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COMMUNICATIONS TO THE EDITOR
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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 latter received 134,000 c.p.m. and was sacrificed COMPOUNDS 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 14,500 4900 6170 199 A (6 hr.) Liver-Int. tolane to hexaphenylbenzene and provides an 1760 3040 39 9 Carcass 5,400 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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Found: C, 93.87; H, G.071 is the product. This formulation is supported chemically by bromination of I1 with N-bromosuccinimide or bromine and dehydrobromination, and by dehydrogenation of I1 with palladium-charcoal, to 1,2,3,4-tetraphenylbenzene. The ultraviolet spectrum of 11, having absorption maxima a t 236 mp, 268 mp, and 326 mp ( e = 15,600, 10,600 and 12,100) is also consistent with the cyclohexadiene structure. It is anticipated that the foregoing reaction will prove to be a general as well as a convenient method for preparing cyclohexadiene ring systems.
on the reactivity of active nitrogen i t was felt that a comparative study with phosphorus might prove informative. An apparatus similar to that used for nitrogen2 was tried for phosphorus. Argon, as a carrier gas,was passed through a bulb containing phosphorus a t a temperature from 25 to 100’. The flow rate of argon was about 50 micromole/sec. a t a pressure of approximately 1 mm. in the reaction bulb. When only argon was allowed to flow through the discharge, no decomposition of reactants was observed. Similarly no reaction was observed when P4was allowed to mix with reactant with no discharge. A definite reaction was obtained between phosphorus, swept through the discharge with argon, and ethylene, propylene, butene-1, propane, methane, ammonia, and hyChHj drazine. Phosphine was the major gaseous conI I1 III stituent produced in all cases. The reactions also Mixed condensation between alkyl groups and were observed when a microwave discharge was acetylenes is shown, perhaps even more strikingly, used to generate the “active phosphorus. I’ by the reaction of trimethylchromium with tolane. Gas chromatographic analysis on the products of In this example the organochromium(II1) reagent methane-active phosphorus reactions indicated contributes a methyl group, forming lI2,3,4-tetra- a t least six volatile products. Phosphine] methylphenylcyclopentadiene, I I I, m.p. 176-1 78O , in phosphine and ethane were obtained in very small addition to the normal product, hexaphenylben- quantities. The ethane was approximately 2% zene. The oxidative potentialities of organo- of the phosphine fraction. A considerable amount chromium(II1) are being examined in other areas of solid was deposited in the reaction zone during of organic synthesis. an experiment. This, along with red phosphorus, appears to be the solid phosphorus hydrides. RESEARCHAND ENGINEERING DIVISION M. TSUTSUI It also was found that with a new discharge MONSANTO CHEMICALCOMPANY DAYTON7 , OHIO H. ZEISS tube and a clean-walled apparatus, a liquid was RECEIVEDOCTOBER12, 1959 produced in relatively large quantities. It was shown not to be PzH4 from physical properties and elementary reactions. ACTIVE PHOSPHORUS Further work along with the identification of the Sir: “liquid” product is now being pursued. An early attempt to produce phosphorus atoms Grateful acknowledgment is made to the Reby a condensed discharge proved unsuccessfu1.l I n view of the work of Winkler and co-workers2 search Corporation for supporting this work. (1) N. M. Gopshtein a n d S. Z. Roginskii, J . P h y j . Chcm. (USSR), 7, 587 (1936). (2) D. A. Armstrong and C. A. Winkler, J . Phys. Chcm., 6 0 , 1100 (1956).
DEPARTMENT OF CHEMISTRY UNIVERSITYOF MANITOBA E. R . ZABOLOTNY H. GESSER WINNIPEG,CANADA RECEIVED OCTOBER9, 1959
BOOK REVIEWS Brandlehre und Chemischer Brandschutz. Eine Einfiihrung in die Grundlagen. Zweite Erganzte und E n d terte Auflage. BY LUDWIGSCHEICHL, Oberregierungsrat. Dr. Alfred Hiithig Verlag, Wilckenstrasse 3, Heidelberg, 424 pp. 16 X 23 cm. Price, Germany. 1958. xiv D M 28.--. This volume is not a scientific and technological treatment of ignition, combustion and explosions, as one would expect it to be if it were a technical book on “Brandlehre,” but rather has as its main objective classifications and descriptions of materials in the technology of “Brandschutz,” i . e . , of fire-proofing, fire-prevention, control and extinction. It would, therefore, have been more descriptive of the contributions of this book if the word “Brandlehre” had been omitted from the title. While technological aspects and classifications in “Chemischer Brandschutz” are well presented in the last two parts (Teil B and C) of the book, the first 207 pages, exclusive of 40 pages of classi-
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fications and definitions pertaining to “Brandlehre” (pages 19-40 and 181-207) comprise good elementary, but unnecessary, reviews of well-known principles of physical chemistry. Pages 19 t o 40 present interesting, but not actually fundamental, classifications of materials of combustion and definitions pertaining to ignition, flames, combustion and explosion. Pages 181 to 207 outline and classify burning processes and mechanisms, but the classifications are incomplete as are the descriptions of burning processes. It is true, however, that attention is called occasionally elsewhere in “Teil A” to applications of particular physico-chemical principles in combustion technology. The actual fundamental principles comprising the science and technology of ignition, combustion and even fireproofing and the control and extinguishing of combustion are merely mentioned briefly in spite of a great deal of the book being devoted to principles one might readily apply in this technology. It is interesting in view of the many
