5896
BOOKREVIEWS
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factor as 0.05, the figure which applies in acetolysis, leads to a Ke value of cu. 5 x lo-”. The standard niolar free energy of the [3.2.0] ester I exceeds that of the [2.2.1] isomer I11 by ca. 14,000 cal./mole.
first overtone of this band should fall very close to the position anticipated for the simple carbonyl stretching frequency of I. That the splitting of the carbonyl band does indeed appear to depend upon DEPARTMEXT OF CHEMISTRY S. WINSTEIN the presence of a band a t 11.6-11.7 p has been UNIVERSITY OF CALIFORKIA FULVIO GADIENT determined by the examination of the spectra of a Los ANGELES24, CALIFORNIA E. T. STAFFORD series of cyclopentenones. Compounds 11, IV and PACLE. KLIKEDINST, JR. V, all without ethylenic hydrogen, show only very RECEIVED SEPTEMBER 25, 1958 weak or no absorption in this region and have single carbonyl-stretching bands, while compounds T H E ANOMALOUS INFRARED SPECTRA OF SOME I, VI and VII, with single ethylenic hydrogen and CYCLOPENTENONES bands a t 11.6-11.7 1.1, have split carbonyl bands. Sir: The case of VI11 is instructive: the compound It has been reported1 recently that the infrared possesses a single ethylenic hydrogen but its bendspectrum of 3,4-diphenyl-2-cyclopenten-l-one (I) ing band falls a t 11.45 p and a single carbonyl band in carbon tetrachloride solution is anomalous in is observed.6 that two bands of comparable intensity occur in the R2 carbonyl-stretching region a t 5.82 and 5.90 1.1; this bifurcation was observed also with solutions in other solvents and with solid state spectra. The spectrum of 2,5-dimethyl-3,4-diphenyl-2-cyclopenten-1-one (11) showed a single band (5.86 1.1, 0 I CCl,), as did that of cis-3,4-diphenylcyclopentanone (111) (5.74 p , CHC13). Since this region is of such extraordinary importance in the application of infrared spectroscopy to structural studies, it Rd = Rs = H V,R1 = CHB, Rz RI was of considerable interest to determine the origin 1-1,R1 = Rz = R3 = Rq = R, = H and generality of this phenomenon. VII, Ri = H , Rz = CHB,R3 = R1 = RF, = H Two possible sources-association or the presence IrIII, Ri = H , R? = CsH5, R3 = H, Ri = R5 = CH3 IX, R1 = D, R? = CeH6, Ra = Ra = Rs = D of a mixture of A2 and A 3 isomers-already have been e1iminated.l Further, the perseverance of the Confirmation for this view was obtained by the double band in the solid state spectra and ultra- preparation of 3,4-diphenyl-2-cyclopenten-l-oneviolet spectral studies made i t most unlikely that 2,4,5,5-d4(IX) by heating I in dioxane with deutethe phenomenon is due to the presence of rotational rium oxide and sodium carbonate; IX was obtained isomers. There remained the possibility of Fermi as colorless needles, m.p. 109.5-110’ (And resonance2 between the carbonyl vibration and a Calcd. for C17Hl0D40: atom yo excess D, 28.57. close-lying overtone. There is in fact a band a t Found: D, 28.69). The spectrum of IX had no 11.63 p3 in the spectrum of I which may be tenta- band a t 11.63 1.1 and showed a single carbonyl band tively assigned to the out of plane bending vibra- a t 5.86 p . Also the deuterated product obtained by tion of the single ethylenic C-H bond of I., The similar treatment of VI1 lacked the band in the (1) 1’. Yates, N. Yoda, W. Brown a n d B Mann, T H I S JOURNAL, 80, 11.6-11.7 1.1 region and had a single band a t 5.86 p 202 (19.58). in place of the two bands of VI1 a t 5.81 and 5.S9 Y.
”j’\f‘“‘
(2) G. Herzberg. “Infrared and Raman Spectra of I’olyatomic Lfolecules,” D. Vat] Nostrand Co., h-ew York, N. Y., 1945, p. 215; E B. Wilson, Jr., J. C. Decius and P. C. Cross, “Molecular Vibrations,” NcCraw-Hill Book Co., New York, N. Y.,1955, p. 198. (3) This and subsequently quoted band positions are for solutions in carbon tetrachloride. (4) Cf. P. Yates, M. I. Ardao and Is. F. Fieser, THISJOURXAI., 78. 650 (1956); R. N. Jones, It. Herliug arid E,. Katzenellenbogcn, ibid.. 77, ti31 (1955).
DEPARTMENT OF CHEMISTRY PETERYATES L. L. WILLIAMS HARVARD UKIVERSITY CAMBRIDGE, MASSACHUSETTS RECEIVED SEPTEMBER 19, 1958 ~~~
( 5 ) I t may be noted t h a t for all of these compouids the first overtones belong t o t h e same symmetry species as the carbonyl-stretching fundamental a n d thus Fermi resonance is allowed; cf. ref. 2.
BOOK REVIEWS Actualit& Biochimiques. KO. 20. Aspects Actuels de la Biochimie des Acides AminCs e t des Protkines. By 1.T. EDSALL, Professeur a I’UiniversitC Harvard. PubliCes Lous la direction de Marcel Florkin et Jean Roche. Masson et Cie., kditeurs, 120, boulevard Saint-Gerrnain, Paris G‘, France. 1958. 156 pp. 16 X 24 crn. 2.000 fr.
Cnlike the review of a manuscript t h a t of a book is sonicthing like reviewing a TV program-it’s too late t o do anything about it. I n the present instance, however, this rcvicwcr would not have done anything about it even if he had Iiad the opportunity. In this comparatively short
monograph the topics for consideration have bceii carcfully selected, are lucidly presented and bring the reader right up to work in progress in the biophysical chemistry of the amino acids, peptides and proteins. In many respects it may be considered a supplement t o the earlier ACS monograph on this subject by Cohn and Edsall. The volume under review is the result of a series of lcctures by Professor Edsall a t the College of France and a t the Sorbonne in late 1955 and early 1956. Translated into easily read French by Professor Jean Rochc and associates the material has been published as number 20 in the “Actualites Biucliiiuic]ucs” papcrhck scrics. T h e almost siinultaneous
