Sept. 5 , 1955
BOOKREVIEWS
4693
quaternization of methyl reserpate tosylate (V) Janot, Goutarel, Prelog, et a1.9 The internal can be most readily accommodated by neighboring quaternization of V, presumed to occur by simple group participation of a C-17 methoxyl placed I ,I trans to the groups a t C-16 and C-18, proceeding \{N) ‘4 through an intermediate oxonium salt (VI),8 followed on the one hand by loss of a proton to yield VI1 and on the other hand by a second displacement a t c-18through backside attack by h’-4, . affording the quaternary salt VIII. Justification C H : , O O C L. y /\ O CH:jOOC/Y\Ofor this interpretation is offered by our observation OCH:3 OCH, that trans-2-methoxycyclohexylbenzenesulfonate, 1); s on being refluxed in collidine, is converted in significant yield to-among other productsdisplacement with inversion a t C-18,4was taken to cyclohexanone enol methyl ether, identified by indicate a cis relationship of the C-18 substituent hydrolysis to cyclohexanone. and the C-15 and C-20 hydrogens, as expressed in both I X and X. This reaction, however, can be I I \/\ considered to proceed, as shown above, by double‘/) inversion with over-all retention of configuration 1 LOT~ > i ’ --+ a t (2-18, consistent with the cis assignment to CHIOOC’ CH,OOC’ \”, hydrogens a t C-18 and C-20 (structure IV). The \O@ CHjO rotational evidence bearing on the relative con17 VI \CH, figuration a t C-3 and C-16 which led to the modificationg of I X to X is automatically accommodated by the expression IV, which also places the C-16 hydrogen trans to that a t C-3. Acknowledgment.-Financial support for this investigation was provided by the Department of Health, Welfare and Education (Grant No. G3892). The authors wish to express their appreciation to S. B. Penick and Co. for the gift of reserpine, and to H. Boaz of the 1,illy Research The stereochemical expression IV stands in Laboratories for the titration data. contrast to the two previously proposed for reser(9) M. 11.Janot, R . Goutarel, A . LeHir. G . Tsatsas and V . Prelog pine: I X by Schlittler, et u Z . , ~ and supported by H e l c . C h i m Actti, 38, 1073 (19.5:). , ~ more recently X, by DEPARTMEXT m’intersteiner, et ~ l . and O F CHEMISTRY
5
~
V) .
8
. I
L 5
(8) Elimination of V leading t o V I requires in V a diaxial-type conformation a t (2-17 and C-18, which can result from I V through appropriaterotations in t h e ring system.
UNIVERSITY OF Wxscoss~s EUGENE E. VAX TAMELEN MADISON,ISCO CONS IS PAULD. HANCE RECEIVED JULY 25, 1955
BOOK REVIEWS -
Monographien zu Angewandte Chemie und Chemietered on the fractionation of mixed solutes rather than oil Ingenieur-Technik. Nr. 67. Verteilungsverfahren im the mere transfer of a solute from one phase to another. Laboratorium. By ERICH HECKER,Max Planck In- The number of extraction stages is shown to depend on the situt fur Biochemie, Tubingen, and ADOLFBUTENASDT, separation factor, determined by the composition of the Max Planck Institut fur Biochemie und Phpsio1.-Chem. solute and the two solvent phases; the volume factor, deInstitut der Universitat, Tubingen, Verlag Chemie, termined by the relative volumes of the phases; the initial G.m.b.H., Weinheim/Bergstrasse, Germany. 1956. 229 concentration of impurities; and the degree of purity desired pp. 15.5 X 23 cm. Price, $4.75. in the product. Laboratory-scale continuous extraction \\.liile such laboratory methods of laboratory separation also is treated, along with some aspects of partition chromatography. :iiiti purification as fractional distillation and chromatogThe special part is essentially a review of the partition rdphy have been well treated in monographs, there has been behavior of organic compounds classified xcording 1 1 0 whole book devoted to a comprehensive account of the theory and practice of liquid-liquid extraction. The need to structure, and metal ions classified as their neutral or anionic complexes. A kind of appendix gives mathematical is now filled. This newest member of an important German derivations and pertinent numerical tables. series is authoritative, well-documented (525 references), Quantitative relationships between partition behavior and up t o date (through 1953). and constitution of solutes and solvents are mostly lacking, The book begins with the Nernst distribution law and a definition of multiplicative partition. Batchwise applica- hut the lack is also in present knowledge. A more serious tioil of the latter is considered in detail, with descriptions possible flaw is the incompleteness of literature coverage. o f cvtractioll batteries, the computation of theoretical parIn spite of its exteiisive bibliograplly, the book cannot be titioil rtirvt‘\, a r i t l i l l ? sever,tl recycling ; i i i t l witlitlr,iw:tl protrti.;tetl to s u p p l y xll rrfrreiices to individual sttitlie.; of tipc w l i i r ~ ~wtiioli ~, : i n ’ c r i t i c : ~ l lv~s,: i l ~ i : t t e ~ l . A i t r l i t i o l i i-. (Y’IIlur:ti!i\ ir i i i i i ~ ~ r i : i l ~ I i. i. tilt- rt~vic\jy:r’\ illil)rc.+i
