WO2006046159A1

WO2006046159A1 - Chromanone derivatives as perfuming ingredients

Info

Publication number: WO2006046159A1
Application number: PCT/IB2005/053170
Authority: WO
Inventors: Jean-Marc Gaudin
Original assignee: Firmenich SA
Current assignee: Firmenich SA
Priority date: 2004-10-28
Filing date: 2005-09-26
Publication date: 2006-05-04
Anticipated expiration: 2007-04-28

Abstract

The present concerns the use as perfuming ingredient of 7-(methyl)-2-chromanone or 7-(ethyl)-2-chromanone to impart odors of the coumarin type.

Description

CHROMANONE DERIVATIVES AS PERFUMING INGREDIENTS

Technical field

The present invention relates to the field of perfumery. More particularly, it concerns the use as perfuming ingredient of 7-(methyl)-2-chromanonc or 7-(ethyl)-2- chromanone, e.g. to impart odors of the coumarin type.

The present invention concerns also the compositions or articles containing said compound.

Prior art

The invention's compounds are known chemicals. For instance one can refer to the patent US 3,144,467 were the invention compounds are used as starting material in the synthesis of various dihydrocoumarin derivatives. However, to the best of our knowledge, the invention's compounds have been reported only as intermediates in various synthesis and none of the prior art documents reports or suggests any organoleptic properties, or their use in the field of perfumery.

The compounds dihydrocoumarin and 6-(mcthyl)-2-chromanone, described in S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, are the known perfuming ingredients having the closest structure to the invention compounds. However, none of said two structural analogues has organoleptic properties that could be seen as suggesting a usefulness of the invention's compounds in the field of perfumery, and even less of any organoleptic properties of the present compounds.

Description of the invention We have now surprisingly discovered that a compound of formula

wherein R represents a methyl or ethyl group; can be used as perfuming ingredient, for instance to impart odor notes of the coumarin type.

The invention's compound wherein R is a methyl group, i.e. 7-methyl-2- chromanone, possesses a quite natural and rich coumarinic, phenolic odor, the latter having also bottom notes with nitro-musk, cinnaminic alcohol and hay tonalities.

When the fragrance of 7-methyl-2-chromanone is compared with the one of coumarin, then the two compounds have a fragrance quite close even if the invention's compound distinguishes itself by a Gaiacol and phenolic character more pronounced. In fact 7-methyl-2-chromanone is well suited to be used to replace coumarin. The invention's compound wherein R is an ethyl group, i.e. 7-ethyl-2-chromanone possesses an odor quite similar to the one of the methyl derivative mentioned above, except for the presence of a fenchylic-camphor note and a stronger phenolic character.

According to a particular embodiment of the invention the use of 7-methyl-2- chromanone is preferred. As mentioned above, dihydrocoumarin and 6-(methyl)-2-chromanone are the known perfuming ingredients having the closest structure to the invention's compounds.

In the one hand, the odor of the invention's compounds lacks the heavy-sweet, coconut-like note so characteristic of the prior art compound 6-(mcthyl)-2-chromanone. In the other hand, when the odor of the invention's compounds is compared with the one of the prior art compound dihydrocoumarin, then the invention's compounds distinguish themself by a clearly stronger coumarin-like note and by lacking the nut-like note so characteristic of the prior art compound.

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 ingredients. 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 compound (I) and which can be advantageously employed in perfumery industry as active ingredients. 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 phthalatc, isopropyl myristate, benzyl benzoate, 2-(2- ethoxycthoxy)-l-ethanol or ethyl citrate, which are the most commonly used.

As solid carrier one may cite, as non-limiting examples, absorbing gums or polymers, or yet encapsulating materials. Examples of such materials, for example, 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 Gchcrmittel 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.

Generally speaking, by "perfumery base" we mean here a composition comprising at least one perfuming co-ingredient. Said perfuming co-ingredient is not of the formula (I). Moreover, by "perfuming co-ingredient" it is meant here a compound, which is used in perfuming preparation or composition to impart a hedonic effect. In other words such a co-ingredicnt, 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 its 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, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, 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. For the compositions which comprise both a perfumery carrier and a perfumery base, other suitable perfumery carrier than those previously specified can be also ethanol, water/ethanol mixtures, limonene or other terpencs, 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).

Generally speaking, 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 their work. Preferably, any mixture resulting directly from a chemical synthesis, e.g. 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.

Furthermore, the invention's compound can also be advantageously used in all the fields of modern perfumery to positively impart or modify the odor of a consumer product into which said compound (I) is added. Consequently, a perfumed article comprising: i) as perfuming ingredient, at least one compound of formula (I), as defined above, or an invention's perfuming composition; and ii) a consumer product base; is also an object of the present invention.

For the sake of clarity, it has to be mentioned that, by "consumer product base" we mean here a consumer product, which is compatible with perfuming ingredients. In other words, a perfumed article according to the invention comprises the functional formulation, as well as optionally additional benefit agents, corresponding to a 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 consumer product 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 its general knowledge and according to the nature and the desired effect of said product. Examples of suitable consumer products include solid or liquid detergents and fabric softeners as well as all the other articles common in perfumery, namely perfumes, colognes or after-shave lotions, perfumed soaps, shower or bath salts, mousses, oils or gels, hygiene products or hair care products such as shampoos, body-care products, deodorants or antiperspirants, air fresheners and also cosmetic preparations. As detergents there are intended applications such as detergent compositions or cleaning products for washing up or for cleaning various surfaces, e.g. intended for textile, dish or hard-surface treatment, whether they are intended for domestic or industrial use. Other perfumed articles are fabric refreshers, ironing waters, papers, wipes or bleaches. 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.

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 15 % 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. 7-Methyl-2-chromanone was obtained according the procedures described by

P.Yates et al. in Can.J.Chem, 1988, 66, 1, and 7-ethyl-2-chromanone was obtained according the procedures described by P.Yates et al. in Can.J.Chem, 1993, 71_, 995.

The invention will now be described in further detail by way of the following examples. Example 1 Preparation of a perfuming composition

An "Eau de toilette" of the oriental-herbaceous type was prepared by admixing the following ingredients :

Ingredient Parts bv weight

Benzyl acetate 60

Geranyl acetate 40

Armoise 20

Bergamot essential oil 400

Lemon essential oil 250

Citronellol 60

Galbex^® 183 ^]) 10

Habanolide^{® 2)} 150

Hedione^{® 3)} HC 250

3-(l,3-Benzodioxol-5-yl)-2-methylpropanal 20

Helvetolide^{® 4)} 60

10%* 1-Phenylvinyl acetate ⁵⁾ 10

Lavender essential oil 60

Cristal moss 20

Muscenone ⁶⁾ 40

Nirvanol ⁷⁾ 40

Patchouli essential oil 100

Tamarine Base 41310 G ^!) 60

Vanilline 150

10%* 2,4-Dimethyl-3-cyclohexene- 1 -carbaldehyde 50

1850

* in dipropyleneglycol

1) Compounded perfumery base; origin: Firmenich SA, Geneva, Switzerland

2) Pentadecenolide; origin: Firmenich SA, Geneva, Switzerland

3) Methyl dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland 4) (lSJ'^^-f l-CS'^'-Dimethyl-r-cyclohexyOethoxyj^-methylpropyl propanoate; origin: Firmenich SA, Geneva, Switzerland

5) origin: Firmenich SA, Geneva, Switzerland

6) 3-Methyl-cyclopentadecenone; origin: Firmenich SA, Geneva, Switzerland 7) 3,3-Dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-l-yl)-4-penten-2-ol; origin:

Firmenich SA, Geneva, Switzerland

The addition of 150 parts by weight of 7-methyl-2-chromanone to the above-described

Eau de toilette imparted to the fragrance of the latter a clear powdery-coumarinic, oriental connotation and provides also a nice hay under note.

The addition of the same amount of 7-ethyl-2-chromanone gave a similar effect but having a champhor-pin character more perceivable.

This organoleptic effect was not reached by the addition of the same amount of dihydrocoumarin or 6-(methyl)-2-chromanone, which instead provided a much less harmonious and balanced scent with undesired lactonic or nut notes as well as a too weak coumarinic connotation.

Example 2 Preparation of a perfuming composition

A perfuming base of the herbaceous-musky type, for a soap, was prepared by admixing the following ingredients :

Ingredient Parts by weight Benzyl acetate 160

Geranyl acetate 40

Phcnylethyl acetate 60

Styrallyl acetate 60

Terpenyl acetate 120 Hexylcinnamic aldehyde 250

10%* Aldehyde Supra ⁰ 40

Eugenol 20 Habanolide^{® 2)} 140

Iralia Total ³⁾ 150

Lavandin Grosso 100

Liliaf ⁴' 140 Linalol 150

Lorysia^{® 5)} 300

Mcthylnaphty ketone 30

Hedione^{® 6)} 80

Roselia - 41014 E ⁷⁾ 60 1900

* in dipropyleneglycol

1) 9-Undecenal; origin: Firmenich SA, Geneva, Switzerland

2) Pentadecenolide; origin: Firmenich SA, Geneva, Switzerland 3) Methylionones; origin: Firmenich SA, Geneva, Switzerland

4) 3-(4-Tert-butylphenyl)-2-methylpropanal; origin: Givaudan-Roure SA, Vernier, Suisse

5) 4-(l,l-Dimethylethyl)-l-cyclohexyl acetate; origin: Firmenich SA, Geneva, Switzerland

6) Methyl dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland 7) Compounded perfumery base; origin: Firmenich SA, Geneva, Switzerland

The addition of 100 parts by weight of 7-mcthyl-2-chromanone to the above-described perfuming base for soap imparted to the overall scent a very nice softness by reinforcing the lavender note and by harmonizing the musk connotation. The addition of 150 parts by weight of 7-ethyl-2-chromanone gave an effect more phenolic, pin and less sweet and oriental than the one provided by the methyl derivative mentioned above.

This organoleptic effect was not reached by the addition of the same amount of dihydrocoumarin or 6-(methyl)-2-chromanonc, which instead provided a much less harmonious and balanced lavander note by introducing undesired lactonic or nut notes with no positive effect on the musk connotation of the fragrance.

Claims

1. Use as perfϊiming ingredient of a compound of formula

wherein R represents a methyl or ethyl group.

2. Use according to claim 1 , characterized in that the compound is 7-methyl-2- chromanone.

3. 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.

4. A perfumed article comprising: i) at least one compound of formula (I), as defined in claim 1 ; and ii) a consumer product base.

5. A perfumed article according to claim 4, characterized in that the consumer product base is a solid or liquid detergent, a fabric softener, a perfume, a cologne or after¬ shave lotion, a perfumed soap, a shower or bath salt, mousse, oil or gel, a hygiene product, a hair care product, a shampoo, a body-care product, a deodorant or antiperspirant, an air freshener, a cosmetic preparation, a fabric refresher, an ironing water, a paper, a wipe or a bleach.