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tion was accomplished most conveniently by oxidiz- filament lamp, ordinarily used as the comparison ing the crude product with chromium trioxide to radiator for measurements of this type, could not 32-isoallospirostan-3,ll-dione (m.p. 236-237", be employed due to the fact that the flame tem[ c u ] ~ ~-17'; D found: C, 75.16; H, 9.22), followed peratwe is above the melting point of tungsten by Raney nickel hydrogenation (room tempera- (3640"K.) ; the same is true of the ordinary carbon ture) to 22-isoaIlospirostan-:3p-ol-lI-one (V) l 3 (tt1.p. arc (sublimation point of carbon 3810°K. a t atm. 223-226", [ C Y ] ~ ~-29'; D found: C , '73.28; H, 9.93. pressure). Since no simple man-made radiator seemed to be available which had the desired charThe acetate14 showed 1n.p. 322-22'24', [ C U ] ~ O D -31'; found: C, 73.92: H, 9.60). Alternately, themixture acteristics the optical train was modified to use the of I11 and IVa was converted with ethanedithiol sun as the comparison source. A two-mirror helioin the presence of zinc chloride to 22-isoallospiro- stat was used in keeping the sun's image focused on st an-Xp-01- 11,12-dione 12-cycloethylenemercaptol the spectroscope slit. A neutral, variable absorb(ni.p. 289-291'; found: S, 11.98), which upon ing agent of good optical quality was used in Raney nickel desulfurization led directly to the 11- adjusting the brightness of the sun so that line-reketone V. This substance (V) has already been versa1 could be readily obtained and easily reprotransformed14 into allopregnan-3p-ol-11,20-dione duced. An optical pyrometer reading of the sun through the same filter then gave the flame temperand thence3 to cortisone. ature. The maximum flame temperature was (13) The 3.11-dione as well as T proved to he identical with specimens prepared from diosgenin by the performic acid method (cf. '2 measured a t 4300°K. using stoichiometric quantiStork, J. Romo, C. Rosenkranz and C. Djerassi, ibid., 73, 3646 (1951)) ties of hydrogen and fluorine. The agreement be(14) E. M. Chamherlin, \T, V. Ruyle, A. E. Erickson, J. M . Chemtween this value and the theoretical temperature is erda. L. A t , Aliminosa, R . L. Erickson, G. E. Sita, and M . Tishler, admittedly fortuitous, the accuracy of our measureibid., 73, 2396 (1931), reported m.p. 224-229'. [ e ] * ' o -39.4" for a sample prepared from diosgenin. ments being approximately f 150'. RESEARCH LABORATORIES CARLDJERASSI In this particular line-reversal application it is SYNTEX,S. A . HOWARD J. RINGOLD not possible to employ the sodium lines for reversal LAGUNAMAYRAN 413 G . ROSENKRANZ due to the occurrence of sodium in the solar spech.IEXIC0 CITY 17, D. F. trum. Lithium was used in the present work RECEIVED OCTOBER1 , 1951 since, for all practical purposes, it does not appear THE TEMPERATURE OF TRE HYDROGEN-FLUORINE in the solar spectrum. Complete details of our theoretical calculation FLAME and experimental work will be published elsewhere. Sir: INSTITUTE OF R. H. WILSON,J R . The reaction Hz(g) f F&) + 2HF(g) is highly T H E RESEARCH UNIVERSITY J. B. CONWAY exothermic and in addition gives rise to a reaction TEMPLE PENNSYLVANIA A . ENGELBRECHT product possessed of exceptional thermal stability. PHILADELPHIA, A. T'. GROSSE These factors combine to produce a very high RECEIVED OCTOBER1, 19,51 flame temperature which heretofore has not been measured. Theoretical calculations based on the method de- THE SYNT-SIS OF THE BLOOD SERUM VASOCONSTRICTOR PRINCIPLE SEROTONIN CREATININE scribed in Wennerl have produced the following SULFATE flame temperature-composition relationships : Sir: Theoretical flame temperature a t 1 atm. Feed composition The existence of a potent vasoconstrictor agent in ? H: total pressure, OK. Mole Vr, E'? the sera of mammals was reported as early as 1868 10.0 90.0 1920 by Ludwig and Schmidt' and since that time has 33.3 66.7 3550 been the . subject of over eighty publications.* 50.0 50. 0 4300 Experiments with sera obtained under various con66.7 33 3 3800 ditions and allowed to stand for variable periods beIn these calculations the latest thermodynamic fore use have produced a maze of conflicting biologdata were employed.2,3,4*5 ical data. This problem has been clarified only reThe construction and operation of the hydrogen- cently by Rapport3>'who isolated from beef serum fluorine torch has already been described by Priest a very active vasoconstrictor substance in crystaland Groese.6 This torch produces a diffusion-type line form. Rapport was able to show that the crysflame due to the present inability to premix hydro- talline material was a complex, or mixed salt, comgen and fluorine. posed of equimolecular proportions of sulfuric acid, The flame temperature was measured by means of creatinine and an indole base.5 On the basis of the line-reversal technique.7 The tungsten ribbon- chemical tests as well as analytical and spectral data (1) R. R. Wenner, "Thermochemical Calculations," McGraw-Hill Rapport has proposed that the indole base is 5-hyBook Co., New York, N. Y., 1941. droxy-3-beta-aminoethylindole(I) (5-hydroxytryp(2) G. M . Murphy and J. E. Vance, J. Chem. Phys., 7 , 8 0 6 (1939). ,
( 3 ) M. G. Evans, E. Warhurst, and E . Whittle, J . Chcm. Soc., 1624 (1950). (4) W. M. Latimer, MDDC-1462, United States Atomic Energy Commission, Declassified Document, November (5) A.P.I. Research Project 44, National Bureau of Standards. (6) H. F. Priest and A. V. Grosse, 2nd. Eng. Chcm., SO, 431 (1947). 17) See B . Lewis and G . v. Elhe's chapter in "Temperature, Its Measurement and Control in Science and Industry," Reinhofd Publ. Corp., New York, N. Y., 1940: and C. W. Jones, B. Lewis, J . B. Friauf. and C. S t . J. Perrott, THISJOURNAL, 68, 869 (1931).
13,1947.
(1) C . Ludwig and A. Schmidt, Arb. physiol. Anstall (1868).
Lcipsig, 1
(2) For literature reviews see (a) T. C. Janeway. H. B. Richardson, and E. A. Park, Arch. Inl. Mcd., 21, 565 (1918); (b) G. Reid and M . Bick, Ausfrai. J. E x p . Bioi. Med. Sci., 20, 33 (1942). (3) M. M . Rapport, A. A. Green and I . H . Page, Science, 108, 329
(1948). (4) M . M. Rapport, A. A. Green and I . H . Page, J . Biol. Chem., 176,
1243 (1948). (6) M . M . Rapport. ;bid. 180, Re1 (1949).
