5322
NOTES
Vol. 72
200-pg. amounts of stable terbium, gadolinium and
This band is lacking from the spectra of the corresponding 22,23-d&ydro derivatives and from the spectra of analogous compounds containing the cholestanyl side chain. An example is provided by the spectra of ergostane and AZ2-ergosteneshown in Fig. 1. A band a t the position designated A in Fig. 1 is observed also in the spectra of ergosterol, ergosteryl acetate, lumisteryl acetate and calciferol, all of which contain a A22-ergostenyl side chain, but it is lacking from the spectra of A’*--ergostene, ergostanol-3p, ergostanyl acetate, cholestane, k5cholestene, cholesterol, cholestenyl acetate, 7dehydrocholesterol, 7-dehydrocholestenyl acetate and vitamin Da which do not contain this group The 974-970 cm.-’ band must be distinguished carefully from a weaker band, designated B in Fig. 1, which is observed at 962-958 ern.-' in most of the above compounds. None of the Az2ergostenyl derivatives possess any bands of significant intensity between 700 and 680 cm.-’. It is therefore to be inferred that the 974-970 ern.-' band is associated with the presence of the DEPARTMENT OF CHEMISTRY AND RADIATION LABORATORY AZ2-doublebond in the molecule which must UNIVRRSKTY OF CALIFORNIA possess the trans configuration. BERKELEY, CALIF. K E C E l V E D JUNE 19. 19M The olefins listed in the A.P.I. “Catalog of Infrared Spectrograms” on which these correlaThe Stereochemical Configuration of the A*?- tions are principally based2 are of a much simpler structure than the steroids considered here. It Ergostenyl Side Chain may therefore be relevant to note that in elaidic BY R. S O R M A N JONBS acid (III), :L band occurs a t 968 cm.-’ which has Althouch the chemical structures of ergosterol been attributed to the trans-disubstituted olefin , ~ spectrum of a liquid film of oleic and its photo-irradiation products have been g r o ~ p . ~The known for several years, the stereochemical con- acid (XV) does not exhibit any pronounced band figuration of the substituents about the AY2-bond near 9tiS nor in the 700-680 em.-‘ region, but when has not been fully established. From a study of such a film is cooled with liquid nitrogen the the X-ray diffraction pattern of calciferol 4-iodo- whole spectrum sharpens to a remarkable degree 5-nitrobenzoate, Crowfoot and Dunitz have and a strong band appears a t 705 em.-’. assigned a trans Configuration to the Cs? and C ~ S A fuller discussion of the spectra of the comhydrogen atoms, arid it is the purpose of this pounds mentioned in this paper will be published communication to draw attention to certain later; the spectra of calciferol and vitamin Ds features of the infrared absorption spectra of have been published el~ewhere.~ steroids containing the A22-ergostenylside chain C€~i(CHn)7\,c/H H\c, (CHaIr(2% which confirm this structure. 1; Sutherland and co-workers2have observed that the out-of-plane deformation modes of vibration Ir/‘\’(CH&COOH H (CHl)r*COOH of the olefinic hydrogen atoms in the trans-ethyl111 IV ene structure I give rise to a strong absorption Experimental.-The steroid spectra were deband near 965 tin.- I, whereas in the &-ethylene structure 11, a characteristic band occurs at 690 termined in carbon disulfide solution using a cm.- *. The spectra of several steroids containing Perkin-Elmer Model 12C spectrometer. europium were added to make spectrographic identification of the peaks possible. The column used was 20 cm. long and 5 mm. in diameter and a flow rate of 0.3 ml./sq. cm./min. was maintained. The Eu and Gd activities appear as a single broad peak ; however, spectrographic analyses make possible the construction of the dashed curves for Eu, Gd and Tb. It is evident on comparing this elution with Fig. 6c of ref. 1 that the activity labeled Gd by Ketelle and Boyd is very likely a terbium activity and that any gadolinium activities they may have had are under the front of the europium peak. It should be noted that the very small separation of gadolinium from europium and the much greater separation of terbium from gadolinium agrees very well with the expected effect of the half-filled 4E electron configuration as was first pointed out by Boyd This work was performed undet the auspices of the U. S. Atomic Energy Cotiiinissioti.
A
NOTEADDED I N PRoor.++ubsequentto the acceptance of this mss. for publication, a s i d a r observation has been reported by Turnbull, Whiffen and Wifson ( C k m . and Id., 33, 626 (1950)).
the A22-ergostenylside chain have recently been measured in this Laboratory, and in all cases a prominent band is observed a t 974-970 ern.-'. (11 Crowfoot and Duaitz, Nulwc, 162, 608 (1048). (2) Barnard. Bateman, Harding, Koch, Sheppard and Sutherjand, J . Chem. SOC.,915 (1950).
Acknow1edgmants.-The author is indebted for the gift of compounds t o Sir Ian Heilbron and Dr. D. H. R. Barton of Imperial College, London; Dr. M. L. Tainter of Winthrop Chemical Co., Rensselaer, N. Y.; and Professor E. R. (3) Rao and Daubert, THTS JOURNAL, TO, 1102 (1948) (4) Lemon and Cross, Con. 1.Rescorch, STB, 610 (1949). (5) Jones. Ckemisfry in Cartodo, 6, 26 (94) (l9SO).
Nov., 1950
I
"1:
NOTES I
I
I
I
.I\ n
t I
I
I
I
CH CH I 3 I 3 G(H3{CH3 CH-CHfCHfCH-
40
2o
5323
OPE
R G 0s T A N E 3 4 8 mg. per ml. Irnrn,call-CSsol.
2
-
I
I
I
I
I
I
I
I
1
CH
I 3
CH-CH=CH-
CH-CH
& "$ A*'-ERCOSTENE 25.6 mp. per ml. Imm. c e l l - CSrol. _,os \-,-
I
1300
I
I
1100
9 00
700
Frequency, crn.-l. Fig. 1.
none oxime. This possibility was coniirmed through the application of the Beckmann rearrangement. The higher melting form rearranged easily with benzenesulfonyl chloride in DIVISIONOF CHEMISTRY pyridine? a t room temperature into isobutyraniTHENATIONAL RESEARCH COUNCIL OF CANADA RECEIVED JUNE14, 1950 lide (11),but the lower melting material had to OTTAWA, CANADA be heated on the steam-bath with the same reagents in order to effect rearrangement. It yielded The Geometric Isomers of Isobutyrophenone a compound which was identified through a mixed Oxime melting point as N-isopropylbenzamide (IV) This amide, which has not been previously BY HENRYM. KISSMANAND JOHNWILLIAMS reported, was prepared from isopropylamine and The melting point of isobutyrophenone oxime benzoyl chloride. has been reported as Bo,' 61-62°,27503 and 94°.4 The results of these rearrangement reactions We have now found that isobutyrophenone oxime indicate that the higher melting form is the when prepared in the usual manner from iso- anti-phenyl (I) and the lower melting substance butyrophenone, hydroxylamine hydrochloride and the syn-phenyl isomer (111) of isobutyrophenone sodium acetate in ethanol melts a t 58-60'. oxime. When this material was recrystallized slowly CeH6C-CH (CH,3)2 --+CeH,NHC-CH (CH3)z from pentane, there could be isolated two sets of II I1 NOH 0 crystals. The less soluble variety formed large I I1 prisms which melted at 96', while the more soluble form crystallized in small plates and CJ&C-CH(CH3)2 +CeHsC--NHCH(CHa)2 melted a t 90'. A mixture of these two substances /I /I HON 0 melted between j8-6Oo. Analyses showed these I11 IV two compounds to be isomeric. Both substances could be cleaved with phthalic anhydride6 to A few attempts toward a chromatographic regenerate isobutyrophenone which was identified separation of these isomers were made. A very by its 2,4-dinitrophenylhydrazinederivative.'j low degree of separation could be obtained when a It seemed probable that we were dealing hexane solution of the oxime mixture was passed with the syn- and anti-isomers of isobutyrophe- through a column of alumina. The lower melting form was adsorbed slightly less strongly than (1) Claus, J . p r a k t . Chem., 46, 481 (1892). the other isomer. This method was, however, (2) Magnani and McElvain, THIS JOURNAL, 60, 819 (1938). (3) Franke and Klein, Monafsh., 85, 1139 (1912). useless for actual separation since it did not give (4) Lapworth and Steele, J . Chem. Soc., 99, 1885 (1911). the higher melting isomer in pure form. ( 5 ) Tiemann, Bcr., 38, 3721 (1900).
H. Jones of Manchester University. His interest in this problem was stimulated by discussion with Dr. Barton.
.
(6) Evans, J . Chem. Soc., 788 (1936).
(7) Werner and Piguet, Ber., 87, 4295 (1904).
