Tetrahedron Lettera, Ro.6,~~3-8, 1959.Pergamon &es@ LM.

Printed in
Great Britain.

I~~CO~SrOR

OF SOME Pm

ENES BY ALBEIEDX CELORIDE

Royaton Y. Roberts and Yuri W. Ran Depertmentof Chemlstry,University of Texas, Austin, Texas (Reoeived5 May 1959)

AS a continuationof our study of alkylbenzenes re have exaatined tha behavior of several pentylbenzenes in the presence of aluminum chloride. Recently Nenitzezouand -oo-vorkers published an account of experi1 mente quite similar to oure. Their observationof the conversionof eec-but&benzene into isobutylbenzene was in agreementwith our ozn2 but, ozing to the qualitativenature of their analysis, they vere unaware of the reversibilityof this rearrangement. These vorkere also reported the conversionof &pentylbenzene into 2-methyl-j-phenylbutane, and of the latter into neopentylbenzene by more extended treatmentwith aluminum ohloride.We now wish to report the reeults of a quantitative study of the reaction of these three pentylbenzenee dth aluminum chloride and to explain the relationshipbetween them in term8 of a mechanism vhioh oorrelatesthis system zith the rearrangements of propyl- and

C. D, Nenitsescu,I. Necsoiu, A. &at% and Y. Zalman, Chem. Be,

g, 10

(1959).

' B, Y. Roberts, Y. W. Han C. H, S&mid and D. A. Davis, J. Amer, Chem. Sot, ii, 640 (1959).

Interconversion .

of some pentylbensenes

by aluminum chloride

butylbenaenes Analysis

of the pentylbensenee

after

treatment with aluminum chloride and vapor chromatography. separated from lower- and

was made by means of infrared The pentylbenaene fraction higher-boiling

spectrometry

was previously

material by fractional treated

distillation. (loO , 1 hr) with water-activated

&-Pentylbenzene was firet aluminum chloride The pentylbensenes 3-phe~lbu~e

in the proportion reoovered

used with set- and isobutylbenaene,* (65$), P-methyl-

were neopentylbensene (5%) .3

(30$) and s-pentylbenaene

After milder treatment

I2

I6

24

30

36

42

(b) 2-Methyl-3-pknylbutane:

a=,-pentylbenzene benzene ~-Z-methyl -3

.- &&yl-phenylbulone

3 These three pentylbenaenes made up 9% of the distillation fraations the other $ consisted of the craoking products sand/or isobutylbenzene (these two were not separated on the vapor chromatogram) end isopropylbenrene.

Interconversion of eome pentylbenzenee by aluminum chloride 0.5 hr) however, the major admponentof (in benzene solution at ca. t30, the pentylbenzenee was 2-methyl-3-phenylbutane (66) in accordancewith Nenitzesaulafinding, accompaniedby neopentylbenzene (2%) and i-pentylbenzene (1%). Further experimentsin which &pentylbensene was isomerized by heating with catalyst for various periods of time are auoniwizedin Fig. 1. At first, 2-methyl+phenylbutane was produced rapidly,

neopentylbenzene lee8 rapidly, but the latter isomer was elorly converted into the former as i-pentylbenzene disappeared. When P-methyl3-phenylbutane was the etarting material, essentiallythe same mixture of isomer8 was produced after 24 hr. When neopentylbenzene was treated leee then 2$ of P-methyl-

similarly for 24 hr it wae virtually unchanged;

3-phenylbutane and about 246of cracking products were found, No evidence of the productionof &y other pentylbenzenes in any of the experiments

was obtained by either infrared epectrometryor vapor chromatography, A meohaniem which ia consistentwith these data is outlined below:

7%
CH3-y-CH2-+ CHs

FH3
CH,Ck( RH Re ti FH3 CH,-+CH-CH, Y I CHz-CH3 t

RH

CH, CH,-L-CHs hH3 II j4 Il.2 c--t

C,
IX4 H-yH-CH3 59 mo

Interconversion of Borne pentylbenzenes by aluminum chloride

This scheme is similar to those proposed by Nenitaescu,'but incorporates the suggestionof Schmerlingand co-workers4of anchimericassistancein the abstractionof RIO from i-pentylbenzene. It is directly analogous to thoae we have recently proposed for the rearrangements of propyl- and

5 In the present system, the intermediateion set- and isobutylbensenes. III is favored over II energetically not only by the hyperconjugative effect, but also by the steric effect, since the i-butyl group causes sev6 ere steric inhibitionof resonance in IIa. Hence 2-methyl-j-phenylbutane is produced more rapidly than neopentylbenoene by the action of aluminum chloride on i-pentylbenzene. Although neopentylbenzene is produced more slowly, the reaction is irreversible. This must be due to the difficultyof abstractingHz@ from the side-chainof neopentylbenzene. The nine primary hydrogensare Y to the ring, there are no &hydrogens, and the two a-hydrogensare shieldedby a &-butyl group. One is led to draw the interestingdeduction that there is a significantsterio requirement for hydride abstraction,by either aluminum chloride-water complex or by a carboniumion. It is probable that this factor is involved in the lack of rearrangementof n-butylbenzene,? isosmylbenzenel and perhaps some other alkylbensenes.*

4 Who first described the rearrangementof t-pentylbensene to P-methylj-phenylbutane; L. Schmerling,R. W. Welch; and J. P, Luvisi, J Amer Chem Sot 14, 2636 (1957)i L. Schmerlingand J. P. West, Ibiw 1917).

5 R. M. Roberts and J. E. Douglass, Chem. k Ind, In press (1959). 6 C. Baddeley,J. Chadwickand H. T. Taylor, J. Chem. SOD, 2405 (1954);
T. C. Van Hoek, P. E. Verkade and B. II.Wepster, Rec. Trav. Chimti 11, 559 (1958). 7 R. M. Roberts, S. G. Brandenberger and S. G. Psnayides,J. Amer, Chem. Sot, 22, 2507 (1958). 8 We are grateful to the National Science Foundationfor a grant which supported this research.