Bridged polycyclic compounds. L. Synthesis, rearrangements, and reactions of some dibenzobicyclo[3.2.2]nonatrienes and dibenzotricyclo[3.3.1.02,8]nonadienes

Photochemistry of alkenes. Direct irradiation in hydroxylic media

“…i 37 °Irradiations were conducted as described in the Experimental Section using 110-ml solutions containing 21 mmol of olefin and, where applicable, 3.0 ml of p-xylene as sensitizer. 6 Sensitized, Vycor filter sleeve employed; H+, solution contained 0.25% sulfuric acid. c Determined by gas chromatographic analysis of aliquots removed from the irradiation mixture.…”

“…This reaction, 0 Irradiations were conducted in sealed quartz tubes as described in the Experimental Section using solutions containing 105 mg of olefin and 1.05 g of solvent. 6 Determined by gas chromatographic analysis. ' Vycor filter sleeve employed.…”

“…Similarly, the acyclic analog 20 gave a mixture of the ethers 26 and 27 (R = CH3) and the hydrocarbons 24 and 25 on direct irradiation in methanol (see Table III and Scheme 0 Unless otherwise indicated, irradiations were conducted as described in the Experimental Section using 200-ml solutions containing 3.40 g of olefin. 6 Determined by gas chromatographic analysis of aliquots removed from the reaction mixture and calculated relative to a saturated hydrocarbon internal standard. c 30% aqueous solution.…”

“…Another major deviation from the photoprotonation process was the finding that irradiation of 20 in methanol-O-d resulted in extensive incorporation of deuterium in the hydrocarbon products 24 and 25 but only minor incorporation in the ethers 26 and 27 (R = CH3), as outlined in Table IV 0 " Determined by mass spectroscopic analysis based on the molecular ion peak. 6 Based on the M -31 peak.…”

“…Additional components of the above mixture appeared to be epoxides and diols. 1156, 1107, 1068, and 899 cm-1; nmr 5.20 (s, 2, CH2=), 6.83 (q, 2,J= 6.5 Hz, CH3Ctf20), 8.28 (s, 3, CH3-2), 8.73 (s, 6, 2 CH3), and 8.90 (t, 3, / = 6.5 Hz, Cif3CH2); m/e 128.1199 (caled for CsH.sO, 128.1201), 113, 87, 85, 83, 69, 67, 59, 57, and 55. Ethyl 1,1,2-trimethylpropyl ether (27, R = C2H5) was obtained as a colorless liquid: t-max 1390, 1374, 1364, 1173, 1153, 1118, 1098, and 1069 cm"1; nmr 6.68 (q, 2, J = 6.5 Hz, CH3CFf20), 8.25 (h, 1, / = 6.5 Hz, CH-2), 8.95 (t, 3, / = 6.5 Hz, Ctf3CH20), 8.83 (s,6,2 CH3),and 9.13 (d,6, J = 6.5 Hz, 2 CH3); m/e 115, 87, 85, 69, and 59.…”