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Although electron-donating substituents such as the methoxy group are expected to increase the positive charge on selenium, the higher stability of the methoxy-substituted zwilterion relative to the unsubslituted compound is probably due to an increase in the basicity of the tertiary amino group. Therefore, the amino groups in compounds 26, 28, and 30 are better bases than the amino substituents in compounds 25, 27, and 29.
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The identification of selenenic and seleninic acids is based on literature data and a number of control experiments. Treatment of the diselenides with H2O2 (5 equiv) produced the selenenic and seleninic acids in the cases of 4, 20, and 21, and only the selenenic acids in the case of 22-24. Treatment of selenols 25-30 with H2O2 produced identical signals in the 77Se NMR. This precludes the possibility of the formation of any thiol esters in the reactions. The reactions of the oxidized species with PhSH are also helpful for assignation of the signals for the selenenic acid and seleninic acid intermediates. While the selenenic acids 38, 40, and 42 required only one equivalent of PhSH each to produce the corresponding selenenyl sulfides quantitatively, higher concentrations of PhSH were required for complete conversions of the oxidized compounds derived from 4, 20, and 21 into the
-
77Se NMR. This precludes the possibility of the formation of any thiol esters in the reactions. The reactions of the oxidized species with PhSH are also helpful for assignation of the signals for the selenenic acid and seleninic acid intermediates. While the selenenic acids 38, 40, and 42 required only one equivalent of PhSH each to produce the corresponding selenenyl sulfides quantitatively, higher concentrations of PhSH were required for complete conversions of the oxidized compounds derived from 4, 20, and 21 into the corresponding selenenyl sulfides. As an example, the signal due to the selenenic acid 37 disappeared completely upon addition of one equivalent of PhSH to a mixture containing selenenic acid 37 and seleninic acid 43. The addition of an excess amount of PhSH to the mixture converted both 37 and 43 into the selenenyl sulfide 31.
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