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).
NOTES
1604
VOl. 61
examined by them, the yield of coupling product was less than that observed with phenyllithium, and in the case of o-tolyllithium the yield of bi-otolyl was 5% and the yield of o-cresol, 54%.
pounds prepared from the acids. p,p'-Methylenebisacetanilide has been prepared previously from acetic anhydride and 4,4'-diaminodiphenylmethane.
Experimental Part
Experimental
A mixture of 1 g. (0.005 mole) of 4,4'-diaminoThe suspension of 4.5 g. of phenyllithium in 100 diphenylmethanel and slightly more than 0.01 cc. of benzene, prepared in a nitrogen atmosphere, mole of the respective acid were mixed in a large was oxidized by dry air, free of carbon dioxide, Pyrex test-tube and heated a t the boiling tema t 10-15'. A negative color test6 was obtained perature until water ceased to be evolved. With in about ten hours. The phenol was characterthe lower members of the series a reflux condenser ized as 2,4,6-tribromophenol, and the p-phenylwas used and the period of heating was approxiphenol as the acetate. mately one hour. The time necessary to comIn three experiments the yields of phenol were plete i h e reaction decreased with the higher mem25.9, 23.1, and 22%; of biphenyl, 25, 23.7 and bers of the series and in the case.of stearic acid 22.6%; and of p-phenylphenol, 0.05, 0.06 and five minutes is sufficient. The products were crys0.05 g., respectively. The extent of the WurtzFittig reaction with the bromobenzene is quite tallized to a constant melting point from a mixslight, for only 0.12 g. of biphenyl was isolated ture of benzene and methanol except with some of from the benzene washings of a 0.1 mole run. TABLE I (6) Gilman and Schulze, T H I S JOURNAL, 47, 2002 (1925).
CONTRIBUTION FROM THE CHEMICAL LABORATORY OF IOWA STATECOLLEGE RECEIVED MARCH29, 1939 AMES,IOWA
4,4'-Diaminodiphenylmethane as a Reagent for the Identification of Monobasic Saturated Aliphatic Acids BY A. W. RALSTON AND M. R. MCCORKLE
4,4'-Diaminodiphenylmethanehas been found to give diamides of aliphatic acids by heating the theoretical proportions of the diamine with the respective acids. C H : ( a NHz z e )
4-2RCOOH ----f
Because of the ease of preparation and purification and their high melting points, these compounds serve as excellent derivatives for the identification of aliphatic acids. With the lower members there was considerable depression of mixed melting points but this became increasingly smaller as the series was ascended. In order to establish the structure of the diamides prepared by this method, the diamides of acetic, propionic and lauric acids were prepared from the diamine and either the anhydrides or the acid chlorides. These gave no depression of mixed nieltiiig poiiits with the corresponding com-
CONSTANTS
Acid
OF
DIAMIDESO F 4,4'-DIAMINODIPHENYLMETHANE Mixed m. D. withnext' M. p , ' C highest (con ) homolog
N Analyses, % Calcd. Found
Acetic"' 227-228 205-210 Propionic 2 12-213 9.03 9.33 188-193 197-198 8.28 8.58 Butyric 185-188 188-189 7.65 7.92 Valeric 179-181 7.10 7.46 185-186 179-181 Caproic 183-184 176-178 6.86 6.64 Heptylic 182-183 6.53 6.22 Caprylic 176-179 176-177 6.11 5.83 175-177 Pelargonic 5.93 5.54 178-179 173-175 Capric 175-176 5 45 5.25 Undecylic 172-174 5.38 4.99 174-175 171-173 Lauricc 5.12 4.78 172-1 73 170-172 Tridecylic 4.73 170-17 1 4.53 Myristic 167-169 167-168 4.36 4.34 Pentadecylic 166-168 167-168 4.39 4.15 164-166 Palmitic 164- 165 4.40 3.99 Margaric 163-165 4.12 164-165 3.83 Stearic In order to purify this sample it was necessary to dissolve it in ethanol and add alkali until basic to phenolphthalein. Upon dilution with water and crystallization from benzene and methanol the product, m. p. 227Stoedel and Hause, Ber., 23, 2577 228', was obtained, (1890); Rivier and Farine, Helw. Chim. Acta, 12, 865 (1929); Parkes and Morley, J . Chem. SOL.,315 (1936); Butler and Adams, THISJOURNAL, 47, 2617 (1925), reported m. p. 236-237". ' The authors are indebted to Mr. W. M. Selby for the samples of lauric, myristic and stearic acids. The remainder of the acids were obtained from the Eastman Kodak Company. I
-
(1) The 4,4'-diaminodiphenylmethaneused was prepnred by crystallization from petroleum ether of Eastman Kodak C o . (practical), '1,4'-diaminodiphr11.ylrnrth~~n~, iii 1,. !lO-
