326 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS -CH = CH-) IR (cm- •): 1744(s), 1648(w), 1240(s), 976(s) Anal. Calcd for C13H2402: -- C, 75.54 H, 11.39. Found: C, 74.95: H, 11.41. 10: Yield: 87% b.p. 74øC/4 mmHg nD 2ø = 1.4406 •H NMR (8, ppm): 0.00 (s, 9H, -Si(CH3)3), 1.00 (d, J = 6.6 Hz, 3H, -CH(CH3)-), 1.41 (d, J = 7.1 Hz, 2H, Si-CH2-CH =), 2.05 (s, 3H, CH__3C(O)-), 4.70 (t, J = 6.8 Hz, 2H, -CH2-CH2-O-), 5.15 (d,J = 16.0Hzsplitond, J = 7.0Hz, 1H, H-4), 5.45 (d,J = 16Hz, split on t, J = 7.1 Hz, 1H, H-5) IR (cm-•) ß 1740(s), 1248(s), 1048(s), 968(s), 860(s) Anal. Calcd for C12H248iO2: C, 63.10 H, 10.59 Si, 12.30. Found: C, 62.95 H, 10.63 Si, 12.42. (E)-3,7,7-TRIMETHYL-4-OCTEN- 1-AL (11) Alcohol 7 (5.1 g, 0.03 mole) was added to a slurry ofpyridinium chlorochromate (15.6 g, 0.07 mole) and anhydrous sodium acetate (1.0 g) in anhydrous methylene chloride (100 cm3), and the mixture was stirred at room temperature for 3 h. Then methylene chloride was evaporated, and the residue was extracted with petroleum ether. The ethereal solution was filtered through "Florosil" and evaporated. The crude product was chromatographed and distilled in vacuo (b.p. 43øC/2.5 mmHg). Pure aidehyde 11 (3.2 g, 64%) nD 20 = 1.4358 was obtained. •H NMR (8, ppm): 0.84 (s, 9H, (CH•)3C-), 1.06 (d, J = 6.0 Hz, 3H, -CH(CH3)-), 1.85 (d, J = 6.0 Hz, 2H, -CH2-CH = CH-), 2.22-2.50 (m, 2H, -CH2-CHO), 5.15--5.70 (m, 2H, -CH=CH-), 9.78 (t, J = 2.5 Hz, 1H, -CH2-CHO) IR (cm- •): 2762(w), 2712(w), 1728-•s), 9)-6(m) Anal. Calcd for CllH2oO: C, 78.51 H, 15.24. Found: C, 78.41 H, 15.37. (E)- 3-METHYL-6-TRIMETHYLSILY-4-HE XEN- 1-AL (12) Chromium(VI) oxide (10 g, 0.1 mole) was added to a solution of pyridine (20 cm 3) in carbon tetrachloride (100 cm3), and the mixture was stirred for 3 h at room temperature. Then alcohol 8 (1.9 g, 0.01 mole) was added to an orange slurry and the stirring was continued for the next 8 h. Carbon tetrachloride was evaporated in vacuo, and the residue was washed three times with ethyl ether. The ethereal solution was washed with water, 5% aqueous solution CuSO 4 and water, and dried (MgSO4). The crude product was purified by column chromatography and distilled in vacuo. Pure aidehyde 12 (1.4 g, 76%) was obtained, b.p. 74øC/2 ramrig, nD 2ø = 1.4435 •H NMR (8, ppm)' 0.012 (s, 9H, -Si(CH3)3), 1.06 (d, J = 6.6 Hz, 3H, -CH(CH0-), 1.41 (d, J = 7.1 Hz, 2H, Si-CH2-CH=), 2.37 (d, J = 5.6 Hz, split on d, J = 2.3 Hz, 2H, -CH2-CHO), 5.25 (d,J = 16.0Hzsplitond, J = 6.6Hz, 1H, H-4), 5.50(d,J = 16.0Hzspliton t, J, = 7.1 Hz, 1H, H-5), 9.72 (t, J = 2.3 Hz, 1H, -CH2-CHO) IR (cm-•): 2768(w), 2712(w), 1728(s), 1248(s), 969(s), 852(s) Anal. Calcd f•rr C•oH2oSiO: C, 65.15 H, 10.93 Si, 15.24. Found: C, 66.02 H, 10.81 Si, 15.37. DIOXOLANES (13A, 14A) AND DIOXANES (13B, 14B) General procedure. The mixture of aidehyde (0.01 mole), ethylene glycol or 1,3- propanediol (0.012 mole), and pyridinium p-toluenesulfonate (0.1 g) in benzene (100 cm 3) was refluxed with the azeotropic removal of water. Then the reaction mixture was diluted with ethyl ether (50 cm 3) and washed with aqueous sodium carbonate and water,

ODORIFEROUS DERIVATIVES 327 and dried (Na2SO4). The residue after the removal of solvents was purified by column chromatography and distilled. The yield and spectral and physical data of the com- pounds obtained are given below: 13a: Yield: 75.5% b.p. 84øC/3.5 mmHg nD 2ø = 1.4456 •H NMR (8, ppm)' 0.86 (s, 9H, (CH3)3C-), 1.03 (d, J = 7.0 Hz, 3H, -CH(CH3)-), 1.48-1.75 (m, 2H, -CH(CH3)-CHI-CH), 1.86 (d, J = 7.0 Hz, 2H, -CH2-CH=CH-), 2.10-2.68 (m, 1H, =CH -CH(CH3)-), 3.63-4.20 (m, 4H, -O-CHi-CH2-O-), 4.88 (t, J = 5.0 Hz, 1H, -CH•-CH), 5.12-5.70 (m, 2H, -CH=CHW) IR (cm-•): 1660(w), 1136(s), 1032(s), 972(s) Anal. Calcd for Cl382402: C, 73.53 H, 11.39. Found: C, 73.03 H, 11.52. 13b: Yield' 83.5% b.p. 84-85øC/3 mmHg nD •ø = 1.4486 •H NMR (8, ppm): 0.93 (s, 9H, (CH3)3C-), 0.99 (d, J = 7.0 Hz, 3H, -CH(CH3)-), 1.43-1.68 (m, 2H, -CH(CH3)-CH2-CH), 1.86 (d, J = 7.0 Hz, 2H, -CH•-CH = CH-), 3.50-4.38 (2m, 4H, -O-CHI-CH•-CH•-O-)4.60 (t, J = 5.5 Hz, 1H, -CH•-CH), 5.10-5.62 (m, 2H, -CH = CH-) IR (cm-•): 1144(s), 1096(s), 972(s) Anal. Calcd for C1482602: C, 74.28 •, 11.•8. Found: C, 74.02 H, 11.64. 14a: Yield: 83.8% b.p. 73øC/2 mm Hg nD lø = 1.4511 •H NMR (8, ppm): -0.019 (s, 9H,-Si(CH3)3), 1.01 (d,J = 6.8 Hz, 3H,-CH(CH3)-), 1.39 (d,J = 7.1Hz, 2H, Si-CH•-CH =), 3.79-3.99 (m, 4H, -CH(OCH2)•), 4.84 (t, J = 5.1 Hz, 1H, -CHI- CH(OCH•)2), 4.96-5.52 (m, 2H, -CH = CHO W, IR (cm- •): 1248(s), 1140(s), 1040(s), 96-•(s), 844(s) Anal. Calcd for C•2H24SiO2: C, 63.10 H, 10.59 Si, 12.30. Found: C, 63.12 H, 10.62 Si, 12.41. 14b: Yield: 79.4% b.p. 79øC/2 mmHg nD lø = 1.4518 •H NMR (8, ppm): -0.003 (s, 9H, -Si(CHs)3), 0.97 (d, J = 6.6 Hz, 3H, -CH(CH3)-), 1.40 (d, J = 7.1 Hz, 2H, Si-CHI-CH=), 3.58-4.20 (m, 4H, -CH(OCH•-)I), 4.52 (t, J = 5.4 Hz, 1H, -CH2- CH(O-)I), 5.13-5.40 (m, 2H, -CH=CH-) IR (cm-•): 1248(s), 1144(s), 968(s), 84-•(s) Anal. Calcd for C13H•6SiO2:-•, 64.04 H, 10.81 Si, 11.59. Found: C, 64.24 H, 10.75 Si, 11.64. ACETALS 15A,B AND 16A, B Generalprocedure. The mixture of aldehyde (0.015 mole) trimethyl or triethyl ottoacetate (0.017 mole) and pyridinium p-toluenesulfonate (0.1 g) in methyl or ethyl alcohol (5 cm 3) was heated at 40øC for 2 h and then was left at room temperature overnight. Then the reaction mixture was diluted with ethyl ether and washed with aqueous sodium carbonate and water. The crude product was chromatographed and distilled. The yields of the reactions as well as the physical and spectral data of acetals obtained are given below: 15a: Yield: 84% b.p. 61øC/3 mmHg nD 20 = 1.4294 1H NMR ($, ppm): 0.83 (s, 9H, (CH3)3C-), 0.94 (d, J = 6.0 Hz, 3H, -CH(CH3)-), 1.81 (d, J = 6.0 Hz, 2H, -CH2-CH=CH-), 3.26 3.28 (2s, 6H, -CH(OCH3)2), 4.39 (t, J = 6.0 Hz, 1H, -C•2-CH(OCH3)2), 5.00-5.73 (m, 2H,-CH=CH-) IR (cm-•): 1648(w), 1128(s), -- 1052(s),•72(s) Anal. Calcd for C•382602: C, 72.84 H, 12.23. Found: C, 72.57 H, 12.32. 15b: Yield: 84% b.p. 87øC/3.5 mmHg nD 20 = 1.4292 1H NMR ($, ppm): 0.83 (s, 9H, (CH03C-), 0.96 (d, J = 6.5 Hz, 3H, -CH(CH3)-), 1.18 (t, J = 7.1 Hz, 6H,