EP1069176B1 - Aliphatic esters and their use as perfume ingredients - Google Patents

Abstract

Use of an optical isomer compound(s) as a perfume for the preparation of perfume compositions or perfumed articles giving a natural scent. Use of an optical isomer compound(s) of formula (I) as a perfume for the preparation of perfume compositions or perfumed articles: R1 = (m)ethyl; R2 = ethyl or propyl; and the undulating line indicates an asymmetric carbon at position 2 and can be R or S. Independent claims are included for: (1) a perfume composition of a perfumed article containing compound (I); and (2) compound (I) per se excluding ethyl (S)-2-tert. butoxypropanoate.

Description

dans laquelle la ligne ondulée indique que le carbone asymétrique situé en position 2, peut adopter une configuration de type R ou S, R₁ représente un radical méthyle ou éthyle et R₂ représente un radical éthyle, propyle linéaire ou ramifié, ou isobutyle, sous forme d'un isomère optiquement actif ou sous forme d'un mélange d'isomères.The present invention relates to the field of perfumery. It relates more particularly to a compound of formula

in which the corrugated line indicates that the asymmetric carbon located in position 2, can adopt a configuration of R or S type, R ₁ represents a methyl or ethyl radical and R ₂ represents an ethyl radical, linear or branched propyl, or isobutyl, under form of an optically active isomer or as a mixture of isomers.

The esters of formula (I) have very useful odorous qualities and appreciated. They can thus be used to prepare perfumes, perfume compositions and scented articles. They are used to impart fragrant notes of character fruity very natural.

The compound of formula (I) in which R ₁ represents a methyl radical and R ₂ represents an ethyl radical, namely ethyl (S) -2-tert-butoxypropanoate, is known. This compound is indeed described as a synthetic intermediate by G. Cainelli, M. Panunzio, E. Bandini, G. Martelli and G. Spunta in Tetrahedron; IN ; 52; 5; 1996; 1685-1698. However, in the prior art there is no description of the smell of this compound or any use in perfumery.

The other compounds represented by the formula (I) are new.

Many esters of structure similar to the compounds (I) are known. We can cite for example Rev. Agroquim. Tecnol. Food. (1986), 26 (4), 597-601 which discloses the use of ethyl 2-ethoxypropanoate as a racemic mixture for the flavoring of cheese, especially parmesan cheese. Many others compounds having a structure close to that of the compounds which are the subject of this invention were described in the field of organic synthesis but to our knowledge, there exists in the prior art no reference or even suggestion of the possible usefulness of these esters as perfuming ingredients.

Now, we have now unexpectedly discovered that the esters of formula (I) have olfactory properties quite surprising in view of the art and make their use in perfumery very interesting.

The compounds of formula (I) are characterized by an odor whose note of Fruity type head, very natural, makes them particularly appreciated by perfumers. The intensity of this note declines from one compound to another. In addition, the sub-notes that accompany it and which also vary from one compound to another, allow to impart base compositions a whole range of olfactory nuances and thus make each composed to contribute to the variety of the perfumer's palette.

Thus, we find for example in the fragrant notes of several esters according to the invention, a chamomile-type connotation. This one is particularly distinct in the odor of ethyl (R) -2- (1,1-dimethylpropoxy) propanoate whose fruity is also very strong. Ethyl (S) -2- (1,1-dimethylpropoxy) propanoate has a more spicy smell but also includes a fragrant subnote of chamomile type, this time with notes reminiscent of 2-acetyl-4-methyl-4-pentanoate (EP B1 0178532, origin: Firmenich SA, Geneva, Switzerland), the dregs of wine, linalool or coriander. The chamomile note of (S) -2-tert-butoxypropanoate of propyl is she accompanied by a liquorice sub-note with a very pretty peach-apricot connotation.

Isobutyl (S) -2-tert-butoxypropanoate and (S) -2- (1,1-dimethylpropoxy) isopropyl propanoate, whose odor also has a connotation reminiscent of chamomile, are less potent in intensity than the last compounds mentioned.

(S) -2-tert-butoxypropanoate ethyl has a scent the fruity character is also velvety, ethereal, sweet, but it also has notes reminiscent of mint. Its fresh smell keeps the natural side common to all compounds of the invention.

Among the compounds of the invention, (S) -2- (1,1-dimethylpropoxy) propanoate Propyl is a fragrant ingredient of choice. It has an odor whose top note fruity is accompanied by smoky and refreshing notes. The smell keeps its side natural. In the background, it is reminiscent of 8-p-menthen-2-ol acetate, floral connotation, linalool, mint citrata. This floral, fruity note with sage connotation sclarée, mint citrata, has a fresh side, very natural, which is worth to be particularly appreciated by perfumers. In addition, (S) -2- (1,1-dimethylpropoxy) propyl propanoate has been compared to dihydromyrcenol (origin: International Flavors & Fragrances), known to bring fragrant notes giving a freshness effect floral and aromatic in perfume compositions. However, we discovered, at term of this comparison, that the compound of the invention presents quite a scent whose freshness is more aromatic type, sage and bergamot, while dihydromyrcenol has a more aromatic, lavandered odor. The current invention thus brings a new and unexpected contribution to the permanent problem of the search for new perfuming ingredients, susceptible to industrial synthesis and of diverse use and at least as advantageous as that of known compounds and available on the market.

The compounds of the invention are equally suitable for use in perfumery, in perfumes, eau de toilette or after-shave lotions, than at other current perfumery jobs such as the perfuming of soaps, shower gels or bath, hygiene products, or products for the treatment of hair such as shampoos or after shampoos or other hair care products, as well as body deodorants and ambient deodorants, or cosmetic preparations.

Esters (I) can also be used in applications such as liquid or solid detergents for the treatment of textiles, textile softeners or in detergent compositions or cleaning products intended for cleaning of dishes or various surfaces, for domestic or industrial purposes.

In these applications, the compounds of the invention can be used alone or mixed with other perfuming ingredients, solvents or adjuvants current in perfumery. The nature and variety of these co-ingredients do not call for more detailed description here, which can not be exhaustive, the person skilled in the art being able to choose them by his general knowledge and according to the nature the product to be perfumed and the desired olfactory effect.

These fragrance ingredients belong to chemical classes too various alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, hydrocarbons terpene, nitrogenous or sulfur-containing heterocyclic compounds and essential oils of natural or synthetic origin. Many of these ingredients are also listed in reference texts such as S. Arctander's book, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature.

The proportions in which the compounds according to the invention can be incorporated in the above-mentioned various products vary within a range of values extended. These values depend on the nature of the article or product that one wants to perfume and the desired olfactory effect, as well as the nature of the coedredients in a composition given when the compounds of the invention are used in admixture with fragrance co-ingredients, solvents or adjuvants commonly used in the art.

By way of example, mention may be made of typical concentrations of the order of 5 to 30% or more, by weight of the compound relative to the weight of perfuming composition in which it is incorporated. Concentrations well below these can be used when this compound is directly applied in the perfuming of various consumption previously mentioned.

a)

, Amberlyst ®

b) R₂OH , tétraisopropylorthotitanate

dans lequel les symboles ont le même sens que dans la formule (I). La fonction hydroxyle du lactate d'éthyle est alkylée dans la première étape ; puis, si nécessaire, une transestérification du produit intermédiaire conduit à l'ester désiré. Ces deux étapes sont des réactions standards, bien connues de l'homme du métier.The compounds of formula (I) are synthesized in one or two stages from ethyl lactate in optically active form or in the form of a mixture of isomers, according to the following general scheme:

at)

, Amberlyst ®

b) R ₂ OH, tetraisopropylorthotitanate

in which the symbols have the same meaning as in formula (I). The hydroxyl function of ethyl lactate is alkylated in the first step; then, if necessary, transesterification of the intermediate product leads to the desired ester. These two steps are standard reactions, well known to those skilled in the art.

The invention will now be described in more detail using the examples in which temperatures are given in degrees Celsius and Abbreviations have the usual meaning in art.

Example 1 Preparation of compounds of formula (I) a) (S) -2- (1,1-dimethylpropoxy) propanoate ethyl

A mixture of 3534 g (50.5 moles) of isoamylene, 600 g (5.08 moles, [α] ^D ₂₀ = -12.4 °) of stirring was maintained under stirring at 10 ° for 66 hours. ) -ethyl lactate and 20 g of Amberlyst® 15. The reaction mixture was then filtered and washed 3 times with 1 l of Na ₂ CO ₃ in 10% solution. After distillation (pressure = 20 × 10 ² Pa, bath at 110 °), 692.2 g of ethyl (S) -2- (1,1-dimethylpropoxy) propanoate were obtained with a purity of 95% and a yield of 69%. %.

Analytical data:

Pe (20 x 10 ² Pa) = 80 °

[α] ^D ₂₀ = -42.21 ° (CHCl ₃ )

NMR ^(1H) (360 MHz; CDCl _3): 0.89 (t, J = 7.2Hz, 3H); 1.13 (s, 3H); 1.14 (s, 3H); 1.27 (t, J = 7.2 Hz, 3H); 1.33 (d, J = 7.2 Hz, 3H); 4.1 (q, J = 7.2 Hz, 1H); 4.18 (split q, J = 7.2 Hz, 2H).

MS: 188 (M ⁺ , O), 173 (3), 159 (18), 115 (19), 101 (21), 71 (100), 43 (65).

b) propyl (S) -2- (1,1-dimethylpropoxy) propanoate

A mixture of 535 g (2.8 moles) of ethyl (S) -2- (1,1-dimethylpropoxy) propanoate obtained under a) was refluxed with stirring, 430 g (7.1 moles ) of propanol and 8 g (28 mmol) of tetraisopropylorthotitanate (origin: Fluka ), and the ethanol produced was separated on a Vigreux column with a distillation head (maximum head temperature: 95 °). After cooling the mixture, it was washed successively with ice / 10% HCl, water, NaHCO ₃ in solution and finally brine. 539 g of propyl (S) -2- (1,1-dimethylpropoxy) propanoate were thus obtained with a purity of 97.2% and a yield of 94%.

Analytical data:

Pe (20 x 10 ² Pa) = 83 °

[α] ^D ₂₀ = -49 ° (CHCl ₃ )

NMR ^(1H) (360 MHz; CDCl _3): 0.89 (t, J = 7.2Hz, 3H); 0.96 (t, J = 7.2 Hz, 3H); 1.13 (s, 3H); 1.14 (s, 3H); 1.35 (d, J = 7.2 Hz, 3H); 4.08 (t, J = 7.2 Hz, 2H); 4.11 (q, J = 7.2 Hz, 1H).

NMR ( ¹³ C) (90.5 MHz, CDCl ₃ ): 8.5 (q); 10.4 (q); 20.5 (q); 22.0 (t); 25.1 (q); 33.5 (t); 66.2 (t); 67.3 (d); 175.2 (s).

MS: 202 (M ⁺ , O), 187 (1), 173 (11), 131 (9), 115 (27), 71 (100), 43 (52).

c, d) (S) -2- (1,1-dimethylpropoxy) propanoate isobutyl and (S) -2- (1,1-dimethylpropoxy) isopropyl propanoate

These two compounds were synthesized in two stages. The first step is that described under a) . The second was carried out according to an operating procedure similar to that described under b) , by choosing the alcohol used as reagent according to the desired final product (see diagram 1).

Analytical data:

• [α]^D ₂₀ = -46,1° (CHCl₃)
• RMN(¹H) (360 MHz ; CDCl₃) : 0,89(t, J=7Hz, 3H) ; 0,95(t, J=7Hz, 6H) ; 1,30 et 1,35(2s, 6H) ; 1,36(d, J=7Hz, 3H) ; 3,9(d, J=7Hz, 2H) ; 4,12(q, J=7Hz, 1H).
• RMN(¹³C) (90,5 MHz ; CDCl₃) : 8,5(q) ; 19,1(q) ; 20,6(q) ; 25,0(q) ; 27,8(d) ; 33,5(t) ; 67,2(d) ; 70,7(t) ; 77,1(s) ; 175,2(s).
• SM : 216(M⁺, 0), 187(4), 145(3), 131(20), 115(25), 71(100), 43(40).
Isobutyl (S) -2- (1,1-dimethylpropoxy) propanoate
• [α] ^D ₂₀ = -46.1 ° (CHCl ₃ )
• NMR ^(1H) (360 MHz; CDCl _3): 0.89 (t, J = 7Hz, 3H); 0.95 (t, J = 7Hz, 6H); 1.30 and 1.35 (2s, 6H); 1.36 (d, J = 7Hz, 3H); 3.9 (d, J = 7Hz, 2H); 4.12 (q, J = 7Hz, 1H).
• NMR ( ¹³ C) (90.5 MHz, CDCl ₃ ): 8.5 (q); 19.1 (q); 20.6 (q); 25.0 (q); 27.8 (d); 33.5 (t); 67.2 (d); 70.7 (t); 77.1 (s); 175.2 (s).
• MS: 216 (M ⁺ , O), 187 (4), 145 (3), 131 (20), 115 (25), 71 (100), 43 (40).
• [α]^D ₂₀ = -49,2° (CHCl₃)
• RMN(¹H) (360 MHz ; CDCl₃) : 0,89(t, J=7Hz, 3H) ; 1,30 et 1,35(2s, 6H) ; 1,50 et 1,52(2d, J=7Hz, 6H) ; 1,32(d, J=7Hz, 3H) ; 4,06(q, J=7Hz, 1H) ; 5,04(hept., J=7Hz, 1H).
• RMN(¹³C) (90,5 MHz ; CDCl₃): 8,5(q); 20,4(q); 21,7(2q); 25(q); 25,1(q); 33,5(t) ; 67,4(d) ; 67,8(d) ; 174,7(s).
• SM : 202(M⁺, 0), 173(6), 145(5), 131(19), 115(20), 71(100), 59(20), 43(47).
Isopropyl (S) -2- (1,1-dimethylpropoxy) propanoate
• [α] ^D ₂₀ = -49.2 ° (CHCl ₃ )
• NMR ^(1H) (360 MHz; CDCl _3): 0.89 (t, J = 7Hz, 3H); 1.30 and 1.35 (2s, 6H); 1.50 and 1.52 (2d, J = 7Hz, 6H); 1.32 (d, J = 7Hz, 3H); 4.06 (q, J = 7Hz, 1H); 5.04 (hept., J = 7Hz, 1H).
• NMR ( ¹³ C) (90.5 MHz, CDCl ₃ ): 8.5 (q); 20.4 (q); 21.7 (2q); 25 (q); 25.1 (q); 33.5 (t); 67.4 (d); 67.8 (d); 174.7 (s).
• MS: 202 (M ⁺ , O), 173 (6), 145 (5), 131 (19), 115 (20), 71 (100), 59 (20), 43 (47).

e) (S) -2-tert-butoxypropanoate ethyl

The compound was prepared in one step according to a procedure similar to that described under a) by selecting the appropriate reagent as described in Scheme 1 (step a).

Analytical data:

[α] ^D ₂₀ = -41 ° (CHCl ₃ )

NMR ^(1H) (360MHz, CDCl _3): 1.20 (s, 9H); 1.28 (t, J = 8Hz, 3H); 1.35 (d, J = 8Hz, 3H); 4.11 (q, J = 7 Hz, 1H); 4.19 (dq, J = 1.7 Hz, 2H).

NMR ( ¹³ C) (90.5 MHz, CDCl ₃ ): 14.2 (q); 20.5 (q); 27.8 (q); 60.6 (t); 67.6 (d); 74.8 (s); 175.1 (s).

MS: 174 (M ⁺ , 1), 159 (4), 101 (40), 73 (12), 57 (100), 45 (10), 41 (21), 39 (6), 29 (19), 27 (8).

f, g) (S) -2-tert-butoxypropanoate and isobutyl (S) -2-tert-butoxypropanoate

These two compounds were synthesized in two stages. The first step is that described under e) . The second was carried out according to an operating procedure similar to that described under b) , by choosing the alcohol used as reagent according to the desired final product (see diagram 1).

Analytical data:

• [α]^D ₂₀ = -50° (CHCl₃)
• RMN(¹H) (360MHz, CDCl₃) : 0,96(t, J=7Hz, 3H) ; 1,20(s, 9H); 1,34(d, J=7Hz, 3H) ; 1,68(m, 2H) ; 4,09(m, 2H) ; 4,12(q, J=7Hz, 1H).
• RMN(¹³C) (90,5MHz, CDCl₃) : 10,4(q) ; 20,6(q) ; 22,0(t) ; 27,8(q) ; 66,3(t) ; 67,6(d) ; 74,8(s) ; 175,2(s).
• SM : 188(M⁺, <0,5), 173(3), 101 (60), 57(100).
(S) -2-propyl tert-butoxypropanoate
• [α] ^D ₂₀ = -50 ° (CHCl ₃ )
• NMR ^(1H) (360MHz, CDCl _3): 0.96 (t, J = 7Hz, 3H); 1.20 (s, 9H); 1.34 (d, J = 7Hz, 3H); 1.68 (m, 2H); 4.09 (m, 2H); 4.12 (q, J = 7Hz, 1H).
• NMR ( ¹³ C) (90.5 MHz, CDCl ₃ ): 10.4 (q); 20.6 (q); 22.0 (t); 27.8 (q); 66.3 (t); 67.6 (d); 74.8 (s); 175.2 (s).
• MS: 188 (M ⁺ ,? 0.5), 173 (3), 101 (60), 57 (100).
• [α]^D ₂₀ = -49,2° (CHCl₃)
• RMN(¹H) (360MHz, CDCl₃) : 0,94(2d, J=7Hz, 6H) ; 1,20(s, 9H); 1,35(d, J=7Hz, 3H) ; 3,90(d, J=7Hz, 2H) ; 4,13(q, J=7Hz, 1H).
• RMN(¹³C) (90,5MHz, CDCl₃): 19,1(2q); 20,6(q); 27,8(d); 27,8(q); 67,5(d); 70,8(t) ; 74,8(s) ; 175,1(s).
• SM : 202(M⁺, <0,5), 131(5), 101(30), 57(100).
(S) -2-Isobutyl tert-butoxypropanoate
• [α] ^D ₂₀ = -49.2 ° (CHCl ₃ )
• NMR ^(1H) (360MHz, CDCl _3): 0.94 (2d, J = 7Hz, 6H); 1.20 (s, 9H); 1.35 (d, J = 7Hz, 3H); 3.90 (d, J = 7Hz, 2H); 4.13 (q, J = 7Hz, 1H).
• NMR ( ¹³ C) (90.5 MHz, CDCl ₃ ): 19.1 (2q); 20.6 (q); 27.8 (d); 27.8 (q); 67.5 (d); 70.8 (t); 74.8 (s); 175.1 (s).
• MS: 202 (M ⁺ , <0.5), 131 (5), 101 (30), 57 (100).

h) (R) -2- (1,1-dimethylpropoxy) propanoate ethyl

This compound was synthesized in one step according to a protocol identical to that described under a) , using the (R) -ethyl lactate ([α] ^D ₂₀ = + 11 °) as starting material.

Analytical data:

[α] ^D ₂₀ = + 48.8 ° (CHCl ₃ )

NMR ^(1H) (360MHz, CDCl _3): 0.89 (t, J = 7Hz, 3H); 1.30 and 1.35 (2s, 6H); 1.28 (t, J = 7Hz, 3H); 1.34 (d, J = 7Hz, 3H); 4.1 (q, J = 7Hz, 1H); 4.19 (split q, J = 7Hz, 2H).

MS: 188 (M ⁺ , O), 173 (4), 159 (13), 115 (18), 101 (16), 71 (100), 55 (15), 43 (62).

i) Propyl -2- (1,1-dimethylpropoxy) propanoate

This compound was synthesized in two stages. The first step is that described under h) . The second step is performed according to a protocol similar to that described under b) , using a suitable reagent as shown in diagram 1.

Analytical data:

[α] ^D ₂₀ = + 51 ° (CHCl ₃ )

NMR ^(1H) (360MHz, CDCl _3): 0.89 (t, J = 7Hz, 3H); 0.96 (t, J = 7Hz, 3H); 1.30 and 1.35 (2s, 6H); 1.35 (d, J = 7Hz, 3H); 4.08 (t, J = 7Hz, 2H); 4.10 (q, J = 7Hz, 1H).

MS: 202 (M ⁺ , O), 187 (3), 173 (13), 131 (10), 115 (36), 71 (100), 43 (36).

Example 2 Preparation of a perfume composition for a men's eau de toilette

A basic composition for male toilet water was prepared from the following ingredients: ingredients Parts by weight Benzyl acetate 40 Geranyl acetate 10 Linalyl acetate 100 cedarleaf 20 Allyl amyl glycolate 10 Ambrox ® 20 Essence of aspic 100 Bergamot essence 180 citral 30 coumarin 20 Tarragon essence 10 Juniper ess. synth 40 English clove oil 10 Essence of lavandin 120 linalool 170 Lyral ® 60 Mandarin essence 30 Crystal foam 50 10% Rose Oxide 20 Siberian pine species 20 Essence of patchouli 150 Polysantol ® 30 Amyl salicylate 20 Benzyl salicylate 440 Ylang extra 30 Zestover at 10% 70 Total 1800

The addition of 300 parts by weight of propyl (S) -2- (1,1-dimethylpropoxy) propanoate to this basic composition, has made it possible to obtain a new composition whose odor has a distinct herbaceous-fresh, slightly hesperidic connotation. The diffusion of the odor is significantly increased compared to that of the base composition. In addition, fragrant notes of this new composition make it more voluminous and also more sparkling.

Example 3 Preparation of a perfuming composition for a body deodorant

A base composition for a body deodorant was prepared from the following ingredients: ingredients Parts by weight Allyl amyl glycolate 20 Ambrox ® at 10% 15 Bergamot synth. 180 Civet synth. at 1% 30 α-Damascone at 10% 50 Lorysia ® 10 Galaxolide ® 50 MIP 45 Galbex ® 30 Essence of Chinese geranium 15 Hedione ® 60 Indolene at 10% 10 Iso E super 10 Iralia ® 10 Lavandin grosso 50 Lyral ® 15 Crystal foam 10% 50 Tonalide ® 40 Vertofix heart 110 Total 750

The addition of 200 parts by weight of propyl (S) -2- (1,1-dimethylpropoxy) propanoate to this basic composition whose smell has a fresh deodorant connotation, significantly increases the freshness of the top note as well as the impact of the fragrance and exalts the fragrant note conferred by the lavender and adds a herbal connotation of type clary sage.

Claims (5)

1. Use of a compound of formula

   

   wherein the wavy line indicates that the asymmetric carbon number 2 can adopt a configuration R or S, R₁ represents a methyl or ethyl group and R₂ represents an ethyl group, a linear or branched propyl group, or an isobutyl group,
   in the form of an optically active isomer or of a mixture of isomers, as perfuming ingredient tor the preparation of perfuming compositions or perfumed articles.
2. A perfuming composition or perfumed article containing as active ingredient a compound of formula (I) as defined in claim 1.
3. A perfumed article according to claim 2, in the form of a perfume, a Cologne, an after-shave lotion, a cosmetic preparation, a soap, a shampoo or hair conditioner or other hair-care product, a shower or bath gel, a body or air deodorant, a detergent or a fabric softener or a household product.
4. A compound of formula (I) such as defined in claim 1, ethyl (S)-2-tert-butoxy-propionate being excluded.
5. As compound according to claim 4, propyl (S)-2-(1,1-dimethylpropoxy)propionate.