304 JOURNAL OF COSMETIC SCIENCE 2, 6-Dimethyl-2-he#te,-4-o/(1). The Grignard reaction of 3-methyl-2-buten- 1 -al (16.8 g, 0.2 mole) with isobutyl magnesium bromide formed from isobutyl bromide (34.2 g, 0.25 mole) and magnesium (6.0 g, 0.25 mole) was carried out in ethyl ether by a method described earlier (2). The crude alcohol 1 was distilled i, vac•o (b.p. 50-51 øC/5 mm Hg) to afford (21.0 g, 75% yield) pure alcohol 3: nD 2ø = 1.4455 (lit. (15) b.p. 74-76øC/12 mm Hg, nD 20 = 1.4410). •H NMR (8): 0.83 (d, J = 6.5 Hz, 6H, -CH(CH3)2) , 1.05-1.42 (m, 3H, -cn2cn(cn3)2), 1.62, (s, 6H, =C(CH3)2), 4.30 (dr, j = 8.3 and 7.3 Hz, 1H, -CH (OH)-). __ Ethyl (E)-3,3,7-trimethyl-4-octe,oate (2). A mixture of alcohol 1 (20.0 g, 0.14 mole), triethyl orthoacetate (180 ml, 1 mole), and 0.3 ml of propionic acid was heated (138- 139øC) with a simultaneous removal of ethanol. Then unreacted orthoacetate was dis- tilled off and the residue was distilled i, vac•o (b.p. 74-76øC/5 mm Hg). In this way 23.2 g (yield 78%) of pure ester 2 was obtained, nD 2ø = 1.4475 •H NMR (8): 0.83 (d, J = 6.6 Hz, 6H, -CH(CH3)2), 1.09 (s, 6H, -C(CH3)2-) 1.21 (t, J = 7.2 Hz, 3H, -OCH2CH3), 1.54 (m 1H, -CH(CH3)2) , 1.81 (t, J = 6.7 Hz, 2H, -CH2CH=CH), 2.23, (s, 2H, -CH2CO2-), 4.07 (q, J = 7.2 Hz, 2H, -OCH2CH3), 5.32 (dr, J = 15.6 and 6.7 Hz, 1H, -CH2CH=CH-) , 5.43 (d, J = 15.6 Hz, -CH2CH=CH-) IR (cm-•): 1736 (s), 1384 (m), 1368 (m), 1136 (s), 976 (s). Anal. Calcd. for C•3H2402: C, 73.53, H, 11.39. Found C, 73.25 H, 11.45. (E)-3,3, 7-Trimethyl-4-octe,-l-ol (3). Reduction of ester 3 (2.2 g, 0.01 mole) with lithium aluminium hydride (0.2 g, 0.006 mole) afforded alcohol 3 in high yield (1.5 g, 89%): b.p. 89-91øC/6 mm Hg nD 2ø = 1.4450 •H NMR (8): 0.84 (d, J = 6.3 Hz, 6H, (CH3)2CH-), 1.01 (s, 6H, -C(CH3)2-), 1.86 (t, J = 6.6 Hz, 2H, -CH2-CH=CH-), 3.64 (t,J = 7 Hz, 2H, -CH2OH) , 5.31 (dt, J = 15.6 and 6.6 Hz, 1H, -CH2CH=CH-), 5.39 (d, J = 15.6 Hz, 1H, -CH2CH=CH-) IR (cm-•): 3320 (s,b), 1364 (m), 1384 (m), 1024 (s), 876 (s). Anal Calcd. for C•H220: C, 77.58 H, 13.12. Found: C, 77.40 H, 13.41. Tetrahy#ro#yra,yl ether of alcohol 3 (5). A mixture of alcohol 3 (11.1 g, 0.065 mole), 3,4-dihydro-2H-pyran (5.7 g, 0.07 mole), and pyridinium p-toluenosulfonate (0.15 g) was stirred for 46 h at room temperature. Then the reaction mixture was diluted with ethyl ether (200 cm3). The ethereal solution was washed with saturated NaHCO3 and water, and dried (MgSO4). The crude product was purified by column chromatography (silica gel, petroleum ether-ethyl acetate, 40:1). Thus 15.3 g (yield 92%) of 5 was obtained: nD 2ø = 1.4530 •H NMR (8): 0.86 (d, J = 6.7 Hz, 6H, -CH(CH3)2) , 1.00 (s, 6H, -C(CH3)2-) , 3.32-3.57 and 3.70-3.86 (m, 4H, -O-CH2-), 4.55 (m, 1H, -O-CH-O), 5.29 (dt, J = 15.6 and 6.5 Hz, 1H, CH2-CH=CH-) 5.36 (d, J = 15.6 Hz, 1H, -CH2-CH=CH-) IR (cm-•): 1384 (s), 1376 (s), 1136 (s), 1080 (s), 1032 (s), 976 (s). Anal. Calcd. for C•6H3oO2: C, 75.52 H, 11.88. Found C, 75.41 H, 11.94. Tetrahydro#yra,yl ether of 3,3, 7-trimethyl-4, 5-e#oxyocta,- 1 -ol (6). m-Chloroperbenzoic acid (4.0 g, 0.023 mole) CH2C12 (25 cm 3) was added dropwise at 0øC to a solution of ether 5 (5.1 g, 0.02 mole) in 30 cm 3 ofCH2C12, and the reaction mixture was warmed to room temperature and stirred for 48 h. Then it was diluted with ethyl ether (200 cm3), washed alternately with saturated solutions of Na2SO 3 and Na2CO3, and dried (MgSO4). A preparative column chromatography of the crude product accorded 4.5 g (84% yield) of pure epox ether 6: no 2ø -- 1.4570 •H NMR (8) 0.89, 0.90, 0.92 and 0.93 (four s 6H, -C(CH3)2-), 0.96 and 0.98 (two d, J = 6.6 Hz, 6H, -CH(CH3)2) , 2.51 (d, J = 2.4 Hz,

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