Thioether-based fragrance precursor compound ii

Abstract

The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) which are derived from selected polyesters having an SH function and selected fragrances. The invention also relates to a process for the preparation thereof. The present invention also relates to detergents or cleaning agents, cosmetic agents, and to a perfume composition, which contain such fragrance precursor compounds. The present invention also relates to a method for long-lasting fragrancing of surfaces using the fragrance precursor compounds and agents according to the invention.

Description

[0001] THIOETHER-BASED FRAGRANCE PRECURSOR III

[0002] The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) derived from polyesters of mercapto acids and polyols, as well as selected fragrances, and to a process for their preparation. Furthermore, the present invention relates to detergents and / or cleaning agents, cosmetic compositions, and perfume compositions containing such fragrance precursor compounds. Furthermore, the present invention relates to a process for the long-lasting perfuming of surfaces using the fragrance precursor compounds and agents according to the invention.

[0003] Detergents and / or cleaning agents, as well as cosmetic products, usually contain fragrances that impart a pleasant smell. Fragrances can also mask the odor of other ingredients, creating a pleasant odor impression for the consumer.

[0004] Fragrances are particularly important components of laundry detergents and / or cleaning products, as the laundry should have a pleasant and, if possible, fresh scent both when wet and dry. The use of fragrances is fundamentally problematic because they are more or less volatile compounds, yet a long-lasting fragrance effect is still desired. Especially with those fragrances that represent the fresh and light notes of perfume and are particularly volatile due to their high vapor pressure, the desired longevity of the fragrance impression is hardly achievable.

[0005] Delayed fragrance release can be achieved, for example, through so-called fragrance precursor compounds. These fragrance precursor compounds are based on fragrance compounds, such as fragrance aldehydes or ketones, which are reacted with other compounds to form the aforementioned fragrance precursor compounds. These compounds are then capable of delayed release of the actual fragrance compound (e.g., through hydrolysis or photochemically). Of particular interest here is the ability to release several different fragrances from one fragrance precursor compound in order to maintain the harmonious fragrance impression.

[0006] Thioether-based fragrance precursor compounds are known from WO 2004 / 105713 A1.

[0007] The object of the present invention was therefore to provide fragrance precursor compounds that can be obtained by simple synthesis. Furthermore, the fragrance precursor compounds should preferably be suitable for use in consumer products, such as detergents and / or cleaning agents or cosmetics. It is also desirable that the fragrance precursor compounds also achieve better adhesion to the surface to which they are applied, preferably a textile. The inventors of the present invention have found that this object can be achieved by the specific fragrance precursor compounds of formula (I), which are derived from thioethers and selected fragrances.

[0008] In one aspect, the invention therefore relates to a fragrance precursor compound of formula (I) where

[0009] R 1 for -(CX 1 X 2 ) m - or -(O-CX3 X 4 -CX 3 X 4 ) n - stands, where X 1 and X 2 independently of one another represent H or a linear or branched, saturated or unsaturated C2-Ci2-alkyl radical,

[0010] X 3 and X 4 independently represent H or CH3, m represents a number from 0 to 10 and n represents a number from 0 to 30,

[0011] R 2 represents a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof or a (2-hydroxyethyl)trimethylammonium chloride group, with the proviso that at least one R 2 represents an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 stands for H or CH3, and z stands for a number from 1 to 50, in particular 5 to 30.

[0012] In a second aspect, the present invention relates to a process for preparing a fragrance procurer compound of formula (I).

[0013] In a third aspect, the present invention relates to a perfume composition comprising at least one fragrance procurer compound of the present invention.

[0014] In a fourth aspect, the present invention relates to a washing and / or cleaning agent comprising at least one fragrance precursor compound of the present invention.

[0015] In a fifth aspect, the present invention relates to a cosmetic agent comprising at least one fragrance precursor compound of the present invention. Finally, in a sixth aspect, the present invention relates to a method for the long-lasting perfuming of surfaces, characterized in that a fragrance precursor compound according to the invention or a perfume composition according to the invention or a washing and / or cleaning agent according to the invention or a cosmetic agent according to the invention is applied to the surface to be perfumed, wherein the perfuming lasts longer than if the respective fragrance compound or an identical agent in which the fragrance precursor compound is replaced by the respective fragrance compound were used.

[0016] These and other embodiments, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Individual features or embodiments of the invention described may be combined with other features or embodiments of the invention without necessarily being described in combination within the scope of the invention. It is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular, the invention is not limited to the examples.

[0017] "At least one," as used herein, refers to 1 or more, for example, 2, 3, 4, 5, 6, 7, 8, 9, or more. In the context of the fragrance procurers described herein, this statement does not refer to the absolute amount of molecules, but rather to the type of compound. "At least one fragrance procurer" therefore means, for example, that only one type of fragrance procurer or several different types of fragrance procurers may be present, without specifying the amount of the individual compounds.

[0018] All quantities stated in connection with the process described herein refer, unless otherwise stated, to wt. %, based on the total weight of the composition. Furthermore, such quantities relating to at least one component always refer to the total amount of that component contained in the composition, unless explicitly stated otherwise. This means that such quantities, for example in connection with "at least one fragrance precursor compound," refer to the total amount of fragrance precursor compounds contained in the composition, unless explicitly stated otherwise.

[0019] Numerical values ​​stated without decimal places refer to the full specified value with one decimal place. For example, "99%" stands for "99.0%."

[0020] Numerical ranges given in the format "in / from x to y" include the stated values. Where multiple preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also included. "Substituted," as used herein in connection with the definition of the fragrance procurer compounds of formula (I) and the compound of formula (II), means that a hydrogen atom is replaced by another radical. Suitable radicals are Ci-C4 alkyl groups.

[0021] The terms "fragrance" and "perfume" are to be used synonymously within the scope of this invention. A fragrance is a compound that has a characteristic odor and contributes to achieving a specific fragrance profile of a perfume oil or composition. Fragrances also include compounds that modify the fragrance profile of a perfume oil or composition to impart a certain depth to the fragrance, which is commonly known to those skilled in the art as the complexity of a fragrance.

[0022] The present invention particularly relates to fragrance precursor compounds of formula (I) where

[0023] R 1 for -(CX 1 X 2 ) m - or -(O-CX 3 X 4 -CX 3 X 4 ) n - stands, where X 1 and X 2 independently of one another represent H or a linear or branched, saturated or unsaturated C2-Ci2-alkyl radical,

[0024] X 3 and X 4 independently of one another represent H or CH3, m represents a number from 0 to 10 and n represents a number from 0 to 30, in particular 1 to 4,

[0025] R 2 represents a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof or a (2-hydroxyethyl)trimethylammonium chloride group, with the proviso that at least one R 2 represents an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 stands for H or CH3, and z stands for a number from 1 to 50, in particular 5 to 30.

[0026] Surprisingly, it has been shown that fragrance precursors of formula (I) are capable of releasing fragrances of the α,β-unsaturated aldehyde, α,β-unsaturated ketone, or α,β-unsaturated ester type over a long period of time. Furthermore, they can be stably incorporated into consumer products.

[0027] In a preferred embodiment of the fragrance procurer compound of formula (I), the fragrance is an α,β-unsaturated ketone selected from the group consisting of α-ionone, β-ionone, γ-lonone, α-damascenone, β-damascenone, γ-damascenone, 5-damascenone, α-damascone, β-damascone, γ-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof.

[0028] Ionone, damascenone, and damascone are a group of closely related chemical compounds found in a variety of essential oils. They belong to a family of chemicals known as rose ketones. Both enantiomers of carvone are found in various essential oils.

[0029] In a further preferred embodiment of the fragrance precursor compound of formula (I), when z > 1, at least one R 2 a (2-hydroxyethyl)trimethylammonium chloride group. The positive charge of the (2-hydroxyethyl)trimethylammonium chloride group can significantly increase the substantivity of the fragrance precursor compound of formula (I), particularly on cotton or keratin.

[0030] In this embodiment, it is advantageous that a maximum of 50% of the substituents R 2per fragrance precursor compound of formula (I) is one (2-hydroxyethyl)trimethylammonium chloride group. Accordingly, the degree of substitution of the (2-hydroxyethyl)trimethylammonium chloride group is a maximum of 0.5.

[0031] In the case that z > 1, it may be advantageous to have at least two R 1 are different. It may also be advantageous that at z > 1 at least two R 3 are different.

[0032] In an advantageous embodiment of the invention, the molecular weight Mw of the fragrance precursor compound of formula (I) is in the range from 500 g / mol to 50,000 g / mol.

[0033] In a particularly preferred embodiment of the fragrance precursor compound of formula (I), m and n are 0, R 2 represents an α,β-unsaturated ketone and / or H, R 3 stands for H and z stands for a number from 5 to 30.

[0034] In a likewise particularly preferred embodiment of the fragrance precursor compound of the formula (I), m and n are equal to 0, at least R 2 represents a (2-hydroxyethyl)trimethylammonium chloride group, at least one R 2 represents an α,β-unsaturated ketone and the remaining R 2 represents an α,β-unsaturated ketone or H, R 3 is H and z is a number from 5 to 30. Furthermore, per fragrance precursor compound of formula (I) a maximum of 50% of the R 2 a (2-hydroxyethyl)trimethylammonium chloride group.

[0035] In an alternative, very particularly preferred embodiment of the fragrance procurer compound of formula (I), R 1 -(O-CX 3 X 4 -CX 3 X 4 ) n , where X 3 and X 4 each stands for H, R stands for 2 R represents an α,β-unsaturated ketone and / or H 3is H, m is 3 and z is a number from 5 to 30. In yet another alternative, very particularly preferred embodiment of the fragrance precursor compound of formula (I), R 1 -(O-CX 3 X 4 -CX 3 X 4 ) n , where X 3 and X 4 each stand for H, at least one R 2 represents a (2-hydroxyethyl)trimethylammonium chloride group, at least one R 2 represents an α,β-unsaturated ketone and the remaining R 2 represents an α,β-unsaturated ketone or H, R 3 for H, m is 3 and z is a number from 5 to 30. Furthermore, per fragrance precursor compound of formula (I) a maximum of 50% of the R 2 a (2-hydroxyethyl)trimethylammonium chloride group.

[0036] The fragrance can be released from the described fragrance precursor compounds of formula (I) by hydrolysis, particularly at acidic pH values, i.e. pH values ​​< 7, for example < 6 or < 5.

[0037] The fragrance precursor compounds of formula (I) can be prepared by reacting a compound of formula (II)

[0038] (II), where

[0039] R 1 for -(CX 1 X 2 ) m - or -(O-CX 3 X 4 -CX 3 X 4 ) n - stands, where X 1 and X 2 independently of one another represent H or a linear or branched, saturated or unsaturated C2-Ci2-alkyl radical,

[0040] X 3 and X 4 independently of one another represent H or CH3, m represents a number from 0 to 10 and n represents a number from 0 to 30, in particular 1 to 4,

[0041] R 2 stands for H,

[0042] R 3 stands for H or CH3, and z stands for a number from 1 to 50, in particular 5 to 30, with a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof.

[0043] It may be advantageous to use a compound of formula (II) in which m and n are 0 and R 3 H. In this embodiment, the compound of formula (II) may, for example, comprise a polyester of mercaptosuccinic acid and ethylene glycol.

[0044] In a further preferred embodiment of the process, a compound of formula (II) is used in which R 1 -(O-CX 3 X 4 -CX 3 X 4 ) n where X 3 and X 4 each stand for H, R 3H and m is 3. In this embodiment, the compound of formula (II) may be, for example, a polyester of mercaptosuccinic acid and tetraethylene glycol.

[0045] In a particularly preferred embodiment of the process, a compound of formula (II) in which z > 1 is reacted with a mixture of a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof and glycidyltrimethylammonium chloride.

[0046] In this embodiment, the compound of formula (II) has at least two SH groups, of which at least one SH group reacts with the fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones and α,β-unsaturated esters and at least one SH group can react with the glycidyltrimethylammonium chloride.

[0047] In various particularly preferred embodiments of the method, the fragrance can be an α,β-unsaturated ketone which is selected from the group consisting of α-ionone, β-ionone, γ-lonone, α-damascenone, β-damascenone, γ-damascenone, 5-damascenone, α-damascone, β-damascone, γ-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof.

[0048] The reaction of the compound of formula (II) and the fragrance, and optionally glycidyltrimethylammonium chloride, preferably takes place under a nitrogen atmosphere. Furthermore, the reaction is preferably carried out in a suitable solvent. A suitable solvent is, for example, dichloromethane, tetrahydrofuran, or acetone. Preference is also given to using a base, for example triethylamine and / or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The reaction mixture comprising the reactants, optionally the base, and the solvent is then stirred at room temperature for several hours, preferably 2 to 60, in particular 12 to 48. The resulting reaction product is isolated and, if appropriate, purified by customary methods.

[0049] The present invention further relates to perfume compositions, washing and / or cleaning agents or cosmetic agents which contain at least one of the fragrance precursor compounds of the present invention.

[0050] In a preferred embodiment, the at least one fragrance precursor compound is contained in a total amount of 0.01 to 20 wt.%, advantageously from 0.1 to 15 wt.%, particularly preferably from 0.5 to 15 wt.%, in each case based on the total weight of the perfume composition.

[0051] In preferred embodiments, the at least one fragrance precursor compound is contained in a total amount of 0.001 to 5 wt.%, advantageously from 0.005 to 3 wt.%, particularly preferably from 0.01 to 1 wt.%, in each case based on the total weight of the washing and / or cleaning agent or cosmetic agent.

[0052] The above-described fragrance precursor compounds of formula (I) can be used in a perfume composition, a washing and / or cleaning agent or a cosmetic agent as mixtures with at least one further fragrance or at least one further fragrance precursor compound which is different from the fragrance precursor compound according to formula (I).

[0053] The other fragrances that may optionally be included in the perfume composition, the washing or cleaning agent, or the cosmetic product are not subject to any particular restrictions. Thus, individual fragrance compounds of natural or synthetic origin, e.g., of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type, may be used. Fragrance compounds of the ester type include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate, and jasmacyclate. Ethers include, for example, benzyl ethyl ether and ambroxan, while aldehydes include the above-mentioned, e.g.,The linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde (3-(4-propan-2-ylphenyl)butanal), lilial, and bourgeonal; the ketones include, for example, the ionones, [alpha]-isomethyl ionone, and methyl cedryl ketone; the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol, and terpineol; the hydrocarbons primarily include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferred, which together create an appealing fragrance.

[0054] The compositions may also contain natural fragrance mixtures obtainable from plant sources, e.g., pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil. Also suitable are clary sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, and labdanum oil, as well as orange blossom oil, neroli oil, orange peel oil, and sandalwood oil. Other conventional fragrances which can be contained in the agents according to the invention within the scope of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, champaca blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil,Copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, oregano oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil as well as ambrettolide, ambroxan, a-amylcinnamaldehyde, anethole, anisaldehyde, Anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, Boisambrene forte, a-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, Eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate,Geranyl acetate, geranyl formate, heliotropin, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnam alcohol, indole, iran, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methyl chavicol, p-methylquinoline, methyl ß-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, ß-naphthol ethyl ether, ß-naphthol methyl ether, nerol, n-nonylaldehyde, nonyl alcohol, n-octyl aldehyde, p-oxyacetophenone, pentadecanolide, ß-Phenylethyl alcohol, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester,

[0055] Cyclohexyl salicylate, santalol, sandelice, skatole, terpineol, thymen, thymol, troenan, y-undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate, diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal and mixtures thereof.

[0056] It is particularly possible for the at least one fragrance precursor compound of formula (I) to be used with the corresponding α,β-unsaturated aldehydes and / or α,β-unsaturated ketones and / or α,β-unsaturated esters. According to a preferred embodiment, such compositions are characterized in that the molar ratio of fragrance aldehyde and / or fragrance ketone and / or fragrance ester to the corresponding precursor compound of formula (I) is 20:1 to 1:20, preferably 10:1 to 1:10, more preferably 5:1 to 1:5, even more preferably 3:1 to 1:3, even more preferably 2:1 to 1:2, and in particular 1:2:1 to 1:1:2.

[0057] In addition to the at least one fragrance precursor compound of formula (I) and the optional further fragrances or natural fragrance mixtures, a perfume composition may comprise further ingredients, in particular a carrier material such as, for example, dipropylene glycol, diethyl phthalate, isopropyl myristate or ethyl citrate.

[0058] In addition to the at least one fragrance precursor compound of formula (I), detergents and cleaning agents may also contain, in particular, anionic, nonionic, cationic, amphoteric, or zwitterionic surfactants or mixtures thereof. Furthermore, these agents may be in solid or liquid form.

[0059] Suitable nonionic surfactants are, in particular, ethoxylation and / or propoxylation products of alkyl glycosides and / or linear or branched alcohols, each containing 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters, and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl moiety, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl radical, are usable. Suitable anionic surfactants are, in particular, soaps and those containing sulfate or sulfonate groups, preferably with alkali ions as cations. Suitable soaps are preferably the alkali metal salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.Useful sulfate-type surfactants include the salts of sulfuric acid monoesters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the aforementioned nonionic surfactants with a low degree of ethoxylation. Useful sulfonate-type surfactants include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates with 12 to 18 carbon atoms, and olefinsulfonates with 12 to 18 carbon atoms, which are formed by reacting corresponding monoolefins with sulfur trioxide, as well as alpha-sulfofatty acid esters, which are formed by sulfonating fatty acid methyl or ethyl esters. Cationic surfactants are preferably selected from the group consisting of esterquats and / or quaternary ammonium compounds (QAC) according to the general formula (R). I )(R")(R III )(R IV )N + X" is selected, in the R 1 to R IVrepresent identical or different C1-22-alkyl radicals, C7-28-arylalkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic bond as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, e.g. a pyridinium or imidazolinium compound, and X" represents halide ions, sulfate ions, hydroxide ions or similar anions. QACs can be prepared by reacting tertiary amines with alkylating agents, such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with one long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions. Amines that have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are used, for example, quaternized with dimethyl sulfate.Possible QACs are, for example, benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalkonium B (m,p-dichlorobenzyldimethyl-Ci2-alkylammonium chloride), benzoxonium chloride (benzyldodecyl-bis-(2-hydroxyethyl)-ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethyl-ammonium bromide), benzetonium chloride (N,N-dimethyl-N [2-[2-[p-(1,1,3,3-tetramethylbutyl)phenoxy]-ethoxy]-ethyl]-benzyl-ammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyl-dimethyl-ammonium chloride, didecyldimethylammonium bromide, dioctyl-dimethyl-ammonium chloride, 1-cetylpyridinium chloride and thiazoline iodide as well as mixtures thereof. Preferred QACs are the benzalkonium chlorides with C8-C22- Alkyl radicals, in particular Ci2-Ci4-alkylbenzyldimethylammonium chloride.

[0060] Preferred esterquats are methyl N-(2-hydroxyethyl)-N,N-di(tallow acyloxyethyl)ammonium methosulfate, bis(palmitoyl)ethylhydroxyethylmethylammonium methosulfate, or methyl N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate. Commercially available examples are the methylhydroxyalkyl dialkoyloxyalkylammonium methosulfates marketed by Stepan under the trademark Stepantex®, the products from BASF SE known under the trade name Dehyquart®, and the products from Evonik known under the name Rewoquat®.

[0061] Furthermore, the detergents and cleaning agents may contain other ingredients that further improve the performance and / or aesthetic properties of the composition, depending on the intended use. Within the scope of the present invention, they may contain, but are not limited to, builders, bleaching agents, bleach activators, bleach catalysts, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-redeposition agents, solvents, enzymes, optical brighteners, graying inhibitors, shrinkage inhibitors, crease inhibitors, dye transfer inhibitors, color protectants, wetting improvers, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, rinse aids, preservatives, antistatic agents, ironing aids, repellents and waterproofing agents, pearlescent agents, polymers, swelling and slip-resistant agents, and UV absorbers.

[0062] In addition to the at least one fragrance precursor compound of formula (I), cosmetic products may comprise other typical ingredients for cosmetic products. Other suitable ingredients include, in particular, anionic surfactants, amphoteric / zwitterionic surfactants, nonionic surfactants, cationic surfactants, nonionic polymers, anionic polymers, cationic polymers, amphoteric polymers, fatty substances, waxes, protein hydrolysates, amino acids, oligopeptides, vitamins, provitamins, vitamin precursors, betaines, bioquinones, purine (derivatives), taurine (derivatives), plant extracts, silicones, ester oils, UV light protection filters, structuring agents, thickeners, electrolytes, pH adjusters, swelling agents, dyes, anti-dandruff agents, complexing agents, opacifiers, pearlescent agents, pigments, stabilizers, propellants, antioxidants, perfume oils, and / or preservatives.

[0063] The quantities of the individual ingredients in the washing and / or cleaning agents as well as in the cosmetic products are based on the intended use of the product in question and the person skilled in the art is generally familiar with the quantities of the ingredients to be used or can obtain these from the relevant specialist literature.

[0064] The statements made regarding the fragrance precursor compound of formula (I), the perfume composition, the washing and / or cleaning agent, and the cosmetic agent apply mutatis mutandis to their use in a process for the long-lasting perfuming of surfaces. In the process, at least one fragrance precursor compound of formula (I) according to the invention, a perfume composition according to the invention, a washing and / or cleaning agent according to the invention, or a cosmetic agent according to the invention are applied to the surface to be perfumed. The perfuming lasts longer than if the respective fragrance compound or an identical agent in which the fragrance precursor compound is replaced by the respective fragrance compound(s) were used.

[0065] Examples

[0066] Example 1 :

[0067] Synthesis of a polyester 1 of formula (II)

[0068] In a 100 mL flask, 11.6 g of mercaptosuccinic acid, 6.3 g of ethylene glycol, 48.5 mg of p-toluenesulfonic acid, and 17 mg of hydroquinone were placed. The mixture was heated to 140°C until a clear melt formed. After 30 minutes, vacuum was applied to expel the water of reaction. The reaction mixture was stirred for 5 hours at 140°C. The reaction mixture was then cooled to room temperature.

[0069] Yield 14.5 g (90% theoretical yield)

[0070] GPC in THF: M n : 1000 g / mol, M w : 1600 g / mol

[0071] Synthesis of a fragrance precursor compound 1 of formula (I)

[0072] In a 100 mL flask, 12.5 g of polyester 1 in 60 mL of acetone were placed. At room temperature, 12.3 g of a-damascone and 6.5 g of triethylamine were added. After 5 minutes, 500 mg of DBU were added, and the mixture was stirred overnight at room temperature. The next day, the

[0073] The fragrance precursor compound 1 was precipitated in 1000 mL of hexane. The solvent was decanted, and the resulting oil was dried in a vacuum oven at 40°C. The oil was dissolved in a small amount of acetone and dialyzed (MWCO=1000).

[0074] Yield 10.3 g (42% theoretical yield)

[0075] GPC in THF: M n : 1600 g / mol, M w : 2700 g / mol

[0076] Example 2:

[0077] Synthesis of a polyester 2 of formula (II)

[0078] A 250 mL flask was charged with 45.96 g of mercaptosuccinic acid (colorless crystals), 58.8 g of tetraethylene glycol (clear, colorless liquid), 145.6 mg of p-toluenesulfonic acid, and 50 mg of hydroquinone. With vigorous stirring, the flask was evacuated several times and then purged with nitrogen. The mixture was heated to 170°C until a clear melt formed, rapidly releasing a few ml of water. After about 60 minutes, a vacuum was applied to completely remove the water of reaction. After 4 hours, the mixture was cooled to room temperature.

[0079] Yield 69 g (69% theoretical yield)

[0080] GPC in THF: Mn: 800 g / mol, Mw: 2600 g / mol

[0081] Synthesis of a fragrance precursor compound 2 of formula (I)

[0082] In a 250 mL flask, 20.9 g of Polyester 2 in 60 mL of acetone were placed. At room temperature, 9.2 g of damascone and 2.7 g of glycidyltrimethylammonium chloride were added. After approximately 5 minutes, 500 mg of DBU were added, and the mixture was stirred overnight at room temperature. The next day, the reaction solution had become cloudy, and a sediment had formed. The mixture was precipitated in 600 mL of hexane. The solvent was decanted off, and the oily residue was dried in a vacuum oven at 40°C. The oil was dissolved in approximately 100 mL of acetone, resulting in a flocculent precipitate, which was filtered off. However, it dissolved due to the humidity, so the solution was rinsed with a little water. The solution was dialyzed against acetone (MWCO=1000). The solvent was then removed on a rotary evaporator.

[0083] Yield: 28 g (88% theoretical yield)

[0084] GPC in THF: Mn: 1800 g / mol, Mw: 2700 g / mol

[0085] The ratio between the damascone and the ammonium ion side chains is 20% ammonium ion and 80% damascone

[0086] Example 3: Smell test

[0087] Fragrance release was investigated in a fabric softener, a liquid detergent, and a powder detergent.

[0088] For this purpose, perfume-free formulations of the fabric softener, the liquid detergent and the powder detergent were each mixed with the fragrance precursor compound prepared in Example 1 or Example 2 or with equimolar amounts of a-damascone and used in a washing / rinsing test in a washing machine.

[0089] Example 3.1

[0090] Fabric softener i. 0.6 wt.% a-damascone ii. 1.61 wt.% fragrance precursor compound 1 according to the invention from Example 1 Liquid detergent i. 0.50 wt.% a-damascone ii. 1.34 wt.% fragrance precursor compound 1 according to the invention from Example 1

[0091] Powder detergent i. 0.30 wt.% a-damascone ii. 0.80 wt.% fragrance precursor compound 1 according to the invention from Example 1

[0092] Laundry treated with one of the six agents (cotton, polyester, mixed fabric) was removed from the washing machine, dried, and after 1 day and 7 days, its odor intensity was assessed olfactorily by a trained panel using an intensity scale of 1 to 6 (1: no odor perceptible; 6: very strong odor perceptible).

[0093] The following table shows the results of odor intensity on different fabrics:

[0094] For formulations ii, i.e., using the fragrance precursor compound from Example 1 instead of the free fragrance, a higher odor intensity was observed after 7 days, with only one exception (powder detergent / cotton). Example 3.2

[0095] Fabric softener iii. 0.9 wt.% a-damascone iv. 2.0 wt.% fragrance precursor compound 2 according to the invention from Example 2

[0096] Liquid detergent iii. 0.70 wt.% a-damascone iv. 1.56 wt.% fragrance precursor compound 2 according to the invention from Example 2

[0097] Powder detergent iii. 0.40 wt.% a-damascone iv. 0.89 wt.% fragrance precursor compound 2 according to the invention from Example 2

[0098] Laundry treated with one of the six agents (cotton, polyester, mixed fabric) was removed from the washing machine, dried, and after 1 day and 7 days, its odor intensity was assessed olfactorily by a trained panel using an intensity scale of 1 to 6 (1: no odor perceptible; 6: very strong odor perceptible).

[0099] The following table shows the results of odor intensity on different fabrics:

[0100] For formulations ii, i.e. when the fragrance precursor compound from Example 2 was used instead of the free fragrance, a consistently higher odor intensity was observed after 7 days.

Claims

Patent claims 1 . Fragrance precursor compound of formula (I) (i), where R 1 for -(CX 1 X 2 ) m - or -(O-CX 3 X 4 -CX 3 X 4 ) n - stands, where X 1 and X 2 independently of one another represent H or a linear or branched, saturated or unsaturated C2-Ci2-alkyl radical, X 3 and X 4 independently of one another represent H or CH3, m represents a number from 0 to 10 and n represents a number from 0 to 30, in particular 1 to 4, R 2 represents a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof or a (2-hydroxyethyl)trimethylammonium chloride group, wherein at least one R 2represents an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 stands for H or CH3, and z stands for a number from 1 to 50, in particular 5 to 30.

2. Fragrance precursor compound according to claim 1, characterized in that the fragrance is an α,β-unsaturated ketone which is selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, 5-damascenone, α-damascone, β-damascone, γ-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof.

3. Fragrance precursor compound according to claim 1 or claim 2, characterized in that when z > 1 at least one R 2 represents a (2-hydroxyethyl)trimethylammonium chloride group.

4. Fragrance precursor compound according to claim 3, characterized in that the degree of substitution on the (2-hydroxyethyl)trimethylammonium chloride group is a maximum of 0.

5.

5. Fragrance precursor compound according to one of claims 1 to 4, characterized in that the molecular weight Mw of the fragrance precursor compound of formula (I) is in the range from 500 g / mol to 50,000 g / mol.

6. Process for the preparation of a fragrance precursor compound of formula (I) where R 1 for -(CX 1 X 2 ) m - or -(O-CX 3 X 4 -CX 3 X 4 ) n - stands, where X 1 and X 2 independently of one another represent H or a linear or branched, saturated or unsaturated C2-Ci2-alkyl radical, X 3 and X 4 independently of one another represent H or CH3, m represents a number from 0 to 10 and n represents a number from 0 to 30, in particular 1 to 4, R 2represents H, a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof or a (2-hydroxyethyl)trimethylammonium chloride group, wherein at least one R 2 represents an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 represents H or CH3, and z represents a number from 1 to 50, in particular 5 to 30, characterized in that a compound of formula (II) (II), where R 1 for -(CX 1 X 2 ) m - or -(O-CX 3 X 4 -CX 3 X 4 ) n - stands, where X 1 and X 2 independently of one another represent H or a linear or branched, saturated or unsaturated C2-Ci2-alkyl radical, X 3 and X 4independently of one another represent H or CH3, m represents a number from 0 to 10 and n represents a number from 0 to 30, in particular 1 to 4, R 2 stands for H, R 3 stands for H or CH3, and z stands for a number from 1 to 50, in particular 5 to 30, is reacted with a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof.

7. A process according to claim 6, characterized in that a compound of formula (II) is used in which m and n are 0 and R 3 H is.

8. Process according to claim 6, characterized in that a compound of formula (II) is used in which R 1 -(O-CX 3 X 4 -CX 3 X 4 ) n where X 3 and X 4 each stand for H, R 3 H and m is 3.

9. The method according to any one of claims 6 to 8, characterized in that a compound of formula (II) with z > 1 is reacted with a mixture of a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof and glycidyltrimethylammonium chloride.

10. The method according to any one of claims 6 to 9, characterized in that the fragrance is an α,β-unsaturated ketone and is selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, 5-damascenone, α-damascone, β-damascone, γ-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof. 1 1. A perfume composition comprising at least one fragrance precursor compound (I) according to any one of claims 1 to 5, wherein the compound is preferably present in a total amount of 0.01 to 20% by weight, advantageously 0.1 to 15% by weight, more advantageously 0.5 to 10% by weight, based on the total weight of the perfume composition.

12. Cosmetic agent containing at least one fragrance precursor compound (I) according to one of claims 1 to 5, wherein the compound is preferably present in a total amount of 0.001 to 5% by weight, advantageously 0.005 to 3% by weight, further advantageously 0.01 to 1% by weight, based on the total weight of the product.

13. Washing and / or cleaning agent containing at least one fragrance precursor compound (I) according to one of claims 1 to 5, wherein the compound is preferably in a Total amount of 0.001 to 5 wt.%, advantageously 0.005 to 3 wt.%, further advantageously 0.01 to 1 wt.%, based on the total weight of the agent.

14. A method for the long-lasting perfuming of surfaces, characterized in that a fragrance precursor compound (I) according to one of claims 1 to 5 or an agent according to claim 11, 12 or 13 is applied to the surface to be scented, the perfuming lasting longer than if the respective fragrance compound(s) or an identical agent in which the fragrance precursor compound(s) is / are replaced by the respective fragrance compound(s) were used.

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