Thioether-based fragrance precursor compound i

Abstract

The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) which are derived from mercaptosilanes 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 also 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 COMPOUND I

[0002] The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) derived from mercaptosilanes and 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 or 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 to provide fragrance precursor compounds that can be obtained by simple synthesis and desirably release at least two different fragrances. 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 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 mercaptosilanes and selected fragrances.

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

[0009] R1 is selected from H, linear or branched Ci-Cs-alkyl groups, linear, branched or cyclic Ce-C25-alkyl, Ce-C25-alkenyl, Ce-C25-alkynyl, Ce-C25-alkadienyl, C6-C25-alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4-alkyl groups, wherein at least one R 1 a linear, branched or cyclic Ce-C25 alkyl, Ce-C25 alkenyl, Ce-C25 alkynyl, Ce-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted by Ci-C4 alkyl groups,

[0010] R 2 and R 3 are independently selected from H, linear, branched or cyclic C1-C25 alkyl, C1-C25 alkenyl, C1-C25 alkynyl, C1-C25 alkadienyl, C1-C25 alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4 alkyl groups or R 2 and R 3including the carbon atoms to which R 2 and R 3 are bonded together to form a saturated or unsaturated ring having 6 to 20 carbon atoms, which ring may in turn be substituted by linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups,

[0011] R 4 is selected from H and -CH3 and

[0012] R 5 is selected from -OR 1 and -CH3.

[0013] In a second aspect, the present invention relates to a process for preparing a fragrance procurer compound of formula (I).

[0014] In a third aspect, the present invention relates to a perfume composition comprising at least one fragrance procurer compound of the present invention.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] "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.

[0019] 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.

[0020] Numerical values ​​stated without decimal places refer to the full specified value with one decimal place. For example, "99%" stands for "99.0%."

[0021] 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.

[0022] 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.

[0023] The present invention particularly relates to fragrance precursor compounds of formula (I) where

[0024] R 1is selected from H, linear or branched Ci-Cs-alkyl groups, linear, branched or cyclic Ce-C25-alkyl, Ce-C25-alkenyl, Ce-C25-alkynyl, Ce-C25-alkadienyl, C6-C25-alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4-alkyl groups, wherein at least one R 1 a linear, branched or cyclic Ce-C25 alkyl, Ce-C25 alkenyl, Ce-C25 alkynyl, Ce-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted by Ci-C4 alkyl groups,

[0025] R 2 and R 3 are independently selected from H, linear, branched or cyclic C1-C25 alkyl, C1-C25 alkenyl, C1-C25 alkynyl, C1-C25 alkadienyl, C1-C25 alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4 alkyl groups or R 2 and R 3including the carbon atoms to which R 2 and R 3 are bonded together to form a saturated or unsaturated ring having 6 to 20 carbon atoms, which ring may in turn be substituted by linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups,

[0026] R 4 is selected from H and -CH3 and

[0027] R 5 is selected from -OR 1 and -CH3.

[0028] Surprisingly, it has been shown that fragrance precursor compounds of formula (I) are capable of releasing two different fragrances, in particular two different fragrance types. In particular, a fragrance precursor compound of formula (I) can release a fragrance of the α,β-unsaturated ketone or α,β-unsaturated aldehyde type and at least one fragrance alcohol.

[0029] In a preferred embodiment of the fragrance procurer compound of formula (I), R 2 or R 3 of type and the other remainder R 2 or R 3 is -CH3 and R 4 is H.

[0030] Fragrance precursor compound of formula (I) having these substituents for R 2 , R 3 and R 4 release ionone, damascenone, and / or damascone. Ionone, damascenone, and damascone are a group of closely related chemical compounds that are components of a variety of essential oils. They belong to a family of chemicals known as rose ketones. Rose ketones are of great commercial interest as fragrances.

[0031] In a further preferred embodiment, in the fragrance precursor compound of formula (I) R 2 and R 3 a ring of the guy and R 4 is -CH3.

[0032] Fragrance precursor compound of formula (I) having these substituents for R 2 , R 3 and R 4 release carvone. Both enantiomers of carvone are components of various essential oils.

[0033] It is further preferred that R 1 from a fragrance alcohol of formula R 1 -OH.

[0034] R 1 of the fragrance alcohol is a linear, branched or cyclic Ce-C25 alkyl, Ce-C25 alkenyl, Ce-C25 alkynyl, Ce-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted with Ci-C4 alkyl groups.

[0035] The fragrance alcohol of formula R is particularly preferred 1-OH ausgewählt aus der Gruppe bestehend aus 2-Phenylethanol, 10-Undecen-1-ol., 2,6-Dimethylheptan-2-ol, 2-Methylbutanol, 2- Methylpentanol, 2-Phenoxyethanol, 2-Phenylpropanol, 2-tert-Butycyclohexanol, 3,5,5- Trimethylcyclohexanol, 3-Hexanol, 3-Methyl-5-phenylpentanol, 3-Octanol, 3-Phenylpropanol, 4- Heptenol, 4-lsopropylcyclohexanol, 4-tert-Butycyclohexanol, 6,8-Dimethyl-2-nonanol, 6-Nonen-1-ol, 9- Decen-1-ol, alpha-Methylbenzylalkohol, alpha-Terpineol, Benzylalkohol, beta-Terpineol, Citronellol, Decanol, Dihydromyrcenol, Dimethylbenzylcarbinol, Dimethylheptanol, Dimethyloctanol, Ethylvanilin, Eugenol, Geraniol, Heptanol, Isoborneol, Isoeugenol, Isopulegol, Linalool, Menthol, Myrtenol, n- Hexanol, Nerol, Nonanol, Octanol, para-Menthan-7-ol, Tetrahydrogeraniol, Tetrahydrolinalool, Thymol, trans-2-Nonen-1-ol, trans-2-Octenol, Undecanol, Vanillin, Zimtalkohol, cis-Hex-3-en-1-ol und Mischungen daraus.

[0036] 2-Phenylethanol smells of roses and is advantageously used together with at least one of the rose ketones in the fragrance precursor compounds of formula (I).

[0037] Also the fragrance alcohol of Formula R 1 -OH particularly advantageously selected from the group consisting of citronellol, geraniol, cis-hex-3-en-1-ol and mixtures thereof.

[0038] In a preferred embodiment, at least two R 1 a linear, branched or cyclic C1-C25 alkyl, C1-C25 alkenyl, C1-C25 alkynyl, C1-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted by C1-C4 alkyl groups. The at least two R 1 may be the same or different, where at least two R 1 are preferably equal.

[0039] In this embodiment of the invention, two fragrance alcohols of the formula R1 -OH released.

[0040] In a likewise preferred embodiment, R 5 -OR 1 and all R 1 are a linear, branched or cyclic C1-C25 alkyl, C1-C25 alkenyl, C1-C25 alkynyl, C1-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted by C1-C4 alkyl groups. The three R 1 can be the same or different, whereby the three R 1 are preferably equal.

[0041] In this embodiment of the invention, two fragrance alcohols of the formula R 1 -OH released.

[0042] The fragrance(s) can be released from the described fragrance precursor compounds of formula (I) by hydrolysis, particularly at acidic pH values, ie pH values ​​< 7, for example < 6 or < 5.

[0043] The fragrance precursor compounds of formula (I) are obtained by a two-step reaction. In a first step, a compound of formula (II) reacted with a mercaptosilane.

[0044] For the compound of formula (II) R 2 and R 3 are independently selected from H, linear, branched or cyclic Ci-C25 alkyl, Ci-C25 alkenyl, Ci-C25 alkynyl, C1-C25 alkadienyl, Ci-C25 alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched Ci-C4 alkyl groups, or R 2 and R 3 including the carbon atoms to which R 2 and R 3 are bonded together to form a saturated or unsaturated ring having 6 to 20 carbon atoms, which ring may in turn be substituted by linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups and R 4 is selected from H and -CH3.

[0045] In various particularly preferred embodiments of the invention, the compound of formula (II) can be selected from the group consisting of a-ionone, ß-ionone, y-ionone, a-damascenone, ß-damascenone, y-damascenone, 5-damascenone, a-damascone, ß-damascone, y-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof.

[0046] It is further preferred that the mercaptosilane is selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyldiethoxymethylsilane, and mixtures thereof. The mercaptosilane is preferably selected from 3-mercaptopropyltriethoxysilane and 3-mercaptopropyldiethoxymethylsilane, with 3-mercaptopropyltriethoxysilane being preferred.

[0047] The reaction of the compound of formula (II) and the mercaptosilane preferably takes place in air or under a nitrogen atmosphere. The reaction can be carried out in bulk or in a suitable solvent. A suitable solvent is, for example, dichloromethane, tetrahydrofuran, or acetone. Preference is also given to using a non-nucleophilic base, for example 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, for example liquid-liquid extraction or column chromatography.

[0048] In a second step, the reaction product obtained in step 1 is reacted with a fragrance alcohol of the formula R 1 -OH, where R 1of the fragrance alcohol is a linear, branched or cyclic Ce-C25 alkyl, Ce-C25 alkenyl, Ce-C25 alkynyl, Ce-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted by Ci-C4 alkyl groups.

[0049] In a preferred embodiment, the fragrance alcohol of the formula R 1-OH ausgewählt aus der Gruppe bestehend aus 2-Phenylethylalkohol, 10-Undecen-1-ol., 2,6-Dimethylheptan-2-ol, 2- Methylbutanol, 2-Methylpentanol, 2-Phenoxyethanol, 2-Phenylpropanol, 2-tert-Butycyclohexanol, 3,5,5- Trimethylcyclohexanol, 3-Hexanol, 3-Methyl-5-phenylpentanol, 3-Octanol, 3-Phenylpropanol, 4- Heptenol, 4-lsopropylcyclohexanol, 4-tert-Butycyclohexanol, 6,8-Dimethyl-2-nonanol, 6-Nonen-1-ol, 9- Decen-1-ol, alpha-Methylbenzylalkohol, alpha-Terpineol, Benzylalkohol, beta-Terpineol, Citronellol, Decanol, Dihydromyrcenol, Dimethylbenzylcarbinol, Dimethylheptanol, Dimethyloctanol, Ethylvanilin, Eugenol, Geraniol, Heptanol, Isoborneol, Isoeugenol, Isopulegol, Linalool, Menthol, Myrtenol, n- Hexanol, Nerol, Nonanol, Octanol, para-Menthan-7-ol, Tetrahydrogeraniol, Tetrahydrolinalool, Thymol, trans-2-Nonen-1-ol, trans-2-Octenol, Undecanol, Vanillin, Zimtalkohol, cis-Hex-3-en-1-ol und Mischungen daraus.

[0050] In a preferred embodiment of the process, a compound of formula (II) selected from the group consisting of a-ionone, ß-ionone, y-ionone, a-damascenone, ß-damascenone, y-damascenone, 5-damascenone, a-damascone, ß-damascone, y-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof and a fragrance alcohol of formula R 1 -OH selected from the group consisting of 2-phenylethyl alcohol, citronellol, geraniol, cis-hex-3-en-1-ol and mixtures thereof.

[0051] In a preferred embodiment of the process, a compound of formula (II) is selected from the group consisting of a-ionone, ß-ionone, y-ionone, a-damascenone, ß-damascenone, y-damascenone, 5-damascenone, a-damascone, ß-damascone, y-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof and 2-phenylethyl alcohol as fragrance alcohol of formula R 1 -OH is used.

[0052] In a further preferred embodiment of the process, a compound of formula (II) is selected from the group consisting of a-ionone, ß-ionone, y-ionone, a-damascenone, ß-damascenone, y-damascenone, 5-damascenone, a-damascone, ß-damascone, y-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof and citronellol as fragrance alcohol of formula R 1 -OH is used.

[0053] In yet another preferred embodiment of the process, a compound of formula (II) is selected from the group consisting of a-ionone, ß-ionone, y-ionone, a-damascenone, ß-damascenone, y-damascenone, 5-damascenone, a-damascone, ß-damascone, y-damascone, 5-damascone, L-carvone, D-carvone and mixtures thereof and geraniol as fragrance alcohol of formula R 1-OH is used. In a likewise preferred embodiment of the process, a compound of formula (II) 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 and cis-hex-3-en-1-ol as fragrance alcohol of formula R 1 -OH is used.

[0054] Surprisingly, it has been shown that the mostly short-chain alkoxy groups of mercaptosilanes, especially the methoxy or ethoxy groups, can be easily replaced by alkoxy groups derived from fragrance alcohols of the formula R 1 -OH can be exchanged.

[0055] This leads to fragrance precursor compounds of formula (I) which are capable of releasing at least two different fragrances, in particular two different fragrance types.

[0056] The reaction of the reaction product obtained in step 1 with the fragrance alcohol R 1 -OH usually takes place in air. Furthermore, the reaction is preferably carried out without solvent. The fragrance alcohol R 1 -OH is used in excess and simultaneously serves as a solvent or reaction medium. A strong base, such as potassium hydroxide, is also preferably used. The reaction mixture of the reaction product obtained in step 1, the fragrance alcohol R 1 -OH and the base are then stirred at elevated temperature and / or under reduced pressure, preferably for several hours, preferably 2 to 60, in particular 10 to 48. The resulting reaction product is isolated and, if appropriate, purified by conventional methods.

[0057] 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.

[0058] 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 10 wt.%, in each case based on the total weight of the perfume composition.

[0059] 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.

[0060] 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).

[0061] 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.

[0062] 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,

[0063] 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.

[0064] It is particularly possible that the at least one fragrance precursor compound of the formula (I) is used with the corresponding α,β-unsaturated aldehydes and / or α,β-unsaturated ketones. According to a preferred embodiment, such compositions are characterized in that the molar ratio of fragrance aldehyde and / or fragrance ketone to the corresponding precursor compound of the 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. Likewise, the at least one fragrance precursor compound of the formula (I) can alternatively or additionally be used together with the fragrance alcohol R 1 -OH may be present.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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®, or the products from Evonik known under the name Rewoquat®. 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, color 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.

[0069] 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.

[0070] 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.

[0071] 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 of the invention, a washing and / or cleaning agent of the invention, or a cosmetic agent of 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. Examples

[0072] Example 1: Synthesis of a fragrance precursor compound of formula (I)

[0073] Step 1 : Reaction of a-Damascone with 3-Mercaptopropyltriethoxysilane

[0074] 3.69 g (15 mmol) of 3-mercaptopropyltriethoxysilane were placed in a flask and dissolved in 100 mL of acetone. Then, 2.88 g (15 mmol) of α-damascone were added, followed by 0.12 g of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) after stirring for 5 min. The reaction solution was stirred at room temperature for 46 hours and then completely concentrated in vacuo. The crude product was dissolved in 100 mL of acetone and treated with 8 spatulas of silica gel. The acetone was then removed in vacuo, and the residue was purified using CombiFlash Rf (80 g silica column, hexane / EtOAc 3:1). This gave 4.4 g of a pale yellow liquid product with 95% purity (NMR).

[0075] Step 2: Conversion of the reaction product from step 1 with 2-phenylethyl alcohol

[0076] 4.95 g (10.9 mmol) of the reaction product from step 1 (3-((3-(triethoxysilyl)propyl)thio)-1-damascone) were placed in a flask together with 4.04 g (32.7 mmol) of 2-phenylethyl alcohol and stirred. Then, 10 mg of finely ground KOH was added with stirring, and the reaction solution was heated to 110°C. After 1 h, the mixture was stirred under reduced pressure (approx. 150 mbar) for a further 5 h. The mixture was then heated at 110°C and stirred under reduced pressure (approx. 100 mbar) for a further 7 h. The mixture was then heated to 130°C and stirred under reduced pressure (approx. 100 mbar) for a further 5 h. The mixture was then cooled to room temperature. This yields 6.07 g of a yellowish, clear, slightly viscous product with a purity of 97% (NMR). Example 2: Smell tests

[0077] The fragrance release was investigated in a fabric softener, a liquid detergent and a powder detergent.

[0078] For this purpose, perfume-free formulations of the fabric softener, the liquid detergent and the powder detergent were mixed with the fragrance precursor compound prepared in Example 1 or with a mixture of equimolar amounts of the two fragrances a-damascone and 2-phenylethyl alcohol as follows and used in a washing / rinsing test in a washing machine.

[0079] Fabric softener i. 0.31 wt.% a-damascone + 0.59 wt.% 2-phenylethyl alcohol ii. 1.09 wt.% fragrance precursor compound according to the invention from Example 1

[0080] Liquid detergent i. 0.24 wt.% a-damascone + 0.46 wt.% 2-phenylethyl alcohol ii. 0.85 wt.% fragrance precursor compound according to the invention from Example 1

[0081] Powder detergent i. 0.14 wt.% a-damascone + 0.26 wt.% 2-phenylethyl alcohol ii. 0.49 wt.% fragrance precursor compound according to the invention from Example 1

[0082] Laundry treated with one of the six agents (cotton, polyester, half-linen) was removed from the washing machine, dried, and after 7 days, assessed olfactory intensity by a trained panel using an intensity scale of 1-6 (1: no odor perceptible; 6: very strong odor perceptible).

[0083] The following table shows the results of odor intensity on different fabrics: In formulations ii, i.e. when the fragrance precursor compound from Example 1 is used instead of a mixture of the two fragrances, a consistently higher odor intensity is observed.

[0084] Example 3:

[0085] Step 1 : Reaction of L-carvone with 3-mercaptopropyltriethoxysilane

[0086] 3.0 g (20 mmol) of L-carvone and 4.92 g (20 mmol) of 3-mercaptopropyltriethoxysilane were placed in a flask under a nitrogen atmosphere. 0.03 g (0.2 mmol) of DBU was added. The reaction solution was stirred at room temperature for 42 h. The reaction solution was then poured into 50 ml of cold HCl (5%) with stirring. The HCl phase was then extracted with 100 ml of diethyl ether. The organic phase was washed three times with 100 ml of water, once with 100 ml of saturated NaHCl solution, and once with 70 ml of saturated NaCl solution. The organic phase was then dried over MgSO, filtered, and completely concentrated in vacuo. This yielded 6.76 g of 3-((3-(triethoxysilyl)propyl)thio)-carvone (95% purity).

[0087] Step 2: Conversion of the reaction product from step 1 with cis-hex-3-en-1-ol

[0088]

[0089] 4.1 g (10 mmol) of 3-((3-(triethoxysilyl)propyl)thio)-carvone (95% purity) were initially charged with 4.1 g (40 mmol) of cis-hex-3-en-1-ol in a flask equipped with a distillation head and stirred. 9 mg of finely ground KOH was then added while stirring, and the reaction solution was heated to 110°C (heating block). Reduced pressure (approx. 150 mbar) was applied at 90-minute intervals until the distillate condensed in the distillation head. After a reaction time of 7 h, the reaction solution was cooled to room temperature. Excess cis-hex-3-en-1-ol was removed from the reaction solution using a rotary evaporator (75°C, 5 mbar) and a Kugelrohr distillation (50°C, 0.04 mbar). 4.61 g of product with a purity of 85% was obtained.

[0090] Example 4:

[0091] Step 1 : Reaction of a-Damascone with 3-Mercaptopropyltriethoxysilane

[0092] 3.85 g (20 mmol) of α-damascone and 4.92 g (20 mmol) of 3-mercaptopropyltriethoxysilane were placed in a flask under a nitrogen atmosphere. 0.03 g (0.2 mmol) of DBU was added to this reaction mixture. The reaction solution was stirred at room temperature for 24 h and then poured into 50 ml of cold HCl (5%) while stirring. The HCl phase was then extracted with 100 ml of diethyl ether. The organic phase was washed three times with 100 ml of water, once with 100 ml of saturated NaHCl solution, and once with 70 ml of saturated NaCl solution. The organic phase was then dried over MgSO, filtered, and completely concentrated in vacuo. This yielded 7.78 g of the product 3-((3-(triethoxysilyl)propyl)thio)-1-damascone (90% purity).

[0093] Step 2, the reaction of 3-((3-(triethoxysilyl)propyl)thio)-1-damascone with phenylethyl alcohol, was carried out as described in step 2 of Example 1.

Claims

Patent claims 1 . Fragrance precursor compound of formula (I) where R 1 is selected from H, linear or branched Ci-Cs-alkyl groups, linear, branched or cyclic Ce-C25-alkyl, Ce-C25-alkenyl, Ce-C25-alkynyl, Ce-C25-alkadienyl, C6-C25-alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4-alkyl groups, wherein at least one R 1 a linear, branched or cyclic Ce-C25 alkyl, Ce-C25 alkenyl, Ce-C25 alkynyl, Ce-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted by Ci-C4 alkyl groups, R 2 and R 3are independently selected from H, linear, branched or cyclic C1-C25 alkyl, C1-C25 alkenyl, C1-C25 alkynyl, C1-C25 alkadienyl, C1-C25 alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4 alkyl groups or R 2 and R 3 including the carbon atoms to which R 2 and R 3 are bonded together to form a saturated or unsaturated ring having 6 to 20 carbon atoms, which ring may in turn be substituted by linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups, R 4 is selected from H and -CH3 and R 5 is selected from -OR 1 and -CH3.

2. Fragrance precursor compound according to claim 1, characterized in that R 2 or R 3 of type is, the other residue R 2 or R 3 -CH3 and R 4 H is.

3. Fragrance precursor compound according to claim 1, characterized in that R 2 and R 3 a ring of the guy form and R 4 -CH3.

4. Fragrance precursor compound according to one of claims 1 to 3, characterized in that at least one R 1 from a fragrance alcohol of formula R 1 -OH.

5. Fragrance precursor compound according to claim 4, characterized in that the fragrance alcohol of the formula R 1 -OH is selected from the group consisting of 2-phenylethanol, 2-phenylethyl alcohol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert- Butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl pentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butycyclohexanol, 6,8-dimethyl-2-nonanol, 6-Nonen-1-ol, 9-Decen-1-ol, alpha-methylbenzyl alcohol, alpha-terpineol, benzyl alcohol, beta-terpineol, citronellol, decanol, dihydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethylvaniline, eugenol, geraniol, heptanol, isoborneol, Isoeugenol, Isopulegol, Linalool, Menthol, Myrtenol, n-Hexanol, nerol, nonanol, octanol, para-menthan-7-ol, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-nonen-1-ol, trans-2-octenol, undecanol, vanillin, cinnamyl alcohol, cis-hex-3-en-1-ol and mixtures thereof.

6. Process for the preparation of a fragrance precursor compound of formula (I) where R 1is selected from H, linear or branched Ci-Cs-alkyl groups, linear, branched or cyclic Ce-C25-alkyl, Ce-C25-alkenyl, Ce-C25-alkynyl, Ce-C25-alkadienyl, C6-C25-alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4-alkyl groups, wherein at least one R 1 a linear, branched or cyclic Ce-C25 alkyl, Ce-C25 alkenyl, Ce-C25 alkynyl, Ce-C25 alkadienyl, C6-C25 Alkatrienyl group or aromatic group, which in turn may be substituted by Ci-C4 alkyl groups, R 2 and R 3 are independently selected from H, linear, branched or cyclic C1-C25 alkyl, C1-C25 alkenyl, C1-C25 alkynyl, C1-C25 alkadienyl, C1-C25 alkatrienyl groups or aromatic groups, each of which may be substituted by linear or branched C1-C4 alkyl groups or R 2 and R 3including the carbon atoms to which R 2 and R 3 are bonded, form a saturated or unsaturated ring with 6 to 20 carbon atoms, which ring may in turn be substituted by linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups and R 4 is selected from H and -CH3 and R 5 is selected from -OR 1 and -CH3, characterized in that in a first step a compound of formula (II) is reacted with a mercaptosilane and in a second step the reaction product from the first step is reacted with a fragrance alcohol of the formula R 1 -OH, where R 1 of the fragrance alcohol is a linear, branched or cyclic Ce-C25 alkyl, Ce-C25 alkenyl, Ce-C25 alkynyl, C6-C25 alkadienyl, C6-C25 alkatrienyl group or aromatic group, which in turn may be substituted by C1-C4 alkyl groups.

7. The process according to claim 6, characterized in that the mercaptosilane is selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane and mixtures thereof.

8. The process according to claim 6 or 7, characterized in that the compound of formula (II) 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.

9. A process according to any one of claims 6 to 8, characterized in that the fragrance alcohol of the formula R 1 -OH is selected from the group consisting of 2-phenylethyl alcohol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2- Methylpentanol, 2-Phenoxyethanol, 2-Phenylpropanol, 2-tert-Butycyclohexanol, 3,5,5- Trimethylcyclohexanol, 3-Hexanol, 3-Methyl-5-phenyl pentanol, 3-Octanol, 3-Phenylpropanol, 4-Heptenol, 4-lsopropyl cyclohexanol, 4-tert-Butycyclohexanol, 6,8-Dimethyl-2-nonanol, 6- Nonen-1-ol, 9-Decen-1-ol, alpha-Methylbenzylalkohol, alpha-Terpineol, Benzylalkohol, beta- Terpineol, Citronellol, Decanol, Dihydromyrcenol, Dimethylbenzylcarbinol, Dimethylheptanol, Dimethyloctanol, Ethylvanilin, Eugenol, Geraniol, Heptanol, Isoborneol, Isoeugenol, Isopulegol, Linalool, Menthol, Myrtenol, n-Hexanol, Nerol, Nonanol, Octanol, para-Menthan-7- ol, Tetrahydrogeraniol, Tetrahydrolinalool, Thymol, trans-2-Nonen-1-ol, trans-2-Octenol, Undecanol, Vanillin, Zimtalkohol, cis-Hex-3-en-1-ol und Mischungen daraus.

10. 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.

11. 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.

12. 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 present in a total amount of 0.001 to 5% by weight, advantageously of 0.005 to 3% by weight, more advantageously of 0.01 to 1% by weight, based on the total weight of the agent.

13. 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 a composition according to claim 10, 11 or 12 is applied to the surface to be scented, the perfuming lasting longer than if the respective fragrance compound(s) or an identical composition in which the fragrance precursor compound(s) are replaced by the respective fragrance compound(s) is / are replaced.

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