Thioether-based fragrance precursor compound vi

Abstract

The invention relates to specific thioether-based fragrance precursor compounds of formula (I) which are derived from selected multithiol compounds and selected fragrances, and to a process for the preparation thereof. The invention also relates to detergents or cleaning agents, cosmetic agents and a perfume composition which contain such fragrance precursor compounds. The 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] Henkel AG & Co. KGaA 2024P00223 WO

[0002] Thioether-based fragrance precursor compound VI

[0003] The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) derived from multithiol compounds and selected fragrances, and to a process for their preparation. Furthermore, the present invention relates to washing and / or cleaning agents, cosmetic compositions, and perfume compositions containing such fragrance precursor compounds. The present invention also relates to a process for the long-lasting fragrance application of surfaces using the fragrance precursor compounds and compositions according to the invention.

[0004] Washing and / or cleaning products, as well as cosmetics, usually contain fragrances that give them a pleasant scent. These fragrances can also serve to mask the odor of other ingredients, thus creating a pleasant scent impression for the consumer.

[0005] Fragrances are particularly important components in the composition of laundry and / or cleaning products, as the laundry should have a pleasant and, ideally, fresh scent both when wet and dry. The use of fragrances is inherently problematic because they are more or less volatile compounds, yet a long-lasting fragrance effect is desired. This is especially true for those fragrances that represent the fresh and light notes of perfume and are particularly volatile due to their high vapor pressure; achieving the desired longevity of the scent is therefore extremely difficult.

[0006] 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 react with other compounds to form the aforementioned fragrance precursor compounds. These precursor compounds are then able to release the actual fragrance compound in a delayed manner (for example, through hydrolysis or photochemical processes). Of particular interest is the ability to release several different fragrances from a single fragrance precursor compound in order to maintain a harmonious fragrance impression.

[0007] Thioether-based fragrance precursor compounds are known from WO 2004 / 105713 A1.

[0008] 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 goods, such as detergents and / or cleaning agents or cosmetics. It is also desirable that the fragrance precursor compounds exhibit 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 selected multithiol compounds and selected fragrances.

[0009] In one aspect, the invention therefore relates to a fragrance precursor compound of formula (I) where

[0010] R 1for H or a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof,

[0011] R 2 for CH3, CH3CH2 or R 1 SCH2CH2(C=O)OCH2 stands, (where at least one R 1 stands for an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester.

[0012] In a second aspect, the present invention relates to a method for producing a fragrance precursor compound of formula (I).

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

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

[0015] In a fifth aspect, the present invention relates to a cosmetic product containing at least one fragrance precursor compound of the present invention.

[0016] Finally, in a sixth aspect, the present invention relates to a method for the long-lasting scenting of surfaces, characterized in that a fragrance precursor compound or a perfume composition or a washing and / or cleaning agent or a cosmetic agent according to the invention is applied to the surface to be scented, wherein the scenting 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. These and further embodiments, features, and advantages of the invention will become apparent to the person skilled in the art from studying the following detailed description and claims.Individual features or embodiments of the invention described herein may be combined with other features or embodiments of the invention without 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 these examples.

[0017] “At least one,” as used herein, refers to one or more, for example, two, three, four, five, six, seven, eight, nine, or more. In the context of the fragrance precursor compounds described herein, this term refers not to the absolute quantity of molecules but to the type of compound. “At least one fragrance precursor compound” therefore means, for example, that only one type of fragrance precursor compound or several different types of fragrance precursor compounds may be present, without specifying the quantity of each compound.

[0018] Unless otherwise stated, all quantities specified in connection with the process described herein are given as percent by weight of the total weight of the composition. Furthermore, any quantity specified relating to at least one component always refers to the total quantity of that type of component contained in the composition, unless explicitly stated otherwise. This means that, for example, any quantity specified in connection with "at least one fragrance precursor compound" refers to the total quantity of fragrance precursor compounds contained in the composition, unless explicitly stated otherwise.

[0019] Numerical values ​​given herein without decimal places refer to the full value given with one decimal place. For example, "99%" means "99.0%".

[0020] Numerical ranges specified in the format "in / from x to y" include the values ​​mentioned. If multiple preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.

[0021] The terms "odorant" and "fragrance" 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 in such a way that the fragrance acquires a certain depth, which is commonly referred to as the complexity of a fragrance. The present invention relates in particular to fragrance precursor compounds of formula (I) where

[0022] R 1 for H or a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof,

[0023] R 2 for CH3, CH3CH2 or R 1 SCH2CH2(C=O)OCH2 stands for at least one R 1 stands for an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester.

[0024] Surprisingly, fragrance precursor compounds of formula (I) have been shown to release 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.

[0025] 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-lonone, β-lonone, 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. α-Damascone is a preferred fragrance.

[0026] Ionones, damascenones, and damascones 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 components of various essential oils.

[0027] In a preferred embodiment of the invention, at least two R are available for each fragrance precursor compound of formula (I). 1for an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester.

[0028] In a more preferred embodiment of the invention, at least three R are available for each fragrance precursor compound of formula (I). 1 for an α,β-unsaturated aldehyde, an α,β-unsaturated ketone, or an α,β-unsaturated ester. The fragrance can be released from the described fragrance precursor compounds of formula (I) by high temperatures and / or changes in the surrounding pH.

[0029] The fragrance precursor compounds of formula (I) can be obtained by reacting a compound of formula (II) where

[0030] R 2 for CH3, CH3CH2 or HSCH2CH2(C=O)OCH2, with a fragrance substance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof.

[0031] In a preferred embodiment of the invention, R 2 in formula (II) for a methyl group:

[0032] Trimethylolethane tris-(3-mercaptopropionate) (CAS number: 10312-58-0) is commercially available.

[0033] In a further preferred embodiment of the invention, R 2 in formula (II) for an ethyl group:

[0034] Trimethylolpropane tris(3-mercaptopropionate) (CAS number: 33007-83-9) is commercially available. In a further preferred embodiment of the invention, R 2 in formula (II) for an HSCH2CH2(C=O)OCH2 group:

[0035] Pentaerythritol tetrakis-(3-mercapto-propionate) (CAS number: 7575-23-7) is commercially available

[0036] Depending on the embodiment, the compound of formula (II) has three or four SH groups, at least one of which reacts with the fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones and α,β-unsaturated esters.

[0037] In various, particularly preferred embodiments of the process, the fragrance may be an α,β-unsaturated ketone selected from the group consisting of α-lonone, β-lonone, 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.

[0038] The reaction of the compound of formula (II) and the fragrance is preferably carried out under a nitrogen atmosphere. The reaction can be performed in a suitable solvent. Suitable solvents include, for example, dichloromethane, tetrahydrofuran, or acetone. Preferably, a base, such as triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and / or potassium hydroxide, is used. The reaction mixture of the reactants, optionally the base, and the solvent is then preferably stirred at room temperature for several hours, preferably 2 to 60, and particularly 12 to 48. The reaction mixture can also be stirred at higher temperatures, i.e., at temperatures up to 50 °C. The resulting reaction product is isolated and optionally purified by conventional methods.

[0039] The present invention further relates to perfume compositions, washing and / or cleaning agents or cosmetic products which contain at least one of the fragrance precursor compounds of the present invention.

[0040] In a preferred embodiment, the at least one fragrance precursor compound is present in a total amount of 0.01 to 20 wt.%, advantageously 0.1 to 15 wt.%, and particularly preferably 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 0.001 to 5 wt.%, advantageously 0.005 to 3 wt.%, and particularly preferably 0.01 to 1 wt.%, in each case based on the total weight of the washing and / or cleaning agent or cosmetic product.

[0041] The fragrance precursor compounds of formula (I) described above may be used in a perfume composition, a washing and / or cleaning agent or a cosmetic product as mixtures with at least one other fragrance or at least one other fragrance precursor compound which is different from the fragrance precursor compound of formula (I).

[0042] Other fragrance substances that may be optionally included in perfume compositions, detergents, cleaning agents, or cosmetic products are not subject to any special restrictions. Individual fragrance compounds of natural or synthetic origin, such as esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons, may be used. Examples of ester-type fragrance compounds include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexyl propionate, styralyl propionate, benzyl salicylate, cyclohexyl salicylate, Floramate, Melusate, and Jasmacyclate. Examples of ethers include benzyl ethyl ether and ambroxane, while aldehydes include those mentioned above.Linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamenaldehyde (3-(4-propan-2-ylphenyl)butanal), lilial, and bourgeonal; ketones such as ionones, [alpha]-isomethyl ionone, and methylcedryl ketone; alcohols such as anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol, and terpineol; and hydrocarbons mainly terpenes such as limonene and pinene. However, mixtures of various fragrances are preferred, as they combine to create an appealing scent.

[0043] The compositions may also contain natural fragrance mixtures available from plant sources, such as 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, frankincense oil, galbanum oil, and labdanum oil, as well as orange blossom oil, neroli oil, orange peel oil, and sandalwood oil. Other conventional fragrances that may be included in the compositions according to the present invention are, for example, essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower 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, and pine needle oil.Copaiba 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, frankincense oil, oregano oil, palmarosa oil, patchouli oil, Peruvian balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento 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, cypress oil, ambrettolide, ambroxan, α-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, heptyne carboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamaldehyde alcohol, indole, ira, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, 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 β-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide β-Phenylethyl alcohol, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate

[0044] salicylic acid cyclohexyl ester, santalol, sandelice, skatole, terpineol, thymene, thymol, troenane, γ-undelactone, vanillin, veratraldehyde, cinnamaldehyde, cinnamyl 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.

[0045] It is particularly possible that the at least one fragrance precursor compound of formula (I) is 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, and even more preferably 2:1 to 1:2, and particularly 1.2:1 to 1:1.2.

[0046] A perfume composition may, in addition to the at least one fragrance precursor compound of formula (I) and the optional, further fragrances or natural fragrance mixtures, include further ingredients, in particular a carrier material, such as dipropylene glycol, diethyl phthalate, isopryl myristate or ethyl citrate.

[0047] Washing and cleaning agents may, in addition to the at least one fragrance precursor compound of formula (I), also contain, in particular, anionic, nonionic, cationic, amphoteric, or zwitterionic surfactants or mixtures thereof. Furthermore, these agents may be 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 with 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 aforementioned long-chain alcohol derivatives with respect to the alkyl moiety, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl group, are suitable.Suitable anionic surfactants are, in particular, soaps and those containing sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a partially neutralized form. Suitable sulfate-type surfactants include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the aforementioned nonionic surfactants with a low degree of ethoxylation. Usable 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 the reaction of corresponding monoolefins with sulfur trioxide, as well as alpha-sulfofaticial esters, which are formed by the sulfonation of fatty acid methyl or ethyl esters.Cationic surfactants are preferably selected from the esterquats and / or the quaternary ammonium compounds (QACs) according to the general formula (R. I )(R")(R III )(R IV )N + X” selected, in the R 1 to R IVThe Ci denotes identical or different Ci-22 alkyl groups, Ci-28 arylalkyl groups, or heterocyclic groups, where two, or in the case of aromatic incorporation as in pyridine, even three groups together with the nitrogen atom form the heterocycle, e.g., a pyridinium or imidazolinium compound, and Xi denotes 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, and also ethylene oxide. The alkylation of tertiary amines with one long alkyl group and two methyl groups is particularly easy; the quaternation of tertiary amines with two long groups and one methyl group can also be carried out under mild conditions using methyl chloride. Amines possessing three long alkyl groups or hydroxy-substituted alkyl groups are less reactive and are, for example, Dimethyl sulfate quaternated.Examples of QAVs that could be considered include benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalkone B (m,p-dichlorobenzyldimethyl-Ci2-alkylammonium chloride), benzoxonium chloride (benzyldodecyl-bis-(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-decyl-dimethylammonium chloride, didecyldimethylammonium bromide, dioctyl-dimethylammonium chloride, 1-cetylpyridinium chloride, and thiazoline iodide, as well as mixtures thereof. Preferred QAVs are the benzalkonium chlorides with C8-C22- Alkyl groups, especially Ci2-Ci4-alkylbenzyl-dimethylammonium chloride.

[0048] Preferred esterquats are methyl-N-(2-hydroxyethyl)-N,N-di(talgacyl-oxyethyl)ammonium methosulfate, bis-(palmitoyl)-ethyl-hydroxyethyl-methyl-ammonium methosulfate, or methyl-N,N-bis(acyl-oxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate. Commercially available examples include the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed by Stepan under the trademark Stepantex®, the products known under the trade name Dehyquart® from BASF SE, and the products known under the name Rewoquat® from Evonik.

[0049] Furthermore, the washing and cleaning agents may contain additional ingredients that further improve the application-related and / or aesthetic properties of the composition, depending on the intended use. Within the scope of the present invention, they may include, but are not limited to, builders, bleaching agents, bleach activators, bleaching catalysts, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-reposition agents, solvents, enzymes, optical brighteners, anti-graying agents, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, color protectants, wetting agents, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, rinse aids, preservatives, antistatic agents, ironing aids, antiphobing and impregnating agents, pearlescent agents, polymers, swelling and slip-resistant agents, and UV absorbers.

[0050] Cosmetic products may contain, in addition to at least one fragrance precursor compound of formula (I), other typical ingredients for cosmetic products. Other suitable ingredients include, in particular, anionic surfactants, amphoteric / zwitterionic surfactants, non-ionic surfactants, cationic surfactants, non-ionic polymers, anionic polymers, cationic polymers, amphoteric polymers, lipids, waxes, protein hydrolysates, amino acids, oligopeptides, vitamins, provitamins, vitamin precursors, betaines, bioquinones, purine (derivatives), taurine (derivatives), plant extracts, silicones, ester oils, UV filters, structuring agents, thickeners, electrolytes, pH adjusters, swelling agents, colorants, anti-dandruff agents, complexing agents, opacifiers, pearlescent agents, pigments, stabilizers, propellants, antioxidants, perfume oils, and / or preservatives.

[0051] The quantities of the individual ingredients in washing and / or cleaning agents as well as in cosmetic products are based on the intended use of the respective product, and the expert is generally familiar with the orders of magnitude of the quantities of ingredients to be used or can obtain this information from the relevant technical literature.

[0052] 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 scenting 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 is applied to the surface to be scented. The scenting 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.

[0053] Examples

[0054] Synthesis of a fragrance precursor compound 1 of formula (I)

[0055] In a 250 mL round-bottom flask, 18.57 g (38 mmol) of pentaerythritol tetrakis-(3-mercapto-propionate) were placed in 100 mL of acetone. 29.3 g (152 mmol) of α-damascone were added and the mixture was stirred for 5 min. Subsequently, 0.058 g (1 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was added to the reaction mixture and the mixture was stirred overnight at room temperature.

[0056] The slightly yellowish solution was transferred to 100 mL of 5% ice-cold HCl and extracted with 200 mL of diethyl ether. The organic phase was extracted three further times with 200 mL of water, once with 200 mL of NaHCOs solution, and once with 140 mL of saturated NaCl solution.

[0057] Subsequently, the organic phase was dried over MgSO4, filtered, and the solvent was removed under reduced pressure.

[0058] The product was isolated as a highly viscous, light yellow oil with a yield of 53 g.

[0059] The purity was 92% (determined by 1 H-NMR spectroscopy).

[0060] Synthesis of a fragrance precursor compound 2 of formula (I)

[0061] In a 50 mL 2-half-bottle, 12 g (80 mmol) of L-carvone and 9.8 g (20 mmol) of pentaerythritol tetrakis-(3-mercapto-propionate) were placed. With stirring, 11 mg of finely ground KOH were added, and the reaction solution was stirred overnight at room temperature.

[0062] The highly viscous product was then stirred for a further 6 hours at a temperature of 50 °C.

[0063] The product was isolated as a highly viscous, light yellow oil with a yield of 18 g.

[0064] The purity was 90% (determined by 1 H-NMR spectroscopy).

[0065] Synthesis of a fragrance precursor compound 3 of formula (I)

[0066] In a 250 mL round-bottom flask, 15.1 g (38 mmol) of trimethylolpropane tris(3-mercaptopropionate) were dissolved in 100 mL of acetone. 21.9 g (114 mmol) of α-damascone were added, and the mixture was stirred for 5 min. Subsequently, 0.058 g (1 mmol) of DBU was added to the reaction mixture, and the mixture was stirred overnight at room temperature. The slightly yellowish solution was transferred to 100 mL of 5% ice-cold HCl and extracted with 200 mL of diethyl ether. The organic phase was extracted three further times with 200 mL of water, once with 200 mL of NaHCCh solution, and once with 140 mL of saturated NaCl solution.

[0067] Subsequently, the organic phase was dried over MgSC, filtered, and the solvent was removed under reduced pressure.

[0068] The product was isolated as a highly viscous, light yellow oil with a yield of 28.3g.

[0069] The purity was 94% (determined by 1 H-NMR spectroscopy).

[0070] smell test

[0071] Fragrance release was investigated in a fabric softener, a liquid detergent, and a powder detergent.

[0072] For this purpose, perfume-free formulations of fabric softener, liquid detergent and powder detergent were mixed with the fragrance precursor compound 1 or 3 or with equimolar amounts of α-damascone and used in a washing / rinsing test in a washing machine.

[0073] Smell test 1

[0074] Fabric softener i. 0.9 wt.% α-Damascone ii. 1.60 wt.% fragrance precursor compound 1 according to the invention iii. 1.62 wt.% fragrance precursor compound 3 according to the invention

[0075] Liquid detergent i. 0.70 wt.% α-Damascone ii. 1.25 wt.% fragrance precursor compound according to the invention iii. 1.26 wt.% fragrance precursor compound according to the invention

[0076] Powder detergent i. 0.40 wt.% α-Damascone ii. 0.71 wt.% fragrance precursor compound 1 according to the invention iii. 0.72 wt.% fragrance precursor compound 1 according to the invention

[0077] Laundry treated with one of the nine agents (cotton, polyester, mixed fabrics) was removed from the washing machine, dried, and after 1 day and 7 days assessed olfactorily by a trained panel regarding odor intensity using an intensity scale from 1 to 6 (1: no odor perceptible; 6: very strong odor perceptible).

[0078] The following table shows the results of the odor intensity on different fabrics:

[0079] In formulations ii and iii, i.e., when using fragrance precursor compounds 1 and 3 instead of the free fragrance, a higher odor intensity was observed after 7 days with only one exception (fabric softener / polyester).

[0080] Smell test 2

[0081] Fabric softener iv. 0.70 wt.% L-Carvone v. 1.41 wt.% fragrance precursor compound according to the invention 2

[0082] Liquid detergent iv. 0.50 wt.% L-Carvon v. 1.01 wt.% fragrance precursor compound according to the invention 2

[0083] Powder detergent iv. 0.30 wt.% L-Carvon v. 0.61 wt.% fragrance precursor compound according to the invention 2

[0084] Laundry treated with one of the six agents (cotton, polyester, mixed fabrics) was removed from the washing machine, dried, and after 1 day and 7 days assessed olfactorily by a trained panel regarding odor intensity using an intensity scale from 1 to 6 (1: no odor perceptible; 6: very strong odor perceptible).

[0085] The following table shows the results of the odor intensity on different fabrics:

[0086] In formulations ii, i.e., when using the fragrance precursor compound 2 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) where R 1 for H or a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof, R 2 for CH3, CH3CH2 or R 1 SCH2CH2(C=O)OCH2 stands for at least one R 1 stands for an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester.

2. Fragrance precursor compound according to claim 1, characterized in that the fragrance is an α,β-unsaturated ketone selected from the group consisting of α-lonone, β-lonone, 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.

3. Fragrance precursor compound according to claim 1 or claim 2, characterized in that R 1for -Damascon and R 2 for R 1 SCH2CH2(C=O)OCH2 stands.

4. Fragrance precursor compound according to claim 1 or claim 2, characterized in that R 1 for a-Damascon and R 2 stands for CH3CH2.

5. Fragrance precursor compound according to any one of claims 1 to 4, characterized in that R 1 for L-Carvon and R 2 for R 1 SCH2CH2(C=O)OCH2 stands.

6. Method for the preparation of a fragrance precursor compound of formula (I) where R 1 for H or a fragrance selected from the group of α,β-unsaturated aldehydes, α,β-unsaturated ketones, α,β-unsaturated esters and mixtures thereof, R 2 for CH3, CH3CH2 or R 1 SCH2CH2(C=O)OCH2 stands, where at least one R 1for an α,β-unsaturated aldehyde, an α,β-unsaturated ketone or an α,β-unsaturated ester is characterized in that a compound of formula (II) where R 2 for CH3, CH3CH2 or HSCH2CH2(C=O)OCH2, 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. Method according to claim 6, characterized in that the fragrance is an α,β-unsaturated ketone and is selected from the group consisting of α-lonone, β-lonone, 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.

8. Perfume composition comprising at least one fragrance precursor compound (I) according to any one of claims 1 to 5, wherein the compound is preferably contained in a total amount of 0.01 to 20 wt.%, advantageously of 0.1 to 15 wt.%, further advantageously of 0.5 to 10 wt.%, based on the total weight of the perfume composition.

9. Cosmetic composition containing 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 0.001 to 5 wt.%, advantageously of 0.005 to 3 wt.%, further advantageously of 0.01 to It contains 1% by weight, based on the total weight of the product.

10. Washing and / or cleaning agent comprising at least one fragrance precursor compound (I) according to any 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.

11. Method for long-lasting fragrance of surfaces, characterized in that a fragrance precursor compound (I) according to one of claims 1 to 5 or an agent according to claim 8, 9 or 10 is applied to the surface to be fragranced, wherein the fragrance 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.

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