BACKGROUND OF THE INVENTION

Since antiquity, ambergris has been highly valued in perfumery for its unique odor and fixative properties. However, due to a decline in the sperm whale population, ambergris is largely unavailable as an item of commerce. Consequently, the fragrance industry.has great interest in synthetic odorants with amber-like properties. Ambergris an compounds possessing amber odors are extensively discussed b G. Ohloff, Chapter 15- in Fragrance Chemistry: The Science o the Sense of Smell, ed. by E.T. Theimer, Academic Press, 1982. Compounds that have strong amber or ambergris-like odors generally have bicyclic or tricyclic structures. For example dodecahydro-3a,6,6,9-tetramethylnaphtho[2,1-b]furan (X) possesses a strong amber odor (see M. Hinder and M. Stoll, Helv. Chim. Acta (1950) 33 1308).

o^-Ambrinol (I_ ) is an important synthetic amber odorant (see M. Stoll and M. Hinder, Helv. Chim. Acta, (1955), .38.1953). Compounds III and IV described by G. Ohloff et al., Helv. Chim. Acta. (1976) 5_9 75 and ibid. (1973) 5£ 1414 also possess amber odors.

Recently, U.S. Patent 4,162,226 (1979) by D. Helmlenger and P. Naegeli described compounds of structure V wherein three of the R groups are methyl and one is hydrogen and one of the R. is hydrogen an the other R _χ is acetyl.

None of the prior art teaches nor indicates that the novel monocyclic compounds of the invention would possess valuable amber or woody amber-like odors.

-~-

An Amber - Odor - Ambrinol Compound

III IV An Amber - Odor An Amber - Odor Compound Compound

V

An Amber - Odor

Compound

Summarv of the Invention

The present invention is directed to alkyltetramethylcyclohexane derivatives and their use in fragrance formulations as amber, woody, spicy or amber-like scents.

The alkytetra ethylcyclohexane derivatives have the formula:

Wherein X is H, R^O- or R^HOH-; Y is H or R ^X CO-; R ¹ is

2 6 hydrogen or alkyl from 1 to 4 carbons; R through R are methyl or lower alkyl or 1 to 4 carbons; indicates a

^" single or double bond; provided that the carbon, at position 4 and 4' has only one double bond, at least four of R 2 ^■ through

R are methyl, and that one but not both of X and Y is always H. The numbers indicate the positions of the carbons of the cyclohexane derivatives.

Preferred derivatives include those wherein Y is H; those

2 3 5 6 1 wherein R , R , R and R are methyl; those wherein R is methyl, ethyl or isopropyl; those wherein X is carbonyl, and those wherein the bonds between carbons 4' and 5' or 3 and 4 are double.

Especially preferred species include

4-(2,2,4,6,6-Pentamethy1-3- cyclo-hexen-l-yl)-4-penten-2-one having strong, woody, spicy amber odor with powdery, fruity notes.

(E,Z)4-(2,2,4,6,6-Pentamethyl-3- cyclohexen-1-yl)-3-penten-2-one having a strong, woody, spicy amber odor with powdery, fruity notes.

10

5-(2,2,4,6,6-Pentamethyl-3-cyclo- hexen-1-yl)-5-hexen-3-one.

20

o , 2,2,4,6,6-Hexamethyl-f- methylene-3-cyclohexene-l-propanol having a stong, woody, earthy, amber

25 odor.

30

(E,Z) 4-(2,2,4,6,6-Pentamethyl-3-

35 cyclohexen-1-yl)-3-penten-2-ol having a woody, amber odor.

40

(E,Z) 3-(2,2,4,6,6-Pentamethyl-3- cyclohexen-1-yl)-2-buten-l-ol.

ά -Ethyl-2,2,4,6,6-pentamethyl-T- methylene-3-cyclohexene-l-propanol having a moderately woody, amber odor with green floral notes.

30

c_-(1-Methylethyl)-2,2,4,6,6- pentamethyl- -methylene-3- cyclohexene-1-propanol having a

35 weak, woody amber odor.

40

_o<_,_V,2,2,4,6,6-Heptamethyl-3- cyclohexene-1-propanol having a weak, woody odor.

___, f,2,2,4,6,6-Heptamethyl- cyclohexane 1-propanol having a ver weak woody odor.

4-(2,2,4,6,6-Pentamethyl-3- cyclohexen-1-yl)-2-pentanone.

4-(2,2,4,6,6-Pentamethyl-l- cyclohexyl)-2-pentanone.

Also included within the invention are perfumed formulations of the foregoing cyclohexane derivatives and a carrier.

These formulations include a cologne, toilet water, perfume, oil, lotion, creme, talc, body powder or a body spray. These formulations are made by combining the carrier with a fragrance oil of the foregoing derivative and an aromatic spirit.

Additionally, these formulations can be used as air freshners, room air fresheners and the like.

DETAILED DESCRIPTION OF THE INVENTION

The derivatives of this invention can be conveniently prepared from 4-(l-methylethenyl)-l-cyclohexene derivative (VI) according to reaction A as follows.

Reaction A

VI Vila VIlb VIIc

The starting material VI may be obtained as described by H.M.R. Hoffman and H. Vathke-Ernst, Chem. Ber. , 114, 1981, 1182-1186. Reaction of VI. with lower allkyl acid anhydrides in the presence of acid catalysts provides a mixture of compounds Vlla-c.

The relative proportions of Vlla-c will vary according to the conditions employed and the identity of R . The presence of compound VIIc does not affect the scent and potency of compounds Vila and b. Under typical reaction conditions.

compound Vllb is produced in a predominant proportion with compound Vila being produced in a minor proportion. (See

CD. Nenitzescu and A.T. Balaban in "Friedel-Crafts" and

Related Reactions. G. Olah, ed.. Vol. 3, Pt. 2, 1963, p. 1033-1152). Instead of anhydrides, acid chlorides may also be used.

Both Lewis acids and protic acids may be employed as catalysts. Protic acids such as polyphosphoric acid, sulfuric acid, phosphoric acid, phosphoric anhydride, methanesulfonic acid, and mixtures thereof may be used. Lewis acids, such as aluminum chloride, ferric chloride, alkyl aluminum chloride, boron trifluoride etherate, zinc chloride, stannic chloride or titanium chloride are the preferred catalysts. The most preferred catalysts are zinc chloride or boron trifluoride etherate. The amount of catalyst may be from 5 to 200 mole percent relative to compound VI with 25 to 75 percent being preferred and 35 to 50 mole percent being especially preferred. f A variety of solvents may be used, such as dichloromethane, hexane, chlorobenzene, carbon tetrachloride, tetrachloroethylene or carbon disulfide. The preferred solvents are dichloromethane or diclorethane.

The reaction may be performed in the temperature range of -10°C to 100°C. The preferred temperature range is from 0° to 50°C. The most preferred temperature range is from 20°C to 45°C. The time for conducting the reaction may be from 1 to 12 hours, preferrably 1 to 6 hours, most preferrably 3 to 5 hours.

Reaction B

VHIa Vlllb

As illustrated in reaction B, foregoing Alcohols Vila and Vllb can be prepared by reduction of ketones Villa and Vlllb by standard methods known to those skilled in the art. See C . Buehler and D.E. Pearson, "Survey of Organic Synthesis", Wiley-Interscience. Vol. 1 (1920), p. 193-207 and Vol. 2 (1977), p. 228-239. Reduction with metal hydrides such as sodium borohydride or lithium aluminum hydride is a convenient method.

Reaction C

VI Villa

Alternatively, alcohol Villa can be prepared as shown in reaction C by condensation of l,3,3,5,5-pentamethyl-4-(l- methylethenyl)-l-cyclohexene (371.) with aldehydes in the presence of Lewis acids (See B.B. Snider e_t al. , Tetrahedron, 3_7 3927-34 (1981)). Alcohol Villa (R = H) can be prepared using any of the foregoing Lewis acids as

catalysts, boron trifluoride etherate and aluminum chloride are preferred. Alcohols Villa (R ¹ = lower alkyl) are best prepared by reacting VI with an aldehyde in the prsence of dimethylaluminum chloride. Many inert solvents may be used in these reactons but dichloromethane or 1,2-dichloroethane are preferred. The reactions are performed in the temperature range of -20°C to 75°C The preferred temperature range is from -10 ^β C to 50°C, most preferrably from 0°C to 40°C Useful solvents include those described above for reaction A. The time for the reaction is like that described for foregoing reaction A.

Reaction D

Villa i Vila and/or Vl b

[0]

Oxidation of alcohol Villa (reaction D) by standard reagents such as chromium trioxide, aluminum t.-butoxide, n- bromosuccinimide and the like affords carbonyl compounds Vila and/or Vllb (See CA. Buehler and D.E. Pearson, "Survey of Organic Synthesis", Wiley-Interscience, Vol. 1 (1970), p. 625-630, p. 545-553, and Vol. 2 (1977) p. 484-487, p. 536- 540). Carbonyl compounds Vila can be readily isomerized (sometimes concomitant with oxidation) to compounds Vllb. Pyridinium chlorochromate (See E.J. Corey and J.W. Suggs,

Tetrahedron Lett, 1975, 2647-2650) is an especially effective reagent for this oxidation. By control of the reaction conditions either Vila or Vllb can be prepared in high yield.

Vila IX X

Compound Vila can be selectively reduced to either compound IX or X by application of the appropriate hydrogenation conditions using such catalysts as palladium, platinum, Raney nickel and the like (see P.N. Rylander, "Catalytic Hydrogenation in Organic Synthesis", Academic Press (1979) p. 51-59).

The reduced alcohols XI or XII may be obtained by reduction of the corresponding ketones IX or X by such reagents as lithium aluminum hydride, sodium borohydride, dialkyl aluminum hydride, sodium cyanoborohydride, hydrogen and noble metal catalysts as well as others. Useful solvents include alcohols, tetrahydrofuran, water, dioxane and ether. Useful temperatures include 0°C to 80°C, preferred 0°C to 60°C, most preferred 10°C to 60°C

Alcohols XI. may also be prepared by reduction of ketones Vila with an alkali metal in the presence of a proton donor (see

H.O. House "Modern Synthetic Reactions", The

Benjamin/Cummings Publishing Co. (1972) p. 145-205). Useful alkali metals include lithium, sodium, calcium and potassium with lithium and sodium being especially preferred. The reduction may be performed in solvents such as alcohols, ether, ammonia or lower alkyl amines. Especially preferred are mixtures of alcohol, ether and ammonia.

Mixtures of derivatives produced according to the foregoing processes can be separated and purified using techniques known to those in the art. Included are vacuum distillation, column chromatography, fractional cyrstallization, high pressure liquid chromatography (HPLC) and the like.

The fragrance compositions prepared from derivatives according to the present invention can be formulated according to methods -known in the perfumer art. The derivative is first compounded with an aromatic spirit to form an oil essence. Useful spirits include ethanol, propanol, ethylene glycol, glycerol and the like. The oil essence is then formulated with a carrier selected from those typically employed for talcs, lotions, sprays, colognes, perfumes and the like. These carriers include ingredients suσh as alcohols, glycerols, emulsifiers, glycols, water, starchs, mineral oil, wax, petrolatums, lanolin derivatives, fatty acids, fatty alcohols, salts, collagen, surfactants, talcs, metal chealates and the like.

The following examples further illustrate the present invention.

EXAMPLE 1

Cyclohexene Butenol Derivative

A solution of boron trifluoride etherate (2 mL) in dichloromethane (30 mL) was added to a mixture of 1,3,3,5,5- pentamethyl-4-(l-methylethenyl)-l-cyclohexene (19.24g, 0.1 mol) and parafor aldehyde (1.5g, 0.05 mol) at 25 ^β C in dichloromethane (200 mL) over 45 min. The mixture was stirred at 25° for 5 hr. Afterwhich a 30% aqueous solution of potassium carbonate (50 mL) was added dropwise. The aqueous layer was extracted with dichloromethane (50 mL) .

_*

The dichloromethane solution was washed with 10% aqueous ♦ potassium hydroxide solution (100 mL), water (100 mL) , brine

(100 mL) and dried over sodium sulfate. Evaporation of solvent and distillation provided 5.5g of 2,2,4,6,6- hexamethyl-Υ-methylene-3-cyclohexene-l-propanol, bp 100-

104°C, o 5 mm (GLC purity 94%). ¹ H-NMR (60 MHz, CDC1 ₃ ) _£

0.94 and 1.03 (12H, 2s), 1.63 (3H, broad s), 1.6-2.7 (6H, m)

3.65-3.98 (2H, m) , 4.93 (IH, broad s), 4.95-5.13 (2H, m) ; IR

( ^v film) ' vmax 3300, 2950, 1640, 1465, 1440, 1380, 1360 cm ^"1 ; MS m/e 222, 207, 204, 189, 126, 111, 96.

EXAMPLE 2

Cyclohexene Pentenol Derivative

Dimethylaluminum chloride (300 mL of a 1M hexane solution) was added to a cooled (10°) solution of 1,3,3,5,5-pentamethyl -4-(l-methylethenyl)-l-cyclohexene (46.18g, 0.24 mol) in dichloromethane (500 mL) . The mixture was stirred at 25°C for 2 hr. Afterwhich the mixture was hydrolyzed by the addition of phosphate buffer solution (200 mL, prepared from 100 mL of 0.1M potassium phosphate, monobasic and 44.8 mL of 0.1M sodium hydroxide 'diluted to 200 mL w-ith water) followed by the addition of sufficient IN hydrochloric acid solution to dissolve the aluminum salts. The layers were separated and the aqueous layer extracted with dichloromethane (200 mL). The combined organic layer was extracted with dichloromethane (200 L) . The combined organic layers were washed with water (100 mL) and saturated sodium bicarbonate solution (2x 100 mL) . The solvents were evaporated and the residue chromatographed. Combination of fractions and distillation provided 27.8g ofo(,2,2,4,6,6,-hexamethyl-Y- methylene-3-cyclohexene-l-propanol, bp 100-105°C, 0.5 mm (GLC purity, two iso ers, 41.4% and 56.6%). ¹ H-NMR (60 MHz, CDC1 ₃ £ 0.92 and 0.98 (12H, 2s), 1.20 (3H,d, J = 6Hz), 1.58 (3H, s), 1.2-2.6 (5H, m) 3.8-4.2 (IH, m) , 4.9-5.2 (3H, m) ; IR ( (ffiillmm)) vv _mmaχ 33334400,, 22995500,, 11663355,, 11444400,, 113370, 1350 cm ^"1 ; MS m/e 236, 221, 218, 203, 140, 125, 107, 96.

EXAMPLE

Cyclohexene Heptenol Derivative

Dimethylaluminum chloride (60 mL of a IM hexane solution) was added dropwise to a solution of 1,3,3,5,5-pentamethyl-4-(l- methylethenyl)-l-cyclohexene (7.70g, 0.04 mol) and propionaldehyde (2.30g, 0.04 mol) in dichloromethane (150 mL) at 25-30°C over a 15 min period. The mixture was stirred at 25°C for 16h. Work-up (as described in Example 2) and chromatography provided 2.20g of σ£-ethyl-2,2,4,6,6- pentamethyl- ^" Y-methyl ^' e ^" ne-3-cyclohexene-l-propanol, bp

(kugelrohr bath) 125°C, 0.5 mm, (GLC purity, two isomers, 40.7% and 57.9%). ^" "Ή-NMR (60 MHz, CDC1 ₃ ) £ 0.98 and 1.03 (12H, 2s), 1.02 (3H, t, J = 4 Hz), 1.63 (3H, s), 1.1-2.6 (8H, m), 3.5-3.9 (IH, m) , 5.0-5.3 (3H, broad s); IR (film) v _7T1=v 3350, 2950, 1640, 1460, 1380, 1360 cm ^"1 ; MS m/e 250, 235, 217, 125, 107, 96. The mass spectra of the diastereomers were nearly identical.

EXAMPLE

Cyclohexene Methyl Heptenol Derivative

Dimethylaluminum chloride (3 mL of a IM hexane solution) was reacted with a solution of l,3,3,5,5-pentamethyl-4-(l- methylethenyl)-l-cyclohexene (0.48g, 0.0025 mol) and isobutyraldehyde (0.18g, 0.0025 mol) in dichloromethane (10 mL) according to the procedure described in Example 3. Work-up and chromatography gave 0.300g (45% yield) of - ( l- methylethyl)-2,2,4,6,6-pentamethyl-Y-methylene-3- cyclohexene-1-propanol, bp (kugelrohr bath) 135°C, 0.5 mm

(GLC purity 94.4%, 2:1 mixture of diastereomers) . H-NMR (60 MHz, CDC1 ₃ ) £ 0.88-1.07 (18H, Id and 1 broad s), 1.4-2.4 (10H, ), 3.2-3.7 (IH, m) 4.9-5.2 (3H, m); IR (film) v _mav 3450, 2950, 1640, 1465, 1380, 1360 cm ^" ; MS m/e 264, 249, 246, 221, 203, 177, 107, 96. The mass spectra of the diastereomers were nearly identical.

EXAMPLE 5

Cyclohexene Butenol Derivative

A solution of acetic anhydride (0.23 mL) in dichloromethane (2 mL) was reacted with a mixture of 2,2,4,6,6-pentamethyl- Y-methylene-3-cyclohexene-l-propanol (0.56g, 0.0025 mol), triethylamine (0.41 mL) , 4-dimethylaminopyridine (0.031g) and dichloromethane at 25°C) . Work-up, chromatography and distillation gave 0.60g of 2,2,4,6,6-pentamethyl-Y- .methylene-3-cyclohexene-l-propanol acetate bp (kugelrohr bath 110-120°C), 0.5 mm (GLC purity: 88%). ¹ H-NMR (60 MHz,

CDC1 ₃ ) £ 0.93 (6H, s), 1.00 and 1.0$' (6H, 2s), 1.60 (3H, s), 2.00 (3H, s), 0.9-2.6 (5H, m), 4.20 (IH, t, J = 7 Hz), 4.96- 5.07 (3H, ); IR (film) v _m= 2960, 1735, 1635, 1440, 1370, 1350 cm ^"1 ; MS (m/e) 264, 249, 221, 204, 189, 108, 96.

EXAMPLE

Cyclohexene Butenol Derivative

Sodium hydride (0.6g of 60% oil dispersion, 0.015 mol) was washed with hexane (2 x 3 mL) and suspended in THF (10 mL) . A solution of 2,2,4,6,6-pentamethyl-Y-methylene-3- cyclohexene-1-propanol (l.llg, 0.005 mol) in THF (5 mL) was added, followed by methyl iodide (1.4g, 0.001 mol). The mixture was heated at reflux for 4 hr. Afterwhich, work-up, chromatography and kugelrohr distillation gave 1.10g of 2,2,4,6,6-pentamethyl-Y-methylene-3-cyclohexene-l-propanol methyl ether. ¹ H-NMR ( 0 MHz, CDC1 ₃ ) 0.95 (6H, s , 1.03 (6H, broad s), 1.63 (3H, broad s), 1.5-2.6 (5H, m) , 3.33 (3H, s) 3.58 (2H, t, J = 7 Hz), 4.85-5.15 (3H, m); IR (film) v _maχ 2960, 1640, 1440, 1380, 1360 cm ^"1 ; MS m/e 236, 221, 204, 189, 140, 125, 96.

EXAMPLE

Cyclohexene Pentenone Derivative

A solution of o^,2,2,4,6,6-hexamethyl-Y-methylene-3- cyclohexene-1-propanol (2.36g, 0.01 mol) in dichloromethane (lOmL) was added over a 30 min period to a mixture of pyridinium chlorochromate (3.25g, 0.015 mol), sodium acetate (2.30g, 0.03 mol) and discloromethane (15 mL) at 25°C The mixture was filtered and the filtrate washed with water (100 mL) and 5% sodium carbonate solution (100 mL) . The sovents were evaporated and the residue" chromatographed to provide after kugelrohr distillation ^' 1.75g (75% yield) ^* of 4- (2,2,4,6,6-pentamethyl-3-cyclohexen-l-yl)-4-penten-2-one (GLC purity: 94%). ¹ H-NMR ■_ 0.93 (3H, s) 0.95 (3H, s), 1.02 (6H, s), 1.62 (3H, s), 1.6-1.8 (2H, ) , 1.97 (IH, s), 2.18 (3H, s), 3.15 (2H, s), 5.05 (2H, broad s); IR (film) v _m=v 2950,

1710, 1630, 1430, 1380, 1350 cm ^"1 ; MS m/e 234, 219, 201, 191, 176, 161, 149, 123, 96.

EXAMPLE 8

Cyclohexene Pentenone Derivative

A mixture of 4-(2,2,4,6,6-pentamethyl-3-cyclohexen-l-yl)-4- penten-2-one (1.50g, 0.00.63 mol) methanol (30 mL) and sodium methoxide (0.02g) was stirred at 25°C for 18 hr. The mixture was then heated at reflux for 3 hr. The mixture was cooled to 25 ^β C and most of the methanol was evaporated under reduced pressure. The residue was partitioned between ether (75 mL) and water (15mL). The aqueous layer was extracted with ether (50mL). The ether extracts were washed with saturated sodium bicarbonate solution, brine and dried. Evaporation of solvents and kugelrohr distillation of the residue provided 1.28g (85% yield) of 4-(2,2,4,6,6-pentamethyl-3-cyclohexen- l-yl)-3-penten-2-one (GLC purity: 93.5%). ^-NMR (60 MHz) £ 0.93 (12h, broad s), 1.57 (3H, s), 1.5-1.9 (2H, m) , 1.88 (IH, broad s), 3.42 (3H, s), 5.01 (IH, broad s), 6.02 (IH, broad s); IR (film) v _m= 2950, 1685, 1600, 1440, 1380, 1365 cm ^"1 ; MS m/e 234, 216, 191, 149, 135, 121.

EXAMPLE

Cyclohexene Pentenone Derivative

Boron trifluoride etherate (9.3 mL, 0.07 mol) was added dropwise over a 1 hr period to a mixture of 1,3,3,5,5,- pentamethyl-4-(l-methylethenyl)-l-cyclohexene (28.83g, 0.15 mol) acetic anhydride (123.5 mL) and dichloromethane (6.5mL) maintained at 40°-45°C The mixture was stirred at 40°C for 3 hr. Most of the excess acetic anhydride was removed under reduced pressure. The _* residue was taken-up in dichloromethane (200 mL) and stirred with a saturated sodium carbonate solution for 0.5 hr. The aqueous layer was extracted with dichloromethane (50 mL) . The combined organic extracts were washed with 5% sodium hydroxide solution (3 x 100 mL), brine (100 mL) and dried. Removal of solvent and distillation of the residue provided 14.4g (41% yield) of ketpnes, bp 100-105°C, 0.5 mm. GLC analysis shows the product contains 76.4% of 4-(2,2,4,6,6-pentamethyl-3- cyclohexene-l-yl)-3-penten-2-one and a 14.6% component which was purified by chromatography (GLC purity 97%) and shown by spectroscopy to be l-[2,2,4,4,6-pentamethyl-3-(l- methylethenyl)-5-cyclohexen-l-yl]-ethanone. H-NMR (60 MHz, CDCl ₃ )£θ.92 (3H, S) , 1.01 (6H, s), 1.13 (3H, s), 1.60 (3H, s), 1.82 (3H, s), 2.20 (3H, s), 2.57 (IH, s), 2.77 (IH, s),

4.75 (IH, broad s), 4.98 (IH, broad s), 5.27 (IH, broad s); IIRR ((ffiillmm)) ' vv _m m _a a _χ x 22995500,, 11771166,, 11663300,, 11444400,, 1380, 1350 cm ^"1 ; MS m/e 234, 219, 216, 201, 191, 149, 135.

EXAMPLE 10

Cyclohexene Pentanol Derivative

Lithium shot (0.5g, 0.071 mol) was added portionwise over a 40 in. period to a cold (-30 to -40°C) mixture of 4-(2,2,4, 6,6-pentamethyl-3-cyclohexene-l-yl)-3-penten-2-one (1.08g, 0.0046 mol), ether (20 mL), ethanol (20 mL) and ammonia (80 mL). Ammonium chloride (8.0g) was added to the blue colored reaction mixture. The ammonia was allowed to evaporate. Ether (100 mL) and water (.200 mL) were added to the residue. The aqueous layer was extracted with ether (100 mL) . The Sbmbined organic extracts were washed with 0.5N HC1 (2 x 100 mL), saturated sodium bicarbonate solution (lOOmL) and dried. Evaporation of solvents, chromatography of the residue and kugelrohr distillation provided 0.850g (78% yield) of c^,γ2,2,4,6,6-heptamethyl-3-cyclohexene-l-propanol. GLC analysis shows 4 isomers of 4.1%, 12.8%, and 82.3% (two peaks incompletely resolved). -""H-NMR (60 MHz, CDC13) £ 0.98 and 1.05 (12H, 2s), 1.12 (3H, d, J = 6 Hz), 1.25 (3H, d, J = 4 Hz), 1.60 (3H, s), 1.0-2.5 (7H, m) , 3.6-4.1 (IH, m) , 5.00 (IH, broad s). IR (film) v _maχ 3320, 2950, 1640, 1470, 1450, 1380, 1360, cm ^"1 ; MS m/e 238, 223, 180, 151, 109, 96.

EXAMPLE 11

The following illustrates the utility of a mixture of 4-(2,2,4,6,6-pentamethyl-3-cyclohexen-l-yl)-3-penten-2-one ^~ and l-[2,2,4,6,6-pentamethyl-3-(l-methylethenyl)-5-cyclo- hexen-l-yl]-ethanone, the compounds from Example 9, in a fragrance composition of the Chypre type.

Compositions similar to the above can be made using the compound from Example 9 at a level of 1% or 3%.

EXAMPLE 12

The following illustrates the utility of c(,2,2,4,6,6- hexamethyl-Y-methylene-3-cyclohexene-l-propanol in a fragrance composition of the Muguet type.

Component Part/Weiαht

Compounds from Example 2 50

Lilial 100 Phenylethyl Alcohol 100

Benzylacetate 100

Terpineol 318 250

Hydroxycitronellol 50

Heliotropine 10 Cyclomenaldehyde 10

Cinnamyl alcohol 20

Geraniol 20

Citronellol 30

Indol (10% in DEP) 10 Hexyl Cinnamaldehyde 50 -

Hydrotropaldehyde Dimethyl Acetal 20

Ethylene Brassylate 10

Methyl Eugenol 10

Stryrallyl Acetate 20 Diethyl Phthalate (DEP) 140.

1000 Compositions similar to the above can be made using the compound from Example 2 at a level of 10% and 15%.