Method for synthesising cyclohexenones and the use of same in the perfume industry

Abstract

The present invention concerns a method for synthesizing cyclohexenone and cyclohexenol compounds having specific fragrances and remanence properties, said method consisting in condensing a ketone on an -methylene-aldehyde in order to obtain, by means of a domino reaction, compounds of formula (I). ##STR00001##

Claims

1. A method of preparation of a compound of formula (I) ##STR00058## in which: R.sub.1 represents a methyl or an ethyl; R.sub.2 independently a hydrogen or a C.sub.1-C.sub.5 alkyl or C.sub.2-C.sub.5 alkenyl group; R.sub.3 represents an alkyl or alkenyl group, optionally substituted by an aryl, or R.sub.3 represents a cyclic alkyl or cyclic alkenyl group, optionally substituted by one or more C.sub.1-C.sub.6 alkyl groups, it being understood that R.sub.3 includes in total 3 to 10 carbon atoms; Z represents C(O) or CR.sub.4(OR.sub.5), with R.sub.4 represents a hydrogen or a C.sub.1-C.sub.8 alkyl or C.sub.2-C.sub.8 alkenyl group; R.sub.5 represents a hydrogen or a C.sub.1-C.sub.8 alkyl or alkanoyl or C.sub.2-C.sub.8 alkenyl or alkenoyl group; knowing that a double bond is present or absent in the ring and that when it is present, it is either in position 2-3 and R.sub.2 is absent in position 2, or in position 3-4 and R.sub.2 is present in position 2 and is such as defined above, wherein said method comprises: i) reaction of an -methylene aldehyde, in the presence of an inorganic base, with a symmetrical ketone to obtain a compound of formula (Ia), ##STR00059## in which R.sub.1 and R.sub.3 are such as defined above, R.sub.2 is a hydrogen and a double bond is present at 2-3 or 3-4 in the ring and this reaction being optionally followed by steps ii), and/or iii), and/or iv), ii) mono- or bis-alkylation reaction in order to obtain a compound of formula (Ia) in which R.sub.2 is a C.sub.1-C.sub.5 alkyl or C.sub.2-C.sub.5 alkenyl group; iii) conversion of the ZC(O) function of the compound obtained in the preceding step into a ZCR.sub.4(OR.sub.5) function, R.sub.4 and R.sub.5 being such as defined above; iv) reduction of the double bond at 2-3 or 3-4 present in the ring of the compound obtained in the preceding step, step iv) being able to be performed after any one of steps i), ii), or iii).

2. The method according to claim 1, wherein step iii) comprises a step iii.a) of reduction of the ketone function of the compound obtained in steps i), ii) or iv) to obtain a compound of formula (Ib): ##STR00060## with R.sub.1, R.sub.2, R.sub.3 such as defined above in step i) and/or ii) in claim 1, R.sub.4 represents a hydrogen or a C.sub.1-C.sub.8 alkyl or C.sub.2-C.sub.8 alkenyl group, and the double bond at 2-3 or 3-4 being absent in the case in which step iv) is performed before step iii.a).

3. The method according to claim 1, wherein the reduction reaction is performed by addition of an organomagnesium or of a metallic hydride.

4. The method according to claim 2 wherein step iii) comprises, in addition to step iii.a), a step iii.b) of alkylation of the alcohol function of the compound (Ib) obtained in step iii.a), to obtain a compound of formula (Ic): ##STR00061## with R.sub.1, R.sub.2, R.sub.3, R.sub.4 such as defined in claim 2, R.sub.5 represents an alkyl or an alkenyl, and the double bond at 2-3 or 3-4 being absent in the case in which step iv) is performed before step iii.b).

5. The method according to claim 4 wherein the alkylation step iii.b) is performed by addition of an alkyl halide.

6. The method according to claim 2, wherein step iii) comprises, in addition to step iii.a), a step iii.c) of esterification of the alcohol function of the compound (Ib) obtained in step iii.a), to obtain a compound (Id) ##STR00062## with R.sub.1, R.sub.2, R.sub.3, R.sub.4 such as defined in claim 2, R.sub.5 represents an alkanoyl or an alkenoyl, and the double bond at 2-3 or 3-4 being absent in the case in which step iv) is performed before step iii.c).

7. The method according to claim 6 wherein the esterification step iii.c) is performed by addition of an acyl chloride or of an anhydride.

8. The method of preparation of a compound of formula (I) according to claim 1 wherein the inorganic base of step i) is selected from the group consisting of KOH, NaOH and LiOH.

Description

EXAMPLE 1

Preparation of 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone

(1) 3-pentanone (129 g, 1.5 mol, 1.5 eq.) methylene-campholenaldehyde (prepared from 153 g, 1 mol, 1 eq. Campholenaldehyde and 1.1 eq. of formaldehyde) and potassium hydroxide (11.2 g, 0.2 mol, 0.2 eq.) in a water/ethanol mixture (300 ml/200 ml) are heated to 65 C. for one night. Once the reaction has finished, the reaction mixture is cooled and 0.2 eq. of acetic acid is added. The aqueous phase is extracted 3 times with methyl and t-butyl ether and the reunited organic phases are washed with brine, dried over magnesium sulphate and filtered.

(2) The solvents are evaporated and the raw product is purified by distillation to give 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone in the form of a colourless oil with a yield of 57% over the 2 steps. It is a mixture of 4 observable isomers in a ratio 12:40:33:15.

(3) B.p.: 105-107 C./0.5 torr

(4) Olfactive profile: Woody (cedar), ambery, spicy (pepper)

(5) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) common protons 1.4-1.90 (m, 2H), 1.55-1.65 (m, 3H), 1.7-1.8 (m, 3H), 1.90-2.2 (m, 2H), 2.2-2.5 (m, 2H), 2.5-2.65 (m, 1H), 5.22 (m, 1H).

(6) Majority isomers (characteristic protons): 0.96 (s, 3H), 1.09 (s, 3H), 1.13 (d, J=7.04 Hz), 6.64 (broad s, 1H)

(7) Second majority isomer (characteristic protons): 0.92 (s, 3H), 1.06 (s, 3H), 1.12 (d, J=6.67 Hz), 6.66 (broad s, 1H)

(8) Minority isomer (characteristic protons): 0.92 (s, 3H), 1.04 (s, 3H), 1.14 (d, J=5.68 Hz), 6.77 (broad s, 1H)

(9) Second minority isomer (characteristic protons): 0.96 (s, 3H), 1.06 (s, 3H), 1.14 (d, J=5.68 Hz), 6.85 (br d, 1H)

(10) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(11) Majority isomer: 12.52; 15.28; 16.43; 19.31; 27.03; 34.75; 35.43; 35.62; 38.23; 47.31; 52.0; 121.24; 133.99; 134.94; 148.82; 202.72.

(12) Second majority isomer: 12.47; 15.67; 16.43; 19.93; 27.44; 33.64; 38.54; 39.28; 41.57; 47.22; 53.80; 121.24; 133.99; 134.94; 148.39; 202.29.

(13) First minority isomer: 12.47; 15.67; 16.43; 20.08; 28.04; 33.95; 37.64; 38.85; 41.73; 46.99; 54.01; 121.19; 133.46; 134.51; 148.68; 202.32.

(14) Second minority isomer: 12.52; 15.85; 16.35; 19.74; 27.24; 34.75; 35.50; 35.83; 37.69; 46.72; 53.18; 120.99; 134.51; 134.94; 148.73; 202.72.

EXAMPLE 2

Preparation of 2,6-dimethyl-4-((R)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone

(15) As described in example 1, 2,6-dimethyl-4-((R)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone is prepared from R-(+)-campholenaldehyde with a yield of 49% over the 2 steps, it is a 12:36:35:17 mixture of observable isomers.

(16) B.p.: 100 C./0.5 torr

(17) Olfactive profile: nutty, anise

(18) The analyses are in accordance with those obtained in example 1.

EXAMPLE 3

Preparation of 2,6-dimethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone

(19) As described in example 1, 2,6-dimethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone is prepared from S-()-campholenaldehyde with a yield of 43% over the 2 steps, it is a 12:43:30:15 mixture of observable isomers.

(20) B.p.: 101-102 C./0.5 torr

(21) Olfactive profile: Roots, woody, vetiver, pepper

(22) The analyses are in accordance with those obtained in example 1.

EXAMPLE 4

Preparation of 2,6-diethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone

(23) 2,6-diethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone is obtained with a yield of 33%, according to example 1, from 5-heptanone and methylene-campholenaldehyde.

(24) It is a 32:40:28 mixture of 3 isomers observable with a non-polar GPC column.

(25) B.p.: 120 C./0.5 torr

(26) Olfactive profile: Spicy, curry

(27) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) common protons 0.8-1.2 (m, 12H), 1.3-1.6 (m, 2H), 1.6 (m, 3H), 1.6-2.1 (m, 4H), 2.15 (q, J=7.4 Hz, 2H), 2.25-2.4 (m, 2H), 2.5-2.65 (m, 1H), 5.21 (m, 1H).

(28) Majority isomers (characteristic protons70%): 6.57 (br s, 1H)

(29) Minority isomer (characteristic protons15%): 6.72 (br s, 1H)

(30) Minority isomer (characteristic protons15%): 6.76 (br d, 1H)

(31) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(32) 2 Majority isomers (70% 50:50): 11.23 & 11.75 (CH.sub.3), 12.43 & 12.49 (CH.sub.3), 13.01 & 13.09 (CH.sub.3), 19.44 & & 20.04 (CH.sub.3), 22.20 & 22.79 & 22.94 (2CH.sub.2), 27.10 & 27.52 (CH.sub.3), 32.48 & 33.48 (CH.sub.2), 34.54 & 35.52 (CH.sub.2), 34.92 & 38.37 (CH), 45.74 & 48.04 (CH), 47.27 (C.sup.IV), 52.67 & 53.98 (CH), 121.25 & 121.31 (CH), 139.67 & 140.85 (C.sup.IV), 146.44 & 148.73 (CH), 148.34 & 148.36 (C.sup.IV), 201.18 & 201.25 (C(O)).

(33) 2 minority isomers (30% 50:50, specific peaks): 11.23 & 11.57 (CH.sub.3), 12.43 & 12.49 (CH.sub.3), 12.83 & 12.88 (CH.sub.3), 13.01 & 13.09 (CH.sub.3), 19.85 & & 20.13 (CH.sub.3), 22.23 & 22.61 & 22.71 & 22.79 (2CH.sub.2), 27.38 & 28.03 (CH.sub.3), 32.21 & 33.48 (CH.sub.2), 33.97 & 34.03 (CH.sub.2), 38.83 (CH), 45.02 & 48.18 (CH), 47.02 (C.sup.IV), 53.48 & 54.30 (CH), 121.22 & 121.03 (CH), 146.58 & 146.67 (CH).

EXAMPLE 5

Preparation of 2,6-dimethyl-4-(2,4,4-trimethylcyclopentyl)cyclohex-2-enone

(34) 2,6-dimethyl-4-(2,4,4-trimethylcyclopentyl)cyclohex-2-enone is obtained with a yield of 25%, according to example 1, from 3-pentanone and 2-(2,4,4-trimethylcyclopentyl)acrylaldehyde (prepared from 2,4,4-trimethylcyclopentanone).

(35) It is a mixture of 5 isomers observable in a ratio 16:31:34:9:5:5.

(36) B.p.: 72 C./0.3 torr

(37) Olfactive profile: Dry woody, spicy, nutty.

(38) NMR-.sup.1H (CDCl.sub.3, 200 MHz): 4 observed diastereoisomers

(39) (ppm) common protons 0.8-1.4 (m, 15H), 1.4-1.75 (m, 3H), 1.75 (m, 3H), 1.75-2.10 (m, 2H), 2.2-2.4 (m, 1H), 2.4-2.7 (m, 1H).

(40) Majority isomers (characteristic protons62%): 6.58 (m, 1H)

(41) 1st minority isomers (characteristic protons18%): 6.49 (m, 1H)

(42) 2nd minority isomers (characteristic protons15%): 6.59 (m, 1H)

(43) 3rd minority isomers (characteristic protons5%): 6.67 (m, 1H)

(44) NMR-.sup.13C (CDCl.sub.3, 50 MHz): 6-7 observed diastereoisomers

(45) Majority isomers (characteristic peaks41%): 202.59 (C(O)), 147.66 & 147.35 (CH), 135.33 & 134.24 (C.sup.IV)

(46) 2nd Majority isomers (characteristic peaks21%): 203.15 (C(O)), 149.71 (CH), 134.54 (C.sup.IV)

(47) 1st minority isomers (characteristic peaks16%): 203.09 (C(O)), 149.15 (CH), 133.28 (C.sup.IV)

(48) 2nd minority isomers (characteristic peaks12%): 202.49 (C(O)), 148.87 (CH), 134.54 & 134.49 (C.sup.IV)

(49) 3rd minority isomers (characteristic peaks6%): 202.79 (C(O)), 148.07 (CH), 133.59 (C.sup.IV)

(50) 4th minority isomers (characteristic peaks3%): 202.96 (C(O)), 147.98 (CH), 133.49 (C.sup.IV)

EXAMPLE 6

Preparation of 2,6-dimethyl-4-(1-phenyl-ethyl)cyclohex-2-enone

(51) 2,6-dimethyl-4-(1-phenyl-ethyl)cyclohex-2-enone is obtained with a yield of 54% during the 2 steps, according to example 1, from 3-pentanone and 2-methylene-3-phenylbutanal (prepared from 3-phenylbutanal).

(52) It is a mixture of 4 observable isomers in a ratio 17:29:23:31.

(53) B.p.: 115 C./0.5 torr

(54) Olfactive profile: floral, balsamic, honey-like.

(55) NMR-.sup.1H (CDCl.sub.3, 200 MHz): 4 observed diastereoisomers

(56) (ppm) common protons 0.95-1.15 (m, 3H), 1.22-1.35 (m, 3H), 1.25-2.10 (m, 2H), 1.62-1.80 (m, 3H), 2.15-2.90 (m, 3H), 7.12-7.35 (m, 5H).

(57) Majority isomers (characteristic protons31%): 6.65-6.70 (m, 1H)

(58) Majority isomers (characteristic protons29%): 6.75-6.80 (m, 1H)

(59) Minority isomers (characteristic protons23%): 6.37-6.42 (m, 1H)

(60) Minority isomers (characteristic protons17%): 6.27-6.35 (m, 1H)

(61) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 4 observed diastereoisomers

(62) Majority isomers (characteristic peaks31%): 202.23 (C(O)), 146.42 (CH), 135.43 (C.sup.IV), 38.37, 36.88 (CH.sub.2), 17.84, 16.35, 15.15.

(63) 2nd Majority isomers (characteristic peaks29%): 202.52 (C(O)), 146.69 (CH), 134.44 (C.sup.IV), 40.12, 34.33 (CH.sub.2), 19.50, 16.47, 15.61.

(64) Minority isomers (characteristic peaks23%): 147.52 (CH), 134.95 (Cr), 39.40, 35.33 (CH.sub.2), 19.44, 16.22, 15.93.

(65) 2nd minority isomers (characteristic peaks17%): 147.28 (CH), 133.73 (C.sup.IV), 38.90, 33.39 (CH.sub.2), 18.04, 15.15, 15.27.

EXAMPLE 7

Preparation of 2,6-dimethyl-6-methylhept-5-en-2-yl)cyclohex-2-enone

(66) 2,6-dimethyl-4-(6-methylhept-5-en-2-yl)cyclohex-2-enone is obtained with a yield of 51% during the 2 steps, according to example 1, from 3-pentanone and 2-methylene-citronella (prepared from citronellal).

(67) It is a mixture of 4 observable isomers in a ratio 25:21:28:25.

(68) B.p.: 109-110 C./0.7 Torr

(69) Olfactive profile: floral, green, root, citronella, clean

(70) NMR-.sup.1H (CDCl.sub.3, 200 MHz): 3 observed diastereoisomers

(71) (ppm) common protons 1.11 (d, J=6.78 Hz, 3H), 1.10-1.70 (m, 4H), 1.58 (s, 3H), 1.66 (s, 3H), 1.74 (s, 3H), 1.75-2.20 (m, 3H), 2.20-2.65 (m, 2H), 5.07 (br t, 1H), 6.45-6.60 (m, 1H).

(72) Majority isomers (characteristic protons28%): 0.91 (d, J=6.06 Hz, 3H)

(73) Other isomers (characteristic protons): 0.87 (d, J=6.76 Hz, 3H, 2 isomers) & 0.82 (d, J=6.86 Hz, 3H)

(74) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 3 to 4 observed diastereoisomers

(75) 203.21 & 203.15 & 202.47 (C(O)), 149.36 & 148.89 & 148.16 & 147.86 (CH), 135.38 & 135.11 & 134.09 & 133.83 (C.sup.IV), 131.54 (C.sup.IV), 124.26 & 124.23 & 124.15 (CH), 42.11 & 41.66 & 41.5 & 41.43 (CH), 39.55 & 39.48 & 37.61 & 37.0 (CH), 36.37 & 36.04 & 36.0 (CH), 34.94 & 34.21 & 34.19 & 33.95 (CH.sub.2), 33.63 & 33.03 & 32.58 & 30.87 (CH.sub.2), 25.95 & 25.88 & 25.80 & 25.74 (CH.sub.2), 25.65 (CH.sub.3), 17.61 & 16.29 (CH.sub.3), 16.74 & 16.36 (CH.sub.3), 16.27 & 16.16 & 15.73 (CH.sub.3), 15.97 & 15.91 & 15.32 & 15.29 (CH.sub.3).

EXAMPLE 8

Preparation of 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enone

(76) 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enone is obtained with a yield of 56% during the 2 steps, according to example 1, from 3-pentanone and 2-methylene-3,5,5-Trimethylhexanal (prepared from 3,5,5-Trimethylhexanal).

(77) It is a mixture of 4 observable isomers in a ratio 23:17:30:30.

(78) B.p.: 88-92 C./0.4 torr

(79) Olfactive profile: woody, ambery, slightly sandalwood, hazelnut.

(80) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.75-1.37 (m, 2H), 0.87-0.95 (m, 12H), 1.12 (d, J=7.2 Hz, 3H), 1.37-2.0 (m, 3H), 1.76 (m, 3H), 2.20-2.62 (m, 2H), 6.45-6.57 (m, 1H).

(81) NMR-.sup.13C (CDCl.sub.3, 75 MHz): selected data

(82) 196.52 (C(O)), 149.06 & 148.64 & 148.60 & 148.20 (CH), 135.75 & 135.37 & 134.33 (C.sup.IV), 48.46 & 47.97 & 47.92 & 47.74 (CH.sub.2), 34.80 & 34.17 (CH.sub.2), 32.40 & 31.67 & 31.02 (C.sup.IV), 29.89 (3 CH.sub.3).

EXAMPLE 9

Preparation of 4-isopropyl-2,6-dimethylcyclohex-2-enone

(83) 4-isopropyl-2,6-dimethylcyclohex-2-enone is obtained with a yield of 54% during the 2 steps, according to example 1, from 3-pentanone and 2-methylene-isovaleraldehyde (prepared from isovaleraldehyde).

(84) It is a mixture of 2 observable isomers in a ratio 27:76.

(85) B.p.: 62 C./1 torr

(86) Olfactive profile: green, citrus, grapefruit peel.

(87) NMR-.sup.1H (CDCl.sub.3, 200 MHz): common protons 1.30-1.55 (m, 1H), 1.62-1.82 (m, 1H), 1.76 (m, 3H), 1.82-2.0 (m, 1H), 2.20-2.41 (m, 1H).

(88) Majority isomers (characteristic protons): (ppm) 0.89 (d, J=6.73 Hz, 3H), 0.92 (d, J=6.66 Hz, 3H), 1.12 (d, J=6.64 Hz, 3H), 2.20-2.41 (m, 1H), 6.55 (m, 1H).

(89) Minority isomers: (ppm) 0.95 (d, J=6.72 Hz, 3H), 0.95 (d, J=6.72 Hz, 3H), 1.12 (d, J=7.2 Hz, 3H), 2.45-2.60 (m, 1H), 6.61 (m, 1H).

(90) NMR-.sup.13C (CDCl.sub.3, 75 MHz):

(91) Majority isomers: 202.60 (C(O)), 148.33 (CH), 135.18 (C.sup.IV), 42.99 (CH), 41.50 (CH), 34.32 (CH.sub.2), 31.81 (CH), 19.40 (CH.sub.3), 19.01 (CH.sub.3), 16.24 (CH.sub.3), 15.32 (CH.sub.3).

(92) Minority isomers, specific peaks: 148.05 (CH), 133.89 (C.sup.IV), 39.28 (CH), 39.01 (CH), 32.38 (CH.sub.2), 31.46 (CH), 20.11 (CH.sub.3), 20.06 (CH.sub.3), 16.35 (CH.sub.3), 15.94 (CH.sub.3).

EXAMPLE 10

Preparation of 4-butyl-2,6-diethylcyclohex-2-enone

(93) 4-butyl-2,6-diethylcyclohex-2-enone is obtained with a yield of 16% over the 2 steps, according to example 1, from 4-heptanone and 2-methylene-hexanal (prepared from hexanal).

(94) It is a mixture of 2 observable isomers in a ratio 51:49.

(95) B.p.: 115 C./0.5 torr

(96) Olfactive profile: woody, hazelnut.

(97) NMR-.sup.1H (CDCl.sub.3, 300 MHz): (ppm) 0.85-1.0 (m, 9H), 1.1-1.55 (m, 8H), 1.58-1.78 (m, 1H), 1.84-1.98 (m, 1H), 2.0-2.3 (m, 3H), 2.32-2.44 (m, 1H), 6.42-6.47 (m, 1H).

(98) NMR-.sup.13C (CDCl.sub.3, 75 MHz): (ppm) 202.27 & 201.41 (C(O)), 147.62 & 147.0 (CH), 140.12 & 138.88 (C.sup.IV), 47.78 & 46.25 (CH), 36.70 & 32.76 (CH), 35.61 & 34.38 (CH.sub.2), 34.50 & 32.44 (CH.sub.2), 29.29 & 28.72 (CH.sub.2), 22.85 & 22.71 & 22.69 & 22.58 & 22.50 & 22.14 (3 CH.sub.2), 13.94 (CH.sub.3), 12.92 & 12.86 (CH.sub.3), 11.79 & 11.11 (CH.sub.3).

EXAMPLE 11

Preparation of 2,6-dimethyl-4-propylcyclohex-2-enone

(99) 2,6-dimethyl-4-propylcyclohex-2-enone is obtained with a yield of 17% over the 2 steps, according to example 1, from 3-pentanone and 2-methylene-valeraldehyde (prepared from pentanal).

(100) It is a mixture of 2 observable isomers in a ratio 54:46.

(101) B.p.: 70 C./0.5 torr

(102) Olfactive profile: grapefruit, very green, cocoa chocolate.

(103) NMR-.sup.1H (CDCl.sub.3, 200 MHz):

(104) (ppm) common protons 0.85-0.97 (m, 3H), 1.1 (d, J=7 Hz, 3H), 1.20-1.50 (m, 4H), 1.70-1.75 (m, 3H), 1.75-2.08 (m, 2H), 2.20-2.60 (m, 2H).

(105) Majority isomers (characteristic proton): 6.54-6.59 (m, 1H)

(106) Minority isomers (characteristic proton): 6.48-6.54 (m, 1H)

(107) NMR-.sup.13C (CDCl.sub.3, 50 MHz):

(108) Majority isomers: 202.98 (C(O)), 148.92 (CH), 133.30 (C.sup.IV), 38.52, 38.28 (CH.sub.2), 35.58 (CH.sub.2), 32.99, 20.53 (CH.sub.2), 16.23, 15.72, 14.08.

(109) Minority isomers: 202.56 (C(O)), 149.56 (CH), 134.32 (C.sup.IV), 41.41, 37.92 (CH.sub.2), 36.57, 36.20 (CH.sub.2), 19.64 (CH.sub.2), 16.12, 15.22, 14.04.

EXAMPLE 12

Preparation of 4-butyl-2,6-dimethylcyclohex-2-enone

(110) 4-butyl-2,6-dimethylcyclohex-2-enone is obtained with a yield of 40% over the 2 steps, according to example 1, from 3-pentanone and 2-methylene-hexanal (prepared from hexanal).

(111) It is a mixture of 2 observable isomers in a ratio 57:43.

(112) B.p.: 65 C./0.8 torr

(113) Olfactive profile: Green, rhubarb, powerful, slightly lavender, mushroom.

(114) NMR-.sup.1H (CDCl.sub.3, 200 MHz):

(115) (ppm) common protons 0.85-0.95 (m, 3H), 1.1 (d, J=7 Hz, 3H), 1.18-1.62 (m, 6H), 1.70-1.75 (m, 3H), 1.76-2.08 (m, 2H), 2.20-2.60 (m, 2H).

(116) Majority isomers (characteristic proton): 6.54-6.59 (m, 1H)

(117) Minority isomers (characteristic proton): 6.48-6.54 (m, 1H)

(118) NMR-.sup.13C (CDCl.sub.3, 50 MHz):

(119) Majority isomers: 202.93 (C(O)), 148.91 (CH), 133.27 (C.sup.IV), 38.51, 35.61 (CH.sub.2), 33.72 (CH.sub.2), 33.23, 29.60 (CH.sub.2), 22.72 (CH.sub.2), 16.20, 15.71, 13.94.

(120) Minority isomers: 202.50 (C(O)), 149.56 (CH), 134.31 (C.sup.IV), 41.40, 38.30 (CH.sub.2), 36.79, 35.40 (CH.sub.2), 28.69 (CH.sub.2), 22.67 (CH.sub.2), 16.10, 15.20, 13.94.

EXAMPLE 13

Preparation of 4-hexyl-2,6-dimethylcyclohex-2-enone

(121) 4-hexyl-2,6-dimethylcyclohex-2-enone is obtained with a yield of 35% over the 2 steps, according to example 1, from 3-pentanone and 2-methylene-octanal (prepared from octanal). It is a mixture of 2 observable isomers in a ratio 48:52.

(122) B.p.: 105 C./0.5 torr

(123) Olfactive profile: aldehyde, fresh and clean linen, household soap, hay-like.

(124) NMR-.sup.1H (CDCl.sub.3, 200 MHz):

(125) (ppm) common protons 0.83-1.04 (m, 3H), 1.12 (d, J=6.8 Hz, 3H), 1.22-1.50 (m, 10H), 1.73-1.78 (m, 3H), 1.75-2.10 (m, 2H), 2.10-2.65 (m, 2H).

(126) Minority isomers (characteristic proton): 6.54-6.59 (m, 1H)

(127) Majority isomers (characteristic proton): 6.50-6.55 (m, 1H)

(128) NMR-.sup.13C (CDCl.sub.3, 50 MHz):

(129) Minority isomers: 198.20 (C(O)), 148.95 (CH), 38.59, 38.36 (CH.sub.2), 35.68 (CH.sub.2), 33.31, 31.78 (CH.sub.2), 29.38 (CH.sub.2), 27.44 (CH.sub.2), 22.62 (CH.sub.2), 16.27, 15.78, 14.06.

(130) Majority isomers: 196.54 (C(O)), 149.60 (CH), 134.38 (C.sup.IV), 41.47, 36.88, 35.78 (CH.sub.2), 34.10 (CH.sub.2), 31.78 (CH.sub.2), 29.33 (CH.sub.2), 26.52 (CH.sub.2), 22.62 (CH.sub.2), 16.17, 15.29, 14.06.

EXAMPLE 14

Preparation of (R)-2,2,6,6-tetramethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enone

(131) To a solution in THF of 2,6-dimethyl-4-((R)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone (obtained according to example 2) are added 1.1 molar equivalent of potassium t-butylate. After 2 hours of agitation at ambient temperature, 1.1 molar equivalent of methyl iodide are added drop by drop to the reaction mixture. 1.1 molar equivalent of potassium t-butylate are also then added and the reaction mixture is heated to 40 C. for 2 hours, then a new 1.1 molar of methyl iodide is added. After agitation at 40 C. for one night, the reaction mixture is diluted with methyl and t-butyl ether and poured into a 10% aqueous HCl solution. The aqueous phase is extracted twice with methyl and t-butyl ether and the reunited organic phases are washed with a saturated aqueous solution of sodium bicarbonate. The organic phase is dried over magnesium sulphate, filtered and the solvents are evaporated. The raw product thus obtained is purified by distillation to give (R)-2,2,6,6-tetramethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enone in the form of a colourless oil with a yield of 64%.

(132) B.p.: 93 C./0.5 torr

(133) Olfactive profile: Dusty, musty

(134) IR (film, cm.sup.1): 564 m, 581 m, 797 m, 857 w, 997 w, 1013 w, 1047 m, 1360 m, 1381 m, 1466 m, 1706 s, 2866 w, 2927 m, 2958 m.

(135) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.75 (s, 3H), 1.05 (s, 3H), 1.09 (s, 3H), 1.11 (s, 3H), 1.11 (s, 3H), 1.13 (s, 3H), 1.58 (m, 3H), 2.10-2.40 (m, 2H), 2.22 (q, J=16.54 Hz, 2H), 2.50 (t, J=8.22 Hz, 1H), 5.22-5.29 (m, 1H), 5.39-5.43 (m, 1H).

(136) NMR-.sup.13C (CDCl.sub.3, 75 MHz): (ppm) 12.67 (CH.sub.3), 21.10 (CH.sub.3), 25.40 (CH.sub.3), 25.61 (CH.sub.3), 26.77 (CH.sub.3), 27.19 (CH.sub.3), 27.21 (CH.sub.3), 33.01 (CH.sub.2), 41.96 (CH.sub.2), 43.08 (C.sup.IV), 43.76 (C.sup.IV), 48.17 (C.sup.IV), 57.83 (CH), 121.36 (CH), 131.70 (CH), 134.91 (C.sup.IV), 147.43 (C.sup.IV), 219.92 (C(O)).

EXAMPLE 15

Preparation of (S)-2,2,6,6-tetramethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enone

(137) (S)-2,2,6,6-tetramethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enone is obtained with a yield of 46% according to example 14 from 2,6-dimethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone (obtained in example 3).

(138) B.p.: 92 C./0.5 torr

(139) Olfactive profile: Woody, fresh, musty

(140) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.76 (s, 3H), 1.05 (s, 3H), 1.10 (s, 3H), 1.12 (s, 6H), 1.14 (s, 3H), 1.59 (m, 3H), 2.10-2.40 (m, 2H), 2.22 (q, J=16.53 Hz, 2H), 2.51 (t, J=8.23 Hz, 1H), 5.23-5.30 (m, 1H), 5.40-5.44 (m, 1H).

(141) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm) 12.66 (CH.sub.3), 21.08 (CH.sub.3), 25.39 (CH.sub.3), 25.60 (CH.sub.3), 26.75 (CH.sub.3), 27.17 (CH.sub.3), 27.19 (CH.sub.3), 33.00 (CH.sub.2), 41.94 (CH.sub.2), 43.06 (C.sup.IV), 43.74 (C.sup.IV), 48.16 (C.sup.IV), 57.81 (CH), 121.35 (CH), 131.68 (CH), 134.89 (C.sup.IV), 147.41 (C.sup.IV), 219.90 (C(O)).

EXAMPLE 16

Preparation of 4-(4,4-dimethylpentan-2-yl)-2,2,6,6-tetramethylcyclohex-3-enone

(142) 4-(4,4-dimethylpentan-2-yl)-2,2,6,6-tetramethylcyclohex-3-enone is obtained with a yield of 30% according to example 14 from 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enone (obtained in example 9).

(143) B.p.: 75 C./0.4 torr

(144) Olfactive profile: Woody, peppery, slightly fruity and ambery.

(145) NMR-.sup.1H (CDCl.sub.3, 300 MHz): (ppm) 0.89 (s, 9H), 0.9-1.35 (m, 1H), 1.01 (d, J=6.93 Hz, 3H), 1.07 (s, 3H), 1.08 (s, 3H), 1.10 (s, 3H), 1.12 (s, 3H), 1.36-1.46 (m, 1H), 2.04-2.2 (m, 2H), 2.23-2.38 (m, 1H), 5.30 (s, 1H).

(146) NMR-.sup.13C (CDCl.sub.3, 75 MHz): (ppm) 220.10 (C(O)), 140.23 (C.sup.IV), 128.24 (CH), 48.04 (CH.sub.2), 43.44 (C.sup.IV), 42.84 (C.sup.IV), 38.16 (CH.sub.2), 37.18 (CH), 31.22 (C.sup.IV), 29.88 (3 CH.sub.3), 27.24 (CH.sub.3), 26.46 (CH.sub.3), 25.52, 25.43, 22.43.

EXAMPLE 17

Preparation of 4-Isopropyl-2,2,6,6-tetramethylcyclohex-3-enone

(147) 4-isopropyl-2,2,6,6-tetramethylcyclohex-3-enone is obtained with a yield of 46% according to example 14 from 4-isopropyl-2,6-dimethylcyclohex-2-enone (obtained in example 10).

(148) B.p.: 86-87 C./9 torr

(149) Olfactive profile: camphor, earthy, woody, animal.

(150) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 1.01 (d, J=6.81 Hz, 1H), 1.09-1.12 (m, 12H), 2.14 (s, 2H), 2.25 (hept, J=13.80 Hz, 1H), 5.28 (s, 1H).

(151) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm) 215.8 (C(O)), 140.12 (C.sup.IV), 127.13 (CH), 43.41 (C.sup.IV), 42.89 (C.sup.IV), 39.11 (CH.sub.2), 34.72 (CH), 27.16 (2CH.sub.3), 25.42 (2CH.sub.3), 20.90 (2CH.sub.3).

EXAMPLE 18

Preparation of 4-Isopropyl-2,6-dimethyl-2,6-dipropylcyclohex-3-enone

(152) 4-isopropyl-2,6-dimethyl-2,6-dipropylcyclohex-3-enone is obtained with a yield of 39% according to example 14 from 4-isopropyl-2,6-dimethylcyclohex-2-enone (obtained in example 10) and 1-bromopropane.

(153) B.p.: 75 C./0.5 torr

(154) Olfactive profile: Weak head, sweat, dusty, dry woody, slightly cassis.

(155) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.83 (t, J=6.81 Hz, 6H), 0.97-1.07 (m, 12H), 1.07-1.37 (m, 5H), 1.37-1.55 (m, 2H), 1.65-2.15 (m, 3H), 2.28 (hept, J=13.70 Hz, 1H), 5.20 (s, 1H).

(156) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm) 217.8 (C(O)), 141.33 (C.sup.IV), 125.40 (CH), 47.61 (C.sup.IV), 46.43 (C.sup.IV), 43.86 (CH.sub.2), 40.0 (CH.sub.2), 37.20 (CH.sub.2), 35.08 (CH), 26.81 (CH.sub.3), 22.55 (CH.sub.3), 21.14 (CH.sub.3), 21.03 (CH.sub.3), 18.52 (CH.sub.2), 17.31 (CH.sub.2), 14.60 (CH.sub.3), 14.53 (CH.sub.3).

EXAMPLE 19

Preparation of 2,2,6,6-tetramethyl-4-((1R)-2,2,3-trimethylcyclo-pentyl)cyclohex-3-enone

(157) A 1M solution in toluene of (S)-2,2,6,6-tetramethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enone (obtained in example 15) with 5% by weight of 5% palladium on carbon is hydrogenated (p(H.sub.2)=20 bars) at ambient temperature. Once the reaction has finished (GPC monitoring), the mixture is filtered over a Celite cake and the solvents are evaporated. The raw oil thus obtained is distilled to give 2,2,6,6-tetramethyl-4-((1R)-2,2,3-trimethylcyclopentyl)cyclohex-3-enone and 2,2,6,6-tetramethyl-4-(2,3,3-trimethylcyclopent-1-enyl)cyclohexanone (72:28) with a yield of 78%.

(158) B.p.: 95 C./0.6 torr

(159) Olfactive profile: Animal, cresol, phenol

2,2,6,6-tetramethyl-4-((1R)-2,2,3 trimethylcyclopentyl)cyclohex-3-enone

(160) NMR-.sup.1H (CDCl.sub.3, 300 MHz): (ppm)

(161) 0.54 (s, 3H), 0.83 (d, J=6.78 Hz, 3H), 0.92 (s, 3H), 1.09 (s, 3H), 1.11 (s, 6H), 1.13 (s, 3H), 1.15-1.30 (m, 1H), 1.50-1.85 (m, 4H), 2.07-2.22 (m, 1H), 2.30 (d, J=15.97 Hz, 1H), 2.12 (d, J=16.45 Hz, 1H), 5.35 (m, 1H).

(162) NMR-.sup.13C (CDCl.sub.3, 75 MHz): (ppm) 220.14 (C(CO)), 134.45 (C.sup.IV), 131.87 (CH), 58.07 (CH), 45.17 (CH), 43.79 (2C.sup.IV), 43.25 (C.sup.IV), 42.14 (CH.sub.2), 29.72 (CH.sub.2), 27.25 (CH.sub.3), 27.18 (CH.sub.3), 26.60 (CH.sub.3), 25.57 (CH.sub.3), 25.46 (CH.sub.2), 25.38 (CH.sub.3), 15.68 (CH.sub.3), 14.11 (CH.sub.3).

2,2,6,6-Tetramethyl-4-(2,3,3-trimethylcyclopent-1-enyl)cyclohexanone

(163) NMR-.sup.1H (CDCl.sub.3, 300 MHz): (ppm)

(164) 0.88 (d, J=6.69 Hz, 3H), 0.90 (s, 3H), 1.06 (s, 3H), 1.08 (s, 3H), 1.09 (s, 3H), 1.11 (s, 3H), 1.19 (s, 3H), 1.55-1.85 (m, 2H), 2.07-2.29 (m, 2H), 2.22 (d, J=16.67 Hz, 1H), 2.34 (d, J=16.02 Hz, 1H), 2.58-2.64 (m, 2H), 5.35 (m, 1H).

(165) NMR-.sup.13C (CDCl.sub.3, 75 MHz): (ppm) 220.55 (C(CO)), 146.79 (C.sup.IV), 122.07 (C.sup.IV), 46.91 (CH), 44.16 (C.sup.IV), 43.91 (C.sup.IV), 43.49 (C.sup.IV), 42.90 (CH.sub.2), 39.82 (CH.sub.2), 30.77 (CH.sub.2), 30.67 (CH.sub.2), 27.09 (CH.sub.3), 26.99 (CH.sub.3), 26.91 (CH.sub.3), 26.85 (CH.sub.3), 26.77 (CH.sub.3), 20.53 (CH.sub.3), 13.48 (CH.sub.3).

EXAMPLE 20

Preparation of 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohexanone

(166) 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohexanone is obtained with a yield of 81% according to example 19 from 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enone (obtained in example 9).

(167) It is a mixture of 2 main isomers (91%) in a ratio 29:71.

(168) B.p.=76 C./0.4 torr

(169) Olfactive profile: Woody, ambery, dusty, slightly flowery.

(170) NMR-.sup.1H (CDCl.sub.3, 300 MHz): common protons (ppm) 0.85-0.94 (m, 12H), 0.94-1.03 (m, 6H), 1.04-1.41 (m, 4H), 1.41-1.55 (m, 1H), 1.6-2.15 (m, 3H).

(171) Majority isomers (characteristic peak): 2.33-2.48 (m, 2H).

(172) Minority isomers (characteristic peak): 2.48-2.62 (m, 2H).

(173) NMR-.sup.13C (CDCl.sub.3, 75 MHz):

(174) Majority isomers: (ppm) 214.81 (C(CO)), 48.54 (CH.sub.2), 44.41 (CH), 44.30 (CH), 43.70 (CH), 40.13 (CH.sub.2), 38.66 (CH.sub.2), 32.76 (CH), 30.95 (C.sup.IV), 29.84 (3 CH.sub.3), 19.09 (CH.sub.3), 14.63 (CH.sub.3), 14.59 (CH.sub.3).

EXAMPLE 21

Preparation of 2,6-diethyl-4-Isopropyl-2,6-dimethylcyclohexanone

(175) 2,6-diethyl-4-isopropyl-2,6-dimethylcyclohexanone is obtained with a yield of 40% over 2 steps (hydrogenation according to example 19, followed by alkylation with bromoethane according to example 14), from cyclohexenone obtained in example 10.

(176) It is a mixture of observable stereoisomers in a ratio 6:16:57:21.

(177) B.p.=63-65 C./0.4 torr

(178) Olfactive profile: Woody, slightly nutty, hazelnut, plastic, slightly rosey.

(179) NMR-.sup.1H (CDCl.sub.3, 300 MHz): common protons (ppm) 0.71-0.83 (m, 6H), 0.84-0.94 (m, 6H), 1.11-1.3 (m, 2H), 1.3-1.58 (m, 4H), 1.58-1.95 (m, 4H).

(180) Majority isomers (characteristic peak): 0.97 (s, 6H).

(181) Minority isomers (characteristic peak): 0.96 & 1.06 & 1.07 (s, 3H).

(182) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 4 observed stereoisomers including 3 majority stereoisomers

(183) Majority isomers: (ppm) 220.09 & 219.40 (C(CO)), 41.45 & 40.70 & 39.31 (CH.sub.2), 39.15 (C.sup.IV), 34.18 (2C) & 34.07 (CH), 33.16 & 32.17 & 31.25 (CH.sub.2), 32.35 (2C) & 32.21 (CH), 26.37 & 24.65 & 24.41 (CH.sub.3), 19.84 & 19.72 & 19.62 (CH.sub.3), 8.75 & 8.38 & 8.27 (CH.sub.3).

(184) Minority isomers (characteristic peaks): (ppm) 38.62 (CH.sub.2), 34.28 (CH), 33.08 (CH.sub.2), 32.27 (CH), 27.57 (CH.sub.3), 19.72 (CH.sub.3), 8.71 (CH.sub.3).

EXAMPLE 22

Preparation of 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol

(185) To a suspension of lithium aluminium hydride (5.8 g, 0.151 mol, 1.3 eq. H) in 500 ml of diethyl ether, is added drop by drop at 20-25 C. 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone (108 g, 0.465 mol, 1 eq., obtained in example 1). Once the reaction has finished, a 10% aqueous HCl solution is added drop by drop to precipitate the alumina. After filtration and drying over magnesium sulphate, the solvents are evaporated and the raw product is purified by distillation to give 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol in the form of a colourless oil with a yield of 76%. It consists in a mixture of 5 observable main isomers in a ratio 6:24:23:32:15 with a non-polar GPC column.

(186) B.p.: 108-110 C./0.46 torr

(187) Olfactive profile: Sandalwood, sweet, milky

(188) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) common protons 0.88-0.93 (m, 3H), 0.93-1.15 (m, 6H), 1.42-1.72 (m, 6H), 1.72-1.81 (m, 3H), 1.81-2.07 (m, 2H), 2.11-2.4 (m, 2H), 5.21 (m, 1H).

(189) Majority isomers (characteristic protons, 32%): 3.65 (m, 1H), 5.43 (m, 1H) 2.sup.nd Majority isomers (characteristic protons, 220%): 3.55 (d, J=4.59 Hz, 1H) & 3.78 (d, J=3.57 Hz, 1H), 5.47-5.52 (m, 1H).

(190) Minority isomers (characteristic protons, 15%): 3.64 (m, 1H), 5.63 (m, 1H)

(191) Other minority isomers (characteristic protons, 6% & 7%): 3.72 & 3.90 (m, 1H), 5.66-5.74 (m, 1H)

(192) NMR-.sup.13C (CDCl.sub.3, 75 MHz): (ppm)

(193) Majority isomers (32%): 148.47 (C.sup.IV), 136.13 (C.sup.IV), 128.59 (CH), 121.42 (CH), 76.75 (CHOH), 54.76 (CH), 47.10 (C.sup.IV), 38.37 (CH), 38.09 (CH2), 37.72 (CH), 33.76 (CH.sub.2), 19.71 (CH.sub.3), 19.51 (CH.sub.3), 19.37 (CH.sub.3), 19.26 (CH.sub.3), 12.48 (CH.sub.3).

(194) Minority isomers (characteristic peaks, 55%): 148.54 & 148.48 & 148.42 (C.sup.IV), 135.79 & 134.97 & 134.14 (C.sup.IV), 129.17 & 129.08 & 128.94 (CH), 121.42 (2C) & 121.25 (CH), 76.75 & 74.79 & 71.61 (CHOH), 54.97 & 53.71 & 52.55 (CH), 47.14 & 47.08 & 46.90 (C.sup.IV).

(195) Other minority isomers (characteristic peaks, 6% & 7%): 149.11 & 148.89 (C.sup.IV), 134.56 & 133.98 (C.sup.IV), 129.13 & 129.06 (CH), 121.10 & 121.0 (CH), 75.28 & 71.43 (CHOH), 54.48 & 53.53 (CH), 46.77 & 46.62 (C.sup.IV).

EXAMPLE 23

Preparation of 2,6-dimethyl-4-((R)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol

(196) 2,6-dimethyl-4-((R)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol is obtained with a yield of 69%, according to example 22, from 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone (obtained in example 2).

(197) It is a mixture of 4 observable main isomers in a ratio 11:15:41:33 with a non-polar GPC column.

(198) B.p.: 100-102 C./0.5 torr

(199) Olfactive profile: Sandalwood, slightly green

(200) The analyses are in accordance with those obtained in example 24.

EXAMPLE 24

Preparation of 2,6-dimethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol

(201) 2,6-dimethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol is obtained with a yield of 66%, according to example 22, from 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone (obtained in example 3). It consists in a mixture of 4 observable main isomers in a ratio of 10:20:33:37 with a non-polar GPC column, 7 observable isomers in a ratio 18:6:2:15:27:24:8 with a GC polar GPC column.

(202) B.p.: 100-102 C./0.5 torr

(203) Olfactive profile: Sandalwood, creamy, gourmand, hazelnut, slightly spicy, leathery

(204) IR (film, cm.sup.1): 564 w, 580 w, 880 m, 1046 s, 1088 m, 1378 w, 2875 w, 2971 w, 3318 w br.

(205) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) common protons 0.85-0.92 (m, 3H), 0.92-1.2 (m, 6H), 1.58 (m, 6H), 1.6-1.85 (m, 4H), 1.85-2.1 (m, 1H), 2.1-2.4 (m, 2H), 5.21 (m, 1H).

(206) Isomer 27% (characteristic protons): 3.64 (d, J=6.50 Hz, 1H), 5.39-5.45 (m, 1H)

(207) Isomer 24% (characteristic protons): 3.55 (d, J=4.83 Hz, 1H), 5.45-5.54 (m, 1H)

(208) Isomer 18% (characteristic protons): 3.78 (d, J=3.89 Hz, 1H), 5.45-5.54 (m, 1H)

(209) Isomer 15% (characteristic protons): 3.64 (d, J=6.50 Hz, 1H), 5.65-5.75 (m, 1H)

(210) Minority isomer (8%, characteristic protons): 3.74 (d, J=3.98 Hz, 1H), 5.60-5.66 (m, 1H)

(211) Minority isomer (6%, characteristic protons): 3.91 (t, J=6.67 Hz, 1H), 5.60-5.66 (m, 1H)

(212) Minority isomer 2% (characteristic protons): 3.78 (d, J=3.89 Hz, 1H), 5.45-5.54 (m, 1H)

(213) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(214) Majority isomers: 12.52, 15.28, 16.43, 19.31, 27.03, 34.75, 35.43, 35.62, 38.23, 47.31, 52.0, 121.24, 133.99, 134.94, 148.82, 202.72.

(215) 2nd Majority isomers: 12.47, 15.67, 16.43, 19.93, 27.44, 33.64, 38.54, 39.28, 41.57, 47.22, 53.80, 121.24, 133.99, 134.94, 148.39, 202.29.

(216) Minority isomers: 12.47, 15.67, 16.43, 20.08, 28.04, 33.95, 37.64, 38.85, 41.73, 46.99, 54.01, 121.19, 133.46, 134.51, 148.68, 202.32.

(217) 2.sup.nd Minority isomers: 12.52, 15.85, 16.35, 19.74, 27.24, 34.75, 35.50, 35.83, 37.69, 46.72, 53.18, 120.99, 134.51, 134.94, 148.73, 202.72.

EXAMPLE 25

Preparation of 2,6-diethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol

(218) 2,6-diethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol is obtained with a yield of 67%, according to example 22, from 2,6-diethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enone (obtained in example 4).

(219) It is a mixture of 4 isomers in a ratio 4:17:32:47.

(220) B.p.: 120 C./0.45 torr

(221) Olfactive profile: Sandalwood, weaker than example 11

(222) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) common protons 0.89-0.94 (m, 3H), 0.94-1.0 (m, 3H), 1.0-1.05 (m, 3H), 1.05-1.16 (m, 3H), 1.16-1.58 (m, 4H), 1.56-1.61 (m, 3H), 1.61-2.12 (m, 4H), 2.12-2.37 (m, 3H).

(223) Isomers 47% (characteristic protons): 3.85 (d, J=9.32 Hz, 1H), 5.41-5.45 (m, 1H, 39%) & 5.63 (d, J=4.76 Hz, 1H, 8%)

(224) Isomers 32% (characteristic protons): 3.8 (d, J=9.4 Hz, 1H), 5.51 & 5.63 & 5.67 (m, 1H, 11% & 14% & 7%)

(225) Isomers 17% (characteristic protons): 3.65-3.73 (m, 1H), 5.48 (m, 1H)

(226) Isomers 4% (characteristic protons): 3.8 (d, J=9.4 Hz, 1H), 5.48 (m, 1H)

(227) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(228) Majority isomers: 148.39 (C.sup.IV), 141.89 (C.sup.IV), 126.81 (CH), 121.52 (CH), 68.61 (CHOH), 54.89 (CH), 47.20 (C.sup.IV), 44.99 (CH), 37.54 (CH), 33.98 (CH.sub.2), 33.55 (CH.sub.2), 27.49 (CH.sub.3), 25.75 (CH.sub.2), 25.52 (CH.sub.2), 19.91 (CH.sub.3), 12.78 (CH.sub.3), 12.47 (CH.sub.3), 11.12 (CH.sub.3).

(229) 2.sup.nd Majority isomers (specific peaks): 127.95 (CH), 121.47 (CH), 73.39 (CHOH)

(230) Minority isomers (specific peaks): 127.55 & 127.08 (CH), 121.31 & 121.03 (CH), 73.51 (CHOH)

EXAMPLE 26

Preparation of 2,6-dimethyl-4-(2,4,4-trimethylcyclopentyl)cyclohex-2-enol

(231) 2,6-dimethyl-4-(2,4,4-trimethylcyclopentyl)cyclohex-2-enol is obtained with a yield of 40%, according to example 22, from 2,6-dimethyl-4-(2,4,4-trimethylcyclopentyl)cyclohex-2-enone (obtained in example 5).

(232) The raw product was purified by chromatography on a silicon column, the expected alcohol consists in a mixture of 2 main isomers (83%) in a ratio of 19:81.

(233) Olfactive profile: Tobacco, smoky

(234) NMR-.sup.1H (CDCl.sub.3, 200 MHz): 3 observable isomers (50:30:20)

(235) (ppm) common protons 0.80-0.97 (m, 6H), 0.97-1.02 (m, 6H), 1.02-1.20 (m, 4H), 1.20-1.75 (m, 8H), 1.72-1.8 (m, 3H), 1.8-2.0 (m, 1H), 2.0-2.35 (m, 1H).

(236) 1st Isomers (characteristic protons): 3.55-3.67 (m, 1H), 5.40-5.46 (m, 1H).

(237) 2nd Isomers (characteristic protons): 3.77-3.82 (m, 1H), 5.33-5.34 (m, 1H).

(238) 3rd Isomers (characteristic protons): 3.50-3.55 (m, 1H), 5.26-5.32 (m, 1H).

(239) NMR-.sup.13C (CDCl.sub.3, 50 MHz): 6 observable isomers

(240) 1st Isomers (characteristic peaks): 136.49 (C.sup.IV), 127.49 (CH), 71.90 (CHOH), 51.90 (CH), 50.64 (CH.sub.2), 44.08 (CH.sub.2), 38.19 (CH), 37.07 (CH.sub.2).

(241) 2nd Isomers (characteristic peaks): 135.45 (C.sup.IV), 129.76 (CH), 77.14 (CHOH), 51.78 (CH), 50.56 (CH.sub.2), 45.81 (CH.sub.2), 38.71 (CH), 30.57 (CH.sub.2).

(242) 3rd Isomers (characteristic peaks): 135.41 (C.sup.IV), 127.10 (CH), 76.94 (CHOH), 51.69 (CH), 50.56 (CH.sub.2), 43.52 (CH.sub.2), 38.25 (CH), 32.54 (CH.sub.2).

EXAMPLE 27

Preparation of 2,6-dimethyl-6-methylhept-5-en-2-yl)cyclohex-2-enol

(243) 2,6-dimethyl-4-(6-methylhept-5-en-2-yl)cyclohex-2-enol is obtained with a yield of 56%, according to example 22, from 2,6-dimethyl-4-(6-methylhept-5-en-2-yl)cyclohex-2-enone (obtained in example 7).

(244) It is a mixture of isomers including 1 main isomer (75%).

(245) B.p.: 104 C./0.8 torr

(246) Olfactive profile: Rosey, citronellol, slightly woody, plastic.

(247) NMR-.sup.1H (CDCl.sub.3, 200 MHz): 2 observable isomers (70:30)

(248) (ppm) common protons 0.75-0.85 (m, 3H), 0.95-1.20 (m, 1H), 1.20-1.57 (m, 5H), 1.59 (s, 3H), 1.68 (s, 3H), 1.82-2.22 (m, 3H), 5.03-5.15 (m, 1H).

(249) 1st Isomers (characteristic protons): 1.08 (d, J=6.38 Hz, 3H), 1.72-1.76 (m, 3H), 3.63 (broad d, J=8.55 Hz, 1H), 5.26-5.34 (m, 1H).

(250) 2nd Isomers (characteristic protons): 0.97 (d, J=6.88 Hz, 3H), 1.76-1.80 (m, 3H), 3.88 (broad t, 1H), 5.36-5.44 (m, 1H).

(251) NMR-.sup.13C (CDCl.sub.3, 50 MHz): 4 observable isomers (2 majority isomers)

(252) (ppm) common peaks 131.18 (C.sup.IV), 124.82 & 124.77 (CH), 25.69 (CH.sub.3), 19.41 & 19.38 & 19.34.

(253) 1st Isomers (characteristic peaks): 136.39 & 136.04 (C.sup.IV), 129.35 & 128.15 (CH), 77.11 & 77.06 (CHOH), 41.33 & 40.78 (CH), 38.55 & 38.41 (CH), 36.71 & 36.69 (CH), 34.02 & 33.77 (CH.sub.2), 33.50 & 31.95 (CH.sub.2), 26.12 & 26.02 (CH.sub.2), 19.25 & 17.62 (CH.sub.3), 16.24 & 15.21 (CH.sub.3).

(254) 2nd Isomers (characteristic peaks): 135.41 & 135.10 (C.sup.IV), 128.25 & 127.32 (CH), 71.92 (2 CHOH), 38.27 & 37.80 (CH), 36.83 & 36.59 (CH), 34.53 & 34.44 (CH.sub.2), 31.79 & 31.73 (CH), 28.70 & 27.41 (CH.sub.2), 25.89 (2CH.sub.2), 20.87 & 20.76 (CH.sub.3), 17.09 & 16.70 (CH.sub.3), 15.21 & 15.08 (CH.sub.3).

EXAMPLE 28

Preparation of 4-(4,6-dimethylhept-5-enyl)-2,6-dimethylcyclohex-2-enol

(255) 4-(4,6-dimethylhept-5-enyl)-2,6-dimethylcyclohex-2-enol is obtained with a yield of 70%, according to example 22, from 4-(4,6-dimethylhept-5-enyl)-2,6-dimethylcyclohex-2-enone (obtained, according to example 1, with a yield of 16% during the 2 steps, from 3-pentanone and 5,7-dimethyl-2-methylene-oct-6-enal (prepared from 5,7-dimethyl-oct-6-enal)).

(256) The raw product is purified by chromatography on a silica column, the expected alcohol consists in a mixture of isomers including 2 main isomers (74%) in a ratio of 32:68.

(257) Olfactive profile: Weak head, slightly soapy, fruity, then woody, dusty.

(258) NMR-.sup.1H (CDCl.sub.3, 300 MHz): 3 observable isomers (60:27:13)

(259) (ppm) common protons 0.89 (d, J=6.60 Hz, 3H), 0.89-0.97 (m, 1H), 1.14-1.47 (m, 6H), 1.60 (s, 3H), 1.68 (s, 3H), 1.72-1.79 (m, 3H), 1.94-2.14 (m, 1H)

(260) 0.75-0.85 (m, 3H), 0.95-1.20 (m, 1H), 1.20-1.57 (m, 5H), 1.59 (s, 3H), 1.68 (s, 3H), 1.82-2.22 (m, 3H), 5.03-5.15 (m, 1H).

(261) Majority isomers (characteristic protons): 1.08 (d, J=6.48 Hz, 3H), 2.16-2.38 (m, 2H), 3.64 (broad d, J=7.8 Hz, 1H), 5.32 (m, 1H).

(262) 1st minority isomers (characteristic protons): 1.12 (d, J=6.78 Hz, 3H), 1.80-1.92 (m, 2H), 3.74 (d, J=3.75 Hz, 1H), 5.45 (m, 1H).

(263) 2nd minority isomers (characteristic protons): 0.99 (d, J=6.87 Hz, 3H), 2.38-2.61 (2H), 3.55 (d, J=4.68 Hz, 1H), 5.42 (m, 1H).

(264) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 3 observable isomers (2 majority isomers)

(265) 1st Majority isomers: (ppm) 135.30 (C.sup.IV), 130.04 & 130.0 (CH), 129.59 (C.sup.IV), 76.96 (CHOH), 38.28 (CH), 37.92 & 37.85 (CH.sub.2), 37.42 & 37.37 (CH.sub.2), 36.84 & 36.79 (CH.sub.2), 36.09 (CH), 32.3, 32.26, 25.75 (CH.sub.3), 24.45 & 24.42 (CH.sub.2), 19.28 (CH.sub.3), 19.25 (CH.sub.3), 17.91 (CH.sub.3).

(266) 2nd Isomers (characteristic peaks): (ppm) 134.39 (C.sup.IV), 129.52 & 129.44 (CH), 129.58 (C.sup.IV), 71.77 (CHOH).

EXAMPLE 29

Preparation of 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enol

(267) 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enol is obtained with a yield of 63%, according to example 22, from 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enone (obtained in example 9).

(268) It consists in a mixture of 6 isomers including 3 main isomers (80%) in a ratio of 30:45:25.

(269) B.p.: 90 C./0.4 torr

(270) Olfactive profile: woody, sandalwood, ambery, slightly flowery and musky.

(271) NMR-.sup.1H (CDCl.sub.3, 200 MHz): 3 observable isomers majoritarily

(272) (ppm) common protons 0.8-1.05 (m, 12H), 1.0-1.65 (m, 5H), 1.65-2.50 (m, 2H).

(273) Majority isomers (characteristic protons): 1.09 (d, J=6.31 Hz, 3H), 1.72-1.76 (m, 3H), 3.59-3.68 (m, 1H), 5.25-5.33 (m, 1H).

(274) Minority isomers (characteristic protons): 0.9-1.0 (m, 3H), 1.76-1.80 (m, 3H), 3.86-3.91 and 3.91-3.97 (2 m, 1H), 5.34-5.39 and 5.39-5.44 (2 m, 1H).

(275) NMR-.sup.13C (CDCl.sub.3, 50 MHz): 4 observable isomers (2 majority isomers)

(276) Majority isomers (characteristic peaks): 136.69 & 136.27 (C.sup.IV), 129.22 & 128.62 (CH), 77.17 & 77.11 (CHOH), 47.79 & 47.64 (CH.sub.2), 43.47 & 43.30 (CH), 38.50 & 38.47 (CH), 33.47 & 32.77 (CH.sub.2), 33.24 & 32.91 (CH), 29.97 (3 CH.sub.3), 28.79 & 27.91 (C.sup.IV).

(277) Minority isomers (characteristic peaks): 128.29 & 127.58 (CH), 72.08 & 71.95 (CHOH), 48.80 & 48.52 (CH.sub.2), 40.16 & 39.49 (CH), 33.38 & 33.09 (CH), 32.11 & 31.66 (CH), 31.07 & 30.98 (CH.sub.2), 29.97 (3 CH.sub.3), 28.79 & 27.91 (C.sup.IV).

EXAMPLE 30

Preparation of 4-Isopropyl-2,6-dimethylcyclohex-2-enol

(278) 4-isopropyl-2,6-dimethylcyclohex-2-enol is obtained with a yield of 73%, according to example 22, from 4-isopropyl-2,6-dimethylcyclohex-2-enone (obtained in example 10). It consists in a mixture of 4 observable isomers including 2 main (86%) in a ratio of 20:80.

(279) B.p.: 60 C./0.48 torr

(280) Olfactive profile: floral, rosey, citronellol.

(281) NMR-.sup.1H (CDCl.sub.3, 300 MHz): 3 observable isomers, 2 main isomers (20:80)

(282) (ppm) common protons 1.3-1.63 (m, 3H), 1.8-2.13 (m, 2H).

(283) Majority isomers (characteristic protons): 0.81 (d, J=6.84 Hz, 3H), 0.84 (d, J=6.78 Hz, 3H), 1.07 (d, J=6.33 Hz, 3H), 1.70-1.74 (m, 3H),

(284) Minority isomers (characteristic protons): 0.86 (d, J=6.66 Hz, 3H), 0.88 (d, J=6.69 Hz, 3H), 0.95 (d, J=6.87 Hz, 3H), 1.75-1.78 (m, 3H)

(285) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 2 observable isomers

(286) Majority isomers: (ppm) 136.29 (C.sup.IV), 128.21 (CH), 76.81 (CHOH), 42.27 (CH), 38.23 (CH), 33.24 (CH.sub.2), 32.07 (CH), 19.37 (CH.sub.3), 19.34 (CH.sub.3), 19.31 (CH.sub.3), 18.47 (CH.sub.3).

(287) Minority isomers: (ppm) 135.12 (C.sup.IV), 127.63 (CH), 71.60 (CHOH), 39.86 (CH), 31.87 (CH), 31.36 (CH), 28.09 (CH.sub.2), 20.87 (CH.sub.3), 20.50 (CH.sub.3), 20.47 (CH.sub.3), 15.42 (CH.sub.3).

EXAMPLE 31

Preparation of 2,6-diethyl-4-Isopropylcyclohex-2-enol

(288) 2,6-diethyl-4-isopropylcyclohex-2-enol is obtained with a yield of 72%, according to example 22, from 2,6-diethyl-4-isopropylcyclohex-2-enone (obtained with a yield of 27% over the 2 steps, according to example 1, from 4-heptanone and 2-methylene-isovaleraldehyde (prepared from isovaleraldehyde)).

(289) It consists in a mixture of 4 observable isomers including 2 main isomers (83%) in a ratio of 46:54.

(290) B.p.: 72 C./0.45 torr

(291) Olfactive profile: woody, fruity.

(292) NMR-.sup.1H (CDCl.sub.3, 300 MHz): 3 observable isomers, 2 main isomers (45:55)

(293) (ppm) common protons 0.81-0.98 (m, 9H), 0.98-1.07 (m, 3H), 1.12-1.43 (m, 2H), 1.43-1.63 (m, 3H), 1.63-1.75 & 1.91-2.04 (m, 1H), 1.76-1.90 (m, 1H), 2.04-2.26 (m, 1H).

(294) Majority isomers (characteristic protons): 3.78 (broad d, J=8.79 Hz, 1H), 5.35 (s, 1H).

(295) 1st Minority isomers (characteristic protons): 3.88 (s, 1H), 5.51 (m, 1H).

(296) 2.sup.nd Minority isomers (characteristic protons): 3.69 (m, 1H), 5.42 (m, 1H).

(297) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 2 observable isomers

(298) Majority isomers: (ppm) 141.11 (C.sup.IV), 126.73 (CH), 68.87 (CHOH), 42.12 (CH), 40.37 (CH), 32.34 (CH), 29.08 (CH.sub.2), 25.69 (CH.sub.2), 25.65 (CH.sub.2), 20.92 (CH.sub.3), 19.98 (CH.sub.3), 12.87 (CH.sub.3), 11.18 (CH.sub.3).

(299) 2nd Majority isomers: (ppm) 142.02 (C.sup.IV), 126.67 (CH), 73.63 (CHOH), 44.94 (CH), 38.26 (CH), 32.06 (CH), 27.57 (CH.sub.2), 25.15 (CH.sub.2), 23.73 (CH.sub.2), 20.92 (CH.sub.3), 19.93 (CH.sub.3), 12.89 (CH.sub.3), 11.84 (CH.sub.3).

(300) Minority isomers (characteristic peaks): 139.88 (C.sup.IV), 126.97 (CH), 71.08 (CHOH).

EXAMPLE 32

Preparation of 4-butyl-2,6-dimethylcyclohex-2-enol

(301) 4-butyl-2,6-dimethylcyclohex-2-enol is obtained with a yield of 71%, according to example 22, from 4-butyl-2,6-dimethylcyclohex-2-enone (obtained in example 12).

(302) It consists in a mixture of 3 observable isomers including 2 main isomers (89%) in a ratio of 18:82.

(303) B.p.: 90 C./0.5 torr

(304) Olfactive profile: Citrus (candied citrus peel), grapefruit, sulphurous, rhubarb.

(305) NMR-.sup.1H (CDCl.sub.3, 300 MHz): 3 observable isomers (50:30:30)

(306) (ppm) common protons 0.83-0.92 (m, 3H), 1.1-1.36 (m, 6H), 1.36-1.70 (m, 2H), 1.77-1.99 (m, 1H), 1.99-2.77 (m, 1H).

(307) Majority isomers (characteristic protons): 1.06 (d, J=6.51 Hz, 3H), 1.70-1.73 (m, 3H), 3.60 (broad d, J=8.4 Hz, 1H), 5.31 (m, 1H).

(308) 1st Minority isomers (characteristic protons): 0.97 (d, J=6.87 Hz, 3H), 1.75-1.77 (m, 3H), 3.72 (broad d, J=2.8 Hz, 1H), 5.51 (m, 1H).

(309) 2.sup.nd Minority isomers (characteristic protons): 0.93 (d, J=6.96 Hz, 3H), 1.73-1.75 (m, 3H), 3.52 (broad d, J=3.9 Hz, 1H), 5.45 (broad d, J=4.11 Hz, 1H).

(310) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 3 observable isomers

(311) Majority isomers: (ppm) 135.48 (C.sup.IV), 129.84 (CH), 76.82 (CHOH), 38.19 (CH), 37.39 (CH.sub.2), 36.33 (CH.sub.2), 36.04 (CH), 33.99 (CH.sub.3), 28.77 (CH.sub.2), 22.81 (CH.sub.2), 19.26 (CH.sub.3), 14.02 (CH.sub.3).

(312) 2nd Majority isomers (characteristic peaks): (ppm) 134.46 (C.sup.IV), 129.33 (CH), 71.66 (CHOH), 34.53 (CH.sub.2), 29.93 (CH.sub.2), 22.84 (CH.sub.2).

(313) 2.sup.nd Minority isomers (characteristic peaks): 133.60 (C.sup.IV), 129.44 (CH), 74.72 (CHOH).

EXAMPLE 33

Preparation of 4-hexyl-2,6-dimethylcyclohex-2-enol

(314) 4-hexyl-2,6-dimethylcyclohex-2-enol is obtained with a yield of 55%, according to example 22, from 4-hexyl-2,6-dimethylcyclohex-2-enone (obtained in example 13).

(315) It consists in a mixture of 3 observable isomers including 2 main isomers (88%) in a ratio of 17:83.

(316) B.p.: 90 C./0.46 torr

(317) Olfactive profile: fatty alcohol, soapy.

(318) NMR-.sup.1H (CDCl.sub.3, 300 MHz): 3 observable isomers (50:30:30)

(319) (ppm) common protons 0.8-0.88 (m, 3H), 1.06-1.36 (m, 10H), 1.36-1.86 (m, 2H), 1.88-2.12 (m, 1H), 2.12-2.69 (m, 1H).

(320) Majority isomers (characteristic protons): 1.03 (d, J=6.48 Hz, 3H), 1.68-1.70 (m, 3H), 3.56 (broad d, J=8.56 Hz, 1H), 5.28 (m, 1H).

(321) 1st Minority isomers (characteristic protons): 0.95 (d, J=6.84 Hz, 3H), 1.73-1.75 (m, 3H), 3.68 (d, J=3.78 Hz, 1H), 5.42 (d, J=3.60 Hz, 1H).

(322) 2.sup.nd Minority isomers (characteristic protons): 0.91 (d, J=6.93 Hz, 3H), 1.70-1.73 (m, 3H), 3.49 (d, J=4.75 Hz, 1H), 5.38 (m, 1H).

(323) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 3 observable isomers

(324) Majority isomers: (ppm) 135.63 (C.sup.IV), 129.60 (CH), 76.64 (CHOH), 38.05 (CH), 37.42 (CH.sub.2), 36.64 (CH.sub.2), 36.05 (CH), 34.0 (CH.sub.3), 31.78 (CH.sub.2), 30.36 (CH.sub.3), 29.45 (CH.sub.2), 29.43 (CH.sub.2), 22.56 (CH.sub.2), 13.97 (CH.sub.3).

(325) 2nd Majority isomers (characteristic peaks): (ppm) 134.46 (C.sup.IV), 129.16 (CH), 71.49 (CHOH).

(326) 2.sup.nd Minority isomers (characteristic peaks): 133.69 (C.sup.IV), 130.49 (CH), 74.61 (CHOH).

EXAMPLE 34

Preparation of 2,2,6,6-tetramethyl-4-((R)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enol

(327) 2,2,6,6-tetramethyl-4-((R)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enol is obtained with a yield of 64%, according to example 22, from (R)-2,2,6,6-tetramethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enone (obtained in example 14).

(328) It is a mixture of 2 isomers in a ratio 44:56.

(329) B.p.: 100 C./0.5 torr

(330) Olfactive profile: Woody, weak.

(331) NMR-.sup.1H (CDCl.sub.3, 200 MHz, common protons): (ppm) 1.43 (d, J=5.38 Hz, 1H), 1.55-1.62 (m, 3H), 1.72-2.0 (m, 2H), 2.02-2.20 (m, 1H), 2.32-2.45 (m, 1H), 3.31 (d, J=5.53 Hz, 1H), 5.21-5.28 (m, 1H).

(332) Majority isomers: 0.74 (s, 3H), 0.94 (s, 3H), 1.01 (s, 6H), 1.04 (s, 3H), 1.06 (s, 3H), 2.20-2.26 (m, 1H), 5.17 (s, 1H).

(333) Minority isomers: 0.77 (s, 3H), 0.93 (s, 3H), 1.0 (s, 6H), 1.01 (s, 3H), 1.07 (s, 3H), 2.26-2.32 (m, 1H), 5.18 (s, 1H).

(334) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(335) Majority isomers: 12.74, 20.67, 20.71, 22.15, 26.70, 29.38, 31.79, 32.71, 35.38, 37.31, 44.30, 48.12, 57.55, 82.54, 121.54, 132.42, 132.81, 147.47.

(336) Minority isomers: 12.74, 20.92, 21.28, 22.33, 26.92, 29.23, 31.63, 33.57, 35.35, 37.26, 42.88, 48.08, 57.16, 82.56, 121.52, 132.98, 133.23, 148.09.

EXAMPLE 35

Preparation of 2,2,6,6-tetramethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enol

(337) 2,2,6,6-tetramethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enol is obtained with a yield of 91% (97% purity), according to example 22, from (S)-2,2,6,6-tetramethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enone (obtained in example 15).

(338) It is a mixture of 2 isomers in a ratio 43:57.

(339) B.p.: 100-103 C./0.5 torr

(340) Olfactive profile: fruity, raspberry.

(341) Similar analyses to those of example 38.

EXAMPLE 36

Preparation of 4-(4,4-dimethylpentan-2-yl)-2,2,6,6 tetramethylcyclohex-3-enol

(342) 4-(4,4-dimethylpentan-2-yl)-2,2,6,6-tetramethylcyclohex-3-enol is obtained with a yield of 28%, over 2 steps (alkylation according to example 14, followed by reduction of the ketone according to example 22), from cyclohexenone obtained in example 9.

(343) B.p.: 75 C./0.4 torr

(344) Olfactive profile: earthy, musty

(345) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.88 (s, 9H), 0.88-0.92 (d, 3H), 0.92-0.98 (m, 3H), 1.0-1.05 (m, 3H), 1.3-1.5 (m, 2H), 1.65-1.95 (m, 2H), 2.05-2.30 (m, 1H), 3.28 (d, J=2.19 Hz, 1H), 5.07 (dd, J=4.97, 2.26 Hz, 1H).

(346) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(347) 138.75 & 138.41 (C.sup.IV), 129.93 & 128.98 (CH), 82.79 & 82.59 (CHOH), 48.76 & 47.94 (CH.sub.2), 40.03 & 39.22 (CH.sub.2), 37.55 & 37.07 (CH), 37.03 & 36.96 (C.sup.IV), 35.02 (C.sup.IV), 31.33 & 30.98 (CH), 31.25 (C.sup.IV), 30.02 & 29.88 (3 CH.sub.3), 29.24 & 21.99 (CH.sub.3), 22.63 (CH.sub.3), 20.82 & 20.26 (CH.sub.3).

EXAMPLE 37

Preparation of 4-isopropyl-2,2,6,6-tetramethylcyclohex-3-enol

(348) 4-isopropyl-2,2,6,6-tetramethylcyclohex-3-enol is obtained with a yield of 47%, by treating an ethanol solution of 4-isopropyl-2,2,6,6-tetramethylcyclohex-3-enone (obtained in example 19), at 0 C., with NaBH.sub.4 (0.5 eq.). Once the transformation is complete (GPC monitoring), the ethanol is evaporated by half and the mixture diluted in methyl and t-butyl ether. A 34% aq. HCl solution is then added and the aqueous phase, decanted, extracted twice with MTBE. The reunited organic phases are washed with a saturated aqueous solution of sodium bicarbonate, then with brine, dried over magnesium sulphate and the solvents are evaporated. The raw product is purified by distillation.

(349) B.p.: 70 C./0.4 torr

(350) Olfactive profile: woody, earthy, camphorated, sweat

(351) NMR-.sup.1H (CDCl.sub.3, 300 MHz): (ppm) 0.89 (s, 3H), 0.93-0.99 (m, 9H), 1.02 (s, 3H), 1.03 (s, 3H), 1.54 (broad s, 1 OH), 1.80 (dd, J=45.77 Hz, J=16.72 Hz, J=2.37 Hz, 2H), 2.12 (hept, J=6.81 Hz, 1H), 3.29 (s, 1H), 5.05 (dd, J=2.40 Hz, J=0.84 Hz, 1H).

(352) NMR-.sup.13C (CDCl.sub.3, 75 MHz): (ppm)

(353) 138.24 (C.sup.IV), 128.29 (CH), 82.61 (CHOH), 40.35 (CH.sub.2), 36.91 (C.sup.IV), 34.98 (C.sup.IV), 34.71 (CH), 31.45 (CH.sub.3), 29.16 (CH.sub.3), 22.14 (CH.sub.3), 21.30 (CH.sub.3), 21.02 (CH.sub.3), 20.44 (CH.sub.3).

EXAMPLE 38

Preparation of 2,2,6,6-tetramethyl-4-(2,3,3-trimethylcyclopent-1-enyl)cyclohex-3-enol

(354) 2,2,6,6-tetramethyl-4-(2,3,3-trimethylcyclopent-1-enyl)cyclohex-3-enol is obtained by treatment of a 1M solution of 2,2,6,6-tetramethyl-4-((S)-2,2,3-trimethylcyclopent-3-enyl)cyclohex-3-enol (obtained in example 25) with triflic acid at 50 C. Once the reaction is finished (GPC monitoring), the mixture is poured onto a saturated aqueous solution of sodium bicarbonate. The aqueous phase is extracted twice with toluene and the reunited organic phases are washed with brine, dried over magnesium sulphate and the solvents are evaporated. The raw product is distilled to give 2,2,6,6-tetramethyl-4-(2,3,3-trimethylcyclopent-1-enyl)cyclohex-3-enol with a yield of 53%.

(355) B.p.: 100 C./0.5 torr

(356) Olfactive profile: Dusty, raw vegetables, musty

(357) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 1.09 (s, 3H), 1.04 (s, 6H), 1.02 (s, 3H), 0.97 (s, 3H), 0.94 (s, 3H), 1.53-1.64 (m, 2H), 1.58-1.60 (m, 3H), 1.80-2.12 (m, 2H), 2.20-2.32 (m, 2H), 3.34 (s, 1H), 5.17 (d, J=2.29 Hz, 1H).

(358) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(359) 140.08 (C.sup.IV), 135.11 (C.sup.IV), 133.62 (CH), 130.64 (C.sup.IV), 82.25 (CHOH), 47.26 (C.sup.IV), 42.51 (CH.sub.2), 38.61 (CH.sub.2), 37.38 (C.sup.IV), 35.16 (C.sup.IV), 32.48 (CH.sub.2), 31.46 (CH.sub.3), 29.15 (CH.sub.3), 26.27 (CH.sub.3), 26.14 (CH.sub.3), 22.19 (CH.sub.3), 20.72 (CH.sub.3), 10.93 (CH.sub.3).

EXAMPLE 39

Preparation of 2,6-dimethyl-4-(2,2,3-trimethylcyclopentyl)cyclohexanol

(360) 2,6-dimethyl-4-(2,2,3-trimethylcyclopentyl)cyclohexanol is obtained according to example 19 from 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol (obtained in example 22) at 60 C. under 30 bars of H.sub.2.

(361) It is a mixture of 8 stereoisomers in a ratio 6:11:12:35:7:5:12:12.

(362) B.p.: 105 C./0.5 torr

(363) Olfactive profile: Aldehyde, fatty, slightly dry woody.

(364) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.54-0.69 (m, 3H), 0.7-0.85 (m, 3H), 0.85-1.04 (m, 9H), 1.04-1.8 (m, 12H), 1.8-2.12 (m, 2H), 3.19 (dd, J=10.24, 4.89 Hz, 1H) and 3.38-3.54 (m, 1H).

(365) NMR-.sup.13C (CDCl.sub.3, 50 MHz): complex spectrum corresponding to 6 stereoisomers (Characteristic peaks) (ppm) 82.87 & 81.80 (majority) & 78.45 & 78.40 & 75.09 & 74.85 (CHOH).

EXAMPLE 40

Preparation of 1-ethyl-4-isopropyl-2,6-dimethylcyclohex-2-en-1-ol

(366) To a solution in THF of 4-isopropyl-2,6-dimethylcyclohex-2-enone (obtained in example 10) is added, at 0 C., a 1M solution of ethylmagnesium chloride in THF (1.2 eq.). Once the reaction is finished (GPC monitoring), the reaction medium is poured slowly into a methyl and t-butyl ether (MTBE)/10% aq. HCl mixture at 0 C. The aqueous phase is extracted twice with MTBE and the reunited organic phases are washed with a saturated aqueous solution of sodium bicarbonate, then with brine. After drying over magnesium sulphate, filtration on paper and evaporation of the solvents, the raw product is purified by distillation under reduced pressure to give 1-ethyl-4-isopropyl-2,6-dimethylcyclohex-2-en-1-ol with a yield of 66%.

(367) It is a mixture of stereoisomers including 4 main isomers (71%) in a ratio 44:14:28:14.

(368) B.p.: 67 C./0.4 torr

(369) Olfactive profile: Woody, camphorated, slightly musty

(370) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.60-1.15 (m, 12H), 1.15-1.65 (m, 4H), 1.65-1.80 (m, 3H), 1.80-2.25 (m, 2H), 2.25-3.0 (m, 1H), 5.35 & 5.42 & 5.49 (m, 1H).

(371) NMR-.sup.13C (CDCl.sub.3, 50 MHz): complex spectrum corresponding to 6 stereoisomers (Characteristic peaks) (ppm) 131.85 (CH, majo), 105.46 (C.sup.IV, majo).

EXAMPLE 41

Preparation of 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enyl acetate

(372) 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enyl acetate is obtained by treating 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enol (obtained in example 19) with 1.2 molar equivalent of acetic anhydride and a catalytic quantity of N,N-dimethylaminopyridine. After 2 hours at ambient temperature, the excess acetic anhydride and the acetic acid formed during the reaction are eliminated under reduced pressure. The raw product is diluted with methyl and t-butyl ether and the organic phase is washed twice with water, then with a saturated aqueous solution of sodium bicarbonate and lastly with brine. After drying over magnesium sulphate, the solvents are evaporated and the raw product is distilled to give 2,6-dimethyl-4-(2,2,3-trimethylcyclopent-3-enyl)cyclohex-2-enyl acetate with a yield of 73%, in the form of a mixture of 3 main stereoisomers (85%) in a ratio of 25:60:15.

(373) B.p.: 96 C./0.5 torr

(374) Olfactive profile: slightly woody, weak.

(375) NMR analyses corresponding to the expected derivative (to be compared with the corresponding alcohol of example 19).

EXAMPLE 42

Preparation of 2,6-dimethyl-4-(phenylethyl)cyclohex-2-enyl acetate

(376) 2,6-dimethyl-4-(1-phenylethyl)cyclohex-2-enyl acetate is obtained with a yield of 75%, according to example 41, from 2,6-dimethyl-4-(1-phenylethyl)cyclohex-2-en-1-ol (obtained with a yield of 72%, according to example 22, from 2,6-dimethyl-4-(1-phenylethyl)cyclohex-2-enone, obtained in example 6).

(377) It is a mixture of 5 observable stereoisomers (91%) in a ratio 12:14:14:25:35.

(378) B.p.: 120 C./0.1 torr

(379) Olfactive profile: flowery, honey-like, crushed lemon pip.

(380) NMR-.sup.1H (CDCl.sub.3, 300 MHz):

(381) (ppm) common protons 0.95-1.22 (m, 1H), 1.37-2.07 (m, 2H), 2.14-2.49 (m, 1H), 2.49-2.73 (m, 1H), 4.87-5.31 (m, 1H), 7.16-7.26 (m, 3H), 7.28-7.37 (m, 2H).

(382) 1st Majority isomers (characteristic protons): 0.89 (d, J=6.54 Hz, 3H), 1.33 (d, J=6.90 Hz, 3H), 1.63-1.67 (m, 3H), 5.31-5.37 (m, 1H).

(383) 2nd Majority isomers (characteristic protons): 0.98 (d, J=6.45 Hz, 3H), 1.25 (d, J=6.96 Hz, 3H), 1.55-1.59 (m, 3H), 5.65-5.69 (m, 1H).

(384) 1st Minority isomers (characteristic protons): 0.83 (d, J=6.71 Hz, 3H), 1.34 (d, J=6.90 Hz, 3H), 1.59-1.62 (m, 3H), 5.82-5.89 (m, 1H).

(385) NMR-.sup.13C (CDCl.sub.3, 75 MHz): 4 observable isomers

(386) Majority isomers: 171.21 (C(O)), 145.46 (C.sup.IV), 133.87 (C.sup.IV), 129.52 (CH), 128.1 (CH), 127.44 (CH), 125.89 (CH), 77.84 (CHOAc), 44.44 (CH), 42.67 (CH), 35.41 (CH.sub.2), 35.08 (CH), 20.80 (CH.sub.3), 19.10 (CH.sub.3), 18.62 (CH.sub.3), 18.14 (CH.sub.3).

(387) 1st Minority isomers (characteristic peaks): 145.68 (C.sup.IV), 133.28 (C.sup.IV), 129.11 (CH), 77.84 (CHOAc), 33.73 (CH.sub.2).

(388) 2nd Minority isomers (characteristic peaks): 146.37 (C.sup.IV), 132.39 (C.sup.IV), 129.15 (CH), 72.69 (CHOAc), 29.45 (CH.sub.2).

EXAMPLE 43

Preparation of 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enyl acetate

(389) 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-enyl acetate is obtained with a yield of 60%, according to example 41, from 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-en-1-ol (obtained in example 29).

(390) It is a mixture of stereoisomers (5 observed), including 2 main stereoisomers (80%) in a ratio 71:29.

(391) B.p.: 95 C./0.4 torr

(392) Olfactive profile: woody, slightly cocoa, rather similar to the corresponding alcohol, but weaker.

(393) NMR-.sup.1H (CDCl.sub.3, 200 MHz):

(394) (ppm) common protons 0.8-0.95 (m, 15H), 0.95-1.32 (m, 2H), 1.40-1.55 (m, 2H), 1.65-1.90 (m, 1H), 1.90-2.25 (m, 1H).

(395) Majority isomers (characteristic protons): 1.56-1.60 (m, 3H), 2.09 (s, 3H), 5.12-5.22 (m, 1H), 5.42-5.50 (m, 1H).

(396) Minority isomers (characteristic protons): 1.62-1.66 (m, 3H), 2.07 (s, 3H), 5.30-5.40 (m, 2H).

(397) NMR-.sup.13C (CDCl.sub.3, 50 MHz): 4 observable isomers

(398) Majority isomers (characteristic peaks): 171.43 (C(O)), 133.78 & 133.39 (C.sup.IV), 130.55 & 130.14 (CH), 78.37 & 78.32 (CHOAc), 47.65 & 47.49 (CH.sub.2), 43.28 & 43.13 (CH), 32.83 & 32.43 (CH.sub.2), 31.03 & 30.97 (C.sup.IV), 29.94 (3 CH.sub.3).

(399) Minority isomers (characteristic peaks): 171.05 (C(O)), 132.05 & 131.77 (C.sup.IV), 129.79 & 129.37 (CH), 74.09 & 73.83 (CHOAc), 48.51 & 48.19 (CH.sub.2), 39.56 & 38.90 (CH), 31.03 & 30.97 (C.sup.IV), 29.94 (3 CH.sub.3), 29.50 & 28.78 (CH.sub.2).

EXAMPLE 44

Preparation of 4-Isopropyl-2,2,6,6-tetramethylcyclohex-3-enyl acetate

(400) 4-isopropyl-2,2,6,6-tetramethylcyclohex-3-enyl acetate is obtained with a yield of 53% over 2 steps (reduction according to example 37, followed by esterification according to example 41), from 4-isopropyl-2,2,6,6-tetramethylcyclohex-3-en-1-one (obtained in example 17).

(401) B.p.: 75 C./0.4 torr

(402) Olfactive profile: Woody, damp, slightly patchouli

(403) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) 0.89 (s, 3H), 0.92 (s, 3H), 0.95 (s, 6H), 0.96 (s, 3H), 0.97 (s, 3H), 1.7-2.0 (m, 2H), 2.10 (s, 3H), 2.14 (hept, J=6.82 Hz, 1H), 4.78 (s, 1H), 5.04 (m, 1H).

(404) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(405) 171.16 (C(O)), 138.52 (C.sup.IV), 127.64 (CH), 82.57 (CHOAc), 39.64 (CH.sub.2), 36.68 (C.sup.IV), 34.75 (CH), 34.62 (C.sup.IV), 30.89 (CH.sub.3), 28.33 (CH.sub.3), 23.76 (CH.sub.3), 22.38 (CH.sub.3), 21.25 (CH.sub.3), 21.03 (CH.sub.3), 20.93 (CH.sub.3).

EXAMPLE 45

Preparation of 4-Isopropyl-2,6-dimethylcyclohexyl acetate

(406) 4-isopropyl-2,6-dimethylcyclohexyl acetate is obtained with a yield of 60%, according to example 41, from 4-isopropyl-2,6-dimethylcyclohexanol obtained with a yield of 44%, over 2 steps (hydrogenation according to example 19, followed by reduction of the ketone according to example 37, from cyclohexenone obtained in example 10).

(407) It is a mixture of stereoisomers (4 observed), including 2 main stereoisomers (82%) in a ratio 65:35.

(408) B.p.: 48 C./0.4 torr

(409) Olfactive profile: citrus, grapefruit, slightly rhubarb, then woody, citrus fruit peel, dusty.

(410) NMR-.sup.1H (CDCl.sub.3, 200 MHz): (ppm) common protons 0.75-1.07 (m, 14H), 1.08-1.25 (m, 1H), 1.27-1.9 (m, 5H),

(411) Majority isomers (characteristic peaks): (ppm) 2.05 (s, 3H), 4.98 (s, 1H).

(412) Minority isomers (characteristic peaks): (ppm) 2.06 (s, 3H), 4.26 (t, J=10.30 Hz, 1H).

(413) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(414) Majority isomers: (ppm) 171.14 (C(O)), 76.11 (CHOAc), 43.38 (CH), 36.0 (CH/CH.sub.3), 32.66 (CH), 31.91 (CH.sub.2), 19.78 (CH.sub.3), 18.19 (CH.sub.3).

(415) Minority isomers: (ppm) 171.14 (C(O)), 82.99 (CHOAc), 42.62 (CH), 37.30 (CH/CH.sub.3), 36.93 (CH.sub.2), 32.23 (CH), 19.76 (CH.sub.3), 18.50 (CH.sub.3).

EXAMPLE 46

Preparation of 4-(4,4-dimethylpentan-2-yl)-1-methoxy-2,6-dimethylcyclohex-2-ene

(416) To a suspension of NaH (1.2 eq.) in THF is added 4-(4,4-dimethylpentan-2-yl)-2,6-dimethylcyclohex-2-en-1-ol. After 4 hours at ambient temperature (end of emission of gas), the mixture is cooled to 0 C. and methyl iodide (1.2 eq.) is added slowly, drop by drop, the reaction medium is then heated to 40 C. over one night. Once the reaction is complete (GPC monitoring), the reaction mixture is poured into a methyl and t-butyl ether (MTBE)/10% aq. HCl mixture. The aqueous phase is extracted twice with MTBE and the reunited organic phases are washed with a 10% aqueous solution of sodium thiosulphate, then with a saturated aqueous solution of sodium bicarbonate and with brine. After drying over magnesium sulphate, filtration on paper and evaporation of the solvents, the raw product is purified by distillation under reduced pressure to give 1-(4,4-dimethylpentan-2-yl)-1-methoxy-2,6-dimethylcyclohex-2-ene with a yield of 57%.

(417) It is a mixture of stereoisomers (8 observed), including 4 main stereoisomers (88%) in a ratio 18:17:33:32.

(418) B.p.: 74 C./0.4 torr

(419) Olfactive profile: woody, chocolate

(420) NMR-.sup.1H (CDCl.sub.3, 200 MHz, common protons): (ppm) 0.8-0.92 (m, 13H), 0.92-1.07 (m, 3H), 1.07-1.4 (m, 2H), 1.4-1.65 (m, 2H).

(421) Majority isomers (characteristic protons): 1.68-1.72 (m, 3H), 3.28 & 3.29 (s, 3H), 3.37-3.42 & 3.42-3.47 (m, 1H), 5.24-5.3 & 5.3-5.34 (m, 1H).

(422) Minority isomers (characteristic protons): 1.71-1.75 (m, 3H), 3.37 & 3.38 (s, 3H), 3.57-3.67 (m, 1H), 5.34-5.38 (m, 1H).

(423) NMR-.sup.13C (CDCl.sub.3, 50 MHz): (ppm)

(424) Majority isomers: 135.95 & 135.49 (C.sup.IV), 130.72 & 130.09 (CH), 85.42 & 85.39 (CHOMe), 55.40 & 55.27 (OCH.sub.3), 47.80 & 47.68 (CH.sub.2), 43.49 & 43.32 (CH), 33.84 & 33.79 (CH), 33.65 & 32.97 (CH.sub.2), 33.26 & 32.93 (CH), 30.99 (C.sup.IV), 29.97 (3CH.sub.3), 19.48 (2(CH.sub.3)), 19.33 (2(CH.sub.3)), 19.27 & 18.97 (CH.sub.3).

(425) Minority isomers: 134.59 & 134.27 (C.sup.IV), 127.41 & 126.91 (CH), 81.57 & 81.54 (CHOMe), 57.45 & 57.19 (OCH.sub.3), 48.19 & 48.01 (CH.sub.2), 39.01 & 38.50 (CH), 33.21 & 32.93 (CH), 30.99 & 29.36 (CH.sub.2), 30.99 (C.sup.IV), 29.97 (3CH.sub.3), 29.26 & 29.21 (CH), 20.29 & 20.22 (CH.sub.3), 19.82 & 19.27 (CH.sub.3), 13.06 & 12.80 (CH.sub.3).