EP1878787B1 - Aldéhydes en place alpha substitués par reste d'alkyle en tant que parfums et aromates - Google Patents

Aldéhydes en place alpha substitués par reste d'alkyle en tant que parfums et aromates Download PDF

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Publication number
EP1878787B1
EP1878787B1 EP07108227A EP07108227A EP1878787B1 EP 1878787 B1 EP1878787 B1 EP 1878787B1 EP 07108227 A EP07108227 A EP 07108227A EP 07108227 A EP07108227 A EP 07108227A EP 1878787 B1 EP1878787 B1 EP 1878787B1
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carbon atoms
aldehydes
alkyl radical
denotes
unbranched alkyl
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German (de)
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EP1878787A1 (fr
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Bernd HÖLSCHER
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Symrise AG
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Symrise AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes

Definitions

  • the present invention relates to the use of certain alpha-substituted by an alkyl radical aldehydes having a total of 13 or a total of 15 carbon atoms as fragrances or flavorings.
  • the invention also relates to perfumed or flavored articles comprising such aldehydes and corresponding processes for imparting, modifying and / or enhancing certain odor and / or flavor notes.
  • fragrances with aldehydigen fragrance notes which are able to produce (in fragrance compositions) in addition to an aldehydigen fragrance note more interesting odor notes and to extend the possibilities of the perfumer with their novel or original fragrance properties.
  • aldehydic scents which are capable are to make a harmonious combination with woody scented fragrances.
  • a superimposition of the different odoriferous aspects and notes should take place in order thereby to produce an overall complex olfactory impression.
  • fragrances with special odor properties which are suitable to serve as a basis for the composition of novel modern perfumes with complex odor character.
  • Preferred odoriferous substances sought should have, in addition to an aldehydic fragrance, further notes and aspects that give them an odor character and complexity.
  • fragrances with aldehydigen fragrances which are paired with other interesting and original odor properties, whereby the fragrances sought novel and original fragrance compositions with enable particular odor notes and aspects.
  • fragrances with aldehydigen fragrances should be found, which are particularly suitable for combination with fragrances, which have a woody fragrance.
  • the perfumes that accomplish this main purpose should also preferably have additional positive secondary properties beyond their primary, namely, odoriferous, properties, such as, e.g. a higher stability under certain conditions of use, a higher yield, a better adhesion, a high substantivity, a remarkable booster effect or a strong blooming, so that sensory remarkable effects or else better dermatological and toxicological properties can be achieved compared to similar fragrances.
  • additional positive secondary properties beyond their primary, namely, odoriferous, properties, such as, e.g. a higher stability under certain conditions of use, a higher yield, a better adhesion, a high substantivity, a remarkable booster effect or a strong blooming, so that sensory remarkable effects or else better dermatological and toxicological properties can be achieved compared to similar fragrances.
  • the aldehydes to be used according to the invention are aldehydes having a total of 13 or a total of 15 C atoms.
  • the aldehydes to be used are those of the formula and have two unbranched alkyl radicals R and R '.
  • the aldehydes to be used according to the invention, the respective total number of C atoms and the respective number of C atoms in the radicals R and R ' are shown in the table below.
  • Table 1 Overview of the aldehydes to be used according to the invention Aldehydes to be used according to the invention Total C-atoms in total Number of C atoms in R Number of C atoms in R ' 2-ethyl-undecanal 13 9 2 2-propyl-decanal 13 8th 3 2-butyl-nonanal 13 7 4 2-pentyl-octanal 13 6 5 2-methyltetradecanal 15 12 1 2-ethyl-tridecanal 15 11 2 2-Propyldodecanal 15 10 3 2-butyl-undecanal 15 9 4 2-Pentyl-decanal 15 8th 5
  • the odor properties of the aldehydes to be used according to the invention are each described as follows: strongly aldehydic, clearer than other aldehydes, strongly coniferous, flowery, greasy sweet, ozone.
  • the aldehydes of type (I) or (II) can be used for imparting, modifying and / or enhancing a corresponding odor and / or flavor.
  • German patent DE 43 44 064 C1 discloses processes for the preparation of alpha-alkyl substituted aldehydes.
  • One example relates to the preparation of isomeric tridecanals from 1-dodecene.
  • a sensory description of the produced aldehydes can be found in the DE 43 44 064 C1 Not. Instead, it is stated that aldehydes containing 8 to 17 carbon atoms, which are substituted by alkyl radicals in the alpha position to the carbonyl group, have technical significance as intermediates.
  • German patent application DE 39 42 954 A1 describes processes for the preparation of aldehydes by hydroformylation of olefinically unsaturated compounds.
  • the DE 39 42 954 A1 contains no sensory descriptions of the aldehydes produced.
  • US 2006/0003913 discloses liquid detergent formulations containing fragrance aldehydes such as undecyl aldehyde, dodecyl aldehyde or 2-methyl undecanal.
  • aldehydes pentadecanal, methyldecylacetaldehyde and tridecanal are in the said publication (S. Arctander) as a whole for the perfumery not very interesting classified.
  • aldehydes have, according to statements in the literature, a sweet, greasy-waxy, fresh-flowery odor with a slightly balsamic undertone (lauric aldehyde) or strongly diffuse herbaceous aldehydic odor notes with a dry amber undertone (methyl undecanal).
  • the present invention is based inter alia on the surprising finding in the light of the prior art that the aldehydes to be used according to the invention (see Table 1 above) have similar and moreover better or different odor properties than those already present with regard to their odor properties aldehydes tridecanal, methyldecylacetaldehyde and pentadecanal described. Surprisingly, therefore, the aldehydes to be used according to the invention are particularly suitable as fragrances and flavorings.
  • aldehydes to be used according to the invention are used in particular for imparting, modifying and / or enhancing an odor and / or flavor with the following aspects: aldehydic, coniferous, flowery, greasy sweet, ozone.
  • the aldehydes to be used according to the invention are usually used in sensory effective amounts in the context of the use according to the invention. Frequently, the aldehydes to be used according to the invention are to be mixed with other fragrances or flavorings. These other fragrances or flavorings may be other aldehydes (including the above-mentioned aldehydes tridecanal, methyldecylacetaldehyde and pentadecanal) or other fragrances or flavorings.
  • the weight ratio of the total amount of fragrances to be used according to the invention (i.e., the fragrances listed in Table 1) to the total amount of other fragrances or flavorings is preferably in the range of 1: 1000 to 1: 0.5.
  • a mixture comprising or consisting of two, three or more aldehydes of the type (I) and / or the type (II).
  • aldehydes to be used according to the invention with woody fragrances (including sandal, musk and amber) and floral fragrances is particularly suitable.
  • Especially suitable for combination flowery fragrances are: Lilial (2-methyl-3- (4-tert-butylphenyl) propanal), hedione (methyl (3-oxo-2-pentylcyclopentyl) acetate), Mayol (4-isopropyl-cyclohexyl) methanol ), Linalool (3,7-dimethyl-1,6-octadien-3-ol), dihydromyrcenol (2,6-dimethyl-7-octene-2-ol), citronellol (3,7-dimethyl-6-octene) 1-ol), phenoxanol (3-methyl-5-phenylpentanol), 2-phenylethyl alcohol, hydroxycitronellal (3,7-dimethyl-7-hydroxyoctan-1-al), alpha-ionone (4- (2,6, 6-trimethyl-cyclohex-2-enyl) -but-3-en-2-one).
  • aldehydes to be used according to the invention leads to brighter and cleaner odor impressions.
  • the mixtures are more natural and fresher.
  • green-fruity fragrances are, for example: Vertral (octahydro-1 H-4,7-methanoindene-5-carbaldehyde), cis-3-hexene-1-ol, beta-damascone (1- (2,6,6-trimethyl -cyclohex-2-enyl) -butene-1-one), vertocitral (2,4-dimethylcyclohex-3-en-1-carbaldehyde), cyclogalbanate (allyl (cyclohexyloxy) acetate), hexyl acetate.
  • Suitable spicy-balsamic fragrances are in particular: eugenol (2-methoxy-4-allylphenol), coumarin (2H-1-benzopyran-2-one), anisaldehyde (4-methoxybenzaldehyde), amyl cinnamaldehyde (2-pentyl-3-phenyl-2 -propenal), isoamylsalicylate (Salicylic acid 3-methylbutyl ester) and cinnamyl alcohol (3-phenyl-2-propen-1-ol).
  • the compounds according to the invention to be used according to Table 1 each have a chiral center; they may be R- or S-configured or used as any mixture of the enantiomers, in particular as a racemate.
  • the aldehydes or aldehyde mixtures to be used according to the invention have, in particular, an unexpectedly strong coniferous and sweet odor with a surprising range of complex olfactory shades.
  • the mixtures of aldehydes to be used according to the invention and in particular mixtures of aldehydes of the formulas (I) and (II), d. H. of aldehydes having 13 and 15 carbon atoms to be used according to the invention give a very complex and varied odor and taste impression which otherwise can only be achieved by complex mixtures of several components (such as, for example, essential oils or herbal or spice mixtures).
  • mixtures of aldehydes to be used according to the invention comprising one, two or more aldehydes of type (I) and one, two or more aldehydes of type (II) and the Weight ratio of the total amount of aldehydes of type (I) to the total amount of aldehydes of type (II) in the range of 100: 1 to 1:10, preferably in the range of 10: 1 to 1: 2, and more preferably in the range of 8 : 1 to 1: 1.
  • Very particularly preferred is a mixing ratio in the range of 5: 1 to 2: 1.
  • the weight ratio of the total amount of aldehydes of the type (I) and (II) to the total amount of pentadecanal, methyldecylacetaldehyde and tridecanal is preferably in the range from 1: 1000 to 1 : 0.1.
  • the compounds of the formulas (I) and (II) to be used according to the invention are able to intensify the intensity of a fragrance mixture even at low dosages and to round off and harmonize the overall appearance of the fragrance mixture and to add more (off) radiation and naturalness to the mixture to lend.
  • the present invention also relates to the use for providing (a) hair, (b) skin or ( c) textile fibers with a - in particular aldehydigen and at the same time coniferigen - scent (with regard to further smell or taste notes see above).
  • the present invention also relates to corresponding processes and (preferably surfactant-containing) mixtures.
  • the present invention also relates to the use of the above-mentioned aldehydes of the type (I) or (II) or a mixture comprising or consisting of two, three or more such aldehydes of the type (I) and / or (II) as Means for increasing the substantivity and / or retention of a fragrance mixture and / or as a fixative and / or as an agent for increasing the perceived via a surfactant-containing aqueous solution odor of other fragrances.
  • aldehydes of the type (I) or (II) or the corresponding mixtures to be used according to the invention have, in addition to their primary, namely olfactory properties, additional positive secondary properties, such as, for example, B. a high stability under certain conditions of use, high yield, good adhesion, high substantivity.
  • Aldehydes of type (I) and / or (II) or corresponding mixtures can be used, in particular, to impart radiation, rounding off and / or harmony to a fragrance or aroma composition (off) and / or to existing odor and / or taste notes strengthen.
  • a perfumed or flavored article of the invention is a fragrance or flavoring composition.
  • a component (b) ie with one, two, three or more other fragrances or flavorings (preferably having a woody and / or floral odor or taste)
  • new fragrance or flavoring compositions can be formed.
  • Fragrances (as component (b)) which are advantageously suitable for combination, are found, for. In S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, NJ 1969, self-published , or K. Bauer et al., Common Fragrance and Flavor Materials, 4th Edition, Wiley-VCH, Weinheim 2001 , Specifically, may be mentioned:
  • Extracts from natural raw materials such as essential oils, concretes, absolues, resines, resinoids, balms, tinctures such.
  • fragrances from the group of hydrocarbons such as 3-carene; ⁇ -pinene; ⁇ -pinene; ⁇ -terpinene; ⁇ -terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -1,3,5-undecatriene; styrene; diphenylmethane; the aliphatic alcohols such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) -2-hexenol; 1-octene-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5
  • Citronellal Citronellal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of Geranial, Neral, the cyclic terpene alcohols such.
  • allyl-3-cyclohexylpropionate Allylcyclohexyloxyacetat; cis- and trans-methyldihydrojasmonate; cis- and trans -methyl-jasmonate; Methyl-2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; Ethyl-2-methyl-1,3-dioxolan-2-acetate; the araliphatic alcohols such as benzyl alcohol; 1-phenylethyl; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) propanol; 1,1-dimethyl-2-
  • An odorant or flavoring composition according to the invention can be prepared, for example, by providing a component (a) or a mixture of components (a) and (c) and mixing this component or mixture with one or more further odoriferous or aromatic substances (as component ( b)) is mixed.
  • the component (a) is used regularly in an amount sufficient to impart, modify and / or enhance in the finished composition an odor or flavor of the type aldehydic, coniferous, floral, greasy-sweet and / or ozone ,
  • a fragrance or flavoring composition according to the invention preferably comprises total amount of component (a) in the range from 0.00001 to 99.9% by weight, preferably 0.001 to 70% by weight and particularly preferably 0.01 to 50% by weight, based on the total amount of the fragrance or flavor composition.
  • the total amount of the component is (A) preferably comparatively low and more preferably in the range of 0.01 to 5 wt .-%, preferably in the range of 0.1 to 2 wt .-%, based on the total amount of the fragrance or flavoring composition.
  • aldehydes or aldehyde mixtures to be used according to the invention can be obtained starting from olefins of the following formulas A or B by means of hydroformylation.
  • the hydroformylation (oxo synthesis) of a compound A and / or B with synthesis gas (a mixture of carbon monoxide and hydrogen) in the presence of transition metal catalysts (often the VII. Subgroup) is performed.
  • This reaction can be carried out in accordance with hydroformylation reactions of dienes such as n-tetradecene-1.
  • the reaction can be carried out homogeneously or heterogeneously.
  • Co or Rh catalysts are used for the hydroformylation preferably Co or Rh catalysts are used.
  • the hydroformylation of the compound A and / or B according to the invention is preferably based on DE 39 42 954 A1 and DE 43 44 064 carried out.
  • reaction parameters in particular with regard to preferred catalysts, ligands, solvents or diluents, temperature, pressure, reaction time, homogeneous or heterogeneous reaction, work-up, etc., reference is made to the statements in said publications.
  • Analogous to DE 39 42 954 A1 can be formed from a compound A and / or B by means of hydroformylation in the presence of a rhodium catalyst such as Rh-2-ethylhexanoate a mixture which in addition to the invention to be used aldehydes also pentadecanal, methyldecylacetaldehyde and / or tridecanal.
  • a rhodium catalyst such as Rh-2-ethylhexanoate a mixture which in addition to the invention to be used aldehydes also pentadecanal, methyldecylacetaldehyde and / or tridecanal.
  • Particularly preferred according to the invention is the use of aldehydes of the type (I) and / or (II) whose radical R 'comprises at least two C atoms.
  • a particularly high proportion of the sensory valuable aldehydes of the type (I) or (II) can be z.
  • B. analog DE 43 44 064 is hydroformylated.
  • the information on production methods can be followed, as described in Fats, soaps, paints (1974), 76 (10), 443-446 ) are described.
  • aldehydes of the type (I) or (II), ie the aldehydes listed in Table 1, are present in the reaction mixture as a result of the preparation, in particular in addition to further aldehydes and / or pentadecanals, methyldecylacetaldehyde and / or tridecanal to be used according to the invention, their isolation can take place preferably from the reaction mixture by conventional methods such as distillation or rectification. If necessary, a precise separation or far-reaching purification, for example by means of fractionation on a rotating band column, by means of HPLC or preparative gas chromatography.
  • Fragrance or flavoring compositions of the invention containing aldehydes of type (I) and / or (II) may be used in liquid form, neat or diluted with a solvent for perfuming or flavoring.
  • Suitable solvents for this are e.g. Ethanol, isopropanol, diethylene glycol monoethyl ether, glycerin, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, triacetin, etc.
  • odoriferous or flavoring compositions according to the invention containing aldehydes of type (I) and / or (II) may be adsorbed to a carrier which promotes both a fine distribution of the odoriferous or aromatic substances in the product and controlled release the application ensures.
  • a carrier may be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsum, clays, clay granules, aerated concrete, etc. or organic materials such as woods, cellulosic based substances, sugars, dextrins (e.g., maltodextrin), or plastics such as PVC, polyvinyl acetates or polyurethanes.
  • the combination of composition according to the invention and carrier represents an exemplary article according to the invention.
  • Fragrance or flavoring compositions of the invention containing aldehydes of type (I) and / or (II) may also be microencapsulated, spray dried, as inclusion complexes or as extrusion products (i.e., inventive articles), and in this form e.g. B. to be perfumed or flavored product.
  • compositions modified in this way can be further optimized by so-called “coating” with suitable materials with a view to a more targeted release of fragrance, to which end preferably wax-like plastics such as polyvinyl alcohol are used.
  • suitable materials with a view to a more targeted release of fragrance, to which end preferably wax-like plastics such as polyvinyl alcohol are used.
  • the resulting products are in turn articles of the invention.
  • the microencapsulation of the odoriferous or flavoring compositions according to the invention to articles according to the invention can be carried out, for example, by the so-called coacervation method with the aid of capsule materials, e.g. made of polyurethane-like substances or soft gelatin.
  • the spray-dried fragrance or flavoring compositions can be prepared, for example, by spray-drying an emulsion or dispersion containing the fragrance or aroma composition, it being possible to use modified starches, proteins, dextrin and vegetable gums as carriers.
  • Inclusion complexes can be e.g. by incorporating dispersions of the fragrance or flavoring composition and cyclodextrins or urea derivatives into a suitable solvent, e.g. Water, to be produced.
  • Extrusion products may be made by fusing the fragrance or flavor compositions together with a suitable waxy substance and by extrusion followed by solidification, optionally in a suitable solvent, e.g. Isopropanol.
  • Aldehydes of the type (I) and / or (II) and fragrance or flavor compositions containing compounds of the type (I) and / or (II) can be used in concentrated form, in solutions or in modified form as described above for the Production of perfumed articles according to the invention such.
  • Perfume extractions eau de perfumes, eau de toilettes, shaving waters, eau de colognes, pre-shave products, splash c perfumes and perfumed towelettes, as well as the perfuming of acidic, alkaline and neutral detergents such as floor cleaners, window glass cleaners, dishwashing detergents , Bath and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powder and foam carpet cleaners, textile fresheners, ironing aids, liquid detergents, powdered detergents, laundry pretreatment agents such as bleach, soak and stain removers, fabric softeners, laundry soap, washing tablets, disinfectants, surface disinfectants and Air fresheners in liquid, gel or solid-applied form, aerosol sprays, waxes and polishes such as furniture polishes, floor waxes, shoe creams and personal care products such as solid and liquid soaps, shower gels, shampoos, shaving creams soaps, shaving foams, bath oils, oil-in-water, water-in-oil and water-in-
  • Skin creams and lotions face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, Tanning creams and lotions, hair care products such as Hair sprays, hair gels, hair setting lotions, hair lotions, permanent and semi-permanent hair dyes, hair styling agents such as cold waving and hair straightening agents, hair lotions, hair creams and lotions, deodorants and antiperspirants such as hair wipes.
  • Underarm sprays roll-ons, deodorants, deodorants, decorative cosmetics, e.g. Eyeshadows, nail polishes, make-ups, lipsticks, mascara and candles, lamp oils, incense sticks, insecticides, repellents and fuels.
  • aldehydes of type (I) and / or (II) or the corresponding mixtures can be incorporated into flavored or flavored articles, in particular in nutrition, oral hygiene or pleasure preparations.
  • the diet or pleasure-serving preparations are, for example, baked goods (eg bread, dry biscuits, cakes, other pastry), confectionery (eg chocolates, chocolate bar products, other bar products, fruit gums, hard and soft caramels, chewing gum), alcoholic or non-alcoholic beverages (eg Coffee, tea, wine, wine-based beverages, beer, beer-based beverages, liqueurs, brandies, brandies, fruit-based sodas, isotonic drinks, soft drinks, nectars, fruit and vegetable juices, fruit or vegetable juice preparations), instant drinks (eg instant cocoa drinks, Instant tea drinks, instant coffee drinks), meat products (eg ham, fresh sausage or raw sausage preparations, spiced or marinated fresh or salted meat products), eggs or egg products (dry egg, egg whites, egg yolk), cereal products (eg breakfast cereals, muesli bars, pre-cooked wholegrain rice -Products), dairy products (eg milk drinks, milk ice cream, yoghurt, kefir, cream cheese, W eich tanninse, hard
  • Formulations according to the invention can be applied, for example, to B. present as a semi-finished product or as seasoning mixture.
  • compositions according to the invention can serve, in particular, as semi-finished goods for the production of further preparations for nutrition or enjoyment, in particular in spray-dried form.
  • Compositions according to the invention may also be in the form of capsules, tablets (non-coated and coated tablets, eg enteric coatings), dragees, granules, pellets, solid mixtures, dispersions in liquid phases, as emulsions, as powders, as solutions, as pastes or as other swallowing agents. or chewable preparations are present as a dietary supplement.
  • Oral preparations according to the invention are, in particular, oral and / or dental care products such as toothpastes, tooth gels, tooth powders, mouthwashes, chewing gums and other oral hygiene products.
  • customary active substances, basic substances, auxiliaries and additives for nutrition, oral care or pleasure-use preparations according to the invention can be used in amounts of 5 to 99.999999% by weight, preferably 10 to 80% by weight, based on the Total weight of the preparation to be included.
  • the preparations comprise water in an amount of up to 99.999999% by weight, preferably 5 to 80% by weight, based on the total weight of the preparation.
  • Preparations according to the invention are prepared according to a preferred embodiment by using one or more aldehydes of the type (I) and / or (II) as substance, as Solution (eg in ethanol, water or 1,2-propylene glycol) or in the form of a mixture with a solid or liquid carrier (eg maltodextrin, starch, silica gel), other flavorings or flavorings and optionally further adjuvants and / or stabilizers ( For example, natural or artificial polysaccharides and / or vegetable gums such as modified starches or gum arabic) in a diet, oral care or pleasure serving base preparation are incorporated.
  • preparations according to the invention present as solution and / or suspension or emulsion can also be converted by spray-drying into a solid preparation according to the invention (semi-finished product).
  • the spray-dried solid preparations according to the invention are particularly suitable as semi-finished goods for the production of further preparations according to the invention.
  • the spray-dried solid preparations according to the invention preferably contain from 50 to 95% by weight of excipients, in particular maltodextrin and / or starch, from 5 to 40% adjuvants, preferably natural or artificial polysaccharides and / or vegetable gums such as modified starches or gum arabic.
  • one or more aldehydes of type (I) and / or (II) and optionally other constituents of the preparation according to the invention are initially prepared in emulsions, in liposomes, for example starting from phosphatidylcholine, in microspheres, in nanospheres or also in capsules, granules or extrudates from a suitable for food and luxury food matrix, for example from starch, starch derivatives (eg modified starch), cellulose or cellulose derivatives (eg hydroxypropyl cellulose), other polysaccharides (eg
  • Dextrin alginate, curdlan, carrageenan, chitin, chitosan, pullulan
  • natural fats natural waxes (e.g., beeswax, carnauba wax)
  • proteins e.g. Gelatin or other natural products (e.g., shellac).
  • the products may be obtained by spray drying, spray granulation, melt granulation, coacervation, coagulation, extrusion, melt extrusion, emulsion processes, coating or other suitable encapsulation processes and optionally a suitable combination of the abovementioned processes.
  • one or more aldehydes of type (I) and / or (II) are first complexed with one or more complexing agents, for example cyclodextrins or cyclodextrin derivatives, preferably .alpha.- or .beta.-cyclodextrin, and in this complexed form used.
  • complexing agents for example cyclodextrins or cyclodextrin derivatives, preferably .alpha.- or .beta.-cyclodextrin
  • a preparation according to the invention wherein the matrix is selected so that one or more aldehydes of the type (I) and / or (II) are released from the matrix delayed, so that a long-lasting effect is achieved.
  • a fat, wax, polysaccharide or protein matrix is particularly preferred.
  • auxiliaries and additives for foods or luxury foods for example water, mixtures of fresh or processed, vegetable or animal raw materials or raw materials (eg raw, roasted , dried, fermented, smoked and / or cooked meat, bones, cartilage, fish, vegetables, fruits, herbs, nuts, vegetable or fruit juices or pastes or mixtures thereof), digestible or non-digestible carbohydrates (eg sucrose, maltose, fructose , Glucose, dextrins, amylose, amylopectin, inulin, xylans, cellulose, tagatose), sugar alcohols (eg, sorbitol, erythritol), natural or hydrogenated fats (eg, tallow, lard, palm fat, coconut fat, hydrogenated vegetable fat), oils (eg sunflower oil, peanut oil , Corn oil, olive oil, fish oil, soybean oil, sesame oil),
  • vegetable or animal raw materials or raw materials eg raw, roasted , dried, fermented,
  • Dental care preparations containing one or more aldehydes of type (I) and / or (II) generally comprise an abrasive system (grinding or polishing agents), such as silicas, calcium carbonates, calcium phosphates, Alumiuniumoxide and / or hydroxylapatites, surface-active substances such as sodium lauryl sulfate, Natriumlaurylsarcosinat and / or Cocamidopropylbetain, humectants such as glycerol and / or sorbitol, thickeners such as carboxymethylcellulose, polyethylene glycols, carrageenan and / or Laponite ® , sweeteners such as saccharin, flavoring agents for unpleasant taste impressions, remainingskorrigemzien for further, usually not unpleasant taste impressions, taste modulating substances (eg inositol phosphate, nucleotides such as guanosine monophosphate, adenos), taste modulating substances (e
  • Chewing gums (as another example of oral care preparations) containing one or more aldehydes of type (I) and / or (II) generally comprise a chewing gum base, i. chewing gum that becomes plastic during chewing, sugar of various types, sugar substitutes, other sweet tasting substances, sugar alcohols, flavoring agents for unpleasant taste impressions, other flavor modulators for further, generally not unpleasant taste impressions, taste modulating substances (eg inositol phosphate, nucleotides such as guanosine monophosphate, adenosine monophosphate or others Substances such as monosodium glutamate or 2-phenoxypropionic acid), humectants, thickeners, emulsifiers, flavors and stabilizers or odor remedies.
  • a chewing gum base i. chewing gum that becomes plastic during chewing, sugar of various types, sugar substitutes, other sweet tasting substances, sugar alcohols, flavoring agents for unpleasant taste impressions, other flavor modulators for further, generally not unpleasant taste impression
  • the preparations according to the invention may preferably also contain an aroma composition in addition to the compound according to the invention in order to round off and refine the taste and / or smell of the preparation.
  • Suitable (additional) flavoring compositions include e.g. synthetic, natural or nature-identical flavorings, fragrances and flavorings as well as suitable excipients and carriers.
  • Example 1 Preparation of a mixture of aldehydes of the type (I) and (II) (based on the process according to DE 39 42 954 )
  • Example 2 Preparation of a mixture of aldehydes of the type (I) and (II) (based on the process according to DE 43 44 064 )
  • the resulting olefin isomer was without separation of the isomerization catalyst and after addition of 3.2 g of triphenylphosphine and 2.2 g of a toluene solution of rhodium 2-ethylhexanoate (corresponding to 125 mg of rhodium, corresponding to a rhodium to phosphorus ratio of 1 to 100) for 6 to 7 hours at a temperature of 130 ° C and a pressure of 26 MPa hydroformylated. After cooling to room temperature, the autoclave was purged with nitrogen. The crude product was filtered (crude yield 440 g) and fractionated on a 30 cm Vigreux column in vacuo.
  • this perfume composition becomes fresher, more radiant, more rounded and more harmonious by the addition of 3% by weight of a mixture of aldehydes of types (I) and (II) of Example 2, with an aldehydic, coniferous and sweet note being added the woody and floral aspects are enhanced.
  • the aldehydes used give the composition by their own smell as well as by their modifying and reinforcing effect (booster effect) their own character and connect the different odoriferous elements.
  • this perfume composition comes to life with the addition of 6% by weight of a mixture of aldehydes of the types (I) and (II) from Example 1.
  • the impression of flowery is greatly enhanced.
  • the composition looks radiant, rounded and harmonious, with an aldehydic, coniferous and sweet note added.
  • the aldehydes used give the composition its own character due to its own odor as well as its modifying and strengthening effect (booster effect) and it combines the different odoriferous elements.
  • a mixture of aldehydes of type (I) and / or (II) from Example 1 was incorporated in a dosage of 0.5% by weight into a shampoo base of the following composition: Sodium lauryl ether sulfate (eg Texapon NSO, Cognis Deutschland GmbH) 12% cocamidopropyl (eg Dehyton K, Cognis Germany GmbH) 2% sodium chloride 1.4% citric acid 1.3% Phenoxyethanol, methyl, ethyl, butyl, and propylparaben 0.5% water 82.8%
  • the pH of the shampoo base was about 6. From this, 100 ml of a 20 wt .-% aqueous shampoo solution were prepared. In this shampoo solution, 2 hair slides were washed together for 2 minutes and then under flowing lukewarm water for 20 seconds rinsed. One strand of hair was wet wrapped in aluminum foil and dried the second strand of hair with a hair dryer. Both strands of hair were judged by a panel odor.
  • Odor description in each case clear aldehydic note, strongly coniferous note, floral, sweet, ozone.
  • Example 3 The perfume composition from Example 3 (after addition of 3% by weight of a mixture of aldehydes of the types (I) and (II) from Example 2) was added in a dosage of 0.5% by weight to a fabric softener base of the following composition incorporated: Quaternary ammonium methosulfate (esterquat), approx. 90% (eg Rewoquat WE 18, Fa. Witco Surfactants GmbH) 5.5% Alkyldimethylbenzylammonium chloride, approx. 50% (eg Preventol R50, Fa. Bayer AG) 0.2% Color solution, about 1% -! G 0.3% water 94.0%
  • the pH of the fabric softener base was in the range of 2 to 3.
  • Two pieces of fabric were mixed with 370 g of a 1% aqueous fabric softener solution based on the 0.5 wt .-% aldehydes of the types (I) and (II ) in a Linetest machine in the softening program 30 minutes at 20 ° C rinsed.
  • the flaps were wrung out and then spun for 20 seconds. A rag was wet-sealed, and one hung up to dry. Subsequently, both flaps were assessed by a panel odor.
  • Odor description flowery, woody, fresh, radiant, aldehydic and coniferous aspects with light sweet undertones, rounded and harmonious olfactory impression.
  • Example 4 The perfume oil composition from Example 4 (after addition of 6% by weight of a mixture of aldehydes of the types (I) and (II) from Example 1) was added in a dosage of 0.4% by weight to a base powder of the following Recipe incorporated: Linear Na-alkylbenzenesulfonate 8.8% Ethoxylated fatty alcohol C12-18 (7 EO) 4.7% Na-soap 3.2% defoamers DOW CORNING (R) 2-4248S POWDERED ANTIFOAM, Silicone oil on zeolite as carrier material 3.9% Zeolite 4A 28.3% Na carbonate 11.6% Na salt of a copolymer of acrylic and maleic acid (Sokalan CP5) 2.4% Na silicate 3.0% carboxymethylcellulose 1.2% Dequest 2066 ([[(phosphonomethyl) imino] bis [(ethylenitrilo) bis (methylene)]] tetrakisphosphonic acid, sodium salt) 2.8% Optical brightener 0.2% Na
  • Odor description strongly flowery, radiant, aldehydic and coniferous note with light sweet and woody undertones, rounded and harmonious olfactory impression.

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Claims (10)

  1. Utilisation en tant que substance odorante ou aromatique d'un aldéhyde substitué par un résidu alkyle dans la position alpha, de formule
    Figure imgb0015
     avec
    (I) 13 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 6, 7, 8 ou 9 atomes de carbone et
    R' représentant un résidu alkyle non ramifié avec 2, 3, 4 ou 5 atomes de carbone ou
    (II) 15 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 8, 9, 10 ou 11 atomes de carbone et
    R' représentant un résidu alkyle non ramifié avec 2, 3, 4 ou 5 atomes de carbone,
    ou d'un mélange comprenant ou constitué de deux, trois ou plus de ces aldéhydes du type (I) et/ou (II).
  2. Utilisation en tant que substance odorante ou aromatique à note conifère d'un aldéhyde substitué par un résidu alkyle dans la position alpha, de formule
    Figure imgb0016
     avec
    (I) 13 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 6, 7, 8 ou 9 atomes de carbone et
    R' représentant un résidu alkyle non ramifié avec 2, 3, 4 ou 5 atomes de carbone ou
    (II) 15 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 8, 9, 10, 11 ou 12 atomes de carbone
    et
    R' représentant un résidu alkyle non ramifié avec 1, 2, 3, 4 ou 5 atomes de carbone,
    ou d'un mélange comprenant ou constitué de deux, trois ou plus de ces aldéhydes du type (I) et/ou (II).
  3. Utilisation selon l'une revendications précédentes, pour conférer, modifier et/ou intensifier une note olfactive et/ou gustative ayant les aspects suivants: aldéhydique, coniférique, fleuri, doux onctueux, ozonique.
  4. Article parfumé ou aromatisé comprenant
    (a) un aldéhyde substitué par un résidu alkyle dans la position alpha, de formule
    Figure imgb0017
     avec
    (I) 13 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 6, 7, 8 ou 9 atomes de carbone et
    R' représentant un résidu alkyle non ramifié avec 2, 3, 4 ou 5 atomes de carbone ou
    (II) 15 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 8, 9, 10, 11 ou 12 atomes de carbone
    et
    R' représentant un résidu alkyle non ramifié avec 1 ,2, 3, 4 ou 5 atomes de carbone,
    ou un mélange comprenant ou constitué de deux, trois ou plus de ces aldéhydes du type (I) et/ou (II),
    de préférence en quantité suffisante pour conférer, pour modifier et/ou pour intensifier une note olfactive ou gustative du type aldéhydique, coniférique, fleuri, doux onctueux et/ou ozonique
    ainsi que
    (b) un, deux, trois ou plus de trois autres substances odorantes ou aromatiques dont aucune n'est un aldéhyde à 13 ou à 15 atomes de carbone, la ou les autres substances odorantes ou aromatiques conférant de préférence une odeur et/ou un goût boisé et/ou fleuri.
  5. Article parfumé ou aromatisé selon la revendication 4, comprenant
    (c) un, deux ou tous les aldéhydes du groupe constitué du pentadécanal, du méthyldécylacétaldéhyde (2-méthyl-dodécanal) et du tridécanal.
  6. Article parfumé ou aromatisé selon la revendication 4 ou 5, comprenant un, deux ou plus de deux aldéhydes du type (I) et un, deux ou plus de deux aldéhydes du type (II),
    le rapport pondéral de la quantité totale d'aldéhydes du type (I) et d'aldéhydes du type (II) étant compris entre 100:1 et 1:10, préférablement entre 10:1 et 1:2 et, plus préférablement encore, entre 8:1 et 1:1.
  7. Article parfumé ou aromatisé selon l'une des revendications 4 à 6, l'article étant une composition de substances odorantes ou aromatiques.
  8. Article parfumé ou aromatisé selon la revendication 7, caractérisé par le fait que la composition de substances odorantes ou aromatiques comprend une quantité totale des composants (a) dans un ordre compris entre 0,00001% et 99,9% en poids, préférablement entre 0,001% et 70% en poids et, plus préférablement encore, entre 0,01% et 50% en poids par rapport à la quantité totale de la composition de substances odorantes ou aromatiques.
  9. Article parfumé ou aromatisé selon l'une des revendications 4 à 6, l'article étant choisi dans le groupe constitué de: extraits de parfums, eaux de parfums, eaux de toilette, lotions après-rasage, eaux de Cologne, produits avant-rasage, eaux toniques pour le corps, lingettes rafraîchissantes parfumées, produits de nettoyage acides, alcalins et neutres, rafraîchisseurs pour textiles, aides au repassage, produits de lavage liquides, produits de lavage en poudre, produits de prétraitement du linge, adoucissants pour le linge, savons de lavage, tablettes de détergent, produits désinfectants, produits de désinfection des surfaces, désodorisants, sprays à aérosol, cires et vernis pour meubles, produits de soin corporel, crèmes et lotions pour les mains, crèmes et lotions pour les pieds, crèmes et lotions anti-chute de cheveux, crèmes et lotions après-rasage, crèmes et lotions de bronzage, produits de soin capillaire, déodorants et anti-perspirants, produits de cosmétique décorative, bougies, huiles lampantes, bâtons d'encens, insecticides, repousseurs d'insectes et produits moussants.
  10. Procédé pour conférer, modifier et/ou intensifier une odeur ou un goût à l'aide d'une, de plusieurs ou de toutes les notes aldéhydique, coniférique, fleurie, douce onctueuse et ozonique, une quantité à action organoleptique
    - d'un aldéhyde substitué par un résidu alkyle dans la position alpha, de formule
    Figure imgb0018
     avec
    (I) 13 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 6, 7, 8 ou 9 atomes de carbone et
    R' représentant un résidu alkyle non ramifié avec 2, 3, 4 ou 5 atomes de carbone ou
    (II) 15 atomes de carbone au total,
    R représentant un résidu alkyle non ramifié avec 8, 9, 10, 11 ou 12 atomes de carbone
    et
    R' représentant un résidu alkyle non ramifié avec 1, 2, 3, 4 ou 5 atomes de carbone,
    ou
    - d'un mélange comprenant ou constitué de deux, trois ou plus de ces aldéhydes du type (I) et/ou (II),
    ou
    - d'une composition de substances odorantes ou aromatiques comprenant ces aldéhydes selon l'une des revendications 7 ou 8
    étant mise en contact ou mélangée avec un produit.
EP07108227A 2006-07-11 2007-05-15 Aldéhydes en place alpha substitués par reste d'alkyle en tant que parfums et aromates Active EP1878787B1 (fr)

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US8043645B2 (en) 2008-07-09 2011-10-25 Starbucks Corporation Method of making beverages with enhanced flavors and aromas
DE102008042421A1 (de) 2008-09-26 2010-04-01 Symrise Gmbh & Co. Kg Geranylaminderivate der Oxalsäure
JP5004198B2 (ja) * 2010-06-08 2012-08-22 長谷川香料株式会社 粉末組成物の製造方法
US9717815B2 (en) 2014-07-30 2017-08-01 Georgia-Pacific Consumer Products Lp Air freshener dispensers, cartridges therefor, systems, and methods
EP3507352A1 (fr) 2016-09-01 2019-07-10 Symrise AG Produit comprenant un récipient en plastique et une composition de substance
AU2020272127B2 (en) 2019-04-12 2022-12-08 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner and methods of making and using the same
US20230174896A1 (en) * 2021-12-03 2023-06-08 The Procter & Gamble Company Liquid detergent compositions
WO2023169670A1 (fr) * 2022-03-09 2023-09-14 Symrise Ag Combinaison de linolal et de parfums fruités et/ou épicés

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GB1561273A (en) * 1976-05-05 1980-02-20 Shell Int Research Aldehydes and alcohols and perfume compositions or perfumed products containing them
US4304689A (en) * 1981-02-12 1981-12-08 International Flavors & Fragrances Inc. Aliphatic C11 branched chain aldehydes and alcohols, process for preparing same and uses thereof in augmenting or enhancing the aroma of perfumes, colognes and/or perfumed articles
DE3942954A1 (de) 1989-12-23 1991-06-27 Hoechst Ag Verfahren zur herstellung von aldehyden
DE4344064C1 (de) * 1993-12-23 1995-06-01 Hoechst Ag Verfahren zur Herstellung von in alpha-Stellung durch einen Alkylrest substituierten Aldehyden
US20060003913A1 (en) * 2004-06-30 2006-01-05 The Procter & Gamble Company Perfumed liquid laundry detergent compositions with functionalized silicone fabric care agents

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US7439403B2 (en) 2008-10-21
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