ODORIFEROUS DERIVATIVES 325 Hz, 2H, -CH2-CH=CH-), 2.29 (d, J = 7.0 Hz, 2H, -CH2C(O)-), 2.45 (m, 1H, -CH(CH3)-), 4.14 (q, J = 7.0 Hz, 2H, -OCH2CH3), 5.30-5.70 (m, 2H, -CH = CH-). IR•m-1): 1724(s), 1652(m), 1048(m), 984(m). Anal. Calcd for C•H2402: C, 73.53 H, 11.39. Found: C, 73.42 H, 11.45. Ester 6 (1.8 g, 66%) was obtained from alcohol 4 (1.9 g, 0.012 mole) and triethyl orthoacetate (16 cm -•, 0.1 mole). The reaction mixture was heated at 138øC for 168 h. The product was purified by column chromatography. 20 Pure ester 6 had the following physical and spectral data: b.p. 97-98øC/6 mmHg, nr) = 1.4439, •H NMR (8, ppm): 0.00 (s, 9H, -Si(CH•) 0, 1.00 (d, J = 6.0 Hz, 3H, -CH(CH•)-), 1.26 (t, J = 7.0 Hz, 3H,-OCH2CH3), 1.32 (d, J = 6.5 Hz, 2H, -Si-CH2-CH =), 2.24 (d, J = 7.0 Hz, 2H, -CH2C(O)-), 2.65 (m, 1H, -CH(CH•)-), 4.14 (q, J = 7.0 Hz, 2H, -OCH2CH3), 5.22 (d, J = 16 Hz, split on d, J = 7.0 Hz, 1H, H-4), 5.48 (d, J = 16 Hz, split on t, J = 6.5 Hz, 1H, H-5). IR (cm- 1): 1756(s), 972(s), 844(m). Anal. Calcd for C12H128iO 2' C, 63.10 H, 10.59 Si, 12.30. Found: C, 63.04 H, 10.53 Si, 12.41. (E)-3,7,7-TRIMETHYL-4-OCTEN- 1-OL (7) (E)-3-METHYL-6-TRIMETHYLSILYL-4-HEXEN- 1-OL (8) Alcohols 7 and 8 were obtained in high yields (92% and 90%) by the reduction of esters 5 and 6, respectively, with LiA1H 4. 7: b.p. 87-88øC/5 mmHg nx) 2ø = 1.4420 1H NMR (8, ppm): 0.80 (s, 9H, (CH3)3C-), 0.97 (d, J = 7.0 Hz, 3H, -CH(CH3)-), 1.37 (s, 1H, -OH), 1.43-1.73 (m, 2H, -CH(CH3)CH2-CH2-), 1.83 (d, J = 6.0 Hz, 2H, -CH2CH=CH-), 2.00-2.50 (m, 1H, -CH(CH3)-), 3.63 (t, J = 7.0 Hz, 2H, -CH2CH2OH) , 5.20-5.78 (m, 2H, -CH = CH-) IR (cm- •): 3336(s, b), 2952(s), 1660(w), 1048(s), 972(s) Anal. Calcd for __ -- CllH220: C, 77.58 H, 13.12. Found: C, 77.41 H, 13.13. 8: b.p. 80-81/7 mm Hg nD 20 = 1.4453 1H NMR (8, ppm): 0.037 (s, 9H, -Si(CH3)3) , 1.04 (d, J = 6.8 Hz, 3H,-CH(CH0-), 1.45 (d, J = 6.8 Hz, 2H, Si-CH2-CH=), 3.70 (t, J = 6.6 Hz, 2H, -CH2OH), 5.20 (d, J = 15.8 Hz split on d, J = 6.8 Hz, 1H, H-4), 5.50 (d, J = 15.8 Hz split on t, J = 6.5 Hz, 1H, H-5) IR (cm-1): 3336(s, b), 1248(s), 1056(s), 968(s), 860(m) Anal. Calcd for CloH22SiO: C, 64.44 H, 11.90 Si, 15.07. Found: C, 64.14 H, 11.93 Si, 15.00. (E)-3,7,7-TRIMETHYL-4-OCTEN- 1-YL ACETATE (9) (E)-3-METHYL-6-TRIMETHYLSILYL-4-HEXEN-1-YL ACETATE (10) Acetates 9 and 10 were quantitatively obtained in a standard manner (reaction with acetyl chloride) from alcohols 7 and 8, respectively. Physical and spectral data of acetates obtained are as follows: 9: Yield: 86% b.p. 68øC/3.5 mmHg nr) •ø = 1.4325 1H NMR (8, ppm): 0.84 (s, 9H, (CH03C), 0.99 (d, J = 6.5 Hz, 3H, -CH(CH3)-), 1.48-1.75 (m, 2H, -CH(CH3)CH2CH2-), 1.84 (d, J = 6.5 Hz, 2H, -CH__2CH=CH-), 2.01 (s, 3H, -C(O)CH3), 4.06 (t, J = 7.0 Hz, 2H, -CH2CH20-), 5.03-5.71 (m, 2H,

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,