CORINUNICATIONS TO THE EDITOR
Nov. 20, 1959
6089
the fractions obtained by ozonolysis of parthenin a t room temperature, which also results in the formation of formic acid, gave a positive iodoform test and the n.m.r. spectrum of parthenin had no signal corresponding to the =C-CHs peaks present, for example, in the n.m.r. spectra of dihydroparthenin (11), anhydroparthenin (VI), neotenulin and santonin. One of the several reduction products of VI, hexahydroanhydroparthenin (VII), proved to be identical with tetrahydr~ambrosin.~ This provides proof for the previously assumed structure of ambrosin (VIII)7 and shows that I and VI11 have the same stereochemistry a t C4, Cg, Ca and C7. The rotatory dispersion curvegof I11 is almost superimposable on that of tetrahydrohelenalin which suggests the absolute configuration a t C1, Cd and Cg. Acknowledgment.-This investigation was supported by a grant from the United States Public Health Service (RG-5814).
lized several times from hot pure n-pentane at - 10’ into hair-like, orange-yellow crystals which agglomerated like cotton fibers; yield, 65%; m.p. 110’. This compound also can be prepared in aqueous solutions. Anal. Calcd. for C4H9N030s: N, 4.53; Os, 61.48; mol. wt., 309. Found: N, 4.68; 60.08; mol. wt., 303 (cryoscopic in benzene). With the thiourea reagent3 t-butyl osmiamate gave an immediate pink coloration characteristic for octovalent osmium. A paper chromatogram developed with ligroin-t-butyl alcohol mixture, 90:10 v./v., gave an Rfof 0.68 (32’). An infrared spectrum 10% in CHC13 showed a strong band, absent in the infrared spectrum of the amine, a t 910-915 cm.-l compared with that of osmium tetroxide a t 951 cm.-’. Bands usually attributed to the amino or hydroxyl hydrogens were absent. An ultraviolet spectrum in t-butyl alcohol gave a maximum a t 323 mp; E , 4066. 1,1,3,3-Tetramethylbutylosmiamate (111) was prepared in exactly the same way as the t-butyl (7) (a) H. Abu-Shady and T. D Soine. J . A m . Pharm. Assoc., 42, 387 (1953); 43, 365 (1954); (b) L. Bernardi and G. Bucbi, Exgerientra, osmiamate; yield, 69%; m.p. 51.5’ (n-pentane). 13, 466 (1967); (c) F. Sorm, M. Such$ and V. Herout, Coll. Czechoslov. Anal. Calcd. for C E H ~ ~ N O ~ O N,S : 3.83; Os, Chem Commun., 24, 1548 (1959). (8)We wish t o thank Dr. V. Herout for carrying o u t t h e compari52.04. Found: N, 3.80; Os, 51.89. son. This osmiamate also gave an immediate pink (9) Kindly determined by Professor C. Djerassi. color with the thiourea reagent and on a paper (10) Recipient of a Fulbright Travel G r a n t 1958-1959. DEPARTMENT OF CHEMISTRY WERNERHERZ chromatogram an Rf value of 0.87 (32’). The infrared spectrum 10% in CHCl3 showed a strong THEFLORIDA STATEUNIVERSITY band a t 910-915 cm.-’ with the amino and hyTALLAHASSEE, FLORIDA HIROSHIWATANAFJE’~ droxyl hydrogen bands absent. The ultraviolet RECEIVED OCTOBER 2, 1959 spectrum in t-butyl alcohol showed a strong band with a maximum a t 323 mp; E , 3650. ORGANIC OSMIAMATESI Both osmiamates react with dilute sulfuric acid Sir: to give osmium tetroxide and the sulfates of the Osmiamates (I)2 in which the osmium is octo- original amines. They deflagrate spontaneously valent are not known in Organic Chemistry. We on a hot plate and show strong oxidizing properwish to report the synthesis of two organic osmi- ties; they react with olefins in the same manner as amates: t-butyl osmiamate (11) and 1,1,3,3- osmium tetroxide. These and other reactions of tetramethylbutyl osmiamate (111) which were ob- osmiamates are now being investigated and will be reported later. Acknowledgment.-The authors are indebted to O C O s G N Me ( CHS)~C--~’ZOS=O Dr. Shin-ichi Sasaki and Mrs. J. A. Hilton for techI$ nical assistance, to Dr. S. Xagy for the nitrogen 0 analysis and to Rohm and Haas for a supply of I I1 CHI 0 1,1,3,3-tetrarnethylbutylamine. I ti (5) W. Geilmann and R. Neeb, Z . anal. Chem., 1 5 6 , 420 (1957).
[
; 1;
;
( CH~)~C-CH~-C-NEO~=~O
I
CH3 111
1.1
0
tained as a result of our general studies on the reaction of osmium tetroxide with various groups of organic compounds. &Butyl osmiamate was prepared by allowing osmium tetroxide (1.0 g.) in 50 cc. of pure ligroin to drop slowly with stirring a t 0’ and preferably in a nitrogen atmosphere into a ligroin solution (25 cc.) of excess (7.0 g.) of tbutylamine. Stirring was continued for 24 hours whereby an orange precipitate separated out and was removed by filtration. This was recrystal3 3 4
(1) Supported by N I H Contract B-l493(C1).
(2) N. V. Sidgwick. “ T h e Chemical Elements and Their Compounds,” Vol. 11, Oxford University Press, 1950, p. 1507. (3) N. A. Milas, J. H. Trepagnier, J. T. Nolan, Jr , a n d h l . I Iliopulos, Tars J O U R N A L , 81, 4730 (1959). (4) N. A Milas and M. I. Iliopiilos, N I H Report, March (1959)
(6) R . Criegee, A n n . , 522, 75 (1936); R. Criegee, B. Marchand and H. Wannowius, ibid., 550, 99 (1942). Criegee, el al , indicated t h a t osmium analyses gave always low values. (7) N I H Postdoctorate Research Assnciate, Fellow.
Fulbright Traveling
DEPARTMELT OF CHEMISTRY NICHOLAS A . MILAS MASSACHUSETTS IXSTITUTE OF TECHNOLOGY CAMBRIDGE 39, MASS. ,MILTIADIS I. ILIOPULOS’ RECEIVED O C T O ~ E13, R 1959 THE BIOLOGICAL CONVERSION OF SYNTHETIC METHOSTENOL-4-C14 TO CHOLESTEROL’
Sir: We have reported recently that sodium acetatel-C14 injected into rats intracardially becomes incorporated into the methostenol (4a-methyl-A’cholesten-3/?-01) of the skin and liver-small in(1) This investigation was supported b y a research g r a n t (H-2458C3) from t h e National Institutes of Health, Public Health Service.
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COMMUNICATIONS TO THE EDITOR
Vol. s1
testine po01.~ Specific activity findings suggested A large fraction of the recovered CI4 was located a precursor relationship between methostenol and in the Saponifiable fraction of the feces (rat A, cholesterol. Methostenol-4-CL4was prepared in 28.67,; rat R , S5.7c1,)presumably as bile acids order to subject this hypothesis to experimental and their derivatives. The rapid conversion of test. Cholesterol-4-C14 (0.05 mC.) diluted with methostenol to cholesterol places methosteriol in the 2.0 g. of cholesterol served as starting material. role of an active intermediate of Cholesterol bioMethostenol-4-CI4was prepared by first synthesiz- synthesis. The recent isolation and characterizaing 7-dehydrocholesterol-4-CI4according to the tion of 4a-rnethyl-As-cholesten-3~-ol from mice method of Hunziker and Xtullner.4 Hydrogenation preputial gland turnors1O suggests the interesting of 7-dehydrocholesterol-4-C14 in dioxane over Ranep possihility that this sterol could give rise to methonickel5 afforded A7 - cholestenol - 4 - C14. hletho- stenol by the migration of the douhle bond at stenol-4-CL4then was prepared from A'-choles- C-8 (9) to C-7, in t h o . tenol-4-C14 by methods previously d e s ~ r i b e d . ~ ~ ' (10) A. A. Kandutsch and A. Is Russell, Tnrs JOURNAL,81, 4111 After repeated chromatography on silicic acid: (1959). Celite (2:l) columns, methostenol-4-C14, m.p. BIOCHEMISTRY DEPARTMENT 143-5', exhibited a specific activity of 9,650 c.p.m./ UNIVERSITY OF PITTSBCRGII WILLIAMIV. WEI.LS mg. A solution of radioactive methostenol in SCHOOL CLARENCE T, 1.ORAII OF MEDICINE PENNSYLVAXIA Tween-80* was fed by stoniach tube to two male PITTSDURGII, RECEIVED SEPTEMBER 30, 1959 albino rats (A and B) of the Holtznian strain, weighing 155 and 110 gm., respectively. The fornier received 89,700 c.p.rn. and was sacrificed r - OF THE TRANSITION ~ METALS. ~ xrr. ~ 6 hours after administration of the meal and the SYNTHESIS WITH ALKYL CHROMIUM AND NICKEL COMPOUNDS latter received 134,000 c.p.m. and was sacrificed 24 hours after intubation. A control was prepared Sir: which consisted of the liver and small intestine One-step syntheses of polynuclear benzenoid of a similar rat to which was added 4,000 c.p.m. hydrocarbons, ;.e., naphthalenes, phenanthrenes of methostenol-4-CI4 and sufficient alcoholic KOH and anthracenes, by cyclic condensation of dito saponify the mixture. At each time of sacrifice, liver-intestine pool, carcass, and feces were sepa- substituted acetylenes on triarylchroniium(II1) rately saponified with alcoholic KOH. The non- compounds have been reported.' In these reactions saponifiable fraction of each preparation was iso- it is clear that the aryl groups bonded to chromium lated with ether, taken to dryness and liver- have participated in the cyclizations and substituted iatestine and carcass mixtures were chrornato- hydrogen has been concurrently abstracted from graphed on silicic acid: Celite (2:l) columns them. Although diarylnickel(I1) derivatives are (1.8 X 20 cm.) using an elution gradient of ben- quite capable of cyclizing acetylenes to the benzene:Skelly C (2:l) against a reservoir of Skelly zene ring system, they do not form polynuclear C. Fractions were plated and radioactivity aromatic structures2 We conclude, therefore, measured with a thin end window gas flow counter. that organochromium(IT1) is a powerful hydrogen Results of the recovery of radioactivity in the acceptor. This conclusion, in experimental trial, methostenol or cholesterol fractions are shown in has led to unique syntheses which we now report. Triethylchroniium(II1) is prepared by the same Table I. Specific activity values for cholesterol were determined after several crystallizations from general method employed in the syiithesis of the methanol and a purification through the dibroi~iide.~corresponding phenyl derivative. In tetrahydrofuran this alkylchromium compound also cyclizes IIelting points were 146-14s'. tolane to hexaphenylbenzene; but also, i t contributes an ethyl group in a mixed condensation TABLE I with tolane, yielding 1,2,3,4-tetraphenylbenzene, T H E RADIOACTIVITY O F CERTAIN STEROLS ISOLATED AFTER I, m.p. 1S7-1S9°.4 Thus, organochromiuni(III), TIIR TSCESTIOX O F A METHOSTENOL-4-C" MEAL BY THE RAT' in addition to providing a two-carbon atom fragRecovery of Cl4 in non-sap. Cholesterol ment for condensation with two molecules of tolane, ----fractionspecific MethoChoactivity has further demonstrated its hydrogen acceptor Total stenol lesterol c.p.m./ capacity by dehydrogenation of the diliydrobenxene R a t no Tissiie c.p.ni. c p.m. c p.m. mg. ring. Control Liver-Iiit. 3,750 3630 120 0 Diethylnickel in tetrahydrofuran also condenses 6170 199 A (6 hr.) Liver-Int. 14,500 4900 tolane to hexaphenylbenzene and provides an 39 9 Carcass 5,400 1760 3040 ethyl group for a mixed condensation. However, 127C 2330 116 4,023 B (24 hr.) Liver-Int. the relatively weak hydrogen accepting character030 2950 21.7 Carcass 3,840 istic of organonickel(I1) is manifested by reaction a Control received 4,000 c.p.111.; rat A, 89,700 c.p.m.; rat B, 134,000 c.p.m. termination a t the dihydro stage, and 1,2,3,4tetraphenyl-l,3-cycZohexadiene,11, m.p. 170-1 71 ( 2 ) C. L. Lorah and W. W. Wells, Fed. Proc., 18, 276 (1959). (3) Nuclear-Chicago Corp. [A.rzal. Calcd. for C30H24:C, 93.71; 13, 6.29. F. Hunziker and F. X. Miillner, Helv. Chim. A c f a . 41, 70 (1958). L. F. Fieser and I. E. Hen, T H r s J O U R N A L , 7 5 , 121 (IY53). W. W. Wells and D. H. Neiderhiser. i b i d . , 79, 6569 (1957). D. H. Neiderhiser and W. W. Wells, Arch. Biachem. b Biophys., 81, 300 (1859). (8) Polyoxyethylene sorbitan monooleate, Atlas Powder Co. (9) E . Schwcnk and N. T . Werthessen, Arch. Biochem. Biophys., 40, 334 (1852). (4) (5) (6) (7)
(1) K. Zeiss and W. Herwig, T H r s JOURNAL,80, 2813 (lc158); 14'. Herwig, W. hletlesics and H. Zeiss, i b i d . , 81, Dec. 5 (1958). (2) M. Tsutsui and H . Zeiss, Abstracts, 134th hleeting. Amer Cliem. SOC.,Chicago, Sept., 1858, p. 59-P. (3) W. Hrrwig and H . Zeiss, THIS JOUXNAL, 81, 4708 (1!15!3). (1) Identification waq made by physical and spectroscopic cimilxirisons with authentic substance.
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