Amine-based fragrance precursor compound ii

Abstract

The present invention relates to specific amine-based fragrance precursor compounds of formula (I), which are derived from aminosilanes and selected fragrances, and to a process for their preparation. The present invention further relates to washing or cleaning agents, cosmetic agents, and a perfume composition which contain such fragrance precursor compounds. Furthermore, the present invention relates to a method for the long-lasting fragrancing of surfaces using the fragrance precursor compounds and agents according to the invention.

Description

[0001] Henkel AG & Co. KGaA

[0002] 2025P00108WO

[0003] AMINE-BASED FRAGRANCE COMPOUND II

[0004] The present invention relates to specific amine-based fragrance precursor compounds of formula (I) derived from aminosilanes and selected fragrances, and to a process for their preparation. The present invention further 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.

[0005] Washing and / or cleaning products or 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.

[0006] 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; the desired longevity of the scent is hardly achievable.

[0007] 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.

[0008] The object of the present invention was to provide fragrance precursor compounds that can be obtained by simple synthesis and that preferably 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 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 aminosilanes and selected fragrances.

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

[0010]

[0011] where

[0012] R 1 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 with 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 with Ci-C4 alkyl groups, is

[0013] R 2 and R 3 are independently selected from H, linear, branched or cyclic C1-C25 alkyl, Ci-C25 alkenyl, Ci-C25 alkynyl, Ci-C25 alkadienyl, Ci-C25 alkatrienyl groups or aromatic groups, each of which may be substituted with linear or branched Ci-C4 alkyl groups or R 2and R 3 including the carbon atoms to which R 2 and R 3 are bonded together to form a saturated or unsaturated ring with 6 to 20 carbon atoms, this ring in turn being substituted with linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups,

[0014] R 4 selected from H and -CH3 and

[0015] R 5 selected is from -OR 1 and -CH3.

[0016] In a second aspect, the present invention relates to a method for producing a fragrance precursor compound of formula (I).

[0017] In a third aspect, the present invention relates to a perfume composition containing at least one fragrance precursor compound of the present invention.

[0018] 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.

[0019] In a fifth aspect, the present invention relates to a cosmetic composition containing at least one fragrance precursor compound of the present invention. 2025P00108WG

[0020] 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.

[0021] These and further embodiments, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the following detailed description and claims. Individual described features or embodiments of the invention can 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 do not limit it, and in particular, the invention is not limited to these examples.

[0022] “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.

[0023] Unless otherwise stated, all quantities specified in connection with the process described herein are expressed as a percentage 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, quantities relating to "at least one fragrance precursor compound" refer to the total quantity of fragrance precursor compounds contained in the composition, unless explicitly stated otherwise.

[0024] Numerical values ​​given herein without decimal places refer to the full value given with one decimal place. For example, "99%" means "99.0%".

[0025] 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.

[0026] “Substituted,” as used herein in connection with the definition of the fragrance precursor compounds of formula (I) and the compound of formula (II), means that a hydrogen atom is replaced by another residue. Suitable residues are Ci-C4 alkyl groups.

[0027] 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.

[0028] The present invention relates in particular to fragrance precursor compounds of formula (I)

[0029]

[0030] where

[0031] R 1selected 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 with 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 with Ci-C4 alkyl groups, is

[0032] R 2 and R 3 are independently selected from H, linear, branched or cyclic C1-C25 alkyl, Ci-C25 alkenyl, Ci-C25 alkynyl, Ci-C25 alkadienyl, Ci-C25 alkatrienyl groups or aromatic groups, each of which may be substituted with linear or branched Ci-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 with 6 to 20 carbon atoms, this ring in turn being substituted with linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups,

[0033] R 4 selected from H and -CH3 and

[0034] R 5 selected is from -OR 1 and -CH3.2025P00108WÖ

[0035] 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. Specifically, a fragrance precursor compound of formula (I) can release a fragrance of the type of α,β-unsaturated ketones or α,β-unsaturated aldehydes and at least one fragrance alcohol.

[0036] In a preferred embodiment of the fragrance precursor compound of formula (I), R 2 or R 3 of type

[0037]

[0038] and the other remainder R 2 or R 3 is -CH3 and R 4 is H.

[0039] Fragrance precursor compound of formula (I) with these substituents for R 2 , R 3 and R 4 They release ionones, damascenones, and / or damascone. Ionones, damascenones, 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 economic interest as fragrances.

[0040] In another preferred embodiment, R forms in the fragrance precursor compound of formula (I) 2 and R 3 a ring of the type

[0041]

[0042] and R 4 is -CH3.

[0043] Fragrance precursor compound of formula (I) with these substituents for R 2 , R 3 and R 4 They release carvone. Both enantiomers of carvone are components of various essential oils.

[0044] It is also preferred that R 1 from a fragrance alcohol of formula R 1 -OH is derived.

[0045] R 1 The fragrance alcohol consists of 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 may in turn be substituted with Ci-C4 alkyl groups. 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.

[0046] 2-Phenylethanol smells like roses and is advantageously used together with at least one of the rose ketones in the fragrance precursor compounds of formula (I).

[0047] The fragrance alcohol of formula R is also 1 -OH particularly advantageously selected from the group consisting of citronellol, geraniol, cis-hex-3-en-1-ol and mixtures thereof.

[0048] In a preferred embodiment, at least two 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 with Ci-C4 alkyl groups. The at least two R 1 can be the same or different, with at least two R 1 preferably be the same.

[0049] In this embodiment of the invention, two fragrance alcohols of formula R are used for each fragrance precursor compound of formula (I).1 -OH released.

[0050] In another preferred embodiment, R 5 -OR 1 and all R 1 are 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. The three R 1 can be the same or different, whereby the three R 1 preferably be the same.

[0051] In this embodiment of the invention, two fragrance alcohols of formula R are used for each fragrance precursor compound of formula (I). 1 -OH released.

[0052] The fragrance(s) can be released from the described fragrance precursor compounds of formula (I) by hydrolysis, especially at acidic pH values, i.e. pH values ​​< 7, for example < 6 or < 5.2025P00108WG

[0053] The fragrance precursor compounds of formula (I) are obtained by a two-step reaction. In a first step, a compound of formula (II) is formed.

[0054]

[0055] reacted with an aminosilane.

[0056] For the combination of formula (II), it holds that 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 with linear or branched Ci-C4 alkyl groups, or R 2 and R 3 including the carbon atoms to which R 2 and R 3are bonded together, forming a saturated or unsaturated ring with 6 to 20 carbon atoms, this ring in turn being substituted with linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups and R 4 The selection is from H and -CH3.

[0057] In various particularly preferred embodiments of the invention, the compound of formula (II) can be 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.

[0058] It is further preferred that the aminosilane be selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, and mixtures thereof. Preferably, the aminosilane is selected from 3-aminopropyltriethoxysilane and 3-aminopropyldiethoxymethylsilane, with 3-aminopropyltriethoxysilane being preferred.

[0059] The reaction of the compound of formula (II) and the aminosilane preferably takes place in air or under a nitrogen atmosphere. The reaction can be carried out in the substance or in a suitable solvent. A suitable solvent is, for example, dichloromethane, tetrahydrofuran, or acetone. The reaction mixture of the reactants and the solvent is then preferably stirred at room temperature for several hours, preferably 2 to 60, particularly 12 to 48. The resulting reaction product is isolated and optionally purified by conventional methods, such as liquid-liquid extraction, distillation, or column chromatography.

[0060] In a second step, the reaction product obtained in step 1 is combined with a fragrance alcohol of formula R 1 -OH implemented, where R 1The 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.

[0061] In a preferred embodiment, the fragrance alcohol of 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.

[0062] In a preferred embodiment of the method, a compound of formula (II) 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, 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.

[0063] In a preferred embodiment of the process, a compound of formula (II) 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, and 2-phenylethyl alcohol as a fragrance alcohol of formula R. 1 -OH used.

[0064] In a further preferred embodiment of the method, a compound of formula (II) is selected in the method 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, and citronellol as a fragrance alcohol of formula R. 1 -OH used.

[0065] In yet another preferred embodiment of the method, a compound of formula (II) 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-2025P00108WG

[0066] Damascone, 5-Damascone, L-Carvone, D-Carvone and mixtures thereof, and geraniol as a fragrance alcohol of formula R 1 -OH used.

[0067] In a further preferred embodiment of the method, a compound of formula (II) 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, and cis-hex-3-en-1-ol as a fragrance alcohol of formula R. 1 -OH used.

[0068] Surprisingly, it has been shown that the mostly short-chain alkoxy groups of aminosilanes, especially the methoxy or ethoxy groups, can be readily replaced by alkoxy groups that differ from fragrance alcohols of the formula R. 1 -OH can be derived and exchanged.

[0069] This leads to fragrance precursor compounds of formula (I) which are able to release at least two different fragrances, in particular two different fragrance types.

[0070] The reaction product obtained in step 1 with the fragrance alcohol R 1 The -OH reaction typically takes place in air. Furthermore, the reaction is preferably carried out without solvents. The fragrance alcohol R is preferably used. 1 -OH is used in excess and simultaneously serves as a solvent or reaction medium. A strong base, for example potassium hydroxide, is also preferably used. The reaction mixture consists of the reaction product obtained in step 1, the fragrance alcohol R. 1 The OH and the base are then preferably stirred for several hours, preferably 2 to 60, particularly 10 to 48, at elevated temperature and / or under reduced pressure. The resulting reaction product is isolated and, if necessary, purified by conventional methods.

[0071] The reaction product can comprise not only the fragrance precursor compounds of the present invention, i.e., fragrance precursor compounds of formula (I), but also oligomeric fragrance precursor compounds. These oligomeric fragrance precursor compounds are derived from oligomeric aminosilanes as starting materials.

[0072] 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.

[0073] In a preferred embodiment, the at least one fragrance precursor compound is contained in a total amount of 0.01 to 20 wt.%, advantageously 0.1 to 15 wt.%, and particularly preferably 0.5 to 10 wt.%, in each case based on the total weight of the perfume composition. In preferred embodiments, the at least one fragrance precursor compound is contained 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.

[0074] 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).

[0075] 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-te / Y-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 like limonene and pinene. However, mixtures of various fragrances are preferred, as they combine to create an appealing scent.

[0076] 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, olibanum 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, pine needle oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, musk seed oil, myrrh oil, 2025P00108WÖ.

[0077] 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, anisyl alcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, 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, heptinecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol,Indole, Iran, Isoeugenol, Isoeugenol methyl ether, Isosafrole, Jasmon, Camphor, Carvacrol, Karvone, 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-Oxy-acetophenone, Pentadecanolide, β-Phenylethyl alcohol, Phenylacetic acid, Pulegone, Safrole, Isoamyl salicylic acid ester, Methyl salicylic acid ester, Hexyl salicylic acid ester salicylic acid cyclohexyl ester, santalol, sandelice, skatole, terpineol, thymene, thymol, troenane, γ-undelactone, vanillin, veratraldehyde, cinnamaldehyde, cinnamal 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, citralCitronellal and mixtures thereof.

[0078] 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. 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 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 particularly 1.2:1 to 1:1.2. Likewise, the at least one fragrance precursor compound of formula (I) can alternatively or additionally be combined with the fragrance alcohol R. 1 -OH are present.

[0079] 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.

[0080] Washing and cleaning agents may, in addition to at least one fragrance precursor compound of formula (I), also contain in particular anionic, non-ionic, cationic, amphoteric or zwitterionic 2025P00108WQ

[0081] They contain surfactants or mixtures thereof. Furthermore, these substances can be in solid or liquid form.

[0082] Suitable non-ionic 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.

[0083] 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 part, as well as of alkylphenols with 5 to 12 C atoms in the alkyl group, are suitable.

[0084] 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.

[0085] Cationic surfactants are preferably classified as esterquats and / or 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 IV The μ represents identical or different Ci-22 alkyl groups, C7-28 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 μ represents halide ions, sulfate ions, hydroxide ions, or similar anions. QAVs are formed by the reaction of tertiary amines with alkylating agents, such as...

[0086] Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, and even ethylene oxide can be synthesized. The alkylation of tertiary amines with one long alkyl group and two methyl groups is particularly straightforward; 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 with three long alkyl groups or hydroxy-substituted alkyl groups are less reactive and are quaternized, for example, with dimethyl sulfate.Examples of QACs in question are 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 2025P00108WQ.

[0087] Thiazoline iodide and mixtures thereof. Preferred QAVs are the benzalkonium chlorides with C8-C22 alkyl groups, in particular Ci2-Ci4-alkylbenzyldimethylammonium chloride.

[0088] 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 of BASF SE known under the trade name Dehyquart®, and the products of Evonik known under the name Rewoquat®.

[0089] 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.

[0090] 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.

[0091] The quantities of the individual ingredients in the washing and / or cleaning agents as well as in the cosmetic products are determined by the intended use of the respective product, and those skilled in the art are 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. The statements made regarding the fragrance precursor compound of formula (I), the perfume composition, the washing and / or cleaning agent, and the cosmetic product 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 product according to the invention is applied to the surface to be scented.The scent lasts longer than if the respective fragrance compound or an identical product in which the fragrance precursor compound is replaced by the respective fragrance compound(s) were used. Examples.

[0092] Example 1: Synthesis of a fragrance precursor compound of formula (I)

[0093] Step 1: Reaction of α-Damascone with 3-Aminopropyltriethoxysilane

[0094]

[0095] 3.85 g (20 mmol) of alpha-damascone were dissolved in 20 ml of THF and placed in a flask under a nitrogen atmosphere. 6.78 g (30 mmol) of 3-aminopropyltriethoxysilane were added. The reaction solution was stirred for 47 hours at room temperature. The solution was then concentrated completely under vacuum, and the resulting yellow liquid residue was purified by bulb distillation (0.1–0.08 mbar & 50–95 °C). 5.85 g of a pale yellow liquid product with 90% purity (NMR) was obtained.

[0096] Step 2: Reaction of the product from step 1 with 2-phenylethyl alcohol

[0097] 2.76 g (6 mmol) of 3-((3-(triethoxysilyl)propyl)amino)-1-damascone (90% purity) from step 1 were placed in a flask together with 2.22 g (18 mmol) of 2-phenylethyl alcohol and stirred. Then, 5.4 mg of finely ground KOH was added while stirring, the reaction solution was heated to 110°C, and stirred under reduced pressure (approx. 150 mbar) for 12 h. The mixture was then cooled to room temperature. 2.91 g of a yellowish, clear, slightly viscous product was obtained.

[0098] The 29 Si NMR shows that 9.4 wt% of the Si atoms are present according to formula (I).

Claims

Patent claims 1. Fragrance precursor compound of formula (I) (I), where R 1 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 with 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 with Ci-C4 alkyl groups, is R 2 and R 3are independently selected from H, linear, branched or cyclic Ci-C25-alkyl, Ci-C25-alkenyl, Ci-C25-alkynyl, Ci-C25-alkadienyl, C1-C25-alkatrienyl groups or aromatic groups, each of which may be substituted with 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, forming a saturated or unsaturated ring with 6 to 20 carbon atoms, this ring in turn being substituted with linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups, R 4 selected from H and -CH3 and R 5 selected is from -OR 1 and -CH3.

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

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

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 is derived.

5. Fragrance precursor compound according to claim 4, characterized in that the fragrance alcohol of formula R 1-OH ausgewählt ist aus der Gruppe bestehend aus 2- Phenylethanol 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-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.

6. Method for the preparation of a fragrance precursor compound of formula (I) where R 1 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 with 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 with Ci-C4-alkyl groups, is R 2 and R 3are independently selected from H, linear, branched or cyclic Ci-C25-alkyl, Ci-C25-alkenyl, Ci-C25-alkynyl, Ci-C25-alkadienyl, C1-C25-alkatrienyl groups or aromatic groups, each of which may be substituted with 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, forming a saturated or unsaturated ring with 6 to 20 carbon atoms, this ring in turn being substituted with linear or branched Ci-C4 alkyl or Ci-C4 alkenyl groups and R 4 selected from H and -CH3 and R 5 selected is from -OR 1 and -CH3 characterized by the fact that in a first step a connection of formula (II) is reacted with an aminosilane and In a second step, the reaction product from the first step is combined with a fragrance alcohol of formula R. 1 -OH is implemented, where R 1 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 with C1-C4-alkyl groups.

7. Method according to claim 6, characterized in that the aminosilane is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane and mixtures thereof.

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

9. Method according to one of claims 6 to 8, characterized in that the fragrance alcohol of formula R 1-OH ausgewählt wird 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-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. 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.

11. Cosmetic 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 0.001 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 composition.

12. 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.

13. 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 10, 11 or 12 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.

Images