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VARIOUS structures(I,1 II,* III,5 I+> have been proposed for humulene. While the nature of the carbon-skeleton is well established,5the position of the ethylene linkages is not known with any certainty,Recently, we have demonstrated6that the closely related sesquiterpene ketone, zerumbone, ha8 the structure (V), We have now examined the proton magnetic resonance , zerumboneand their hy~oderivatives, and the (PMRf spectra of humulene data permit us to assign unequivocallythe structure (IV) to humulene. The PMR speatrum*of zerumbonehad peaks (all well-resolved) at 147.7
F. Sorm, b,Streibl, 3. Pliva snd P. Herout, Coil, Czech. C&em, Coz=, ii, 639 (1951). G. R. Clemo and J. 0. Harris, Ohem & Ind 799 (195l)g R, W, Fawcett and J. 0. Harris, Ibid, 18 (lgm. Sac, 2675 (1954). Sukh Rev, Curr. Soi, 22, 296 (1951). P. Clarke and 0. R. Ramage, J. Chem. Soo, 4354 (1954). F, Sorm et al,, Coil, Gzeoh, Chem. Comm. 22, 570 (1954). Sukh Rev, Chem. & Ind, 1051 (1956). The spectra were determinedat 40 mc on 2% solutions in carbon tetrachloride, with a Varian Model V-43003 high resolution spectrophotometer.The chemical shifts were measured relative to water. The assignmentsfor zerumboneare confirmedby the PMR spectra of tetrahydroserumbone, hexahydrozerumbone, and humulane.
12
Structure of humulene
13
protons),
(two E-dimethyl
proton), and -37.9 countsfsec (two olefinic hydrogen6 @ to the carbonyl and one olefinia proton a to the aarbonyl). It should be noted here that methyl groups end the methylene the 'saturated' methyl groups, 'olefinia'
\ g \
Ip
\ \ \ a
P
groups are well-separatedin a characteristic manner, The PM? spectrum of humuleneu is almost identicalwith that of zerumbone in the methyl and methylene proton region [peaks at 152, 137.8, 128.8, and 113.2 (with a small peak at 122.2) counts/seawith the areas approximatelyin the ratios 2:1:1:2] and this would indicate that humulene also hae four methyl ETOUW, which is in accord with structure (IV) only. Besides these bands, humulene showed the remaining 'extra'methylene group at position 9, ae expected, at a still lower field strength (peaks at 90.8 and 98.6 aounts/eeawith
* These protons are well-eeparatedfrom the =C-CH peaka by virtue of all the methylene group8 being allylic to thejethyleniolinkages,
s;zbet5, fter precise fractionationhad; b.p, ll4-1150 5 mm, II -0.31, nitrosoahloride m.p. 175-176'~ trioxidem.p, 122O:
14
the areas inteneity oomplex approximately of a single
the olefinio
protons located
showed up aa a
group of bandz,
at -1.0,
-16.8,and
-24.6oounte/seo.
Aooording group, and this to previous contention involving workers , humulene oontains is based ozonolysls.l products, on the infra-red Since, ozonolysie of CR2 (IV). one exo-oyolio data,7 of =CR2
determinations
abnormal
estimations
Ae for
the infra-red
of humulene quantita-
the relevant
1665 ( 6 20.8),
clear from this
885 ( 6 32),
end 820 cm
-1 the peak at 885 cm , on which the presence workers, of ie very weak,* -=(X2 group. and hence
=CR2 group had been baaed by these not a forcing presented as (IV), argument for
the presence
Thus,
the evidence
in this This
paper allows
formulation
of humulene
structure
Is directly
to that
system,
trying
and J. Pliva,
Call.
Czech.
Chem,
C=CH2 ie ( for v The intensities of the other bands~~09~(~~ tranob% -115. -IiT = $X-) and 820 am-l (two -HF-C-) are ae antioipated. (R. IV. Jones and C. Sandorfy in A. Weiaebergere Technique of 0r~ani0 Chemistry Vol. IX, pp. 367-384. Intersoienoe, Wew York (1956).
Structure of humulene
15
A fuller aaount of this work xl11 be reported shortly in Tetrahedron. A&norledgement - This work was aarriea out at the IVoyes Chemical Laboratory,University of Illinois,Urbana, and the author wishes to plaoe on record his ainaere gratitude to Professor E. J. Corey for these facilities.