5,5-dimethyl-2-propyl-hexahydro-2,4a-methano-naphthalen-1-one as a fragrance agent

Abstract

The invention relates to a compound of general formula (I) shown hereafter: ##STR00001##
as well as a composition comprising at least said compound of general formula (I), and its uses in perfumery.

Claims

1. A compound of the following general formula (I): ##STR00021## wherein the compound has an odor having no undesirable camphoraceous notes.

2. A compound according to claim 1, wherein the decalin group is in a cis configuration (Ia) or (Ib). ##STR00022##

3. A compound according to claim 1, wherein the decalin group is in a trans configuration (Ic) or (Id). ##STR00023##

4. A composition comprising at least one compound of general formula (I), (Ia), (Ib), (Ic) or (Id) as defined in claim 1, in the form of a stereoisomer, or a mixture of stereoisomers, or a racemic mixture.

5. The composition according to claim 4 further comprising at least one other odorizing substance.

6. The composition according to claim 4, wherein the compound is present in a concentration of between 0.1 and 99% by weight relative to the total weight of the composition.

7. The composition according to claim 6, wherein the compound is present in a concentration of between 0.1 and 30% by weight relative to the total weight of the composition.

8. A method of imparting a fragrance to a cosmetic composition or household product comprising adding at least one compound of formula (I) as defined in claim 1 as a fragrant agent to said composition or product.

9. The method according to claim 8, wherein the compound of formula (I) is used in combination with at least one other aromatic or perfuming ingredient, and/or at least one solvent, and/or at least one additive.

10. The method according to claim 8 wherein the compound confers modifies or reinforces the organoleptic properties of a substance, a composition, or an article.

11. The method according to claim 8 wherein the compound is in the form of a racemic mixture comprising the cis-decalin compounds (Ia) and (Ib), and said compound is used to modify or reinforce the organoleptic properties of a substance, a composition, or an article.

12. A method of mask ng or neutralizing an odor in a cosmetic composition or household product comprising adding at least one compound of formula (I) as defined in claim 1 as an odor-masking or odor-neutralizing agent to said composition or product.

Description

EXAMPLE 1

Comparison of the Olfactory Evaluations of the Compound of Formula (I) Relative to the Compounds of the Prior Art

(1) TABLE-US-00001 Olfactory Olfactory Olfactory evaluation of evaluation by evaluation of the compounds MANE of the the compounds disclosed in patent compounds of the Disclosed compounds or disclosed in patent U.S. Pat. No. prior art and the compounds of the invention EP 0029259 4,250,338 present invention Woody, green, minty, camphorated Woody camphorated, sweet with minty and amber traces Aromatic, camphorated, sweet, slightly earthy Green, camphorated, woody Woody, with green, acid, cardamom traces Camphorated, woody, resinous traces 0 Very weak, practically odourless Warm rich amber notes, clean, powerful without camphorated or earthy notes. Linear and very persistent notes Same olfactory evaluation as that for cis- decalin compound, but with a weaker intensity

EXAMPLE 2

Olfactory Evaluation of the Ketone Compounds of the Prior Art Relative to the Compound According to the Invention

(2) TABLE-US-00002 Olfactory Olfactory Olfactory evaluation of evaluation by evaluation of the compounds MANE of the the compounds disclosed in patent compounds of the Disclosed compounds or disclosed in patent U.S. Pat. No. prior art and the compounds of the invention EP 0029259 4250338 present invention amber, woody dry woody (cedar, vetiver), amber-type and sandalwood type aromas amber, woody dry woody, amber-type, castoreum, cedar aroma, patchouli Woody, amber, cedar aroma with green and fruity traces Woody, amber, sandalwood- type and oriental aroma amber, woody, camphorated, aromatic sweet-fruity profile Warm rich amber notes, clean, powerful without camphorated or earthy notes. Linear and very persistent notes 0 Same olfactory evaluation as that for cis-decalin compound, but with a weaker intensity

EXAMPLE 3

Synthesis of a Racemic Mixture of the Compounds (Ia) and (Ib)

(3) Myrcene (136 g:1 mol) is reacted with 2-methylene pentanal (120 g:1.22 mol) in the presence of AlCl.sub.3 (8 g) in 350 ml of toluene for 16 hours at ambient temperature. After a flash distillation (boiling point: 100 C., 1 Torr), 107 g are obtained of a material which is then subjected to a cyclisation by a treatment using H.sub.2SO.sub.4 (4 g) dissolved in 600 ml of toluene, at 60 C. for 24 hours. After purification by distillation (boiling point: 104 C., 0.8 Torr), 81 g of a compound of formula (I) are obtained. If necessary, the compound of formula (I) can be crystallised with the aid of hexane at 28 C. in order to obtain crystals with a melting point of 45 C.

(4) Spectroscopic Analysis:

(5) NMR .sup.1H (CDCl.sub.3, 200 MHz): 0.89 (t, 3H, J=7 Hz); 0.95 (s, 3H); 0.99 (s, 3H); 1.17-1.93 (m, 16H); 2.00-2.06 (m, 1H).

(6) NMR .sup.13C (CDCl.sub.3, 50 MHz): 14.96 (q); 19.47 (t); 21.02 (t); 21.96 (t); 22.54 (t); 23.56 (q); 26.28 (q); 31.55 (t); 32.68 (t); 33.61 (s); 36.77 (t); 41.05 (t); 51.97 (s); 53.84 (d); 59.37 (s); 220.72 (s).

(7) IR: 1465, 1730, 2870, 2934, 2960 cm.sup.1

(8) MS: 234 (61, M.sup.+.), 205 (13), 191 (40), 177 (22), 165 (14), 164 (15), 163 (22), 151 (12), 150 (40), 149 (100), 135 (29), 126 (36), 122 (30), 121 (22), 109 (76), 108 (49), 107 (30), 105 (14), 95 (15), 93 (34), 91 (36), 81 (23), 79 (35), 77 (25), 69 (11), 67 (33), 55 (24), 41 (29).

EXAMPLE 4

Synthesis of a Racemic Mixture of Compounds (Ic) and (Id)

(9) A mixture of the compounds (Ia) and (Ib) is_refluxed in methanol in the presence of KOH (10% w/w) for 24 hours until complete isomerisation into compounds (Ic) and (Id).

(10) NMR 1H (CDCl3, 200 MHz): 0.89 (m, 9H); 1.12-1.85 (m, 16H); 1.89-2.00 (m, 1H).

(11) NMR 13C (CDCl3, 50 MHz): 14.96 (q); 19.37 (t); 20.76 (t); 23.93 (q); 24.11 (t); 25.94 (q); 29.64 (t); 30.90 (t); 31.45 (t); 32.05 (s); 37.90 (t); 38.43 (t); 50.44 (s); 52.21 (d); 58.89 (s); 220.59 (s).

(12) IR: 1462, 1739, 2869, 2929, 2955 cm1.

(13) MS: 234 (66, M+.), 205 (14), 191 (40), 177 (24), 165 (16), 164 (16), 163 (26), 151 (13), 150 (43), 149 (96), 135 (33), 126 (46), 125 (11), 123 (10), 122 (36), 121 (25), 110 (11), 109 (100), 108 (66), 107 (34), 105 (17), 95 (20), 93 (41), 91 (43), 81 (36), 80 (12), 79 (44), 77 (31), 69 (18), 67 (46), 65 (11), 55 (36), 53 (14), 43 (15), 41 (44), 39 (14).

EXAMPLE 5

Olfactory Evaluation of the Compounds (Ia) and (Ib) in Racemic Mixture

(14) The compounds (Ia) and (Ib) were evaluated in a 50% solution of methyl myristate: an amber, intense and linear odour which lasts for a very long time (in excess of two weeks) is noted.

EXAMPLE 6

Comparative Evaluation of a Formula Comprising or Not Comprising the Compound of Formula (I)

(15) TABLE-US-00003 Composition 1 Composition 2 Parts (by Parts (by Substance involved weight) weight) Violettyne.sup.1) 10 10 Compound of formula (I).sup.2) / 60 Calon 1951 Cal.sup.3) 10 10 Veramoss.sup.4) 4 4 Ethyl linalool.sup.5) 100 100 Florol.sup.6) 20 20 Methyl dihydro jasmonate.sup.7) 574 574 Helional.sup.8) 60 60 Iso E Super.sup.9) 40 40 Lilial.sup.10) 20 20 Melonal.sup.11) 2 2 Methylionantheme.sup.12) 10 10 Benzyl salicylate 20 20 Cis-3 hexenyl acetate.sup.13)14) 4 4 Styrallyl acetate.sup.14) 10 10 Allyl amyl glycolate.sup.14) 2 2 Galbex.sup.15) 4 4 Cis-3 hexenol.sup.14) 4 4 Liffarome.sup.16) 4 4 Triplal.sup.14)17) 2 2 DPG 100 40 Total 1000 1000 .sup.1)(E)-Undeca-1,3-dien-5-yne; origin: Firmenich, Switzerland .sup.2)Compound of formula (I) in the form of a racemic mixture; origin: V. Mane Fils, France. .sup.3)7-Methyl-benzo[b][1,4]dioxepin-3-one; origin: Symrise, Germany. .sup.4)2,4-Dihydroxy-3,6-dimethyl-benzoic acid methyl ester; origin: International Flavours and Fragrances, USA. .sup.5)origin: Givaudan, Switzerland. .sup.6)2-Isobutyl-4-methyl-tetrahydro-pyran-4-ol; origin: Firmenich, Switzerland. .sup.7)[3-Oxo-2-((E)-pentyl)-cyclopentyl]-acetic acid methyl ester; origin: Firmenich, Switzerland. .sup.8)3-Benzo[1,3]dioxol-5-yl-2-methyl-propionaldehyde; origin: International Flavors and Fragrances, USA. .sup.9)1-(2,3,8,8-Tetramethyl-1,2,3,4,5,6,7,8-octahydro-naphthalen-2-yl)-ethanone; origin: International Flavours and Fragrances, USA. .sup.10)3-(4-tert-Butyl-phenyl)-2-methyl-propionaldehyde; origin: Givaudan Switzerland. .sup.11)2,6-Dimethyl-hept-5-enal; origin: Givaudan Switzerland. .sup.12)(E)-3-Methyl-4-(2,6,6-trimethyl-cyclohex-2-enyl)-but-3-en-2-one; origin: Firmenich, Switzerland. .sup.13)origin: V. Mane Fils, France. .sup.14)10% in dipropylene glycol. .sup.15)origin: Firmenich, Switzerland. .sup.16)Carbonic acid (E)-hex-3-enyl ester methyl ester; origin: International Flavors and Fragrances, USA. .sup.17)2,4-Dimethyl-cyclohex-3-enecarbaldehyde; origin: International Flavors and Fragrances, USA. .sup.18)Ethoxy-methoxy-cyclododecane; origin: Henkel, Germany.
Evaluation of Composition 2/Composition 1:

(16) Top: powerful amber-woody note from the beginning of evaporation. Strengthens the composition's fruity and green notes.

(17) Middle and base: elegant woody and amber harmony, goes very well with the composition's sea odour, creating a unique and powerful character. Persists for a long time on a smelling strip.