WO2012045608A1

WO2012045608A1 - Odorant alcohols

Info

Publication number: WO2012045608A1
Application number: PCT/EP2011/066713
Authority: WO
Inventors: Robert Moretti
Original assignee: Firmenich Sa
Priority date: 2010-10-05
Filing date: 2011-09-27
Publication date: 2012-04-12

Abstract

The present invention relates to the use as perfuming ingredient to impart floral and indol notes of a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein n represents 0 or 1 and at least one R represents a methyl group and the other a hydrogen atom or a methyl group.

Description

ODORANT ALCOHOLS

Technical field

The present invention relates to the field of perfumery. More particularly, it concerns a 1-alkyl-cyclohexanol or cyclopentanol derivative, as defined herein below, as perfuming ingredient to impart floral and indol notes. Therefore, following what is mentioned herein, the present invention comprises the invention' s compound as part of a perfuming composition or of a perfuming consumer product.

Prior art

Floral and indol fragrance notes are quite useful in perfumery. However compounds possessing the two notes together, in a balanced and useful manner, are quite rare, and therefore there is a need for such ingredients.

To the best of our knowledge, only two compounds of formula (I), as defined herein below, are known from the prior art, namely l-(2,2-dimethylpropyl)-cyclopentanol and l-(2,2-dimethylpropyl)-cyclohexanol which are disclosed as chemical intermediates only (see M. Salamone et al. in Journal of Organic Chemistry (2004), 69, 5281 or M. Stratakis et al. in Synthetic Communications (1993), 23, 425). However, said disclosures do not suggest any organoleptic properties of the compounds of formula (I), or any use of said compounds in the field of perfumery.

Very recently, EP 2234948 reported the use in perfumery of similar compounds having an unsaturated branched chain, instead of the saturated branched chain of the present invention. However said prior art compounds have a very different odor. Moreover, this prior art document does not report or suggest any organoleptic properties of the compounds of formula (I), or any use of said compounds in the field of perfumery.

Description of the invention

We have now surprisingly discovered that a compound of formula

in the form of any one of its stereoisomers or a mixture thereof, and wherein n represents 0 or 1 and at least one R represents a methyl group and the other a hydrogen atom or a methyl group;

can be used as perfuming ingredient, for instance to impart odor notes of the floral and indol type.

According to a particular embodiment of the invention, n represents 1.

According to any one of the above embodiments of the invention, said compound (I) is a Cn or Ci₂ compound.

According to any one of the above embodiments of the invention, one of said R is a methyl group and the two others represent hydrogen atoms.

As specific examples of the invention's compounds, one may cite, as non-limiting example, l-(3-methylbutan-2-yl)-cyclohexanol which has an odor combining floral notes, of the lily of the valley type, and a very interesting jasmine, indolic aspect. The overall odor combines together the freshness of lily of the valley with the warm, animal/indolic note of the jasmine flower family.

As other example, one may cite l-(2,2-dimethylbutyl)-cyclohexanol, which possesses an odor similar to the one mentioned above but distinguishing itself by having a stronger indolic note.

According to a particular embodiment of the invention, the compound of formula (I) is l-(3-methylbutan-2-yl)-cyclohexanol.

When the odor of the invention's compounds is compared with that of the prior art compound disclosed in EP 2234948, then the invention's compounds distinguish themselves by a totally different note, for instance by not having a sap character but possessing a floral, indol character, the latter being absent in the prior art analogues. Said differences lend the invention's compounds and the prior art compounds to be each suitable for different uses, i.e. to impart different organoleptic impressions.

As mentioned above, the invention concerns the use of a compound of formula (I) as perfuming ingredient. In other words, it concerns a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least a compound of formula (I). By "use of a compound of formula (I)" it has to be understood here also the use of any composition containing a compound (I) and which can be advantageously employed in perfumery industry.

Said compositions, which in fact can be advantageously employed as perfuming ingredients, are also an object of the present invention.

Therefore, another object of the present invention is a perfuming composition comprising:

i) as perfuming ingredient, at least one invention's compound as defined above;

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.

By "perfumery carrier" we mean here a material which is practically neutral from a perfumery point of view, i.e. that does not significantly alter the organoleptic properties of perfuming ingredients. Said carrier may be a liquid or a solid.

As liquid carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive. However, one can cite as non-limiting example solvents such as dipropyleneglycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2- ethoxyethoxy)-l-ethanol or ethyl citrate, which are the most commonly used. For the compositions which comprise both a perfumery carrier and a perfumery base, other suitable perfumery carriers than those previously specified, can be also ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar^® (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol^® (origin: Dow Chemical Company).

As solid carrier one may cite, as non-limiting examples, absorbing gums or polymers, or yet encapsulating materials. Examples of such materials may comprise wall- forming and plasticizing materials, such as mono, di- or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins, or yet the materials cited in reference texts such as H. Scherz, Hydrokolloids : Stabilisatoren, Dickungs- und Gehermittel in Lebensmittel, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitat, Behr's VerlagGmbH & Co., Hamburg, 1996. The encapsulation is a well known process to a person skilled in the art, and may be performed, for instance, using techniques such as spray-drying, agglomeration or yet extrusion ; or consists of a coating encapsulation, including coacervation and complex coacervation techniques.

By "perfumery base" we mean here a composition comprising at least one perfuming co-ingredient.

Said perfuming co-ingredient is not of formula (I). Moreover, by "perfuming co- ingredient" it is meant here a compound, which is used in a perfuming preparation or a composition to impart a hedonic effect. In other words such a co-ingredient, to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.

The nature and type of the perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to intended use or application and the desired organoleptic effect. In general terms, these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds.

By "perfumery adjuvant" we mean here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in perfuming bases cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.

An invention's composition consisting of at least one compound of formula (I) and at least one perfumery carrier represents a particular embodiment of the invention as well as a perfuming composition comprising at least one compound of formula (I), at least one perfumery carrier, at least one perfumery base, and optionally at least one perfumery adjuvant.

It is useful to mention here that the possibility to have, in the compositions mentioned above, more than one compound of formula (I) is important as it enables the perfumer to prepare accords, perfumes, possessing the odor tonality of various compounds of the invention, creating thus new tools for his work.

For the sake of clarity, it is also understood that any mixture resulting directly from a chemical synthesis, e.g. a reaction medium without an adequate purification, in which the compound of the invention would be involved as a starting, intermediate or end-product could not be considered as a perfuming composition according to the invention as far as said mixture does not provide the inventive compound in a suitable form for perfumery. Thus, unpurified reaction mixtures are generally excluded from the present invention unless otherwise specified.

Furthermore, the invention's compound can also be advantageously used in all the fields of modern perfumery, i.e. fine or functional perfumery, to positively impart or modify the odor of a consumer product into which said compound (I) is added. Consequently, a perfuming consumer product which comprises:

i) as perfuming ingredient, at least one compound of formula (I), as defined above; and ii) a perfumery consumer base;

is also an object of the present invention.

The invention's compound can be added as such or as part of an invention's perfuming composition.

For the sake of clarity, it has to be mentioned that, by "perfuming consumer product" it is meant a consumer product which is expected to deliver at least a perfuming effect, in other words it is a perfumed consumer product. For the sake of clarity, it has to be mentioned that, by "perfumery consumer base" we mean here the functional formulation, as well as optionally additional benefit agents, corresponding to a consumer product which is compatible with perfuming ingredients and is expected to deliver a pleasant odor to the surface to which it is applied (e.g. skin, hair, textile, or home surface). In other words, a perfuming consumer product according to the invention comprises the functional formulation, as well as optionally additional benefit agents, corresponding to the desired consumer product, e.g. a detergent or an air freshener, and an olfactive effective amount of at least one invention' s compound. The nature and type of the constituents of the perfumery consumer base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature and the desired effect of said product.

Non-limiting examples of suitable perfumery consumer base can be a perfume, such as a fine perfume, a cologne or an after-shave lotion; a fabric care product, such as a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, or a bleach; a body-care product, such as a hair care product (e.g. a shampoo, a coloring preparation or a hair spray), a cosmetic preparation (e.g. a vanishing cream or a deodorant or antiperspirant), or a skin-care product (e.g. a perfumed soap, shower or bath mousse, oil or gel, or a hygiene product); an air care product, such as an air freshener or a "ready to use" powdered air freshener; or a home care product, such as a wipe, a dish detergent or hard- surface detergent.

Some of the above-mentioned consumer product bases may represent an aggressive medium for the invention's compound, so that it may be necessary to protect the latter from premature decomposition, for example by encapsulation or by chemically bounding it to another chemical which is suitable to release the invention's ingredient upon a suitable external stimulus, such as an enzyme, light, heat or a change of pH.

The proportions in which the compounds according to the invention can be incorporated into the various aforementioned articles or compositions vary within a wide range of values. These values are dependent on the nature of the article to be perfumed and on the desired organoleptic effect as well as the nature of the co-ingredients in a given base when the compounds according to the invention are mixed with perfuming co- ingredients, solvents or additives commonly used in the art.

For example, in the case of perfuming compositions, typical concentrations are in the order of 0.001 % to 30 % by weight, or even more, of the compounds of the invention based on the weight of the composition into which they are incorporated. Concentrations lower than these, such as in the order of 0.01% to 10% by weight, can be used when these compounds are incorporated into perfumed articles, percentage being relative to the weight of the article.

The invention's compounds can be prepared according to a method as described herein below in the Examples. Examples

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 CDCI₃ (if not stated otherwise) with a 360 or 400 MHz machine for H and ¹³C, the chemical shifts δ 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)

a) Preparation of l-(3-methylbutan-2-yl)-cyclohexanol

l-(3-methylbut-3-en-2-yl)-cyclohexanol

A 1 molar solution of n-propylmagnesium bromide in diethyl ether (190 ml, 190 mmol) was transferred via cannula onto freshly distilled isoprene (13.2 g, 190 mmol) at room temperature and under nitrogen. After 15 minutes, bis (cyclopentadienyl) titanium dichloride (0.5 g, 1.9 mmol) was added to the reaction, which was stirred overnight. The reaction was cooled into an ice-water bath and cyclohexanone (24.3 g, 247 mmol) was added over 1.5 hours. The reaction was stirred at room temperature overnight. After cooling into an ice-water bath, the reaction was quenched by the slow addition of a saturated, aqueous solution of ammonium chloride (500 ml). The phases were separated. The organic phase was washed with more ammonium chloride solution (500 ml) and brine (300 ml). Each aqueous phase was re-extracted with diethyl ether (500 ml). Combined extracts were dried over solid anhydrous sodium sulfate. The product was purified by column chromatography on silica gel (eluent: heptanes/ethyl acetate 5: 1) followed by bulb-to-bulb distillation. 29.3 g of pure compound were obtained as a colorless liquid (174 mmol, yield = 92 %).

B.p. = 71 °C/l mbar

¹³C-NMR: 148.45 (s); 112.68 (t); 72.41 (s); 50.14 (q); 36.30 (t); 35.15 (t); 25.84 (t); 22.85

(d); 22.22 (t); 22.08 (t); 13.77 (q).

^-NMR : 4.85 (m, 1 H) ; 4.75 (m, 1 H) ; 2.20 (q, J = 7, 1 H) ; 1.30 (broad s, 3 H) ; 1.63- 1.47 (m, 7 H) ; 1.45-1.30 (m, 2 H) ; 1.40 (s, 1 H) ; 1.25-1.12 (m, 1 H) ; 1.05 (d, J = 7, 3 H). l-(3-methylbutan-2-yl)-cyclohexanol

l-(3-methylbut-3-en-2-yl)-cyclohexanol obtained above (7.8 g, 46.4 mmol) was hydrogenated in methanol (20 ml) at 20 bars and room temperature in presence of 5 % palladium on carbon (0.15 g) until the theoretical amount of hydrogen had been absorbed. The product was purified by bulb-to-bulb distillation. 7.57 g of a 99 % pure compound were obtained as a colorless liquid (44 mmol, yield = 95 %).

B.p. = 71 °C/2 mbar

¹³C-NMR: 74.18 (s); 47.22 (d); 35.54 (t); 35.44 (t); 26.08 (d); 25.91 (t); 24.11 (q); 22.19

(t); 22.09 (t); 17.60 (q); 7.29 (q).

^-NMR : 2.10 (m, 1 H) ; 1.62-1.32 (m, 10 H) ; 1.25-1.08 (m, 2 H) ; 0.90 (d, J = 7, 3 H) ;

0.84 (d, J = 7, 3 H); 0.81 (d, J = 7, 3 H). b) Preparation of l-(2,2-dimethylbutyl)-cyclohexanol

l-(2,2-dimethylbut-3-enyl)-cyclohexanol

1,2-dibromoethane was added to a suspension of magnesium turnings (18.85 g, 768 mmol) in dry diethyl ether (350 ml). Once a visible reaction had started, 1,5-dibromopentane (105 g, 443 mmol) in dry diethyl ether (350 ml) was added at a rate such as to maintain a mild reflux (addition took 3 hours). The reaction was further refluxed for 2 hours, at which point a 2 phase mixture was observed. The reaction was cooled into an ice-water bath and methyl 3,3-dimethylpent-4-enoate (45.5 g, 307 mmol) was added over 30 minutes. The reaction was warmed up to RT, then refluxed for 3 hours. After cooling to 0 °C, a saturated aqueous ammonium chloride solution (500 ml) was added slowly. After warming up to RT, the phases were separated. The organic phase was washed with water (1 liter) and brine (500 ml). Each aqueous phase was re-extracted with diethyl ether (500 ml). Combined extracts were dried over solid anhydrous sodium sulfate. The product was purified by column chromatography on silica gel (eluent: heptanes/ethyl acetate 10: 1) followed by bulb-to-bulb distillation. 22 g of a 96 % pure compound were obtained as a colorless liquid (121 mmol, yield = 39 %).

B.p. = 80 °C/l.l mbar

1³C-NMR: 149.46 (d); 110.46 (t); 72.87 (s); 54.50 (t); 39.40 (t); 37.16 (s); 29.34 (q);

25.76 (t); 22.19 (t).

^-NMR: 6.05 (m, 1 H); 5.00 (m, 2 H); 1.65-1.48 (m, 7 H); 1.58 (s, 1 H); 1.46-1.32 (m, 4

H); 1.28-1.15 (m, 1 H); 1.10 (s, 6 H). l-(2,2-dimethylbutyl)-cyclohexanol

l-(2,2-dimethylbut-3-enyl)-cyclohexanol obtained above (4.6 g, 24 mmol) in ethyl acetate (20 ml) was hydrogenated at ambient pressure and temperature in presence of 5 % palladium on carbon (0.3 g) until the theoretical amount of hydrogen had been absorbed. The product was purified by bulb-to-bulb distillation. 4.35 g of a 97.5 % pure compound were obtained as a colorless liquid (23 mmol, yield = 95 %).

B.p. = 75 °C/1 mbar

¹³C-NMR: 73.21 (s); 52.65 (t); 39.53 (t); 36.93 (t); 34.07 (s); 28.44 (q); 25.79 (t); 22.25

(t); 8.59 (q).

^-NMR : 1.70-1.40 (m, 10 H) ; 1.42 (s, 1 H) ; 1.35 (q, J = 7, 2 H) ; 1.28-1.16 (m, 2 H) ;

1.00 (s, 6 H) ; 0.82 (t, J = 7, 3 H).

Example 2 Preparation of a perfuming composition

A perfuming composition for soap was prepared by admixing the following ingredients:

Parts bv weight Ingredient

1500 Benzyl acetate

50 (Z)-3-Hexen-l-ol acetate

1000 Hexylcinnamic aldehyde

50 Methyl anthranilate

100 Gamma undecalactone

50 Gamma nonalactone

10 Maltol

50 Eugenol

600 Lilial^{@ 1)}

1500 Linalol

30 Cis jasmone

2000 Hedione^{® 2)}

10 (E)-8-Decen-5-olide

1000 Phenethylol 50 (Z)-3-Hexen-l-ol

1000 Benzyl salicylate

9000 1) 3-(4-tert-butylphenyl)-2-methylpropanal; origin: Givaudan SA, Vernier, Switzerland 2) methyl cis-dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland

The addition of 1000 parts by weight of l-(3-methylbutan-2-yl)-cyclohexanol to the above-described composition imparted to the latter a white floral fresness. The use of the prior art compounds of EP 2234948 provided totally different results introducing a strong green note or earthy note without any effect on the floral aspect of the fragrance and unbalancing the freshness of the fragrance.

Example 3

Preparation of a perfuming composition

A perfuming composition for eau de toilette, of the fresh type, was prepared by admixing the following ingredients:

Parts bv weight Ingredient

100 Benzyle acetate

100 Geranyl acetate de

50 Vetyveryl acetate

80 Aldehyde C 10

20 Aldehyde C 8

50 Aldehyde C 9

100 Wormwood essential oil

1500 Lemon essential oil

30 Citronellal

20 Coumarine

200 3 -( 1 , 3 -B enzodioxol- 5 -y 1) -2-methylpropanal

600 Hydroxycitronellal

300 Iralia^{® υ} total 100 Iso E^{® 2)} super

200 Lavender essential oil

100 Mandarine essential oil

20 2,6-Dimethyl-5-heptanal

70 Crystal moss

10 Cis jasmone

900 Hedione^{® 3)}

600 Neroli

350 Patchouli essential oil

300 Petitgrain essential oil

1500 Orange essential oil

100 Rosemary essential oil

100 Clary sage essential oil

7500

1) mixture of methylionones isomers; origin: Firmenich SA, Geneva, Switzerland

2) l-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-l-ethanone; origin: International Flavors & Fragrances, USA

3) methyl cis-dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland

The addition of 2500 parts by weight of l-(3-methylbutan-2-yl)-cyclohexanol to the above-described composition imparted to the latter a reinforced white floral connotation, which became cleaner. The use of the prior art compounds of EP 2234948 provided totally different results, introducing strong green, earthy notes without any effect on the white flower aspect of the fragrance.

Claims

1. perfuming ingredient of a compound of formula

in the form of any one of its stereoisomers or a mixture thereof, and wherein n represents 0 or 1 and at least one R represents a methyl group and the other a hydrogen atom or a methyl group.

2. Use according to claim 1, characterized in that n represents 1.

3. Use according to claim 1, characterized in that said compound (I) is a Cn or Ci2 compound.

4. Use according to claim 1, characterized in that said compound is l-(3- methylbutan-2-yl)-cyclohexanol.

5. A compound of formula

in the form of any one of its stereoisomers or a mixture thereof, and wherein n represents 0 or 1 and at least one R represents a methyl group and the other a hydrogen atom or a methyl group, provided that l-(2,2-dimethylpropyl)-cyclopentanol and l-(2,2- dimethylpropyl)-cyclohexanol are excluded.

6. A compound according to claim 5, characterized in that said compound is l-(3-methylbutan-2-yl)-cyclohexanol.

7. A perfuming composition comprising

i) at least one compound of formula (I), as defined in any one of claims 1 to 4;

iii) optionally at least one perfumery adjuvant.

8. A perfuming consumer product comprising:

i) at least one compound of formula (I), as defined in any one of claims 1 to 4; and ii) a perfumery consumer base.

9. A perfuming consumer product according to claim 8, characterized in that the perfumery consumer base is a perfume, a fabric care product, a body-care product, an air care product or a home care product.

10. A perfuming consumer product according to claim 8, characterized in that the perfumery consumer base 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.