benzenethiol, or might well be ascribed to non-ideal behaviour in the relatively concentrated benzenethiol solutions
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29
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0001694931
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2Cl at 123 K (see: G. S. Denisov, N. S. Golnber, J. Mol. Struct. 1981, 75, 311-326). Under the given conditions the ion pair is in equilibrium with the hydrogen-bonded adduct.
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Keto-enol equilibrium constants
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33
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0013451606
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note
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Analogous results were observed with methyl vinyl ketone, which gave the addition product 4-(phenylthio)-2-butanone in virtually quantitative yield at a comparable rate. In the presence of the uranyl-salophen catalyst, however, the kinetics showed considerable scatter that was reduced, but not eliminated, when methyl vinyl ketone was freshly purified by distillation from calcium hydride in vacuo. Better reproducibility of results occurred also when ethyl vinyl ketone was distilled
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35
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Manuel, G.5
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