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COMMUNICATIONS TO THE EDITOR
d i t h i ~ h y d a n t o i nand ~ 5-hexyl-5-methyl-2,4-dithioTABLE I hydantoin (m.p. 98.5-99.6'. Anal. Calcd.. N, COMPOSITION O F T H E RADIOACTIVE HYDROCARBONS FORXIBI) 12.16; S, 2'7.83. Found: N, 12.20; S, 27.83.) BY THE IRRADIATION OF A 5 MOLEPERCENT. S m u n t i y oii Doses of the order of 200-300 mg. /kg./day of 5ASILIKE IN NORMAL PEN~ANE n-heptyl-Zthiohydantoin were required to protect 5% of total C I 4 was extractable into 12 S FICl all mice infected intravenously with ill. tuberculosis Per c e n t . o f t!ic Chemical form totirl r:i well tolerated by these species. I n view of these 2 45-2 90' 3 is results it is felt t h a t 5-n-heptyl-2-thiohydantoin Residue 9 worthy of clinical trial as an antitubercular drug. I t seems more than a coincidence that the groupIt is clear from these preliminary results, which S were duplicated by a second run in which ethyl'1 ing, -NH-C-SHor a tautomeric form thereof amine was substituted for aniline, that a high velooccurs so frequently in in vivo tuberculostatically city carbon-14 on colliding with the liquid aliphatic active drugs. The thiosemicarbazones, the thio- hydrocarbon has a very good chance of entering the ureas reported by H ~ e b n e rthe , ~ mercaptotriazin- chain. The reasons for this may be debatable, but ones of Hagenbach5 and now the thiohydantoins the facts seem to be clear. I t should be realized that the hexane and heavier hydrocarbons produced all have in common the thioureido function. in the above-described bombardment were essen( 3 ) H C C a r r i n g t o n , J Chem Soc , 681 (1947) tially carrier free except for any which may have (4) C F H u e b n e r , e l ~l , T H I SJOURNAL, 76, 2274 11953) been produced by gamma and fast neutron radia(5) R F H a g e n b a c h , E Hodel a n d H Gysm, Expev:enlra, 10, 620 tion. It would seem therefore that the process (1954) E FROELICHdescribed can produce radioactive hydrocarbons of ALICE FRUEHANhigh specific activity. It is further clear that as STERLIUGWINTHROP MARYJACKMAN far as neutron economy is concerned, this process RESEARCH INSTITUTE FREDK RIRCHNER could well compete with any organic synthesis, for RENYSELAER, V Y E J ALEXANDER S ARCHER the sole labor involved is the purification of the original chemical, the preparation of the samples for RECEIVED MAY1, 1954 irradiation, and the subsequent distillation and separation. There is reason to believe that the DIRECT PRODUCTION OF RADIOACTIVE ALIPHATIC procedure outlined would also serve to introduce radiocarbon into heavy lubricating oils. HYDROCARBONS BY PILE IRRADIATION' )
Sir: Study of the hot atom chemistry of carbon-14 by the irradiation of nitrogenous organic materials in the heavy water pile a t the Argonne National Laboratory (CP-3') has led us to observe a method of producing saturated aliphatic hydrocarbons in radioactive form in high yield and high specific activity. -2 5 mole per cent. solution of aniline in normal pentane, 20 cc. of which was enclosed in a quartz tube and irradiated for one week in the CP-3' pile at a flux of 1011 neutrons per cm.2 per second, proved to yield about 25y0 of the radiocarbon in the form of radioactive normal pentane, with less than 1% as iso- or neo-pentane; about 15% in the form of radioactive hexane, which apparently is about two-thirds normal hexane; and the remainder in heavier hydrocarbons. The distribution is given in Table I.
DEPARTMENT OF CHEMISTRY AND INSTITUTE FOR S U C L E A R S T U D I E S UNIVERSITY OF CHICAGO CHICAGO, ILLINOIS
ARIEL G . SCHRODT F. T,rnnv
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RECEIVED MAY10, 1954 ____.~_._
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ENZYMATIC REDUCTION OF CORTISONE'
Sir: Previous in viBo and in vitro studies reveal that the major pathway of cortisone metabolism is the reduction of the A4-3 ketone group to the satu, ~ . should ~ like to rated 3-alcohol by the l i ~ e r . ~ We report the presence of an enzyme system in rat liver
(1) T h i ? research was supported h y t h e United S t a t e s Air F o r c e t h r o u g h t h e Office of Scientific Research of t h e Air Research and De-
(1) Abbreviations a s used in t h i s communication are: cortisone (A4-pregnene-l7u,21 diol-3,11,20-trione), dihydrocortisone (pregnane17a.21-diol-3,11,20-trione), t e t r a h y d r o r o r t i s o n e (pregnane-3a.17n.21triol-1 1,20-dione), T P N H a n d T P N (reduced a n d oxidized triphoqphopyridine nucleotide, respectively), D P N H a n d D E " (reduced a n d oxidized diphosphopyridine nucleotide, respectively). ( 2 ) J. J. Schneider, J . Biol. Chem., 194, 337 (1952). (3) J. J. Schneider a n d P. hl. H o r s t m a n n , i b i d . , 196, 629 (1952). , L e v y a n d 0. M. Hechter. Arch. Biochcm., 46, I69 (4) E . Y C ~ s p iH.
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(19.53)
