3614
CLAIRJ. COLLINS AND NEWELL S. BOWMAN
sodium bicarbonate solution, and the extract then acidified and extracted continuously with ether. Distillation of th; ethereal solution gave 1.6 g. (39%) of an oil, b.p. 140-145 3500-2500 (carboxyl), 1710 cm.-l (car(1.5 mm.); ImaX bonyl). Anal. Calcd. for C8H1203: C, 61.5; H , 7.7. Found: C, 62.1; H , 8.0. The oil was identified as X by its semicarbazone of m.p. 196O.l Dehydrohalogenation of VI1.--A solution of 6 g. of VI1 in 10 ml. of pyridine was refluxed for 10 hours. Benzene and, with cooling, hydrochloric acid were added and the benzene solution was washed with 10% hydrochloric acid and 10% sodium carbonate solution. Distillation of the benzene layer gave 1.1 g. (36%) of X I as an oil boiling a t 109-112° (4 mm.); G,, 1070 (vinyl hydrogen), 1765 (7lactone carbonyl), 1668 (C=C stretching), 1621, 1430, 1337, 1303, 1231, 1178, 1100, 1077, 1057, 1000, 970, 937, 905. 885 an.-'. Anal. Calcd. for CsH1002: C, 69.6; H, 7.3. Found: C, 69.2; H , 7.6. The alkaline solution was acidified and extracted with benzene. Distillation yielded 0.7 g. (227,) of an oil, b.p. 117-118" (5 mm.), Gmmsr 3500-2500 (carboxyl), 3040 (vinyl Analysis and infrared hydrogen), 1705 cm.-' (C=O). snectrum showed that VI had formed. Anal. Calcd. for C8HI2O?: C, 68.6; H , 8.6. Found: C, 68.3; H , 8.2.
[ C O S T R I B W ~ I O XFROM THE CHEMISTRY
Molecular Rearrangements.
Vol. 81
Reaction of VI1 with Ethyl Sodioma1onate.-To a solution of 2.5 g. of sodium metal in 50 ml. of absolute ethanol, 8.5 g. of diethyl malonate and then, dropwise during 7 hours a t reflux, 13.3 g. of VI1 dissolved in 50 ml. of absolute ethanol was added. The heating wa5 continued for 3 hours more, and the solution cooled, acidified, diluted with water and extracted with ether. The ethereal layer was distilled and gave 0.8 g. of an oil boiling a t 110-115° (1.5 mm.), 2 . 5 g. of an oil XV, b.p. 150-160° ( 1 mm.), and 0.8 g. of an oil (XIV), b.p. 180-185" (1 mm.). The first fraction XI11 showed the characteristic infrared peak a t 1780 cm.? (carbonyl of a y-lactone). Anal. Cdlcd. for CiOH1603: C, 65.2; H, 8.7. Fouiitl: C, 65.1; H , 8.8. The product XV absorbed a t 1780 (;-l,~tiineJ .itid 1730 cm. -l (ester carbonyl). Anal. Calcd. for C12HISO~:C, 6 3 . 7 ; H , 8 0. Fouiid: C, 63.4; H , 8.3. The oil XIV showed a peak of 1780 (-,-lactone) and 1730 cm.-' (ester carbonyl). Anal. Calcd. for C16H2206: C, 60.4; H, 7.4. Found: C, 61.0; H, 7.7. The product boils, on slow distillation, a t 150-155' (0.8 mm.), to give a product identical with XV. ISRAEL
JERCSALEM,
DIVISIONO F
OAK
RIDGENATIOXAL
LABORATORY]
XVI. The Pinacol Rearrangement of the Diphenyl-rntolylethylene Glycols
BY CLAIRJ. COLLINSAND NEWELLS. B O W X A N ~ RECEIVED JANUARY 16, 1959 The rearrangements of threo- and erythro-1,2-diphenyl-l-m-tolylethylene glycol ( I ) and l,l-diphenyl-2-m-tolylethylene glycol (11) in concentrated sulfuric acid a t 0" have been examined. The yields of the two ketones (IV and V) produced have been determined by the isotope dilution method, and the fates of various carbon-14 labels of I and I1 have been established. From the foregoing data the contributions of several paths t o the rearrangements of I and I1 were calculated, and it is shown from these that the m-tolyllphenyl migration ratio in the rearrangement of the conjugate acid of diphenyl-lntolylacetaldehyde is no less than 1. The present results support in every detail the mechanism previously8-12proposed for the rearrangements of triaryl glycols and triarylacetaldehydes.
OH OH OH OH Introduction I 1 ' I From 1930 to 1933, McKenzie and his coPHC-CHPh P~~-CHR PhiCCHO w o r k e r ~ , ~Roger ,~ and McKay4,' and Koelsch6 I I I1 R I11 R I reported the identities of the products formed during the acid-catalyzed rearrangements of the tolyl- catalyst upon the rearrangements has been ; ( 2 ) the relationship between the substituted glycols I (R = 0 , m or p-tolyl). In elucidated8f12 five recent papers8-12 we have studied the rear- pinacol and the aldehyde-ketone rearrangements rangements of the diphenyl o-tolyl'O and of the has been demonstratedg and (3) the question diphenyl p-tolylg compounds I, I1 and I11 (R = o- of the apparent reversal of migratory abilities of tolyl and p-tolyl) plus the analogous phenyl di- the groups involved during the aldehyde-ketone p-tolyl system.l' Thus: (1) the effect of acid rearrangementg-I1 has been answered. Of the compounds (I) studied by the earlier (1) This paper is based upon work performed a t Oak Ridge Sational investigators, 3--7 we had previously neglected the Laboratory, which is operated for the Atomic Energy Commission by Union Carbide Corporation. rearrangement of 1,2-diphenyl-1-m-tolylethylene (2) Research Participant from the University of Tennessee, June(I, R = m-tolyl). We therefore underglyc01~
