Thioether-based fragrance precursor III

Abstract

The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) derived from selected polyesters with an SH function and selected fragrances, and to a process for their preparation. Furthermore, the present invention relates to detergents or cleaning agents, cosmetic compositions, and a perfume composition 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.

Description

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 a process for their preparation. The present invention further relates to detergents and / or cleaners, cosmetic compositions and perfume compositions which comprise such perfume precursor compounds. The present invention further relates to a method for long-lasting fragrancing of surfaces using the fragrance precursor compounds and agents according to the invention.Detergents and / or cleaning agents or cosmetic agents usually contain fragrances which impart a pleasant odor to the agents. The fragrances can also serve to mask the odor of other ingredients, so that a pleasant odor impression is produced at the consumer.In particular in the field of detergents and / or cleaning agents, fragrances are important constituents of the composition, since the laundry should have a pleasant and as fresh as possible fragrance both in the moist and in the dry state. The use of fragrances is fundamentally problematic, since these are compounds which are more or less volatile, but nevertheless a long-lasting fragrance effect is sought. In particular in the case of those fragrances which represent the fresh and light notes of the perfume and are particularly volatile as a result of their high vapor pressure, the desired longevity of the fragrance impression is hardly achievable.Delayed release of odour can be effected, for example, by what are known as fragrance precursor compounds. These perfume precursor compounds are based on perfume compounds, for example perfume aldehydes or ketones, which are reacted with further compounds to form the perfume precursor compounds mentioned, these then being capable of releasing the actual perfume compound again in a delayed manner (for example by hydrolysis or photochemical). It is of particular interest here to release a plurality of different fragrances from a fragrance precursor compound in order to maintain the harmonies of the fragrance impression.WO 2004 / 105713 A1 discloses thioether-based fragrance precursor compounds.The object of the present invention was therefore to provide fragrance precursor compounds which can be obtained by simple synthesis. Furthermore, the perfume precursor compounds should preferably be suitable for use in consumer products, such as, for example, detergents and / or cleaners or cosmetic agents. It is also desirable here that the fragrance precursor compounds also achieve better adhesion to the surface to which they are applied, preferably a textile.The present inventors have found that the object can be achieved by the specific fragrance precursor compounds of formula (I) derived from thioethers and selected fragrances.In one aspect, the invention therefore relates to a fragrance precursor compound of the formula (I) where R 1 is -(CX 1 X 2)m- or -(O-CX 3 X 4- CX 3 X 4)n- where X 1 and X 2 independently of one another are H or a linear or branched, saturated or unsaturated C2-C12alkyl radical, X 3 and X 4 independently of one another, are H or CH 3 m is a number from 0 to 10 and n is a number from 0 to 30, R 2 is 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 is an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 is H or CH 3 and z is a number from 1 to 50, in particular 5 to 30.In a second aspect, the present invention relates to a process for preparing a fragrance precursor compound of formula (I).In a third aspect, the present invention relates to a perfume composition containing at least one perfume precursor compound of the present invention.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.In a fifth aspect, the present invention relates to a cosmetic agent containing 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 fragrancing of surfaces, characterized in that a perfume 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 fragrancing, wherein the fragrancing lasts longer than if the respective perfume compound or an identical agent in which the perfume precursor compound is replaced by the respective perfume compound were used.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. In this case, individual features or embodiments of the invention described can be combined with other features or embodiments of the invention without these having been described in combination within the scope of the invention. It is 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."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 pro-perfume compounds described herein, this specification does not refer to the absolute amount of molecules, but to the type of compound. "At least one pro-perfume compound" therefore means, for example, that only one type of pro-perfume compound or several different types of pro-perfume compounds may be included without giving any details about the amount of the individual compounds.All amounts given in connection with the process described herein are based, unless otherwise stated, on % by weight, in each case based on the total weight of the composition. Furthermore, such amounts relating to at least one constituent always relate to the total amount of this type of constituent contained in the composition, unless explicitly stated otherwise. That is, such amounts, for example in connection with "at least one pro-perfume compound", refer to the total amount of pre-perfume compounds contained in the composition, unless explicitly stated otherwise.Numerical values indicated herein without decimal places each refer to the full indicated value with one decimal place. For example, "99%" means "99.0%".Numerical ranges indicated in the format "in / from x to y" include the above values. When several preferred numerical ranges are specified in this format, it is understood that all ranges arising from the combination of the various endpoints are also detected."Substituted" as used herein in connection with the definition of the pro-perfume compounds of formula (I) and the compound of formula (II) means that one hydrogen atom is replaced by another radical. Suitable radicals are C 1- C 4- alkyl groups.The terms "perfume" and "perfume" are to be used interchangeably within the scope of this invention. A perfume is a compound which has a characteristic odor and contributes to achieving a specific perfume profile of a perfume oil or composition. Fragrances also include those compounds that alter the fragrance profile of a perfume oil or composition to a degree that the fragrance is to a certain depth, which is commonly known to those skilled in the art as the complexity of a fragrance.The present invention relates in particular to fragrance precursor compounds of the formula (I) where R 1 is -(CX 1 X 2)m- or -(O-CX 3 X 4- CX 3 X 4)n- where X 1 and X 2 independently of one another are H or a linear or branched, saturated or unsaturated C2-C12alkyl radical, X3and X4each independently of one another are H or CH3, m is a number from 0 to 10 and n is a number from 0 to 30, in particular from 1 to 4, R 2 is a fragrance selected from the group of the α,β-unsaturated aldehydes, the α,β-unsaturated ketones, the α,β-unsaturated esters and mixtures thereof or a (2-hydroxyethyl)trimethylammonium chloride group, with the proviso that at least one R 2 is an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 is H or CH 3 and z is a number from 1 to 50, in particular from 5 to 30.Surprisingly, it has been found that fragrance precursor compounds of formula (I) are capable of releasing fragrances of the type of α,β-unsaturated aldehydes, α,β-unsaturated ketone or α,β-unsaturated esters over a long period of time. Moreover, they can be incorporated stably into consumer products.In a preferred embodiment of the fragrance precursor compound of formula (I), the fragrance is an α,β-unsaturated ketone selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone, and mixtures thereof.Ionones, damascenones and damascone are a number of closely related chemical compounds which are part of a variety of essential oils. They belong to a family of chemicals called rose ketones. Both enantiomers of carvone are part of different essential oils.In a further, preferred embodiment of the fragrance precursor compound of the formula (I), at z >1, at least one R 2 is a (2-hydroxyethyl)trimethylammonium chloride group. The positive charge of the (2-hydroxyethyl)trimethylammonium chloride group can significantly increase the substantivity, especially on cotton or keratin, of the fragrance precursor compound of the formula (I).In the context of this embodiment, it is advantageous that not more than 50% of the substituents R 2 per fragrance precursor compound of the formula (I) are a (2-hydroxyethyl)trimethylammonium chloride group. Accordingly, the degree of substitution on the (2-hydroxyethyl)trimethylammonium chloride group is at most 0.5.In the case where z > 1, it may be advantageous that at least two R 1 are different. It can likewise be advantageous that at z>1, at least two R 3 are different.In an advantageous embodiment of the invention, the molecular weight M w of the fragrance precursor compound of the formula (I) is in the range from 500 g / mol to 50,000 g / mol.In a very particularly preferred embodiment of the fragrance precursor compound of the formula (I), m and n are 0, R 2 is an α,β-unsaturated ketone and / or H, R 3 is H and z is a number from 5 to 30.In a likewise very particularly preferred embodiment of the fragrance precursor compound of the formula (I), m and n are 0, at least R 2 is a (2-hydroxyethyl)trimethylammonium chloride group, at least one R 2 is an α,β-unsaturated ketone and the remaining R 2 are an α,β-unsaturated ketone or H, R 3 is H and z is a number from 5 to 30.In an alternative, very particularly preferred embodiment of the fragrance precursor compound of the formula (I), R is 1-( O-CX 3 X is 4- CX 3 X is 4)n, where X is 3 and X is 4 each denote H, R is 2 an α,β-unsaturated ketone and / or H, R is 3 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 the formula (I), R is 1-( O-CX 3 X 4- CX 3 X 4)n, where X 3 and X 4 are each H, at least one R 2 is a (2-hydroxyethyl)trimethylammonium chloride group, at least one R 2 is an α,β-unsaturated ketone, and the remaining R 2 are an α,β-unsaturated ketone or H, R3is H, m is 3 and z is a number from 5 to 30. furthermore, it holds true that for each fragrance precursor compound of the formula (I) at most 50% of the R 2 are a (2-hydroxyethyl)trimethylammonium chloride group.From the described perfume precursor compounds of formula (I), the perfume can be released by hydrolysis, especially at acidic pH values, i.e. pH values < 7, for example < 6 or < 5.The perfume precursor compounds of formula (I) may be prepared by reacting a compound of formula (II) wherein R 1 is -(CX 1 X 2)m- or -(O-CX 3 X 4- CX 3 X 4)n- wherein X 1 and X 2 independently of one another are H or a linear or branched, saturated or unsaturated C2-C12alkyl radical, X 3 and X 4 independently of one another, stand for H or CH 3 m stands for a number from 0 to 10 and n stands for a number from 0 to 30, in particular 1 to 4, R 2 stands for H, R 3 stands for H or CH 3 and z stands for a number from 1 to 50, in particular 5 to 30, with a fragrance selected from the group of the α,β-unsaturated aldehydes, the α,β-unsaturated ketones, the α,β-unsaturated esters and mixtures thereof.It may be advantageous here for a compound of the formula (II) to be used in which m and n are 0 and R 3 is H. In this embodiment, the compound of formula (II) may comprise, for example, a polyester of mercaptosuccinic acid and ethylene glycol.In a further preferred embodiment of the process, a compound of the formula (II) is used in which R is 1-( O-CX 3 X is 4- CX 3 X is 4)n where X is 3 and X is 4 each denote H, R is 3 H and m is 3. In this embodiment, the compound of formula (II) may be, for example, a polyester of mercaptosuccinic acid and tetraethylene glycol.In a particularly preferred embodiment of the process, a compound of the formula (II) in which z >1 is reacted with a mixture of a fragrance selected from the group of the α,β-unsaturated aldehydes, the α,β-unsaturated ketones, the α,β-unsaturated esters and mixtures thereof and glycidyltrimethylammonium chloride.In this embodiment, the compound of formula (II) has at least two SH groups, of which at least one SH group is able to react with the fragrance selected from the group of the α,β-unsaturated aldehydes, the α,β-unsaturated ketones and the α,β-unsaturated esters and at least one SH group is able to react with the glycidyltrimethylammonium chloride.In various particularly preferred embodiments of the method, the fragrance can be an α,β-unsaturated ketone selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damasceneone, β-damasceneone, γ-damasceneone, δ-damasceneone, α-damasceneone, β-damasceneone, γ-damasceneone, δ-damasceneone, δ-damasceneone, β-damasceneone, γ-damasceneone, δ-damasceneone, L-carvone, D-carvone, and mixtures thereof.The reaction of the compound of the formula (II) and the fragrance and optionally glycidyltrimethylammonium chloride takes place preferably under a nitrogen atmosphere. Further, the reaction is preferably carried out in a suitable solvent. A suitable solvent is, for example, dichloromethane, tetrahydrofuran or acetone. Preferably, a base, for example triethylamine and / or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), is also used. The reaction mixture of the starting materials, optionally the base and the solvent is then preferably stirred at room temperature for a plurality of hours, preferably 2 to 60, in particular 12 to 48. The reaction product obtained is isolated by conventional methods and, if appropriate, purified.The present invention further relates to perfume compositions, detergents and / or cleaners or cosmetic compositions containing at least one of the perfume precursor compounds of the present invention.In a preferred embodiment, the at least one fragrance precursor compound is contained in a total amount of 0.01 to 20 wt %, advantageously of 0.1 to 15 wt %, particularly preferably of 0.5 to 15 wt %, in each case based on the total weight of the perfume composition.In preferred embodiments, the at least one fragrance precursor compound is present in a total amount of from 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.The above-described perfume 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 perfume or at least one further perfume precursor compound which is different from the perfume precursor compound of formula (I).The further fragrances, which may optionally be present in the perfume composition, the washing or cleaning agent or the cosmetic agent, are not subject to any particular restrictions. Thus, individual perfume compounds of natural or synthetic origin, for example of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon types, can be used. Perfume compounds of the ester type include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate and jasmacyclate. The ethers include, for example, benzyl ethyl ether and ambroxan; the aldehydes include the abovementioned, for example, the linear alkanals having 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]-isomethylionone and methyl cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used which together produce an appealing scent note.The compositions may also contain natural perfume mixtures as are available from vegetable sources, e.g., pine, citrus, jasmine, patcholoy, rose, or ylang-ylang oil. Also suitable are muscatell sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and also orange blossom oil, neroli oil, orange peel oil and sandalwood oil. Further conventional fragrances which may be present in the compositions according to the invention in the context of the present invention are, for example, the essential oils such as angelica root oil, anis oil, arnica flower oil, basil oil, bay oil, Champacablütenöl edeltannic oil, edeltann cone oil, elemi oil, eucalyptus oil, fenchel oil, spruce needle oil, galbanum oil, geranium oil, gingegras oil, guajacwood oil, gurujunbalam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, kalmus oil, chamomillen oil, and the like, Camphor oil, canaga oil, cardiomene oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, herbal mint oil, cowmel oil, kumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, mossy grain oil, myrrhen oil, clove oil, neroli oil, niaouli oil, olibanum oil, origanum oil, palmarosa oil, patchuli oil, perubalsam oil, petitgraine oil, pepper oil, peppermint oil, pement oil, pine oil, rose oil, Rosemary oil, sandalwood oil, celery oil, spik oil, sternal anis oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiger oil, juniper beer oil, wermut oil, wneter green oil, Ylang-Ylang oil, Ysop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil, and zygpress oil, as well as ambrettolide, ambroxan, α-amylcinnamaldehyde, anethol, anisaldehyde, anis alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, Benzyl formate, benzyl valerate, borneol, bornyl acetate, boisambrene forte, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptus, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iran, isoeugenol, isoeugenol methyl ether, isosefrol, jasmone, camphor, carvacrool, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, Methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavikol, p-methyl quinoline, methyl β-naphthyl ketone, methyl n-nonyl acetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy acetophenone, pentadecanoylide, β-phenylethyl alcohol, phenylacetic acid, pulegone, safrol, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, santalol, sandelice, skatol, terpineol, thymene, thymol, troenan, γ-undelactone, vanillin, veratralaldehyde, cinnamic aldehyde, cinnamic alcohol, cinnamic acid, ethyl cinnamic acid ester, benzyl cinnamic acid ester, diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal and mixtures thereof.It is possible in particular for the at least one fragrance precursor compound of the formula (I) to be used with the corresponding a,β-unsaturated aldehydes and / or a,β-unsaturated ketones and / or a,β-unsaturated esters. According to a preferred embodiment, such compositions are distinguished in that the molar ratio of perfume aldehyde and / or perfume ketone and / or perfume 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.A perfume composition can comprise, in addition to the at least one fragrance precursor compound of the formula (I) and the optional, further fragrances or natural fragrance mixtures, further ingredients, in particular a carrier material, such as dipropylene glycol, diethyl phthalate, isopropyl myristate or ethyl citrate.In addition to the at least one fragrance precursor compound of the formula (I), detergents and cleaners may also comprise, in particular, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants or mixtures thereof. Furthermore, these agents can be present in solid or liquid form.Suitable nonionic surfactants are, in particular, ethoxylation and / or propoxylation products of alkyl glycosides and / or linear or branched alcohols each having 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 with respect to the alkyl moiety to the long-chain alcohol derivatives mentioned, and of alkyl phenols having 5 to 12 C atoms in the alkyl radical, are usable. Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Soaps which can be used are preferably the alkali metal salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful sulfate surfactants include the salts of the sulfuric monoesters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the above-mentioned nonionic surfactants having a low degree of ethoxylation. Surfactants of the sulfonate type which can be used include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl part, alkanesulfonates having 12 to 18 carbon atoms, and olefinsulfonates having 12 to 18 carbon atoms which are formed during the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfo fatty acid esters which are formed during the sulfonation of fatty acid methyl esters or ethyl esters. Cationic surfactants are preferably selected from esterquats and / or quaternary ammonium compounds (QAV) according to the general formula (R I)( R II)( R III)( R IV) N + X - in which R I to R IV are identical or different C 1-22- alkyl radicals, C 7-28- arylalkyl radicals or heterocyclic radicals, two or, in the case of an aromatic bond as in pyridine, even three radicals together with the nitrogen atom forming the heterocycle, e.g. a pyridinium or imidazolinium compound, and X - represents halide ions, sulfate ions, hydroxide ions or similar anions. QAVs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines having a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines having two long radicals and one methyl group can also be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are sparingly reactive and are quaternized, for example, with dimethyl sulfate. QAVs which can be used are, for example, benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalcon B (m,p-dichlorobenzyldimethyl-C 12- alkylammonium chloride, benzoxonium chloride (benzyldodecylbis(2-hydroxyethyl)ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethylammonium bromide), benzetonium chloride (N,N dimethyl-N [2-[2-[p-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, 1-cetylpyridinium chloride and thiazoline iodide, and mixtures thereof. Preferred QAVs are the benzalkonium chlorides with C 8- C 22- alkyl radicals, in particular C 12- C 14- alkylbenzyldimethylammonium chloride.Preferred ester quats are methyl-N-(2-hydroxyethyl)-N,N-di(tallowacyloxyethyl)ammonium methosulfate, bis-(palmitoyl)ethyl hydroxyethylmethylammonium methosulfate or methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate. Commercially available examples are the Methylhydroxyalkyldialkoyloxyalkylammoniummethosulfate marketed by Stepan under the trade name Stepantex ® or the products from BASF SE known under the trade name Dehyquart ® or the products from Evonik, known under the name Rewoquat ® respectively.The detergents and cleaners may also contain further ingredients which further improve the application and / or aesthetic properties of the composition, depending on the intended use. In the context of the present invention, they may comprise builders, bleaches, bleach activators, bleach catalysts, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescent agents, dyes, hydrotropes, foam inhibitors, antiredeposition agents, solvents, enzymes, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, color stabilizers, wetting improvers, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, rinse aids, preservatives, antistatic agents, ironing auxiliaries, repellents and impregnating agents, pearlescent agents, polymers, anti-swell agents and anti-slip agents and UV absorbers, without being restricted thereto.In addition to just the at least one fragrance precursor compound of the formula (I), cosmetic agents can comprise further typical ingredients for cosmetic agents. Further 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-scaling active ingredients, complexing agents, opacifiers, pearlescent agents, pigments, stabilizers, propellants, antioxidants, perfume oils and / or preservatives.The amounts of the individual ingredients in the detergents and / or cleaners and in the cosmetic agents are each oriented to the intended use of the agent in question, and the skilled worker is familiar in principle with the orders of magnitude of the amounts of the ingredients to be used or can derive these from the associated technical literature.What has been said about the perfume precursor compound of the formula (I), the perfume composition, the washing and / or cleaning agent and the cosmetic agent applies mutatismutatally to its use in a process for long-lasting fragrancing of surfaces. In the method, at least one fragrance precursor compound of the 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 fragrancing thereby continues longer than if the respective perfume compound or an identical agent in which the perfume precursor compound is replaced by the respective perfume compound(s) were used.ExamplesExample 1:Synthesis of a polyester 1 of formula (II)In a 100 mL flask were placed 11.6 g of mercaptosuccinic acid, 6.3 g of ethylene glycol (48.5 mg of p-toluenesulfonic acid and 17 mg of hydroquinone. The mixture was heated to 140°C until a clear melt was obtained. After 30 minutes, vacuum was applied to drive off the water of reaction. The reaction mixture was stirred at 140°C for 5 hours. The reaction mixture was then cooled to room temperature.Yield 14.5 g (90% theoretical yield) of GPC in THF: M n: 1000 g / mol, M w: 1600 g / molSynthesis of a Perfume Precursor Compound 1 of Formula (I)12.5 g of polyester 1 in 60 ml of acetone were placed in a 100 ml flask. At room temperature, 12.3 g of α-damascone and 6.5 g of triethylamine were added. After 5 minutes, 500 mg of DBU was added and then stirred overnight at room temperature. The next day wasThe pro-perfume compound 1 was precipitated into 1000 mL hexane. The solvent was decanted off and the oil obtained was dried in a vacuum drying cabinet at 40°C. The oil was dissolved in some acetone and dialyzed (MWCO=1000).Yield 10.3 g (42% theoretical yield) of GPC in THF: M n: 1600 g / mol, M w: 2700 g / molExample 2:Synthesis of a polyester 2 of formula (II)In a 250 mL flask were placed 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 flooded with nitrogen. The mixture was heated to 170° C. until a clear melt was obtained, and a few ml of water were rapidly formed. After about 60 minutes, vacuum was applied to drive off the reaction water completely.After 4 hours, the reaction was cooled to RT. Yield 69 g (69% theoretical yield) of GPC in THF: Mn: 800 g / mol, Mw: 2600 g / molSynthesis of a Perfume Precursor Compound 2 of Formula (I)20.9 g of polyester 2 in 60 ml of acetone were placed in a 250 ml flask. At room temperature, 9.2 g of damascone and 2.7 g of glycidyl trimethylammonium chloride were added. After about 5 minutes, 500 mg of DBU were added and the mixture was then stirred at RT overnight. The next day, the reaction solution became turbid and a precipitate had formed. Precipitation was effected in 600 ml of hexane. The solvent was decanted off and the oily residue was dried in a vacuum drying cabinet at 40° C. The oil was dissolved in about 100 ml of acetone to give a flaky precipitate which was filtered off. However, it dissolved in the atmospheric moisture, and then rinsed with some water. The solution was dialyzed against acetone (MWCO=1000). The solvent was then removed on the Roti.Yield: 28 g (88% theoretical yield) of GPC in THF: Mn: 1800 g / mol, Mw: 2700 g / molThe ratio between the damascon and ammonium ion side chains is 20% ammonium ion and 80% damasconExample 3: Odor testPerfume release was studied in a fabric softener, a liquid detergent and a powder detergent.To this end, perfume-free formulations of the fabric softener, of the liquid detergent and of the powder detergent were in each case admixed with the fragrance precursor compound prepared in Example 1 or Example 2 or with equimolar amounts of α-damascone and used in a washing / rinsing test in a washing machine.Example 3.1Fabric softener0.6 wt % α-damascone ii 1.61 wt % fragrance precursor compound 1 according to the invention from example 1Liquid Detergent0.50% by weight of α-damascone ii 1.34% by weight of fragrance precursor compound 1 according to the invention from example 1Powder Laundry Detergent0.30% by weight of α-damascone ii 0.80% by weight of fragrance precursor compound 1 according to the invention from example 1Laundry treated with one of the six agents (cotton, polyester, mixed fabric) was taken from the washing machine, dried and, after 1 day and 7 days, assessed olfactory for odor intensity by a trained panel on an intensity scale of 1 to 6 (1: no odor perceptible; 6: very strong odor perceptible).The following table shows the results of odor intensity on various tissues:Fabric softener / cotton2,51,31,12,2Fabric softener / polyester3,31,11,11,8Fabric softener / blend fabric1,71,11,12Liquid Laundry Detergent / Cotton1,71,31,32Liquid Detergent / Polyester1,81,21,32,2Liquid Detergent / Mixed Fabric1,21,31,51,8Powder Laundry Detergent / Cotton1,62,21,81,6Powder Laundry Detergent / Polyester2,12,622,5Powder Washing Agent / Mixed Fabric1,62,51,61,8In formulations ii, i.e. when the fragrance precursor compound from example 1 was used instead of the free fragrance, a higher odor intensity was found after 7 days with only one exception (powder laundry detergent / cotton).Example 3.2Fabric softener0.9% by weight of α-damascone2.0% by weight of fragrance precursor compound 2 according to the invention from Example 2Liquid Detergent0.70% by weight of α-damascone1.56 wt % fragrance precursor compound 2 according to the invention from Example 2 iv.Powder Laundry Detergent0.40 wt% α-damascone0.89% by weight of fragrance precursor compound 2 according to the invention from Example 2.Laundry treated with one of the six agents (cotton, polyester, mixed fabric) was taken from the washing machine, dried and, after 1 day and 7 days, assessed olfactory for odor intensity by a trained panel on an intensity scale of 1 to 6 (1: no odor perceptible; 6: very strong odor perceptible).The following table shows the results of odor intensity on various tissues:Fabric softener / cotton1,82,51,21,8Fabric softener / polyester3,22,31,52,5Fabric softener / blend fabric1,51,81,22,5Liquid Laundry Detergent / Cotton1,61,81,21,8Liquid Detergent / Polyester1,82,31,21,8Liquid Detergent / Mixed Fabric1,31,41,01,6Powder Laundry Detergent / Cotton1,81,81,82,3Powder Laundry Detergent / Polyester2,22,31,31,8Powder Washing Agent / Mixed Fabric1,61,61,21,8Formulations ii, i.e. when the fragrance precursor compound from example 2 was used instead of the free fragrance, consistently exhibited a higher odor intensity after 7 days.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Patent Literature citedWO 2004 / 105713 A1

[0005]

Claims

Fragrance precursor compound of the formula (I) wherein R 1 is -(CX 1 X 2)m- or -(O-CX 3 X 4- CX 3 X 4)n- wherein X 1 and X 2 independently of one another are H or a linear or branched, saturated or unsaturated C2-C12 alkyl radical, X3 and X4 independently of one another are H or CH3, m is a number from 0 to 10 and n is a number from 0 to 30, in particular 1 to 4, R 2 is 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, where at least one R 2 is an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 is H or CH 3 and z is a number from 1 to 50, in particular 5 to 30.The perfume precursor compound of claim 1, characterized in that the perfume is an α,β-unsaturated ketone selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damasceneone, β-damasceneone, γ-damasceneone, δ-damasceneone, α-damascenecon, β-damascenecon, γ-damascenecon, δ-damascenecon, L-carvone, D-carvone, and mixtures thereof.Fragrance precursor compound according to Claim 1 or Claim 2, characterized in that, at z >1, at least one R 2 is a (2-hydroxyethyl)trimethylammonium chloride group.Fragrance precursor compound according to Claim 3, characterized in that the degree of substitution on the (2-hydroxyethyl)trimethylammonium chloride group is not more than 0.5.Fragrance precursor compound according to any of Claims 1 to 4, characterized in that the molecular weight M w of the fragrance precursor compound of the formula (I) is in the range from 500 g / mol to 50,000 g / mol.A process for preparing a perfume precursor compound of formula (I) wherein R 1 is -(CX 1 X 2)m- or -(O-CX 3 X 4- CX 3 X 4)n- wherein X 1 and X 2 independently of one another are H or a linear or branched, saturated or unsaturated C2-C12 alkyl radical, X3 and X4 independently of one another are H or CH3, m is a number from 0 to 10 and n is a number from 0 to 30, in particular from 1 to 4, R 2 is 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, where at least one R 2 is an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester, R 3 is H or CH 3 and z is a number from 1 to 50, in particular from 5 to 30, characterized in that, a compound of the formula (II) where R 1 is -(CX 1 X 2)m- or -(O-CX 3 X 4- CX 3 X 4)n- where X 1 and X 2 are each independently H or a linear or branched, saturated or unsaturated C2-C12-alkyl radical, X3 and X4 are each independently H or CH3, m is a number from 0 to 10 and n is a number from 0 to 30, in particular from 1 to 4, R 2 is H, R 3 is H or CH 3 and z is a number from 1 to 50, in particular from 5 to 30, is reacted with a fragrance selected from the group of the α,β-unsaturated aldehydes, the α,β-unsaturated ketones, the α,β-unsaturated esters and mixtures thereof.Process according to Claim 6, characterized in that a compound of the formula (II) is used in which m and n are 0 and R 3 is H.Process according to Claim 6, characterized in that a compound of the formula (II) is used in which R is 1-( O-CX 3 X is 4- CX 3 X is 4)n where X is 3 and X is 4 each denote H, R is 3 H and m is 3.Process according to any of Claims 6 to 8, characterized in that a compound of the formula (II) where z >1 is reacted with a mixture of a fragrance selected from the group of the α,β-unsaturated aldehydes, the α,β-unsaturated ketones, the α,β-unsaturated esters and mixtures thereof and glycidyltrimethylammonium chloride.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-damasceneone, β-damasceneone, γ-damasceneone, δ-damasceneone, α-damasceneone, β-damasceneone, γ-damasceneone, δ-damasceneone, L-carvone, D-carvone, and mixtures thereof.Perfume composition containing at least one perfume precursor compound (I) according to any one of claims 1 to 5, wherein the compound is preferably contained in a total amount of from 0.01 to 20 wt.%, advantageously from 0.1 to 15 wt.%, more advantageously from 0.5 to 10 wt.%, based on the total weight of the perfume composition.Cosmetic agent containing at least one fragrance precursor compound (I) according to one of Claims 1 to 5, wherein the compound is preferably contained in a total amount of 0.001 to 5 wt.%, advantageously of 0.005 to 3 wt.%, further advantageously of 0.01 to 1 wt.%, based on the total weight of the agent.Washing and / or cleaning agent, comprising at least one fragrance precursor compound (I) according to any of Claims 1 to 5, wherein the compound is preferably contained in a total amount of from 0.001 to 5% by weight, advantageously from 0.005 to 3% by weight, further advantageously from 0.01 to 1% by weight, based on the total weight of the agent.A method for long-lasting fragrancing surfaces, characterized in that a fragrance precursor compound (I) according to any one of claims 1 to 5 or an agent according to claim 11, 12 or 13 is applied to the surface to be fragrancing, wherein the fragrancing lasts 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.