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COMhIUNICATIONS TO THE EDITOR
Yol. 80
TRANSPARENT BaFe1201 AND SrFellOl 8 242 nip, log E 4.23). Mild alkaline hydrolysis of V, VI and VI1 afforded Ga-fluoro compound "S" Sir: (VII) (m.p. 203-203", [ a ] D + I % " , Xmax 236 mp, By a solid state reaction of barium fluoride and log e 4.21), CiP-fluoro compound "S" (IX) (m.p. ferric oxide in the ratio 1:6, under oxygen, a red, 222-224', [ a ] D +14', Amax 2% nip, log E 4.09) transparent, single crystalline form of RaFelaOlg and A'-dehydro-Ga-fluoro compound "S" (X) was obtained. The hexagonal platelets, approxi(m.p. 210-212", [ a ] +CjC,', ~ A,, 241 i ~ l p ,log E mately 50 microns thick and up to 2 nim. in dia4.22 j, respectively. meter, are perfectly suitable for the obser~.ation Adrenal incubation6 of both VI11 and X followed and study of TTeiss domains, which in the virgin by monoacetylation a t C-21 gave, in good yield, state are about 1 micron wide. As an alternate Ocr-fluorohydrocortisone acetate (XI) (n1.p. 215- technique, the reaction of ferric oxide in molten 2 1 i o , [ a ] D +14g0 (diox.), Xmax 237 n1p) log e 4.23) barium chloride or strontium chloride under oxyand 6cr-fluoroprednisolone acetate (XIIj (n1.p. 235- gen, also yielded transparent platelets of RaFelsOle 237", [ a ] D + I l l o (diox.), Amax 242 nip, log t 4.2.51, and SrFelzOlu. The compositions of the reaction respectively. Selenium dioxide oxidation: of XI products were established by chemical analysis and gave XII. Chromic acid oxidation of X I and XI1 single crystal X-ray studies. -hi apparently similar provided Gcr-fluorocortisone acetate (XITI) (1n.p. form of BaFe&g was described recently by C. L'15-L'1Go, [a]D +l!>oo, Xmax 233 nip, log E 4.21) Kooy, without indicating the method of prepand Ga-fluoroprednisone acetate (XIV) (m.p. 228- aration. 230", [cr]D -/-142' (diox.),, , ,A 237 nip, log t 4.23). (1) C . G o y , Plzziips ?echnirizl l i ~ r i e w 1 , 9 , 2% (1958). An alternative completely chemical route t o the RESEARCH DIVISIOX 6-fluoro corticoids proceeded from cortisone ace- P I G M E S T S DEPARTXEXT LOTHAR13. BRIXNER tate 3-monoketal (XJTj.i .lcetyliition of X V a t E. I. DU POSTDE SEMOKRS ASV CO~IPASY, INC. '2-17 and peracid epoxidatiori of the resulting 1i')21- ~ f . I L I M I N G T O N 98, DELATYARE RECEIVED JCLY 16, 1938 diacetate (XITI) (m.p. 180~-182O , [ c r ] ~- 20 ") afforded the ,ja,ficr-epoxide (XVII) (111.p. 233-234", [a]D -lSo). Boron trifluoride opening of XVII RADIOLYTIC SYNTHESIS OF THE C I S - AND gave the corresponding ,ja-hydroxy-BP-fluoro-3- THE /;(l?/:-ISOMERS OF 1,2-DICHLOROETHYLENE OXIDE ketal (XVIII) (m.p. 231-232', [.ID -9") which was directly converted by acid treatment to 6cr- Sir : In the course of some investigations on tht. fluorocortisone 17,Pl-diacetate (XTX) (1n.p. 2702iTBo, [cr]u +loso,Amax 233 n i p , log E 4.20). Xlka- radiation chemistry of the symmetrical dichloroline hydrolysis of XIX and subsequent mono- ethylenes, the cis and trans forms of l,2-dichloroacetylatioii gave X I I I . Milder acid treatment of ethylene oxide have been produced. These comXT'III afforded fi,b'-fluorocortisone 17.21-diacetate pounds have not been reported previously, and in (XX) (m.p. 212--213', [ c r ] + ~ G o .Amax 230 in@,log view of the current interest in radiation utilization, we are presenting preliminary data on the radiolytic e 4.00). I n the anti-inflamniatory and thymolytic as- synthesis and physical properties of these comsays,8 (io-fluorocortisone acetate (XIII), Gcr-fluoro- pounds. The cis and trans forms of 1,2-dichloroethylenc hydrocortisone acetate (XI), Ga-fluoro-prednisolone acetate (XII) and Ga-fluoroprednisone acetate were irradiated in glass cells in oacuo with 40-Mev. (XIV) had respective activities of (10,6), (10,S), helium ions inipingent on the liquid. After irradi( 2 0 , W ) (20,23) times that of hydrocortisone ace- ation, the low-boiling products plus the bulk of thts tate. In the adrenalectomized nonsalt loaded 1,2-dichloroethylene were stored in glass-stoppered rat X I , XI1 and XIV promoted sodium e x ~ r e t i o n . ~bottles in the presence of air after preliminar?. The details of this work together with the syn- analysis for high-boiling products. In samples that theses of other 6-fluoro steroid hormones4b,10 will be had stood several months, two peaks were found iii GLP chromatograms (nonyl phthalate column) described in future publications. that were not present in samples chromatoRESEARCH LABORATORIES grammed immediately after irradiation. Thesc SYSTES, S.A. .I,BOKERS .IPT)o. POSTAL Zi79 H. J . RINGOLD peaks were concentrated in the pot liquid by distillaM E X I C O , r).1:. tion through a small Vigreux column and were fur RECEIVED J C N E 23, 1058 ther concentrated and purified by running repeat GLP chromatograms of the pot liquid, collecting the (6) A. Zaffaroni, 13. J . Ringold, ;.C Ilosenkranz, F. Sondheimer, respective peaks each time. By this means SamG. R. Thomm and C Djera,;si, THISJ O U R N A L . 80, October (1858). (7) I
