100 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Table III Spectral Data and Elemental Analysis of Products Compound % C, % H, and IR (cm-•) •H-NMR (CDC13) (8) (2?3) and lot-Methyl-4- Calcd: 67.66 8.29 3050, 2970 isopropyl-7,7-di- Found: 67.70 8.30 2890, 1750 methoxy carbonylbi- C•3H2204 1740, 1620 cyclo (4.1.0) hept-3- 1440, 1025 ene (5?6) and lot-Methyl,4- isopropyl-7,7-di- methoxy carbonylbi- cyclo (4.1.0) Heptane (7) 6-Dimethylmalonyl-(R)- p-meth-l-ene (8) 10-Dimethylmalonyl- ( 1S)-ot-pinene (1) p-Menth-4-en-cis- 1,2- diol (4) p-Menthane-cis- 1,2-diol (9) Cyclooctan-cis- 1,2-diol Calcd: 67.16 8.95 2970, 2885 Found: 67.36 8.90 1740, 1460 C15H2404 1440, 1020 Calcd: 67.16 8.95 3015, 2975 Found: 67.38, 8.90 2875, 1770 C15H240 4 1740, 1640 1450, 1440 Calcd: 67.66 8.27 3100, 3000 Found: 67.72 8.42 2970, 2920 C15H220 4 2850, 1740 1650, 1440 Calcd: 70.58, 10.58 3400, 2960 Found: 70.70 10.42 2900, 1670 C•oH•302 m.p. 63 ø 1360, 1050 Calcd: 69.76 11.62 Found: 69.90 11.61 CloH2oO2 m.p. 74øC Calcd: 66.66, 11.11 Found: 66.78 11.14 C8H1602 m.p. 76øC 3425, 2925 286O, 1360 34OO, 325O 29OO, 285O 1050 5.52 and 5.13 (m, vinyl, 1H) 3.70 and 3.76 (s, ester, 3H) 3.63 and 3.59 (s, ester, 3H) 2.70 and 2.41 (m, allylic, 2H) 2.53 and 2.30 (m, allylic, 2H) 1.25 and 1.29 (s, methy, 3H) 1.00 and 0.93 (dd, J: 1.4, J: 6.99 and J: 1.8, J: 6.35 Hz, 6H) 3.70 (s, ester, 6H) 0.83 (s, methyl, 3H) 0.825 (d, J: 6.67 hz, 6H) 1.00-2.2 (m, 9H) and 3.73 (s, ester, 6H) 0.83 (s, methyl, 3H) 0.817 (d, J: 6.69 hz, 6H) 1.00-2.2 (m, 9H) 51 (m, vinyl, 1H) 3.736 (s, ester, 3H) 3.73 (s, ester, 3H) 3.55 (d, J: 8.47 Hz, malonyl, 1H) 2.89 (m, substituted allyl, 1H) 1.61 (s, methyl, 3H) 0.85 (d, J: 6.4 Hz, 6H) 1.00-2.00 (m, 6H) 5.29 (m, vinyl, 1H) 3.72 (s, ester, 6H) 3.51 (t, J: 7.6 Hz, mal- onyl, 1H) 2.57 (dd, J: 7.7 and 1.5 Hz, substituted allylic, 2H) 1.26 (s, methyl, 3H) 0.78 (s, methyl, 3H) 1.07-2.09 (m, 3H) 5.31 (m, vinyl, 1H) 3.64 (dd, J: 11.2 and 5.6 Hz, 1H) 2.25 (s, OH, 1H) 2.30 (s, OH, 1H) 1.22 (s, methyl, 3H) 1.00 (d, J: 6.5 Hz, 6H) 1.9-2.18 (m, others) 3.35 (dd, J: 10.8 and 4.5 Hz, 1H) 1.90 (s, 20H, 2H) 1.26 (s, methyl, 3H) 0.88 (d, J: 7 Hz, 6H) 1.17-1.84 (m, 7H) 3.29 (d, J: 8.3 Hz, 2H) 2.28 (s, 20H, 2H) 2.0-1.52 (m, 12H)

NEW ODOROUS TERPENES 101 Table III (continued) Compound % C, % H, and IR (cm-•) •H-NMR (CDC13) (8) (lO) 1,3,3-Trimethyl-7-iso- Calcd: 74.28 10.47 2920, 2850 propyl-2,4-dioxabi- Found: 74.49 10.36 1360, 1200 cyclo (4.3.0) non-7- C13H220 2 1140 erie (11) 1,3,3-Trimethyl-7-iso- Calcd: 73.58 11.32 2910, 2850 propyl-2,4-dioxabi- Found: 73.74 11.48 1360, 1200 cyclo (4.3.0) nonane C13H240 2 1140 (12) 3,3-Dimethyl-l,5-dioxa- Calcd: 69.76 11.63 2900, 2800 bicyclo (6.3.0) unde- Found: 69.72 11.84 1200, 1140 cane CloH200 2 5.44 (m, vinyl, 1H) 4.08 (dd, J: 2.8 and 7.6 Hz, 5-H, 1H) 0.98-1.02 (d, J: 7.08 Hz, 6H) 1.37 (s, acetalmethyl, 6H) 1.31 (s, 1-methyl, 3H) 1.9-1.6 (m, others, 4H) 3.90 (trip J: 5.8 Hz, 5-H, 1H) 1.46 (s, acetalmethyl, 3H) 1.38 (s, acetalmethyl, 3H), 1.31 (s, 1-methyl, 3H) 0.88 (trip, J: 7 Hz, 6H) 1.41-1.89 (m, others, 8H) 12 (m, 1-H and 5-H, 2H) 1.41 (s, acetalmethyl, 3H) 1.33 (s, acetalmethyl, 3H) 1.89-1.14 (m, others, 12H) GENERAL PROCEDURE OF ACETAL SYNTHESIS Diols (0.01 mol) were dissolved in anhydrous acetone (10 ml), and then p-toluenesul- phonic acid (0.01 g) was added and the mixture allowed to stand at room temperature for 24 hours. Then it was diluted with water, alkalized with 10% Na2CO 3 solution, and extracted several times with n-hexane. After drying over Na2804, the solvent was removed. Purity was controlled by GLC. Spectral data and elemental analysis are summarized in Table III. REFERENCES (1) M. Elliot and N. F. Janes, Synthetic pyrethroids--A new class of insecticide, Chem. Soc. Rev., 7, 473-505 (1978). (2) H. Sadowska and J. Gora, Synthesis and odor properties of carene and carane derivatives, Perfum. Flavorist, 7(1), 52-56 (1982). (3) W. Cocker and D. H. Grayson, The chemistry of terpenes. Part 23. Reaction of (+)-carane-3, 4- diol with sulphuric acid, J. Chem. $oc. Perkin Trans., I., 155-159 (1978). (4) A Henarich and Piatkowski, Stereochemistry of the carane system. Oxidation products of isomeric 3,4-carane diols obtained from (+)-3-carene, PolishJ. Chem., 58, 73-84 (1984). (5) E. Miiller, Houben-Weyl, Methoden der Organischen Chemie, Alkohole I 6/la/1 (Georg Thieme Verlag, Stuttgart, 1979), pp. 592-637. (6a) J. L. Simonsen, The constituents of Indian turpentine from pinus longifolia, roxb. Part I, J. Chem. $oc., 117, 570-574 (1920). (6b) P. P. Pillay and J. L. Simonsen, The constituents of Indian turpentine from pinus longifolia, roxb. Part IV, J, Chem. Soc., 359-364 (1928). (7) M. Jones and R. A. Moss, Carbenes (Wiley Interscience, New York, 1973). (8) N. S. Isaacs, "Reactive Intermediates," in Organic Chemistry (Wiley Interscience, New York, 1974), pp. 375-406.