5190
Hashish, a Novel Cannabinoid Containing a Cyclic Peroxide
The presence of only one exchangeable proton in the nmr and the absence of infrared absorption bands in the 3560-cm-I (nonbonded, typical of hydroperoxides) reSir: gion rule out the presence of a hydroperoxide structure. We wish to report the isolation of another compound The position of the C-1 methyl singlet at 1.52 ppm and from the pyridine-catalyzed reaction of citral with olithe C-6 proton at 4.95 ppm is in excellent agreement veto11,2and propose that it is the novel cannabinoid 1 with the dioxetane 2. possessing a four-membered cyclic peroxide ring. The multiplet at 6 2.12 is assigned to one of the C-5 Recently Kopecky and Mumford3 have reported the protons on the basis of collapse of the 3-cps coupling synthesis of 3,3,4-trimethyl-1,2-dioxetane(2). This is during irradiation of C-6 at 6 4.95. The double resothe first example of isolation of a dioxetane, although nance experiments (100 Mcps) suggest that the 14-cps the products from a number of reactions have been exportion of the C-5 multiplet may be due either to gemplained as occurring uia such four-membered cyclic inal coupling at C-5 or to coupling with the C-4 proton. peroxides. Furthermore, the benzylic C-3 proton (6 3.44) appears We have found that further elution of the reaction to be coupled to one of the C-2 protons with a coupling mixturela with 12:88 and 15:85 ether-petroleum ether constant 14 cps. The remaining 6-cps coupling con(bp 30-40") gave a yellowish oil. This was rechrostant may be either with the C-4 or the remaining C-2 matographed on a thick silica gel plate to give a colorless proton. In addition the irradiation experiments indiresin in 5% yield, homogeneous on tlc; nmr (CDC13) cate a small long-range couplings between the benzylic 60.84(3H,t,~-CH3),1.18,1.28(6H,2~),1.52(3H,~), proton and the C-5 proton at 6 2.12, but unfortunately 2.12 (1 H, double doublet, J = 3 and 14 cps), 3.44 our spectra were not sufficiently resolved to allow us to (1 H, m, J = 6 and 14 cps), 4.95 (1 H, d, J = 3 confirm this last indication. We were unable to detercps), 6.34 (1 H, d, J = 3 cps, aromatic H), 6.41 mine the coupling constant for the C-3-C-4 interaction. (1 H, d, J = 3 cps, aromatic H), 6.2 (1 H, broad, However, the position of the benzylic C-3 proton in 1 O H ; DzO exchangeable); ":A: 280 (e 2170) and 222 indicates a cis stereochemistry at the ring fusion, as it is mp sh (e 8670); ir (cm-', CCl,) 3610 (OH), 1130 more in agreement with cis rather than trans compounds (s, ether), 895 (m), and 850 ( w ) . ~ The mass spectrum in cannabinoids. indicates a molecular ion peak mje 346 corresponding When 1 was passed through a vpc column (10% SEto C21H3004 and in addition shows (inter alia) peaks at 31 on 80-100 mesh Chromosorb W ; gas, helium; oven mie 231, 196 (base), 151, 139, and 123, which are extemperature, 220°), a single peak was observed.1° Its plicable on the basis of structure 1,6,6a It gives a positive mass spectrum showed a molecular ion peak at m / e 314 peroxide test.' (different from 1 ; i.e., less 32) and in addition included peaks at 299 (M+ - CH3),271 (M+ - C3H7),258 (M+ FHJ C4Hs), 246, 231 (base), and 193, which are characteristic of tetrahydrocannabinols. Treatment of 1 in the presence of hydrogen-10% palladium on charcoal in methanol for 16 hr afforded a crystalline compound, mp 94-95 O, to which we assign structure 3;'* nmr (CDC1,) 6 0.88 (3 H, t, u-CH~),1.1 1, 1.25 (6 H, 2s,gem-dimethyl), 1.41 (3 H, s), 2.5 (1 H, m), ,. I L 3.55 (3 H, s, OCH3),4.84 (1 H, d , J = 7 cps, hemiacetal), 4.0, 5.94 (2 H, broad, DzO exchangeable), 6.18 (1 H, (1) (a) V. V. I
