1426
COMMUNICATIONS TO THE EDITOR
Vol. 72
Am(V) absorption which was accompanied by a forded two angularly methylated stereoisomers,6 rapid growth of the 991 peak (Am(V1)) and Am- PI, m. p. 146.6-147.2' (Anal. Calcd. for C27H30(111) absorption. Insufficient evidence has been 0 2 : C, 83.90; HI 7.82. Found: C, 83.88; H, accumulated to establish whether this dispropor- 7.83) and P2, m. p. 147.0-147.8' (Anal. Found: tionation gives Am(1V) in observable amounts. C, 84.01; H, 7.85). Oxidation of the p2 benzal The authors would like to express appreciation derivative? with ozone afforded dl-homomaxiranolic to E. Staritzky for the crystallographic identifica- acid methyl ether, m. p. 225.2-227.5' ( r e p ~ r t e d , ~ 225-227'), which on heating with lead carbonate tion and to F. H. Ellinger for the X-ray analysis. L. B. ASPREY yielded dZ-estrone methyl ether, m. p. 143.2A comparison of Los ALAMOSSCIENTIFIC LABORATORYS. E. STEPHANOU 144.0' (reported,* 143-144'). Los ALAMOS, N. M. R. A. PENNEMAN the crystals with natural estrone methyl ethers RECEIVEDFEBRUARY 6, 1950 indicated that they possess identical form and optical properties. Infrared spectrographic analysisg gave identicar curves for the two materials. DeTHE TOTAL SYNTHESIS OF ESTRONE AND methylation with pyridine hydrochloride afforded THE REMAINING STEREOISOMERS dl-estrone, m. p. 252.8-254.8' ( r e p ~ r t e d 251,~ Sir: 254'), which showed 50% of the activity of U.S.P. As early as 1935l extensive research programs estrone in ovariectomized rats. lo Resolution via directed toward the total synthesis of the female the I-menthoxyacetate gave d-estrone l-menthoxysex hormone estrone were well under way. These acetate, m. p. 132-135', undepressed on admixture studies have since been continued with increasing with the ester (m. p. 133.5-135') prepared from interest in laboratories all over the world. In natural estrone. 1942 Bachmann, Kushner and Stevenson2 sucThe 4' benzal derivative yielded a new stereoceeded in synthesizing a stereoisomer of the hor- isomer, estrone g (presumably & lumiestrone), mone, ''estrone a." Using essentially the same m. p. 238.5-240' (AnaZ. Calcd. for C18H2202: C, synthetic scheme as Bachmann, et al., Anner and 79.96; H, 8.20. Found: C, 79.80; H, 8.22); Miescher3recently were able to isolate additional methyl ether, m. p. 109-110' (Anal. Calcd. for stereoisomers including dl-estrone. Six of the eight CleHZ4O2:C, 80.24; H, 8.51. Found: C, 80.25; possible racemic forms, estrone, a-f, have now H, 8.44). Similar studies in the a-series yielded been reported.4 what is apparently estrone d, m. p. 180.6-181.4' In the present communication we are reporting ( r e p ~ r t e d 184-186'), ,~ methyl ether, m. p. 115a completely new synthesis which has yielded, in 116.2' ( r e p ~ r t e doil), , ~ derived from the homomaraddition to the natural product (estrone b), the rianolic acid methyl ether, rn. p. 169.8-170.5° two remaining stereoisomersg and h. The potas- ( r e p ~ r t e d 170-171'); ,~ and the new estrone h, sium salt of m-methoxyphenylacetylene (prepared m. p. 197.0-198.1' (Anal. Calcd. for ClsHzzOz:C, from m-hydroxyacetophenone) was added to 13- 79.96; H, 8.20. Found: C, 80.14; H, 8.19), methyl decalindionesin a 1:1 molecular ratio. The acet- ether, m. p. 67-68.3' (Anal. Calcd. for C19H2402: ylenic bond of the resulting carbinol was hydro- C, 80.24; H, 8.51. Found: C, 80.19; H, 8.19). genated over palladium catalyst and the product (7) Cf.Johnson ibid.. 66, 215 (1944). dehydrated with formic acid. The unsaturated (8) The crystallographic examinations were kindly performed by ketone, produced in 70% over-all yield from the Dr. R. L. Clarke of the Sterling-Winthrop Research Institute. (9) Kindly carried out by Dr. R N. Jones of the National Research diketone, was cyclized with hydrogen chloride Council, Canada. and aluminum chloride in benzene, giving an oily (10) Tests kindly performed by Drs. R. K. Meyer and E. G.Shipmixture from which were crystallized in about ley of the Zoology Department, University of Wisconsin. equal amounts two stereoisomeric 1-keto-8-meth- LABORATORY WILLIAMS. JOHNSON OF ORGANIC oxy - lI2,3,4,4a,4b,5,6,lob,11,12,12a-dodecahydroD. K. BANERJEE CHEMISTRY P. SCHNEIDER WILLIAM OF WISCONSIN chrysenes: a-form, m. p. 168.4-170' (Anal. UNIVERSITY C. DAVIDGUTSCHE Calcd. for C18H2402:C, 80.24; H, 8.51. Found: MADISON,WISCONSIN 17, 1950 RECEIVED FEBRUARY C, 80.60; H, 8.37) and ,&form, m. p. 153.4-154.8' (Anal. Found: C, 80.11; HI 8.13). The p-isomer gave a benzal derivativeJ6m. p. 152-153.1' THE DIELECTRIC CONSTANT OF (Anal. Calcd. for CzaHsO2: C, 83.83; H, 7.58. TRIFLUOROACETIC ACID Found: C, 83.49; H, 7.66), which on treatment Sir : with potassium t-butoxide and methyl iodide afThe dielectric constant of trifluoroacetic acid (1) See for example, Robinson and Schlittler, J . Ckem. SOC., has been found to increase with increasing temper1288 (1935). ature in the range of - 10 to +30°. This appears (2) Bachmann, Kushner and Stevenson, THIS JOURNAL, 64, 974 to be an unusual property for a liquid, as a search (1942). of the literature has failed to disclose any other (3) Annu and Miescher, Erfinirnlia, 4, 25 (1948); Hclv. Ckim. Acta, $1, 2173 (1948). substances showing this property to this extent. (4) Annu and Miescher, ibid., 83, 1957 (1949). The dielectric cell had cylindrical electrodes of (5) Prepared from 1,5-dihydroxyn~phtheneby a modification nickel and had a calibration of 61.5 microOf the method of Hudron and Robinson, J . Chcm. Soc., 891 (1942), farads. The substitution method was employed (6) Cf. Johnson, T ~ JOWWAL, D 68,1817 (1948).
