112 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS 1.4758, •r• 2ø = + 14.0 ø, was transformed, via crystalline (-)-3,4-dibromocarane, to the trans-3-acetyl-6,6-dimethylbicyclo[3.1.O]hexane (6) according to the known procedure (6). GENERAL PROCEDURE FOR THE WADSWORTH-EMMONS REACTION Appropriate phosphonate W• or W 2 (0.09 mole) was added dropwise to a suspension of Nail (0.09 mole) in anhydrous DMF (50 ml), and the mixture was stirred vigorously until the evolution of hydrogen ceased. To the solution of sodium salt of phosphonate was added dropwise ketone or aidehyde (0.03 mole) in DMF (40 ml), and it was heated at 60-65øC approximately 2-3 h. When TLC control showed absence of starting ketone or aidehyde, the mixture was diluted with water (300 ml), extracted with diethyl ether, and dried over MgSO 4. The residue after removal of the solvent was purified by column chromatography and distilled in vacuo. GENERAL PROCEDURE FOR THE WITTIG REACTION WITH STABILIZED YLIDS The solution of aidehyde (0.03 mole) and acetonylidenophosphorane W 3 (0.06 mole) in anhydrous methylene chloride (200 ml) was refluxed to the moment when TLC control showed absence of substrate. Then methylene chloride was evaporated and hexane (100 ml) was added to the residue. Precipitated triphenylphosphine oxide was filtered off and washed several times with hexane. After evaporation of the solvent, the crude product was chromatographed on a column and distilled in vacuo. GENERAL PROCEDURE FOR THE GRIGNARD REACTION Aldehyde or ketone (0.03) in anhydrous diethyl ether (20 ml) was added dropwise to the Grignard reagent formed from appropriate alkyl halide (0.03 mole) and magnesium (0.03 mole) in anhydrous diethyl ether (60 ml). The mixture was stirred for 2-4 h. Then NH4C1 solution was added, and the product was extracted with diethyl ether. The etheral solution was washed with saturated NaCI solution and dried (MgSO4). The crude product was purified by column chromatography (if necessary) and distilled in vacuo. GENERAL PROCEDURE FOR OXIDATION WITH PCC Alcohol (0.03 mole) was added in one portion to a slurry of pyridinium chlorochromate (0.07 mole) and anhydrous sodium acetate (0.012 mole) in anhydrous methylene chlo- ride (100 ml). The mixture was stirred at room temperature for 3 h. Then the methylene chloride was evaporated and the residue was extracted with petroleum ether. The etheral solution was filtered through "Florisil" and evaporated. The crude aidehyde was chro- matographed on a column immediately before use (readily oxidizable in air). GENERAL PROCEDURE FOR REDUCTION WITH LiA1H 4 Carbonyl compound (ester, ketone 0.030 mole) in diethyl ether (35 ml) was added dropwise to the suspension of lithium aluminium hydride (0.050 mole) in diethyl ether

6,6-DIMETHYLBICYCLO[3.1.0]HEXANE DERIVATIVES 113 Table II Spectral Data and Elemental Analysis of Products Compound 1H-NMR IR (CC14, 8) (cm -1) Elem. Anal. %C, %H, %N 8 9 10 11a,b 12 1.24 (s, 6H, (CH3)2C) 1.38 (s, 6H, -C(CH3)2OH) 2.34 (s, 1H, -OH) 1.25 (s, 6H, (CH3)2C) 1.32 (s, 3H, CH3-C-OH) 5.20 (q, 2H, J=7Hz, -CH2CH3) 1.30 (s, 6H, (CH3)2C) 1.38 (s, 3H, CH3-C-OH) 1.81 (s, 1H, -OH) 2.41 (d, 2H, J=7Hz, -CH 2-CH=CH2) 3.55-3.95 (m, 1H, -CH(OH)-) 5.21-5.43 (m, 2H, H2C=CH-) 5.84-6.28 (m, 1H, H2C=CH-) 1.24 (s, 6H, (CH3)2C) 1.41 (d, 3H, J=6Hz, CH•CH-) 2.24 (s, 3H, CH3CO-) 4.88 (qt, 1 H, J = 6Hz, - HCOAc) a: 1.27 and 1.28 (2s, 6H, (CH3)2C) 1.54 (t, 3H, J=7Hz, CH3CH20-) 2.40 (s, 3H, =CCH_•), 2.93 (qt, 1H, J=8Hz, H at C-3) 4.37 (q, 2H, J=7Hz, CH3CH2-) 5.85 (s, 1H, =CH-) b: 1.26 and 1.36 (2s, 6H, (CH3)2C) 1.54 (t, 3H, J=7Hz, CH3CH2-) 2.13 (s, 3H, =CCH0 4.37 (q, 2H, J=7Hz, CH3CH2-) 4.62 (qt, 1H, J=8Hz, H at C-3) 5.75 (s, 1H, =CH-) 1.23 (s, 6H, (CH3)2C) 1.40 (d, 3H, J=6Hz, -CHCH3) 1.54 (t, 3H, J=7Hz, CH3CH2-) 4.36 (q, 2H, J=7Hz, CH3CH2-) 3380 (vs,vb), 3000 (s), 2965 and 2930 (vs), 2865 (m), 1465 and 1460 (m), 1365 (s), 1125 (s) 3415 (vs,vb), 3000 (s), 2970 and 2940 (vs), 2865 (s), 1455 (s), 1370 (s), 1120 (s) 3440 (vs,vb), 3085 (m), 3020 (m), 2985 (w), 2930 (vs), 2865 (s), 1640 (m), 1115 (s) 990 (m), 905 (s) 3005 (m), 2975 (m), 2975 (s), 2940 (s), 1725 (s), 1455 (s) 1365 (m), 1235 (s) a: and b: 301.0 (m), 2980 (m), 2940 (s), 2865 (m), 1705 (vs), 1640 (s) 3005 (m), 2955 (s), 2920 (vs), 2865 (s), 1735 (vs), 1155 (s) CllH2o ¸ (168.28) Calcd: 78.51, 11.98 Found: 78.38, 12.02 C12H220 (182.31) Calcd: 79.06, 12.16 Found: 78.89, 12.19 C13H220 (194.30) Calcd: 80.35, 11.41 Found: 80.26, 11.34 C• •H2oO2(184.28) Calcd: 73.43, 10.27 Found: 73.27, 10.41 C•4H2202(222.23) Calcd: 75.63, 9.97 Found: 75.41, 10.07 C•4H2402(224.34) Calcd: 77.95, 10.78 Found: 77.59, 10.82