114 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table II (continued) Compound •H-NMR IR (CC14, 8) (cm -•) Elem. Anal. %C, %H, %N 14 15a 16a,b 17 18 2O 21a,b 1.22 (s, 6H, (CH3)2C) 2.15 (s, 1H, -OH) 3.75-4.02 (m, 1H, -CHOH-), 5.22-5.46 (m, 2H, -CH=CH2), 5.86-6.30 (m, 1H, -CH2-CH-CH2) 1.22 (s, 6H, (CH3)2C) 2.43 (s, 3H, CH3CO-) 6.24 (d, 1H, J=16Hz, -CH=CH-CO-) 6.93 (dr, 1H, -C(Hc)2CHb=CHa -, Jab = 16Hz, Jbc=8Hz) 1.27 and 1.37 (2s, 6H, (CH•)2C) 2.32 (s, 3H, =CCH3) 2.91 (qt, 1H, J=8Hz, H at C-3, isomer E) 3.50-3.70 (m, 1H, H at C-3, isomer Z) 5.18 (s, 1H, =CH-, isomer Z) 5.33 (s, 1H, =CH-, isomer E) 1.30 (s, 6H, (CH3)2C) 1.41 (d, 3H, J=6Hz, -CHCH 3) 1.12 and 1.28 (2s, 6H, (CH3)2C) 2.03 (s, 3H, =CCH3) 3.20 (s, 2H, -CH2CN) 1.22 (s, 6H, (CH3)2C) 1.99 (s, 1H, -OH) 3.47-3 70 (m, 1H, -CH(OH)-) 5.21-5.43 (m, 2H, H2C=CH) 5.84-6.28 (m, 1H, H2C=CH-) 1.26 and 1.35 (2s, 6H, (CH•)2C) 2.60-3.08 (m, 1H, H at C-3, isomer E) 3.13-3.60 (m, 1H, H at C-3, isomer Z) 5.35 (s, 1H, -CH=CHCN, isomer Z) 5.41 (s, 1H, -CH=CHCN, isomer E) 6.58 (dd, 1H, -CHcCHb=CHa-, Jab= 10Hz, Jbc=9Hz, isomer Z) 6.79 (dd, 1H, CHcCHb=CHa-, Jab= 16Hz, Jbc=9Hz, isomer E). 3355 (vs,vb), 3080 (w), 3005 (m), 2925 (vs), 2865 (s), 1640 (w), 1445 (m), 1365 (w). 3005 (s), 2925 and 2865 (vs), 1690 and 1665 (vs), 1620 (s), 1445 and 1425 (s), 1370 and 1355 (s) 3010 (m), 2940 (s), 1865 (m), 2220 (m), 1635 (s), 1450 and 1375 (m) 3020 (vs), 2950 (vs), 2870 (vs), 2220 (m), 1460 (s), 1375 (s) 3030 (s), 2995 (vs), 2265 (m), 1440 (s), 1420 (s), 1375 (s) 3365 (vs,vb), 3075 (m), 3005 (s), 2980 (w), 2935 (vs), 2860 (s), 1640 (m), 1005 (s), 990 (m), 905 (s) 3020 (m), 2940 (s), 2865 (m), 2215 (s), 1620 (m), 1450 and 1375 (m), 975 (s) 715 (m) C15H260 (222.37) Calcd: 81.02, 11.79 Found: 81.10, 11.71 C15H240 (220.35) Calcd: 81.76, 10.98 Found: 81.51 11.10 C•2H•7N (175.27) Calcd: 82.23, 9.78, 7.99. Found: 82.40, 9.80, 8.10 C•2H•9N (177.29) Calcd: 81.30, 10.80, 7.90 Found: 81.52, 10.83, 7.95 C12H2o ¸ (180.29) Calcd: 79.94, 11.18 Found: 79.52, 11.28 CnH•5N (161.25) Calcd: 81.94, 9.38, 8.69. Found: 82.03, 9.30, 8.77

6,6-DIMETHYLBICYCLO[3.1.0]HEXANE DERIVATIVES 115 Table II (continued) •H~NMR IR Elem. Anal. Compound (CC14, 8) (cm -•) %C, %H, %N 22a 1.26 and 1.29 (2s, 6H, 3015 (s), 2935 and 2865 C12H180 (178.27) (CH3)2C) 2.13 (d, 4H, (rs), 1675 (rs), 1625 (s), Calcd: 80.85, 10.18 J=7Hz, 1445 and 1425 (s), Found 80.68, 10.23 -CH2CHCH2-) 2.42 1370 and 1355 (s), 980 (s, 3H, CH3CO-) (s) 2.63-3.08 (m, 1H, H at C-3) 6.01 (d, 1H, J = 16Hz, -CH=CH-CO-) 6.83 (dd, 1H, - CHcCH b = CH a-, Jab = 16Hz, Jbc = 8Hz) 23a 1.27, 1.30 (2s, 6H, 3005 (m), 2980 (m), 2940 C•3H2oO2(208.30 ) (CH3)2C) 1.55 (t, 3H, (s), 2865 (m), 1715 (vs), Calcd: 71.70, 10.94 J=7Hz, CH3CH2-) 1645 (s), 1445 (s), 1370 Found: 71.23, 11.02 2.03-2.23 (m, 4H, and 1355 (s), 985 (s) -CH2CHCH2-) 2.91 (qt, 1H, J=SHz, H at C-3) 4.39 (q, 2H, J=7Hz, CH3CH2-) 5.86 (d, 1H, J=16Hz, -CH=CH-CO-) 7.40 (dd, 1H, -CHcCHb=CHa- , Jab = 16Hz, Jb• = 8Hz) 24 1.22 (2s, 6H, (CH3)2C) 3010 (m), 2990 (s), 2935 C•3H2202(210.32) 1.54 (t, 3H, J=7Hz, (rs), 2870 (s), 1735 (rs), Calcd: 70.92, 11.90 CH3CH20-) 4.36 (q, 1150 (s) Found: 71.22, 11.75 2H, J= 7Hz, CH_3CH2-) 25 1.24 (s, 6H, (CH3)2C) 3340 (s), 3005 (m), 2920 Cl•H2o ¸ (168.28) 1.97-2.23 (m, 4H, (s), 2860 (m), 1450 and Calcd: 78.51, 11.98 -CH2CHCH2-) 3.20 1375 (w), 1050 (m) Found: 78.29, 12.11 (s, 1H, -OH) 3.77 (t, 2H, J=6Hz, -CH2OH ) (30 ml). The reaction mixture was refluxed up to the moment when TLC control did not show the presence of the substrate, and then quenched with distilled water. The pre- cipitate was filtered off, the organic layers were separated, and the water layer was extracted three times with diethyl ether. The organic layers were combined, and after drying the solvent (MgSO4) was removed and the crude product was distilled in vacuo. GENERAL PROCEDURE FOR THE HYDROGENATION REACTION The unsaturated compound (0.025 mole) was dissolved in methanol (50 ml) and hy- drogenated in the presence of nickel-Raney prepared in a standard manner from 1.30 g Ni-AI alloy. When TLC control showed absence of the unsaturated substrate, the cata- lyst was filtered off, the solvent was evaporated, and the crude product was distilled in