Perfuming ingredient with lily of the valley scent

Abstract

The present invention mainly relates to the use of 3-(4-isobutyl-2-methyl-cyclohexyl) propanal, 3-(4-isobutyl-6-methyl-cyclohexyl-1,5-diene-1-yl) propanal, 3-(4-isobutyl-6-methylene-cyclohexene-1-yl) propanal or 3-(4-isobutyl-6-methyl-cyclohexene-1-yl) propanal as a flavoring ingredient. In addition, the present invention relates to a fragrance composition comprising the aforementioned flavoring ingredients and a scented product. More particularly, the present invention relates to a method for producing the scented product and a method for imparting and / or increasing i) floral and / or ii) green and / or iii) lily of the valley odor characteristics to the scented product. The present invention also relates to 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexane-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal or 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal and a method for preparing the compounds.

Description

Technical Field

[0001] The present invention mainly relates to the use of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal or 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal as a perfuming ingredient. In addition, the present invention relates to a fragrance composition and a scented product comprising the aforementioned perfuming ingredients. More particularly, the present invention relates to a method for producing the scented product and a method for imparting and / or increasing i) floral and / or ii) green and / or iii) lily of the valley odor characteristics to a scented product. The present invention also relates to 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal, or 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal and a method for preparing the compounds. Background Art

[0002] Compounds with floral odors are indispensable components in the perfume industry and in the production of cosmetics, body care products, and cleaning products. A particularly valuable class of these floral fragrances are compounds with the odor of lily of the valley.

[0003] Some representatives of this class of perfuming ingredients have a structure comprising 4-alkyl-phenylpropionaldehyde as backbone structure, for example 3-(4-tert-butylphenyl)-2-methylpropionaldehyde (other name: Lilial), 3-(4-tert-butylphenyl)propionaldehyde (other name: Bourgeonal), 3-(4-isopropylphenyl)-2-methylpropionaldehyde (Cyclamal), 3-(3-isopropylphenyl)-butyraldehyde (other name: Florhydral) and 3-(4-isobutyl-2-methylphenyl)propionaldehyde.

[0004] For example, WO 2014 / 180945 A1 discloses the use of 3-(4-isobutyl-2-methylphenyl)propanal as a perfuming ingredient.

[0005] 3-(4-tert-butylphenyl)-2-methylpropanal has long been one of the most important industrial perfumes with floral compositions with the smell of lily of the valley, and is used in large quantities in the cosmetics and soap industries. However, the results of animal tests indicate that 3-(4-tert-butylphenyl)-2-methylpropanal may be reproductively toxic. In addition, it was found that the compound may be an allergen and may cause contact dermatitis in sensitive people.

[0006] Studies have shown that 3-(4-tert-butylphenyl)-2-methylpropanal is enzymatically degraded in rats and dogs to tert-butylbenzoic acid (t-BBA), which is known to inhibit glucose synthesis and fatty acid synthesis in vitro (McCune et al., Arch Biochem Biophys (1982) 214(1): 124-133). Tert-butylbenzoic acid is also known to cause testicular effects in male rats (Hunter et al., Food Cosmet. Toxicol. 1965, 3: 289-298; Cagen et al., J. Am. Coll. Toxicol. 1989, 8(5): 1027-1038).

[0007] Despite the large number of perfuming ingredients already available, there is still a general demand in the perfumery industry for new perfuming ingredients with floral notes, in particular lily of the valley. Summary of the invention

[0008] The main problem to be solved by the present invention is to provide a perfuming ingredient with a floral scent, in particular a lily of the valley scent. The perfuming ingredient should impart an odor impression that is largely similar to the complexity of the natural odor of the lily of the valley.

[0009] Therefore, these perfuming ingredients should preferably meet one, several or preferably all of the following requirements:

[0010] - easy to obtain,

[0011] - high efficiency at low concentrations, preferably with an inherent odor that is undetectable or barely detectable at low concentrations,

[0012] - completely or largely colorless,

[0013] - high stability in the various mixtures or preparations, wherein in particular no discoloration and / or separation and / or turbidity occurs,

[0014] - lazy behavior,

[0015] - No toxicity and / or sensitization to humans.

[0016] Furthermore, for the present invention, particularly novel, advantageous perfume compositions comprising such perfuming ingredients should be provided. Such perfume compositions are preferably suitable for perfumes or certain perfume products.

[0017] In addition, corresponding fragrance-emitting products and methods for producing such products should also be provided.

[0018] The main object of the present invention is solved by using a compound selected from the group consisting of 3-(4-isobutyl-2-methyl-cyclohexyl)propionaldehyde, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propionaldehyde, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propionaldehyde and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propionaldehyde as a perfuming ingredient.

[0019] Surprisingly, it was found that the odor impression imparted by 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal is very close to the complexity of the natural odor of lily of the valley. In other words, the odor impression imparted by these compounds is characterized by outstanding naturalness and complexity, especially with respect to the odor of lily of the valley. Such a complex odor impression, which is largely similar to the natural odor of lily of the valley, has not been achieved before with fragrances with a lily of the valley odor known from the prior art.

[0020] The search for a suitable substance having the odor of lily of the valley was hampered by the following circumstances, which led to the present invention:

[0021] -The mechanisms of odor perception are not fully understood;

[0022] - The relationship between the perception of specific odors on the one hand and the chemical structure of the relevant fragrances on the other hand has not been fully studied and does not give the ability to predict the odor properties of molecules;

[0023] -Even slight changes in the structural composition of known flavors often lead to drastic changes in the organoleptic properties and impair the compatibility of the compound with the human body.

[0024] Therefore, the success of the search for the right spice depends largely on the intuition of the person doing the search.

[0025] Furthermore, no evidence was found that 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal or 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal are toxic and / or show sensitization effects in humans. Since this compound is not aromatic (from an organic chemistry point of view), enzymatic degradation to tert-butylbenzoic acid (t-BBA) or other benzoic acids is not possible.

[0026] Further aspects of the invention can be seen from the following description, the examples, the drawings and the appended patent claims.

[0027] In the present context, a perfuming ingredient is any substance which is suitable for producing an olfactory impression, ie for imparting an olfactory impression, or for modifying (changing or intensifying) the olfactory perception of another substance.

[0028] 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal are compounds of formula (I)

[0029] in

[0030] a) All dashed bonds represent single bonds, R is CH3(3-(4-isobutyl-2-methyl-cyclohexyl)propanal),

[0031] b) The dotted bonds between C1 and C6 and between C2 and C3 are all double bonds, and the remaining dotted bonds represent single bonds. R is CH3 (3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl) propanal),

[0032] c) The dotted bonds between C1 and C6 and between C2 and R are double bonds, and the remaining dotted bonds represent single bonds. R is CH2 (3-(4-isobutyl-6-methylene-cyclohexen-1-yl) propanal).

[0033] or

[0034] d) The dotted bond between C1 and C2 is a double bond, the remaining dotted bonds represent single bonds, and R is CH3 (3-(4-isobutyl-6-methyl-cyclohexen-1-yl) propanal). It can be seen from the general formula (I) that all these compounds have an important structural element and belong to the same class of compounds.

[0035] 3-(4-isobutyl-2-methyl-cyclohexyl)propanal is a compound of the following formula (A):

[0036] 3-(4-isobutyl-2-methyl-cyclohexyl)propanal is another aspect of the present invention. 3-(4-isobutyl-2-methyl-cyclohexyl)propanal has three stereocenters, giving eight possible stereoisomers (A1 to A9) shown below. 3-(4-isobutyl-2-methyl-cyclohexyl)propanal can be used as a mixture of all or several stereoisomers (A1 to A9), or stereoisomers A1 to A9 can be used individually.

[0037]

[0038] 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal is a compound of the following formula (B):

[0039] 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal is another aspect of the present invention. 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal has one stereocenter, giving two possible enantiomers (B1 to B2) shown below. 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal can be used as a racemic mixture or as a mixture of two enantiomers.

[0040]

[0041] 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal is a mixture of the following formula (C):

[0042] 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal is another aspect of the present invention. 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal has one stereocenter, giving two possible enantiomers (C1 and C2) shown below. 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal can be used as a racemic mixture or as a mixture of two enantiomers.

[0043]

[0044] 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal is a compound of the following formula (D):

[0045] 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal is another aspect of the present invention. 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal has two stereocenters, giving four possible stereoisomers (D1 to D4) (diastereomers) shown below. 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal can be used as all or a mixture of several stereoisomers (D1 to D4).

[0046]

[0047] The present invention also relates to a compound selected from the group consisting of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal.

[0048] The use according to the invention is preferred, wherein the perfuming ingredient has i) floral and / or ii) green and / or iii) lily of the valley odor notes. The use according to the invention is preferred, wherein the perfuming ingredient has a further sweet or creamy odor note.

[0049] According to the foregoing, another aspect of the present invention particularly relates to a fragrance composition, which comprises at least one compound selected from the group consisting of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal.

[0050] The fragrance composition according to the invention is generally liquid at 25° C. and 1013 hPa and is generally a homogeneous solution.

[0051] Perfume compositions usually comprise a synthetic or natural (preferably) taste and odor neutral carrier oil containing odor or fragrance substances (as artificial or natural substances) in highly concentrated form (and aromatic solvents and / or auxiliary materials, if applicable). The same applies correspondingly to the perfume compositions according to the invention described herein.

[0052] Preferably, the fragrance composition according to the invention comprises one or more additional fragrance ingredients.

[0053] Examples of generally preferred fragrance ingredients that can be used as components of the fragrance composition according to the invention can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969, author's edition or H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 5th Ed., Wiley-VCH, Weinheim 2006.

[0054] The preferred essential oils, concentrates, absolutes, resins, balms, balsams and / or tinctures which can be the aroma component of the fragrance composition according to the invention are preferably selected from the group consisting of:

[0055] Ambergris tincture; sandalwood oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; moss absolute; bay oil; wormwood oil; benzoin resin; bergamot oil; beeswax absolute; birch tar; bitter almond oil; savory oil; cheek leaf oil; Brazilian sandalwood oil; juniper oil; calamus oil; camphor oil; vetiver oil; cardamom oil; quinoa oil; cinnamon oil; cinnamon absolute; castoreum absolute; cedar leaf oil; cypress oil; labdanum oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress essential oil; davana oil; dill Oil; Dill Seed Oil; Buchu Absolute; Oakmoss Absolute; Elemi Resin Oil; Tarragon Oil; Lemon Eucalyptus Oil; Eucalyptus Oil; Anise Oil; Fir Oil; Grenache Oil; Grenache Resin; Geranium Oil; Grapefruit Oil; Guaiac Wood Oil; Guar Balsam; Guar Balsam Oil; Helichrysum Absolute; Helichrysum Oil; Ginger Oil; Iris Root Absolute; Iris Root Oil; Jasmine Absolute; Calamus Oil; Blue Chamomile Oil; Roman Chamomile Oil; Carrot Seed Oil; Quinoa Oil; Pine Needle Oil; Spearmint Oil; Caraway Oil; Labdanum Oil; Labdanum Absolute; Labdanum Resin; Lavandula Absolute; Lavandula Oil; Lavender absolute; lavender oil; lemongrass oil; angelica oil; distilled lime oil; pressed lime oil; agarwood oil; litsea cubeba oil; bay leaf oil; nutmeg oil; oregano oil; orange oil; cassia bark oil; mimosa absolute; ambrette oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; frankincense absolute; frankincense oil; myrrh oil; orange flower absolute; orange oil; oregano oil; palmarosa essential oil; patchouli oil; perilla seed oil; Peruvian balsam oil; parsley leaf oil; parsley seed oil; orange leaf oil; pepper Peppermint oil; peppermint oil; allspice oil; pine oil; mint oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; Japanese star anise oil; styrax oil; marigold oil; fir oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla essence; violet leaf absolute; verbena oil; vetiver oil; juniper oil; lees oil; wormwood oil; wintergreen oil; ylang-ylang oil; hyssop oil; musk oil; cinnamon leaf oil; cinnamon bark oil.

[0056] Preferably single aroma substances which can be preferably used as aroma ingredients of the aroma composition according to the invention are selected from the group consisting of:

[0057] Hydrocarbons, preferably 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; afarnesene; limonene; longifolene; myrcene; ocimene; valenene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0058] Aliphatic alcohols, preferably hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexanol; (E) and (Z)-3-hexanol; 1-octen-3-ol; a mixture of 3,4,5,6,6-pentamethyl-3 / 4-heptan-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecanol; 4-methyl-3-decen-5-ol; 1-octen-3-ol;

[0059] Aliphatic aldehydes and acetals thereof, preferably hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptanal, 10-undecanal, (E)-4-decenal, 2-dodecenal, 2,6,10-trimethyl-9-undecenal, 2,6,10-trimethyl-5,9-undecadienal; heptaldehyde diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyl acetaldehyde ether; 1-(1-methoxy-propoxy)-(E / Z)-3-hexene;

[0060] Aliphatic ketones and their oximes, preferably 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;

[0061] Aliphatic sulfur-containing compounds, preferably 3-methylthiohexanol; 3-trimethylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acylthiohexyl acetate; 1-menthene-8-thiol;

[0062] Aliphatic nitriles, preferably 2-nonenenitrile; 2-tridecenenitrile; 2,12-tridecenenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0063] Esters of aliphatic carboxylic acids, preferably (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-ol acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate Esters; (E)- and (z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynoate; methyl 2-nonynoate; propenyl 2-isopentyloxyacetate; methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl-crotonate;

[0064] Acyclic terpene alcohols, preferably citronellol, geraniol, nerol, linalool, lavandulol, nerolidol, farnesol, tetrahydrolinalool, tetrahydrogeraniol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol, 2,6-dimethyl-5,7-octadien-2-ol, 2,6-dimethyl-3,5-octadien-2-ol, 3,7-dimethyl-4,6-octadien-3-ol, 3,7-dimethyl-1,5,7-octatrien-3-ol, 2,6-dimethyl-2,5,7-octatrien-1-ol, and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid enols and 3-methyl-2-butenoate;

[0065] Acyclic terpene aldehydes and ketones, preferably geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral and 7-hydroxy-3,7-dimethyloctanal;

[0066] Cyclic terpene alcohols, preferably isopulegol; α-terpineol; terpineol-4; menth-8-ol; menth-1-ol; menth-7-ol; camphenol; isocamphenol; linalool oxide; nopol; cedrol; ambroxanol; vetivol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid enols and 3-methyl-2-butenoates; menthyl formate; menthyl propionate; menthyl butyrate; menthyl isobutyrate; menthyl isovalerate; menthyl hexanoate; menthyl crotonate; menthyl tiglic acid;

[0067] Cyclic terpene aldehydes and ketones, preferably menthone; isomenthone; 8-mercaptomenth-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; β-n-methylionone; β-isomethylionone; α-irone; α-damascenone; β-damascenone; β-damascenone; δ-damascenone; γ-damascenone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-butane 1-ene-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanolnaphthalene-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; oleanone; dihydrooleanone; 4,6,8-megatrien-3-one; α-orangealdehyde; β-orangealdehyde; acetylated pine oil (methyl cedarwood ketone);

[0068] Cyclic alcohols, preferably 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isobornylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0069] Cycloaliphatic alcohols, preferably α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl)-pentane-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentane-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexane-3-ol;

[0070] Cyclic ethers and cycloaliphatic ethers, preferably eucalyptol; methyl cedarwood ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-epoxycedarwood; 3a,6,6,9a-tetramethyl-dodecahydronaphthalene[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphthalene[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]tridecene-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

[0071] Cyclic ketones and macrocyclic ketones, preferably 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-Methyl-5-cyclopentadecenone; 3-methylcyclopentadecenone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentylmethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[0072] Alicyclic aldehydes, preferably 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0073] Cycloaliphatic ketones, preferably 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthylmethyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienone; tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)ketone;

[0074] Cyclic alcohol esters, preferably 2-tert-butyl cyclohexyl acetate; 4-tert-butyl cyclohexyl acetate; 2-tert-pentyl cyclohexyl acetate; 4-tert-pentyl cyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl- 2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methano-octahydro-5 or 6-indenyl acetate;

[0075] An ester of a cycloaliphatic alcohol, preferably ethyl 1-cyclohexylcrotonate;

[0076] Esters of cycloaliphatic carboxylic acids, preferably allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate;

[0077] Aromatic aliphatic alcohols, preferably benzyl alcohol; 1-phenylethanol; 2-phenylethanol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpropanol; 3-methyl-5-phenylpropanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;

[0078] Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, preferably benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; α-trichloromethylbenzyl acetate; α,α-dimethylphenethyl acetate; α,α-dimethylphenethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[0079] Aromatic aliphatic ethers, preferably 2-phenethyl methyl ether; 2-phenethyl isopentyl ether; 2-phenethyl-1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydrogenated atroaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

[0080] Aromatic and aromatic aliphatic aldehydes, preferably benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydroataldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde, 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxy-benzaldehyde 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal;

[0081] Aromatic and aromatic aliphatic ketones, preferably acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanmethylketone; 6-tert-butyl-1,1-dimethyl-4-indanmethylketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indanyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-naphthylacetonone;

[0082] Aromatic and aromatic aliphatic carboxylic acids and their esters, preferably benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidyl propionate; ethyl 3-methyl-3-phenylglycidyl propionate;

[0083] Nitrogen-containing aromatic compounds, preferably 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenyl-pentanenitrile; methyl anthranilate; methyl N-methyl anthranilate; the Schiff base of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal; 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; methylindole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0084] Phenols, phenyl ethers and phenyl esters, preferably estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate;

[0085] Heterocyclic compounds, preferably 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0086] Lactones, preferably 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonanolactone; 1,4-decanolactone; 8-decene-1,4-lactone; 1,4-undecanoic acid lactone; 1,4-dodecanoic acid lactone; 1,5-decanolactone; 4-methyl-1,4-decanolactone; 1,15-pentadecanolactone; cis- and trans-11-pentadecanolactone-1,15-lactone; cis- and trans-12-pentadecanolactone-1,15-lactone; 1,16-hexadecene-1,16-lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecanolactone; 11-oxa-1,16-hexadecanolactone; 12-oxa-1,16-hexadecanolactone; 1,13-tridecanediolactone; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.

[0087] Therefore, another aspect of the present invention relates to a scented product. The scented product according to the present invention preferably comprises at least one compound selected from the group consisting of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal, 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal and 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal in an organoleptically effective amount.

[0088] Preferred scented products according to the invention are detergents and cleaning products, hygiene or care products, in particular products from the body and hair care sector, cosmetics and household products.

[0089] Preferred products are, for example, perfume extracts, perfumes, eau de toilette, aftershaves, colognes, preshave products, cologne sprays and scented wipes as well as scented and to-be-scented acidic, alkaline and neutral detergents, such as floor cleaners, window cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring agents, solid or liquid toilet cleaners, toilet sticks, toilet blocks (liquid or solid), powdered or foamed carpet cleaners, liquid detergents, powdered detergents, laundry pretreatment agents, such as bleaches, soaking agents and stain removers, fabric softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants and air fresheners in liquid or gel form or applied to a solid carrier, in particular for deodorizing exhaust gases from air conditioning units and industrial processes, and air fresheners in the form of aerosols or pump sprays, waxes and polishes, such as furniture polishes, floor waxes, shoe polishes, strengthening, impregnating or deodorizing fabric treatments, diapers, sanitary napkins, underpants pads, deodorant patches, and personal care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, wet cleansing cloths, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, such as skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, skin Hair products such as hair sprays, gels, strengthening lotions, conditioners, permanent or semi-permanent hair dyes, hair styling agents such as cold waves and straighteners, hair toners, creams and lotions, deodorants and antiperspirants such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, decorative makeup products such as eye shadow, make-up products, lipstick, mascara, as well as candles, lamp oil, incense sticks, animal litter, cat litter, insecticides, insect repellents, liquid and gas fuels, heating oil and gas.

[0090] Particularly preferred scented products according to the invention are selected from the group consisting of perfume extracts, perfumes, eau de toilette, aftershave, cologne, pre-shave products, cologne sprays, scented wipes, acidic, alkaline and neutral detergents, textile fresheners, ironing aids, liquid detergents, powdered detergents, laundry pre-treaters, fabric softeners, laundry soaps, laundry tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, personal care agents, hand creams and hand lotions, foot creams and foot lotions, depilatory creams and depilatory lotions, aftershave creams and aftershave lotions, tanning creams and tanning lotions, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides, mosquito repellents and fuels.

[0091] For the sake of clarification, it has to be mentioned that within the context of this text a (fragrant) product according to the invention is to be understood as an intentionally induced or produced product and not a naturally occurring mixture of substances, such as can be obtained, for example, from plant raw materials by extraction methods.

[0092] The compound according to the invention is preferably a component of the perfume composition according to the invention. Therefore, in a preferred embodiment, the product that emits fragrance comprises the perfume composition according to the invention and a carrier or matrix, wherein the carrier or matrix is ​​in direct contact with the perfume composition. The matrix is, for example, a solid matrix or the carrier is, for example, a solid carrier. The carrier or matrix ensures a fine distribution of the perfume composition in the product and a controlled release during application. Such carriers can be porous inorganic materials, such as silica gel, zeolite, gypsum, clay, clay particles, aerated concrete, etc., or organic materials, such as wood and cellulose-based substances.

[0093] The compounds according to the invention or the fragrance compositions according to the invention to be used according to the invention may also be present in microencapsulated or spray-dried form, as inclusion complexes or as extruded products, and can be added to the products in this form.

[0094] If applicable, the properties of the compounds according to the invention to be used according to the invention or the fragrance compositions according to the invention can be further optimized with regard to a more targeted release by so-called "coating" with the aid of suitable materials, preferably using waxy plastic materials such as, for example, polyvinyl alcohol.

[0095] The microencapsulation of the compound according to the invention or the flavor composition according to the invention used according to the invention can be carried out, for example, by means of a so-called coacervation process with capsule materials such as polyurethanes or soft gelatin. The spray-dried compound according to the invention can be prepared, for example, by spray-drying the compound according to the invention, i.e., an emulsion or dispersion containing the compound according to the invention or the flavor composition according to the invention, wherein modified starch, protein, dextrin and / or plant-based gum can be used as carrier material. Inclusion complexes can be produced, for example, by adding a dispersion to a suitable solvent such as water, which is or contains the compound according to the invention or the flavor composition according to the invention, and cyclodextrin or urea derivatives. The extruded product can be carried out by melting the compound according to the invention or the flavor composition according to the invention with a suitable waxy substance and then solidifying and extruding in a suitable solvent such as isopropanol, if applicable.

[0096] The compounds according to the invention or the fragrance compositions according to the invention can be used in a number of preparations or products, wherein they are preferably combined with one or more of the following excipients or active ingredients:

[0097] Protective agent, abrasive, anti-acne agent, anti-skin aging agent, antibacterial agent, anti-fat agent, anti-dandruff agent, anti-inflammatory agent, anti-irritant, irritation inhibitor, antimicrobial agent, antioxidant, astringent, antiperspirant, preservative, antistatic agent, adhesive, buffer, carrier material, chelating agent, cell stimulant, cleaning agent, care agent, depilatory agent, surfactant, deodorant, antiperspirant, plasticizer, emulsifier, enzyme, essential oil, fiber, color fixing agent, foaming agent, foam stabilizer, anti-foaming substance, foaming agent, bactericide, paste agent, gelling agent, hair care product, hair styling product, hair straightener, moisturizer, wetting agent, moisturizing substance, bleaching agent, (textile) enhancer, stain remover, brightener, impregnation agent, stain repellent, friction reducer, lubricant, protective Cream, ointment, sunscreen, plasticizer, covering agent, polish, glazing agent, polymer, powder, protein, regreaser, abrasive, silicone, skin soothing agent, skin cleanser, skin care agent, skin healing agent, skin lightening agent, skin protectant, skin softener, cooling agent, skin cooling agent, warming agent, skin warming agent, stabilizer, UV absorber, UV filter, detergent, fabric softener, suspending agent, skin tanning agent, thickener, vitamin, oil, wax, fat, phospholipid, saturated fatty acid, monounsaturated fatty acid or polyunsaturated fatty acid, alpha-hydroxy acid, polyhydroxy fatty acid, liquefier, dye, color fixative, pigment, preservative, fragrance, flavor, aromatic substance, polyol, surfactant, electrolyte, organic solvent or silicon derivative.

[0098] According to one embodiment of the present invention, the preferred products according to the present invention, in particular deodorants, etc., additionally contain (depending on the desired mode of action) one or more of the following active substances:

[0099] (1) Antimicrobial active substances which inhibit the development of microorganisms that cause sweat odor; for example, (5-chloro-2-(2,4-dichlorophenoxy)phenol), triclocarban, chlorhexidine, chlorhexidine hydrochloride, chlorhexidine diacetate, chlorhexidine digluconate, 2-phenoxyethanol, farnesol, glyceryl esters and glyceryl ethers, such as glyceryl monolaurate, glyceryl monocaproate, hexoxyglycerol, octoxyglycerol (= ethylhexylglycerol, 3-(2-ethylhexyloxy-1,2-propanediol), or SC 50 (Schülke & Mayr), aliphatic 1,2-diols, such as 1,2-decanediol (EP 1 269 983), aromatic aliphatic alcohols, such as, for example, those described in EP 799 174, preferably 4-methyl-4-phenyl-2-pentanol (Vetikol; WO 03 / 024907) or 2-methyl-4-phenyl-2-butanol (1,1-dimethyl-3-phenylpropanol, α,α-dimethylphenethylmethanol), 1-menthyl methyl ether described in WO 02 / 41861, 2-benzylheptan-1-ol (Jasmol; 2-n-pentyl-3-phenylpropane-1-ol), 2,2-dimethyl-3-phenylpropanol (muguet alcohol; see US 4,091,090), antimicrobially active secondary alcohols, such as, for example, those described in WO 2005 / 004601, in particular 3-methyl-6-phenyl-2-hexanol, 4-(2,4-dimethylphenyl)-2-butanol, 6-(4-isopropylphenyl)-3-methyl-2-hexanol, 4-(2,4,5-trimethylphenyl)-2-butanol, 3,3-dimethyl-4-phenyl-2-butanol, 3-methyl-4-(2-methylphenyl)-2-butanol, 6-(3,4-dimethylphenyl)-2-hexanol), aliphatic carboxylic acids such as 2-hexyloctanoic acid, 2-hexyldecanoic acid, 2-butyloctanoic acid or 2-butyldecanoic acid;

[0100] (2) Enzyme inhibitory substances, which inhibit the action of enzymes involved in the formation of sweat odor; for example, citrate esters and metal chelates, such as EDTA (ethylenediaminetetraacetic acid), EGTA [ethylenebis(oxyethylene)-tetraacetic acid] and DTPA (diethylenetriaminepentaacetic acid, triaminepentaacetic acid);

[0101] (3) Odor-absorbing substances, which absorb substances that cause sweat odor; for example, zinc ricinoleate, cyclodextrin;

[0102] (4) Antiperspirants, which inhibit sweat secretion and thus eliminate the breeding grounds for bacteria that cause body odor. Astringent metal salts are generally preferably used as antiperspirants, in particular inorganic and organic metal salts of the elements aluminum, zinc, magnesium, tin and zirconium and mixtures thereof, with halides being used in particular, such as aluminum chloride, basic aluminum hydroxychloride, zirconium oxychloride and zirconium hydroxychloride and mixtures thereof. These aluminum and zirconium salts and mixtures thereof are generally also used in complexed form, with propylene glycol, polyethylene glycol or glycine being preferably used as complexing agents.

[0103] The invention also relates to a method for producing a fragrance product, in particular a scented product according to the invention, comprising the following steps:

[0104] i) providing a compound according to the invention or a fragrance composition according to the invention,

[0105] ii) providing one or more further components of the scented product to be prepared, and

[0106] iii) contacting or mixing the other components provided in step ii) with the organoleptically effective amount of the components provided in step i).

[0107] The present invention also relates to a method for imparting and / or increasing i) floral and / or ii) green and / or iii) lily of the valley odor characteristics to a scented product, said method comprising the step of adding a compound according to the invention or a fragrance composition according to the invention to said scented product.

[0108] A further problem underlying the present invention was to provide novel processes for producing the compounds according to the invention.

[0109] The process according to the invention for producing the compounds according to the invention comprises the following steps

[0110] (I)

[0111] Wherein the group R' is an alkyl group, preferably an ethyl group, the reaction takes place in the presence of a base (i), preferably piperidine as base (i).

[0112] (II)

[0113] Wherein the group R' is an alkyl group, preferably an ethyl group, the groups R" and R'" are independently an alkyl group, preferably a methyl group or an ethyl group, or are connected via an alkyl group, preferably an ethane-1,2-diyl group or a propane-1,2-diyl group to form a ring, and Hal is a chloride, a bromide or an iodide, preferably a bromide. In a preferred embodiment of this reaction step (II), 3-bromo-1,1-dimethoxypropane is used as a reactant. The product of reaction step (I) can be used as a reagent for reaction step (II).

[0114] (III)

[0115] Wherein the group R' is an alkyl group, preferably an ethyl group, the groups R" and R'" are independently an alkyl group, preferably a methyl group or an ethyl group, or are connected via an alkyl group, preferably an ethane-1,2-diyl group or a propane-1,2-diyl group to form a ring. Step ii) of the reaction step is a saponification reaction, and step iii) of the reaction step is a decarboxylation step. The reaction step (III) is carried out in the presence of a base, preferably sodium hydroxide or potassium hydroxide. The product of the reaction step (II) can be used as a reagent for the reaction step (III).

[0116] (IV)

[0117] Wherein the groups R "and R"' are independently alkyl, preferably methyl or ethyl, or are connected via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring, the reaction being carried out in the presence of a reducing agent (iv), preferably lithium aluminum hydride (LAH). The product of reaction step (III) can be used as a reagent for reaction step (IV).

[0118] (V)

[0119] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are connected via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring. Step v) of the reaction step is a methylation reaction, and step vi) of the reaction step is an elimination step. The reaction step (V) is carried out in the presence of a base, preferably triethylamine. The product of the reaction step (IV) can be used as a reagent for the reaction step (V).

[0120] (VI)

[0121] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are linked via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring. This reaction step (VI) is carried out in the presence of an acid, preferably a carboxylic acid, especially formic acid. The product of reaction step (V) can be used as a reagent for reaction step (VI).

[0122] (VII)

[0123] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are linked via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring. Step u) of the reaction step is a mesylation reaction, and step vi) of the reaction step is an elimination step. The reaction step (VII) is carried out in the presence of a base, preferably triethylamine. The product of the reaction step (IV) can be used as a reagent for the reaction step (VII).

[0124] (VIII)

[0125] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are linked via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring. This reaction step (VIII) is carried out in the presence of an acid, preferably a carboxylic acid, especially formic acid. The product of reaction step (VII) can be used as a reagent for reaction step (VIII).

[0126] (IX)

[0127] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are connected via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring. The reaction step (VIII) is preferably carried out at high temperature and high pressure in the presence of hydrogen (vii) and palladium on activated carbon as a catalyst. The product of reaction step (V), the product of reaction step (VII), or a mixture of the products of reaction steps (V) and (VII) can be used as one or more reagents (crude reagents) of reaction step (IX).

[0128] (X)

[0129] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are linked via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl, to form a ring. This reaction step (X) is preferably carried out in the presence of an acid, preferably a carboxylic acid, especially formic acid. The product of reaction step (IX) can be used as a reagent for reaction step (X).

[0130] (XI)

[0131] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are linked via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring. This reaction step (VIII) is preferably carried out in the presence of hydrogen (vii) and palladium on activated carbon as a catalyst. The product of reaction step (V), the product of reaction step (VII), or a mixture of the products of reaction steps (V) and (VII) can be used as one or more reagents for reaction step (XI).

[0132] (XII)

[0133] Wherein the groups R" and R"' are independently alkyl, preferably methyl or ethyl, or are linked via an alkyl group, preferably ethane-1,2-diyl or propane-1,2-diyl to form a ring. This reaction step (XII) is carried out in the presence of an acid, preferably a carboxylic acid, especially formic acid. The product of reaction step (XI) can be used as a reactant for reaction step (XII).

[0134] The process for preparing the compounds according to the present invention comprises at least one, two, three, four, five or six of the above-mentioned reaction steps (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI) and (XII).

[0135] The method for preparing 3-(4-isobutyl-2-methyl-cyclohexyl)propanal according to the present invention comprises at least one, two, three, four, five, six, seven or eight of the above-mentioned reaction steps (I), (II), (III), (IV), (V), (VII), (IX) and (X).

[0136] The method for preparing 3-(4-isobutyl-2-methyl-cyclohexyl)propanal according to the present invention comprises at least the above-mentioned reaction step (X).

[0137] The method for preparing 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal according to the present invention comprises at least one, two, three, four, five or six of the above-mentioned reaction steps (I), (II), (III), (IV), (VII) and (VIII).

[0138] The method for preparing 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal according to the present invention comprises at least the above-mentioned reaction step (VIII).

[0139] The method for preparing 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal according to the present invention comprises at least one, two, three, four, five, six, seven or eight of the above-mentioned reaction steps (I), (II), (III), (IV), (V) and (VI).

[0140] The process for preparing 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal according to the present invention preferably comprises at least the above-mentioned reaction step (VI).

[0141] The method for preparing 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal according to the present invention comprises at least one, two, three, four, five, six, seven or eight of the above-mentioned reaction steps (I), (II), (III), (IV), (V), (VII), (XI) and (XII).

[0142] The process for preparing 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal according to the present invention preferably comprises at least the above-mentioned reaction step (XII). DETAILED DESCRIPTION

[0143] In the following, the invention will be described in more detail by means of selected examples. Unless otherwise stated, all specifications herein relate to weight.

[0144] Example:

[0145] Example 1: Fragrance composition A:

[0146]

[0147]

[0148]

[0149] By adding 5% by weight of compound A, B, C or D or a mixture of compounds A, B, C or D to fragrance composition A2, the floral aroma is enhanced relative to fragrance oil A1 (without compound A, B, C or D). In addition, compound A, B, C or D gives the composition containing fragrance oil A2 more strength and fullness than the composition containing fragrance oil A1; overall, the addition of compound A, B, C or D or a mixture of compounds A, B, C or D produces an odor impression reminiscent of lily of the valley.

[0150] Example 2: Fragrance composition B:

[0151]

[0152]

[0153]

[0154] By adding 1.5% by weight of compound A, B, C or D or a mixture of compounds A, B, C or D to fragrance composition B2, the floral and natural scent is enhanced relative to fragrance oil B1 (without compound A, B, C or D). In addition, compound A, B, C or D gives the composition containing fragrance oil B2 more strength and fullness than the composition containing fragrance oil A1; overall, the addition of compound A, B, C or D or a mixture of compounds A, B, C or D produces an odor impression reminiscent of lily of the valley.

[0155] Example 3: Fragrance composition C:

[0156]

[0157]

[0158]

[0159] By adding 6.5% by weight of a compound A, B, C or D or a mixture of compounds A, B, C or D to the fragrance composition C2, the fruity character is enhanced relative to the fragrance oil C1 (without compounds A, B, C or D). In addition, in the fragrance composition C2 containing compounds A, B, C or D, the diffusion capacity is increased relative to the fragrance composition C1 without compounds A, B, C or D; overall, the addition of compounds A, B, C or D produces an odor impression reminiscent of lily of the valley.

[0160] Example 4: Synthesis of 6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylic acid ethyl ester:

[0161] 201.4g (1.54mol) of ethyl acetoacetate (CAS No.: 141-97-9) and 53.0g (0.62mol) of isovaleraldehyde (CAS No.: 590-86-3) were added to a three-necked round-bottom flask. At room temperature, 5.2g of piperidine in 35mL of ethanol was added to the reaction mixture. Then, the reaction mixture was stirred under reflux for 5 hours. Subsequently, the reaction mixture was cooled to room temperature and methyl tert-butyl ether was added. The layers were separated and the aqueous phase was washed with methyl tert-butyl ether. The organic phase was collected, washed twice with water, and dried with sodium sulfate (30g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by distillation. 6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylic acid ethyl ester (138.5g, 93,8%) was obtained in liquid form.

[0162] MS: m / z (%) = 238, 165, 154, 126, 121, 109, 98, 79, 57, 41, 29.

[0163] 1 1H NMR (400 MHz, chloroform-d) δ 5.97 (d, J = 2.6 Hz, 1H), 5.97 - 5.94 (m, 1H), 4.24 (dtd, J = 10.7, 7.3, 3.6 Hz, 2H), 4.20 (dd, J = 14.3, 7.2 Hz, 2H), 3.19 (d, J = 5.0 Hz, 1H), 3.06 (d, J = 6.4 Hz, 1H), 2.66 (dd, J = 16.2, 4.6 Hz, 1H), 2.59 (d, J = 3.0 Hz, 1H), 2.59 - 2.48 (m, 1H), 2.43 - 2.31 (m, 1H), 2.33 - 2.25 (m, 1H), 2.09 (dd, J = 16.5, 8.2 Hz, 1H), 1.98 (d, J = 1.3 Hz, 3H), 1.97 - 1.95 (m, 3H), 1.75 (dp, J = 13.5, 6.7 Hz, 1H), 1.69 - 1.53 (m, 1H), 1.37 - 1.23 (m, 2H), 1.30 (t, J = 7.1 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H), 1.24 - 1.13 (m, 2H), 0.90 (d, J = 6.6 Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H), 0.86 (d, J = 6.5 Hz, 3H).

[0164] 13 13C NMR (101 MHz, CDCl3) δ = 199.39, 198.12, 171.86, 170.26, 156.69, 155.72, 128.45, 128.11, 61.31, 61.18, 53.07, 51.01, 42.98, 42.37, 40.37, 39.09, 35.35, 34.79, 24.98, 24.46, 23.38, 23.20, 23.09, 22.61, 22.49, 21.70, 14.31, 14.22.

[0165] Example 5: Synthesis of 3-(3,3-dimethoxypropyl)-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1- Ethyl carboxylate:

[0166] 5.5g (49.0mmol) potassium tert-butoxide is added to 100mL tert-butanol. 0.2g tetrabutylammonium iodide (TBAI) and 10.0g 6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylic acid ethyl ester (40.8mmol) are added to the mixture at room temperature. The mixture is stirred for 4 hours at 65°C. The mixture is then cooled to room temperature, and 9.0g (49.0mmol) 3-bromo-1, dimethoxypropane is added dropwise. Tert-butyl oxide is then removed under reduced pressure. Methyl tert-butyl ether and water are added to the residue. The layers are separated and the aqueous phase is washed with methyl tert-butyl ether. The organic phase is collected, washed twice with water, and dried with sodium sulfate (30g). The solvent is removed under reduced pressure. Subsequently, the crude product is purified by distillation. 3-(3,3-Dimethoxypropyl)-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylic acid ethyl ester (7.5 g, 51.5%) was obtained in liquid form with a purity of 97%.

[0167] MS: m / z (%) = 325, 308, 277, 203, 147, 109, 82, 67, 41.

[0168] 1 H NMR (400 MHz, deuterated chloroform) δ 4.35 (tt, J = 5.7, 1.6 Hz, 2H), 4.26-4.16 (m, 4H), 3.31 (d, J = 1.0 Hz, 12H), 3.20 (dd, J = 5.5 Hz, 1H), 3.07 (dd, J = 11.8, 6.3 Hz, 1H), 2.71-2.60 (m, 1H), 2.49-2.40 (m, 1H), 2.40-2.32 (m, 6H), 2.32 (s, 2H), 2.16-2.07 (m, 2H), 1.97 (s, 3H), 1.94 (d, J=0.8Hz, 3H), 1.82-1.70 (m, 1H), 1.68-1 .56 (m, 5H), 1.31-1.27 (m, 6H), 1.25 (dd, J=7.1, 3.3Hz, 2H), 1.23-1.10 (m, 2H), 0.95-0.82 (m, 12H).

[0169] 13C NMR (101MHz, CDCl3) δ198.32, 197.16, 172.46, 170.86, 150.10, 148.62, 136.72, 136.50, 104.14, 104.12, 61.17, 60.99, 54.49, 52.72, 52.6 5, 52.59, 42.93, 42.54, 40.71, 39.54, 34.62, 33.88, 31.17, 24.99, 24 .37, 23.14, 22.67, 22.51, 21.82, 20.74, 20.69, 20.24, 19.77, 14.33.

[0170] Example 6: Synthesis of 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-ene-1-one:

[0171] 20g (3.4mmol) of 3-(3,3-dimethoxypropyl)-6-isobutyl-2-methyl-4-oxo-cyclohex-2-ene-1-carboxylic acid ethyl ester was mixed with 24mL of methanol. 4g (50mmol) of sodium hydroxide and 30g of water were added at room temperature. The mixture was stirred at reflux for 5 to 7 hours. Methanol was then removed under reduced pressure. Methyl tert-butyl was added to the residue. The layers were separated and the aqueous phase was washed with methyl tert-butyl ether. The organic phase was collected, washed twice with water, and dried with sodium sulfate (30g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by distillation. 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-ene-1-one (13.2g, 72.4%) was obtained in liquid form with a purity of 98%.

[0172] MS: m / z (%) = 253, 236, 221, 205, 191, 75, 71, 41.

[0173] 1 H NMR (400 MHz, deuterated chloroform) δ 4.35 (t, J = 5.7 Hz, 1H), 3.32 (s, 6H), 2.51-2.44 (m, 1H), 2.32 (dt, J = 13.9, 7.2 Hz, 3H), 1.96 (s, 3H), 1.95 (s, 3H), 1.72-1.58 (m, 1H), 1.66-1.58 (m, 2H), 1.20 (t, J = 6.7 Hz, 2H), 0.88 (d, J = 2.5 Hz, 3H), 0.87 (d, J = 2.3 Hz, 3H).

[0174] 13C NMR (101MHz, CDCl3) δ198.97, 154.80, 134.65, 104.21, 52.61, 52.56, 45.29, 44.34, 39.79, 31.99, 31.47, 24.62, 22.74, 22.63, 21.16, 20.46.

[0175] Example 7: Synthesis of 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-en-1-ol:

[0176] 0.38g (10.0mmol) lithium aluminum hydride is added to 60mL THF and cooled to 5°C. At this temperature, 8.04g (30mmol) 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-ene-1-one is carefully added. The mixture is stirred at room temperature for three hours. The mixture is then quenched with water. Methyl tert-butyl is added to the residue. The layers are separated and the aqueous phase is washed with methyl tert-butyl ether. The organic phase is collected, washed twice with water, and dried with sodium sulfate (30g). The solvent is removed under reduced pressure. Subsequently, the crude product is purified by distillation. 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-ene-1-ol (8.0g, 98.8%) is obtained in liquid form with a purity of 98%.

[0177] MS: m / z (%) = 238, 223, 206, 167, 149, 123, 105, 75, 41.

[0178] 1 H NMR (600 MHz, benzene-d6) δ 4.44 (t, J = 5.7 Hz, 1H), 4.11 (q, J = 6.5 Hz, 1H), 3.20 (s, 3H), 3.19 (s, 3H), 2.51 (ddd, J = 14.8, 9.6, 6.3 Hz, 1H), 2.34 (ddd, J = 13.5, 9.4, 6.8 Hz, 1H), 1.98-1 .88 (m, 3H), 1.78 (q, J=11.1, 10.5Hz, 1H), 1.60 (d, J=1.7Hz, 3H), 1.59-1.51 (m, 3H), 1 .26 (d, J=6.5Hz, 1H), 1.09-1.00 (m, 3H), 0.85 (d, J=6.6Hz, 3H), 0.84 (d, J=6.5Hz, 3H).

[0179] 13C NMR (151MHz, C6D6) δ133.86, 129.07, 104.57, 70.08, 52.28, 51.87, 46.49, 40.94, 39.79, 31.89, 30.48, 24.94, 23.55, 23.16, 22.80, 19.34.

[0180] Example 8: Synthesis of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene (methoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene:

[0181] 6.0g (22.2mmol) 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohex-2-ene-1-ol was dissolved in 60mL toluene, and 360mg 4-dimethylaminopyridine (DMAP) and 18g (0.18mol) triethylamine were added at room temperature. The mixture was cooled to 0 to 5°C, and 4.8g (44.4mmol) methanesulfonyl chloride was added dropwise at this temperature. The mixture was stirred at room temperature for at least 12 hours, and then stirred for two hours under reflux. Subsequently, the mixture was cooled to 0 to 5°C, and 50mL water was added to the mixture, and the mixture was stirred for 1 hour. The phases were separated, and the aqueous phase was extracted twice with toluene. The organic phase was collected, washed with water and dried with sodium sulfate (30g). The solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 4.8 g of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene are obtained as a mixture.

[0182] 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene:

[0183] MS: m / z (%) = 252, 220, 175, 131, 119, 105, 88, 75, 58, 41.

[0184] 1H NMR (600MHz, benzene-d6) δ5.65-5.60 (m, 1H), 5.13-5.09 (m, 1H), 4.87-4.84 (m, 1H), 4.39 (t, J=5.6Hz, 1H), 3.17 (s, 3H), 3.16 (s, 3H), 2.46-2.39 (m, 2H), 2.39 (ddd, J=14.9, 3.0, 1.3Hz, 1H), 2.08 (dt, J=17.7, 4.8Hz, 1H), 2.00 (ddt, J=13.6, 11.3, 2 .0Hz, 1H), 1.94 (ddt, J=9.6, 6.6, 5.6Hz, 2H), 1.80-1.72 (m, 1H), 1.65 (ddhept, J=17.8, 9.5, 1.4Hz, 1H), 1.61-1.53 ​​(m, J=6.7Hz, 1H), 1.08 (dt, J=14.1, 7.1Hz, 1H), 1.03 (dt, J=13.5, 7.2Hz, 1H), 0.83 (d, J=6.8Hz, 3H), 0.82 (d, J=6.8Hz, 3H).

[0185] 13 C NMR (151 MHz, benzene-d6) δ 143.66, 136.75, 127.22, 108.32, 104.49, 52.23, 52.65, 45.72, 39.83, 33.39, 32.34, 32.21, 28.26, 25.07, 23.11, 22.81.

[0186] 2-(3,3-Dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene

[0187] 1 H NMR (400MHz, benzene-d6) δ5.56 (t, J=4.7Hz, 1H), 5.52-5.48 (m, 1H), 3.17 (s, 3H), 3.16 (s, 3H), 2.29-2.21 (m, 3H), 2.04-1.97 (m, 1H), 1.87-1. 80 (m, 3H), 1.78 (t, J=1.8Hz, 3H), 1.77-1.68 (m, 1H), 1.60-1.53 ​​(m, 1H), 1.40-1.17 (m, 2H), 0.85 (d, J=6.6Hz, 3H), 0.84 (d, J=6.5Hz, 3H).

[0188] 13C NMR (101 MHz, benzene-d6) δ 137.67, 132.83, 128.98, 121.20, 104.27, 52.25, 52.20, 44.12, 32.44, 31.59, 30.04, 28.18, 25.31, 22.97, 22.84, 19.72.

[0189] Example 9: Synthesis of 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal and 3-(4-isobutyl- 6-methylenecyclohexen-1-yl)propanal (B+C):

[0190] A mixture of 1 g of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene was mixed with 1.2 g of formic acid and stirred at room temperature for 1.5 hours. The mixture was then added to sodium bicarbonate (NaHCO 3 ). The organic phase was separated, washed twice with water, dried over sodium sulfate, and the solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 0.7 g of 3-(4-isobutyl-6-methyl-cyclohexa-1,5-diene-1-yl) propanal and 3-(4-isobutyl-6-methylenecyclohexene-1-yl) propanal were obtained in a mixture with a purity of 93%. Both aldehydes can be separated by preparative GC.

[0191] 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal (B):

[0192] Smell: Floral, green, lily of the valley.

[0193] MS: m / z (%) = 206, 131, 119, 105, 91, 79, 41.

[0194] 1 H NMR (600MHz, benzene-d6) δ9.32 (t, J=1.6Hz, 1H), 5.46 (p, J=3.6, 1.8Hz, 1H), 5.33 (t, J=4.7Hz, 1H), 2. 21 (dddd, J=9.7, 7.6, 5.8, 4.1, 2.1Hz, 1H), 2.17 (tq, J=7.7, 1.7Hz, 2H), 2.08-2.02 (m, 1H), 2.0 1-1.97 (m, 2H), 1.80-1.72 (m, 1H), 1.62 (t, J=1.9Hz, 3H), 1.64-1.56 (m, J=6.7Hz, 1H), 1.26 (dt, J=13.3, 7.4Hz, 1H), 1.12 (dt, J=13.3, 7.4Hz, 1H), 0.85 (d, J=6.6Hz, 3H), 0.83 (d, J=6.6Hz, 3H).

[0195] 13 C NMR (151 MHz, benzene-d6) δ 200.29, 136.39, 132.25, 129.23, 121.40, 43.98, 42.66, 31.41, 29.85, 25.29, 25.15, 22.92, 22.82, 19.56.

[0196] 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal (C):

[0197] Smell: Floral, green, lily of the valley.

[0198] MS: m / z (%) = 206, 188, 164, 149, 131, 121, 105, 91, 79, 41.

[0199] 13 C NMR (151 MHz, benzene-d6) δ 200.41, 143.27, 135.44, 127.74, 108.27, 45.59, 42.76, 39.60, 33.21, 32.17, 25.21, 25.05, 23.07, 22.79.

[0200] 1 H NMR (600MHz, benzene-d6) δ9.33 (t, J=1.6Hz, 1H), 5.45-5.40 (m, 1H), 4.85-4.80 (m, 1H), 4.78-4.73 ( m, 2H), 2.41-2.33 (m, 1H), 2.35-2.29 (m, 1H), 2.14-2.09 (m, 2H), 2.01 (dt, J=17.9, 5.0Hz, 1H) , 1.92 (ddt, J=13.5, 11.2, 2.0Hz, 1H), 1.73-1.64 (m, 1H), 1.63-1.55 (m, 1H), 1.60-1.49 (m, J= 6.9Hz, 1H), 1.04 (dt, J=14.1, 7.1Hz, 1H), 0.99 (dt, J=13.5, 7.2Hz, 1H), 0.81 (dt, J=7.0Hz, 6H).

[0201] Example 10: Synthesis of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal (A):

[0202] A mixture of 1,1 g (2.15 mmol) of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene is mixed with 2 ml of cyclohexane. 80 mg of palladium on activated carbon are added. The mixture is hydrogenated with hydrogen at 100° C. to 190° C. and a pressure of 20-25 bar for 8 hours. The catalyst is filtered off. 1.0 g of 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methylcyclohexane is obtained with a purity of 95%.

[0203] 1 g of 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methylcyclohexane was mixed with 1.2 g of formic acid and stirred at room temperature for 1.5 hours. The mixture was then added to sodium bicarbonate (NaHCO 3 ). The organic phase was separated, washed twice with water, dried over sodium sulfate, and the solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 0.7 g of 3-(4-isobutyl-2-methyl-cyclohexyl) propanal (A) was obtained with a purity of 94%.

[0204] Smell: Floral, green, lily of the valley, sweet.

[0205] MS: m / z (%) = 210, 192, 166, 151, 135, 109, 95, 81, 67, 55, 41, 29.

[0206] 1 H NMR (400MHz, benzene-d6) δ9.38 (t, J=1.7Hz, 1H), 1.96-1.75 (m, 3H), 1.70-1.58 (m, 2H), 1.52-1.43 (m, 2H), 1 .40-1.18 (m, 5H), 1.06-0.97 (m, 3H), 0.89 (d, J=6.6Hz, 6H), 0.80 (d, J=7.0Hz, 3H), 0.69-0.56 (m, 1H).

[0207] 13 C NMR (101MHz, C6D6) δ200.94, 47.34, 42.62, 38.36, 36.48, 35.77, 35.71, 29.22, 27.03, 24.95, 23.11, 23.08, 20.10, 17.00.

[0208] Example 11: Synthesis of 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methyl-cyclohexene:

[0209] A mixture of 1.1 g (4.36 mmol) of 1-(3,3-dimethoxypropyl)-4-isobutyl-6-methylene-cyclohexene and 2-(3,3-dimethoxypropyl)-5-isobutyl-3-methyl-cyclohexa-1,3-diene is mixed with 2 ml of cyclohexane. 20 mg of palladium on activated carbon are added. The mixture is hydrogenated with hydrogen at 50° C. and a pressure of 2 bar for 5 hours. The catalyst is filtered off. 1.0 g of 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methyl-cyclohexene is obtained with a purity of 95%.

[0210] MS: m / z (%) = 222, 207, 190, 133, 107, 93, 79, 75, 67, 55, 41.

[0211] 1 H NMR (400MHz, CDCl3) δ4.32 (t, J=5.7Hz, 1H), 3.32 (s, 6H), 2.03 (ddt, J=12.0, 7.2, 3.9Hz, 2H), 1.99-1.8 9 (m, 2H), 1.76-1.63 (m, 5H), 1.60 (s, 3H), 1.60-1.47 (m, 2H), 1.17-1.06 (m, 3H), 0.87 (d, J=6.6Hz, 6H).

[0212] 13 C NMR (101MHz, CDCl3) δ128.82(C-4), 126.20(C-5), 104.25(C-10), 52.49(C-12), 52.47(C-14), 46.27(C-15), 39.02(C-6), 31.73(C-1), 30.80(C-9), 29.98(C-2), 29.60(C-8), 28.09(C-3), 24.88(C-16), 23.10(C-17), 22.75(C-18), 18.96(C-7).

[0213] Example 12: Synthesis of 3-(4-isobutyl-6-methyl-cyclohexen-1-yl)propanal (D):

[0214] 1 g of 1-(3,3-dimethoxypropyl)-4-isobutyl-2-methyl-cyclohexene was mixed with 1.2 g of formic acid and stirred at room temperature for 1.5 hours. The mixture was then added to sodium bicarbonate (NaHCO 3 ). The organic phase was separated, washed twice with water, dried over sodium sulfate, and the solvent was removed under reduced pressure. Subsequently, the crude product was purified by column chromatography. 0.7 g of 3-(4-isobutyl-6-methyl-cyclohexene-1-yl) propanal (D) was obtained with a purity of 93%.

[0215] Smell: Floral, sweet, lily of the valley, creamy.

[0216] MS: m / z (%) = 208, 190, 165, 151, 133, 107, 81, 67, 55, 41, 29.

[0217] 1 H NMR (600 MHz, benzene-d6) δ 9.37 (t, J = 1.8 Hz, 1H), 2.12 (dd, J = 7.4, 2.8 Hz, 2H), 2.00 - 1.96 (m, 2H), 1.84 - 1.79 (m, 1H), 1.75 - 1.70 (m, 1H), 1.65 - 1.58 (m, 2H), 1.54 - 1.49 (m, 2H), 1.48 (t, J = 1.9 Hz, 3H), 1.41 - 1.33 (m, 1H), 1.07 - 1.02 (m, 3H), 0.88 (d, J = 2.5 Hz, 3H), 0.87 (d, J = 2.6 Hz, 3H).

[0218] 13 C NMR (151 MHz, benzene-d6) δ 200.66, 128.32, 126.84, 46.52, 42.52, 39.22, 31.92, 30.16, 29.60, 25.85, 25.15, 23.26, 22.89, 19.06.

Claims

1. Use of a compound selected from the group consisting of 3-(4-isobutyl-2-methyl-cyclohexyl)propanal, 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal and 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal as a perfuming ingredient, wherein the perfuming ingredient has i) floral and / or ii) green and / or iii) lily of the valley odor characteristics.

2. Use according to claim 1, wherein the flavoring ingredient has a further sweet or creamy taste character.

3. A compound which is 3-(4-isobutyl-2-methyl-cyclohexyl)propanal.

4. A compound which is 3-(4-isobutyl-6-methyl-cyclohexa-1,5-dien-1-yl)propanal.

5. A compound which is 3-(4-isobutyl-6-methylene-cyclohexen-1-yl)propanal.

6. A fragrance composition comprising a compound as defined in claim 1.

7. A flavour composition according to claim 6 comprising one or more additional flavour ingredients.

8. A scented product comprising a compound as defined in claim 1 or a fragrance composition according to claim 6 or 7.

9. The scented product of claim 8, wherein the product is selected from the group consisting of perfume extracts, perfumes, colognes, pre-shave products, scented wipes, textile fresheners, ironing aids, liquid detergents, powdered detergents, laundry pre-treaters, fabric softeners, laundry soaps, laundry tablets, disinfectants, air fresheners, aerosol sprays, waxes and polishes, personal care agents, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, incense sticks, insecticides, mosquito repellents and fuels.

10. The scented product of claim 8, wherein the product is selected from the group consisting of perfume extracts, eau de toilette, aftershave, pre-shave products, cologne sprays, scented wipes, acidic, alkaline and neutral detergents, textile fresheners, ironing aids, laundry pre-treaters, fabric softeners, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams, tanning creams and lotions, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides and mosquito repellents.

11. A method for producing a scented product, the method comprising the steps of: i) providing a compound as defined in claim 1 or a fragrance composition according to claim 6 or 7, ii) providing one or several other components of the scented product to be produced, and iii) contacting or mixing the other components provided in step ii) with the organoleptically effective amount of the components provided in step i).

12. The method of claim 11, wherein the scented product is a scented product according to claim 8, 9 or 10.

13. A method for imparting and / or increasing i) floral and / or ii) green and / or iii) lily of the valley odor characteristics to a scented product, said method comprising the step of adding to said scented product a compound as defined in claim 1 or a fragrance composition as defined in claim 6 or 7.

14. A method for preparing a compound as defined in claim 1, comprising at least one, two, three, four, five or six of the following reaction steps: (i) (ii) (iii) (iv) (v) (we) (vii) (viii) (ix) (x) (xi) Wherein R' is an alkyl group, R" and R'" are independently alkyl groups, or are connected via an alkyl group to form a ring.

15. The method of claim 14, wherein R' is ethyl.

16. The method according to claim 14 or 15, wherein R" and R'" are independently methyl or ethyl, or are connected via an ethane-1,2-diyl group or a propane-1,2-diyl group to form a ring.

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