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The Journal of Organic Chemistry 1957 Volume.22 No.3

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The Journal of Organic Chemistry 1957 Volume.22 No.3 THE JOURNAL OF Organic Chemistry Volume 22, Number 3 by the society Ap«i 29, 1957 ____ Maxell [C ontribution p r o m t h e C h e m i c a l L aboratories o p t h e U n i v e r s i t y o p N o t r e D a m e ] Racemization of Phenylalkanes in Presence of Lewis Acids ERNEST L. ELIEL, PHILIP H. WILKEN,1 a n d FABIAN T. FANG Received September J, 1956 Optically active 2-phenylbutane racemizes rapidly and completely in the presence of aluminum chloride at 0°C. at which temperature there is little disproportionation to m- and p-di-s«c-butylbenzene. Racemization appears to be due to formation of the 2-phenyl-2-butylcarbonium ion followed by transfer of a hydride ion from a 2-phenylbutane molecule in a chain reaction, since in the presence of a,f}-dideuterocumene, substantial amounts of deuterium are transferred to the 2-phenyl­ butane. Optically active a-deuteroethylbenzene is not completely racemized under much more drastic conditions. Burwell and Shields2 3 have recently reported on d-C6H5CH(CH3)C2Hs + AlCl., + HC1 — >- the racemization of 2-phenylpentane in the pres­ C0H6 + dZ-CH3C+HC2H5 + AlCLr-— > ence of aluminum chloride. In the course of an in­ dZ-C6H6CH(CH3)C2H,, + AlCl, + HC1 (a) vestigation which was nearly complete when we d-C6H6CH(CH3)C2H6 + A id, + HC1 — > learned of the prior work of Burwell and Shields df-C6H5C+(CH3)C2H5 + AlCl«" + H2 we have confirmed and extended certain observa­ dbC6H5C+(CH3)C2H5 + d-C6H5CH(CH3)C2H6 — > tions of these authors using 2-phenylbutane and a- dZ-C6H6CH(CH3)C6H6 + dZ-C6H5C+(CH3)C2H6 (b) deuteroethylbenzene as substrates. Burwell and Shields2 have already pointed out When active 2-phenylbutane was heated with (for the case of 2-phenylpentane) that mechanism aluminum chloride at 100°, it was extensively dis- (b) is more likely since racemization takes place proportionated to benzene and a dialkylbenzene under conditions where transalkylation (which fraction which proved to be a mixture of the meta may involve the 2-pentylcarbonium ion3b) is al­ and para isomers. The recovered starting material most inoperative. In the case of 2-phenylbutane, was completely racemized. A priori, two mecha­ complete racemization occurs with aluminum chlo­ nisms might be suggested for the racemization; one ride in 12 hr. at room temperature and even in 2 (a) in which the alkyl group comes off as a carbo- hr. at ice-bath temperature, though in the latter nium ion and then returns and another (b) involv­ case the yield of transalkylation product is re­ ing a hydride transfer chain from an alkylbenzene duced to 9%. to an aralkyl carbonium ion:3a A more compelling argument for mechanism (b) was obtained from a treatment of equimolar (1) Peter C. Reilly Fellow, 1952-53; Socony Vacuum Fellow, 1953-54. This work is taken in part from the Ph.D. amounts of 2-phenylbutane and a,|3-dideuterocu- dissertation of P. H. W. and was presented before the Organic mene with aluminum chloride at ice-bath tempera­ Division of the American Chemical Society at Minne­ ture. The recovered 2-phenylbutane contained apolis, Minnesota, on September 14, 1955. 0.28 atom of deuterium per molecule as indicated (2) R. L. Burwell, Jr., and A. D. Shields, J. Am. Chem. by mass spectrometry. Statistical distribution of Soc., 77, 2766 (1955). (3) (a) The initiation step in mechanism (b) is not the «-deuterium and a-hydrogen atoms among the definitive; several reasonable alternatives exist. The in­ cumene and 2-phenylbutane molecules should clusion of HC1 in the initiation steps requires comment: have given 2-phenylbutane containing 0.50 atom of no hydrochloric acid was added to the reaction mixture, but the formation of traces of this reagent due to adventi­ Brown and H. Jungk, Ibid., 78, 2182 (1956). However, tious moisture is quite likely, (b) This point is arguable in even if the transalkylation is an Sn2 reaction, a version of the case of a secondary alkyl group; cf. D. A. McCaulay mechanism (a) can be written which will lead to racemiza­ and A. P. Lien, J. Am. Chem. Soc., 75, 2411 (1953); H. C. tion: 2d-C6H6R* — meso-CJhR** + C6H6 2dt-CJhR* Brown and C. R. Smoot, Ibid., 78, 2176 (1956); H. C. where R* is an asymmetric alkyl group such as 2-butyl. 231 232 ELIEL. WILKEN, AND FANG v o l . 22 deuterium; the discrepancy is undoubtedly due to PhCILCHi — > PhCHBrOHj — > the fact, evident from mass spectrum and elemen­ PhCH(CHs)CH(C02Et)2 — >- tary deuterium analysis, that the a,/3-dideuterocu- PhCH(CH3)CH(C02H)2 — > PhCH(CH3)CH2C02H mene used in this investigation was not isotopi- Ethylbenzene was brominated photochemically in cnlly pure. 81% yield employing carbon tetrachloride as a When optically active a-deuteroethylbenzene4 5 solvent. Alkylation of malonic ester with the bro­ was heated with aluminum chloride at 65-70° for mide was effected in 82% yield by using sodium several hours, the recovered starting material still hydride as the base and a mixture of benzene and retained one third of its original activity.6 This fact dimethylformamide as solvent.10 Decarboxylation is consistent with mechanism (b) [though it does of the malonic acid was effected conveniently in not exclude (a)], since a hydride transfer reaction boiling 2,6-lutidine. In the resolution of /3-phenyl- involving the secondary a-phenethyl carbonium butyric acid (best effected by means of a-phenethyl- ion: amine) it was found convenient to let the racemate rh-C6Hr,C+DCH3 + d-C6H5CHDCH3 — =- crystallize from a petroleum ether solution of the dl-C6H5CHDCH3 + dPC6H6C+DCH3 (c) partly resolved material. This increased the optical purity of the acid from 56 to 76%. should involve higher activation energy than the corresponding reaction [Equation (b)] involving the tertiary 2-phenylbutyl carbonium ion.6 EXPERIMENTAL11 One of our experiments involving racemization of a-Phenethyhnalonic ester. A suspension of 20 g. (1.13 g. 2-phenylbutane was carried out under conditions atom) of sodium hydride in 800 ml. of sodium-dried benzene identical with those used7 in the alkylation of ben- and 300 ml. of pure dimethylformamide (technical material ene with optically active butanol-2 in the presence was azeotropically distilled with benzene, b.p. 150-150.5°) in a three-necked flask equipped with stirrer, reflux con­ of aluminum chloride. The fact that 2-phenylbutane denser and dropping funnels, was cooled to 5-10° under a racemizes totally under these conditions while it does slow stream of nitrogen. Ethyl malonate (180 ml., 190 g., not racemize extensively in the presence of boron 1.19 mole) diluted with its own volume of benzene, was trifluoride8 may explain why Price and Lund ob­ added at such a rate that hydrogen was evolved gently. tained slightly active material in the alkylation of After the solution had become homogeneous, 201 g. (1.08 mole) of a-phenethyl bromide12 was added and the tem­ benzene with active butanol-2 in the presence of perature gradually raised to 75-80° and maintained there boron trifluoride but not with aluminum chloride for 2 hr. by the application of a hot water hath. The mix­ which yielded totally racemized product.7 ture was then cooled, washed with water in a separatory It is of interest that although 2-phenylbutane is funnel, and the water layer twice extracted with benzene. racemized rapidly by aluminum chloride, we have The combined benzene layers were washed twice with dilute hydrochloric acid, once with water, once with 10% found that it can be acetylated to give an optically aqueous sodium carbonate, and again with water, dried active product with acetyl chloride in the presence over sodium sulfate, concentrated, and the residue distilled of aluminum chloride. The same is true of 2-phen- at reduced pressure. The product boiling at 131-133 °/0.8 ylpentane9 and of «-deuteroethylbenzene.4 Prob­ mm. (lit.13 13871.5 mm.) weighed 234.1 g. (82%). f)-Phenylbutyric acid. The above ester (132 g., 0.5 mole) ably the acetyl chloride as well as the ketone formed was boiled under reflux for 1 hr. with a solution of 118 g. in the acylation complexes with the catalyst in (2 moles) of potassium hydroxide in one liter of 95% ethanol. such a way as to make it ineffective for the promo­ The alcohol was then distilled on a steam bath and replaced tion of reaction sequence (b). by water, 250 ml. of water being added each time 250 ml. A few improvements were made in the synthesis of distillate had been collected until the total distillate amounted to almost one liter. The aqueous solution was of active 2-phenylbutyric acid required as an inter­ then poured into an excess (4-5 moles) of concentrated mediate for active 2-phenylbutane. The reaction hydrochloric acid'4 and the a-phenethylmalonic acid which sequence employed was the following: precipitated was collected and dried, m.p. 142-143° (lit..13 142-143°); yields as high as 92% were obtained. (4) E. L. Eliel, J. Am. Chem. Soc., 71, 3970 (1949). (5) The diethylbenzene fraction isolated from this (10) This excellent technique was first described by A. W. experiment was inactive. We are continuing the study of Burgstahler, Ph.D. dissertation, Harvard University, the optical course of the Priedel-Crafts transalkylation as 1953. well as the rearrangement reaction. (11) All melting and boiling points are uncorrected. (6) Only hydride transfer is shown in equation (c) for Mass spectrometric analyses were carried out by Mr. the sake of clarity.
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