Alcohol Reaction conditions Product composition CHKHClCH=CHz SOCl2, no solvent 33% CHaCHClCH=CHs 6770 CH&H=CHCHICl CHaCH=CHCHzOH SOC12, no solvent 71% CHoCHClCH=CH* CHaCH=CHCHzOH SOC12 in Et20 99% CHsCHClCH=CHt CHaCHOHCH=CHz SOClz in Et20 100% CHsCH=CHCHzCl ( -)trans-CHsCH=CHCHOHCHa SOCl, in EtzO CHsCH=CHCHClCHs CsHsCH=CHCHzOH 0.1 M R O H + 0.1 MSOCl, in Et20 100% CeHsCHClCH=CHz CsHbCH=CHCH*OH 60% CsHrCHClCH=CHz 40% CeHsCH=CHCHzCl 29 7 0 CH,CH=CCH CHzCl 100% (-1 tram-show a-phenylallyl chloride is the product. This thermodynamically less stable secondary chloride is rearranged only very slowly in the reaction solution.Our present evidence is still insufficient to decide whether the SNi' mechanismZ involves a one-stage concerted process or ionization to an intimate, rigidly oriented carbonium chlorosulfinate ion pairI6 followed by internal returne of the chloride component of the chlorosulfinate anion to give rearranged chloride. It is very clear that the SNi' mechanisms does not involve a carbonium chloride ion pair of the type employed by Cram' in his preferred mechanism for the action of thionyl chloride on the 3-phenyl-2-butanols. A carbonium chloride ion pair in the a, y-dimethylallyl system would lead to a trans-chloride which is 100% racemic instead of the inverted chloride actually observed. Further, a carbonium chloride ion pair would not lead to the specific structural results obtained with the butenols and cinnamyl alcohol.The dominant role of the SNi' reaction is soinetimes difficult to preserve. In the case of cinnamyl alcohol, even the use of 1 M concentrations of reactants changes the polarity of the medium and results in the product ion of a mixture of 60% cinnamyl chloride and 40% a-phenylallyl chloride from the reaction itself since a-phenylallyl chloride is stable under the conditions used.
Vol. 78 thionyl chloride. The excess thionyl chloride was removed in vacuo and the acid chloride was distilled b.p. 142-144°( 17 mm.) to give 19.3 g. (82%).The anilide was prepared and after crystallization from methanol had m.p. 172-173°. Oxygen analysis 0.87, 0.87 atom % oxygen-18 calculated for localization in the carbonyl. j>-Methoxy-¿> '-nitrobenzoyl Peroxide-Anisoyl Carbonyl-O18 (III).-This compound was prepared according to LefHer's procedure. From 17.8 g. (0.105 mole) of anisoyl chloride-C018Cl there was obtained after crystallization from acetone-pentane 3.4 g. (11%) of III, m.p. 108-108.5°.Labeled p-Nitrobenzoyl-^-methoxyphenyl Carbonate (IV).-The mixed peroxide III, 3.2 g. (0.010 mole), was heated for 1.5 hours under reflux in 50 ml. of purified thionyl chloride.11 The thionyl chloride was removed in vacuo to give a solid which was crystallized from acetone-hexane twice to give 0.70 g. of material which softened at 106°and formed a very viscous melt at 122°. A sample of IV prepared in a trial run softened at 121°and melted 126-128°, after standing for five months this sample melted from 121-127°. A pinkish color had developed in the sample indi-(11) L. F. Fieser, "Experiments in Organic Chemistry," D. C. Heath and Co., New York, N. Y., 1941, pp. 381. eating the presence of ^-methoxyphenol. The infrared spectra of labeled IV and unlabeled IV were identical except for a shoulder at 5.56 µ in the labeled sample which did not appear in the unlabeled material. We attribute this to ^-nitrobenzoic anhydride which could be easily formed under the conditions of the reaction. A mixed melting point of labeled IV and unlabeled IV was 120-127°. Oxygen-18 analysis showed 0.65, 0.68 atom % oxygen-18 calculated for localization in one position. On the basis of the acid and anilide the analysis should have been 0.86 atom % oxygen-18.^-Methoxyphenol (V).-The carbonate IV, 0.50 g. (0.00158 mole), was refluxed for 15 min. with 0.50 g. (0.0125 mole) of sodium hydroxide in 8 ml. of water. The mixture was cooled, acidified to pH 7 and extracted with three 10-ml. portions of ether. The ether was washed with 5 ml. of water and then dried over magnesium sulfate. The ether was evaporated to give 0.16 g. of an oil which crystallized from water to afford 0.09 g. (53%) of p-m ethoxy phenol, m.p. 54-55°, infrared identical with that of an authentic sample of J>-methoxyphenol. Oxygen-18 analysis 0.19, 0.19 atom % oxygen-18. An authentic sample showed 0.20 atom % oxygen-18.
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