306 JOURNAL OF COSMETIC SCIENCE (cm-•): 1724 (s), 1384 (m), 1375 (m), 1244 (s), 1092 (s), 972 (m), 832 (s). Anal. Calcd. for C•2824OSi: C, 63.10 H, 1059. Found: C, 63.02 H, 10.70. 2-[Dimethyl-(4-methyl-1 (E)-penten-l-yl)sily/]ethanol (12). The reduction of ester 10 (2.0 g, 0.0088 mole) with LiAIH 4 (0.25 g, 0.0066 mole) in ethyl ether (50 cm 3) afforded alcohol 12 (1.4 g, 84% yield). Its physical and spectral data are as follows: b.p. 62øC/2 mm Hg nD 2ø = 1.4527 •H NMR (8): 0.46 (s, 6H, -Si(CH3)2-), 0.86 (d, J = 6.5 Hz, 6H, -CH(CH3)2) , 0.98 (m, 2H, -CH2CH2OH), 1.23 (s, 1 H, -OH), 1.66 (m, 1H, -CH(CH3)2), 1.98 (td, J -- 6.7 and 1.5 Hz, 2H, -CH2CH=CH-), 3.71 (m, 2H, -CH2OH), 5.56 (dt, j = 18.5 and 1.5 Hz, 1H, -CH2CH=CH-), 6.01 (dr, j -- 18.5 and 6.7 Hz, 1H, -CH2CH=CH-) IR (cm-t): 3320 (s,b), 1615 (m), 1384 (m), 1375 (m), 1240 (s), 1035 (s), 992 (s), 835 (s). Anal. Calcd. for CloH22OSi: C, 64.44 H, 11.90. Found: C, 64.51 H, 12.01. Dimethyl-(4-methyl-l-pentyn-l-yl)-vinylsilane (14). n-BuLl (54 cm 3 of 1.6 M solution in hexane, 0.086 mole) was added dropwise under nitrogen to a cooled (-78øC) solution of 4-methyl-l-pentyne (10 cm 3, 0.086 mole) in ethyl eter (50 cm3). After 20 minutes, dimethylvinylchlorosilane (11 cm 3, 0.08 mole) was added and the reaction mixture was warmed to room temperature. Then the mixture was diluted with ethyl ether (100 cm 3) and quenched with water (20 cm3). The ethereal solution was washed with brine and dried (MgSO4). The product was distilled in vacuo: (b.p. 64-66øC/16 mm Hg) to give 11.2 g (yield 84%) of pure silane 14. Its physical and spectral data are as follows: nD 20 = 1.4270 •H NMR (8): 0.18 (s, 6H, -Si(CH3)2-), 0.96 (d, J = 6.6 Hz, 6H, -CH(CH3)2) , 1.80 (m, 1H, -CH(CH3)2) , 2.11 (d, J = 6.6 Hz, 2H, -CH2-), 5.82 (dd, J = 19.5 and 4.4 Hz, 1H, -CH=CH 2 trans), 5.97 (dd, J = 14.5 and 4.4 Hz, 1H, -CH=CH 2 cis), 6.12 (dd, J = 19.5 and 14.5 Hz, 1H, -CH=CH2) IR (cm-•): 3048 (m), 2176 (s), 1248 (s), 824 (s). Anal. Calcd. for C•oH•8Si: C, 72.21 H, 10.90. Found: C, 72.07 H, 10.95. Dimethyl-(4-methyl-l-pentyn-l-yl)epoxyethylsilane (15). Vinyl silane 14 (6.0 g, 0.036 mole) was added to a dried solution of m-chloroperbenzoic acid (9.5 g, 0.0433 mole) in CH2CI 2 (100 cm3), and the mixture was stirred at room temperature for 48 h. The reaction mixture was concentrated in vacuo up to 3/4 of volume and then was diluted with petroleum ether (250 cm3). m-Chlorobenzoic acid was filtered off, and the crude product was purified by column chromatography. Pure epoxide 15 (5.4 g, yield 82%) had the following physical and spectral data: nD 2ø = 1.4513 •H NMR (8): 0.14 and 0.21 (two s, 6H, -Si(CH3)2-) , 0.95 (d, J = 6.6 Hz, 6H, -CH(CH3)2) , 1.80 (m, 1H, -CH(CH3)2) , 2.10 (d, J = 6.6 Hz, 2H, -CH2-), 2.24 (dd, J = 5.4 and 3.9 Hz, 1H, /ox -CH-CH2) , 2.66 (dd, j = 5.9 and 3.9 Hz, 1H, -CH-CH2) , 2.92 (dd, j = 5.9 and 5.4 Hz, 1H, -CH-CH2) IR (cm-•): 2176 (s), 1248 (s), 1232 (m), 880 (s), 824 (s). 2-[Dimethyl-(4-methyl-1-pentyn-1-yl)silyl]ethanol (16). Epoxide 15 (1.3 g, 0.0071 mole) in hexane (35 cm 3) was reduced with diisobuthylaluminum hydride (8 cm 3 of 1M solution in hexane). After purification of the crude product (column chromatography) 1.05 g (80% yield) of alcoohol 16 was obtained: b.p. 65øC/2 mm Hg nD 2ø = 1.4540 •H NMR (8): 0.12 (s, 6H, -Si(CH3)2-), 0.93 (d, J = 6.6 Hz, 2H, -CH(CH3)2) , 0.99 (t, J = 7.9 Hz, 2H, CH2CH2OH), 1.75 (m, 1H, -CH(CH3)2) , 1.93 (s, 1H, -OH), 2.07 __ (d, J = 6.6 Hz, 2H, -CH2-C=C), 3.77 (t, J = 7.9 Hz, 2H, -CH2OH) IR (cm-•): 3368

3,3,7-TRIMETHYL-4-OCTEN-1-OLS 307 (s,b), 2176 (s), 1248 (s), 1172 (m), 1036 (s), 840 (s). Anal. Calcd. for C•oH2oOSi: C, 65.15 H, 10.93. Found: C, 65.03 H, 10.78. 2- (Dimethyl- (4-methyl- 1 (Z)-pe,te,- 1 -y/)si/yl]eth•,ol (17). Diisobutylaluminum hydride (4 cm 3 of 1M solution in hexane) was added under nitrogen to a hexane (10 cm 3) solution of alcohol 16 (0.3 g, 1.63 mmole), and the reaction mixture was stirred for 4 h. Then the reaction mixture was diluted with ethyl ether (50 cm •) and a 10% solution of NaCI (20 cm'•). The product was extracted with ethyl ether and after work-up was purified by column chromatography. In this way, 0.25 g of pure alcohol 17 was ob- tained: b.p. 63øC/2 mm Hg n•) 2ø = 1.4539 1H NMR (8): 0.11 (s, 6H, -Si(CH•)2-), 0.88 (d, J = 6.7 Hz, 2H, -CH(CH•)2), 1.03 (t, J = 8.3 Hz, 2H, -CH2CH2OH) , 1.48 (s, 1H, -OH), 1.63 (m, 1H, -CH(CH3)2) , 1.99 (ddd, J = 7.3, 6.9 and 1.3 Hz, 2H, -CH2CH=CH), 3.72 (t, J = 8.3 Hz, 2H, -CH2OH), 5.46 (d,t, J = 14.2 and 1.3 Hz, 1H, -CH2CH=CH-), 6.33 (dt, J = 14.2 and 7.3 Hz, 1H, -CH•CH=CH-) IR (cm-•): 3344 (s,b), 1604 (m), 1248 (s), 1172 (m), 1036 (s), 836 (s), Anal. Calcd. for C•oH22OSi: C, 64.45 H, 11.90. Found: C, 64.32 H, 11.74. Alcohol 17 was also obtained in 79% yield by the reduction of epoxide 15 with two equivalents of diisobutylaluminum hydride. Synthesis of •cet•tes 4, 9, 13, 18, •nc119. General procedure: A solution of acetyl chloride (0.0025 mole) in ethyl ether (5 cm •) was added to a cooled (0øC) solution of alcohol (0.002 mole) and anhydrous pyridine (0.004 mole) in ethyl ether (30 cm•), and the reaction mixture was stirred for 2 h. Then water (20 cm •) was added and the product was extracted with ethyl ether (2 x 20 cm•). The combined ethereal solution was washed with 10% CuSO 4 solution, 10% NaHCO3 solution, and brine, and dried (MgSO4). The crude acetates were purified by column chromatography. Their physical and spectral data are given below: 4: Yield: 94% b.p. 62øC/2 mm Hg nD 2ø = 1.4356 1H NMR (8): 0.84 (d, J = 6.6 Hz, 6H, -CH(CH3)•), 0.99 (s, 6H, -C(CH3)•), 1.56 (m, 1H, -CH(CH3)•), 1.60 (t, J = 7.6 Hz, 2H, -CH2CH•O-), 1.84 (m, 2H, -CH:CH=CH-), 2.00 (s, 3H, -C(O)CH3), 4.02 (m, 2H, -CH20-), 5.23-5.30 (m, 2H, -CH=CH-) IR (cm-1): 1740 (s), 1384 (s), 1368 (m), 1244 (s), 1032 (s), 976 (s). Anal. Calcd. for C13H2402: C, 73.54 H, 11.39. Found: C, 73.41 H, 11.42. 9: Yield: 95% b.p. 65øC/2 mm Hg nD 2ø = 1.4410 •H NMR (8): 0.88 (d, J = 6.6 Hz, 6H, -CH(CH3)•, 1.11 (s, 6H,-C(CH3):-) , 1.54 (m, 1H, -CH(CH3):) , 1.71 (t,J = 6.7 Hz, 2H, CH2CH20-), 2.01 (s, 3H, -C(O)CH3), 2.02 (m, 2H, -CH2CH=CH-) , 4.09 (t, J -- 6.7 Hz, 2H, -CH•CH20-), 5.21-5.24 (m, 2H, -CH=CH-) IR (cm-1): 1748 (s), 1468 (s), 1384 (s), 1364 (s), 1236 (s), 1032 (s), 712 (m). Anal. Calcd. for C•3H2402: C, 73.54 H, 11.39. Found: C, 73.35 H, 11.45. 13: Yield: 78% b.p. 64øC/2 mm Hg nD 2ø = 1.4420 1H NMR (8): 0.07 (s, 6H, -Si (CH3)•)-) , 1.02 (m, 2H, -CH:CH20), 0.85 (d, J = 6.6 Hz, 6H, -CH(CH3):), 1.40 (m, 1H, -CH(CH3):), 1.98 (m, 2H, -CH•CH=CH-), 2.00 (s, 3H, -C(O)CH3), 4.11 (m, 2H, -CH:CH:O-), 5.56 (dt, J = 18.5 and 1.3 Hz, 1H, -CH2CH=CH-), 6.00 (dt, J = 18.5 and 6.7 Hz, 1H, -CH•CH=CH-) IR (cm-1): 1740 (s), 1616 (w), 1372 (m), 1360 (m), 1244 (s), 1048 (s), 952 (m), 826 (s). Anal. Calcd. for C•2Hi•O•Si: C, 64.23 H, 8.98. Found: C, 64.15 H, 9.05.