Sensory impact of substituted chromanones and furochromanones

Abstract

The present invention relates to sensorial chromanones and furochromanones and their impact on the aroma profile.

Description

[0001] Sensory Impact of substituted Chromanones and Furochromanones

[0002] The present invention relates to sensory impact of chromanones and furochromanones and their use in modulating, e.g., enhancing and / or improving, the aroma profile of a flavor, odorant or fragrance

[0003] Native cold-pressed lime oils are often described to be the “champagne” of citrus oils (Colombo et al. Citrus Oils in Food and Beverages: Uses and Analyses. In Citrus: The Genus Citrus; Dugo, G., Di Giacomo, A., Eds.; Medicinal and Aromatic Plants-lndustrial profiles; Taylor & Francis: London; New York, 2002; pp 539-556). They have been held in high regard for their unique aroma for more than 300 years (Flavourings: Production, Composition, Applications, Regulations, 2., compl. rev. ed.; Ziegler, H., Ed ; Wiley-VCH: Weinheim 2007; Di Giacomo, A. Development of the Citrus Industry: Historical Note. In Citrus: The Genus Citrus; Medicinal and Aromatic Plants-lndustrial profiles; Taylor & Francis: London New York, 2002; pp 63-70). Today, the annual production of limes and lemons exceeds more than 20 million tons worldwide, whereas about 6% of the crop is further processed into juices and essential oils (FAOSTAT: Food and Agriculture Data. Food and Agriculture Organization of the United Nations. Citrus fruit fresh and processed Statistical bulletin 2020; Food and Agriculture Organization of the United Nations Rome, 2021). An important commodity are cold pressed lime oils, which are widely used in flavourings for non-alcoholic and alcoholic beverages, sweets and savory products, in pharmaceutical preparations, cleaning products and perfumes (Colombo et al., supra; Buccellato, F. Citrus Oils in Perfumery and Cosmetic Products In Citrus: The Genus Citrus; Medicinal and Aromatic Plants— Industrial profiles; Taylor & Francis: London ; New York, 2002; pp 557-567.). Newest findings reveal a wide spectra of lime varieties of which only two are currently of commercial interest: Citrus aurantifolia and Citrus latifolia. Their native cold-pressed oils can be produced in various ways.

[0004] Cold-pressed lime oils and their volatiles have already been extensively analyzed and characterized in the past (Citrus Oils: Composition, Advanced Analytical Techniques, Contaminants, and Biological Activity; Dugo, G., Mondello, L., Eds.; Medicinal and aromatic plants- industrial profiles; CRC Press: Boca Raton, FL, 2011 ; Gonzalez-Mas et al. Volatile Compounds in Citrus Essential Oils: A Comprehensive Review. Front. Plant Sci. 2019, 10, 12.). The typical volatile components, such as terpenes, sesquiterpenes, aldehydes, oxygenated terpenes and esters contribute primary to the overall lime aroma.

[0005] Oxygen heterocyclic compounds, including coumarins, are present in the non-volatile fraction of lime oils (Russo et al. Coumarins, Psoralens and Polymethoxyflavones in Cold- Pressed Citrus Essential Oils: A Review. J. Essent. Oil Res. 2021 , 33 (3), 221-239). Coumarin and its derivatives are generated during the secondary metabolism of various plant species and are involved in plant growth, photo synthesis and defense mechanisms (Onder, A. Anticancer Activity of Natural Coumarins for Biological Targets. In Bioactive Natural Products; Studies in Natural Products Chemistry; Elsevier B.V.: Amsterdam, 2020; Vol. 64, pp 85-109).

[0006] Lately, coumarins and psolarens also became prominent as marker substances for the authenticity assessment of lime and lemon juices (Jungen et al. Coumarins, Psoralens, and Quantitative 1 H-NMR Spectroscopy for Authentication of Lemon (Citrus Limon [L.] Burm.f.) and Persian Lime (Citrus x Latifolia [Yu. Tanaka] Tanaka) Juices. Food Chem. 2021 , 359, 129804.). However, their sensory contribution and impact onto the overall lime aroma have not yet been thoroughly studied. Although they seem to have a significant contribution to the aroma, especially coumarin-like notes in lime are not completely understood until today (Liu et al. Dietary Bioactives and Essential Oils of Lemon and Lime Fruits. Food Sci. Hum. Wellness 2022, 11 (4), 753-764).

[0007] There is sustained interest in finding substances for the creation of new aromas. Especially naturally occurring substances, which can be produced by green, environmentally friendly methods, are of great interest. Thus, the object of the present invention is to provide compounds with unexplored sensory impact that can be used for modulating the profile of aroma compositions. DESCRIPTION OF THE INVENTION

[0008] By combining distillation, fractionation, olfactory detection and structure elucidation, the responsible key aroma components of cold pressed lime oil were identified. This distillation ensured the removal of the most volatile compounds like monoterpenes, and enrichment of the compound class of interest. Oxygen heterocyclic compounds accumulated in the bottom fraction were further separated by means of MPLC. 17 MPLC fractions were obtained for each oil, and subsequently investigated by using GC / MS-O with the help of three panelists. Unknown peaks with an intense coumarin-like odor were detected and characterized based on their MS spectra. Identity was finally confirmed by synthesizing and analysis of the postulated compounds. Following this approach, the inventors identified a combination of coumarins and their corresponding saturated chromanones that contribute significantly to the typical coumarin-like aroma, including three new constituents that were not yet described in literature as lime oil constituents: 7-methoxy-2-chromanone (3,4-dihydro- 7-methoxy-2H-1-benzopyran-2-one; CAS 20921-02-2), 5,7-dimethoxy-2-chromanone (3,4- dihydro-5,7-dimethoxy-2H-1-benzopyran-2-one; CAS 82243-01-4) and 5,6-dihydrobergap- tene (5,6-dihydro-4-methoxy-7H-furo[3,2-g][1]benzopyran-7-one; CAS 29050-61-1). Sensory evaluation of the impact of those components on the overall lime aroma and their interactions have shown synergistic and modulative effects. The accompanying research activities on the present invention will be submitted for publication (LJ Schulze, U Schafer, L Zygalski, M Verwohlt, S Otte-Hblscher, A Issa, F Hentschel, M Wiist, G Krammer. Sensory Impact of Novel Dihydrocoumarins in Native Lime Oils. JAFC, 2023 in preparation).

[0009] According to a first aspect, the object is achieved by using at least one compound of formula (I) or (II) wherein Ri, R2, R3 and R4 are independently selected from the group consisting of H, OH, OCH3 or OCH2CH3, wherein a compound of formula (1) in which R1, R2, R3 and R4 are all H is excluded, for modulating the profile of an aroma composition. To arrive at the present invention, the inventors sought to reveal compounds with unexplored sensory activities in lime oils. Specifically, distillation and fractionation experiments starting from native cold-pressed oil of C. latifolia and of cold-pressed C. aurantifolia oil have been conducted with the specific focus to enrich the coumarin rich parts of the native oils and to identify and characterize unexplored components for the sensory contribution to the typical aroma profile of cold pressed lime oils and to reveal their interactions.

[0010] Three specific compounds have been identified for their sensory contribution to the aroma profile. These include 3,4-Dihydro-7-methoxy-2 / 7-1-benzopyran-2-one (also referred herein to as 7-methoxy-2-chromanone), 3,4-Dihydro-5,7-dimethoxy-2 / 7-1-benzopyran-2- one (also referred herein to as 5,7-dimethoxy-2-chromanone) and 5,6-Dihydro-4-methoxy- 7H-furo[3,2-g][1]benzopyran-7-one (also referred herein to as 5,6-dihydrobergaptene), represented by the following formulas (l-a), (l-b) and (ll-a), respectively:

[0011] Further objects, aspects and embodiments of the present invention become apparent from the following explanations, the appended examples and, in particular, the appended patent claims.

[0012] The compounds of formulas (l-a), (l-b) and (II) form a particular preferred embodiment of the present invention. They have been characterized to contribute significantly to the typical coumarin-like aroma of cold pressed lime oils (C. latifolia, C. aurantifolia). They can be used individually or in combination with each other. Reference is made in this respect to the example section. Specific combinations include the following (the signs “+” and mean that the respective compound is respectively included in and I or excluded from the combination):

[0013] In the present invention, the at least one compound of formula (I) or (II) is used in a sensory effective amount. This means that in the amount used it provides a perceptible effect on the aroma profile of a composition. To determine the sensory effective amount, the compounds of formula (I) or (II) were profiled in their naturally occurring concentrations alone and in combination on a neutral tasting solution. Furthermore, their sensory impact was evaluated by using a lime base reproducing the basic aroma of native cold pressed lime oils but lacking coumarins and dihydrocoumarins, and by combining the lime base with compounds of formula (I) or (II), alone and in combination with each other. On the base of the results, the following amount(s) is / are preferred:

[0014] Preferably, the aroma composition contains the at least one compound of formula (I) or (II) in an amount of:

[0015] • more than 10 ppb compound of formula (l-a); and / or

[0016] • more than 20 ppb compound of formula (l-b); and / or more than 20 ppb compound of formula (ll-a). Advantageously, the compounds of the present invention have manifold aroma modulation capabilities. In many embodiment, the modulation is an improvement or enhancement of, or a shifting towards, aroma or taste notes selected from the group consisting of coumarin- like, juicy, fruity, floral, honey-like, fresh, lime, lemon, zesty, herbaceous, earthy, buttery, aniseed, caramel, toffee, sweet, sour or creamy. On the base of their capabilities, the compounds of the present invention are particularly suitable for being used (as part of an aroma composition) in foodstuff, luxury food, food supplements, pharmaceutical preparations, medicinal preparations, cosmetic preparations, oral hygiene preparations, fragrances, preparations consumed for pleasure, and semi-finished products thereof.

[0017] Another aspect of the present invention is a mixture comprising at least one compound of formulas (l-a), (l-b) and (ll-a):

[0018] (i) more than 10 ppb, preferably more than 50 ppb, more preferably more than 500 ppb, compound of formula (l-a); and / or

[0019] (ii) more than 20 ppb, preferably more than 100 ppb, more preferably more than 1000 ppb, compound of formula (l-b); and / or (iii) more than 20 ppb, preferably more than 100 ppb, more preferably more than 1000 ppb, compound of formula (ll-a).

[0020] Preferred mixtures of the invention contain: a. a compound of formula (l-a) and a compound of formula (l-b); or b. a compound of formula (l-a) and a compound of formula (ll-a); or c. a compound of formula (l-b) and a compound of formula (ll-a); or d. a compound of formula (l-a), a compound of formula (l-b) and a compound of formula (ll-a).

[0021] In the mixtures, the amount of the respective compound is independently selected from those given above for the respective compound.

[0022] Preferably, the mixture is not derived by use of essential oils or extracts. This means, for instance, that the mixture includes an amount and / or a ratio of compounds of formulas (I) and (II) which exceeds the amount of formulas (I) and (II) introduced by naturally occurring amounts in essential oils or extracts when used in an aroma composition in a pleasant tasting dosage.

[0023] In further preferred embodiments, mixtures of the invention comprises (iv) a flavoring other than a compound of formulas (I) and (II). Another flavoring may be selected from the group consisting of aliphatic flavoring substances, especially saturated aliphatic alcohols, such as ethanol, isopronanol, butanol, isoamyl alcohol, hexanol, 2-heptanol, octanol (1 / 2 / 3), decanol, unsaturated aliphatic alcohols, such as cis-2 pentenol, cis-3 hexenol, trans-2 hexenol, trans-3 hexenol, cis-2 octenol, 1-octen-3-ol, cis-6 nonen-1-ol, trans-2, cis-6 nonadienol, aliphatic aldehydes such as saturated aliphatic aldehydes (e.g. acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isolvaleraldehyde, homoeriodictyol, hexanal, 3-methyl hexanal, octanal, nonanal, or mono- or multi-unsaturated aliphatic aldehydes, such as 2-methyl but-2-enal, trans-2 hexenal, cis-3 hexenal, cis-4 hex- enal, trans-2 octenal, trans-2 nonenal, cis-6 nonenal, trans- 2, cis-6 nonadienal, trans 2 decenal, trans-2, trans-decadienal, aliphatic ketones, e.g. saturated ketones (such as 2- butanone, 2-pentanone, 2- heptanone, 2-octanone, 2-methylheptan-3-one, 2-decanone, 2- undecanone), unsaturated ketones (such as 1-penten-3-one, 1-hexen-3-one, 5-methyl-3- hexenone, 3-hepten-2-one, 1-octen-3-one, 2-octen-4-one, 3-octen-2-one, 3- none-2-one), aliphatic diketones and aliphatic diketoles, e.g. diacetyl, acetyl methyl carbinol, 2,3-hex- anedione, aliphatic acids, such as straight-chain saturated acids, such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, heptanoic acid, octanoic acid, decanoic acid, branched- chain saturated acids, such as 2-methyl heptanoic acid, 4-ethyl octanoic acid, and unsaturated acids, such as 2-butenoic acid, 2-pentenoic acid, 4-pentenoic acid, 2-methyl pentenoic acid, trans-3 hexenoic acid, cis-3 hexenoic acid, 3- octenoic acid, linoleic acid), aliphatic esters, such as saturated esters, e.g. methyl acetate, methylbutyrate, methyl-2-methylbutyrate, methyl hexanoate, ethylacetate, ethylbutyrate, ethyl-2- methylbutyrate, ethyl-3-methylbutyrate, ethyl hexanoate, ethyl decanoate, isopropyl acetate, isobutyl acetate, isobutyl valerate, isoamyl acetate, isoamyl butyrate, isoamyl isovalerate, hexyl acetate, hexyl hexanoate, 3-octyl acetate and unsaturated esters, such as methyl 2-hexenoate, allyl hexanoate, cis-3 hexenyl acetate, cis-3 hexenyl butyrate, aliphatic thiols and dithiols (e.g. propane thiol, allyl mercaptan, 1- methoxy-3-methylbutane-

[0024] 3-thiol, dimethyl sulfide, dimethyl trisulfide, dipropyl sulfide, diallyl trisulfide, other aliphatic sulfur compounds, such as 2-mercapto- 3-butanol, methyl thio propanal, 3-mercapto-pen- tanone, 4-methoxy-2-methyl- 2-mercaptobutanone, methyl thiobutyrate, methyl thiobutyrate, methyl 3- methylthiopropionate, aliphatic nitrogen compounds, such as butyl amine, trimethyl amine, allyl isothiocyanate, isopropyl isothiocyanate, alicyclic compounds, such as alicyclic ketones, e.g. cis-jasmone, isophorone, 4-ketoisophorone, alicyclic esters such as methyl jasmonate, hedione, terpenes, e.g. terpene alcohols, such as linalool, citronellol, geraniol, nerol, alpha terpineol, menthol, 8-p-menthene-1 ,2-diol, fenchol, borneol, nerolidol, hotrienol, terpene aldehydes such as geranial, neral, citronellal, beta-sinensal, terpene ketones, such as alpha-ionone, (D)-carvone, (L)-carvone, nootkatone, piperitone, menthone, alpha damascene, beta damascene, damascenone, terpene esters, such as linalyl acetate, geranyl acetate, citronellyl actetate, carvyl acetate, fenchyl acetate, terpene sulphur compounds, 4-mentha-8-thiol-3-one, thiogeraniol, para-menth-1-ene-8-thiol, mercapto p-menthan-3-one, terpene hydrocarbons, such as D-limonene, L- limonene, alphapinene, beta-pinene, ocimene, alpha-terpinene, gammaterpinene, beta-bisabolene, valen- cene, terpene oxides, such as 1 ,8-cineole, rose oxide, mint lactone, menthofuran, aromatic compounds, e.g. aromatic alcohols, such as benzyl alcohol, cinnamyl alcohol, 2-phenyl alcohol, aromatic aldehydes, such as benzaldehyde, cinnamic aldehyde, 5-methyl-2- phe- nylhexenal, salicylaldehyde, 4-hydroxy benzaldehyde, cyclamen aldehyde, 2-phenyl-2-bu- tenal, aromatic acids, such as 2-phenyl acetic acid, cinnamic acid, aromatic esters such as benzyl acetate, benzyl salicylate, anisyl acetate, methyl phenyl acetate, methyl benzoate, methyl salicylate, methyl cinnamate, aromatic phenols, such as phenol, ortho-cresol, paracresol, 2,3-dimethyl phenyl, 2-ethyl phenol, 2,3,5-trimethyl phenol, 4-vinyl phenol, guaiacol,

[0025] 4-vinyl guaiacol, eugenol, thymol, carvacrol, aromatic sulphur compounds, such as thiophenol, diphenyl disulphide, aromatic nitrogen compounds, such as methyl anthranilate, methyl N-methyl anthranilate, aromatic ethers such as vanillin, ethylvanillin, anethol, aromatic oxides, such as heliotropine, diphenyl oxide, aromatic lactones, such as coumarin, dihydro coumarin, heterocyclic compounds, such as heterocyclic lactones, e.g. gamma butyrolactone, gamma-nonalactone, gamma decalactone, delta decalactone, jasmin lactone, delta dodecalactone, ambrettolide, heterocyclic furanes, such as furfuryl alcohol, furfural,

[0026] 2-acetyl furan, theaspirane, 2-methyl tetrahydro furan-3-one, furfuryl mercaptane, 2- methyl

[0027] 3-furanthiol, 2-methyl 3- tetrahydro furanthiol, difurfuryl sulfide, difurfuryl disulfide, heterocyclic pyrans, such as maltol, ethyl maltole, rose oxide, maltol isobutyrate, heterocyclic pyrroles such as indole, 2-acetyle pyrrole, pyrrolidine, heterocyclic pyrazines, such as 2- methyl pyrazine, 2,3- dimethyl pyrazine, 2-methyl 3-ethyl pyrazine, trimethyl pyrazine, 2- acetyl pyrazine, 2-methoxy 3-methyl pyrazine, 2-methoxy 3-ethyl pyrazine, 2- methoxy 3- isobutyl pyrazine, 2-ethyl 3-methylthio pyrazine, heterocyclic thiazoles, such as thiazole, 2- methyl thiazole, 4-methyl 5-vinyl thiazole, 2- isobutyl thiazole, 2-acetyl thiazole, flavoring raw materials and flavoring preparations, e.g. essential oils, concretes, absolutes, extract or tinctures from raw materials such as citrus (e.g. lemon, lime, mandarine, bergamot, grapefruit bitter orange, peel or essence oils), herbs (dill, parsley, cumin, rosemary, sage, clary sage, basil, tarragon, thyme, oregano, savoury, majoram, all spice, mace, nutmeg, clove leave, clove bud, caraway, cinnamom leaves, cinnamom bark, cassia, cardamom, ginger, galangal, turmeric, coriander seed, coriander leaf, fenugreek, juniper berry, wormwood, laurel leaves, eucalyptus, white pepper, green pepper, white pepper, carrot seed, celery seed, lovage leaf, asa foetida, onion, leek, garlic, mustard, horse radish, capsicum, paprika, sea weed, valerian oil, fir needle, spearmint, peppermint, Wintergreen, buchu leaf, black currant buds, fennel, star anise, jambu, long pepper, davana, orris, mimosa, cassie, violet leaves, ho leaf, jasmin, ylang ylang, cananga, osmanthus, angelica, clary sage, am- brette seed, hops, camomile, lavender, rose, geranium, citronella, palmarosa, litsea cubeba, lemon grass, tagetes, neroli, petitgrain, mate, cognac oil, coffee, cola nut, cocoa, green tea, black tea, white tea, gentian, tolu balm, benzoe resin, peru balm, cascarilla, galbanum, vetiver, labdanum, patchouli, sandalwood, cedarwood, guaiac wood, oak wood, massoi bark, vanilla pods, tonka bean, as well as enriched fractions thereof, juice concentrates, such as orange juice, lemon juice, strawberry, cherry juice, or passion fruit juice concentrates, waterphases and recoveries from raw materials such as citrus (lemon, lime, orange, mandarine, grapefruit), apple, pear, quince, mispel, red fruits (raspberry, strawberry, blueberry, blackberry, Amellanchia (June plum), rose hip, cranberry, plum, prune, red and black currant, etc.) yellow fruits (peach, apricot, nectarine, banana, etc.), tropical fruits (mango, passionfruit, pineapple, lychee, etc.), vegetables (e.g. cucumber, tomato) and spices (e.g. ginger), acetophenone, allyl caproate, alpha-ionone, beta-ionone, anisaldehyde, anisyl acetate, anisyl formate, benzaldehyde, benzothiazole, benzyl acetate, benzyl alcohol, benzyl benzoate, beta-ionone, butyl butyrate, butyl caproate, - 33 - butylidene phthalide, carvone, camphene, caryophyllene, cineol, cinnamyl acetate, citral, citronellol, citronellal, citronellyl acetate, cyclohexyl acetate, cymene, damascene, decalactone, dihydrocoumarin, dimethyl anthranilate, dodecalactone, ethoxyethyl acetate, ethylbutyric acid, ethyl butyrate, ethyl caprate, ethyl caproate, ethyl crotonate, ethylfuraneol, ethylguaiacol, ethylisobutyrate, ethylisovalerate, ethyl lactate, ethylmethyl butyrate, ethyl propionate, eucalyptol, eugenol, ethyl heptylate, 4-(p-hydroxyphenyl)-2- butanone, gamma-decalactone, geraniol, geranyl acetate, geranyl acetate, grapefruit aldehyde, methyl dihydrojasmonate (e.g. Hedion®), heliotropin, 2- heptanone, 3-heptanone, 4-heptanone, trans-2-heptenal, cis-4-heptenal, trans-2-hexenal, cis-3-hexenol, trans-2-hexenoic acid, trans-3-hexenoic acid, cis-2-hexenyl acetate, cis-3-hexenyl acetate, cis-3-hexenyl caproate, trans-2- hexenyl caproate, cis-3-hexenyl formate, cis-2-hexyl acetate, cis-3-hexyl acetate, trans-2-hexyl acetate, cis-3-hexyl formate, para-hydroxybenzyl acetone, isoamyl alcohol, isoamyl isovalerate, isobutyl butyrate, isobutyraldehyde, isoeugenol methyl ether, isopropyl methylthiazole, lauric acid, levulinic acid, linalool, linalool oxide, linalyl acetate, menthol, menthofuran, methyl anthranilate, methylbutanol, methylbutyric acid, 2- methylbutyl acetate, methyl caproate, methyl cinnamate, 5-methylfurfural, 3,2,2-methylcyclopentenolone, 6,5,2- methylheptenone, methyl dihydrojasmonate, methyl jasmonate, 2-methylmethyl butyrate, 2-methyl-2- pentenol acid, methylthiobutyrate, 3,1-methylthiohexanol, 3-methylthiohexyl acetate, nerol, nerol acetate, trans, trans-2, 4-nonadienal, 2,4-nonadienol, 2,6- nonadienol, 2,4-nonadienol, nootkatone, delta-octalactone, gammaoctalactone, 2-octanol, 3-octanol, 1 ,3-octenol, 1 -octyl acetate, 3-octyl acetate, palmitic acid, paraldehyde, phellandrene, pentanedione, phenylethyl acetate, phenylethyl alcohol, phenylethyl isovalerate, piperonal, propionaldehyde, propyl butyrate, pulegone, pulegol, sinensal, sulfurol, terpinene, terpineol, terpinolene, 8,3-s thiomenthanone, 4,4,2-thiomethylpentanone, thymol, delta- undecalactone, gamma-undecalactone, valencene, valeric acid, vanillin, acetoin, ethylvanillin, ethylvanillin isobutyrate (=3-ethoxy-4- isobutyryloxybenzaldehyde), 2,5-dimethyl-4-hy- droxy-3 (2H)-furanone and derivatives thereof (here preferably homofuraneol (=2-ethyl-4- hydroxy-5- methyl-3(2H)-furanone), homofuronol (=2-ethyl-5-methyl-4-hydroxy-3(2H)- furanone and 5-ethyl-2-methyl-4-hydroxy-3(2H)-furanone), maltol and maltol derivatives (here preferably ethyl maltol), coumarin and coumarin derivatives, gamma-lactones (here preferably gamma-undecalactone, gammanonalactone, gamma-decalactone), delta-lac- tones (here preferably 4- - 34 - methyldeltadecalactone, massoilactone, deltadecalactone, tuberolactone), methyl sorbate, divanillin, 4-hydroxy-2(or 5)-ethyl-5 (or 2)-methyl-3 (2H)furanone, 2-hydroxy-3-methyl-2-cyclopentenone, 3-hydroxy-4,5- dimethyl-2(5H)- furanone, acetic acid isoamyl ester, butyric acid ethyl ester, butyric acid-n-butyl ester, butyric acid isoamyl ester, 3-methyl-butyric acid ethyl ester, n-hexanoic acid ethyl ester, n- hexanoic acid allyl ester, n-hexanoic acid-n-butyl ester, n-octanoic acid ethyl ester, ethyl- 3-methyl-3- phenylglycidate, ethyl-2-trans-4-cis-decadienoate, 4-(p-hydroxyphenyl)-2- bu- tanone, 1 ,1-dimethoxy-2,2,5-trimethyl-4-hexane, 2,6-dimethyl-5-hepten-1- al and phenylacetaldehyde, 2-methyl-3-(methylthio)furan, 2-methyl-3- furanthiol, bis(2-methyl-3-furyl)di- sulphide, furfurylmercaptan, methional, 2- acetyl-2-thiazoline, 3-mercapto-2-pentanone, 2,5-dimethyl-3-furanthiol, 2,4,5- trimethylthiazole, 2-acetylthiazole, 2,4-dimethyl-5-ethylthi- azole, 2-acetyl-1- pyrroline, 2-methyl-3-ethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, 2- ethyl-3,6- dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, 3-isopropyl-2- methoxypyrazine, 3-isobutyl-2-methoxypyrazine, 2-acetylpyrazine, 2- pentylpyridine, (E,E)-2,4-decadienal, (E,E)-2,4-nonadienal, (E)-2-octenal, (E)-2-nonenal, 2-undecenal, 12-methyltridecanal, 1- penten-3-one, 4-hydroxy-2,5- dimethyl-3 (2H)-furanone, guaiacol, 3-hydroxy-4,5-dimethyl- 2(5H)-furanone, 3-hydroxy-4-methyl-5-ethyl-2(5H)-furanone, cinnamaldehyde, cinnamon alcohol, methyl salicylate, isopulegol and (here not explicitly stated) stereoisomers, enantiomers, positional isomers, diastereomers, cis / trans isomers or epimers of these substances.

[0028] Preferably, the flavoring contains a component with taste modifying properties selected from the group consisting of hesperetin, hesperetindihydrochalcone, phloretin, naringenin, phyllodulcin, acetylated trilobatin, eriodictyol, homoeriodictyol, matairesinol, madecasso- side terminoloside, 3',7-Dihydroxy-4'-methoxyflavan, 1-(2,4-dihydroxyphenyl)-3-(3-hy- droxy-4-methoxyphenyl)propan-1-one, hydrangenol, and mixtures thereof. More preferably the flavoring is selected among flavorings of the type lime, lemon, vanilla, caramel, green tea, tomato, cherry and raspberry.

[0029] Further components of preferred mixtures of the invention include (v) a sweetener, an acid- ifier and / or (vi) water or milk.

[0030] A sweetener in the context of the invention may be one or more substances selected from the following group: natural sweeteners, preferably naturally occurring sweet tasting substances, including plant extracts, sweet tasting proteins (such as miraculin, pentaidin, monellin, thaumatin, curculin, brazzein, mabinlin), D-amino acids (such as D-phenylalanine, D- tryptophan) or extracts or fractions obtained from natural sources containing these amino acids and / or proteins and the physiologically acceptable salts of these amino acids and / or proteins, particularly the sodium, potassium, calcium or ammonium salts thereof; neohesperidindihydrochalkone, naringindihydrochalkone, stevi- olgylc- oside, stevioside, steviolbioside, rebaudioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside G, rebaudioside H, rebaudioside M, rebaudioside N, rebaudioside X, dulcoside, rubu- soside, mogrosides, such as mogroside V, hernandulcine, monatin, glycyrrhetinic acid and its derivatives, particularly glycyrrhizin, preferably glycyrrhizin ammonium salt or other natural sweetener as described in WO2022148540; extracts or enriched fractions of such extracts such as extracts of thaumatococcus or stevia ssp., particularly stevia rebaudiana, swingle extracts, particularly momordica or siratio grosven- orii or Luo-Han- Guo, extracts of glycerrhyzia ssp., particularly glycerrhyzia glabra, extracts of rubus ssp., particularly rubus suavissimus, extracts of lippia dulcis, extracts of mycetia balansae, preferably comprising balansin A and / or balansin B, or further extracts as described in EP 11168468; synthetic sweeteners, preferably synthetic sweet tasting substances, preferably selected from the group consisting of magap, sodium cyclamate or other physiologically acceptable salts of cyclamic acid, acesulfam K; neohesperidindihydrochal- cone, naringindihydrochalcone, saccharin, saccharin sodium salt, aspartam, super- aspartam, neotam, alitam, advantam, perillartin, sucralose, lugduname, carrelame, sucrononate orsucrooctate; sweet tasting carbohydrates, preferably selected from the group consisting of sucrose, trehalose, lactose, maltose, melizitose, melibiose, raffinose, palatinose, lactulose, D-fructose, D-glucose, D-galactose, l-rhamnose, D-sorbose, D-mannose, D- tagatose, D-allulose, D-arabinose, l-arabinose, D-ribose, D-glyceraldehyde, maltodextrin, and vegetable preparations comprising one or more of these carbohydrates, preferably in an amount of at least 5 wt.-%, preferably at least 15 wt.-%, wherein in these preparations the carbohydrates can be present as naturally occurring or synthetic carbohydrates or a mixture thereof, such as preferably honey, in- vert sugar syrup or highly enriched fructose syrup from maize starch, and / or the physiologically acceptable salts of these carbohydrates, particularly sodium, potassium, calcium or ammonium salts thereof; sugar alcohols, preferably naturally occurring sugar alcohols, preferably selected from the group consisting of glycerin, erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltit, dulcitol, lactitol and the physiologically acceptable salts thereof, particularly the sodium, potassium, calcium or ammonium salts thereof, or a combination of two or more of the above. An acidifier in the context of the invention can contain at least one compound conveying a sour taste, preferably one or more food acids, preferably selected from the group consisting of acetic acid, adipic acid, aspartic acid, benzoic acid, sorbic acid, caffeotannic acid, citric acid, iso-citric acid, fumaric acid, galacturonic acid, gluconic acid, glucuronic acid, glyceric acid, glycolic acid, ketoglutaric acid, [alpha]-ketoglutaric acid, lactic acid, lactoisocitric acid, malic acid, maleic acid, oxalacetic acid, oxalic acid, phosphoric acid, pyruvic acid, quinic acid, shikimic acid, succinic acid, tannic acid, and tartaric acid, in particular preferred one or more food acids selected from adipic acid, citric acid, fumaric acid, gluconic acid, glucuronic acid, lactic acid, malic acid, phosphoric acid, succinic acid, and tartaric acid.

[0031] A further aspect of the present invention relates to a product selected from the group of foodstuffs, luxury food, food supplements, pharmaceutical preparations, medicinal preparations, cosmetic preparations, oral hygiene preparations, fragrances, preparations consumed for pleasure, and semi-finished preparations thereof, comprising a mixture as defined herein.

[0032] Preferred products are selected from among bakery products (for example bread, dry biscuits, cakes, other pastry products), confectionery (for example chocolates, chocolate bar products, other bar products, fruit gums, hard and soft caramels, chewing gum), alcoholic or non-alcoholic beverages (for example coffee, tea, iced tea, wine, beverages containing wine, beer, beverages containing beer, liqueurs, spirits, brandies, (carbonated) fruit-containing beverages, (carbonated) isotonic beverages, (carbonated) soft drinks, nectars, spritzers, fruit and vegetable juices, fruit or vegetable juice preparations, instant beverages (for example instant cocoa beverages, instant tea beverages, instant coffee beverages, instant fruit beverages), meat products (for example ham, fresh or cured sausage preparations, spiced or marinated fresh or cured meat products), eggs or egg products (dried egg, egg white, egg yolk), cereal products (for example breakfast cereals, muesli bars, precooked ready rice products), dairy products (for example milk beverages, buttermilk beverages, milk ice cream, yoghurt, kefir, curd cheese, soft cheese, hard cheese, dried milk powder, whey, whey beverages, butter, buttermilk, partially or fully hydrolyzed milk proteincontaining products), products made from soya protein or other soya bean fractions (for example soya milk and products made therefrom, fruit beverages with soya protein, soya lecithin-containing preparations, fermented products such as tofu or tempe or products made therefrom), products from other vegetable sources of protein, for example oat protein drinks, fruit preparations (for example jams, fruit ice cream, fruit sauces, fruit fillings, frozen fruit products or fruit sorbets), vegetable preparations (for example ketchup, sauces, dried vegetables, deep-frozen vegetables, precooked vegetables, preserved vegetables), snack articles (for example baked or fried potato chips or potato dough products, maize- or pea- nut-based extrudates), fat- or oil-based products or emulsions thereof (for example mayonnaise, remoulade, dressings), other ready-to-serve meals and soups (for example dried soups, instant soups, precooked soups), spices, seasoning mixtures and in particular powdered seasonings, which are for example used in snack food applications. The prepara- tions / products for the purposes of the invention may also be used as semi-finished preparations for the production of further preparations / products serving for nutrition or for pleasure. The preparations / products for the purposes of the invention may also be nutritional supplements in the form of capsules, tablets (uncoated and coated tablets, for example coatings resistant to gastric juices), sugar-coated tablets, granules, pellets, mixtures of solids, dispersions in liquid phases, as emulsions, as powders, as solutions, as pastes or as other swallowable or chewable preparations. Beverages and dairy products are most preferred.

[0033] According to preferred embodiments, the product of the present invention comprises (in addition to the compound(s) of formulas (I) and / or (II) as specified above):

[0034] (iv) the flavoring otherthan a compound of formulas (I) and (II) or at least one component with taste modifying properties or mixtures thereof in an amount ranging from 0.001 to 5 wt.%, preferably 0.005 to 2 wt.%, more preferably 0.01 to 1 wt.%, relative to the total weight of the product; and / or

[0035] (v) the sweetener in an amount ranging from 0.001 to 15 wt.-%, preferably 0.2 to 10 wt.%, more preferably 0.5 to 8 wt.%, relative to the total weight of the product; and / or the acidifier in an amount ranging from 0,001 to 5 wt.%, preferably 0.01 to 2 wt.%, more preferably 0.1 to 1 wt.%, relative to the total weight of the product; and / or

[0036] (vi) the water or milk in an amount ranging from 60 to 99.5 wt.%, preferably 70 to 99.5 wt.%, more preferably 80 to 99.5 wt.%, most preferably 90 to 99.5 wt.%, relative to the total weight of the product.

[0037] According to a final aspect of the present invention, a method for producing a compound of formula (I) or (II) as defined herein comprises the following steps: providing an ene-reductase or an ene-reductase harboring microorganism; and reducing therewith a double bond of a corresponding coumarin or furocoumarin as a precursor, thereby producing the compound of formula (I) or (II). The ene-reductase may be provided in the form of an isolated enzyme, a cell lysate in which the enzyme is contained, a partially purified fraction thereof, a microorganism naturally expressing the enzyme, or a microorganism genetically altered to express the enzyme. For instance, the ene-reductase harboring microorganism may be a recombinant E. coli strain such as strain K12 W31 10, or yeast such as Klyveromyces marxianus, Torulaspora delbrueckii or Saccharomyces cerevisiae.

[0038] Preferably, the compound of formula (I) or (II) is selected from the group consisting of compounds of formulas (l-a), (l-b) and (ll-a) as defined herein. The precursor is respectively selected from the group consisting of compounds of formulas (lll-a), (lll-b) and (lll-c): en).

[0039] The precursor may be obtained synthetically or naturally.

[0040] In the following, the invention is explained in more detail with reference to representative examples. EXAMPLES

[0041] 1 . CHEMICAL SYNTHESIS OF CHROMANONES

[0042] 1 .1 Chromanone [l-a] (CAS 20921 -02-2)

[0043] 3.80 g 7-Methoxycoumarin (21 .0 mmol, 1 .00 eq.) were dissolved in 100 mL acetic acid and 0,76 g of 5 % palladium / carbon (20 wt%) were added. The suspension was stirred under hydrogen atmosphere for 4,5 h at rt. The mixture was filtered through a pad of celite and the filtrate solvent was concentrated under reduced pressure. The residue was added to 150 mL water and the aqueous layer was extracted with ethyl acetate (3 x 100 mL). The combined organic layers were washed with sat. aq. sodium hydrogen carbonate (3 x 50 mL) and sat. aq. NaCI (50 mL), dried over sodium sulfate and the solvent was removed under reduced pressure, to obtain 3.8 g 7-methoxy-2-chromanone [l-a] (21.3 mmol, 99%) as white solid.

[0044] NMR:1H-NMR (400 MHz, CDCI3): 6 = 7.07 (dtd, 1 , J = 8.3 Hz, 0.9 Hz, 0.3 Hz, CArHCArHCAr), 6.64 (dd, 1 , J = 8.3 Hz, 2.6 Hz, CArOCH3CArHCArH), 6.60 (dq, 1 , J = 2.5 Hz, 0.3 Hz, CArCArHCArOCH3), 3.78 (s, 3, CArHCArOCH3CArH). 2.96 - 2.91 (m, 2, CArCH2CH2). 2.79-2.74 (m, 2, CH2CH2CO2).13C-NMR (100 MHz, CDCI3): 6 = 168.55, 159.65, 152.70, 128.44, 114.38, 1 10.40, 102.53, 55.53, 29.48, 23.00.

[0045] GC / MS (El, 70 eV, two most intense ions each 14 ions above m / z 20): 27 (2), 29 (1), 39 (9), 42 (3), 50 (5), 51 (11), 53 (5), 63 (9), 65 (15), 77 (22), 78 (19), 91 (11), 92 (4), 107 (10), 108 (29), 121 (15), 124 (6), 136 (32), 137 (16), 149 (26), 150 (41), 161 (7), 162 (1), 178 (100), 179 (11).

[0046] Purity (GC / MS): 99 %

[0047] 1 .2 Chromanone [l-b] (CAS 82243-01 -4)

[0048] 1.00 g 5,7-Dimethoxycoumarin (4.75 mmol, 1.00 eq.) was dissolved in 15 mL tetrahydro- furane and 250 mg of 5% palladium / carbon (25 wt%) were added. The suspension was stirred in an autoclave under 10 bar hydrogen for 2 h at 80 °C. The mixture was cooled to rt, filtered through a syringe filter and the solvent of the filtrate was removed under reduced pressure. The crude product was purified by column chromatography on silica (n-hexane / ethyl acetate 100:0 -> 80:20) to obtain 0.95 g 5,7-dimethoxy-2-chromanone [l-b] (4.56 mmol, 96 %) as white solid. NMR:1H NMR (400 MHz, CDCI3): 6 = 6.25 (d, 1 , J = 2.3 Hz, CArOCH3CArHCArOCH3), 6.23 (d, 1 , J = 2.3 Hz, CArOCH3CArHCAr), 3.82 (s, 3, CArHCArOCH3CAr), 3.78 (s, 3, CAPHCA-rOCH3CArH), 2.92 - 2.84 (m, 2, CArCH2CH2), 2.77 - 2.68 (m, 2, CH2CH2CO2).13C NMR (101 MHz, CDCI3): 6 = 168.73, 160.12, 157.33, 153.23, 103.42, 94.73, 93.88, 77.35, 77.04, 76.72, 55.71 , 55.57, 28.86, 17.12.

[0049] GC / MS (El, 70 eV, two most intense ions each 14 ions above m / z 20): 27 (1), 29 (1), 39 (5), 42 (3), 51 (6), 53 (5), 65 (7), 69 (13), 77 (11), 78 (7), 91 (4), 95 (1 1), 108 (4), 109 (14), 121 (5), 123 (8), 137 (18), 138 (37), 149 (5), 151 (5), 165 (19), 166 (71), 179 (6), 180 (5), 191 (3), 193 (1), 208 (100), 209 (12).

[0050] Purity (GC / MS): 99 %

[0051] 1 .3 Chromanone [I l-a] (CAS 29050-61 -1 )

[0052] 1.00 g Bergaptene (4,62 mmol, 1.00 eq.) was dissolved in 58 mL toluene under nitrogen atmosphere. 5.80 mL Triethylsilane (36,3 mmol, 8.00 eq.) and 230 mg rhodium triphenylphosphine chloride (0.25 mmol, 0,015 eq.) were added and the suspension was stirred at 65 °C for 6 h. The mixture was cooled to rt, filtered through a syringe filter and the solvent of the filtrate was removed under reduced pressure. The crude product was purified by column chromatography on silica (cyclohexane / ethyl acetate 100:0 -> 70:30) to obtain 155 mg 5,6-Dihydrobergaptene [ll-a] (0.71 mmol, 16 %) as white solid.

[0053] NMR:1H NMR (400 MHz, CDCI3): 6 = 7.54 (d, 1 , J = 2.3 Hz, CArHCArHO), 6.96 (s, 1 , CAr- CArHCAr), 6.91 (dd, 1 , J = 2.3 Hz, 1.0 Hz, CArCArHCArH), 4.12 (s, 3, COCH3), 3.05 (dd, 2, J = 8.2 Hz, 6.3 Hz, CH2CH2CAr). 2.78 - 2.72 (m, 2, CO2CH2CH2).13C NMR (101 MHz, CDCI3): 6 = 168.85, 155.44, 150.32, 149.53, 144.20, 114.11 , 108.07, 104.57, 94.86, 59.91 , 28.96, 17.94.

[0054] GC / MS (El, 70 eV, two most intense ions each 14 ions above m / z 20): 27 (1), 29 (1), 38 (2), 39 (6), 50 (8), 51 (19), 63 (11), 65 (8), 77 (15), 89 (11), 90 (6), 91 (14), 104 (2), 105 (5), 118 (5), 131 (6), 133 (37), 134 (4), 146 (40), 147 (26), 161 (37), 162 (5), 176 (100), 177 (12), 189 (2), 190 (12), 202 (1), 203 (0.5), 218 (96), 219 (13).

[0055] Purity (GC / MS): 99 % 2. BIOTECHNOLOGICAL SYNTHESIS OF CHROMANONES

[0056] 2.1 Transformation of plasmid DNA into Escherichia coli cells

[0057] Plasmid DNA was transformed into chemically competent Escherichia coli (E. coli) DH5a cells (New England Biolabs, Frankfurt am Main, Germany) for plasmid propagation. For generation of expression strains, plasmid DNA was transformed into chemically competent E. coli BL21 (DE3) cells.

[0058] 50 pL of the respective E. coli strain were incubated on ice for 5 minutes. After addition of 1 pl of plasmid DNA, the suspension was mixed and incubated for 30 minutes on ice. Transformation was performed by incubating the cell suspension for 45 s at 42 °C in a thermoblock followed by incubation on ice for 2 minutes. After addition of 350 pl SOC Outgrowth Medium (New England Biolabs, Frankfurt am Main, Germany) cells were incubated at 37 °C and 200 rpm for 1 hour. Subsequently, the cell suspension was spread out on LB- Agar plates (Car Roth GmbH, Karlsruhe, Germany) containing the respective antibiotic and incubated for 16 hours at 37 °C.

[0059] 2.2 Generation of expression plasmids

[0060] The sequences according to SEQ ID NO 1 to SEQ ID NO 16 coding for sequences according to SEQ ID NO 17 to SEQ ID NO 32, respectively, were synthesized and cloned into the pET28a vector between Ncol and Xhol restriction sites (Twist BioScience, San Francisco, USA) to obtain plasmids listed in Table 1. These expression vectors are transformed as described in Example 1 into E. coli BL21 (DE3) cells according to example 1 .

[0061] Table 1 : Obtained plasmids and organisms, the enzyme sequences are obtained of.

[0062] 2.3 Cultivation of E. coli cells and biotransformation with ene reductases

[0063] E. coli BL21 (DE3) cells containing one of the pET28a plasmids from Table 1 were used to inoculate 5 mL LB medium (Carl Roth GmbH, Karlsruhe, Germany) with the necessary antibiotics, respectively. After incubation of 16 h (37 °C, 200 rpm), cells were used to inoculate 50 mL TB medium (Carl Roth GmbH, Karlsruhe, Germany) at ODeoo of 0.1 with necessary antibiotics. Cells were grown (37 °C, 200 rpm) to ODeoo of 0.5 - 0.8 and 1 mM iso- propyl-p-D-thiogalactopyranoside were added to the cultures. Cell cultures were incubated for 16 h (22 °C, 200 rpm), centrifuged (10 min, 10,000 rpm) and supernatant discarded. The cell pellet was lysed using B-PER protein extraction reagent (Thermo Fisher Scientific, Bonn, Germany) according to manufacturer’s instructions. After subsequent centrifugation (10 min, 20.000 rpm) the supernatant was used for biotransformation by addition of 1 .5 mM nicotinamide adenine dinucleotide phosphate, 1.5 mM nicotinamide adenine dinucleotide, 1 M glucose, 1 U glucose dehydrogenase and 50 ppm substrate. Bergaptene, 7-methoxy coumarin or 5,7-dimethoxy coumarin were used as substrate, respectively. The reaction mixture was incubated at 30 °C for 16 h. After stopping the reaction with acetonitrile (1 volume reaction mixture + 1 volume acetonitrile with 0.2 % formic acid), the sample was centrifuged (20 min, 20,000 rpm) and the supernatant used for LC and LC-MS analytics.

[0064] 2.4 Cultivation of yeast and biotransformation of substrates

[0065] Microorganisms from Table 2 were used to inoculate 5 mL YPD medium (Carl Roth GmbH, Karlsruhe, Germany, respectively. After incubation of 16 h (30 °C, 200 rpm), cells were used to inoculate 50 mL YPD medium (Carl Roth GmbH, Karlsruhe, Germany) at ODeoo of 0.2. Cells were grown (30 °C, 200 rpm) to ODeoo of 1 and 50 ppm of the respective substrate (bergaptene, 7-methoxy coumarin or 5,7-dimethoxy coumarin) was added to the cultures. Cell cultures were incubated for 16 h (30 °C, 200 rpm) and stopped with acetonitrile (1 volume culture + 1 volume acetonitrile with 0.2 % formic acid). The sample was centrifuged (20 min, 20,000 rpm) and the supernatant used for LC and LC-MS analytics.

[0066] Table 2: Used microorganisms for the biotransformation of substrates.

[0067] According to literature, the biotransformation of simple coumarin into dihydrocoumarin and its corresponding acid has already been investigated (Haser et al. Biocatalytic Production of Dihydrocoumarin from Coumarin by Saccharomyces cerevisiae. J. Agric. Chem. 2006, 54, 6236-6240; Serra et al. Biocatalytic Synthesis of Natural Dihydrocoumarin by Microbial Reduction of Coumarin. Catalysts 2019, 9, 665; Serra et al. Two Biotechnological Approaches to the Preparative Synthesis of Natural Dihydrocoumarin. Catalysts 2022, 12, 28).

[0068] The results of the aforementioned biotransformation of substituted coumarins as precursors (7-Methoxycoumarin, 5,7-Dimethoxycoumarin and Bergaptene) into 7-Methoxy-2- chromanone, 5,7-Dimethoxy-2-chromanone, 5,6-Dihydrobergaptene and their corresponding acids are shown in Table 3.

[0069] Table 3: Results of biotransformation screening experiments (+ = detected, traces = traces detected, - = not detected, * = tentatively identified).

[0070] 3. APPLICATION EXAMPLES

[0071] 3.1 Example 1

[0072] In a lemonade made from 91.84% water, 8% sucrose, 0.15% citric acid and 0.01 % of a lime type flavor, a clearly perceptible coumarin note could be produced by adding 0.1 ppm (parts per million) of 7-methoxy-2-chromanone. This coumarin note is described as typical for the taste of virgin cold-pressed lime oils. Furthermore, the juiciness and authenticity of the application could also be significantly improved. A combined addition of 0.1 ppm 7- methoxy-2-chromanone and 1 ppm 5,7-dimethoxy-2-chromanone was able to further enhance the coumarin-like note, while another combination of 0.1 ppm 7-methoxy-2-chroma- none and 1 ppm 5,7-dimethoxy-2-chromanone and 1 ppm 5,6-dihydrobergaptene resulted in a very typical, rounded profile reminiscent of cold-pressed lime juice.

[0073] Ingredients of the lime type flavor (specification of 100):

[0074] Lime oil preparation consisting of the extractable portions of a mixture of 16% lime peel oil distilled, 16% lime peel oil cold pressed and 68% 1 ,2-propylene glycol (38), lemon oil preparation, consisting of 14% extractable fractions of a cold-pressed lemon peel oil and 86% 1 ,2-propylene glycol (18), grapefruit oil preparation consisting of 5% extractable fractions of grapefruit peel oil and 95% 1 ,2-propylene glycol (41) and citral (3).

[0075] 3.2 Example 2

[0076] In a lemonade containing 91 .8% water, 8% sucrose, 0.15% citric acid and 0.05% of a lemon type flavor, an improved perception of juiciness and sweetness, as well as an herbaceous, earthy flavor note reminiscent of distilled lime, was described by the addition of 0.8ppm 5,7-dimethoxy-2-chromanone. This note is also known from clear lemon and lime sodas. A combined addition of 0.8ppm 5,7-dimethoxy-2-chromanone and 0.08ppm 7-methoxy-2- chromanone further enhanced the lime-like notes. A third combination of 0.8ppm 5,7-di- methoxychromanone, 0.08ppm 7-methoxy-2-chromanone and 0.8ppm 5,6-dihydrobergap- tene was able to significantly modulate the aroma profile of citronella towards cold-pressed lime with pronounced floral, juicy and candy-like notes.

[0077] Ingredients of the lemon type flavor: (specification of 100):

[0078] Orange peel oil enriched (0.4), lemon peel oil, enriched (4), lemon peel oil terpenes (2.5), citral (1), ethanol 96% by volume (77.1) and water (15).

[0079] 3.3 Example 3

[0080] In a dairy beverage consisting of 93.9% whole milk with 3.8% fat, 6% sucrose and 0.1 % of a natural vanilla extract and 10 ppm Hesperetin. The addition of 1 ppm 7-methoxy-2-chro- manone significantly modeled flavor perception. Subjects described buttery, aniseed and caramel-like notes and a significant enhancement of overall aroma intensity.

[0081] Additional addition of 1 ppm 5,7-dimethoxy-2-chromanone produced a further effect: the complexity and intensity of the flavor were significantly enhanced, as well as rounding out the overall profile with additional creamy notes could be achieved.

[0082] Components of the vanilla extract: (specification of 100)

[0083] Vanilla bean equivalents (27), ethanol 96 vol.% and water.

[0084] 3.4 Example 4

[0085] In a milk drink consisting of 93.95% whole milk with 3.8% fat, 6% sucrose and 0.05% of an aroma type caramel, a clearly perceptible shift of the aroma profile towards toffee, butter, cream, but also a rounding off of the previously existing toasted notes could be achieved by adding 1 ppm 7-methoxy-2-chromanone. In parallel, 1 ppm 5,7-dimethoxy-2-chromanone was added to this milk beverage, which significantly enhanced the milk-typical character, as well as creamy notes. The clearest effect was shown by a combination of 1 ppm each of 7-methoxy-2-chromanone and 5,7-dimethoxy-2-chromanone in this beverage example: the toffee, butter and creamy notes could be emphasized in a very positive way, and furthermore the overall aroma intensity was enhanced. Components of the caramel type flavoring: (specification of 100)

[0086] 1 ,2-propylene glycol (83.3), furaneol (3), cocoa powder extract consisting of 15% extractable portion of cocoa powder and 50% 1 ,2-propylene glycol and 50% water (8.5), acetylmethylcarbinol (1), diacetyl (1) methylcyclopentenolone-3,2,2 (0.7), maltol (0.5), vanilla extract consisting of 27% extractable portion of vanilla bean, ethanol 96 vol. % and water.

[0087] 3.5 Example 5

[0088] In a green tea beverage consisting of 99.2% water and 0.8% of a green tea preparation, the addition of 0.8ppm 5,7-dimethoxy-2-chromanone brought out fermented notes very typical of a green tea. Overall, however, tea-like notes were also significantly enhanced. Thus, this substance can optimize the authentic taste of green tea.

[0089] Ingredients of the green tea preparation: (specification of 100)

[0090] Ethanol 96 vol.% (34.47), green tea CO2 extract consisting of 30% extractable green tea ingredients and 70% ethanol 96 vol.% (2), black tea CO2 extract consisting of 35% extractable black tea ingredients and 65% ethanol 96 vol. % (0.5), tea distillate consisting of 10% distillable black tea ingredients, 10% ethanol 96 vol.% and 90% water (51), mate leaf distillate consisting of 20% distillable mate tea ingredients, 45% ethanol 96 vol.% and 55% water (12), linalool (0.027).

[0091] 3.6 Example 6

[0092] A tasting base consisting of 98.91 % water, 0.2% salt, 0.8% sucrose, 0.03% citric acid was spiked with a flavoring type tomato (0.06%). The addition of 1 ppm of 5-7-dimethoxy-2- chromanone significantly enhanced important flavor characteristics of tomato type profile, such as fruity, spicy and tomato pulp notes.

[0093] Ingredients of tomato type flavoring (data from 100): 1 ,2-propylene glycol (88.98), eugenol acetate (3), furaneol (0.6), dimethyl sulfide (2), maltol (4), 3-methylthiopropanal (0.2), geranyl butyrate (1), beta ionone (0.2), isobutyl thiazole (0.02).

[0094] 3.7 Example 7

[0095] To a tasting base consisting of 93.97% water, 6% sucrose and 0.03% of a cherry type flavor, 1 ppm 5,7-dimethoxy-2-chromanone was added. The floral and fruity aroma profile was enhanced by the modulating properties of 5,7-dimethoxy-2-chromanone, especially the juiciness and typical flavor of dark morello cherries were emphasized.

[0096] Ingredients of the cherry type flavoring (data from 100)

[0097] Ethyl acetate (0.4), ethyl butyrate (0.2), cinnamaldehyde (0.1), 3Z-hexenol (0.05), ethyl benzoate (0.02), butyric acid (0.04), benzyl acetate (0.02), beta-ionone (0.02), isoamyl isovalerate (0.02), anisaldehyde (0.01) and ethanol 96 vol.% (99.12).

[0098] 3.8 Example 8

[0099] A tasting base consisting of 93.99% water, 6% sucrose and 0.01 % of a raspberry type flavor was spiked with 0.4ppm 7-methoxy-2-chromanone. This significantly modeled the previously slightly fruity, juicy and estery-green flavor profile. The profile generated by the addition of the 7-methoxy-2-chromanone, was described as sweeter, more balanced, ripened and reminiscent of candy notes. In contrast, a combination of 0.4ppm 7-methoxy-2- chromanone and 1 ppm 5,7-dimethoxy-2-chromanone was able to model warm woody and balsamic notes. Ingredients of the raspberry type flavoring (number of 100)

[0100] Ethyl acetate (2), hydroxybenzyl acetone (2.5), benzyl acetate (1.5), maltol (1), furaneol (0.3), alpha-ionone (0.5), isoamyl acetate (0.5), 3Z-hexenol (0.5), 3Z-hexenyl acetate (0.5), acetaldehyde (0.25), beta-damascenone (0.05), ethanol 96 vol. % (90,9).

Claims

CLAIMS1 . Use of at least one compound of formula (I) or (II)wherein Ri, R2, R3 and R4 are independently selected from the group consisting ofH, OH, OCH3 or OCH2CH3, whereby a compound of formula (I) in which R1, R2, R3 and R4 are all H is excluded, for modulating the profile of an aroma composition.

2. Use of claim 1 , wherein the at least one compound of formula (I) or (II) is selected from the group consisting of compounds of formulas (l-a), (l-b) and (ll-a) )(ll-a) and mixtures thereof.

3. Use of claim 2, wherein the aroma composition contains: more than 10 ppb compound of formula (l-a); and / or more than 20 ppb compound of formula (l-b); and / or more than 20 ppb compound of formula (ll-a).

4. Use of any of the previous claims, wherein the modulation is an improvement or enhancement of, or a shifting towards, aroma notes selected from the group consisting of coumarin-like, juicy, fruity, floral, honey-like, fresh, lime, lemon, zesty, herbaceous, earthy, buttery, aniseed, caramel, toffee, milky, spicy, earthy, sweet, sour or creamy.

5. Use of any of the previous claims, wherein the aroma composition is a product selected from the group consisting of foodstuff, luxury food, food supplements, pharmaceutical preparations, medicinal preparations, cosmetic preparations, oral hygiene preparations, fragrances, preparations consumed for pleasure, and semi-finished preparations thereof.

6. Mixture containing at least one compound of formula (I) or (II) as defined in claim 1 , preferably at least one compound of formulas (l-a), (l-b) and (ll-a) as defined in claim 2, in an amount of(i) more than 10 ppb, preferably more than 50 ppb, more preferably more than 500 ppb compound of formula (I), preferably formula (l-a); and / or(ii) more than 20 ppb, preferably more than 100 ppb, more preferably more than 1000 ppb compound of formula (I), preferably formula (l-b); and / or(iii) more than 20 ppb, preferably more than 100 ppb, more preferably more than 1000 ppb compound of formula (II), preferably formula (ll-a).

7. Mixture of claim 6, wherein the mixture contains: a. a compound of formula (l-a) and a compound of formula (l-b); or b. a compound of formula (l-a) and a compound of formula (ll-a); or c. a compound of formula (l-b) and a compound of formula (ll-a); or d. a compound of formula (l-a), a compound of formula (l-b) and a compound of formula (ll-a).

8. Mixture of claim 6 or 7, wherein the mixture is not derived from essential oils or extracts.

9. Mixture of any of claims 6 to 8, further comprising:(iv) a flavoring otherthan a compound of formulas (I) and (II), wherein the flavoring is preferably selected among flavorings of the type lime, vanilla, caramel, green tea, tomato, cherry and raspberry.

10. Mixture of any of claims 6 to 9, further comprising one or more of the following:(v) a sweetener and / or acidifier; and(vi) water or milk.11 . Product selected from the group of foodstuff, luxury food, food supplements, pharmaceutical preparations, medicinal preparations, cosmetic preparations, oral hygiene preparations, fragrances, preparations consumed for pleasure, and semi-finished preparations thereof, comprising a mixture of any of claims 6 to 10.

12. Product of claim 11 , selected from the group consisting of bakery products, confectionery, alcoholic or non-alcoholic beverages, meat products, eggs or egg products, cereal products, dairy products, products made from soya protein or other soya bean fractions, products from other vegetable sources of protein, for example oat protein drinks, fruit preparations, vegetable preparations, snack articles, fat- or oil-based products or emulsions thereof, other ready-to-serve meals and soups, spices, seasoning mixtures, nutritional supplements in the form of capsules, tablets, sugar- coated tablets, granules, pellets, mixtures of solids, dispersions in liquid phases, as emulsions, as powders, as solutions, as pastes or as other swallowable or chewable preparations, preferably beverages and dairy products.

13. Product of claims 11 or 12, comprising(iv) the flavoring other than a compound of formulas (I) and (II) or at least one component with taste modifying properties or mixtures thereof in an amount ranging from 0.001 to 5 wt.%, preferably 0.005 to 2 wt.%, more preferably 0.01 to 1 wt.%, relative to the total weight of the product; and / or(v) the sweetener in an amount ranging from 0.001 to 15 wt.-%, preferably 0.2 to 10 wt.%, more preferably 0.5 to 8 wt.%, relative to the total weight of the product, and / orthe acidifier in an amount ranging from 0.001 to 5 wt.-%, preferably 0.01 to 2 wt.%, more preferably 0.1 to 1 wt.%, relative to the total weight of the product,; and / or(vi) the water or milk in an amount ranging from 60 to 99.5 wt.%, preferably 70 to 99.5 wt.%, more preferably 80 to 99.5 wt.%, most preferably 90 to 99.5 wt.%, relative to the total weight of the product.

14. Method for producing a compound of formula (I) or (II) as defined in claim 1 , comprising:providing an ene-reductase or an ene-reductase harboring microorganism; and reducing therewith a double bond of a corresponding coumarin or furocoumarin as a precursor, thereby producing the compound of formula (I) or (II).

15. Method of claim 14, wherein the compound of formula (I) or (II) is selected from the group consisting of compounds of formulas (l-a), (l-b) and (ll-a) as defined in claim2; and / or the precursor is selected from the group consisting of compounds of formulas (lll-a), (lll-b) and (lll-c):

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