EP0073984B1 - Perfuming and/or flavouring compositions containing unsaturated acids - Google Patents

Description

The invention relates to fragrance and / or flavoring compositions which are characterized by the addition of cis-3,7-dimethylocta-3,8-dienoic acid.

The invention further relates to methods for improving the smell of fragrance compositions or the taste of flavoring compositions, which are characterized in that an amount of cis-3,7-dimethylocta-3,6-diene acid which is effective in terms of smell or taste is used.

Finally, the invention relates to the use of cis-3,7-dimethylocta-3,6-dienoic acid as a fragrance and / or flavoring.

ist z. B. aus J. Chem. Soc. (1960), 2864 - 2869 und J. Am. Chem. Soc. 89 (1967), 3828 - 3841 bekanntgeworden. Aus der Literatur gehen keinerlei organoleptische Eigenschaften oder Verwendungsmöglichkeiten von I hervor. Überraschenderweise ist I auch geruchlich völlig verschieden von der bekannten strukturell nahverwandten trans-Isogeraniumsäure I' bzw. den Geraniumsäuren I".

was aus folgender Tabelle sofort ersichtlich ist:

cis-3,7-dimethylocta-3,6-dienoic acid, the cis-isogeranic acid of the formula

is z. B. from J. Chem. Soc. (1960), 2864-2869 and J. Am. Chem. Soc. 89 (1967), 3828-3841. No organoleptic properties or possible uses of I have been found in the literature. Surprisingly, I is also completely different in smell from the known structurally closely related trans-isogeranic acid I 'or the geranic acids I ".

which is immediately apparent from the following table:

kombinieren lässt. Die Kombination I + II zeigt überraschende organoleptische Eigenschaften. Insbesondere unterstützt II die natürlichen Noten von I; II wirkt in solchen Kompositionen insbesondere auch abrundend, und I, kann die harzige Note von I unterstützen.In the course of the present investigations it was also found that I was very good with the 2,2,4-trimethyl-cyclohex-3 (or 4) -en-carboxylic acid, ie the compound of the formula

can be combined. The combination I + II shows surprising organoleptic properties. In particular, II supports the natural notes of I; II also rounds off in such compositions, and I can support the resinous note of I.

The olfactory properties of II can be described as follows:

Very natural, notes of incense, olibanum, cistus, ambry, leather, myrrh, animal, opoponax, antique wood.

The compound of formula II is also known, see e.g. B. J. Org. Chem. 34 (1968) 2196-2203.

Although the individual isomers of II are easily accessible, the mixture of isomers is expediently used.

The compound of the formula I, or the mixtures I + II, are particularly suitable for modifying known compositions owing to their natural odor notes.

• - Naturprodukte wie Basilikumöl, Baummoos absolue, Benzoebalsam, Bergamotteöl, Castoreum, Cedernholzöl, Cistusöle, Citronenöl, Corianderöl, Cypressenöl, Elemiöl, Fichtennadelöl, Galbanumöl, Grapefruitöl, Jasmin absolue, Lavendelöl, Mandarinöl, Mastix absolue, Moschusöle, Myrtenöl, Palmarosaöl, Patchouliöl, Petitgrainöl Paraguay, Pfefferminzöle, Pfefferöl, Rosmarinöl, Sandelholzöl, Terpentinöle, Thymianöl, Vetiveröl, Wermutöl, Ylangöl, Zibetextrakte, etc.
• - Alkohole, wie Citronellol, Geraniol, Linalool, Nerol, Phenyläthylalkohol, Rhodinol, Sandalore® (3-Methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol), Sandela^® (3-Isocamphyl-(5)-cyclohexanol), Zimtalkohol, etc.
• - Aldehyde, wie Anisaldehyd, Benzaldehyd, Citral, Helional (a-Methyl-3,4-methylendioxy- hydrozimtaldehyd), Heliotropin, a-Hexylzimtaldehyd, Hydroxycitronellal, Laurinaldehyd, Lilial® (p-tert-Butyl-a-methyl-hydrozimtaldehyd), Methylnonylacetaldehyd, Undecylenaldehyd, Vanillin, Zimtaldehyd, etc.
• - Ketone, wie Acetophenone (z. B. p-Methyl, p-Methoxy), Acetylcedren, Allyljonon, Irone,a-Jonon,ß-Jonon, Ketonmoschus, Methyljonone, etc.
• - Ester, wie Äthyl-acetoscetat, Allyl-phenoxyacetat, Anthranilsäureester, Benzylacetat, Cinnamylpropionat, Dimethylbenzylcarbinyl-butyrat, Fettsäureester, Linalylacetat, Methambrat® (1-Acetoxy-1-methyl-2-sec.butyl-cyclohexan), Methyl-dihydrojasmonat, Salicylate, Styrallylacetat, Vetiverylacetat, etc.
• - Lactone, wie Äthylenbrassilat, Cumarin, y-Nonalacton, y-Undecalacton, C₁₄-Aldehyd (5-Undecalacton), etc.
• - Äther, wie Caryophyllenepoxyd, Cyclododecanoläther wie Madrox® (1-Methyl-1-methoxy- cyclododecan), Epoxycedren, etc.
• - verschiedene, in der Parfümerie oft benützte Komponenten, wie Ambrettemoschus, Celestolid (4-Acetyl-6-tert.butyl-1,1-dimethylindan), Eugenol, Galaxolid (1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethyl- cyclopenta-y-2-benzopyran), Indol, Isobutylchinolin, p-Menthan-8-thiol-3-on, Methyleugenol, Musk 174 (12-Oxahexadecanolid), etc.

Acids I and II combine with numerous known fragrance ingredients of natural or synthetic origin, the range of natural raw materials including both volatile, medium and low volatile components, and that of the synthetic substances can include representatives from practically all classes of substances, as follows from the following Compilation can be seen:

• - Natural products such as basil oil, tree moss absolue, benzo balsam, bergamot oil, castoreum, cedar wood oil, cistus oils, lemon oil, coriander oil, cypresse oil, elemi oil, spruce needle oil, galbanum oil, grapefruit oil, jasmine absolute, lavender oil, mandarin oil, mastic oil, mousse oil, musk oil, musk oil Petitgrain oil Paraguay, peppermint oils, pepper oil, rosemary oil, sandalwood oil, turpentine oils, thyme oil, vetiver oil, wormwood oil, ylang oil, civet extracts, etc.
• - Alcohols, such as citronellol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, Sandalore® (3-methyl-5- (2,2,3-trimethylcyclopent-3-en-1-yl) pentan-2-ol), Sandela ^® (3-isocamphyl- (5) -cyclohexanol), cinnamon alcohol, etc.
• - Aldehydes, such as anisaldehyde, benzaldehyde, citral, helional (a-methyl-3,4-methylenedioxy-hydrocinnamaldehyde), heliotropin, a-hexylcinnamaldehyde, hydroxycitronellal, lauric aldehyde, Lilial® (p-tert-butyl-a-methyl-hydrocinnamaldehyde) , Methylnonylacetaldehyde, undecylenaldehyde, vanillin, cinnamaldehyde, etc.
• - Ketones, such as acetophenones (e.g. p-methyl, p-methoxy), acetylcedrene, allyl jonone, irone, a-jonon, ß-jonon, ketone musk, methyljonone, etc.
• - Esters, such as ethyl acetoscetate, allyl phenoxy acetate, anthranilic acid esters, benzyl acetate, cinnamyl propionate, dimethylbenzylcarbynyl butyrate, fatty acid esters, linalyl acetate, Methambrat® (1-acetoxy-1-methyl-2-sec.butyl-cyclohexane), methyl-cyclohexane) Salicylates, styrallyl acetate, vetiveryl acetate, etc.
• Lactones, such as ethylene brassilate, coumarin, y-nonalactone, y-undecalactone, C ₁₄ aldehyde (5-undecalactone), etc.
• - Ether, such as caryophyllene epoxy, cyclododecanol ether such as Madrox® (1-methyl-1-methoxycyclododecane), epoxycedrene, etc.
• - Various components often used in perfumery, such as ambrush musk, celestolide (4-acetyl-6-tert-butyl-1,1-dimethylindane), eugenol, galaxolide (1,3,4,6,7,8-hexahydro) 4,6,6,7,8,8-hexamethyl-cyclopenta-y-2-benzopyran), indole, isobutylquinoline, p-menthan-8-thiol-3-one, methyleugenol, Musk 174 (12-oxahexadecanolide), etc .

It is remarkable how the compound I (or I + II) gives the olfactory notes of known compositions, e.g. B. oriental (i.e. heavier, sweeter) notes, amber, powdery notes, citrus notes in colognes round off and harmonize, even embossed. So she underlines z. B. in perfume bases z. B. in flowery like rose bases the sought-after character of the heavy, sweet and somewhat fruity-looking Bulgarian rose.

Threshold value determinations have shown that I is almost 2 powers of ten more intense than I 'or I ". I is therefore a typical" impact chemical ".

In fruit bases, e.g. B. of the apricot type I or I + II can be successfully used to achieve a stronger and more naturally fruity and rounding effect.

The compound of the formula I (or the mixture I + II) can be used within wide limits, which can range, for example, from 0.01 (detergents) -10% (alcoholic solutions) in compositions, without these values, however, being intended to represent limit values , because the experienced perfumer can achieve effects with even lower concentrations or build up new complexes with even higher doses. The preferred concentrations are between 0.1 and 5%. The compositions made with I. can be used for all types of perfumed consumer goods (Eaux de Cologne, Eaux de Toilette, Extraits, lotions, creams, shampoos, soaps, ointments, powders, toothpastes, mouthwashes, deodorants, detergents, tobacco, etc.).

The compound I (or the mixture I + II) can accordingly be used in the production of compositions and - as the above composition shows - using a wide range of known fragrances or mixtures of fragrances. In the production of such compositions, the above-mentioned known fragrances or mixtures of fragrances can be used in a manner known to the perfumer, such as, for example, B. from W.A. Poucher, Perfumes, Cosmetics, Soaps 2, 7th edition, Chapman and Hall, London 1974.

The compound of formula 1 or their mixtures with II are also excellently suitable for use in flavors, in particular in fruit flavors of all kinds, but in particular also for flavoring tobacco.

As flavorings, the compounds I can be used, for example, to improve, reinforce, increase or modify fruit flavors of all kinds, e.g. B. raspberry or apricot flavors can be used. Foods (yogurt, confectionery, etc.), luxury foods (tea, tobacco, etc.) and drinks (lemonade, etc.) can be used as an area of application for these flavors.

The pronounced taste qualities of compound I (or its mixtures with 11) enable it to be used as a flavoring in low concentrations. A suitable dosage includes, for example, the range of 0.01 ppm - 100 ppm, preferably the range of 0.1 ppm - 20 ppm in the finished product, i.e. the flavored food, luxury food or drink.

When flavoring, for example, tobacco, the dosage, for example in the case of a top flavor, can range from 0.1 to 2 ppm in the end product.

The compounds can be mixed in a conventional manner with the constituents used for flavoring compositions or added to such flavors. The aromas used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or distributed in edible materials. They contain, for example, about 0.1-10, in particular 0.5-3,% by weight. They can be converted into the usual forms of use, such as solutions, pastes or powders, using methods known per se. The products can be spray dried, vacuum dried or lyophilized.

The known flavorings expediently used in the production of such flavors are either contained in the above compilation or can be found in the relevant literature, see e.g. B. J. Merory, Food Flavors, Composition, Manufacture and Use, Second Edition, The Avi Pubishing Company, Inc., Westport, Conn. 1968, or G. Fenaroli, Fenaroli's Handbook of Flavor Ingredients, Second Edition, Volume 2, CRC-Press, Inc. Cleveland, Ohio 1975.

The following carrier materials, thickeners, flavor improvers, spices and auxiliary ingredients, etc. are suitable for the production of the usual forms of use:

Gum arabic, tragacanth, salts or brewer's yeast, alginates, carrageenan or similar absorbents; Indoles, maltol, dienals, spice oleoresins, smoke flavors; Cloves, diacetyl, sodium citrate; Monosodium glutamate, disodium aminosin 5'-monophosphate (IMP), disodium guanosine 5-phosphate (GMP); or special flavors, water-ethanol, propylene glycol, glycerin.

As far as tobacco is concerned, acid I (or the mixture of I + II) can serve in particular to improve the organoleptic properties of tobacco products.

"Tobacco product" is a common term in the industry, which not only includes tobacco itself, but also tobacco by-products such as reconstituted and homogenized leaves and stems, tobacco surrogates (e.g. lettuce and cabbage leaves, etc.), materials, used in tobacco processing, such as paper, filters etc. and flavor compositions used for tobacco products. The term "tobacco product" includes cigarette tobacco, cigar tobacco, chewing tobacco and pipe tobacco, etc.

The addition of compound I or the mixture of I + II to a tobacco mixture improves both the smell of fresh tobacco and the smell and taste of tobacco when smoking. A comparison of treated and untreated tobacco shows that the smell of the mixtures containing I is stronger, more rounded and lighter than the untreated tobacco.

The differences between the treated and untreated tobacco are even more noticeable when smoking. The untreated cigarettes have an undesirable tartness when smoking, an effect that is reduced by the addition of I or I + II. The treated cigarettes give a smoother, lighter and more rounded taste when smoking, which is why they are clearly preferred to the untreated ones.

The amount of acid 1 or mixture of I + II that is expediently added can depend on various factors, including the desired effect, the type and amount of other additives used at the same time and / or the personal preference of the aromatist. Even quantities of 0.01 ppm, based on the weight of the tobacco, have proven to be effective, but quantities of 10 ppm can still be used. However, amounts of 0.1 ppm to 2 ppm are preferably used.

Of course, the limits proposed above are only intended to indicate the preferred amounts; however, these are also dependent on the skill of the aromatist and the effect he wants to achieve.

The compounds I and II can the tobacco product (cigarette paper, etc.) according to the expert known methods, e.g. B. atomization, immersion, coating, etc. can be added or mixed.

The following examples are intended to be illustrative of the preferred embodiments of the present invention and not as a limitation. They should therefore also include variations which can be derived therefrom and which are obvious to the person skilled in the art.

As for the ratio of I: II, this can vary within wide ranges. A suitable range is, for example, that from 90: 1 to 1:90.

Examples

Gibt man zu dieser blumigen Komposition 5 Teile I, so wirkt diese viel runder und wärmer. Die Lakton-Note (Jasminnote) wird sehr angenehm unterstrichen.

If you add 5 parts I to this floral composition, it looks much rounder and warmer. The lactone note (jasmine note) is very pleasantly underlined.

If you add 10 parts I to this complex, you can immediately see in the 24-hour value that it blends in very harmoniously and the somewhat angular impression of the original base can disappear. The freshly dipped grapefruit note now appears underlined. On the other hand, the same amount of geranic acid would give rise to an undesirable eau de cologne note in this composition.

The freshness effect of the base is significantly increased by adding 2 parts I. In contrast, geranium acid does not fit into the base at all.

By adding 5 parts I, the soft Jonon note of the base is comfortably emphasized in the 48-hour value. On the other hand, the addition of geranic acid emphasizes the cedar note too much, the resulting base looks too dry.

If you add 5 parts of a 10% solution of I to this chypre base, the base appears much more diffusive, sweeter. An advantageous vetiver citrus note is determined in the 24 hour value (rear). On the other hand, an equivalent addition of geranic acid to the composition causes the appearance of unpleasant dusty, musty notes.

If you add 3 parts I to this gardenia base, the base is rounded off in a very pleasant way; on the other hand, the addition of 3 parts of geranic acid has a negative effect on the base: it is by no means rounded.

If 10 parts of cis-isogeranic acid are added to the above base, the animal note becomes even more pronounced, which effect cannot be achieved with the same additions of geranic acid. The latter acid makes the base appear unbalanced flowery, with the aldehyde note standing out. After 24, 48, 72 and 96 hours, the base note in the former case has the warmest, most voluminous and, in a typical way, the most animalistic effect on the smell strip.

The addition of 10 parts of cis-isogeranic acid to the above base (in contrast to geranic acid) enormously enhances the citrus character, while at the same time enhancing the wood note. It leads this citrus character harmoniously down to the base, in which a fine, warm, moist, acidic nuance manifests itself after 24 hours and persists on the scent strip for over 96 hours. Geranic acid additives, on the other hand, only damage the harmony of the composition.

Adding 10 parts of cis-isogeranic acid to the above base results in a clearer, stronger wood note, which can also be felt on the scent strip after 48, 72 and 96 hours. Geranium acid does not produce this effect.

If 10 parts of cis-isogeranic acid are added to the above base, the composition on the freshly dipped smelling strip appears stronger and, above all, more balanced than when the same amount of geranic acid is added. This strength and harmony remain in the base note after 24, 48 and 96 hours.

By adding 10 g of the above acid mixture, the base base (woody, woody) is changed significantly in the direction of incense (olibanum, encens, frankincense) and is much more resinous. The composition looks even more powerful after 72 hours in the rear; the incense character is completely preserved.

By adding I to composition A, the existing fruity note is significantly enhanced.

When the flavored tobacco is smoked, a significantly more pronounced fruit note is noticeable, and the tobacco note is also significantly enhanced.

Claims (6)

1. An odorant and/or flavouring composition, characterized by an addition of cis-3,7-dimethylocta-3,6-dienoic acid.

2. An odorant and/or flavouring composition in accordance with claim 1, characterized by a content of cis-3,7-dimethylocta-3,6-dienoic acid in combination with 2,2,4-trimethylcyclohex-3 (or 4)-ene-carboxylic acid.

3. The use of cis-3,7-dimethylocta-3,6-dienoic acid as an odorant and/or flavourant or as a modifier of odorant and/or flavouring compositions.

4. The use of cis-3,7-dimethylocta-3,6-dienoic acid in combination with 2,2,4-trimethylcyclohex-3 (or 4)-ene-carboxylic acid as an odorant and/or flavourant or as a modifier of odorant and/or flavouring compositions in accordance with claim 3.

5. A method for improving the odour of odorant compositions or the flavour of flavouring compositions, characterized by adding an olfactorily or gustatorily effective amount of cis-3,7-dimethylocta-3,6-dienoic acid.

6. A method for improving the odour of odorant compositions or the flavour of flavouring compositions in accordance with claim 5, characterized by adding an olfactorily or gustatorily effective amount of cis-3,7-dimethylocta-3,6-dienoic acid in combination with 2,2,4-trimethylcyclohex-3 (or 4)-ene-carboxylic acid.