5, 5-disubstituted tetrahydrofuran-2-ones as perfume compounds

Abstract

The use of at least one compound # imgabs0 # of formula I as a perfume is proposed.

Description

Field of the Invention

[0001] The present invention relates to the use of compounds of formula I as fragrances or fragrance compounds. In addition, the present invention relates to fragrance compositions comprising said compounds of formula I, their use and methods for imparting, modifying and / or enhancing certain fragrance notes. In addition, the present invention relates to perfumed products comprising compounds of formula I. Background Art

[0002] As far as the perfume industry is concerned, there is a permanent need for new perfume creations. However, the creation of new fragrances or fragrance compositions involves many challenges. For example, it is necessary to select a specific composition of several fragrances from an almost infinite number of possible structures known from the prior art in order to meet specific needs of the market and to provide a product that matches the specific characteristics desired by the customer. Suitable fragrances exhibit very beneficial properties, but in combination with other fragrances may produce unpleasant and therefore harmful odors, making them difficult or even impossible to use for a specific purpose.

[0002] Furthermore, the current trend in the fragrance industry is towards renewable products. However, identifying renewable compounds that can be part of renewable products and also have positive odor properties is a challenging task. Furthermore, a fragrance or fragrance composition should not only have a specific odor profile, but also so-called secondary beneficial properties. In fact, many fragrance compositions known on the market have significant disadvantages in use, such as poor solubility and storage stability, but also have deficiencies in subjective issues such as richness, charm, etc. In addition, many known fragrance compositions require high dosages to achieve the desired odor results. Another requirement for fragrances today is high biodegradability as well as dermatological and toxicological safety. Therefore, there is a particularly high demand for providing fragrances that have a great influence on other fragrances even in small doses and transform a rather unpleasant odor impression into a positive odor impression and / or enhance a pleasant odor impression.

[0003] The problem underlying the present invention is therefore to provide a new fragrance which is able to enhance the positive and beneficial aroma aspects of other fragrances and / or (at the same time) reduce, suppress and / or mask the undesirable unpleasant odor aspects. Furthermore, the new fragrance should be renewable and stable. Finally, the fragrance composition itself should have excellent biodegradability and be harmless to humans and the environment. Summary of the invention

[0005] This is accomplished by using at least one compound of formula I As a spice to solve, R 1represents H, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, vinyl, allyl, 2-methylprop-1-enyl or 2-methylallyl; R 2 represents H, methyl or ethyl and Dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds.

[0006] The compounds of the formula I used according to the invention may be present in any stereoisomeric form or in any mixture of stereoisomers.

[0007] What is stated herein for the compounds of the formula I, in particular the advantages stated herein, also applies to the stereoisomer mixtures of the compounds of the formula I used according to the invention or to different mixtures of compounds of the formula I.

[0008] The compounds of formula I have very unique olfactory properties, which are clearly different from and also exceed the olfactory properties of known odorous substances. The suitability of the compounds of formula I as fragrances was previously unknown. It is therefore particularly surprising that in an area that has been well studied, a fragrance with valuable, interesting and complex olfactory properties can be found.

[0009] As mentioned above, the suitability of the compounds of formula I as fragrances is not clear. Likewise, there is no precise odor description, however, according to the inventors, the compounds of formula I smell in particular fruity, apricot, coumarin, creamy, coconut, green, minty, sweet, almond, fresh, soft, natural, tonka, tobacco and / or hay.

[0010] Therefore, the inventors surprisingly found that the compounds of formula I are suitable as fragrances and produce special effects in combination with other fragrances at small doses, which are not necessarily related to their own smell, but can convey completely different fragrance notes when combined with other fragrances, especially floral fragrances.

[0011] For the sake of clarity, the expression "the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond" or similar expressions refers to the normal meaning understood by those skilled in the art, that is, the entire bond (solid line and dashed line) between the carbon atoms connected by the dashed line is a single bond or a double bond.

[0012] In a preferred embodiment according to the present invention, R 1 represents methyl, ethyl, butyl, vinyl, allyl, 2-methylprop-1-enyl, 2-methylallyl, octyl or nonyl; R 2 Represents methyl or ethyl.

[0013] In another preferred embodiment according to the present invention, the compound of formula I is selected from the group consisting of 5,5-dimethyltetrahydrofuran-2-one, 5-ethyl-5-methyl-tetrahydrofuran-2-one, 5,5-diethyltetrahydrofuran-2-one, 5-methyl-5-vinyl-tetrahydrofuran-2-one, 5-allyl-5-methyl-tetrahydrofuran-2-one, 5-methyl-5-(2-methylprop-1-enyl)tetrahydrofuran-2-one, 5-methyl-5-(2-methylallyl)tetrahydrofuran-2-one, 5-methyl-5-octyl-tetrahydrofuran-2-one, 5-methyl-5-nonyl-tetrahydrofuran-2-one, 5-butyl-5-ethyl-tetrahydrofuran-2-one, and 5-butyl-5-ethylfuran-2-one.

[0014] Preferred compounds according to the present invention have the following structural formula and odor characteristics: Table 1: Preferred compounds of formula I

[0015] In the most preferred embodiment according to the present invention, the compound of formula I is 5,5-dimethyltetrahydrofuran-2-one. Preferably, 5,5-dimethyltetrahydrofuran-2-one has the following fragrance notes: fruity, apricot, coumarin, creamy.

[0016] In a preferred embodiment according to the present invention, at least one compound of formula I is used in the flavor composition to obtain at least one of the following notes: fruity, apricot, coumarin, creamy, coconut, green, minty, sweet, almond, fresh, soft, natural, tonka, tobacco and / or hay. It is further preferred that at least one compound of formula I is used to impart, modify and / or enhance the flavor composition to make it more rounded, more natural, more rich, more honey-flavored, more intense and / or more fruity and / or to impart, modify and / or enhance the flavor composition to make it less greasy and / or less mushroom-flavored. However, because some compounds of formula I do not have any fruity, juicy or floral and / or even have less pleasant odors, such as 5-methyl-5-octyl-tetrahydrofuran-2-one, 5-methyl-5-nonyl-tetrahydrofuran-2-one or 5-butyl-5-ethyl-furan-2-one, the above-mentioned odor description is particularly surprising.

[0017] The fact that the compounds of the formula I used according to the invention can impart very complex and varied overall sensory impressions, which can usually only be achieved through mixtures of several components (eg essential oils or perfume mixtures), is particularly surprising.

[0018] Besides their main, olfactory properties, the compounds of the formula I additionally have positive secondary properties, in particular high substantivity compared with fragrances having similar olfactory properties, as well as high stability in certain media and formulations, high extensibility and are also biodegradable.

[0019] With regard to the preferred use of imparting, modifying and / or enhancing fragrance notes, it is also recognized that the compounds of formula I can act very well as so-called enhancers (amplifiers; intensifiers). Therefore, on the one hand, the present invention relates to the use of at least one compound of formula I for enhancing one or more odor notes. As mentioned above, the odor to be enhanced is preferably selected from mellow, natural, rich, honey, strong and / or fruity. Preferably, at least one compound of formula I is 5,5-dimethyltetrahydrofuran-2-one.

[0020] In addition, the compounds of formula I used according to the present invention can enhance the intensity of the fragrance mixture (fragrance composition) and make the overall smell of the mixture mellow. Therefore, the compounds described herein can be used to give the fragrance composition more fullness, freshness, (divergence) intensity, brightness, mellowness, harmony, naturalness and / or less greasy feeling, in particular, the compounds can be used to give the fragrance composition more naturalness, better mellowness and / or fresher.

[0021] Furthermore, the compounds of the formula I are suitable as agents for increasing the substantivity and / or retention of fragrance compositions.

[0022] The compounds of formula I can be used in a variety of products; they can be used as single fragrances, but they can be particularly advantageously combined with other fragrances in different proportions to form fragrance mixtures, and can also produce novel and original fragrance compositions. Therefore, one aspect of the present invention also relates to fragrance mixtures and possible other ingredients (solvents, etc.), which contain at least one compound of formula I, preferably 5,5-dimethyltetrahydrofuran-2-one.

[0023] The fragrance composition according to the invention comprises at least one compound of formula I in R 1 represents H, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, vinyl, allyl, 2-methylprop-1-enyl or 2-methylallyl; R 2 represents H, methyl or ethyl and Dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. and at least one other flavoring, or consisting thereof.

[0023] In a preferred embodiment according to the present invention, R1 represents methyl, ethyl, butyl, vinyl, allyl, 2-methylprop-1-enyl, 2-methylallyl, octyl or nonyl; and R2 represents methyl or ethyl.

[0024] In another preferred embodiment according to the present invention, the compound of formula I is selected from the group consisting of 5,5-dimethyltetrahydrofuran-2-one, 5-ethyl-5-methyl-tetrahydrofuran-2-one, 5,5-diethyltetrahydrofuran-2-one, 5-methyl-5-vinyl-tetrahydrofuran-2-one, 5-allyl-5-methyl-tetrahydrofuran-2-one, 5-methyl-5-(2-methylprop-1-enyl)tetrahydrofuran-2-one, 5-methyl-5-(2-methylallyl)tetrahydrofuran-2-one, 5-methyl-5-octyl-tetrahydrofuran-2-one, 5-methyl-5-nonyl-tetrahydrofuran-2-one, 5-butyl-5-ethyl-tetrahydrofuran-2-one, 5-butyl-5-ethylfuran-2-one. Most preferably, the compound of formula I is 5,5-dimethyltetrahydrofuran-2-one.

[0025] Preferably, the fragrance composition according to the present invention comprises at least one compound of formula I and two or more other fragrances or consists thereof. More preferably, the fragrance composition according to the present invention comprises at least one compound of formula I and three or more other fragrances or consists thereof. Most preferably, the fragrance composition according to the present invention comprises at least one compound of formula I and four or more other fragrances or consists thereof.

[0026] Preferably, the fragrance composition according to the present invention comprises 5,5-dimethyltetrahydrofuran-2-one and two or more other fragrances or consists thereof. More preferably, the fragrance composition according to the present invention comprises 5,5-dimethyltetrahydrofuran-2-one and three or more other fragrances or consists thereof. Most preferably, the fragrance composition according to the present invention comprises 5,5-dimethyltetrahydrofuran-2-one and four or more other fragrances or consists thereof.

[0027] The compounds of the formula I according to the invention are generally used in a sensory effective amount, ie in such a total amount that they exert their sensory effect.

[0028] Preferably, the weight ratio of at least one compound of formula I to the total amount of other fragrances is in the range of 1:10 to 1:100. More preferably, the weight ratio of at least one compound of formula I to the total amount of other fragrances is in the range of 1:600 ​​to 1:400.

[0029] In this context, preference is given to a total amount of at least one compound of the formula I of 0.0001 to 99.9% by weight, preferably 0.001 to 99.5% by weight, particularly preferably 0.01 to 99% by weight, 0.01 to 90% by weight, 0.01 to 50% by weight, 0.01% to 20% by weight, 0.01 to 10% by weight and particularly preferably 0.01 to 5% by weight, in particular 0.05 to 2.0% by weight, in each case based on the total weight of the composition.

[0030] In a preferred embodiment according to the present invention, the compound of formula I is contained in the flavor composition in an organoleptically effective amount, which is sufficient to modify existing flavors to make them rounder, more natural, more intense, more honey-like, more intense and / or more fruity and / or to impart, modify and / or enhance the aroma composition to make it less greasy and / or less mushroomy.

[0031] Examples of fragrances which can advantageously be combined with the compounds of formula I in the context of the present invention can be found, for example, in S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, NJ 1969, self-published, or K. Bauer ei a / ., Common Fragrance and Flavor Materials, 4th Edition, Wiley-VCH, Weinheim 2001.

[0032] Particular mention is made of: extracts of natural raw materials, such as essential oils, extracts, absolutes, resins, balsams, balsams, tinctures. Ambergris tincture, sandalwood oil, angelica seed oil, angelica root oil, fennel oil, valerian oil, basil oil, tree moss absolute, bay leaf oil, wormwood oil, benzoin resin, bergamot oil, beeswax absolute, birch tar, bitter almond oil, savory oil, buchu leaf oil, Brazilian sandalwood oil, juniper oil, calamus oil, camphor oil, ylang-ylang oil, cardamom oil, quinoa oil, cinnamon oil, acacia absolute, castoreum absolute, cedar leaf oil, cedarwood oil, labdanum oil, citronella oil, lemon oil, copaiba balsam, copaiba balsam oil, coriander oil, costus root oil, cumin oil, cedar oil, davana oil, dill grass oil, dill seed oil, Eau de brouts-Absolue; Oakmoss Absolute, Elemi Oil, Tarragon Oil, Lemon Eucalyptus Oil, Eucalyptus Oil, Fennel Oil, Fir Needle Oil, Glehnia Oil, Glehnia 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, Thin Lotus oil, caraway oil, rock rose oil, rock rose absolute oil, rock rose resin, lavender absolute oil, lavender oil, lavender absolute oil, lavender oil, lemongrass oil, round-leaf angelica oil, distilled white lemon oil, pressed white lemon oil, agarwood oil, litsea cubeba oil, bay leaf oil, nutmeg oil, sweet oregano oil, citrus oil, Massoirbarkoil, mimosa absolute oil, ambrette seed oil, ambrette tincture, sage oil, nutmeg oil, myrrh absolute oil, Myrrh Oil, Myrtle Oil, Clove Leaf Oil, Clove Flower Oil, Neroli Oil, Frankincense Absolute, Frankincense Oil, Oopso Oil, Neroli Absolute, Orange Oil, Oregano Oil, Palmarosa Oil, Patchouli Oil, Perilla Seed Oil, Peru Balsam Oil, Parsley Leaf Oil, Parsley Seed Oil, Petitgrain Oil, Peppermint Oil, Chili Oil, Allspice Oil, Pine Oil, Poleyoil, Rose Absolute, Rosewood Oil, Rose Oil, Rosemary Oil, Dalmatian Sage Oil, Spanish Sage Oil , sandalwood oil, rapeseed oil, spike lavender oil, star anise oil, benzoin oil, marigold oil, cedar needle oil, tea tree oil, turpentine oil, thyme oil, tolu balsam, tonka bean absolute, tuberose absolute, vanilla extract, violet leaf absolute, verbena oil, vetiver oil, juniper oil, grapeseed oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, civet absolute, cinnamon leaf oil, cinnamon bark oil, and fractions thereof or contents separated therefrom;

[0033] A single flavoring agent selected from hydrocarbons, such as 3-carene, α-pinene, β-pinene, α-terpinene, γ-terpinene, p-cymene, bisabolol, camphene, caryophyllene, cedrene, farnesene, limonene, longifolene, myrcene, ocimene, valencene, (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane; Fatty alcohols, such as hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, 1-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-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-undecenol, 4-methyl-3-decenyl-5-ol; Aliphatic aldehydes and their acetals, such as hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, 2-methyloctanal, 2-methylnonanal, (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal, 10-undecenal, (E)-4-decenal, 2-dodecenal, 2,6,10-trimethyl-9-undecenal, 2,6,10-trimethyl-5,9-undecadienal, heptanal diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyloxyacetaldehyde, 1-(1-methoxy-propoxy)-(E / Z)-3-hexene; Aliphatic ketones and their oximes, such as 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; Aliphatic sulfur-containing compounds, such as 3-methylthiohexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, 3-mercaptohexyl acetate, 3-mercaptohexyl butyrate, 3-acetylthiohexyl acetate, 1-menthene-8-thiol; Aliphatic nitriles, such as 2-nonenoic acid nitrile, 2-undecenoic acid nitrile, 2-tridecenoic acid nitrile, 3,12-tridecadienoic acid nitrile, 3,7-dimethyl-2,6-octadienoic acid nitrile, 3,7-dimethyl-6-octenoic acid nitrile; Aliphatic carboxylic acid esters, such as (E) and (Z)-3-hexenyl formate, ethyl acetoacetate, isoamyl acetate, 3,5,5-trimethyl-hexyl acetate, 3-methyl-2-butenyl acetate, (E)-2-hexenyl acetate, (E) and (Z)-3-hexenyl acetate, octyl acetate, 3-octyl acetate, 1-octen-3-acetate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, isobutyl butyrate Acid (E) and (Z)-3-hexenyl esters, 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-octenoate, methyl 2-nonenoate, allyl 2-isopentyloxyacetate, methyl 3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate; Acyclic terpene alcohols, such as geraniol, nerol, lavadulol, nerolidol, farnesol, tetrahydrolinalool, tetrahydrogeraniol; 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol; 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-di Methyl-4,6-octadien-3-ol, 3,7-dimethyloct-6-en-1-ol, (2E)-3,7-dimethyloct-2,6-dien-1-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, Tiglinates and 3-methyl-2-butenoates; Acyclic terpene aldehydes and ketones, such as citronellal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, geranylacetone, and the dimethyl and diethyl acetals of geranial and neral; Cyclic terpene alcohols such as menthol, isopulegol, alpha-terpineol, terpene alcohol-4, menthan-8-ol, menthan-1-ol, menthan-7-ol, bornyl alcohol, isobornyl alcohol, linalool oxide, nopol, cedrol, ambroxanol, vetivol, guaiacol, and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, Tiglinate, 3-methyl-2-butenoate; Cyclic terpene aldehydes and ketones, such as menthone, isomenthone, 8-mercaptomenthan-3-one, carvone, camphor, fenchone, α-ionone, β-ionone, α-n-methylionone, β-n-methylionone; α-isomethylionone, β-isomethylionone, α-irone, β-damascenone, 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methylenenaphthylamine-8(5H) -ketone, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, nootkatone, dihydronootkatone, 4,6,8-megatrien-3-one, α-auricularial, β-auricularial, acetyl cedar oil (methyl cedar ketone); cyclic alcohols, such as, for example: 4-tert-butyl cyclohexanol, 3,3,5-trimethyl-cyclohexanol, 3-isobornyl cyclohexanol, 2,6,9-trimethyl-(Z2,Z5,E9)-cyclododecatrien-1-ol, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; 4-cyclohexylbutan-2-ol; Cycloaliphatic alcohols, such as 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, 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-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)pentan-3-ol, 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; Cyclic and alicyclic ethers, for example: eucalyptol, methyl cedar ether, cyclododecyl methyl ether, 1,1-dimethoxycyclododecane, (ethoxymethoxy)cyclododecane, α-epoxycedrene, 3a,6,6,9a-tetramethyldodecahydronaphthol[2,1-b]furan, 3a-ethyl-6,6,9a-trimethyldodecahydronaphthol[2,1-b]furan, 1,5,9-trimethyl-13-oxabicyclo[10.1.0]-tridecyl-4,8-diene, rose oxide, 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane; Cyclic ketones and macrocyclic ketones, such as, for example: 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-methylcyclopentadecanone, 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, 4-tert-pentylcyclohexanone, 5-cyclohexadecene-1-one, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 8-cyclohexadecene-1-one, 9-cycloheptadecene-1-one, cyclopentadecanone, cyclohexadecanone; Cyclic aliphatic aldehydes, such as 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; Cycloaliphatic ketones, for example: 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-cyclododecantrienone, tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone; Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, 2-tert-amylcyclohexyl acetate, 4-tert-amylcyclohexyl acetate, 3,3,5-trimethylcyclohexyl acetate, decahydro-2-naphthyl acetate, 2-cyclopentyl cyclopentyl crotonate, 3-pentyl-tetrahydro-2H-pyran-4 acetate, decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate, 4,7-formyloxy-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl acetate, 4,7-formyloxy-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl propionate, 4,7-formyloxy-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl isobutyrate, 4,7-formyloxy-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl acetate, Esters of cycloaliphatic alcohols, for example 1-cyclohexylethyl crotonate; Cycloaliphatic carboxylic acid esters, for example allyl 3-cyclohexylpropionate, allyl cyclohexyloxyacetate, methyl cis- and trans-dihydrojasmonate, methyl cis- and trans-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; Aromatic aliphatic alcohols, such as benzyl alcohol, 2-phenylethanol, 1-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-phenylpentanol, 3-methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol, 4-methoxybenzyl alcohol, 1-(4-isopropylphenyl)ethanol; Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, for example 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-dimethylphenyl ethyl acetate, α,α-dimethylphenyl ethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate, 4-methoxybenzyl acetate; Aromatic ethers, such as 2-phenylethyl methyl ether, 2-phenylethyl isopentyl ether, 2-phenylethyl-1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, hydratropaaldehydedimethylacetal, phenylacetaldehyde glycerol acetal, 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 4,4a,5,9b-tetrahydroindene-[1,2-d]-m-dioxine, 4,4a,5,9b-tetrahydro-2,4-dimethylindene[1,2-d]-m-dioxine; Aromatic and aromatic aliphatic aldehydes such as, for example: benzaldehyde, phenylacetaldehyde, 3-phenylpropanal, Hydratropaaldehyd, 4-methylbenzaldehyde, 4-methylphenylacetaldehyde, 3-(4-ethylphenyl)-2,2-dimethylpropanal, 2-methyl-3-(4-isopropylphenyl)propanal, 2-methyl-3-(4-isobutylphenyl)propanal, 3-(4-tert-butylphenyl)propanal, cinnamaldehyde, α-butylcinnamaldehyde, α-hexylcinnamaldehyde, 3-methyl-5-phenylvaleraldehyde, 4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3-ethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 2-methyl-3-(4-methoxyphenyl)propanal, 2-methyl-3-(4-isopropylphenyl)propanal, 2-methyl-3-(4-isobutylphenyl)propanal, 3-(4-tert-butylphenyl)propanal, methyldioxyphenyl)propanal; aromatic and aromatic aliphatic ketones, for example 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-benzofuranethanone, 3-methyl-2-benzofuranyl)ethanone, benzophenone, 1,1, 2,3,6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone, 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-naphthone; Aromatic and araliphatic carboxylic acids and their esters, for example benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methylphenyl acetate, ethylphenyl acetate, geranylphenyl acetate, phenylethyl phenylacetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate; cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl 3-phenylglycidate, ethyl 3-methyl-3-phenylglycidate; Heterocyclic compounds, such as 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; Lactones, such as 1,4-octanolactone, 3-methyl-1,4-octanolactone, 1,4-nonanolactone, 1,4-decanolactone, 8-decene-1,4-lactone, 1,4-undecalactone, 1,4-dodecalactone, 1,5-decanolactone, 1,5-dodecalactone, 4-methyl-1,4-decanolactone, 1,15-pentadecalactone, 1,16-hexadecanolactone, 9-hexadecene-1,16-lactone, 10-oxo-1,16-hexadecanolactone, 11-oxo-1,16-hexadecanolactone, 12-oxo-1,16-hexadecanolactone, vinyl-1,12-dodecyl-dialactone, vinyl-1,13-tridecyl-dialactone, 2,3-dihydrocoumarin, octahydrocoumarin.

[0034] In a further preferred embodiment of the invention, the compounds of the formula I are preferably combined with one or more, particularly preferably with two, three, four, five or more, further fragrances having floral odor notes.

[0035] Accordingly, the present invention also relates to a fragrance composition comprising one, two, three, four, five or more other fragrances imparting a floral odor note.

[0036] The compounds used according to the invention advantageously achieve, at least in part, an odor enhancement of floral perfume notes.

[0037] In a preferred embodiment according to the present invention, at least one other fragrance is selected from the group consisting of 4-cyclohexylbutan-2-ol (Cyclohexylmagnol), 2-methyl-5-phenylpentan-1-ol (Rosaphen), 2-phenylethanol (phenylethanol), methyl-3-oxo-2-pentyl-1-cyclopentyl acetate (Hedion), 1-(4-isopropylcyclohexyl)-ethanol) (Mugetanol), 3,7-dimethyloct-6-en-1-ol (Citronellol), (2E)-3,7-dimethyloct-2,6-dien-1-ol (Geraniol), 2,6-dimethyl-7-octen-2-ol (Dihydromyrcenol) and / or 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majanthol) and / or benzyl 2-hydroxybenzoate (Benzyl salicylate).

[0038] Preferably, 5,5-dimethyltetrahydrofuran-2-one is combined with one or more, particularly preferably with two, three, four, five or more of those preferred further fragrances.

[0039] The perfume oil compositions (= perfume mixtures) containing at least one compound of the formula I are advantageously used for perfuming in liquid form, undiluted or diluted with a solvent. Suitable solvents for this are, for example: ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.

[0040] Furthermore, the fragrance composition according to the invention can be adsorbed on a carrier, which ensures both a fine distribution of the fragrance in the product and a controlled release during use. Such a carrier can be a porous inorganic material, such as light sulfate, silica gel, zeolite, gypsum, clay, clay particles, aerated concrete, etc., or an organic material, such as wood, cellulose-based substances, sugar, dextrin (such as maltodextrin) or plastic, such as PVC, polyvinyl acetate or polyurethane. The final combination of the composition according to the invention and the carrier substance should also be understood as the fragrance composition according to the invention.

[0041] The fragrance composition according to the invention can also be microencapsulated, spray-dried, as inclusion compound or as extruded product and added in this form to the product to be perfumed.

[0042] If desired, the properties of the composition modified in this way can be further optimized by so-called "coating" with suitable materials for a more targeted release of the fragrance, for which purpose waxy plastics such as polyvinyl alcohol are preferably used. The resulting product in turn represents the article according to the invention.

[0043] Another aspect of the invention relates to the use of a flavor composition to modify an existing flavor to make it rounder, more natural, more rich, more honeyed, more intense and / or more fruity and / or to impart, modify and / or enhance a flavor composition to make it less oily and / or less mushroomy. The preferred embodiments listed above also apply to the use of the flavor composition.

[0044] The perfume compositions according to the invention can advantageously be used in concentrated form, in the form of solutions or in the modified forms described above for the production of perfumed articles according to the invention, such as perfume extracts, perfume concentrates, eau de toilette, aftershaves, colognes, pre-shave products, cologne pomades and perfumed wet wipes, for the perfuming of acidic, alkaline and neutral cleaners, such as floor cleaners, glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring creams, solid and liquid toilet cleaners, carpet cleaners in powder and foam form, textile fresheners, ironing aids, liquid washing compositions, powdered washing compositions, laundry pretreatment preparations such as bleaches, soaking agents and stain removers, fabric softeners, washing soaps, laundry tablets, disinfectants, air fresheners in liquid form, gel form or in the form of an application to a solid carrier, aerosol sprays, waxes and polishes, such as furniture polishes, polishes, floor waxes, shoe creams and personal care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, 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 repair creams and lotions, hand creams and lotions, foot creams and lotions, hair removal creams and lotions, aftershave creams and lotions, suntan creams and lotions, hair care products such as hair sprays, hair gels, styling creams, conditioners, permanent and semi-permanent hair colorants, hair styling products such as cold wave and hair straightening products, hair nourishers, hair creams and shampoos, deodorants and antiperspirants such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, decorative cosmetics such as eye shadows, nail polishes, lipsticks, mascaras and candles, lamp oils, scented candles, insecticides, insect repellents and propellants.

[0045] Of course, the fragrance composition according to the present invention can also be contained in a cosmetic composition or a household composition.

[0046] Another aspect of the invention relates to a method for modifying an existing flavor to make it fruitier, juicier, milder, crisper, fresher, sweeter and / or more floral, Include or consist of the following steps: (a) providing at least one compound of formula I in R 1 represents H, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, vinyl, allyl, 2-methylprop-1-enyl or 2-methylallyl; R 2 represents H, methyl or ethyl and Dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. (b) providing at least one other flavorant; and (c) adding at least one compound of formula (I) to at least one other flavor in a sensory effective amount sufficient to modify an existing flavor to make it rounder, more natural, more rich, more honeyed, more intense and / or more fruity and / or to impart, modify and / or enhance the flavor composition to make it less greasy and / or less mushroomy.

[0047] Preferably, the weight ratio of at least one compound of formula I to the total amount of other fragrances is in the range of 1:10 to 1:100. More preferably, the weight ratio of at least one compound of formula I to the total amount of other fragrances is in the range of 1:600 ​​to 1:400.

[0048] In this context, preference is given to a total amount of at least one compound of the formula I of 0.0001 to 99.9% by weight, preferably 0.001 to 99.5% by weight, particularly preferably 0.01 to 99% by weight, 0.01 to 90% by weight, 0.01 to 50% by weight, 0.01 to 20% by weight, 0.01 to 10% by weight and particularly preferably 0.01 to 5% by weight, in particular 0.05 to 2.0% by weight, in each case based on the total weight of the composition.

[0049] In a preferred embodiment according to the present invention, at least one other fragrance is selected from the group consisting of 4-cyclohexylbutan-2-ol (Cyclohexylmagnol), 2-methyl-5-phenylpentan-1-ol (Rosaphen), 2-phenylethanol (phenylethanol), methyl-3-oxo-2-pentyl-1-cyclopentyl acetate (Hedion), 1-(4-isopropylcyclohexyl)-ethanol) (Mugetanol), 3,7-dimethyloct-6-en-1-ol (Citronellol), (2E)-3,7-dimethyloct-2,6-dien-1-ol (Geraniol), 2,6-dimethyl-7-octen-2-ol (Dihydromyrcenol) and / or 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majanthol) and / or benzyl 2-hydroxybenzoate (Benzyl salicylate).

[0050] Preferably, the compounds of the formula I are combined with one or more, particularly preferably with two, three, four, five or more of those preferred further fragrances.

[0051] Preferably, 5,5-dimethyltetrahydrofuran-2-one is combined with one or more, particularly preferably with two, three, four, five or more of those preferred further fragrances.

[0052] The other preferred embodiments listed above are also applicable to the method of the present invention.

[0053] Another aspect of the invention relates to a perfuming product comprising at least one compound of formula I in R 1 represents H, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, vinyl, allyl, 2-methylprop-1-enyl or 2-methylallyl; R 2 represents H, methyl or ethyl and Dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds, and Two or more other flavors and optionally other ingredients, characterized in that the product comprises at least one compound of formula (I) in an amount capable of modifying the olfactory properties of the two or more other flavors to make them rounder, more natural, more rich, more honeyed, more intense and / or more fruity and / or to impart, modify and / or enhance the flavor composition to make it less greasy and / or less mushroomy.

[0054] In a preferred embodiment, the perfumed product is selected from cosmetics, hygiene products and / or household products.The further preferred embodiments listed above also apply to the perfumed product according to the invention.

[0055] Preferably, the perfumed household product is selected from the group comprising detergents and cleaning agents, hygiene or care products, preferably in the field of body and hair care, cosmetics and household, preferably selected from the group comprising perfume extracts, perfumes, eau de toilette, aftershave, cologne, pre-shave products, cologne pomades, perfumed freshening tissues, acidic, alkaline or neutral detergents, textile fresheners, ironing aids, liquid washing compositions, powdered washing compositions, laundry pretreatment preparations, fabric softeners, laundry tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, personal care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, suntan creams and lotions, hair care products, decorative cosmetic products, candles, lamp oils, scented candles, insecticides, insect repellents and propellants. Most preferably, the perfumed product is selected from alcohol perfumes, personal hygiene products or cleaning or care products for household use.

[0056] Furthermore, the perfumed product according to the invention preferably comprises a sensory effective amount of at least one compound of formula I, which amount is sufficient to provide the consumer with one or more olfactory properties selected from the group consisting of rounder, more natural, more intense, more honeyed, more intense and / or more fruity and / or for imparting, modifying and / or enhancing a perfume composition to make it less oily and / or less mushroomy.

[0057] It is also preferred that the total amount of compounds of formula I is between 0.00001 and 10% by weight, preferably between 0.0001 and 5% by weight, particularly preferably between 0.001 and 2% by weight, more preferably between 0.1 and 2% by weight, based on the total weight of the perfumed product.

[0058] The above-mentioned additives, auxiliaries and / or active substances are preferably not odoriferous substances. These can be, for example, preservatives, antimicrobials, chelating agents, detergents, emulsifiers, fats, etc., and in principle all substances which are used as additives, auxiliaries and / or active ingredients in cosmetics, in particular perfume compositions and household compositions.

[0059] The other preferred embodiments listed above also apply to the perfumed product of the invention.

[0060] Next, the present invention will be further described based on examples. DETAILED DESCRIPTION

[0061] Example 1: Synthesis of 5,5-dimethyltetrahydrofuran-2-one

[0062] First Preparation Example

[0063] Under N2 atmosphere, between m-10 and 0 ℃, slowly add methylmagnesium bromide (1.4M in THF, 26.7mL, 82.8mmol) to 4-oxopentanoic acid methyl ester in the solution of 50ml dry THF. After adding, the reaction temperature is raised to room temperature and kept until the reaction is completed (~2h). Add saturated NH4Cl solution to the reaction mixture, use MTBE (50mL x 3) to extract the compound and evaporate in a rotary evaporator (60 ℃ / 450-10mbar) to obtain crude product (7.2g). Purify by Kugelrohr distillation (145 ℃, 10.0mbar) to obtain 6.6g title compound.

[0064] Second Preparation Example a) Synthesis of 4-hydroxy-4-methylbutyl valerate: Free Radical Reaction - A mixture of isopropanol (1950.5 g, 32.5 mol), butyl acrylate (208.0 g, 1.63 eq) and 2-tert-butylperoxy-2-methylpropane (22.0 g, 0.2 mol) (DTBP) was heated to 155-160°C in a 5L autoclave under nitrogen and maintained at 10-20 bar for 1 hour. The crude product (2212 g) was distilled (Destbrücke) at 130-168°C to give the title compound (23.5 g). GC-MS:188,173,115,99,74,59,43,28 b) Synthesis of 5,5-dimethyltetrahydrofuran-2-one A mixture of 4-hydroxy-4-methyl-butyl pentanoate (23.0 g, about 100 mmol), methanol (50 mL) and 19 g NaOH (32%, about 150 mmol) was refluxed for 2 hours. A large amount of methanol was evaporated off in a rotary evaporator (60° C. / 350-90 mbar) to obtain a crude product, to which a 10% H SO solution (100 ml) was added and heated at 40° C. for one hour. NaCl was added at room temperature and the compound was extracted with MTBE (100 ml). The organic layer was dried and evaporated (50° C., 400-70 mbar) with Na SO followed by Kugelrohr distillation (100° C., 15-5 mbar) to obtain 4.1 g of the title compound. 1H NMR (400MHz, CDCl3) δ2.62 (t, J = 8.2Hz, 2H), 2.06 (t, J = 8.2Hz, 2H), 1.43 (s, 6H). 13C NMR (101MHz, CDCl3) δ176.70,84.62,34.70,29.39,27.75,27.75. MS:114,99,81,70,55,43,39,28. Smell: Fruity, apricot, tonka, coumarin, creamy

[0065] Example 2: Synthesis of 5-ethyl-5-methyl-tetrahydrofuran-2-one

[0066] Synthesis of 4-methylhex-3-enenitrile (Step 1): A mixture of ammonium acetate (2.9 g, 0.04 mol), acetic acid (8.9 g, 0.15 mol), toluene (250 mL), methyl-2-butyraldehyde (32.0 g, 0.37 mol) and 2-cyanoacetic acid 98% ig (42.0 g, 0.49 mol) was refluxed until aldehyde was completely consumed (~8 hours). Further the reaction mixture was maintained between 105-115 ° C for 1 hour to eliminate water and decarboxylation for 5 hours. After this, by washing with 5% H SO (50 mL x 2) neutralize the reaction mixture and evaporate to obtain a crude product (17.2 g). Kugelrohr distillation (60 ° C, 0.5 mbar) obtains 4.6 g of 4-methylhexyl-3-enenitrile E: Z mixture (7: 3). 1H NMR (400MHz, C6D6) δ4.75 (tdt, J=6.9, 2.5, 1.4Hz, 1H), 2.27–2.21 (m, 2H), 1.67 (qd, J=7.5, 3.9Hz, 2H), 1.19–1.14 (m, 3H), 0.74 (mc, 3H). 13C NMR (101MHz, C6D6) δ143.15,118.32,111.31,31.99,15.79,15.75,12.16. MS:109,94,82,67,56,41,27 Smell: Herbal, Lovage, Almond, Cinnamon, Vegetable

[0067] ii) Synthesis of 5-ethyl-5-methyl-tetrahydrofuran-2-one A solution of 4-methylhex-3-enenitrile (2.0 g, 18.3 mmol) in toluene (10 mL) was added very slowly (30 min) to a mixture of concentrated H2SO4 (2.7 mL) and water (2.7 mL) at 140°C, and the reaction temperature was maintained between 117-120°C until the reaction was complete (~5 h). Cold water (10 mL) was added at room temperature, and the organic layer was washed with water until the pH of the aqueous layer was neutral and evaporated to give the crude product (0.9 g). Kugelrohr distillation (70°C, 0.76 mbar) gave 0.6 g of the title compound 5-ethyl-5-methyl-tetrahydrofuran-2-one. 1H NMR (400MHz, CDCl3) δ2.70–2.52(m,2H),2.15–2.03(m,1H),1.97(ddd,J=12.8,9.5,6.6Hz,1H),1.80–1.62(m,2H),1.38(s,3H),0.97(t,J=7.5Hz,3H). 13C NMR (101MHz, CDCl3) δ176.90,87.23,33.61,32.42,29.22,25.17,8.19. MS:128,113,99,84,73,86,43,27. Smell: lactone, coconut, green

[0068] Example 3: Synthesis of 5,5-diethyltetrahydrofuran-2-one

[0069] Synthesis of 4-ethylhex-3-enenitrile - Step 1 Reflux ammonium acetate (1.16g, 15mmol), acetic acid (2.17mL, 38mmol), toluene (100mL), 2-ethylbutyraldehyde (10.2g, 100mmol) and 2-cyanoacetic acid 98%ig (9.36,110mmol), azeotropic distillation until reaction is completely consumed. After this, by washing with water several times, neutralize reaction mixture and evaporate to obtain crude product (7.2g). Kugelrohr distillation (65 ℃, 0.5mbar) obtains 4.5g 4-ethylhexyl-3-enenitrile nitrile E:Z mixture (7:3). MS:123,108,96,81,67,55,41,27 1H NMR (400MHz, CDCl3) δ5.11 (t, J = 7.1Hz, 1H), 3.06 (d, 2H), 2.12–2.00 (m, 4H), 1.05–0.96 (m, 6H). 13C NMR (101MHz, CDCl3) δ149.62,118.89,109.86,28.90,23.54,15.86,12.58,12.25 Smell: Mushroom, almond, watery

[0070] ii) Synthesis of 5,5-diethyltetrahydrofuran-2-one - Step 2 A solution of 4-ethylhex-3-enenitrile (4.0 g, 32.5 mmol) in toluene (20 mL) was added very slowly (30 minutes) to a mixture of concentrated H2SO4 (5.0 mL) and water (2.7 mL) at 140°C. The reaction was maintained between 128-135°C until the reaction was complete (approximately 5 hours). At room temperature, cold water (10 mL) was added, and the organic layer was washed with water until the pH of the aqueous layer was neutral and evaporated to give a crude product (2.7 g). Kugelrohr distillation (80°C, 0.9 mbar) gave 1.8 g of the title compound 5,5-diethyltetrahydrofuran-2-one. 1H NMR (400MHz, CDCl3) δ2.65–2.52(m,2H),2.01(dd,J=9.1,8.0Hz,2H),1.81–1.57(m,4H),0.94(t,J=7.5Hz,6H). 13C NMR (101MHz, CDCl3) δ177.12,89.63,30.87,30.87,29.82,29.23,7.80,7.80. MS:142,127,109,99,87,71,56,43,27 Odor: lactone, green, fatty, weak coconut

[0071] Example 4: Synthesis of 5-methyl-5-vinyl-tetrahydrofuran-2-one Allylmagnesium bromide (1.0M in DEE, 100.0mL, 99.8mmol) was slowly added to a 50ml dry THF solution of methyl 4-oxopentanoate (44.5g, 617.1mmol) at -10°C to 0°C. After addition, the reaction temperature was raised to room temperature and maintained until the reaction was complete (~3.5h). A saturated solution of NH4Cl was added to the reaction mixture, and the compound was extracted with MTBE (60mL x 3) and evaporated in a rotary evaporator (40°C / 450-10mbar) to obtain a crude product (11.89g). Purification by Kugelrohr distillation (90-115°C, 0.1mbar) gave 6.9g of the title compound. 1H NMR (400MHz, CDCl3) δ5.96–5.86(m,1H),5.34–5.26(m,1H),5.19–5.13(m,1H) ,2.63–2.52(m,2H),2.26–2.17(m,1H),2.14–2.04(m,1H),1.54–1.49(m,3H). 13C NMR (101MHz, CDCl3) δ176.68,140.01,113.73,85.41,33.82,28.74,26.29 MS:126,111,99,83,67,55,43,27. Smell: Minty, sweet, almond

[0072] Example 5: Synthesis of 5-allyl-5-methyl-tetrahydrofuran-2-one Vinyl magnesium chloride (1.0M in THF, 100.0g, 99.0mmol) was slowly added to a 50ml dry THF solution of methyl 4-oxopentanoate (12.0g, 92.3mmol) at -10°C to 0°C. After addition, the reaction temperature was raised to room temperature and maintained until the reaction was complete (~2h). A saturated solution of NH4Cl was added to the reaction mixture, and the compound was extracted with MTBE (60mL x 3) and evaporated in a rotary evaporator (40°C / 450-10mbar) to obtain a crude product (10.0g). The product was purified by Kugelrohr distillation (70-130°C, 0.1mbar) and then by column chromatography (cyclohexane / ethyl acetate, 20:1) to obtain 11.7g of the title compound. 1H NMR(600MHz, CDCl3) δ5.79(ddt,J=16.9,10.3,7.3Hz,1H),5.18(ddt,J=10.3,2.0,1.0Hz ,1H),5.17(dq,J=17.0,1.9,1.4Hz,1H),2.62(ddd,J=18.0,9.5,7.6Hz,1H),2.57(ddd,J= 18.1,9.5,6.7Hz,1H),2.44(ddt,J=14.0,7.5,1.0Hz,1H),2.41(ddt,J=14.0,7.4,1.0Hz, 1H), 2.16 (ddd, J=12.9, 9.5, 7.6Hz, 1H), 1.96 (ddd, J=13.0, 9.6, 6.8Hz, 1H), 1.40 (s, 3H). 13C NMR (151MHz, CDCl3) δ176.69,132.05,119.78,85.96,45.25,32.15,29.15,26.12. MS.140,125,107,99,71,55,43,39,27 Scent: Fresh, Coconut, Soft, Natural

[0073] Example 6: Synthesis of 5-methyl-5-(2-methylprop-1-enyl)tetrahydrofuran-2-one and 5-methyl-5-(2-methylallyl)tetrahydrofuran-2-one

[0074] Synthesis of 5-(2-hydroxy-2-methyl-propyl)-5-methyl-tetrahydrofuran-2-one: A mixture of 2-methyl-2,4-pentanediol (472.7 g, 4.0 mol) and a catalytic amount of aluminum isopropoxide (250 g) was heated to 155° C. A pre-prepared mixture of methyl acrylate (43.04 g, 0.50 mol), 2-methyl-2,4-pentanediol (118.18 g, 1.0 mol) and DTBP (7.32 g, 0.05 mol) was added very slowly between 150 and 155° C. over about 3 hours. After the addition, the alcohol was first distilled off, and then the product (23.4 g) (R T =110-150℃, H T =46-96°C, 0.1 mbar) to proceed to the next step.

[0075] Synthesis of 5-methyl-5-(2-methylprop-1-enyl)tetrahydrofuran-2-one and 5-methyl-5-(2-methylallyl)tetrahydrofuran-2-one: Use vigreux column (RT =152℃,H T =148-150 ℃, 0.1mbar) distilled a mixture of 5-(2-hydroxy-2-methyl-propyl)-5-methyl-tetrahydrofuran-2-one (23.4g) and a catalytic amount of K-10 (2.3g) to obtain 17.6g of 5-methyl-5-(2-methylprop-1-enyl)tetrahydrofuran-2-one, 5-methyl-5-(2-methylallyl)tetrahydrofuran-2-one product (1:3). 1 H NMR (600 MHz, CDCl3) δ 5.39 (m c ,1H),4.95(dd.J=1.5,2.2Hz,1H),4.79(dd.J=0.9,2.2Hz,1H),2.58(m c ,4H),2.42(dd.J=13.9,0.9Hz,1H),2.37(dd.J=0.9,13.9Hz,1H),2.19(m c ,3H),1.94(ddd.J=6.3,9.4,12.9Hz,1H),1.81(dd.J=1.5,0.9Hz,3H),1.77(d,J=1.7Hz,3H),1.73(d,J=1.7Hz,3H),1.56(s,3H),1.39(s,3H). 13 C NMR (151MHz, CDCl3) δ176.84,176.72,140.95,136.21,127.61,116.09,86.42, 86.06,48.67,36.11,32.97,29.18,29.14,27.29,26.82,26.09,24.06,19.11. Smell: tonka, coconut, tobacco

[0076] Example 7: Synthesis of 5-methyl-5-octyl-tetrahydrofuran-2-one

[0077] Synthesis of 4-methyldodec-3-enenitrile: A mixture of ammonium acetate (2.3 g, 0.03 mol), acetic acid (6.9 g, 6.6 mL, 0.11 mol), toluene (150 mL), 2-methyldecanal (75.0 g, 0.38 mol) and 2-cyanoacetic acid 98% ig (32.50 g, 0.38 mol) was refluxed until the aldehyde was completely consumed (~8 h). The further reaction mixture was maintained between 113-118 ° C to eliminate water for 1 hour and decarboxylate for 5 hours. Thereafter, the reaction mixture was neutralized by washing with 5% H2SO4 (100 mL×2) and evaporated to obtain a crude product (71.6 g). Kugelrohr distillation (121 ° C, 0.7 mbar) gave 51 g of a nitrile E:Z mixture (7:3) of 4-methyldodec-3-enenitrile. 1 H NMR (400MHz, CDCl3) δ5.15 (tp, J=6.9, 1.4Hz, 2H), 3.04 (dq, J=7.0, 1.0Hz, 4H), 2.06–1.98 (m, 4H), 1.74 (q,J=1.3Hz,3H),1.66(d,J=1.4Hz,3H),1.45–1.31(m,4H),1.31–1.20(m,20H),0.88(t,J=6.8Hz,6H). 13 C NMR (101MHz, CDCl3) δ142.84,142.74,118.71,118.67,111.91,111.28,39.23,31.93,31.88,31.89,31.87, 29.53,29.48,29.44,29.25,29.21,27.51,27.51,23.16,22.67,22.66,16.27,16.20,16.09,14.10,14.10. MS:193,178,164,150,136,122,109,96,81,70,56,41,29 Smell:Coriander

[0078] Synthesis of 5-methyl-5-octyl-tetrahydrofuran-2-one A solution of 4-methyldodec-3-enenitrile (20.0 g, 0.1 mol) in toluene (20 mL) was added very slowly (30 min) to a mixture of concentrated H2SO4 (8.2 mL) and water (4.1 mL) at 140°C. The reaction was maintained between 130-135°C until the reaction was complete (~5 h). Cold water (10 mL) was added at room temperature, and the organic layer was washed with water until the pH of the aqueous layer was neutral and evaporated to give the crude product (19.8 g). Kugelrohr distillation (130°C, 0.9 mbar) gave 17.2 g of the title compound 5-methyl-5-octyl-tetrahydrofuran-2-one. 1 H NMR (400MHz, CDCl3) δ2.68–2.51(m,2H),2.13–2.04(m,1H),2.02–1.92(m,1H),1.73–1.58(m,2H),1.38(s,3H),1.38–1.17(m,12H),0.88(t,3H). 13 C NMR (101MHz, CDCl3) δ176.89,86.99,41.02,32.95,31.84,29.85,29.46,29.21,29.21,25.66,23.86,22.65,14.10. GC / MS(EI):212,197,179,114,99,83,71,55,43 Odor: Weak lactone and fat

[0079] Example 8: Synthesis of 5-methyl-5-nonyl-tetrahydrofuran-2-one

[0080] Synthesis of (E / Z)4-Methyltridecene-3-nitrile A mixture of ammonium acetate (2.3 g, 0.03 mol), acetic acid (6.9 g, 6.6 mL, 0.11 mol), toluene (150 mL), 2-methylundecane (70.0 g, 0.38 mol) and 2-cyanoacetic acid 98% ig (32.50 g, 0.38 mol) was refluxed until the aldehyde was completely consumed (~8 h). The further reaction mixture was maintained between 113-118 ° C to eliminate water for 1 hour and decarboxylate for 5 hours. Thereafter, the reaction mixture was neutralized by washing with 5% H2SO4 (100 mL×2) and evaporated to obtain a crude product (61.9 g). Kugelrohr distillation (128 ° C, 0.7 mbar) gave 42.6 g of an E:Z mixture (2:1) of 4-methyltridecenenitrile. 1H NMR (400MHz, CDCl3) δ5.15 (ddq, J=6.9, 5.6, 1.4Hz, 2H), 3.04 (dq, J=7.0, 0.9Hz, 4H), 2.02 (dd, J=8.8, 6.7Hz, 4H),1.74(q,J=1.3Hz,3H),1.66(q,J=1.0Hz,3H),1.48–1.35(m,4H),1.34–1.20(m,24H),0.94–0.83(m,6H). 13 C NMR (101MHz, CDCl3) δ142.84,142.75,118.71,118.61,111.91,111.28,39.24,31.94,31.90,31.88,29.55, 29.53,29.48,29.36,29.32,29.31,29.21,27.52,23.16,22.68,22.68,16.27,16.20,16.09,14.11,14.11. MS:207,192,178,164,150,136,112,96,83,70,55,43,29. Smell: Orange, nitrile, fat

[0081] Synthesis of 5-methyl-5-nonyl-tetrahydrofuran-2-one A solution of 4-methyltridecenenitrile (20.0 g, 0.1 mol) in toluene (20 mL) was added very slowly (30 min) to a mixture of concentrated H2SO4 (8.2 mL) and water (4.1 mL) at 140 °C. The reaction was maintained between 130–135 °C until the reaction was complete (~5 h). Cold water (10 mL) was added at room temperature, and the organic layer was washed with water until the pH of the aqueous layer was neutral and evaporated to give the crude product (19.3 g). Kugelrohr distillation (130 °C, 0.9 mbar) gave 17.6 g of the title compound 5-methyl-5-nonyl-tetrahydrofuran-2-one. 1 H NMR(400MHz, CDCl3) δ2.69–2.50(m,2H),2.09(ddd,J=12.9,9.3,8.0Hz,1H),1.97(ddd,J=12 .8,9.4,6.6Hz,1H),1.70–1.57(m,2H),1.38(s,3H),1.36–1.19(m,14H),0.94–0.82(m,3H). 13C NMR (101MHz, CDCl3) δ176.88,86.98,41.02,32.95,31.87,29.85,29.53,29.51,29.29,29.21,25.66,23.86,22.68,14.11. MS:226,211,193,171,151,127,114,99,83,71,55,43,29. Odor: Very weak lactone odor.

[0082] Example 9: Synthesis of 5-butyl-5-ethyl-tetrahydrofuran-2-one

[0083] Synthesis of (E / Z)-4-ethyloct-3-enenitrile: prepared according to WO 2018192665 1 H NMR (400MHz, CDCl3) δ5.17–5.08(m,2H),3.07(s,4H),2.13–1.97(m,8H),1.35(s,8H),1. 01(t,J=7.4Hz,3H),1.00(t,J=7.6Hz,3H),0.92(t,J=7.1Hz,3H),0.91(t,J=7.2Hz,3H). 13 C NMR (101MHz, CDCl3) δ148.29,148.21,118.87,118.85,110.81,110.41,35.87,30.27, 30.13,29.89,29.31,23.35,22.77,22.41,16.05,15.88,13.94,13.94,12.56,12.30. Smell: Rose, Green, Nitrile, Iris, Carrot, Dry

[0084] Synthesis of 5-Butyl-5-ethyl-tetrahydrofuran-2-one A solution of concentrated H2SO4 (75.0 g) in water (25.5 g) was heated to 140°C. 4-ethyl-oct-3-enenitrile (Lit: Symrise AG; WO2018192665) (100.0 g, 0.66 mol) was added very slowly over about 1 h (very strong exotherm) and the reaction was maintained at 130-135°C for 2 hours. At room temperature, the reaction mixture was poured into cold water, neutralized, and evaporated to give a crude product (99.8 g). Purification by spaltrohr and then kugelrohr distillation gave 77.6 g of the product. MS:141,113,95,81,69,57,41 1 H NMR(400MHz, CDCl3) δ2.58(dd,J=9.1,8.0Hz,2H),2.02(dd,J=9.1,8.0Hz,2H),1.77–1 .66(m,2H),1.68–1.60(m,2H),1.41–1.24(m,4H),0.94(t,J=7.4Hz,3H),0.91(t,3H). 13 C NMR (101MHz, CDCl3)δ171.10,89.41,38.00,31.34,30.33,29.22,25.57,22.99,13.97,7.86. Odor: coconut, lactone, fruity

[0085] Example 10: Synthesis of 5-butyl-5-ethyl-furan-2-one

[0086] Synthesis of 4-ethyloctane-3,5-dienenitrile: A mixture of ammonium acetate (4.7 g, 0.06 mol), acetic acid (13.8 g, 0.23 mol), toluene (300 g), 2-ethylhex-2-enal (100.0 g, 0.75 mol) and 2-cyanoacetic acid 98% ig (64.50 g, 0.76 mol) was refluxed until the aldehyde was completely consumed (~8 h). The reaction mixture was further maintained between 113-118 ° C to eliminate water for 1 hour and decarboxylate for 5 hours. Thereafter, the reaction mixture was neutralized by washing with 5% H2SO4 (100 mL×2) and evaporated to obtain a crude product (113.8 g). Kugelrohr distillation (60–90 ° C, 0.5 mbar) gave 59 g of an E:Z mixture (7:3) of the title compound nitrile. 1 H NMR(400MHz, CDCl3)δ5.92(d,J=15.9Hz,1H),5.85–5.79(m,1H),5.26(t,J=7.2Hz,1 H),3.15(d,J=7.2Hz,2H),2.31–2.17(m,2H),2.17–2.07(m,2H),1.13–0.98(m,6H). 13 C NMR (101MHz, CDCl3) δ145.40,132.73,130.07,118.29,114.53,25.87,20.21,16.11,13.61,13.28.MS:149,134,120,10 Smell: Green, Cucumber, Soap, Nitrile

[0087] Synthesis of 5-Butyl-5-ethyl-furan-2-one A solution of concentrated H2SO4 (7.5 g) in water (2.6 g) was heated to 140°C. 4-ethyl-octa-3,5-dienenitrile (7.5 g, 0.07 mol) was added very slowly over about 30 minutes (very strong exotherm) and the reaction was maintained at 130-135°C for 2 hours. At room temperature, the reaction mixture was poured into cold water, neutralized, and evaporated to give a crude product (1.7 g). Purification by kugelrohr distillation (105°C, 0.8 mbar) gave 0.6 g of product. MS:168,139,113,95,67,57,41,29 GC-Sniff: Pungent, technical, earthy

Claims

1. At least one compound of formula I Used as a spice, in R 1 represents H, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, vinyl, allyl, 2-methylprop-1-enyl or 2-methylallyl; R 2 represents H, methyl or ethyl and Dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds.

2. The use according to claim 1, wherein R 1 represents methyl, ethyl, butyl, vinyl, allyl, 2-methylprop-1-enyl, 2-methylallyl, octyl or nonyl; and R 2 Represents methyl or ethyl.

3. The use according to claim 1 and / or 2, wherein the compound of formula I is selected from the group consisting of 5,5-dimethyltetrahydrofuran-2-one, 5-Ethyl-5-methyl-tetrahydrofuran-2-one, 5,5-diethyltetrahydrofuran-2-one, 5-methyl-5-vinyl-tetrahydrofuran-2-one, 5-allyl-5-methyl-tetrahydrofuran-2-one, 5-methyl-5-(2-methylprop-1-enyl)tetrahydrofuran-2-one, 5-methyl-5-(2-methylallyl)tetrahydrofuran-2-one, 5-methyl-5-octyl-tetrahydrofuran-2-one, 5-methyl-5-nonyl-tetrahydrofuran-2-one, 5-butyl-5-ethyl-tetrahydrofuran-2-one, 5-butyl-5-ethylfuran-2-one.

4. The use according to claim 1 and / or 2, wherein the compound of formula I is 5,5-dimethyltetrahydrofuran-2-one.

5. Use of claims 1 to 4 in a fragrance composition to obtain at least one of the following notes: fruity, apricot, coumarin, creamy, coconut, green, minty, sweet, almond, fresh, soft, natural, tonka, tobacco, hay.

6. Use according to claims 1 to 5 for imparting, modifying and / or enhancing a flavor composition to make it rounder, more natural, more intense, more honeyed, more intense and / or more fruity and / or for imparting, modifying and / or enhancing a flavor composition to make it less oily and / or less mushroomy.

7. A fragrance composition comprising at least one compound of formula I in R 1 represents H, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, vinyl, allyl, 2-methylprop-1-enyl or 2-methylallyl; R 2 represents H, methyl or ethyl and Dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. and at least one other flavoring, or consisting thereof.

8. The flavor composition according to claim 7, wherein the compound of formula I is selected from the group consisting of 5,5-dimethyltetrahydrofuran-2-one, 5-Ethyl-5-methyl-tetrahydrofuran-2-one, 5,5-diethyltetrahydrofuran-2-one, 5-methyl-5-vinyl-tetrahydrofuran-2-one, 5-allyl-5-methyl-tetrahydrofuran-2-one, 5-methyl-5-(2-methylprop-1-enyl)tetrahydrofuran-2-one, 5-methyl-5-(2-methylallyl)tetrahydrofuran-2-one, 5-methyl-5-octyl-tetrahydrofuran-2-one, 5-methyl-5-nonyl-tetrahydrofuran-2-one, 5-butyl-5-ethyl-tetrahydrofuran-2-one, 5-butyl-5-ethylfuran-2-one.

9. The fragrance composition according to claim 7 and / or 8, wherein the weight ratio of at least one compound of formula I to the total amount of other fragrances is in the range of 1:10 to 1:

100.

10. The flavor composition according to claim 9, wherein the weight ratio of at least one compound of formula I to the total amount of other flavors is in the range of 1:600 ​​to 1:

400.

11. The fragrance composition according to claims 7 to 10, wherein the amount of at least one compound of formula I is in the range of 0.01 to 5% by weight, based on the total weight of the fragrance composition.

12. Flavor composition according to at least one of claims 7 to 11, wherein at least one compound of formula I is contained in a sensory effective amount, which is sufficient to modify existing flavors to make them rounder, more natural, more tangy, more honey-like, more intense and / or more fruity and / or to impart, modify and / or enhance flavor compositions to make them less greasy and / or less mushroomy.

13. The fragrance composition according to at least one of claims 7 to 12, wherein at least one other fragrance is selected from the group consisting of 4-cyclohexylbutan-2-ol (Cyclohexylmagnol), 2-methyl-5-phenylpentan-1-ol (Rosaphen), 2-phenylethanol (Phenylethyl alcohol), methyl-3-oxo-2-pentyl-1-cyclopentyl acetate (Hedion), 1-(4-isopropylcyclohexyl)-ethanol) (Mugetanol), 3,7-dimethyloct-6-en-1-ol (Citronellol), (2E)-3,7-dimethyloct-2,6-dien-1-ol (Geraniol), 2,6-dimethyl-7-octen-2-ol (Dihydromyrcenol) and / or 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majanthol) and / or benzyl 2-hydroxybenzoate (Benzyl salicylate).

14. Use of a flavor composition according to at least one of claims 7 to 13 to modify existing flavors to make them rounder, more natural, more intense, more honeyed, more intense and / or more fruity and / or to impart, modify and / or enhance a flavor composition to make it less oily and / or less mushroomy.

15. Perfumed product containing at least one compound of formula I in R 1 represents H, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, vinyl, allyl, 2-methylprop-1-enyl or 2-methylallyl; R 2 represents H, methyl or ethyl and Dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. Two or more other spices and optional other ingredients, characterized in that The product comprises at least one compound of formula (I) in an amount capable of modifying the olfactory properties of two or more other flavors to make them rounder, more natural, more rich, more honeyed, more intense and / or more fruity and / or to impart, modify and / or enhance the flavor composition to make it less greasy and / or less mushroomy.

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