EP0424787B1 - Use of unsaturated macrocyclic ketones as perfuming ingredients - Google Patents

Description

possédant une double liaison de configuration trans dans l'une des positions 11 ou 12 telles qu'indiquées par les lignes pointillées.The present invention relates to the field of perfumery. It relates more particularly to the use as perfuming ingredient of at least one pentadecenolide of formula

having a trans configuration double bond in one of positions 11 or 12 as indicated by the dotted lines.

The above-mentioned compounds are unsaturated macrocyclic lactones whose chemical structure is known. They have, in fact, been cited as secondary or intermediate products of a process for the preparation of odoriferous saturated macrolides such as pentadecanolide, known under the trade name of EXALTOLIDE® (origin: Firmenich SA, Geneva, Switzerland), and the like [see, for example, French Patent FR-A-2,043,784 or J. Becker and G. Ohloff, Helv. Chim. Acta 54 , 2889 (1971)]. According to this process, an appropriate peroxide was split by means of thermal energy or radiation, or else chemical agents, to obtain a mixture containing the desired saturated lactones, as well as the corresponding unsaturated lactones. The saturated lactones were then either separated from this mixture by the usual separation techniques, or obtained by hydrogenation of said mixture or of the unsaturated lactones contained. Thus formulated, the process described in the cited prior art provided a solution to the problem posed by the preparation of EXALTOLIDE® and the like, the corresponding unsaturated derivatives obtained at the same time being only unwanted products of said process. Indeed, the individual olfactory value of these unsaturated derivatives having not been recognized, the cited process constantly included a hydrogenation step capable of transforming said unsaturated derivatives into the desired saturated lactones. This step was also claimed as an essential characteristic of the process described in the prior art.

Now, we have now discovered that the unsaturated lactones, and in particular those of trans configuration mentioned above, namely the trans-pentadec-12-en-15-olide and trans-pentadec-11-en-15-olide, have properties very interesting odorants and that they can therefore be used advantageously for the preparation of perfume compositions and perfumed products. We have established that these lactones and their mixtures are used to develop fragrant notes of musk, animal type, very powerful and very effective for notes of this type, the smell of trans-pentadec-11-en-15-olide being however less potent than that of trans-pentadec-12-en-15-olide. The latter also has a more marked musk-ambrette and fruity-pear connotation and is preferred according to the invention.

Compared to their saturated analogue, namely pentadecanolide or EXALTOLIDE®, the aforementioned pentadecenolides, as well as their mixtures, have clearly more animal-like fragrant notes, with a connotation reminiscent of natural musk. In addition, they have the advantage of having fragrant notes whose power, volume and tenacity are much higher than those of the fragrant note characterizing pentadecanolide. In particular, the substantivity of their note turns out to be clearly superior not only to that of the note of EXALTOLIDE®, but also to the substantivity of the fragrant note of an aromatic musky body well known and appreciated by perfumers, namely GALAXOLIDE® 50 IPM (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-γ-2-benzopyrane; origin: IFF Inc.), as This is confirmed by the examples presented below.

When we compared pentadecenolides (I) and their mixtures with another isomeric macrolide known from the state of the art, namely pentadec-10-en-15-olide, described in US patents 4,490,404, 4,541,950, 4,559,168 and 4,568,470, we have also found that the above-mentioned chemical compositions of the present invention have olfactory properties clearly superior to those of the known compound cited. Indeed, it has been observed that the known compound, or pentadec-10-en-15-olide, has a musky note much less powerful and tenacious than that of the compounds according to the invention, also more aldehyde and a little fatty. Its smell was reminiscent of that of the cyclopentadecanone, marketed under the name of EXALTONE® (origin: Firmenich SA, Geneva), and totally devoid of the ambrette and fruity-pear side which makes the compounds on which the invention is based particularly interesting.

possédant une double liaison de configuration cis dans l'une des positions 11 ou 12 telles qu'indiquées par les lignes pointillées. Ces derniers présentent, en effet, des notes olfactives de type musqué, moins animales et élégantes, ainsi que moins puissantes, que celles des trans-pentadécénolides (I) correspondantes.On the other hand, we have also found that the compounds of formula (I) have odorous notes which are distinct from those of their isomers represented by the formula

having a double bond of cis configuration in one of the positions 11 or 12 as indicated by the dotted lines. The latter present, in fact, musky-type olfactory notes, less animal and elegant, as well as less powerful, than those of the corresponding trans-pentadecenolides (I).

According to the invention, the abovementioned unsaturated macrocyclic lactones can be used in perfumery in very varied applications. They lend themselves as well to the preparation of perfumes and colognes, as to the scenting of functional products such as soaps, shower or bath gels, shampoos, body or room air fresheners, cosmetic products and cleaning products. Due to the substantiality of their rating, they prove to be particularly advantageous for the perfuming of detergents or textile conditioners.

In these applications, these unsaturated lactones can be used in the pure state or in a mixture with one or more perfuming ingredients, solvents or usual supports. In particular, these pentadecenolides combine very harmoniously with one another, or else with the corresponding saturated lactone already mentioned, namely pentadecanolide. The mixtures of trans-pentadec-11-en-15-olide and trans-pentadec-12-en-15-olide may contain relative proportions of these two lactones varying over a very wide range of values. We have found that mixtures containing equivalent amounts of trans-pentadec-12-en-15-olide and trans-pentadec-11-en-15-olide, or a surplus of the former, are very advantageous from the point of view olfactory, with odorous properties of a value comparable to that of their individual components. We have nevertheless established that relative proportions of these two lactones other than those mentioned provided perfume mixtures whose olfactory quality was always higher than that of EXALTOLIDE® and whose use for applications according to the invention was always advantageous.

On the other hand, although the isomers of cis configuration represented by the formula (II) have odorous notes less animal than those of the pentadecenolides (I), their presence in mixtures of isomers does not harm the overall olfactory effect , provided that said mixtures contain a predominant amount of pentadecenolides (I) of trans configuration, that is to say that the weight of these trans compounds is 60% or more of the weight of the mixture. Mixtures of unsaturated isomers having an overall content of pentadecenolides (I) of the order of 70% by weight or more are preferred according to the invention. These mixtures of the four isomers exhale a powerful musky note slightly ambrette.

These mixtures of unsaturated isomers of trans and cis configuration, as well as the mixtures described below which still contain pentadecanolide, have olfactory properties which are perfectly suitable for the applications according to the invention and have the advantage of being less expensive. than the other chemical compositions according to the invention, since they can be obtained directly from the synthesis, as described below, and do not require a separation of the individual ingredients.

We have also observed that when trans-pentadec-12-en-15-olide or trans-pentadec-11-en-15-olide, or a mixture of the two or containing a preponderant amount of both, is added to EXALTOLIDE®, fragrance ingredients are obtained according to the invention, the musky note is much more powerful and tenacious than that of the latter, the animal connotation of this note also being reinforced. In this context, and depending on the desired perfuming effect, these saturated and unsaturated lactones can be mixed in very varied relative proportions, without affecting the harmony of the mixture. Furthermore, this enriching effect from the olfactory point of view is clearly revealed, even for low concentrations of unsaturated lactones, for example of 5% by weight or even less, relative to the concentration of EXALTOLIDE®.

The proportions in which the trans-pentadec-11-en-15-olide and trans-pentadec-12-en-15-olide, or their mixtures, can be used for the perfume applications according to the invention can vary within a range. of very wide values. Those skilled in the art know from experience that these proportions depend on the nature of the product which it is desired to flavor, as well as that of the co-ingredients to which these lactones are added to prepare a given perfume composition. Thus, concentrations of the order of 1 to 10%, or even 20% by weight, relative to the weight of composition in which these lactones are incorporated, can be used. These concentrations may be lower than the values quoted when perfuming articles such as soaps and shower or bath gels, shampoos, cosmetic products or detergents or textile conditioners.

The aforementioned unsaturated macrocyclic lactones can be prepared from 2- (3-hydroxypropyl) -1-cyclododecanone (the preparation of which is described in patent FR-A-2 043 784 cited above) according to a process analogous to that described by SL Schreiber and aI. in J. Am. Chem. Soc. 102 , 6163 (1980) and 107 , 2980 (1985) for the preparation of macrolides. The specific conditions for the preparation of these lactones were as follows. In a 4-necked flask equipped with a mechanical stirrer, an introduction bulb, a thermometer, a cooler and kept under nitrogen, 30 g (125 mmol) of 2- (3- hydroxypropyl) -1-cyclododecanone and 137.5 g (2.29 mole) of glacial acetic acid. The whole was stirred at room temperature until a homogeneous mixture was obtained. A cold mixture of 12.5 g of water and 12.5 g of a 50% aqueous sulfuric acid solution was then added. The reaction mixture was cooled to 0 ° C and then 10 ml of 70% hydrogen peroxide was added dropwise for 15 min; the temperature rose to 7 ° C. After the end of this introduction, stirring was continued for 15 min. at 0 ° C. The precipitate formed was filtered, washed with water, then with dilute NaHCO ₃ (aqueous). 62.0 g of wet product were obtained. After drying, 25.6 g (yield 80%) of 14a-hydroxyperyoxy-cyclododeca [b] -pyran were obtained, which was used for the rest of the synthesis. P. f. 104 ° -106 ° C.

Analytical data:

IR (KBr):

3320, 2920, 2850, 1465, 1445, 1430, 1415, 1370, 1350, 1310, 1280, 1250, 1220, 1205, 1190, 1180, 1160, 1150, 1120, 1090, 1080, 1055, 1015, 980, 950, 900, 870, 840, 795, 725, 640, 595 cm ^-1

NMR ( ¹ H, 360MHz, CDCl ₃ ):

7.39, 7.40 (2s, 1H); 3.84-3.70 (m, 2H); 2.06-1.94 (m, 1H); 1.88-1.00 (m, 24H) δ ppm

NMR ( ¹³ C, 360MHz, CDCl ₃ ):

107.96 (s); 61.55 (t); 36.07 (d); 28.88 (t); 26.66 (t), 26.29 (t), 26.22 (t), 25.72 (t), 25.00 (t), 24.10 (t), 22.55 (t), 22 , 39 (t), 21.64 (t), 19.62 (t) δ ppm

SM:

238 (M ⁺ -H ₂ O, 1), 223 (23), 210 (1), 197 (3), 178 (1), 161 (2), 151 (3), 137 (4), 123 (9 ), 109 (15), 95 (32), 81 (41), 71 (86), 55 (100), 41 (64).

In a 3-necked flask, equipped with a magnetic stirrer, a thermometer, a condenser and kept under nitrogen, a saturated solution of cupric acetate [Cu (OAc) ₂ , 8.5 g] was prepared. in methanol (200 ml). It was filtered to separate the undissolved salt. To the blue solution, 12.8 g (50 mmol) of 14a-hydroxyperyoxy-cyclododeca [b] -pyran were added in portions and, after 30 min. stirring, 1.5 g of FeSO ₄ , followed, 2 h later, by a further addition of 1.5 g of FeSO ₄ . The reaction mixture was allowed to stir at room temperature overnight. Poured onto saturated aqueous NaCl, extracted with isopropyl ether and then washed with saturated aqueous NaCl and saturated aqueous NaHCO ₃ . The organic phase was dried over Na ₂ SO ₄ , filtered and concentrated. 11.4 g of crude product were thus obtained. This product was then distilled on a Vigreux column to provide 8.7 g of pure product. Analysis of this product showed that it was a mixture containing approximately 43% of trans-pentadec-11-en-15-olide, 26% of trans-pentadec-12-en-15-olide, 18% cis-pentadec-11-en-15-olide, 5% cis-pentadec-12-en-15-olide and 8% pentadecanolide.
P. eb. 88-93 ° C / 40 Pa
This mixture was subjected to a chromatographic separation on a 30 m long and 0.53 mm diameter DBWax capillary column using helium (50 KgPa) as carrier gas, to provide the two aforementioned trans-pentadecenolides in pure form. and a mixture of the two cis-pentadecenolides mentioned above.

temps de rétention :

25,35 min

RMN(¹H,360MHz,CDCl₃) :

1,18-1,42(m,10H) ; 1,72(m,4H) ; 1,75(m,2H) ; 2,04(m,2H) ; 2,18(m,2H) ; 2,34(m,2H) ; 4,10(t,J≈6Hz,2H) ; 5,36(dt,J≈16,6Hz,1H) ; 5,41(dt,J≈16,6Hz,1H) δ ppm

SM :

238(M⁺,6), 178(2), 150(4), 136(4), 123(7), 109(12), 95(36), 81(80), 68(100), 55(49), 41(54)

trans-pentadéc-12-én-15-olide

temps de rétention :

25,59 min

RMN(¹H,360MHz,CDCl₃) :

1,18-1,70(m,16H) ; 2,06(m,2H) ; 2,30(t,J≈7Hz,2H) ; 2,32(m,2H) ; 4,11(t,J≈5Hz,2H) ; 5,44(m,2H) δ ppm

SM :

238(M⁺,5), 178(1), 150(3), 136(4), 123(12), 109(16), 95(36), 82(63), 68(100), 55(64), 41(60)

cis-pentadéc-11-én-15-olide (A) et cis-pentadéc-12-én-15-olide (B)

temps de rétention :

26,11 min

RMN(¹H,360MHz,CDCl₃) :

1,18-1,72(m) ; 1,67(m,2H,A) ; 2,04(m,2H de A et 2H de B) ; 2,19(m,2H,A) ; 2,30(tJ≈7Hz,2H,B); 2,35(t,J≈6Hz,2H,A) ; 2,41(m,2H,B) ; 4,12(t,J≈6Hz,2H,B) ; 4,14(t,J≈6Hz,2H,A) ; ≈5,3-5,6(m, 2H,B); 5,34(m,1H,A) ; 5,41(m,1H,A) δ ppm

SM :

238(M⁺,5), 178(1), 150(4), 136(4), 123(7), 109(14), 95(35), 81(66), 68(100), 55(54), 41(57)

The analytical data for these compounds were as follows:
trans-pentadec-11-en-15-olide

retention time :

25.35 mins

NMR ( ¹ H, 360MHz, CDCl ₃ ):

1.18-1.42 (m, 10H); 1.72 (m, 4H); 1.75 (m, 2H); 2.04 (m, 2H); 2.18 (m, 2H); 2.34 (m, 2H); 4.10 (t, J≈6Hz, 2H); 5.36 (dt, J≈16.6Hz, 1H); 5.41 (dt, J≈16.6Hz, 1H) δ ppm

SM:

238 (M ⁺ , 6), 178 (2), 150 (4), 136 (4), 123 (7), 109 (12), 95 (36), 81 (80), 68 (100), 55 ( 49), 41 (54)

trans-pentadec-12-en-15-olide

retention time :

25.59 min

NMR ( ¹ H, 360MHz, CDCl ₃ ):

1.18-1.70 (m, 16H); 2.06 (m, 2H); 2.30 (t, J≈7Hz, 2H); 2.32 (m, 2H); 4.11 (t, J≈5Hz, 2H); 5.44 (m, 2H) δ ppm

SM:

238 (M ⁺ , 5), 178 (1), 150 (3), 136 (4), 123 (12), 109 (16), 95 (36), 82 (63), 68 (100), 55 ( 64), 41 (60)

cis-pentadec-11-en-15-olide (A) and cis-pentadec-12-en-15-olide (B)

retention time :

26.11 min

NMR ( ¹ H, 360MHz, CDCl ₃ ):

1.18-1.72 (m); 1.67 (m, 2H, A); 2.04 (m, 2H of A and 2H of B); 2.19 (m, 2H, A); 2.30 (tJ≈7Hz, 2H, B); 2.35 (t, J≈6Hz, 2H, A); 2.41 (m, 2H, B); 4.12 (t, J≈6Hz, 2H, B); 4.14 (t, J≈6Hz, 2H, A); ≈5.3-5.6 (m, 2H, B); 5.34 (m, 1H, A); 5.41 (m, 1H, A) δ ppm

SM:

238 (M ⁺ , 5), 178 (1), 150 (4), 136 (4), 123 (7), 109 (14), 95 (35), 81 (66), 68 (100), 55 ( 54), 41 (57)

The invention will now be described in more detail using the following examples, presented for illustrative purposes only. In these examples, trans-pentadec-11-en-15-olide, trans-pentadec-12-en-15-olide, as well as their mixtures according to the invention, are designated under the generic name of (E, Z ) -pentadéc-11 (12) -én-15-olide. We have, in fact, found that, despite the olfactory differences mentioned above between the different isomers of this pentadecenolide, the conclusions of the comparative tests described in the examples which follow were equally valid for any of the chemical compositions mentioned above.

Example 1 Substance substantivity test

To an unscented standard fabric softener, (E, Z) -pentadéc-11 (12) -én-15-olide, EXALTOLIDE® (origin: Firmenich SA, Geneva, Switzerland) and GALAXOLIDE® 50 IPM have been added, respectively. (origin: IFF Inc.), in the quantities indicated in the Table (parts by weight) below, to prepare three samples of a perfumed fabric softener. Board Ingredients Sample 1 Sample 2 Sample 3 Standard unscented fabric softener 99.9 99.9 99.8 (E, Z) -Pentadéc-11 (12) -én-15-olide 0.1 - - EXALTOLIDE ® - 0.1 - GALAXOLIDE ® 50 IPM - - 0.2

In three washing machines, three batches of standard mixed textiles, containing cotton, acrylic fiber and nylon textiles, were treated separately with samples 1, 2 and 3 respectively prepared above. The three batches of textiles thus treated were then blindly evaluated by a panel of seven perfume experts both in the wet state and after drying.
The results of these comparative evaluations showed that, in the opinion of six of the seven perfumers, the batch of textiles treated with sample 1, containing the (E, Z) -pentadéc-11 (12) -én-15- olide, exhaled a much more powerful odor at the exit of the washing machine, and lasting after drying, than the odor of the laundry treated with sample 3, containing GALAXOLIDE® 50 IPM. Only a perfumer preferred this last batch.
On the other hand, the evaluation of the batch of textiles treated with sample 1, compared to that treated with sample 2 containing EXALTOLIDE®, also established the superiority of the fragrant note of the (E, Z ) -pentadéc-11 (12) -én-15-olide, from the point of view of power and substance, on that of EXALTOLIDE®, the perfumers having all preferred the smell of the batch of textiles mentioned in the first place.

Example 2 Preparation of a masculine eau de toilette

A basic musk-type perfume composition was prepared for a masculine cologne by mixing the following ingredients:

To this basic composition, 400 parts by weight of (E, Z) -pentadec-11 (12) -en-15-olide were added on the one hand to prepare a new composition A and, on the other hand, 400 parts by weight of EXALTOLIDE® to prepare a composition B. Compositions A and B were evaluated by a panel of expert perfumers. In the unanimous opinion of the latter, composition A had a much more musky, animal and powerful fragrant note than that of composition B.

Claims (9)

1. A mixture containing at least 60% by weight, relative to the weight of the mixture, of pentadecenolides of formula

   

   having a double bond of E-configuration in one of the positions 11 or 12 indicated by the dotted lines, together with lesser amounts of their isomers of formula

   

   having a double bond of Z-configuration in one of the positions 11 or 12 indicated by the dotted lines.
2. A mixture according to claim 1, characterized in that it contains 70% by weight or more of pentadecenolides of formula (I).
3. A mixture according to claim 1 or 2, characterized in that it contains equivalent amounts of (E)-pentadec-12-en-15-olide and of (E)-pentadec-11-en-15-olide, or a surplus of the former.
4. A mixture according to any one of claims 1 to 3, characterized in that it further comprises pentadecanolide.
5. A mixture according to claim 4, characterized in that it contains about 43% by weight of (E)-pentadec-11-en-15-olide, 26% by weight of (E)-pentadec-12-en-15-olide, 18% by weight of (Z)-pentadec-11-en-15-olide, 5% by weight of (Z)-pentadec-12-en-15-olide and 8% by weight of pentadecanolide.
6. A perfuming composition or a perfumed product, comprising as a perfuming ingredient a mixture according to any one of claims 1 to 5.
7. As a perfumed product according to claim 6, a perfume or a Cologne, a soap, a bath or shower gel, a shampoo, a cosmetic, an air or body deodorant, a detergent or a fabric softener, or a household product.
8. Use of a mixture according to any one of claims 1 to 5, as a perfuming ingredient, for the preparation of a perfumed composition or product.
9. Use according to claim 8, characterized in that said mixture is added to the composition or product to be perfumed in an amount sufficient to impart thereto an odour note of the musky-ambrette and fruity-pear type.