Dec., 1950
COMMUNICATIONS TO THE EDITOR
5793
gives a satisfactory qualitative accounting for the (hkO), (hkl), (hk2), and (hk3) Weissenberg intensities (CuKa), including a prediction of weak (hRO) reflections which are perhaps not altogether inconsistent with those observed. Until intensity work (now in progress) has yielded quantitative data, a choice between this space group and D:d - P3n2 (obtainable with small dis- P4nm tortions of the above structure) or (permitting a closely related structure derived from the “ideal” structure by shifting I1 and IV about 1/4 in z) cannot be made. All other space . groups have been ruled out. The identities of the atoms are not yet known. They may be very difficult to determine because OAKRIDGENATIONAL LABORATORYGEORGE E. MOORE iron and chromium have nearly the same scatterOAK RIDGE,TENNESSEE KURTA. KRAUS ing factors. RECEIVED NOVEMBER 6, 1950 This work is being continued. We are indebted to Professor Pol Duwez and Mr. Paul PietrokowTHE CRYSTAL STRUCTURE OF A SIGMA PHASE, sky of this Institute for the sample of a-FeCr. FeCr’ We are grateful t o Professor Linus Pauling for Sir: helpful discussions, and t o Miss Linda Pauling Despite the importance of the sigma phase in and Mrs. Nan Arp for computational assistance. transition group alloys, the crystal structure of GATESAND CRELLINLABORATORIES OF CHEMISTRY the phase has not heretofore been determined, CALIFORNIA INSTITUTE OF TECHNOLOGY CALIFORNIA DAVIDP. SHOEMAKER primarily because the materials, prepared by PASADENA, No. 1488 BRORGUNNARBERGMAN solid-state transition, are microcrystalline and CONTRIBUTION RECEIVED NOVEMBER 11, 1950 not well suited for single crystal work, while powder photographs have proved too complicated for satisfactory interpretation. SYNTHESIS OF 11-HYDROXYLATED CORTICAL However, we have succeeded in isolating from a STEROIDS. ~~(LY)-HYDROXYCORTICOSTERONE specimen of u-FeCr (46.5 at. yo Cr) two single Sir : crystals roughly 0.1 mm. in size. Single crystal We wish to report the synthesis of 17(a)-hyand powder photography gave a 30-atom primi- droxycorticosterone known as Reichtive tetragonal cell (Laue symmetry D4h), with stein’s Compound Motherwise 1 or Kendall’s Compound ao = 8.799 8.and Ca = 4.546 A. The only observable (hkO) reflections (aside F,2 a substance found by preliminary studies3 to therapeutic activity similar to Cortisone. from a few faint ones a t large Bragg angles) within have The biosynthesis of 17(a)-hydroxycorticosterthe CuKa limit are uniformly strong, and are one from 1l-desoxy-17(a)-hydroxycorticosterone those ({410) , { 3301, { 5501, {720}, { 8201, { 6601, has been demonstrated techniques of perfu{ 9601, { 11.1.01, and { 10.5.0)) which would result sion in the isolated beefusing adrenal gland4 and of infrom fifteen atoms a t the points of a slightly dis- cubation with adrenal homogenates.s torted hexagonal net (with the following typical have synthesized 17(cr)-hydroxycorticoster(x,y)coordinates with respect t o a vertical two- oneWestarting with 20-cyano-17-pregnene-21-01-3,fold axis: I (1) (0, 0); I1 (2) (1/5, 1/5); I11 (2) CHIOR CHzOCOCHs (2/5, 2/5); IV (2) (2/3, 1/31; V (4) (7/15, I I 2/15); VI (4) (11/15, 1/15)) plus fifteen others C-CN CO in a n equivalent net rotated 90’ with respect t o the first. The relative positions of the two nets are as in an “ideal” structure with space group D$ - P4/mnm, as indicated by n-glide extinctions in (Okl) Weissenberg data (CuKa). That “ideal’) structure is ruled out by the general (hkl) intensities. However, atoms IV in the 0 (I) R H (11) second layer have (x,y) coordinates (1/6, 1/6, (Ia) R = CHaCO etc.) very close t o those of I1 in the first layer, and if the eight atoms I1 and IV are moved t o (1) Reichstein, Helo. Chim. Acfa, 80, 953 (1937). (2) Mason, Hoehn and Kendall, J . Biol. Chcm., 114, 459 (1938). new positions S ( j ) with x = 11/60, z = 1/4, a (3) Hench, Kendall, Slocumb and Polley, Arch. I n f . Mcd., 86, 545 structure with space group D$ is obtained which (1950). nection other ions of oxidation number three are of particular interest. Of these, aluminum, chromium and rare earths have been tested to date and they all were found to be practically not adsorbed from strong HC1 solutions. To illustrate the effectiveness of the method an iron impurity (30 mg./l.) was separated from a 2 M aluminum chloride solution in 3 M HC1 using a 10 cm. column of 0.024 sq. cm. cross-section. After passage of 30 ml. of solution (flow rate ca. 0.25 ml. cm. -2 min.-’), when the experiment was interrupted, iron could be detected (visually) only in the first 0.6 cm. of the column. Thus large volumes of solution could be processed with small amounts of resin.
(1) Work done in part under a contract with the Office of Naval Research and in part under a program sponsored by the Carbide and Carbon Chemicals Corporation.
(4) Hechter. Jacobsen, Jeanloz, Levy, Marshall, Pincus and Schenker, Arch. Biochem., 16, 457 (1950). (5) McGinty, Smith, Wilson and Worrd, Science, 111, 506 (1950).
Vol. 72 11-dione prcpared previously by Sarettfi i t i coli/ , \ uection with the synthesis of Cortisone ('11 1 This cyanopregnerie in the form of its 3-tliethyl 0 / \A,/$,.() hetal was reduced with lithium borohydride7 scLllB] lectively at position 11. After removal of the ke l i tal grouping, 20-cyano-17-pregnene-] 1 (8),21-diol::-one (I) was obtained; m.p. 207-21 O", solidifies I 11, Iz = 0 , 111, 1z = IT? a i d remelts a t 21i.5-221.53 [a]"D f22.4' (1.08, Dihydroresorcinol was alkylated with l-tliethylacetone); hEzoH 2230 A,, E:c21. ; < S i ; A n d . Found: C, 74.12; H, S.73. Alcetylation oi (I) amino-3-pentanone methiodide, the product (11i.p. 84.5-85'; found: C, 67.07; H, 8.06) was cyclized afforded the 21-acetate (Ia) . :n.p. li'O-171.tj'; as the isopropyl or methyl enol ether and hydro[ O ( ] ~ ~+32.4' D (1.02, acetone) : A n d . Found C, 71.93; H, 8.37. Hydroxylation of (Ia) with lyzed to the enol of 5methyloctahydronaphthalmax 242 r n p osmium tetroxide6 yielded 4,5-dihydro-li(a)- ene-1,6-dione (IV), m.p. 95-98'; hydroxycorticosterone-21-acetate. m . p 217.6- (log 1: = 3.84) and 345 inw (3.89). Anal. Calcci. 219.8; [ a I z 5 ~ S6.G (1.03, acetone); Anal. for Cl1Hl4O2: C , 74.13; H, 7.92. Found C, Found: C, 68.20: H, S.19. I3romination of the 73.98; H, 7.93. Alkali converted this in part to latter followed by dehydrobromination with semi (i-hydroxy-5-niethyl-1-tetralone. I V and inethyl carbazide acetates afforded 17(a)-hydrouycortico- \ inyl hetone led t c i 3-y-hetobutyl-3-iii~tli~i~'a-"-octalin-l,ti-dloiie (V), n1.1). 142.2 -1 4:3" sterone acetate (11); xi1.p. 218.3-220.3" ; [a]25~1 150.7 (0.5, acetone) 2420 EicTn,371 ; inax. 246 inp (.3,93); found: C, 72.73; H, S.11. Anal. Found: C , BS.47; Ei, S.11. .I niixed U-ith acid this was isomerized to the As - S a coiiimelting point of synthetic (11) with an authentic pound (TI),m.p. 195.5-19i0, max. 240 nip s,tmpleg of 17(cr)-hydroxycorticosteroiie acetate (3.97); found: C, 72.86; H, 8.11, Alkaline cywas not depressed; comparative infrwed spectra clization of each isomer led to the same tricyclic diketone formulated as I, m.p. 122-123.5", max. of the two samples were identical in all respects. 240..5 nip (4.38). Anal. Calcd. for C15Hi802. 1 6 ) Sarett THISJOURNAL, 70, 1434 (1948) C, 78.22; H, 7.88. Found: C, 77.96; H, 7.94. ( 7 ) Nystrom, Chaikin a n d Brown ( $ b i d , 71, 3245 (1949)) h a \ e Alkaline palladium hydrogenation of I gave a I uiuced rarhonyl groups in the p r e w i ~ c e of estrr functions wxth mono-unsaturated diketone formulated as 11, n1.p. this reagent. ( 8 ) Koechlin. Kritchevsky and Gallagher, J B i d Chem , 184, 393 61.5-63', max. 245 mp (4.14). Anal. Calcd. for (1950). also, Djerassi THISJomuizr 71, 1003 (1949): Ilershberg, C16H2002: C, 77.55; H, 8.68. Found: C, 77.51; J O t g Chcin 13, 542 (1948) H, 8.91. Formation of the 7-dibenzyl mercaptole (9) The authors are indebted to Dr Arnold Ott of the U p ~ o h nCo of I1 and desulfurization with Raney nickel has for authentic samples of 17(a)-hpdroxycorticosterone and its acetate for identification purposrs given the ketone I11 synthesized by Bachmanii N. I,. WENDLER and Dreiding2from cis-9-methyl-1-decalone; seinItESEARCH ~,ABORATOHI7 R P. GRABER icarbazone, 1n.p. 229-231', 2,4-dinitropheiiylhyI
