Key indicatorsSingle-crystal X-ray study T = 296 K Mean '(C±C) = 0.004 A Ê R factor = 0.041 wR factor = 0.134 Data-to-parameter ratio = 14.6For details of how these key indicators were automatically derived from the article, see
Most alkyl phenyl sulfones are readily alpha-chlorinated with CCl(4) and alpha-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily alpha-chlorinated with CCl(4), it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting alpha-anion formation. This effect is reversed by the electron-withdrawing influence of two alpha-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily alpha-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the alpha-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the alpha-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-alpha-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that alpha,alpha-dihalogenation is attained while much substrate is still present and the mono-alpha-halogenated product is not detected. The ease of reductive debromination of alpha-bromo sulfones with Cl3C- was correlated with the stability of the formed alpha-anions, explaining the success with alpha-bromobenzylic sulfones but failure with alpha-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the alpha-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes.
The achiral meso title compound, C9H14O3, is an intermediate for a series of structurally unique compounds. Intermolecular O—H⋯O hydrogen bonds produce centrosymmetric R22(8) rings which dimerize the molecules through the carboxyl group, while C—H⋯O interactions through the carboxyl α‐H atom and the ketone O atom interconnect the dimers via centrosymmetric R44(24) rings, producing infinite one‐dimensional dimeric ribbons.
The synthesis of (1SR,2SR,5RS,6RS)‐5‐ethyl‐4‐(4‐methoxyphenyl)‐2,6‐dimethyl‐3‐cyclohexenecarboxylic acid was accompanied by the formation of a by‐product shown to differ only by the absence of the 5‐ethyl group. That mixture was subjected to an enantiomer resolution process utilizing (−)‐menthol and dicyclohexylcarbodiimide (DCC), and the expected diastereomers of both compounds were formed along with their anhydrides and an unexpected, but related, compound in both cases. The unexpected compound formed from the substrate lacking the 5‐ethyl group was unequivocally identified by X‐ray analysis as the title compound, C29H42N2O3, (I), a result that, together with the NMR spectra, similarly identified the corresponding product from the compound possessing the 5‐ethyl substituent. The two enantiomers of (I) appear to be disordered and superimposed in the asymmetric unit, differing only in the position of the double bond, a rare phenomenon made possible by the unusual stereochemistry of (I).
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