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Vol. 81
to conjugated enones,6but hetisine, which has been comparison of the infrared spectrum of VI (5.82 p oxidized to mono- and dicarbonyl compounds, gives with shoulder a t 5.81 p ) with that of 2,2-dimethylno such enone. Further, the infrared spectrum of quinuclidone-6 (5.77 p)ll is the basis of the assignJacobs' desmethylhetisine,2 111, shows no >C=O ment of an K-C, bond (bicyclo-2,2,2 system) absorption but does have peaks a t 8.75 and 8.99 p rather than a N-C3 or N-Clo bond (bicyclo-2,2,1 consistent with a hemiketal f o r m ~ l a t i o n . ~Similar system) to hetisine.12 Base hydrolysis of IV peaks 8.72 and 8.98 p , no C=C absorption, are produces a keto-carboxylate, 5.85 p (C=Oj, found in the spectrum of an aqueous sulfuric acid- 6.33 and 7.27 p ( C 0 2 - ) . catalyzed isomerization product of hetisine, m.p. Jacobs' oxidation product of dihydrodesmethyl278-279.5'. (Anal. Found: C, 72.94; H, 8.04.) hetisine must be a carbinol-amine ether3 because Cr03-pyridine oxidation of hetisine produces the borohydride reduction reconverts it to dihydroketo-"lactam," IV, CzoH23N03, m.p. 236-238' desmethylhetisine (infrared evidence) and because (Anal. Found: C, 74.01; H, 7.02). The low its spectrum shows reduced hydroxyl absorption, pKa' of I V (6.72) compared to that of hetisine no carbonyl absorption, but has peaks a t 8.67, (9.85) (both in 1:1 methanol-water) is explicable 8 . i 5 , 8.90 and 9.07 p (0-C-0 and 0-C--N). in IV on the basis of inductive effect,8 but is too If the nitrogen is bonded to CS or Clo, the third great to be so explained by a carbonyl further re- hydroxyl must be cis to nitrogen and on C3 or Cd. moved from nitrogen than the a - p o s i t i ~ n . A ~ ~ ~The ~ stability of the hydrolysis product of IV leads us to tentatively assign the hydroxyl to C3.I3 (6) S. W. Pelletier and W. A. Jacobs, THIS J O U R N A L , 76, 449t3 (1954).
(7) Models indicate t h a t t h e ketone derived from the secondary alcohol in I would not be suitably disposed for internal herniketal formation. (8) 2,2-Dimethylquinuclidone-6has a pKa' 5.33 (nater)l'; quinuclidine has a pKa' 10.65 (water). (9) T h e low pKa's reported for some alkaloids having carbonyl groups y or 6 t o t h e nitrogen atom undoubtedly are caused by trans/'-\ C.'O T h e strreocherniatry of annular effects the type O=CT
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&/
lietisine prohibits such an interaction.
THEROCKEFELLER ISSTITVTEi4 A. J . SOLO SEW YORK21, SEK PORK S. W , PELLETIER RECEIVED JUNE 17, 1959 (10) S .J. L e o n a r d R. C . F o x and hl. Oki, i b i d . , 76, 5708 (195%). (11) H Pracejus, L i t e m B e l . , !488 (1939). (12) As no evidence has appeared t o t h e contrary, hypoynavine also may have a S-Cs rather than a n N-Cio bond. (13) I f the hydroxyl is a t Cd, then I V would give a 0-ketocarboxylate o n hydrolysis. (14) This investigation was supported in part by grant RG5807 from the National Institutes of Health, United States Public Health Service.
BOOK REVIEWS Gmelins Handbuch der Anorganischen Chemie. Alchtc volume on platinum published in 1 9 5 i reviews through l!J*7:3, Vollig Keu Bearbeitete Auflage Zirkonium. System-Num- and it seems unfortunate t h a t the coverage for zirconium a n t i mer 42. E. H . ERICHPIETSCH,Editor. Verlag Chemic- hafnium, particularly the latter as a supplementary volume, G . m . b . H . , (17a) IVeinheimlBergstr., Pappelallee 3, Ger- was not extended beyond 1949. many. 1938. xxxvii 448 pp. 17 X 25 cni. Price, Despite this limitation these books will be valuable adtlitions t o the shelves of every major chemistry library. Oiic Kart. D M 261.--; Geb. D M 266.--. only wishes t h a t a lower price could be established for individGmelins Handbuch der Anorganischen Chemie. Xchte ual purchasers, as is done by Chemical ilbstincls, so that Vollig Keu Bearbeitete Auflage. Hafnium. Erganzungsband. System-n'ummer 43. E. H. ERICH PIETSCH, the specialist could afford pertinent volumes for his private library. Editor, Verlag Chemie, C . m . b . H . , (17a) \Veinheim/'BergDEPARTMESTOF CHEMISTRY str., Pappelallee 3, Germany. 1958. ii 23 pp. 1 i X 25 THE UNIVERSITY O F COSSECTICLT C A R L \v. > I \ l I I l . I . U K c m Price, K a r t . DkI 17.--; Geb. Dhf 2 2 . - - . STORRS, COhTECTICUr The high standards of the earlier volumes of tlie eighth cdition of Ginelin have been continued in the digest uf zirconium publications. Both the breadth of the coverage and Equilibrium. By EDLAKI)lI:\t,A, J i k I l'ic,li, the absence of errors in the details were noted with approval; Vapor-Liquid and O ~ A K AYRI L M TrLtns1,ttctl 1)) C;. V O J T ~ C IFRIED I the extensive use of diagrams and graphs is commendable. STANDART. Pergainon Press, Iuc., 122 E'tst 3.itli SLl-rrt, The discovery, geochemistry, and mineralogy of zirconium Yew X-ork 22, K. I '. 1958. sviii 402 p p . l l i X are covered in the first 50 pages. T h e treatment of ores cm. Price, $14.00. and t h e applications of the metal and its compounds require This book is intended pritnarily for the c1ieinic:il ciiginccr 34 pages. Then a very complete discussion of the preparation of the element in various forms and of the physical prop- or technologist who is concerned with vapor-liquid cotill)[Isition d a t a in the design and operation o f fractional distilluerties is contained in the next 70 pages. The rest of the book describes the preparations and t h e properties of allo>-> tiori equipment. and compounds of zirconium. For convenience the book is divided iiito tlirre parts. '1'11~ first deals with the basic thermodynamic equations exprviiThe short supplementary volume uti hafiiiutn devotes a proportionate amount of space t o each of the above topics t o iiig the relation hetween the vapor-liquid composition :tnd the temperature and pressure. A n excellent review is giveii review articles published mostly between 1940 and 1949. of the various methods that have been proposed for calcuT h e Table of Contents shows in parallel columns the page numbers of the items in t h e supplement and in the main lating these data. The practical value to the technologist volume on hafnium, system number 43, published in 1941. is greatly enhanced b y the inclusion of illustrative examples Although there are a few references t o articles published showing how to apply the theoretical equations. after 1949 and some books published as late as 1957 are I n the second part the direct determination of vaporlisted, the complete coverage as stated in the publication liquid equilibrium data including the measurement of tempages extends only through 1949 for both books. As experature and pressure and the correlation of the rcsults, is amples of what can be done, the volume on selenium p u b described in considerable detail. I I u c h helpful informatinu lished i n 19% reviews the literature through 1932 and the is given about the design aiid uperxtioii, and thc \r.e& points
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