Sept. 5, 1958 COENZYME Q.
BOOKREVIEWS
4753
11. SYNTHESIS OF 6-FARNESYL-
tion reaction. When phytol was used for the alcohol. 2,3-dimethoxy-5-methyl-6-phytylbenzoqui5-METHYLBENZOQUINONE AND RELATED ANALOGS none (IV) was obtained; 272 mp Sir: 291) (Anal. Calcd for C29H4804: C, 75.60; H, Evidence's2 was obtained that coenzyme Q is 10.50. Found: C, 76.31; H, 10.60). characterized as a group of 2,3-dimethoxy-5Nuclear magnetic resonance spectra of benzomethylbenzoquinones, substituted with homolo- quinones I and I1 were consistent with the strucgous isoprenoid chains. A series of such benzo- tures assigned and show a broad resonance r e g i ~ n , ~ quinones containing isoprenoid substituents in as expected, with center a t 3.8 C.P.S. (-CH=), the 6-position was synthesized for comparisons with I the coenzyme Q group. resonance a t -34 C.P.S. (=C-OCH,), a doublet 2,3-Dimethoxy-5-methy1benzoquinone3 vras reI resoduced with sulfur dioxide to 2,3-dimethoxy-5- a t -63 and -70 C.P.S. (=C-C_H2-CH=), methylhydroquinone, m.p. 77-78", (Anal. Calcd, I and ring for C9HI2O4: C, 58.69; H, 6.57. Found: C, nance a t - 113 C.P.S. (=C-CH*CE&CH= I 58.80; H, 6.71). Reaction of this compound with which were not resoIved in the specfarnesol and various condensing agents yielded =C-C&, 40 mc.), and resonance a t -1125 c.p.s. trum a t 2,3 - dimethoxy - 5 -methyl - 6 - farnesylhydroquinone Benzoquinone 111 showed similar which was oxidized to 2,3-dimethoxy-5-methyl-6- (chain =C-). I iarnesylbenzoquinone, I, red liquid; X&~'""c 272 CH3 mfi; (Ei2m, 328); (Anal. Calcd. for C24Ha4O4: bands with the exception that the band a t -113 C, 74.57; H I 8.87. Found: C, 74.68; H, 8.87). I I also was obtained when the isomeric tertiary C.P.S. was due entirely to ring =C-C&. The alcohol, nerolidol, was substituted for farnesol. phytyl analog, IV, showed the above bands and an additional doublet a t - 154 and - 159 C.P.S. due to I, n = 3 paraffinic protons. The nuclear magnetic resoCH, II>n = 2 nance spectra for the coenzyme Q group are fully cCH30 i ' 0 4 (CH2CH=CCH&,H 111, n = 1 compatible with those of the synthetic compounds. The infrared spectra in carbon disulfide of com0 pounds I-IV showed bands a t 6.03, 6.18 and 7.9 p characteristic of 2,3-dimethoxybenzoquinonefunc0 tionality. CH30P\C& CH3 YH3 Dr. Frederick L. Crane of the Institute for CH&./CH&H= I I' CHZ(CHZCH&H-CH2)3H Enzyme Research of the University of Wisconsin I1 and Dr. David Hendlin of our laboratories have 0 IV found compounds I, 11, and I V above active in 2,3-Dimethoxy-5-methyl- 6 - geranylbenzoquinone replacing coenzyme Qlo in the isooctane-extracted (II)Ak~~'aaa 272 mp (E:&, 440) ; (Anal. Calcd. for E T P succinoxidase system.s Details on the C~H2804: C, 71.67, H I 8.23. Found: C, 72.08; enzymatic activities of these compounds will be H, 8.00), and 2,3-dimethoxy-5-methyl-6-(3'- published shortly. methyl-2'-butenyl)-benzoquinone( I I I ) X 2 F e270 (4) The hands refer to 40 mc. spectra in carbon tetrachloride, + mp 539); (Ami. Calcd. for CI4Hl8O4:C, 67.18; means at lower fields than water protons while - means a t higher H, 7.26. Found: C, 67.64, H I 7.01) were obtained, fields. ( 5 ) F. L. Crane, Y . Hatefi, R. L. Lester and C. Widmcr. Biockim. respectively, when geraniol and 3-methyl-2-buten1-01were substituted for farnesol in the condensa- Biophrs. Acta, 25, 220 (1957).
AND 6-PHYTYL-DERIVATIVES OF 2,J-DIMETHOXY-
?&
A-
(1) R. L. Lester, F.L. Crane and Y. Hatefi, THISJOURNAL, 80,7451 (1058). (2) D. E. Wolf, C. H. Hoffman, N. R. Trenner, B. H. Arison, C. H. Shunk, B. 0. Linn, J. F. McPherson and K. Folkers, ibid., 80, 7452 (1958). (3) W. K. A n l o w . J. AT. Ashley and H. Raistrick, J . Chem. Sac., 439 (1938).
CONTRIBUTION FROM THE CLIFFORD H. SHLXK MERCK,SHARPAND Damn? BRUCE0. LINN RESEARCH LABORATORIES EMILYL. WONG DIVISIONOF MERCRAND Co,, INC. PAULE. WITTREICH NEWJERSEY FRANKLIN &I. ROBINSON RAHIVAY, KARLFOLKERS RECEIVED AUGUST13, 1958
BOOK REVIEWS chemistry of the Rare Radioelements. Polonium-Actinium. BSc., Ph.D., Atomic Energy Research By K. W. BAGNALL, Establishment, Harwell, Eng. Academic Press Inc., Publishers, 111 Fifth Avenue, New York 3, N. Y. 1957. x 177 pp. 22 X 14.5 cm. Price, $5.00.
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these radioelements, especially in weighable amounts. Dr. Bagnall is very well informed, in the chemistry and handling of such elements and has made many important contributions to the chemistry of polonium to which about half the space of the book is devoted. He has written with the object of collecting all the published data . and to give some account of the methods used for the study of their chemistry." U'hile the former aim is somewhat unrealized, the author has, on the whole, accomplished his mission successfully. I'.
Here is a valuable book on a group of six radioelements, Po, At, Fr, Ra and Ac, atomic numbers 84-89. Few chemists, except those in government institutions, have had the opportunity to investigate the properties of all of
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2754
BOOKREVIEWS
VOl. 80
The book is essentially a concise and critical survey with The high price for the regular volumes of this series is excellent bibliography for each element. It is a compact evidently a necessity, in view of the amount of work obvi5ource of well chosen information on each of the radio- ously going into them. On the other hand the price of the elements, with emphasis on techniques of separation and “Systematik,” a special volume outside the regular series, is tracer chemistry. The general reader cannot but be im- puzzling. Hardly more than a pamphlet, this is a detailed pressed with the practical importance of the Periodic outline covering the headings systematically used in the Table in the development of separation and purification Handbuch, and it is presented in both English and Gerinaii, techniques and its aid in understanding the chemical be- side by side on every page. It offers a numerical cataloguing havior of each radioelement. Dr. Bagnall constantly scheme, mith about 2000 headings, of particular value in cardstresses the importance of the similarities and differences filing and in cross-referencing, for the indexing and filing of which exist between each radioelement and its homologs: the information available in the Handbuch. Although Po and Te; At and I; Fr and Cs; Rn and the inert gases; simply an outline of headings, the price is the same as that of Ra and Ba; Ac and the rare earths, especially La. the regular Gmelin volumes themselves, namely, about 13 A strong point of the book is the considerable emphasis cents per page, with many of the pages, moreover, practically on the techniques of handling curie-level activities of radioblank. elements. His discussion of health hazards, glove-box The price of these books has long ago left the individual techniques, and methods for contamination control is not behind as a purchaser, but one begins to wonder even how included as an afterthought, but is the subject of two many modestly endowed libraries can afford them. Bechapters and is also woven into the text. The reader, there- cause of their great value, however, one hopes that every fore, is kept aware of the prime importance of good hot- research library can have them available. laboratory techniques. This is no business for careless OF CHEMISTRY amateurs, especially when dealing with milligram amounts DEPARTMEST J O H N E. RICCI NEW YORKUNIVERSITY of elements such as Poz10and Ac 227! NEWYORK,N. Y. ARGONNENATIONAL LABORATORY ILLINOIS JACK SCHUBERT LEMONT, Organic Syntheses. Volume 37. JAMES CASON,Editor-inChief. John Wiley and Sons, Inc., 440 Fourth Avenue, 109 pp. 15 X 23.5 cm. Kew York, 16, N. Y . 1957. vii Gmelins Handbuch der Anorganischen Chemie. Achte Price, $4.00. Vollig Neu Bearbeitete Auflage. Calcium. Teil BLieferung 2. Verbindungen Bis Dithionit. SystemThe importance of “Organic Syntheses” preparations to Nummer 28. E. H. ERICHPIETSCH,’Editor. Verlag organic chemists all over the world, whether inexperienced Chemie, G.m.b.H., (17a) Weinheim/Bergstr., Germany. or experienced, students or masters of the art, has been so 392 pp. 17.5 X 25.5 cm. Price, D M 219. well-recognized that this new volume needs no more intro1957. xvi ($52.56). duction than the announcement of its publication and a Gmelins Handbuch der Anorganischen Chemie. Achte listing of the preparations included. The fact that the editor of the current volume is Cason guarantees that its VBllig Neu Bearbeitete A d a g e . Kupfer. Teil BLieferung 1. Verbindungen Bis Kupfertellurate. Sys- users will find the high level of reliability of procedures ant1 tem-Nummer 60. E. H. ERICHPIETSCH,Editor. Verlag degree of usefulness expected on the basis of the preceding Chemie. G.m.b.H.. f 17a) Weinheim/Berestr.. Germanv. volumes. Not so well-recognized, particularly among j-oungi’i1958. xxvii 624’pp.’ 17.5 X 2k.5 Cm. ‘Price, DM chemists, is the tremendous amount of time and effort 011 349.-($83.76). the part of the volume editor, the other members of the Gmelins Handbuch der Anorganischen Chemie. 8th editorial board and collaborators in their laboratories, as Edition. Systematik der Sachverhalte. E . H. ERICH well as by the submitters, which is necessary to ensure this PIETSCH, Editor. Verlag Chemie, G.m.b.H., (17a) degree of excellence and reproducibility of the preparations 116 pp. included. The careful preliminary screening of every prepWeinheim/Bergstr., Germany. 1957. xiv aration submitted, and the repeated checking in the labora17.5 X 25.5 cm. Price, D M 72.-($17.28). tory of one of the associate editors of each considered poThe calcium volume numbered B-2 is actually the &st tentially suitable-an experimental process that takes more section on the physical and chemical properties of the com- than a week in the best cases and has extended over several pounds of calcium, the “B-1” part having covered the tech- years in more than a few-has been the key factor which iiology of both the element and its compounds, material has ensured the high quality and reproducibility, in the usually given in the “A” volumes of the Gmelin series. The opinion of the reviewer. iiew volume covers the compounds of calcium with the first I n the present volume each preparation was chosen for eight (helium-iodine) of the elements according to the some useful reason. In some cases this is because the product Gmelin system numbers, and some of its compounds with is of more than limited use or the procedure represents :L sulfur, no. 9. The volume on copper (B-1) corresponds to good example of a generally useful reaction; included are: “B-2” for calcium, taking up not the technology but the 2-chloro-2-methylcyclohexanone and 2-methyl-2-cyclohexcusual physical properties and chemical relations of the com- none, 2-chloronicotinonitrile, diaminouracil hydrochloride, pounds; it covers the copper compound with the elements l-diethylamino-3-butanone, diethyl benzoylmalouate (use through tellurium (system number 11). of mixed benzoic-carbonic anhydride), trans-2-dodecenuic The presentation is all that we have come to expect in acid, ethyl t-butyl malonate, i-ethyl-2-methyl-2-octelloic these magnificent digests, distinguished by regularity of acid, ethyl a-nitrobutyrate, glutaric acid and glutariinitlc, order, clarity of headings, completeness of information with n-heptamide, 3-n-heptyl-j-cyanocytosine, 4-hydroxy-1-bunumerous diagrams and numerical tables, critical evaluation tanesulfonic acid sultone, isophorone oxide, 3-methyloxinand comments, and full and valuable documentation. dole, nicotinamide-1-oxide, norbornylene, pseudopelletieThe extreme condensation of the presentation necessitates rine, stearolic acid and ar-tetrahydro-a-naphthol (lithiumso many word abbreviations that some of the sentences ammonia reduction). Two preparations, benzoylacetanilide appear cryptic. At the same time the Handbuch con- and oleoyl chloride, illustrate the utility of a convenient tinues to present literature references in its familiar clear and laboratory-size continuous reactor. The remaining proeeconvenient fashion, repeating them fully in every new dures, which might well be included in the first category by paragraph or section when necessary. Although some space another reviewer, and apparently were chosen for miscellaneous reasons, including novelty, comprise the following: might be saved by the invention of still another “number system” for this purpose, the clarity and the immediate benzofurazan oxide, 3-benzoylpyridine, 3,4-dinitro-3-hesene, availability of the references justify the space used. 1,4-diphenyl-5-amino-l,2,3-triazoleand its rearrangement Both volumes presumably cover the literature through to 4-phenyl-5-anilino-l,2,3-triazole,ethyl benzoylacetate 1949 completely, and the copper volume, it is stated, also (use of aqueous sodium hydroxide for the acylation), p:mbanic acid and trichloromethylphosphonyl dichloride. includes the literature through 1954 “in special cases.” hTow that “Organic Syntheses” is nearing the end of i t > Actually, a considerable number of references through 1953 also appear in the calcium volume. In neither case, how- fourth decade, and in light of the advances of niodcrti ever, would the reader be safe in assuming a coverage later organic chemistry, the questions :ire heard: Is the IJreswt character of “Org:niic Sgnthcsrs” tht: I m t f o r l i l t . E i i t 1 i t . r ’ thaii 1940 for any particular item. Ltn
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