2944
COMMUNICATIONS TO THE EDITOR
Vol. 86
34,000), 272 (5470), and 298 mp (3690); Amin 252 4280) and 286 mp (3250)*; vz,”: 3350, 819, and 802 cm.-’; [ a ] D +225.9 Demethylation of Ib with pyridine hydrochloride gave 3-hydroxy-1,ll-iminoestra1,3,5(10),9(11)-tetraen-17-one(Ia, 81% yield), m.p. 290-300’ dec. ; A,, 229 ( e 32,000), 270 (5050), and 301 ml.c (3530); vf;: 3380, 1725, and 828 cm.-’; [ a ] ~ 4-331 ’ (pyridine). Further work is in progress on the synthesis of steroids containing an indole nucleus. (E
(E
( 8 ) T h e ultraviolet absor1)tion spectrum of I b compared very favorably with t h a t of 2,3-dimethyl-6-methoxyindole:N A’euss. H . E . Boaz, and J . W. Forbes, J. A m . Chem. Soc., 1 6 , 2463 (1954). (9) Additional support for t h e structure Ih as well as for IIIb and IV was obtained by mass spectrometric analysis, which will be discussed in the full length paper on this synthesis.
ORGANIC CHEMICAL RESEARCH SECTION E. W. CANTRALL LEDERLE LABORATORIES R. B. CONROW A DIVISIONOF AMERICAN CYANAMID Co. SEYMOUR BERNSTEIN PEARLRIVER,NEWYORK RECEIVED MAY19, 1964
f(Y)
Fig. 1.-Correlations
of u ( Y ) with
UI
and u for YCsH4S02.
0.4
Electronic Effects of the Sulfonyl Group in Aromatic Systems. Relationships between Inductive and d-Orbital Resonance Contributions’
Sir: Recent reports2 have discussed possible relationships between resonance and induction parameters of substituted benzenes. Although Tafta proposed U R and U I as independent parameters which in general are not directly interrelated, McDaniel’s correlations4suggested that in benzoic acids a linear meta-para relationship may exist for families of substituents bonded to the ring through a common atom, e.g., SCH3, SH, SC(O)CH3, S ( 0 )CH3, S02NH2, and S02CH3. The corresponding phenols, however, deviated substantially from linearity. Subsequently, TaftZademonstrated that better linearity is realized if comparison is restricted to series of more closely related substituents, e.g., m- and pF C ~ H ~ S O Z(X X is F, C1, CH3, CzHs, “2, 0-).Significantly, S(O)CH3 and SF5 did not qualify for the S 0 2 Xline. We now report that for acetic acids, benzoic acids, and phenols substituted with S02CsH4Y1b~5~6 the parameters of SO2X and relative influence of Y can be correlated for each series; other factors influencing the S-X bond remain virtually constant (cf.above). From the data (Table I)7 several significant relationships become apparent. (1) (a) Supported by grants from the Petroleum Research Fund and Army Research O 5 c e (Durham); (b) preceding paper: C. Y. Meyers, Gnez. chim. i l d , 98, 1206 (1963). (2) (a) R . W. T a f t , E. Price, I. R . Fox, I. C. Lewis. K . K . Andersen. and G. T. Davis. J . A m . Chem. Sac., 86, 3146 (1963); (b) L. A. Cohen and W. M. Jones, ibid., 86, 3397, 3402 (1963); (c) D. R . Eaton and W. A. Sheppard, ibid., 86, 1310 (1963); (d) 0 . Exner, Telvahedvan Lellevs. 815 (1963). (3) R. W. T a f t , J . Phys. Chem., 64, 1808 ( 1 9 6 0 ) . (4) L). H . Mcllaniel, J . O r g . Chem., ‘26, 4692 (1961). (.5) C. Y . Meyers, G. hloretti, and I*, Maioli, ibid., 41, 626 (1962), B. Cremonini. Doctoral Dissertation, University of Bologna, 1962. ( 6 ) C . Y. Meyers. G. 1,ombardini. and I*. Bonoli. J. A m . Chem. SOL., 84, 4603 (1902). ( 7 ) I-effects from m e l a and para positions were considered equivalent; by definition, R-effects reflect all influences of =-interaction between the substituent and the system into which it is introduced: 6. ref. 2b, 2d. 3, K . W. Tart and I . C. I,ewis, Telvahedvon, 6 , 210 (19591, and M. J . S. Dewar and P J Grisdale, J A m Chem Sac., 84, 3529 (19621, el seq
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