EP0838215B1 - Use of unsaturated aliphatic esters in perfumery - Google Patents

Description

The present invention relates to the field of perfumery. It relates more particularly to the use as a perfuming ingredient of a compound of formula having a double bond in one of the positions indicated by the dotted lines.

The structure of the esters of formula (I) is known. For example, ethyl 2,4-dimethyl-2-pentenoate and its cis and trans configuration isomers have been described in the literature, in particular in the context of organic syntheses (see, for example, VJ Lee, AR Branfman, TR Herrin, and KL Rinehart, JACS, vol. 100, 1978 , 4229-4234 or even O. Miyata, T. Shinada, I. Ninomiya, T. Naito, Synthesis, 1990 , 1123-1124). However, we could not find any mention of any useful odor properties of these compounds.

In fact, to our knowledge, no document of the prior art suggests the use of unsaturated aliphatic esters of formula (I) as perfuming ingredients for the perfuming of everyday consumer products and for the preparation of perfumes and of scented bases.

Now, we have now discovered that the compounds according to the invention have very interesting odorous properties and that they can, therefore, be used for the preparation of perfume compositions or perfumed articles of varied nature.

We have also found that the compounds of formula (I) according to the invention are capable of imparting to the perfuming compositions or perfumes in which they are incorporated a pleasant and fresh scent.

Furthermore, we have discovered that the unsaturated aliphatic esters according to the invention have distinct olfactory properties, and in particular that ethyl 2,4-dimethyl-2-pentenoate exhales a well-marked floral-chamomile note, having a slight character. taget type, while ethyl 2,4-dimethyl-3-pentenoate has a slightly camomile, anise-fennel fruity character accompanied by a honey sub-note, and a nice top note reminiscent of the particularly refreshing apple.

Curiously, ethyl 2,4-dimethyl-2-pentenoate and its isomers of configuration (E) and (Z) have distinct olfactory notes, the two isomers exhaling very powerful scents in which the top note of chamomile type is very powerful and is accompanied by a very natural fruity character.

Thus (E) -2,4-dimethyl-2-pentenoate turns out to be a perfuming ingredient of choice, its odor having a fruity, herbaceous character with strong Roman chamomile connotation, as well as a sub - honey note evoking the characteristic smell of phenylacetic acid. It is a pretty camomile olfactory note with a fruity character, very distinct and natural, recalling the smell of the esters of angelic acid, without however possessing the fatty butyric character of these compounds.

In addition, although evoking by its chamomile note the known chamomile esters, (E) -2,4-dimethyl-2-pentenoate of ethyl is endowed, compared to these, of a more natural note , more powerful. We have indeed found that in a synthetic chamomile essence, it has been found to be significantly richer, more complex than methylcamomile (butyl 2-methyl-pentanoate; origin: Givaudan-Roure, Vernier, Switzerland), more elegant in the natural fruity side than the angelic acid ester, more fruity-chamomile than isopropyl methylbutyrate.

For its part, (Z) -2,4-dimethyl-2-pentenoate is also a useful perfuming ingredient developing a fruity, chamomile, pleasant and fresh scent, very natural, just as elegant as that of the isomer (E).

Furthermore, we have observed that the mixtures of these isomers, in all their possible relative proportions, also prove to be ingredients useful perfumers. In particular, the mixtures in which the (E) isomer predominates are effective perfuming ingredients according to the invention, possessing the odorous characteristics typical of this compound.

Due to its olfactory qualities, ethyl (E) -2,4-dimethyl-2-pentenoate is suitable for use in perfumery in compositions of various nature. This is how it can prove to be very advantageous in a floral composition, for example, where it develops a camomile smell clearly more powerful, more fruity and more complex than, for example, that of 1,3-dimethyl-3- butenyl-isobutyrate (see, for example, US 4,387,047), and thereby gives a new olfactory effect to the perfume. US4000327 describes the use of ethyl 2-methyl-3-pentenoate as a fuel ingredient.

Thus, by their odorous properties, the compounds of formula (I) lend themselves as well to applications in fine perfumery as in functional perfumery. Because of its very varied use, an ester according to the invention constitutes a perfuming ingredient which can prove to be very advantageous both in the isolated state and in mixture with other odorous ingredients. Among the articles in which it can be used as a perfuming ingredient, mention may be made of perfumes or eau de toilette, soaps, shower or bath gels, shampoos or other hair care products, cosmetic preparations, body or room air fresheners, detergents or fabric softeners, or cleaning products.

The proportions in which the compounds according to the invention can be incorporated into the various products mentioned above vary within a very wide range of values. These values are dependent on the nature of the article or product which it is desired to perfume and on the desired olfactory effect, as well as on the nature of the co-ingredients in a given composition when a compound of the invention is used as a mixture with perfume co-ingredients, solvents or adjuvants commonly used in the art. Of course, a compound according to the invention can also be added to the perfumed compositions and articles either alone or in solution in common solvents.

By way of example, mention may be made of concentrations of the order of 1 to 5%, or even 10% or more by weight of compound of formula (I), relative to the weight of perfuming composition in which it is incorporated. Concentrations much lower than these can be used when this compound is applied in the perfume of various consumer products mentioned above.

By perfuming composition is meant here a composition consisting of a mixture of perfuming ingredients which can be chosen from various chemical classes, comprising for example esters, aldehydes, alcohols, ethers, ketones, acetals, nitriles, terpene hydrocarbons, heterocyclic nitrogen or sulfur compounds, as well as essential oils of natural or synthetic origin.

The compounds of the present invention having a double bond in position 2 were prepared as mentioned above according to the syntheses described in the cited references.

• RMN(¹H): 1,19(d, J=7, 3H); 1,25(t, J=7, 3H); 1,66(d, J=1, 3H) ; 1,72(d, J=1, 3H); 3,30(d, J=9 ; q, J=7, 1H); 4,12(q, J=7,2H) ; 5,15(d, J=9 ; t, J=1, 1H) δppm.
• RMN(¹³C): 175,6(s) ; 133,9(s) ; 124,0(d) ; 60,3(t) ; 39,1(d); 25,7(q); 18,1(q); 18,0(q); 14,2(q) δppm.
• SM : 156(M⁺, 14), 141(4), 83(100), 67(10), 55(42).

Ethyl 2,4-dimethyl-3-pentenoate was prepared as follows. Under nitrogen in a 25 ml flask equipped with a condenser, 1.0 g (6.4 mmol) of ethyl 2,4-dimethyl-2-pentenoate and 0.975 g (6.4 mmol) of DBU (1 , 8-diazabicyclo [5.4.0] undéc-7-en) are heated to 160 ° C. After 18 hours, once cooled, the reaction mixture is poured onto water and extracted with ether. The organic phase is washed successively with a 5% aqueous HCl solution, water, a saturated NaHCO ₃ solution, and brine, then dried over Na ₂ SO ₄ and concentrated. After distillation in a ball oven (80-100 ° C., 5.32 x 10 ² Pa), 0.734 g of a 55:45 mixture of 2,4-dimethyl-2-pentenoate and 2.4 is obtained. -dimethyl-3-pentenoate. The two compounds were separated by flash chromatography [SiO ₂ (30 g), cyclohexane: ethyl acetate = 98: 2]. 0.180 g of ethyl 2,4-dimethyl-3-pentenoate were obtained.

• NMR ⁽¹ H): 1.19 (d, J = 7, 3H); 1.25 (t, J = 7.3H); 1.66 (d, J = 1.3H); 1.72 (d, J = 1.3H); 3.30 (d, J = 9; q, J = 7, 1H); 4.12 (q, J = 7.2H); 5.15 (d, J = 9; t, J = 1, 1H) δppm.
• NMR ( ¹³ C): 175.6 (s); 133.9 (s); 124.0 (d); 60.3 (t); 39.1 (d); 25.7 (q); 18.1 (q); 18.0 (q); 14.2 (q) δppm.
• MS: 156 (M ⁺ , 14), 141 (4), 83 (100), 67 (10), 55 (42).

The present invention will now be described in more detail with the aid of the following examples.

Example 1 Preparation of a perfume composition

A basic perfume composition was prepared by mixing the following ingredients: Ingredient Parts by weight Benzyl acetate 170 Cyclanol acetate 20 Verdyl acetate 20 citronellol 40 Ethyl vanillin 10% * 20 Exaltex ® ¹⁾ 140 heliotrope 40 Iralia ® ²⁾ 100 Lilial ® ³⁾ 100 linalool 120 Phénéthylol 40 Amyl salicylate 40 Benzyl salicylate 120 $\overline{\text{970}}$ * in dipropylene glycol 1) pentadecanolide; origin: Firmenich SA, Geneva, Switzerland 2) methyl ionone; origin: Firmenich SA, Geneva, Switzerland 3) 2-methyl-3- (4-tert-butyl-1-phenyl) -propanal; origin: Givaudan-Roure, Vernier, Switzerland

By adding to the basic composition of the herbaceous type indicated above 30 parts by weight of (E) -2,4-dimethyl-2-pentenoate, a new composition is obtained whose particularly fruity top note recalls the scent of Roman Chamomile, which gives the whole a more lively, more powerful and clearly more elegant appearance.

Example 2 Preparation of a perfume composition

A basic perfume composition with a powdery-floral, woody connotation was prepared by mixing the following ingredients: Ingredient Parts by weight Cyclanol acetate 30 Verdyl acetate 80 Anisde aldehyde 30 Dihydromyrcenol ¹⁾ 30 P-tert-butyl-cyclohexyl acetate 210 Exaltex ® ²⁾ 150 Isoraldeine ® ³⁾ 80 Jasmal ® ⁴⁾ 80 Amyl salicylate 60 Tonalid ® ⁵⁾ 60 Vertofix heart ⁶⁾ 80 Essence of violet 80 Total $\overline{\text{970}}$ 1) 2,6-dimethyl-7-octen-2-ol; origin: International Flavors & Fragrances, USA 2) pentadecanolide; origin: Firmenich SA, Geneva, Switzerland 3) origin: Givaudan-Roure, Vernier, Switzerland 4) 4-phenyl-1,3-dioxolane; origin: International Flavors & Fragrances, USA 5) (5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl) -1-ethanone; origin: PFW, Holland 6) origin: International Flavors & Fragrances, USA

The addition of 30 parts by weight of (E) -2,4-dimethyl-2-pentenoate to this floral base composition gives it a strong fruity connotation while imparting, in a more marked manner, a pleasant character fresh.

Example 3 Preparation of a perfume composition

A basic perfume composition with a fern-lavender-floral odor was prepared by mixing the following ingredients: Ingredient Parts by weight Benzyl acetate 45 Linalyl acetate 60 Styrallyl acetate 30 Verdyl acetate 80 Essence of Aspic 80 benzophenone 60 coumarin 30 Cyclomethylene citronellol 60 eugenol 45 Exaltex ® ¹⁾ 30 Lilial ® ²⁾ 45 linalool 110 Iralia ® ³⁾ 80 methyl hexyl 45 methyl naphthyl ketone 80 Verdyle propionate 45 Amyl salicylate 45 γ-undecalactone 15 Total $\overline{\text{985}}$ 1) pentadecanolide; origin: Firmenich SA, Geneva, Switzerland 2) 2-methyl-3- (4-tert-butyl-1-phenyl) -propanal; origin: Givaudan-Roure, Vernier, Switzerland 3) methyl ionone; origin: Firmenich SA, Geneva, Switzerland

The addition of 15 parts by weight of ethyl (E) -2,4-dimethyl-2-pentenoate to this very classic fern-type composition gives it an enriching chamomile note, giving it a particularly modern fresh and chamomile appearance. .

Claims (7)

1. Use as perfuming ingredients of a compound of formula having a double bond in one of the positions indicated by the dotted lines.
2. Use according to claim 1 of ethyl 2,4-dimethyl-2-pentenoate.
3. Use according to claim 2, characterized in that ethyl 2,4-dimethyl-2-pentenoate is in the form of one of its isomers of (Z) or (E) configuration.
4. Perfuming composition or perfumed article containing as a perfuming ingredient a compound of formula having a double bond in one of the positions indicated by the dotted lines.
5. Perfuming composition or perfumed article according to claim 4, containing ethyl 2,4-dimethyl-2-pentenoate.
6. Perfuming composition or perfumed article according to claim 5, characterized in that ethyl 2,4-dimethyl-2-pentenoate is in the form of one of its isomers of (Z) or (E) configuration.
7. Perfumed article according to any one of claims 4 to 6, in the form of a perfume or cologne, a soap, a bath or shower gel, a shampoo or other hair-care product, a cosmetic preparation, a body deodorant, an air-freshener, a detergent or fabric softener, or an all-purpose household cleaner.