SEN AND GHOSH PHLOROACETOPHENONE. 61 VII I.-Phlo~oacetophenor~e. By KIEMUD BEHARI SEN and PRAPHULLA CHANDRA GHOSH. PHLOROACETOPHENONE is an important compound for the synthesis of many natrural dyes (Goschke and Tambor Ber. 1912 45 1237). Biilow and Wagner obtained it by first condensing phloroglucinol with benzoyl chloride and then degrading the resulting ppranol (Ber. 1901 34 1'798). Leuchs and Sperling (Ber. 1915 48 135) prepared i t by the action of water at 170° on Jerdan's lactones (T., 1897 71 1111). I n no case was the direct synthesis achieved. Resacetophenone gallacetophenone and similar compounds are easily and directly prepared from the corresponding phenols by heating them with acetic acid and zinc chloride. It was therefore thought that phloroglucinol on similar treatment might give phloro-acetophenone and thus a direct synthesis might be effected.When, however phloroglueinol is heated with acetic acid and zinc chloride there is produced a yellow crystalline compound dissolving in potass-Y 62 SEN AND GHOSH PHLOROACETOPHENONE. ium hydroxide solution with a pink colour and fluorescence. From the analysis and the determination of the molemlar weight by the ebullioscopic method in alcohol it is concluded that phloroaceto-phenone is first formed but that two molecules a t once combine, giving a pyrm derivative resembling Nencki's resacetein (p. 61). On boiling the pyran derivative (I) with 10 per cent. sodium hydroxide solution the heterocyclic ring is broken and phloroaceto-phenone (11) is obtained. The melting point of phloroacetophenone was found to be 284-285O; according to Bulow and Wagner it does not melt up to 280° and Leuchs and Sperling give 2 1 8 O .The substance obtained by the latter authors contained one molecule of water of crystallisa-tion which may account for the difference in melting point. E X P E R I M E N T A L . 5 7-Dih ydroxy-2 -0-0-p- trihydrox y pheny 1 -4-me t h y lene-l ; 4- b enzo-Two grams of phloroglucinol were dissolved in 2 C.C. of glacial acetic acid 3 grams of zinc chloride added and t.he whole was gently boiled for ten to fifteen minutes. The yellow liquid was dissolved in hot hydrochloric acid and the clear solution on cooling deposited yellow needles (0.9 gram). The substance is soluble in alcohol and dissolves in potassium hydroxide solution giving a pink fluorescent solution.PYran (1). It does not melt up to 290O: 0.1256 gave 0.2751 CO and 0.0502 H20. C=59.7; H=4.45.* 0.5713 in 18 C.C. alcohol gave E=0*18O. M.W.=275. Cl,Hl,0G,H20 requires C = 60.3 ; H = 4.4 per cent. M.W. = 300. Acetyl Derivative.-One gram of the above compound 10 C.C. of acetic anhydride and a few drops of pyridine were boiled gently for an hour. The semi-solid mass obtained on pouring into water was dissolved in acetic acid and precipitated with water being finally crystallised from dilute acetic acid. The compound melts a t 80° and begins to decompose a t about 90°: 0*1202 gave 0.2680 CO and 0.0560 H,O. C=60*8; H=5*1. C2,H220, requires C = 61.16 ; H=4*31 per cent. Yhloroacetophenone (11). Three grams of the pyran were dissolved in 75 C.C.of 10 per cent. sodium hydroxide solution the solution boiled for ten t o twelve minutes and after cooling acidified with dilute hydrochloric acid. The precipitate was collected dried and finally crystallised from WORSLEY AND ROBERTSON THE PEROXIDES OF BISMUTH. 63 mixture of alcohol and dilute hydrochloric acid. The product (0.8 gram) was almost colourless and dissolved in potassium hydroxide solution with only a pale yellow colour. It melted a t 284-285O. (Found C=56*44; H=5*2. C,E,O requires C=67*1; H=4*8 per cent .) Yhenylhydrazone.-This was prepared in the ordinary way by dissolving the phloroacetophenone in a mixture of alcohol and acetic acid adding a little more than the theoretical quantity of phenyl-hydrazine hydrochloride and sodium acetate and warming for a few minutes. To the clear solution water was added and the precipi-tate was collected dried and finally crystallised from dilute alcohol. It decomposes a t 237-2+0°: 0.1150 gave 11.65 C.C. N a t 32O and 761 mm. CHEMIOLL LAI~ORATORIES, N=11-3. CI4Hl4O3N2 requires N = 10.8 per cent. DACCA AND PRESIDENOY COLLEGE, BENGAL INDIA. [Received July 31st 1919.