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Vol. 64
COMMUNICATIONS TO THE EDITOR
with ether and the oil left after removing the ether was distilled under reduced pressure. There was obtained a 45.7% yield (based on the diazoniuni fluorosulfonate) of liearly coiorless Oil, distilling a t 135-137' ( 5 mm.) ; d264 1.2905; n , 2 5 ~1.5508. When cooled to -78" the oil crystallized, m. p. 33--34.5" (uiicor.). The compound had a slightly aromatic odor and was soluble in acetone, niethmol, chloroform, benzene and hexane; it was insoluble in
water and ethylene glycol. Anal. Calcd. for CI2HeSo3F: F, 7 , s ; hydrolysis value, 7.59 mi. of 0.5221 N NaOH. Found: F, 7.40; hydrolysis value, 7.27 ml. of 0.5221 j+$ NaOH.8 CENTRAL
DEPARTMENT
M~~~~~~~ cHEMICAL coMPANV DAYTON, OHIO MARYW. RENOLL RECEIVED MARCH2, 1942
COMMUNICATIONS T O T H E EDITOR THE SYNTHESES OF LACTOSE AND ITS EPIMER
able to publish a t this time the results of some preliminary physico-chemical studies .on the metaReferring to our articles which describe the bolic product of Penicillium citrinum: namely, syntheses of epi-cellobiose and cellobiose [THIS citrinin, which recently has been shown to inhibit JOURNAL, 63, 1724 (1041); 64, 12x9 11942)], we the growth of Staphylococcus aureus.2d now report that the combination of acetone-DCitrinin, C13H14O5, a yellow crystalline solid, mannosan with acetobronio-D-galactose has been ni. p. 170-1 71 (with decomposition), was isolated accomplished, and that by reactions which are and purified by the method of Hethering and Raisentirely like those used in the indicated syntheses, trick3 It was obtained from the culture, P. ciwe have produced, first, the epimer of lactose and, trin.wnz #13(i-3730.G.4 The characteristic propersecond, lactose itself. The yield of synthetic ties of our product were in good agreement with crystalline tr-epi-lactose octaacetate by the indi- those reported previously.3 cated combination was 30% and the deacetylation We have found that citrinin in concentrations of the octaacetate generated synthetic epi-lactose of 0.001-0.003 -11 gives well-defined currentwhich is identical with that produced from lactose. voltage curves a t the dropping mercury cathode Synthetic epi-lactose octaacetate was converted in acid, ethanol solutions, buffered and unto acetobromo-epi-lactose, which was in turn re- buffered. The limiting current was found to be duced to the known lactal hexaacetate, from which proportional to the concentration of citrinin. The $-lactose octaacetate was obtained in good yield by half-wave potential in the buffered alcoholic soluoxidation with perbenzoic acid, followed by acetyla- tion (PH 2.03) is in the range of -0.80 to -0.82 tion. Deacetylation of this octaacetate generated volt applied versus the saturated calomel referlactose. Publication oi the full details will follow. ence electrode. Citrinin is also reduced in 0.1 N The syntheses of epi-lactose and lactose were an- KC1-75yo ethanol solution. It is not reduced in nounced at the llemphis meeting of the Society in acetate alcoholic buffer (pH 6.0) nor in phosphate the Division of Organic Chemistry, April 21, 19-22. alcoholic buffer (pH 7.4). The manual apparatus I)IVISION O F CHEMISIRY W T. HASKINS used in these studies was similar to that described NArIONAI, INSTITUTE OF HEALTH KAYMOND M. HANN previously.5 Attempts to use standard potentioI3ETNESDA, &IAKYI,ASD C. S HUDSON metric procedures with TiC136as a reducing agent RECEIVED MAX'14,1942 proved unsuccessful since stable potentials were never reached within a reasonable and workable POLAROGRAPHIC DETERMINATION OF CITRININ' length of tinie. Sir : ( 3 ) Hethering and Raistrick, Roy. Sac. Phil. T r a m . , B220, 269 In view of the growing interest in anti-bacterial I). substances obtained from it seeins desir- ( 193 ti) Furnished through the courtesy of Dr. K. B. Raper, U. 8.
Sir:
(1) Taken from thc thesis of H \\-. Hirschy, hubmilted in p a r t i d inlfillment for a Master's Degree iu Cheniistry, June, 194 I . ( 2 ) (a) Abraham, Baker. Chain. I'lorey, Holiday and Robinsoti. IVutzirr, 149, 356 (1942); (b) Dawson, Hobby, Meyer and Chaffee. Jouu. Clin. Iizzesl., 20, 438 (1941); < c ) Oxford, Raistrick and Smith, Chmz. and Iwd.. 61, 2% (1942); (d) Kaistrick and Smith, ibid., 60, 81'8 (I!Mll; (e) UTiksm:u1, AuL!.Tic?,, 6, 263 ( 1 9 4 1 ) : ( 0 Wicsner, \ ~ i ! i < r
