icals have, in fact, been photolytically generated from secondary amines in strongly acidic media.16 Parallelling our present results, spontaneous production of aminium radicals from protonated chloramines under mild conditions was observed,16 and subsequent fast addition to unsaturated hydrocarbons. If ordinary aliphatic aminium radicals are generated in weakly basic, neutral, or weakly acidic aqueous media, we have found,17 rapid loss of a protons occurs with subsequent oxidative dealkylation. Hence, the characteristic reactions of aminium ions near neutrality are different from those in strongly acidic media.
Experimental SectionWater and triethylenediamine perchlorate were purified as previously described.1 Aqueous hypochlorous acid solutions (16) W.
The 13C chemical shifts and 13C-H coupling constants of 1, l-disubstituted and trisubstituted olefinic hydrocarbons have been examined to elucidate the influence of ring strain and bulky substituents on these parameters.THERE is continuing interest in the correlation of 13C-H coupling constants and 13C chemical shifts1s2 with the molecular structure of 01efins.~~~ We now report the lSC spectra of selected 1,l-disubstituted and trisubstituted olefins. These spectra were obtained on a Varian XL-100-15 operating a t 25.2 MHz in the Fourier transform mode of operation. The precision of the measurements of the chemical shifts and coupling constants (see Figure and Table) is 0.1 p.p.m. and 0.5 Hz, respectively.The olefinic JCH for the methylenecycloalkanes reported here and values for cyclic olefins in the literature2e are all greater than 153 Hz. However, for 1,l-di-t-butylethylene, trimethylethylene, and tri-t-butylethylene the coupling
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