Carbon-13 chemical shifts for 33 methyl phenyl sulfides, sulfoxides, and sulfones are reported. Observed trends are discussed in terms of the steric and electronic influences of the substituent groups. Additivity correlations for para-disubstituted materials are noted. In general, the shieldings of methyl carbons bonded to sulfur are rather insensitive to the nature of the aromatic substituents. By contrast to the proton shieldings, the CH3SO and CH3SO2 carbons exhibit nearly identical chemical shifts.

Reaction of 15 (0.2 g in 1 ml of DMSO-de) with 1 equiv of potassium ieri-butoxide was observed directly by nmr. The AB pattern of the benzylic protons disappeared rapidly but there was no significant change in the chemical shift of the vinylic, SCH3, or OCHg resonances of 15. Attempts to isolate the product(s) of this reaction led only to the isolation of a sticky red solid which could not be recrystallized. Reaction of 15 with sodium hydride in dry THF in an inert atmosphere led to the immediate evolution of hydrogen, precipitation of NaBF4, and formation of a dark red solution which, after evaporating at reduced pressure, gave a red oil which solidified on washing repeatedly with pentane. Analysis by tic showed the presence of at least three components. Separation was unsuccessful, and the nmr of the crude product in CDC13 gave very broad signals which were uninformative as to structure.S-Benzyl-S-methyl-S-phenacylsulfonium ylide ( 14) was prepared from the corresponding sulfonium bromide salt by treatment with sodium hydride in THF.84 The sulfonium bromide was prepared from benzyl methyl sulfide and phenacyl bromide in benzene.Preparation of Sulfonium Salts 20.-Each of the salts was prepared from the corresponding sulfide by methylation with trimethyloxonium fluoroborate, as described above for 10. The salts so obtained were recrystallized to analytical purity from absolute ethanol. The sulfides were in turn prepared by the reaction of the appropriate thiophenol under basic conditions (sodium ethoxide in ethanol) with the appropriate phenacyl (24) K. W.

other ROX type intermediates with ethyl iodide could give ether. To shed light on the mechanism of ether formation, reactions of alkyl iodides with hypochlorites were studied. X RI + ROX -RI^-* ROR + IX OR Chlorine oxide, CI2O, and I2O5 could be formed from ICIO3 by a self-oxidation reaction, with transfer of oxygens from chlorine to iodine. The reaction of chlorine oxide with 2 mol of ethyl iodide in carbon tetrachloride at 0°was found to give ethyl chloride (40% yield), diethyl ether (20%), and ethyl acetate (8%). Since chloride was not detected in the dichlorine heptoxide reaction, chlorine oxide cannot be the reactive intermediate.

A number of androstenone, estrone, and pregnenone derivatives of cysteamine have been prepared by reacting the steroid amines with ethylene monothiolcarbonate. The amides of androstenone carboxylic acid with mercaptoethylamine and cysteine have also been prepared.

The benzyl proton shifts in 11 series of para-substituted toluenes bearing different cc substituents have been determined. I n each series, a plot of the benzylic shift against the Hanimett o values of the parasubstituent is linear. The slope of these plots varies from 0.2 to 0.0 p.p.m./o. The variation is found to be conformationally dependent, a fact which is not explicable by current theory. A hyperconjugative interaction is proposed to account for these results and for several anomalies in the literature.Canadian Journal of Chemistry, 46. 1595 (1968) In the last decade a large number of authors have presented data showing a correlation between the effect of substituents on the chemical shifts (SCS) of protons on a benzene ring, and the Hammett o values of the substituents (1-3). More recently, correlations between o values and the SCS of protons in the side chain of aromatics have been reported (4, 5, and references therein). It is usually assumed that the SCS results from the inductive and resonance effects of the substituent, which alter the electron density at the ring carbon atoms. This change is then transmitted through the n electrons to the proton in question. An alternative explanation involving field and mesomeric effects (the F-M correlation) has recently been put forward by Dewar and Takeuchi (6).We wish to report the determination of the para-substituent effect on the benzylic proton shifts, in eleven series of compounds of the formula X-C6H5-CH,-Z.For each Z, at least five X substituents were studied whose range of o values was 0.95 or greater.' An example of the Hammett correlation for the benzylic protons of eight tetrahydropyranyl ethers is shown in Fig. 1. This plot is typical of 'All chemical shifts were measured on a Varian DA-60 nuclear magnetic resonance spectrometer using dilute solutions (0.2 M ) in CDCI,, except in the case of compounds whose methylene protons were magnetically non-equivalent. In these cases 0.3 M solutions were used. In each series, 0.1 M solutions were also studied and dilution shifts beyond the experimental error of 0.2 c.p.s. could not be detected. Satisfactory elemental analyses were obtained for all new compounds included in this study.