EP1229893A1

EP1229893A1 - Use of a fatty alcohol in a perfume composition

Info

Publication number: EP1229893A1
Application number: EP00966370A
Authority: EP
Inventors: Hubert Mimoun; Günter HOLZNER; Joel Pastori
Original assignee: Firmenich SA
Current assignee: Firmenich SA
Priority date: 1999-11-10
Filing date: 2000-10-19
Publication date: 2002-08-14
Also published as: WO2001034110A1; US6806250B2; US20020183236A1; JP2003513900A

Abstract

The invention concerns a fatty alcohol obtainable by a method which consists in reducing the carbonyl function of a vegetable or animal oil, the method consisting in: reacting said vegetable or animal oil with appropriate amounts of polymethyl-hydroxysiloxane (PMHS) in the presence of a catalytic system prepared from a metal salt or complex and a reduction agent, followed by hydrolysis of the resulting siloxane with a basic agent and separating and purifying the desired alcohol thus formed. Said alcohol can be used in a perfume composition, in particular as solubilizing agent.

Description

Use of a fatty alcohol in a perfume composition

Technical area

The present invention relates to the field of perfumery. It relates more particularly to the use in a perfuming composition of a fatty alcohol capable of being obtained by a process for reducing the carbonyl function of a vegetable or animal oil with appropriate quantities of polymethyl-hydroxysiloxane.

Prior art

The use of fatty alcohols in cosmetic compositions is well known in the prior art. Mention may be made, for example, of patent application WO 96/37285, which discloses the use of fatty alcohols in emulsifying cosmetic compositions, or even application WO 97/01326, which describes cream compositions comprising in particular, among the hydrophobic agents used, fat. In this type of application, the fatty alcohols used have a function of structuring agent to assist the rheological characteristics of the composition. More generally, long-chain fatty alcohols are therefore used in cosmetic or pharmaceutical compositions as emollients, structuring agents in emulsions, or even stabilizers in an emulsifying system. They are frequently found in compositions of hair care products, moisturizers for dry skin or in pharmaceutical bases.

However, to our knowledge, these alcohols have never been used in perfume compositions.

Statement of the invention

Now, we have discovered quite surprisingly that the fatty alcohols capable of being obtained by reduction of the carbonyl function of a vegetable or animal oil of natural origin could be advantageously used in compositions Fragrant. In particular, and according to a preferred embodiment of the invention, these fatty alcohols can have, quite unexpectedly, a function of solvent or cosolvent in these perfume compositions.

The use of the fatty alcohols of the invention in perfume compositions, in particular as solubilizers of the perfume ingredients which form part of these compositions, has numerous advantages. In the preparation of perfumes, toilet waters and colognes for example, the use of solvents such as ethanol or isopropanol is very widespread. Ethanol makes it possible to dissolve the perfume ingredients well which the perfumer uses. Perfumes and colognes that ^are found on the market usually contain between 50 and 95% ethanol by volume. However, this type of solvent commonly used in perfumes or other perfume compositions may be subject to restrictions of use by the legislation of certain countries. This is why we seek to replace this type of solvent in the aforementioned products. However, we have discovered that fatty alcohols from vegetable or animal oils can advantageously replace all or part of the aforementioned solvents commonly used in perfumery. These products of natural origin easily dissolve any type of perfuming ingredient.

Other advantages will appear during the description and in the examples. The fatty alcohols of the present invention are capable of being obtained by reduction of the carbonyl function of a vegetable or animal oil. This process comprises reacting said oil with appropriate quantities of polymethyl-hydroxysiloxane (PMHS) in the presence of a catalytic system prepared from a metal salt or complex and a reducing agent, followed by the hydrolysis of the siloxane obtained by means of a basic agent and the separation and purification of the desired alcohol thus formed. The exact process for the preparation of these alcohols is described in US patent 5,831,133 and in international patent application WO 99/12877. The first of these documents describes, for example, an original reduction process, in particular of esters, with polymethylhydrosiloxane. catalyzed by soluble hydrides of metals such as zinc, manganese or iron. PMHS is a cheap and abundant co-product in the silicone industry. Stable in air and ^water, it is particularly easy to use in ^any other unknown multipurpose reactor, while the use of hydrides such as LiAlH ₄ and NaBH used in reductions "classic" need to work inert and dry reactor.

One of the remarkable properties of this technology is to allow the direct reduction oils and animal stalls vee ^g with ^excellent yields. This reaction is preferably catalyzed by soluble zinc hydrides generated for example by reaction between a soluble zinc carboxylate and a hydrogen donor such as NaBH ₄ .

The process described in WO 99/12877 is also suitable for the preparation of fatty alcohols used according to the present invention and it has the additional advantage of dispensing with the use of NaBH.

The contents of US Patent 5,831,133 and WO 99/12877 and the teachings of these documents relating to the reduction of appropriate natural oils and the application of these methods to this reduction, are included here by reference. These methods are advantageously used to prepare the fatty alcohols which are the subject of the invention since they allow the structure and stereochemistry of the starting products to be preserved, that is to say vegetable or animal oils. In other words, if we compare the reduction described in the documents included here with reference to the conventional catalytic hydrogenation commonly used for the reduction of animal or vegetable fatty oils, the latter requires their prior transesterification into the corresponding methyl ester, and is carried out on a large scale under drastic conditions of temperature and pressure, which affects the position and stereochemistry of the double bonds, and therefore the natural character of the product. The methods described in US 5,831,133 and WO 99/12877, on the contrary, make it possible to conserve them, so that the reaction product, namely fatty alcohol, has the same stereochemistry as the starting vegetable or animal oil, thus keeping its natural side, which represents a considerable asset. We have also found that the fatty alcohols thus obtained could have very advantageous properties for the purpose of the invention.

The present invention therefore relates to the use in a perfuming composition of a fatty alcohol capable of being obtained by a process for reducing the carbonyl function of a vegetable or animal oil, said process comprising the reaction of said oil with quantities appropriate PMHS in the presence of a catalyst system prepared from a metallic salt or complex and a reducing agent, followed by ^hydrolysis of the siloxane obtained by means of a basic agent and the separation and purification of the desired alcohol thus formed.

Among the fatty alcohols used according to ^the invention, there may be mentioned as preferred those which constitute the reduction product ^of a selected vegetable oil from the group consisting of ^the ^olive oil, ^sunflower oil, palm oil, ^cottonseed oil. rapeseed oil, soybean oil, sesame oil, jojoba oil or coconut oil.

In addition to the fact that they retain the positioning and the stereochemistry of the double bonds of the natural oils from which they are derived, the fatty alcohols of the invention have other advantages when they are used in a perfuming composition. For example, these compounds give the composition to which they are added a feel that is both soft and non-greasy when it is applied to the skin, while a conventional solvent such as ethanol will tend to dry the skin.

The alcohols of the invention are of particularly advantageous use not only in perfumes, colognes and toilet waters, but also in applications such as perfumed oils for the skin or the hair.

It goes without saying that the use of fatty alcohols from vegetable or animal oils according to the invention is not limited to the aforementioned products, but may also be suitable for other perfumery applications, in particular in functional perfumery. Examples of this type of application include shower and bath gels, shampoos, deodorants or antiperspirants. By their natural character, their emollient properties, their non-greasy character, their softness to the touch and their power of penetration, the natural alcohols according to the present invention are therefore useful in numerous applications. According to a preferred embodiment of the invention, the natural fatty alcohols resulting from the reduction of a vegetable or animal oil have a solvent or co-solvent function in a perfuming composition. Indeed, these components solubilize advantageously any type ^of perfuming ingredient.

The fatty alcohols of the invention can be used as solvents both in a perfume composition comprising in addition to the perfume additives and adjuvants dependent on the final application, as in a base composition or concentrated perfume comprising only perfume raw materials . The solvents generally used in these latter compositions, namely diethyl phthalate or dipropylene glycol, are solvents suitable for dissolving all the raw materials, both liquid and solid. However, we unexpectedly discovered that the fatty alcohols of the invention could also dissolve these substances and thus replace in particular diethyl phatalate or dipropylene glycol. The invention also relates to a perfume composition characterized in that it contains a fatty alcohol capable of being obtained by the reduction process described in US 5,831,133 or WO 99/12877.

In a particularly advantageous embodiment of the invention the natural fatty alcohol present in a perfume composition according to the invention advantageously replaces, totally or in part, the solvent generally used. It therefore acts either as the sole solvent, or as co-solvent in admixture with ethyl alcohol, isododecane or other solvents known to those skilled in the art and used in this type of composition. Thus, the proportion of ethanol for example can be reduced or even eliminated.

Furthermore, in applications such as perfumed massage oils which contain, in addition to perfuming ingredients, paraffin oil (or an equivalent), the compounds of the invention advantageously make it possible, thanks to their structure, to dissolve the scent in the oil. This property of fatty alcohols makes them very useful in any type of perfuming composition containing an oil such as paraffin oil. Indeed, they retain the properties of the natural oils from which they come while dissolving all the ingredients of the composition.

The perfume composition according to the invention may contain, in addition to a fatty alcohol derived from an oil of natural origin and a perfume ingredient, a volatile agent. For volatile agent present in the perfuming composition according to ^the invention may be mentioned as preferred volatile hydrocarbons, volatile silicone oils, isopentane or a mixture of these compounds. The latter are cited by way of nonlimiting examples, the person skilled in the art being able to choose other suitable volatile agents than those mentioned. A person skilled in the art is also able to choose one or more perfuming ingredients according to the nature of the product to be perfumed and the desired olfactory effect. These perfuming ingredients can belong to classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons. heterocyclic nitrogen or sulfur compounds, as well as essential oils of natural or synthetic origin. Many of these ingredients are also 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 similar nature. In addition to the different types of ingredients mentioned, the perfume composition according to the invention can also comprise other adjuvants such as antioxidants, chelating agents, or propellants, the skilled person being able to choose them depending on the desired final application or the type of packaging used for the composition of the invention.

Furthermore, according to a preferred embodiment of the invention, the perfuming composition comprises a fatty alcohol as mentioned above in admixture with a natural oil (for example olive or sunflower oil). Thus combined, we have indeed found that the fatty alcohols obtained by reduction of a vegetable or animal oil of natural origin were capable of reducing, on the skin, the fatty-sticky effect of compositions containing original fatty oils. natural. The presence of isopentane or ^other volatile hydrocarbons also acts in this way.

The proportions in which the compounds according to the invention can be incorporated into the various products mentioned above vary over a wide range of values. These values depend on the role played by fatty alcohols in the composition, namely a role of single solvent or co-solvent; they also depend on the proportion of perfuming ingredient to be dissolved, that is to say indirectly on the nature of the perfuming composition and on the desired olfactory effect.

By way of example, there may be mentioned typical proportions of the order of 0.5 to 80%, preferably 10 to 40% of fatty alcohol relative to the weight of perfuming composition in which it is incorporated.

Due to their emollient properties, their non-greasy character and their softness to the touch, they make the perfume or the perfume composition very pleasant to the touch when applied to the skin. The invention will now be described in more detail in the following examples in which the abbreviations have the usual meaning in the art.

Example 1

Preparation ^of fatty alcohols derived from animal or vegetable oils of natural origin

Fatty alcohols according to ^the invention were all prepared according to the following general method: General method

The fatty alcohols mentioned in Table I were prepared by reduction of vegetable and animal oils by injecting PMHS (2 equivalents per ester function) on the substrate containing the metal catalyst, in particular zinc (0.5-2% mol ) dissolved in toluene, isopropyl ether or methyl tertioamyl ether. At the end of the reaction, the polysilylether formed was hydrolyzed on an aqueous potassium solution (1.2 eq KOH / mol of PMHS). After decantation, the organic solution was evaporated to recover the solvent, and the residue distilled under vacuum to give the alcohol in practically pure form with chemical yields generally exceeding 90%.

About twenty vegetable and animal oils could thus be reduced to fatty alcohols by using Zn (dimethylacetate) ₂ (dimethylaminoethanol) as zinc catalyst with excellent chemical yields as shown in Table 1 below. These alcohols correspond exactly, in their relative proportions and their stereochemistry, to the fatty ester and triglyceride precursors.

Other metallic catalysts which can be used, in particular zinc catalysts, are described in detail in WO 99/12877 and the content of this document is included here by reference. Identical products could be obtained using the process described in

US 5,831,133 and the metal catalysts described therein, in particular (2-ethylhexanoate) Zn.

^r ableau I

C ₁₀ = 1 -decanol (capric alcohol) Ci8 ₁ = (9Z) -octadecen-l -ol (oleyl alcohol) C ₁₂ = 1 -dodecanol (lauric alcohol) Cι _{8 2} = (9Z, 12Z) -octadecadien-l- ol (linoleyl alcohol) C ₁₄ = 1 -tetradecanol (myristic alcohol) Cig 3 = (9Z, 12Z, 15Z) -octadecatrien-1-ol (indenyl alcohol) Ci ₆ = 1-hexadecanol (cetyl alcohol) C20 1 = (1 lZ) -eicosen-l-ol C is = 1 -octadecanol (stearyl alcohol) C22 ₁ = (13Z) -docosen-l-ol

C ₂₄ 1 = (15Z) -tetracosen-l-ol

Example 2

Perfuming composition

A perfume composition was prepared by mixing the following ingredients

Ingredients Part by weight Isododecane 39,800 Soybean fatty alcohol '' 30,000 Tenox ^® GT-2 ²⁾ 0.100 Irganox ^® PS-800 ³⁾ 0.050 Diethyl citrate ⁴⁾ 0.050 Perfume ^ 10,000 Isopentane 20,000

Total 100,000

1) see Table I

2) Tocopherol; origin: Eastman

3) dilauryl thiodipropionate; origin: Ciba Specialty Chemicals

4) origin: Morflex

5) The fragrance was obtained by mixing the following ingredients:

Ingredients Part by weight

Benzyl acetate 92

Dimethyl benzyl carbinyl acetate 6

Linalyl acetate 10

Benzyl alcohol 50

Phenylethyl alcohol 35

Amylcinnamic aldehyde 24

Aldehyde Cl 4 at 10% * 8 α-Ionone 8

Methyl anthranilate 10

Sunflower fatty alcohol 500

Benzvle butvrate 10 Dihydrojasmone 1% * 17

Habanolide ^{® 0} 8

Hedione ^{® 2)} 100

Indol at 10% * 10

Linalol 30

Mayol ^{® 3)} 52

Benzyl propionate 16

Benzyl salicylate 14

Total 1000

* in dipropylene glycol (DIPG)

1) pentadecenolide; origin: Firmenich SA, Geneva, Switzerland

2) methyl dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland

3) cis-7-p-menthanol; origin: Firmenich SA, Geneva, Switzerland

Of course, other perfume ingredients can be used, depending on the desired odor effect.

The natural soy alcohol constitutes with isodecane the solvent of this perfume composition with a jasmine-like odor which confers, when it is applied to the skin, a feel that is both soft and non-greasy, while perfuming it.

Example 3

Perfuming composition

A fragrance composition was prepared by mixing the following ingredients:

Ingredients Part by weight Isododecane 24,800

Soy fatty alcohol "30,000

Tenox ^® GT-2 ²⁾ 0.100

Ir anox ^® PS-800 ⁾ 0.050 Diethyl citrate ⁴⁾ 0.050

Perfume ⁵⁾ 25,000

Isopentane 20,000

Total 100,000

1) see Table I

2), 3), 4) see Example 2

5) The perfume used is of the same composition as that described in Example 2.

In this perfume composition devoid of ethanol, the soy alcohol plays the role of co-solvent. It perfectly solubilizes the perfume used and makes the composition very pleasant to apply to the skin, which it softens without lubricating it.

Example 4

Perfuming composition

A perfume composition was prepared by mixing the following ingredients

Ingredients Part by weight

Ethanol at 96 ° 29,800

Olive fatty alcohol ⁿ 20,000

Tenox ^® GT-2 ²⁾ 0.100

Irganox ^® PS-800 ³⁾ 0.050 Diethyl citrate ⁴⁾ 0.050

Perfume ⁵⁾ 30,000

Isopentane 20,000

Total 100,000

1) see Table I

2). 3), 4) see Example 2

5) The perfume used is of the same composition as that described in Example 2. Natural olive alcohol replaces part of the ethanol at 96 ° in this composition. While retaining the properties of natural olive oil, it dissolves the scent used in high concentration. We thus obtained a perfume which makes the skin soft and pleasant to the touch.

Example 5

Perfuming composition

A fragrance composition was prepared by mixing the following ingredients:

Ingredients Part by weight

Ethanol at 96 ° 64,800

Sesame fatty alcohol ^{! )} 25,000 Tenox ^® GT-2 ²⁾ 0.100

Irganox ^® PS-800 ³⁾ 0.050

Diethyl citrate ⁴⁾ 0.050

Perfume ⁵⁾ 10,000

Total 100,000

1) see Table I

2). 3), 4) see Example 2

5) The perfume used is of the same composition as that described in Example 2.

Natural sesame alcohol is used as a co-solvent with ethanol. It reduces the proportion of the latter in the composition and gives it the characteristics of natural oil so that the application to the skin makes it very soft to the touch. Example 6

Scented massage oil

A perfuming composition for massage oil was prepared by mixing the following ingredients:

Ingredients Part by weight

Sunflower fatty alcohol ^]) 5,000 Vaseline oil 45,000

Witconol EC 1,127 ²⁾ 2,500

Hostaphat KL 340 N ³⁾ 2,000

Zetesol l00 ⁴⁾ 39,800

Mackalene 16 ⁵⁾ 0.500 Comperlan KD ⁶⁾ 3.000

Kathon ^® CG ⁷⁾ 0.100

Tenox ^® GT-2 ⁸⁾ 0.500

Irganox ^® PS-800 ⁹⁾ 0.100

Perfume ¹⁰⁾ 1,500 Total 100,000

1) See Table I

2) C] ₂ -Cι ₄ monoalkyl ethercitrate; origin: Witco Surfactants

3) Trilaureth-4-phosphate; origin: Clariant 4) MIPA-laureth sulfate and laureth 4 and cocamide DEA; origin: Zschimmer & Schwarz

5) ricinoleamidopropyl dimefhylamine lactate; origin: Mcintyre

6) Cocoamide DEA; origin: Henkel

7) Methylchloroisothiazohnone and methylisothiazolinone; origin: Rohm & Haas

8) Tocopherol; origin: Eastman 9) Dilauryl thiodipropionate; origin: Ciba Specialty Chemicals

1) The perfume used is of the same composition as that described in Example 2. The fatty alcohol of sunflower perfectly solubilizes all the ingredients of this composition. The oil obtained easily penetrates when applied to the skin. The latter, after application of said oil remains very soft to the touch while being very little greasy.

According to a variant of this composition, a mixture was prepared comprising 90% of the massage oil, the composition of which is described above and 10% of isopentane. We thus obtained a "post-foam" product which is applied to damp skin like a cream. By rubbing on the skin, the product develops a foam that just needs to be rinsed off. After application, the skin is soft and clean without being oily.

Example 7

Perfuming composition for a deodorant stick

A perfuming composition was prepared for application as a deodorant stick by mixing the following ingredients:

Ingredients Part by weight

Dow Corning 345 fluid ^!) 46,000

Lorol C18 ²⁾ 21,000

Ucon fluid AP ³⁾ 1,800

Cutina HR ⁴⁾ 1,000

Eutanol G ^" 3,200

Cotton fatty alcohol ⁶⁾ 5,000

Zirkonal P10 ⁷⁾ 21,000

Perfume ⁸⁾ 1,000

Total 100,000

1) Cyclomethicone: origin: Dow Corning 2) Stearyl alcohol; origin: Henkel

3) Butyl ether; origin: Amerchol

4) Hydrogenated beaver oil; origin: Henkel

5) Octyldodecanol; origin: Henkel

6) see Table I 7) Aluminum zirconium trichlorohydrex; origin: Giulini

8) The perfume used is of the same composition as that described in Example 2.

Cyclomethicone, stearyl alcohol, butyl ether, hydrogenated beaver oil, Foctyldodecanol and natural cotton alcohol were mixed and then heated to reflux. The mixture was kept stirring at 70 ° C until all the solids were dissolved, then the aluminum zirconium trichlorohydrex was dispersed in the initial mixture and stirred well. Finally the perfume was added to the mixture which was then poured into containers suitable for 55 ° C.

The resulting deodorant is very gentle on the skin and not very aggressive. Its texture that is both soft and non-oily provides a very pleasant effect on the skin.

Claims

claims

1. Use in a perfuming composition of a fatty alcohol capable of being obtained by a process for reducing the carbonyl function of an animal or vegetable oil, the process comprising the reaction of said vegetable or animal oil with appropriate amounts of polymethyl-hydroxysiloxane (PMHS) in the presence of a catalytic system prepared from a metal salt or complex and a reducing agent, followed by the hydrolysis of the siloxane obtained by means of a basic agent and the separation and purification desired alcohol so formed.

2. Use according to claim 1 of a fatty alcohol capable of being obtained by reduction of a vegetable oil selected from the group consisting of olive oil, sunflower oil, palm oil, l cottonseed oil, rapeseed oil, soybean oil, sesame oil, jojoba oil or coconut oil.

3. Use as a solvent in a perfuming composition of a fatty alcohol capable of being obtained by a process for reducing the carbonyl function of an animal or vegetable oil, the process comprising the reaction of said vegetable or animal oil with appropriate quantities of polymethyl-hydroxysiloxane (PMHS) in the presence of a catalytic system prepared from a metal salt or complex and a reducing agent, followed by the hydrolysis of the siloxane obtained by means of a basic agent and separation and purification of the desired alcohol thus formed.

4. Perfuming composition characterized in that it contains a fatty alcohol capable of being obtained by a process for reducing the carbonyl function of a vegetable or animal oil, the process comprising the reaction of said vegetable or animal oil with quantities appropriate polymethyl hydroxysiloxane (PMHS) in the presence of a catalyst system prepared from a metallic salt or complex and ^a reducing agent, followed by hydrolysis of the siloxane obtained by means of a basic agent and separation and purifying the desired alcohol so formed.

5. Perfuming composition according to claim 4, characterized in that ^the vegetable oil is selected from the group consisting of olive oil, sunflower oil. Palm oil, cottonseed oil, rapeseed oil, soybean oil, sesame oil, jojoba oil or coconut oil.

6. Perfuming composition according to claim 4, characterized in ^that it comprises a volatile agent and at least one perfuming ingredient.

7. Perfuming composition according to claim 4, characterized in that it additionally comprises a vegetable oil.

8. Perfuming composition according to claim 6. characterized in that the fatty alcohol is a solubilizer of the perfuming ingredient.

9. Perfuming composition according to claim 4, characterized in that the proportion of fatty alcohol is between 0.5 and 80% and preferably between 10 and 40% of said composition.

10. Perfuming composition according to claim 4, in the form of a perfume, an eau de toilette, or an essential oil.