5864
FORREST D. THOMAS, 11, MAURICESHAMMA AND W. CONARD FERNELIUS [CONTRIBUTION FROM THE
Vol. 80
DEPARTMENT OF CHEMISTRY, THEPENNSYLVANIA STATE UNIVERSITY]
A Study of the Double Fries Rearrangement’s’ BY FORREST D. THOMAS 11, MAURICE SHAMUA ASD IV. CONARD FERNELIUS RECEIVED MAY8, 1958 The di-p-tolyl esters of aliphatic dicarboxylic acids from succinic to sebacic acid, and the di-p-tolyl esters of the aromatic acids isophthalic and terephthalic acid have been successfully rearranged (Fries rearrangement) in the presence of aluminum chloride to their corresponding bis-(o-hydroxyketones). Attempted rearrangement of the di-p-tolyl esters of oxalic, malonic and phthalic acids did not result in the formation of bis-(o-hydroxyketones), but gave 2-hydroxy-5-methylbenzoic acid, 4hydroxy-6-methylcoumarin and l-hydroxy-4-methylanthraquinone,respectively.
For certain studies on coordination i t was necessary to prepare a series of aromatic his- (o-hydroxyketones) of the type
arrangement is by Sinith and Holmes,’ who rearranged di - (2,3,5- trimethylphenyl) succinate. They used varying experimental conditions but were only able to obtain a relatively pure product, 1,4-bis-(2 - hydroxy-3,4,6-trimethylphenyl) -butane1,4-dione, in about 2070 yield. I n the present work the di-p-tolyl esters of aliphatic dicarboxylic acids from succinic to sebacic CH: were prepared from p-cresol and the respective acids by the action of phosphorus oxychloride. where X represents (CHz), or m or 9-phenylene. The most practical approach to such a series of T h e yields were from 4676 for the adipate to 87% compounds appeared to be via a double Fries re- for the sebacate ester. Our first attempts a t the rearrangement of the arrangement of the diesters of dicarboxylic acids. diesters of aliphatic acids involved essentially the However, a literature survey showed that no systematic study of the double Fries rearrangement mixing of the diester and aluminum chloride in the had been undertaken, The few isolated ex- ratio of 1 :2.5, respectively, and heating to about amples found in the literature either did not 130’. These conditions, tried in three different state yields in the rearrangement or else gave cases (see Table 11), gave relatively low yields of a low yield for the purified rearranged prod- 44yo or less. I t was subsequently found, however, uct. As against usual yields of 70-9070 in that with chlorobenzene as solvent, the reaction the mono Fries r e a r r a ~ ~ g e m e n tthe , ~ yields, proceeded much more satisfactorily, with yields up where given for the double Fries rearrangement, to 79% of the expected bis-(0-hydroxyketone). were of the order of 2OyOor less. I n the present The only exception to this upward trend was the study the di-p-tolyl esters were chosen in order to rearrangement of di-p-tolyl succinate which, with prevent any rearrangement to p-hydroxyketones. chlorobenzene as solvent, gave a yield of only 43% Rearrangement of the Diesters of Succinic Acid of the rearranged product. Rearrangement of the Diesters of Aromatic Diand Higher Homologs.-The first successful atand Patelski,s working tempt to rearrange diesters of aliphatic acids was carboxylic Acids.-Blicke on esters of aromatic dicarboxylic acids, obtained made by Fries and bar ten^,^ who reported the rearrangements of di-$-tolyl succinate and di-(3,5- the expected Fries rearrangement products 1,3-bisdimethylphenyl) succinate to 1,Phis- (2-hydroxy-5- (4-hydroxybenzoyl)-benzene and 1,4-bis-(4-hymethylpheny1)-butane-1,4-dione and 1,4-bis-(2-hy- droxybenzoy1)-benzene from diphenyl isophthalate droxy-4,6-dimethylphenyl) -butane-1,4-dione, re- and diphenyl terephthalate, respectively. HOWspectively. However, no yields were given in this ever, attempted rearrangement of diphenyl phthalstudy. Schwenk and Priewej reported the re- a t e g resulted in the formation of phenolphthalein The di-p-tolyl arrangement of di-m-tolyl adipate to 1,6-bis-(2- and 1-hydroxyanthraquinone. esters of the aromatic acids, phthalic, isophthalic hydroxy-4-methylphenyl)-hexane-l ,B-dione, but again no yields were given. Huebner and Link6 and terephthalic acid, were prepared from pfound that diphenyl glutarate rearranged to the cresol and the corresponding acid chloride. The present work was in accordance with previextent of BOY0 with the formation of a mixture of the ortho and para isomeric hydroxyketones, ous results, since rearrangement of the di-p-tolyl of isophthalic and terephthalic acids with from which they were able to isolate 1,5-bis-(?- esters hydroxyphenyl)-pentane-1,5-dionein 11y0 yield. aluminum chloride in chlorobenzene gave the The latest publication on the double Fries re- expected bis-(0-hydroxyketones) in yields of 31.6 and 25.6%, respectively; but attempted rearrange(1) This research was supported in whole by the United States Air ment of di-p-tolyl phthalate gave 1-hydroxy-4Force under Contract AF33(616)2742, monitored by T h e Materials niethylanthraquinone in 14y0 yield. Laboratory, Wright Air Development Center, Wright-Patterson 9 i r Rearrangement of the Diesters of Oxalic and Force Base, Ohio. Malonic Acid.-The rearrangements of the esters ( 2 ) A portion of a thesis presented by Forrest D. Thomas I1 in partial fulfillment of t h e requirements for the degree of Doctor of of oxalic and malonic acid fall in a special category, Pnilosophy, 1958. since in no case are bis-(0-hydroxyketones) ob(3) A. H . Blatt. “Organic Reactions,” Vol. I, chapter 11, John Wiley tained. and Sons, Inc., New York, N. Y., pp. 342-369. (4) K. Fries and K. Bartens, A n n . , 442, 270 (1925). ( 5 ) E. Schwenk and H. Prieme, THISJ O U R N A L , 66, 2101 (1934). ( C ) P. Huebner and K. P. Link, J . Bid. Chem., 138, 520 (1941).
t i ) 1.. 1. Smith and I
