SPIRANES CONTAINING OXYGENHETEROCYCLES
March, 1949 I C O K T R I B U T I O N FROM T H E
DIVISION OF
CHEMISTRY,
LABORATORIES OF T H E Mouwr
829
S I N A I HOSPITAL]
Synthesis and Properties of Spiranes Containing Oxygen Heterocycles BY J. D. CHANLEY This investigationle concerns itself with the preparation and properties of the dl-bis-epoxide of symmetric dicyclohexylethane (IV). This compound contains a new and interesting dispirane system. Numerous investigations of the ultraviolet absorption spectra of compounds containing a cyclopropyl groupld or epoxy group,1c,2 adjacent to an unsaturated grouping, such as an ethylenic linkage, a carbonyl, phenyl, or pyridyl group, have shown that such compounds exhibit a shift of absorption to the longer wave lengths. This phenomenon as well as chemical evidence3 indicates that three-membered rings resemble in many respects the ethylenic linkage. I n these systems, the observed shift in the spectrum is commonly attributed to the participation of the three-membered ring in some of the excited (ionic) states of the molecule.la-d It was of interest to investigate whether an epoxy-group, adjacent to a second one or to an acetylenic linkage, would display similar spectral properties. The dl-bisepoxide of sym-dicyclohexylethane (IV) was prepared and proved to be completely transparent down to X = 214 mp. A possible explanation is that such excited states as
which presumably would favor a shift in the spectrum toward the longer wave lengths, are extremely improbable. In this connection, i t is of interest to know that the maximum of the 3,4epoxide of 1-cyclohexenyl-3-methyl-1-butyne is f-“$
to possess double bond character. It is extremely unlikely that hypothetical excited states as CH3 /
which would produce a shift of absorption to longer wave lengths, occur. The synthesis and proof of structure of the bis-epoxide (IV) are outlined in the Scheme. The assigned cis configuration for 1,l’-vinylenebis-cyclohexanol (11) is based on the general experience that mild catalytic hydrogenation of an acetylenic linkage produces the cis ethylenic der i ~ a t i v e . ~The ci,P-(l,l’-dihydroxycyclohexyl)a,@-dibromoethane (111), obtained by bromination of the ethylenic compound (11))is a racemate since bromine adds trans to ethylenic linkages. The assigned structure for compound I11 was further confirmed by catalytic reduction of the dibromide to the sym-1,l’-ethylene bis-cyclohexanol (XII), identical with the product resulting from the complete catalytic reduction of 1,l’ethynylene-bis-cyclohexanol (I), or of 1,l’-vinylene-bis-cyclohexanol (11). Dehydrohalogenation of the double bromohydrin I11 yielded the dZ-bis-epoxide of sym-dicyclohexylethane (IV). Since it is generally accepted that, both in the opening and in the formation of epoxy rings, an inversion a t one of the carbon atoms ensue^,^^-^ it is therefore postulated that the racemic form only of the bis-epoxide IV may be expected from the racemic double bromohydrin 111, since inversion would occur a t each of the carbon a t o r n ~ , ’ ~ bearing ~ g ~ ~ bromine atoms in 111. Other conceivable structures for the new compound with the correct empirical elementary composition such as 0
o--kc-R
as low as 230 m ~ The . ~ max. values4 for systems of the type
, with K denoting a
saturated group, lie in the range 227-229 mp. The epoxy group in this instance does not appear (1) (a) Carr and Burt, THISJOURNAL, 40, 1590 (1918); (b) Klota, i b i d . , 66, 88 (1944); ( c ) Rogers, ibid., 69, 2544 (1947); (d) Mariella, Peterson and Ferris, ibid., 70, 1494 (1948); (e) the results of this investigation were presented before the Section of Organic Chemistry at the Semi-Annual Meeting of the American Chemical Society, August 30, 1948, in Washington, D. C. (2) Heilbron, Johnson, Jones and Spinks, J . Chcm. Soc.. 727 (1942). (3) Kohler and Conant, T H IJOURNAL, ~ a9, 1404 (1917). (4) Sobotka and Chanley, ibid., 70, 3914 (1948); cf. Milos, et 02.. i b i d . , 70, 1584 (1948).
(A)
(B)
arid VI1
were coiisidered a t the time, but eliminated for the following reasons: (a) Compound IV gave no ketonic derivatives; (b) Compound A has been (5) Bourguel, Bull. SOC. chim., [4] 45, 1067 (1929); Campbell and O’Connor, THISJOURNAL, 61, 2897 (1939). ( 6 ) Hammett, “Physical Organic Chemistry,” McGraw-Hill Book Co., New York, N. Y . , 1940, p. 147. (7) (a) Kuhn and Ebel, Bcr., 58, 919 (1925); (b) B8eseken. Rbc. fro% chim., 47, 683 (1928); (c) Wilson and Lucas, THIS JOURNAL, 18, 2386 (1936); (d) Winstein and Lucas, i6id., 61, 1578, 1681 (1939); (e) Lucas, Schlatter and Jones, ibid., 68, 22 (1941); (0 Lucas and Gould, ibid., 68, 2641 (1941); (g) Winstein and Grunwald, i b i d . , 70, 828 (1948); (h) Swern. i b i d . . 70, 1235 (1948).
J. D. CHANLEY
830
Vol. 71
SCHEME OH OH
OH H H OH
I
t
H
OH
I11 (d)
Br
OH
H
H
4
1
Br
VI
H
X I trans ( d l )
CeHsCOOOH
NaOH
H
I V (dl)
\
VI1 cis (meso)
4
HWH
+
Hz0
