NOTES
June, 1939 Structural Identity of Polysulfones Prepared by Peroxide Catalysis and Under the Influence of Ultraviolet Light' BY C. S. MARVEL AND WM.H. SHARKEY
Olefins of the type RCH=CH2 combine with sulfur dioxide in the presence of peroxides to give polysulfones with the structure shown in formula I.2 The unusual orientation of the units sug[-~HCHZSO~CHZC!HSOZ-]. R
I
1603
Treatment of 3 g. of this polymer with 150 cc. of liquid ammonia as described previously2 followed by recrystallization of the resulting product from alcohol gave 0.9 g. (30%) of 2,G-di-n-propyl1,4-dithian-bis-(dioxide),m. p, 267'. This product was identical with the synthetic product and that formed by the action of liquid ammonia on 1pentenepolysulfone prepared in the presence of peroxides2 CHEMICAL LABORATORY UNIVERSITY OF ILLINOIS , ~ R B A N A ,ILLINOIS
RECEIVED MARCH3, 1939
gested to us that the peroxides present might be exerting an effect similar to that which has been The Oxidation of Phenyllithium discovered by Kharasch and his students3in conBY H. A. PACEVITZ AND HENRYGILMAN nection with the addition of hydrogen bromide to olefins. It ha9 been reported4 that ultraviolet The formation of significant quantities of COUlight promotes the addition of sulfur dioxide to pling or R.R compounds by oxidation of RLi olefins. While previous work in this Laboratory compounds of the dibenzofuran series1 suggested has indicated that it will not induce polymer for- an examination of the oxidation products of phenmation in all c a ~ e swe , ~ have now found that i t yllithium. Ether-free phenyllithium was used does bring about the combination of 1-pentene because we wished to exclude the marked secondwith sulfur dioxide. This has made it possible for ary reactions known to take place when ether us to compare the structure of l-pentenepolysul- solutions of arylmagnesium halides are oxidized. fone prepared with peroxide catalysts with that We found that biphenyl and phenol are formed of the polymer prepared by photochemical acti- in essentially equal quantities. In addition, a vation in the absence of peroxides. The two small quantity of 9-phenylphenol was isolated products apparently are identical and beyond from each of the oxidation reactions. I t is posquestion have the same structural units. sible that the p-phenylphenol may owe its forma1-Pentene was shaken with concentrated aque- tion to the oxidation of some p-phenylphenylous hydrochloric acid until i t gave no test for lithium formed by metalation of biphenyl, for peroxides with ferrous sulfate and ammonium biphenyl is known to metalate in a para position." thiocyanate.6 The olefin was then distilled and It was also observed that when phenyllithium again found to give no test for peroxides. A 5-cc. was allowed to take fire in the air, a pronounced sample of this peroxide-frec olefin and 3 cc. of odor of biphenyl accompanied the combustion. liquid sulfur dioxide were placed i n a P-yrex tube Incidentally, the solid phenyllithium, phenylarid nitrogen was passed through the tube for sodium, and phenylpotassium, like the phenylabout twenty minutes to remove all of the air. magnesium halides, show chemiluminescence when The tube was then sealed and placed under an oxidized. ultraviolet lamp. Evidence of polymer formation Muller and ?'iipelb have just reported on Lhc was noticed after twenty-four hours. After one oxidation of some organolithium compounds. week the tube was opened and the polymer was Working in ether solutions, these authors found isolated. The yield was 5 to 5 . 2 g. The poly- more biphenyl, but less phenol than we did under meric product had the same physical properties our conditions. Their phenylmethylcarbinol arose and solubilities as reported for the l-pentene- as a consequence of the usual secondary reaction polysulfone prepared by peroxide catalysts. with ether,2 and they found no other products. (1) This is the ninth communication on The Reaction between With most of the other aryllithium compounds Sulfur Dioxide and Olefins. For the eighth see THISJOURNAL, 60, 2622 (1938). (2) Glavis, Kyden and Marvel, ibid., 69, 707 (1937). (3) For leading references see Kharasch, Norton and Mayo, J . Org. Chcm., S, 48 (1938). (4) Mathews and Elder, British Patent 11,635 (1914); C. A , , 9, 2971 (1915). ( 5 ) Frederick, Cogan and Marvel, THISJOURNAL, 66, 1815 (1934). (6) Kharasch and Mayo, ibid., 66, 2468 (1933).
(1) Gilman, Cheney and Willis, THISJOURNAL, 61, 951 (1939). (2) Wuyts, Compt. uend., 148, 930 (1909); Porter and Steele, T H I S JOURNAL, 42, 2650 (1920); Gilman and Wood, ibid., 48, 806 (1926). (3) Gilman and Bebh, ibid., 61, 109 (1939).
(4) Ether solutions of phenyllithium were reported earlier to show chemiluminescence on oxidation [Gilman, Zoellner and Selhy, ibid.. 64, 1957 (1932)l. ( 5 ) Mtiller and Topel, Ber., 72, 273 (1939).
