Compound with a woody odour

Abstract

The present invention concerns 2-methyl-5-[2-methyl-3-methylene-bicyclo[2.2.1]hept-5-en-2-yl)]-2-penten-1-ol in any of its stereometric forms or a lower ester thereof and their use as perfuming ingredient, in particular to impart sandalwood and cedar wood notes.

Claims

1. A compound of formula ##STR00005## in the form of any one of its stereoisomers or a mixture thereof; wherein R represents a hydrogen atom, and wherein the compound of formula (I) imparts sandal and cedar wood odor notes.

2. A compound according to claim 1, wherein said compound is in the form of a mixture of stereoisomers comprising more than 50% (w/w) of the (1SR,2SR,4RS) stereoisomer and of a mixture of isomers E and Z wherein said isomers Z represent at least 75% (w/w) of the total mixture.

3. A perfuming ingredient comprising a compound of formula (I), as defined in claim 2.

4. A perfuming composition comprising i) at least one compound of formula (I), as defined in claim 2; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant.

5. A perfuming consumer product, wherein it comprises at least one compound of formula (I), as defined in claim 2.

6. A perfuming consumer product according to claim 2, wherein said product is a perfume, a fabric care product, a body-care product, an air care product or a home care product.

7. A perfuming consumer product according to claim 2, wherein said product is a fine perfume, a cologne, an after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a shampoo, a coloring preparation, a hair spray, a vanishing cream, a deodorant or antiperspirant, a perfumed soap, shower or bath mousse, oil or gel, a hygiene product, an air freshener, a ready to use powdered air freshener, a wipe, a dish detergent or hard-surface detergent.

8. A compound according to claim 1, wherein said compound is ()-(2Z)-2-methyl-5-[(1R,2R,4S)-2-methyl-3-methylenebicyclo[2.2.1]hept-5-en-2-yl]-2-penten-1-ol.

9. A perfuming ingredient comprising a compound of formula (I), as defined in claim 8.

10. A perfuming composition comprising i) at least one compound of formula (I), as defined in claim 8; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant.

11. A perfuming consumer product, wherein it comprises at least one compound of formula (I), as defined in claim 8.

12. A perfuming consumer product according to claim 8, wherein said product is a perfume, a fabric care product, a body-care product, an air care product or a home care product.

13. A perfuming consumer product according to claim 8, wherein said product is a fine perfume, a cologne, an after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a shampoo, a coloring preparation, a hair spray, a vanishing cream, a deodorant or antiperspirant, a perfumed soap, shower or bath mousse, oil or gel, a hygiene product, an air freshener, a ready to use powdered air freshener, a wipe, a dish detergent or hard-surface detergent.

14. A perfuming ingredient comprising a compound of formula (I), as defined in claim 1.

15. A perfuming consumer product, wherein it comprises at least one compound of formula (I), as defined in claim 14.

16. A perfuming consumer product according to claim 14, wherein said product is a perfume, a fabric care product, a body-care product, an air care product or a home care product.

17. A perfuming consumer product according to claim 14, wherein said product is a fine perfume, a cologne, an after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a shampoo, a coloring preparation, a hair spray, a vanishing cream, a deodorant or antiperspirant, a perfumed soap, shower or bath mousse, oil or gel, a hygiene product, an air freshener, a ready to use powdered air freshener, a wipe, a dish detergent or hard-surface detergent.

18. A perfuming composition comprising i) at least one compound of formula (I), as defined in claim 1; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant.

19. A perfuming consumer product, wherein it comprises at least one compound of formula (I), as defined in claim 1.

20. A perfuming consumer product according to claim 19, wherein said product is a perfume, a fabric care product, a body-care product, an air care product or a home care product.

21. A perfuming consumer product according to claim 19, wherein said product is a fine perfume, a cologne, an after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a shampoo, a coloring preparation, a hair spray, a vanishing cream, a deodorant or antiperspirant, a perfumed soap, shower or bath mousse, oil or gel, a hygiene product, an air freshener, a ready to use powdered air freshener, a wipe, a dish detergent or hard-surface detergent.

Description

EXAMPLES

(1) The invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade ( C.); the NMR spectral data were recorded in CDCl.sub.3 (if not stated otherwise) with a 360 or 400 MHz machine for .sup.1H and .sup.13C, the chemical shifts are indicated in ppm with respect to TMS as standard, the coupling constants J are expressed in Hz.

Example 1

Synthesis of Compounds of Formula (I)

(2) The invention's compound was obtained according to the following reaction Scheme:

(3) ##STR00004##

Preparation of ()-(1R,2R,3R,4S)-21

(4) Compound ()-(1R,2R,3R,4S)-12 (obtained as described in WO2012/110375, pg 26) was converted into ()-(1R,2R,3R,4S)-21 by the addition of ethynyl as described in WO2012/110375, pg 19 for the racemic compound (21a in WO2012/110375).

(5) The optically active target compound was obtained in 82% yield, with NMR spectra identical to the one of the reported racemic compound and an [].sub.D.sup.20=3.3 at c=2.2% in CHCl.sub.3.

Preparation of ()-(1R,2R,4S)-22

(6) Compound ()-(1R,2R,3R,4S)-21 was converted into ()-(1R,2R,4S)-22 by elimination as described in WO2012/110375, pg 20 for the racemic compound (22 in WO2012/110375). The optically active target compound was obtained in 84% yield, with NMR spectra identical to the one of the reported racemic compound and an [].sub.D.sup.20=150.2 at c=1.6% in CHCl.sub.3.

Preparation of ()-(1R,2R,4S)-23

(7) Compound ()-(1R,2R,4S)-22 was converted into ()-(1R,2R,4S)-23 by the rearrangement as described in WO2012/110375, pg 23 for the racemic compound (23 in WO2012/110375).

(8) The optically active target compound was obtained in 60% yield, with NMR spectra identical to the one of the reported racemic compound and an [].sub.D.sup.20=417.5 at c=3.8% in CHCl.sub.3 (e.g. of about 90%).

Preparation of ()-(E)-(1R,2R,4S)-2-Methyl-3-methylene bicyclo[2.2.1]hept-5-en-2-yl]prop-2-en-1-ol: ()-(1R,2R,4S)-51

(9) Aldehyde ()-(1R,2R,4S)-23 (100 mg, 0.574 mmol) in THF (5 ml) was added dropwise to a suspension of LiAlH.sub.4 (43.6 mg, 1.15 mmol) in THF (5 ml) at 10 C. After five minutes, 15% w/w aqueous NaOH (5 ml) was added dropwise at 0 C. and the reaction mixture which was then filtered, separated, dried (Na.sub.2SO.sub.4), concentrated and purified by CC/SiO.sub.2 (cyclohexane/AcOEt 85:15) to afford quantitatively the pure desired allylic alcohol.

(10) [].sub.D.sup.20=435.5 at c=2.5% in CHCl.sub.3.

(11) .sup.1H-NMR: 1.07 (s, 3H); 1.33 (brs, 10H); 1.54 (dt, J=8.6, 1.4, 1H); 1.74 (dt, J=8.6, 1.4, 1H); 2.63 (brs, 1H); 3.19 (brs, 1H); 4.13 (dd, J=1.2, 5.7, 2H); 4.65 (s, 1H); 5.06 (s, 1H); 5.74 (dt, J=15.5, 5.7, 1H); 5.84 (dt, J=15.5, 1.2, 1H); 6.13-6.17 (m, 2H).

(12) .sup.13C-NMR: 157.5 (s); 140.8 (d); 136.0 (d); 135.9 (d); 126.7 (d); 104.5 (t); 64.0 (t); 52.4 (d); 52.0 (d); 48.8 (s); 48.1 (t); 26.8 (q).

Preparation of 3-((1R,2R,4S)-2-methyl-3-methylenebicyclo[2.2.1]hept-5-en-2-yl)propanal: ()-(1R,2R,4S)-52

(13) According to the general procedure described by C. Chapuis et al. in Helv. Chim. Acta 2001, 84, 230. MeOBiphep (13.88 mg, 0.024 mmol) was added to a solution of [Rh(cod).sub.2]BF.sub.4 (9.68 mg, 0.024 mmol), in THF (2 ml), followed, after 1 hour at 20 C., by a solution of allylic alcohol ()-(1R,2R,4S)-51 (60 mg, 0.34 mmol) in THF (8 ml). This mixture was refluxed under Ar for 18 hours, then filtered at 20 C., concentrated and purified by CC/SiO.sub.2 (cyclohexane/AcOEt 97:3 to 95:5) to afford pure aldehyde ()-(1R,2R,4S)-52 (34% yield, 68% yield based on recovered starting material).

(14) [].sub.D.sup.20=213.3, at c=0.5% in CHCl.sub.3.

(15) .sup.1H-NMR: 0.95 (s, 3H); 1.55 (dt, J=8.5, 1.6, 1H); 1.77 (dt, J=8.5, 1.6, 1H); 1.81-1.87 (m, 2H); 2.57-2.59 (m, 2H); 2.60 (brs, 1H); 3.18 (brs, 1H); 4.62 (s, 1H); 4.95 (s, 1H); 6.11-6.15 (m, 2H); 9.81 (t, J=1.6, 1H).

(16) .sup.13C-NMR: 202.6 (d); 160.0 (s); 136.7 (d); 135.6 (d); 103.2 (t); 52.3 (d); 50.4 (d); 47.8 (t); 45.0 (s); 40.4 (t); 33.3 (t); 25.3 (q).

Preparation of the Invention's Compounds

(17) ()-(2Z)-2-methyl-5-[(1R,2R,4S)-2-methyl-3-methylenebicyclo[2.2.1]hept-5-en-2-yl)]-2-penten-1-ol Coll 64199 A3: ()-(Z)-(1R,2R,4S)-54a or ()-dehydro--santalol ()-(2Z)-2-methyl-5-[(1R,2R,4S)-2-methyl-3-methylidenebicyclo[2.2.1]hept-5-en-2-yl]-2-penten-1-yl formate: ()-(Z)-(1R,2R,4S)-54b or ()-dehydro--santalyl formiate

(18) nBuLi (1.6 M/hexane, 0.215 ml, 0.343 mmol) was added dropwise at 0 C. to a solution of ethyltriphenylphosphonium iodide (144 mg, 0.343 mmol) in THF (13.5 ml). The resultant solution was cooled to 78 C. and a solution of aldehyde ()-(1R,2R,4S)-52 (55 mg, 0.312 mmol) in THF (1.5 ml) was added dropwise. After 15 minutes, a solution of nBuLi (1.6 M/hexane, 0.234 ml, 0.377 mmol) was added dropwise, then after 20 minutes, the temperature was equilibrated to 0 C. for 2 hours. Dry paraformaldehyde (56.2 mg, 1.872 mmol) was added and the reaction mixture was stirred at 20 C. for one day, before being put onto saturated aqueous NH.sub.4Cl. The reaction mixture was extracted with CH.sub.2Cl.sub.2, dried (Na.sub.2SO.sub.4), concentrated and purified by CC/SiO.sub.2 cyclohexane/AcOEt 99:1 to afford ()-(Z)-(1R,2R,4S)-54a in 15% yield, and ()-(Z)-(1R,2R,4S)-54b in 12% yield.

()-(Z)-(1R,2R,4S)-54a

(19) [].sub.D.sup.20=229.0, at c=0.6% in CHCl.sub.3.

(20) .sup.1H-NMR: 0.96 (s, 3H); 1.25 (brs, 10H); 1.52 (ddd, J=1.7, 7, 10.4, 2H); 1.53 (d, J=8.9, 1H); 1.76 (d, J=8.9, 1H); 1.79 (d, J=1.1, 3H); 2.06-2.20 (m, 2H); 2.67 (brs, 1H); 3.15 (brs, 1H); 4.15 (s, 2H); 4.59 (s, 1H); 4.90 (s, 1H); 5.31 (t, J=7.4, 1H); 6.10 (dd, J=3.1, 5.4, 1H); 6.14 (dd, J=3.1, 5.4, 1H).

(21) .sup.13C-NMR: 160.9 (s); 137.0 (d); 135.4 (c); 134.1 (s); 128.9 (c); 102.5 (t); 61.6 (t); 52.2 (d); 50.0 (d); 47.8 (t); 45.6 (s); 42.1 (t); 25.3 (q); 23.4 (t); 21.2 (q).

()-(Z)-(1R,2R,4S)-54b

(22) [].sub.D.sup.20=172.0, at c=0.5% in CHCl.sub.3.

(23) .sup.1H-NMR: 0.97 (s, 3H); 1.51-1.55 (m, 4H); 1.76 ((d, J=1.1, 3H); 2.10-2.22 (m, 2H); 2.67 (s, 1H); 3.16 (s, 1H); 4.59 (s, 1H); 4.70 (dd, J=11.7, 16.0, 2H); 4.91 (s, 1H); 5.43 (t, J=7.2, 1H); 6.10 (dd, J=3.0, 7.4, 1H); 6.14 (dd, J=3.0, 7.4, 1H); 8.11 (t, J=0.8, 1H).

(24) .sup.13C-NMR: 161.1 (c); 160.9 (s); 137.0 (d); 135.4 (d); 131.9 (d); 128.9 (s); 102.5 (t); 62.5 (t); 52.2 (c); 50.0 (d); 47.8 (t); 45.6 (s); 41.7 (t); 25.3 (q); 23.7 (t); 21.4 (q).

Example 2

Preparation of a Perfuming Composition

(25) A perfume composition for woman was prepared by admixing the following ingredients:

(26) TABLE-US-00001 Parts by weight Ingredient 400 Benzyl acetate 50 2-Methyl-1-phenyl-2-propanol 200 Citronellyl acetate 100 Styrallyl acetate 150 Cinnamic alcohol 100 10%* Anisic aldehyde 50 10%* C 10 aldehyde 100 10%* C 12 aldehyde 100 10%* Aldehyde MNA 25 Armoise oil 250 Bergamot essential oil 100 10%* Raspberry ketone 50 Benzyl cinnamate 250 Coranol .sup.1) 100 Coumarine 50 2-Heptyl-1-cyclopentanone 100 Geranium oil 500 Hydroxycitronellal 750 Iralia .sup.2) 200 Isoeugenol 200 Jasmal .sup.3) 250 Linalool 900 Lyral .sup.4) 150 Methylisoeugenol 500 Muscenone .sup.5) Delta 1500 Benzyl salicylate 1000 Australian Santal oil 200 Styrax essential oil 25 Vanilline 1000 Vertofix .sup.6) Coeur 400 Wardia .sup.7) 250 Ylang oil 10000 *in dipropyleneglycol .sup.1) 4-cyclohexyl-2-methyl-2-butanol; origin: Firmenich SA, Geneva, Switzerland .sup.2) mixture of methylionones isomers; origin: Firmenich SA, Geneva, Switzerland .sup.3) tetrahydro-3-pentyl-2h-pyran-4-yl acetate; origin: International Flavors & Fragrances, USA .sup.4) 4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde; origin: International Flavors & Fragrances, USA .sup.5) 3-methyl-5-cyclopentadecen-1-one; origin: Firmenich SA, Geneva, Switzerland .sup.6) methyl cedryl ketone; origin: International Flavors & Fragrances, USA .sup.7) compounded perfumery base; origin: Firmenich SA, Geneva, Switzerland

(27) The addition of 200 parts by weight of ()-dehydro--santalol to the above-described composition imparted to the latter a much more natural connotation which was very similar to the one obtained using a Indian sandalwood oil instead of the Australian one (the best ever type of sandalwood oil is the Indian one, but now not more available on the market since protected species). The invention's compound also adds an unusual cedar wood twist, not obtained when instead was added ()--santalol.

Example 3

Preparation of a Perfuming Composition

(28) A perfume composition for woman, of the agarwood type, was prepared by admixing the following ingredients:

(29) TABLE-US-00002 Parts by weight Ingredient 60 Citronellyl acetate 120 Geranyl acetate 30 Phenylethyl acetate 60 10%* C 7 aldehyde 60 Poplar oil 60 Benzylacetone 300 Castoreum oil 150 Cedar oil 60 Citral 1500 Citronellol 150 Coranol .sup.1) 120 10%* Damascenone 60 10%* Ethyl decanoate 90 10%* Etaspirene .sup.2) 900 Geraniol 15 Geranium oil 60 Clove oil 180 Alpha Irone 300 Labdanum oil 90 Methylisoeugenol 45 Nutmeg oil 330 Nerol 30 Linalyl oxide 30 Rose oxide 690 Phenethylol 30 10%* Cis-3-hexenol 225 1%* Para Cresol 15 Safranal 1500 Sandela .sup.3) 1200 Australian Santal oil 30 Origanol 30 Terpineol Alpha 240 Vetyver oil 30 Beta Ionone 210 (1S,2S,3S)-2,6,6-Trimethyl-bicyclo[3.1.1]heptane-3 spiro-2-cyclohexen-4-one 9000 *in dipropyleneglycol .sup.1) 4-cyclohexyl-2-methyl-2-butanol; origin: Firmenich SA, Geneva, Switzerland .sup.2) 6-ethyl-2,10,10-trimethyl-1-oxaspiro[4.5]deca-3,6-diene; origin: Firmenich SA, Geneva, Switzerland .sup.3) 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol; origin: Givaudan SA, Vernier, Switzerland

(30) The replacement of 200 parts by weight of Australian Santal oil with the same amount of ()-dehydro--santalol in the above-described composition astonishingly boosted the santal notes and reinforced the lait de santal effect imparting also a more natural effect. Such effect was not obtainable when using the commercially available synthetic sandalwood odorants such as the campholenic ones described in the literature.