3,3,7-TRIMETHYL-4-OCTEN-1-OLS 305 1H,-CH2-CH-CH-), 2.87 (m, 1H,-CH2-CH-CH-), 3.44-3.53 (m, 2H, -OCH 2- -- THP part), 3.80-3.91 (m, 2H, -OCH2- , alcohol part), 4.57 (m, 1H, -OCHO-) IR (cm-•): 1032 (s), 1080 (s), 1140 (s), 1372 (m), 1380 (m), 1382 (m). Tetrahy#ropyrany/ ether of (Z)-3,3,7-trimethy/-•-octe,-l-o/ (7). Epoxy ether 6 (3.4 g, 0.0125 mole) in (50 cm 3) THF was added at room temperature and under nitrogen to a solution of lithium diphenylphosphide prepared in THF (40 cm .3) from chlorodi- phenyphosphine (6.2 g, 0.028 mole) and lithium (0.4 g, 0.056 mole). The reaction mixture was stirred at room temperature for 16 h. Then methyl iodide (3.8 cm 3, 0.06 mole) was added, and the mixture was kept at room temperature for the next 1 h. The reaction mixture was quenched with water and the product was extracted with ethyl ether. The ethereal solution was washed with brine and dried (MgSO4). The crude product was purified by column chromatography. Thus 3.4 g (50% yield) of pure ether 7 was obtained: nD 20 -- 1.4583 •H NMR (8): 0.90 (d, J = 6.6 Hz, 6H, -CH(CH3)2) , 1.12 (s, 6H, -C(CH.3)2-), 2.05 (t, J = 6.5 Hz, 2H, -CH2-CH=CH-), 3.41-3.46 (m, 2H, -CH20- THP part), 3.78-3.87 (m, 2H, -CH20- alcohol part), 4.56 (m, 1H, -OCHO-), 5.21 (dt, J = 12.1 and 6.5 Hz, 1H, -CH2-CH--CH-), 5.27 (d, J = 12.1 Hz, 1H, -CH2CH--CH-) IR (cm-•): 1384 (s), 1376 (s), 1120 (s), 1080 (s), 1032 (s), 712 (m). (Z)-3,3, 7-Trimethy/-•-octe,-l-o/ (8). Ether 7 (2.3 g, 0.009 mole) in ethyl alcohol (25 cm )) with pyridinium p-toluenosulfonate (0.3 g) was heated at 50øC for 12 h. The reaction mixture was diluted with ethyl ether (100 cm)), washed with brine, and dried (MgSO4). Pure alcohol 8 (1.5 g, 96% yield) was obtained after column chromatography. Its physical and spectroscopic data are as follows: b.p. 60øC/2 mm Hg nD 2ø = 1.4523 •H NMR (8): 0.89 (d, J = 6.6 Hz, 6H, -CH(CH3)2) , 1.11 (s, 6H, -C(CH.3)2-), 1.54 (s, 1H, -OH), 1.58 (m, 1H, -CH(CH3)2) , 1.68 (t, J = 7.2 Hz, 2H, -CH2-CH2-O-), 2.05 (t,J = 6.5 Hz, 2H, -CH2CH=CH-), 3.68 (m, 2H, -CH2OH) , 5.23 (d, t,J = 12.2 and 6.5 Hz, 1H, -CH2CH=CH-) , 5.28 (d, J -- 12.2 Hz, 2H, -CH2CH=CH-) IR (cm •): 3336 (s,b), 1460 (s), 1384 (s), 1976 (s), 1240 (m), 1056 (s), 1024 (s), 712 (s). Anal. Calcd. For CllH220: C, 77.58 H, 13.12. Found: C, 77.65 H, 13.15. Ethyl dimethyl-(4-methyl-1 (E)-penten-l-yl)si/ylacetate (10). A mixture of 4-methyl- 1- pentyne (4.5 g, 0.055 mole), chlorodimethylsilane (5.8 cm 3, 0.052 mole) and five drops of 7% solution of hexachloroplatinic acid in ethanol was placed in a hermetically closed flask (50 cm 3) and was stirred for 1 h at room temperature and 3 h at 60øC. Crude 4-methyl-l-pentene-l-yl-dimethylchlorosilane, together with ethyl bromoacetate (5.8 cm 3, 0.052 mole) in THF (30 cm3), was added through a dropping funnel under nitrogen to zinc (3.6 g, 0.055 mole) in THF (10 cm3). The reaction was activated by adding an iodine crystal. The reaction mixture was diluted with petroleum ether (200 cm3), the solid ZnBrC1 was filtered off, and the solvent was evaporated. Crude product (7.35 g, 62% yield), a mixture of esters 10 and 11, was purified by means of preparative column chromatography on silica gel impregnated with AgNO 3 (4%) and activated at 250øC. In that way, pure (above 95%) ester 10 (4.7 g) was obtained: nD 2ø -- 1.4430 b.p. 70øC/2 mm Hg •H NMR (8): 0.13 (s, 6H, -Si(-cn3)2-), 0.84 (d, J = 6.6 Hz, 6H, -CH(CH3)2) , 1.21 (t, J = 7.0 Hz, 3H, -OCH2CH3), 1.63 (m, 1H, -CH(CH3)2) , 1.98 (m, 2H, -CH2CH=CH2-), 4.04 (q, J = 7.0 Hz, 2H, -OCH2CH3) , 5.56 (d, J -- 18.5 Hz, 1H, -CH2CH=CH-) , 6.05 (dt, J -- 18.5 and 6.7 Hz, 1H, -CH2CH=CH-) IR

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