EP0424787A2 - Use of unsaturated macrocyclic ketones as perfuming ingredients - Google Patents

Abstract

Unsaturated macrocyclic lactones of formula <IMAGE> containing a double bond of trans configuration in either of positions 11 and 12 as indicated by the dotted lines, and their mixtures, are useful as perfuming ingredients for preparing perfuming compositions and scented articles, to which they impart musky and animal notes of a rare power and substantivity.

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

The above-mentioned compounds are unsaturated macrocyclic lactones, the chemical structure of which is known. They have, in fact, been cited as secondary or intermediate products of a process for the preparation of saturated odorous macrolides such as pentadecanolide, known under the trade name of EXALTOLIDE® (origin: Firmenich SA, Geneva, Switzerland), and the like [see, for example, French Patent No. 7019709 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 therein. 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 serve to develop odorous 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 according to the invention 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 cis configuration double bond in one of 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 perfuming of functional products such as soaps, shower or bath gels, shampoos, body or room air fresheners, cosmetic products and cleaning products. Because of 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 as a mixture with one or more perfuming ingredients, solvents or usual carriers. 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 supplied 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 cis configuration isomers represented by formula (II) have less animal odorous notes than those of 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. A person skilled in the art knows from experience that these proportions depend on the nature of the product which one wishes 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 above-mentioned unsaturated macrocyclic lactones can be prepared from 2- (3-hydroxypropyl) -1-cyclododecanone (the preparation of which is described in patent FR 70 19709 cited above) according to a process analogous to that described by SL Schreiber et 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.
30 g (125 mmol) of 2- (3-) were introduced into a 4-necked flask equipped with a mechanical stirrer, an introduction bulb, a thermometer, a condenser and kept under nitrogen. hydroxypropyl) -1-cyclododecanone and 137.5 g (2.29 mole) of glacial acetic acid. The whole was kept stirring 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 NaHCO₃ (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 (¹H, 360MHz, CDCl₃): 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 (¹³C, 360MHz, CDCl₃): 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⁺-H₂O, 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 was added 12.8 g (50 mmol) of 14a-hydroxyperyoxy-cyclododeca [b] -pyran in portions and, after 30 min. stirring, 1.5 g of FeSO₄, followed, 2 h later, by a further addition of 1.5 g of FeSO₄. 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 NaHCO₃. The organic phase was dried over Na₂SO₄, 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 DBWax capillary column 30 m in length and 0.53 mm in diameter using helium (50KgPa) as carrier gas, to provide the two trans-pentadecenolides mentioned above in the pure state. and a mixture of the two cis-pentadecenolides mentioned above.

The analytical data for these compounds were as follows:
trans-pentadec-11-en-15-olide
retention time: 25.35 min
NMR (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-pentadec-12-en-15-olide
retention time: 25.59 min
NMR (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-pentadec-11-en-15-olide (A) and cis-pentadec-12-en-15-olide (B)
retention time: 26.11 min
NMR (¹H, 360MHz, CDCl₃): 1.18-1.72 (m); 1.67 (m, 2H, A); 2.04 (m, 2H A and 2H B); 2.19 (m, 2H, A); 2.30 (t, J≈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, in spite of 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: Ingredients Parts by weight Benzyl acetate 20 Cinnamic alcohol at 50% * 50 n-Octanal at 10% * 5 n-Decanal at 10% * 25 n-Dodecanal at 10% * 30 Hexylcinnamic aldehyde 40 10% hydroxycitronellal methylantranilate * 20 Bergamot essence 80 Lemon essence 30 Coumarin 10 Ethylvanillin 10% * 25 10% galbanum essence * 25 LILIAL® ¹⁾ 50 IRALIA® ²⁾ 20 Essence of labdanum 10 Lavender absolute 50 Essence of frizzy mint 5 Methyl everninate 20 HEDIONE® ³⁾ 100 Petitgrain essence 5 Terpineol 15 Iso E Super ⁴⁾ 55 α-Ionone 10 AMBROX® DL ⁵⁾ at 10% * 20 Essence of ylang extra 10 Clary sage essence 25 Jasmine absolute 10 Lavender essence 35 Total 800 * in dipropylene glycol 1) 3- (4-tert-butyl-1-phenyl) -2-methylpropanal; origin: L. Givaudan SA, Vernier, Switzerland 2) methylionone; origin: Firmenich SA, Geneva, Switzerland 3) methyl dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland 4) 2-acetyl-1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene; origin: IFF Inc. 5) tetramethyl perhydronaphtofuran; origin: Firmenich SA, Geneva, Switzerland

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. Use as a perfuming ingredient of at least one pentadecenolide of formula

having a double trans configuration link in one of positions 11 or 12 as indicated by the dotted lines. 2. Use according to claim 1 of trans-pentadec-12-en-15-olide. 3. Use according to claim 1 of a mixture containing a predominant amount of pentadecenolides of formula (I), accompanied by lesser amounts of pentadecenolides of formula

having a cis configuration double bond in one of positions 11 or 12 as indicated by the dotted lines. 4. Use according to claim 3, characterized in that the content of the mixture of pentadecenolides of formula (I) is approximately 70% by weight or more. 5. Use according to claim 3 or 4, characterized in that said mixture contains, as an additional, pentadecanolide. 6. Use according to claim 5, characterized in that the content of the pentadecenolide mixture is at least 3% by weight, relative to the weight of the mixture. 7. Perfuming composition containing as a perfuming ingredient a pentadecenolide or a mixture of pentadecenolides as defined in one of claims 1 to 6. 8. Perfumed product containing as a perfuming ingredient a pentadecenolide or a mixture of pentadecenolides as defined in one of claims 1 to 6. 9. As a perfumed product according to claim 8, a perfume or eau de toilette, a soap, a shower or bath gel, a shampoo, a cosmetic product, a body or air freshener, a detergent or a textile conditioner, or a cleaning product.