June, 1942
NEWCOMPOUNDS
1489
chloric acid for twenty minutes, transferred to an evaporat- procedure used for a-naphthalenesulfonyl fluoride.2 I t ing dish, and heated for an additional fifteen minutes on was recrystallized several times from hexane to give a 3.1% the water-bath. I t was decolorized with charcoal and yield of tiny colorless plates, m. p. 76-78', uncor. neutralized with 5 N NaOH to pH 3.5. After cooling in Anal. Calcd. for C12HgS02F: F, 8.04; hydrolysis ice, the sulfanilylcystine, colorless needles, was filtered off, value, 8.11 ml. of 0.5221 N NaOH. Found: F, 8.17; washed with ice cold water, 95% alcohol, and ether; yield, hydrolysis value, 8.18 mi. of 0.5221 N NaOH (method of 2.1 g. (68%). Dried in a vacuum desiccator over sulfuric Davies and Dicka). acid, it mclted a t 165-166" (uncor.) with foaming and deThe structure was established by conversion with aluinicompositioii. The loss in weight of the desiccator dried n u m chloride2 to 4-biphenylsulfonyl chloride; ni. p. 113material upon further drying in a pistol a t the boiling ll5', uncor. (GFbriel and Deutsch4 give 115"). This pilint of toluene indicated a mole of water of hydration, compound was identical with a sample of the sulfonyl and thc melting point became 193-.194" (uncor.) with chloride prepared from potassium 4-bipheriylsulfonate, foaming and decomposition. The sulfanilyl-l-cystine is m . p. and mixed m. p. 113-115". uegative to the Sullivan reaction for cystine and positive to 4,4'-Biphenyldisulfonyl Fluoride.-To 777 g. (7.8 molcs) t h e nitroprusside test after reduction with sodium cyanide. of colorless, freshly distilled fluorosulfonic acid in a Pyrex I t gavc a positive reaction with 1,2-naphthoquinone-4flask was added 195 g. (1.26 moles) of biphenyl, with stirsodium sulfonate.2 The desiccator dried sample was used ring. The addition a t 70" required about four hours and for the analysis. heating was continued for three hours longer. After standAnal. Calcd. for C I ~ H ~ ~ O S SS,~ N 23.27; ~ : N, 10.18. ing for fourteen hours a t room temperature, the reaction Found: S,23.12; N, 10.11. mixture was poured into ice water and the disulfonyl fluoride extracted by shaking the whole with methylene CHEDIO-MEDICAL RESEARCH INSTITUTE FILADELFO IRREVERRE GEORGETOWN UNIVERSITY chloride. The solvent was removed from the methylene M. X. SULLIVAN chloride layer by distillation and the residue dissolved in a WASHINGTON, D. C. RECEIVED APRIL17, 1942 methylene chloride-hexane mixture (equal volumes of each). After decolorizing with carbon the product was pC yclohexylphenyl-phenylsulf one crystallized by cooling in a salt-ice mixture. A yield of Ten grams of phenylcyclohexane and 11.6 g. of benzene- 264.5 g. (66%) of the crude disulfonyl fluoride, m. p. 185sulfonyl chloride were placed together with 50 ml. of car- 200 ', was obtained. After two additional crystallizations bon disulfide in a small flask. Ten grams of aluminum from methylene chloride-hexane the 4,4'-biphenyldisulchloride was added gradually in small amounts. No im- fonyl fluoride melted a t 197-200", uncor. Under the mediate reaction occurred, but after a short time 'the mix- microscope the fine white powder appears as colorless prisms. The compound is soluble in methylene chloride, ture turned dark red and a vigorous reaction ensued with copious evolution of hydrogen chloride. The mixture was ethanol, 'acetone, benzene and nitrobenzene, slightly solallowed to stand overnight, whereupon the product was uble in carbon bisulfide and carbon tetrachloride, and inpoured onto crushed ice. The organic layer was washed soluble in hexane and in water. I t is stable when boiled with water and the solvent allowed to evaporate. The with water and with 0.5 N sulfuric acid. When heated on sulfone was recrystallized four times from 95% ethanol and a copper bar it is entirely stable a t 260"; very slight browntwice from high boiling ligroin. Glistening white leaflets ing is evident a t 285". Anal. Calcd. for ClzHsF2S204: F, 11.94; hydrolysis were formed which melted a t 108-109.5"; yield, 50%. value, 12.04 ml. of 0.5221 N NaOH. Found: F, 12.00; Anal. Calcd. for C18H2002S: S, 10.67. Found: S, hydrolysis value, 12.13 ml. of 0.5221 N NaOH.3 10.82. The structure was established by conversion with alumiThe position of the cyclohexyl group was determined by num chloride2 to 4,4'-biphenyldisulfonyl chloride, m. p. oxidation with chromic acid.' The resulting carboxylic acid was obtained in almost quantitative yield. It 202-204", uncor. (Gabriel and Deutsch' give 203 "). 2-Biphenyl F1uorosulfonate.-This compound was premelted a t 273-274" and had properties similar to the p pared by the method of Lange6 for aryl fluorosulfonates. phenylsulfonylbenzoic acid of Newell. To a well-stirred solution of the diazonium chloride pre(1) Sewell, A m . Chem. J . , 90, 304 (1898). pared from 169 g. of 2-aminobiphenyl, 200 cc. of concentrated hydrochloric acid, 76 g. of sodium nitrite and 300 221 1 BURLINC STREET CHICAGO, ILLINOIS RICHARD D. KLEENE cc. of water, was added 117 g. of solid ammonium fluoroRECEIVED MARCH 30, 1942 sulfonate6 a t 0 '. The precipitated diazonium fluorosulfonate was filtered, washed with water, alcohol and ether and dried in vacuo: yield 207 g. (73,9%); decomposition Fluorine Derivatives of Biphenyl point 83-84". The diazonium fluorosulfonate (0.4 to 0.6 Two sulfonyl fluorides of biphenyl' were prepared by mole) was decomposed in small portions a t 95", and the the method of Steinkopfzfor sulfonyl fluorides of the benresidue was steam-distilled. The distillate was extracted zene and naphthalene series. ... 4-Biphenylsulfonyl Fluoride.-This sulfonyl fluoride was ( 4 ) Davies and Dick, J . Chrm. .Sot., PI04 (1931). (4) Gabriel and Deutsch. Bel., 19, 386 (1880). prepared from biphcnyl and fluorosulfonic acid by the (1) T h e reaction of fluorosulfonic acid with biphenyl was investigated a t the suggestion of MI. Gaston DuBois. ( 2 ) Steinkopf. et al., J . p v a k t . Chem., 117, 1 (1927).
( 5 ) 1-ange, ibid., 60, N i 2 (lt127); 1,ange and Miiller, i b i d . , 63,2083 (1930). (6) Prepared according t o the procedure of Traube, Hoerenz and Wunderlich, ibid., 62, 1272 (1919).
1is0
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 a t 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
