Vol. 66
THOMAS I d . J.iCOBS AND SCOTT SEARLES, JR.
GMj
of acetone and alcohol, forming large whire needles, which melted to a deep red liquid at 158.1-158.6" c u r . The
with 0.1 g. of fused sodium acetate in 2.5 ml. of acetic anhydride or: a steam-bath for one hour. The mixture was theri poured over ice and stirred until the oil had solidified. The amorphous solid was centrifuged out and recrystallized three times from ethyl alcohol, giving fine white needles of the diacetate, which softened at 121"' but melted at 125.9-126.9' cor. Anal. Calcd. for CaHm04S: C, 69.5; H, 5.26; S, 8 4 2 . Found: C, 69.7; H, 5.29; S, 8.26. Formation of the Thiophene h Two Steps.-Approxirnately 2 g. of "Anhydro-p-methoxypropiophenonedisulfide" was re3uxed in 30 ml. of xylene for three hours. The solulion became deep purple in color. The xylene was distilled off under vacuum, and theresidual brown oilwas taken up in ethanol and stored in the refrigerator. No crystal3 were obtained iii twenty-four hours, although both 2,4-dip-anisyl-3,5-dimethylthiopheneand "anhydro-p-rnethoxyi)ropiophenone disulfide" are readily crystallized from &ohol. A few drops of the alcohol solution decolorized ari acetone solution of potassium permanganate, indicating urisaturation. The alcohol solution was refluxed for two hours with copper chromite. Upon cooling the filtered alcohol solution, yellow needles were obtained, m. p . 112113.5'. Mixed with 2,4-di-p-anisyl-3,5dimethylthiophene, the melting point was 112-113'.
yield was 11 g. or 53.5% of the theoretical. Anal. Calcd. for C30H&S2: C, 71.2; t 13.6. Found: C , 71.8; $1, 6.41; S, 12.75, Reaction of "Anhydro-pmethoxypropiophenone Disulfide" with Copper Chromite.---Two grams of the sulfur compound was dissolved in 40 ml. of dry xylene arid 10 g of finely ground copper chromite was added, The mixture was stirred and refluxed for tbvo and one-half houri After cooling, the mixture was filtered aud the xylene removed by vacuum distillation. The residue of browii oil was dissolved in about 10 volumes of hot methanol and cooled, giving yellowish crystals which were recrystallized from methanol in yellow needles, in, p. !'h' e yield was 0.85 g., or 66:; of t h o theor Anal. Calcd. for C P O H ~ ~ ZC S, :74 9.87. Found; C,74.5; H , < j , l V ;S,9.T!. Demethylation. -The procedure given by Kharasche for demethylation of stilbestrols \vas used: 1.07 g of the dianisylthiophene was dissolved iri 25 ml. of ethylene glycol, 2.5 g. of potassium hydroxide added, and the mixture sealed in a glass bomb under a pressure of U.6 mni. of mercury. I t was kept at 225" for eighteen hours. When fool it was opened, and the contents diluted with 2 volumes of water and filtered. When 8 ml. of concentrated hydroSummary chloric acid was added, the solution set to a gel immediately. It was digested on a steam-bath, filtered aud washed . A new method for the synthesis of 2,4-diaryl. with water and dried. I t was recrystallized with difficulty from benzene or toluene. After t w o recrystallizations from thiophenes, in yields of 65 to 85% based on the reaction of "anhydroketone disulfides" with benzene, the gray material 194-196'. The yield was 0. copper chromite, is described. The compound is a phenol, 'The mechanism of this reaction is discussed. ferric chloride and the solub Fc:ur new compounds, "Anhydro-p-rnethoxyAnal. Calcd. for CMIII~O&:C , 2 . U ; $1, 5 . 4 1 ; S. propiophenone disulfide," 2,4-di-p-hydroxyphenyl:0.81. Found: C , 72.5; XI, 5.37; S , ld.RJ. Acetylation.--The 2,4-di-p-hydroxypheilyI-Y,5-diirieth-Y,klimethylthiophene, and its dimethyl ether ylthiophene was readily acetylated 1)y heating 0 i y. m t i tliacetate, are characterized. (9) Kharasch and Kleiman, I HIS J U U K N A L , 66, 1I , 1 ~ 4 3 )
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