Organic compounds

Abstract

The invention relates to oral care compositions comprising at least one compound of formula (I) wherein R1 is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety; R2, R3, R4, R5, and R6 at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring; and an oral care base.

Description

[0001] ORGANIC COMPOUNDS

[0002] TECHNICAL FIELD

[0003] The present invention relates generally to oral care compositions comprising esters of monomethylbenzoic acid and dimethylbenzoic acid and the use of said compound in such compositions.

[0004] BACKGROUND

[0005] Compounds suitable for oral care need to be selected carefully for their organoleptic and toxicological properties. Especially, excellent taste profile and mouthfeel properties of such compounds are required providing sensations of oral cleanliness and hygiene. Specialized flavourists are looking for novel compounds that can be added to their ingredients palette. It is therefore desirable to provide new or improved compounds suitable for oral care compositions.

[0006] Some esters of orf o-methylbenzoic acid are well known compounds in the chemical industry. The odor characteristics of the methyl ester (described by IFF in US 2005 / 0170998) and the ethyl ester (described by Symrise in WO 2023 / 232237) were disclosed. However, their use in oral care compositions was not described.

[0007] SUMMARY

[0008] In accordance with a first aspect of the present invention there is provided an oral care composition comprising at least one compound of formula (I) wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety; R2, R3, R4, R5, and R6at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring; and an oral care base.

[0009] In accordance with a second aspect of the present invention there is provided a use of a compound of formula (I) in an oral care composition.

[0010] In accordance with a third aspect of the present invention there is provided a method of improving, enhancing, or modifying an oral care composition, comprising the step of adding thereto a compound of formula (I).

[0011] In accordance with a fourth aspect of the present invention there is provided a group of novel compounds which can be useful compounds for oral care compositions.

[0012] Certain embodiments of any aspect of the present invention may provide one or more of the following advantages:

[0013] • novel versatile ingredient which can be used is a well-balanced way in mint and hesperidic oral care aromas;

[0014] • providing freshness and hygienic mouthfeel associated to green, salicylate notes, in particular methyl / ethyl salicylate or Wintergreen notes;

[0015] • providing products with improved shelf live stability;

[0016] • providing compacted formula in which the active ingredient can be dosed at lower concentrations.

[0017] The details, examples and preferences provided in relation to any particular one or more of the stated aspects of the present invention will be further described herein and apply equally to all aspects of the present invention. Any combination of the embodiments, examples and preferences described herein in all possible variations thereof is encompassed by the present invention unless otherwise indicated herein, or otherwise clearly contradicted by context.

[0018] DETAILED DESCRIPTION

[0019] The present invention is based on the surprising finding that the esters of mono and dimethylbenzoic acid can be used advantageously in oral care applications.

[0020] Therefore, there is provided herein an oral care composition comprising a) at least one compound of formula (I) wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety;

[0021] R2, R3, R4, R5, and R6at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring; and b) an oral care base.

[0022] This means that the R1group is defined by a sum of C atoms. Said R1group consists of a C1 to C9 hydrocarbon moiety, which is straight or branched, contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety. The atoms of the cyclic or aromatic moiety are included in the counting of C atoms of the C1 to C9 hydrocarbon moiety.

[0023] It was found that the compound of formula (I) can be successfully incorporated in oral care compositions, especially wintergreen-like and hesperidic aromas. The compound contributes to a clean and hygienic mouthfeel, harmonizes well with green metallic salicylate notes, and can be considered as salicylate replacer or enhancer, in particular as methyl and / or ethyl salicylate replacer or enhancer. It is surprising, that the methyl group in the compounds of the present invention mimics a hydroxyl group of certain salicylates. Oral care market requires aromas in which the dose levels of salicylates are reduced (due to their CMR2 properties).

[0024] The compound of formula (I) may exist as a mixture of regioisomers, or they may be resolved as isomerically pure forms. If it is desired to prepare individual regioisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective syntheses, or simply by using as starting material the desired isomerically pure form, which are available from natural resources.

[0025] For example, in the compound of formula (I) R1is a linear C1 to C9 alkyl, like methyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl. Preferably, in the compound of formula (I) R1is methyl, ethyl or propyl.

[0026] For example, in the compound of formula (I) R1is a branched C1 to C9 alkyl, like / -propyl, / - butyl, sec-butyl, f-butyl, / -pentyl, / -hexyl, / -heptyl, or others.

[0027] For example, in the compound of formula (I) R1is a cyclic C3 to C9 alkyl, like cyc / o-propyl, cyc / o-butyl, cyc / o-butyl, cyc / o-pentyl, cyc / o-hexyl, cyc / o-heptyl, cyc / o-octyl, or cyc / o-nonyl.

[0028] For example, in the compound of formula (I) R1is further containing saturated and unsaturated bonds and / or aromatic moieties or cyclic residues, like 1-propenyl, 2-propenyl, 3-butenyl, 3- methylbut-2-en-1-yl, 3-hexenyl, benzyl, 2-phenylethyl, or others.

[0029] For example, in the compound of formula (I) R2is Me, and R3, R4, R5and R6are H.

[0030] For example, in the compound of formula (I) R3is Me, and R2, R4, R5and R6are H.

[0031] For example, in the compound of formula (I) R4is Me, and R2, R3, R5and R6are H.

[0032] For example, in the compound of formula (I) R2and R3is Me, and R4, R5and R6are H.

[0033] For example, in the compound of formula (I) R2and R4is Me, and R3, R5and R6are H.

[0034] For example, in the compound of formula (I) R2and R5is Me, and R3, R4and R6are H.

[0035] For example, in the compound of formula (I) R2and R6is Me, and R3, R4and R5are H.

[0036] For example, in the compound of formula (I) R3and R4is Me, and R2, R5and R6are H.

[0037] For example, in the compound of formula (I) R3and R5is Me, and R2, R4and R6are H.

[0038] For example, the compound of formula (I) in the oral care composition is selected from the group consisting of methyl 2-methylbenzoate, ethyl 2-methylbenzoate, methyl 3- methylbenzoate, methyl 4-methylbenzoate, methyl 3,4-dimethylbenzoate, methyl 2,5- dimethylbenzoate, methyl 2,4-dimethylbenzoate, methyl 2,3-dimethylbenzoate, methyl 2,6- dimethylbenzoate, allyl 2-methylbenzoate, propyl 2-methylbenzoate, isopropyl 2- methylbenzoate, but-3-en-1-yl 2-methylbenzoate, isobutyl 2-methylbenzoate, butyl 2- methylbenzoate, cyclopentyl 2-methylbenzoate, 3-methylbut-2-en-1-yl 2-methylbenzoate, pentyl 2-methylbenzoate, isopentyl 2-methylbenzoate, hex-3-en-1-yl 2-methylbenzoate, cyclohexyl 2-methylbenzoate, hexyl 2-methylbenzoate, benzyl 2-methylbenzoate, heptyl 2- methylbenzoate, cyclopropylmethyl 2-methylbenzoate, 2-phenylethyl 2-methylbenzoate, pentyl 3-methylbenzoate, pentyl 4-methylbenzoate, pentyl 3,4-dimethylbenzoate, pentyl 2,5- dimethylbenzoate, pentyl 2,4-dimethylbenzoate, pentyl 2,3-dimethylbenzoate, pentyl 2,6- dimethylbenzoate and 3-methylbut-3-en-1-yl 2-methylbenzoate.

[0039] In particular, the compound of formula (I) in the oral care composition is selected from the group consisting of methyl 2-methylbenzoate and ethyl 2-methylbenzoate.

[0040] For example, there is provided an oral care composition comprising at least one ester of ortho- methylbenzoic acid, which is a compound of formula (II) wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety. The compound of formula (II) is a compound of formula (I) wherein R2is Me, and R3, R4, R5and R6are H.

[0041] The term “oral care composition” refers to any product used for care of the teeth and the mouth. For example, an oral care composition is selected from the group consisting of toothpastes, tooth gels, subgingival gels, denture adhesives, denture cleaner, mouthwashes, mouthrinses, mouth sprays, chewing gums, lozenges, flosses and breath mints, or others.

[0042] As used herein, "oral care base" means a composition for use as oral care composition to fulfill specific actions, such as cleaning, refreshing, and caring or the like.

[0043] In one specific embodiment, the oral care composition comprises an oral care base selected from the group consisting of chalk base, hydrogen peroxide base or silica base. Chalk-based toothpaste refers to toothpastes that use calcium carbonate, a type of chalk, as one of its main abrasive ingredients. This abrasive helps in cleaning and polishing the teeth by removing plaque and surface stains. While chalk (calcium carbonate) is a common abrasive, other materials like silica are also frequently used. The stability of Wintergreen flavoring agents such as methyl salicylate and natural oil containing methyl salicylate is challenging in chalkbased oral care bases as described in US4844883A.

[0044] Other oral care bases include sodium carbonate or sodium bicarbonate (baking soda). Sodium carbonate is used in toothpastes, where it acts as an abrasive and foaming agent. Sodium bicarbonate was used, for example, in US4623536A as the sole abrasive.

[0045] For example, the oral care composition comprises an oral care base selected from the group consisting of chalk base, hydrogen peroxide base, silica base, sodium carbonate base or sodium bicarbonate base and mixtures thereof.

[0046] Hydrogen peroxide is incorporated in oral care bases as an active ingredient for its bleaching and antimicrobial properties, helping to whiten teeth and combat bacteria. It is typically included at low concentrations, often in whitening toothpastes, and can be stabilized within the toothpaste base to prevent premature decomposition. Hydrogen peroxide can be added as such or, alternatively, in the form of a precursor form to the oral care base. For example, the precursor can be a carbamide peroxide (urea peroxide). Carbamide peroxide is a stable compound that breaks down in the presence of water (like saliva) to release hydrogen peroxide, which is the active ingredient for whitening. Other precursors include calcium peroxide, magnesium peroxide, sodium perborate and sodium percarbonate. These compounds also release hydrogen peroxide when they react with water. Hydrogen peroxide precursors such as carbamide peroxide, calcium peroxide, magnesium peroxide, sodium perborate and sodium percarbonate can be used alone, in mixtures and in combination with free hydrogen peroxide in the oral care base.

[0047] For example, the oral care composition, in which the oral care base further comprises at least one hydrogen peroxide precursor selected from the group consisting of carbamide peroxide, calcium peroxide, magnesium peroxide, sodium perborate and sodium percarbonate or combinations thereof.

[0048] The stability of hydrogen peroxide and hydrogen peroxide-releasing oral care compositions is challenging due to the inherent instability of hydrogen peroxide and affects shelf life of oral care products, as described for example in US4839156A, US4891211A and US20130108559A1. The stability of oral care compositions is influenced by various factors, including pH, the presence of stabilizers like citric acid, and the overall formulation. Other stabilizers to reduce degradation of hydrogen peroxide in the oral care composition include metal chelating and sequestering agents (such as, phosphates, pyrophosphates, and ethylenediaminetetraacetic acid and derivatives) chelating acids (such as, phosphoric acid, citric acid, lactic acid, malic acid, fumaric acid, tartaric acid), and antioxidants (such as, mono- and dihydroxybenzenes and their analogs).

[0049] Overall, the oral care base can impact the stability of the compound of formula (I) in terms of flavour stability and appearance, which means that over time the flavour can change and / or discoloration can occur. It is desired to provide compounds that remain stable in the oral care compositions, so that the flavour and / or the appearance does not change over time.

[0050] The compound of formula (I) can be added in different amounts to oral care compositions.

[0051] For example, the at least one compound of formula (I) is present in an amount of at least 0.00005% per weight in an oral care composition.

[0052] For example, the at least one compound of formula (I) is comprised in an amount of at least 0.5 ppm or more, for example 1 ppm or more, for example 5 ppm or more, for example 10 ppm or more, for example 20 ppm or more, for example 50 ppm or more, for example 100 ppm or more, for example 250 ppm or more, for example 500 ppm or more, in an oral care composition.

[0053] For example, a mixture of two or more compounds of formula (I) is present in an amount of at least 0.00005% per weight in an oral care composition.

[0054] For example, a mixture of two or more compounds of formula (I) is comprised in an amount of at least 0.5 ppm or more, for example 1 ppm or more, for example 5 ppm or more, for example 10 ppm or more, for example 20 ppm or more, for example 50 ppm or more, for example 100 ppm or more, for example 250 ppm or more, for example 500 ppm or more in an oral care composition.

[0055] The compound of formula (I) or a mixture of two or more compounds of formula (I) can enhance or replace salicylates, in particular methyl and / or ethyl salicylates in oral care compositions. For example, the mixture of two or more compounds of formula (I) comprises methyl 2- methylbenzoate, ethyl 2-methylbenzoate and / or propyl 2-methylbenzoate.

[0056] In one specific embodiment, the oral care composition according to the invention is free of, or essentially free of methyl salicylate. For example, no methyl salicylate is employed in the oral composition, or the amount of methyl salicylate in the oral care composition is lower than 20 ppm, for example lower than 5 ppm, or lower than 1 ppm.

[0057] Alternatively, the compound of the present invention can partially replace methyl salicylate and / or ethyl salicylate. For example, mixtures of compounds of the present invention and methyl salicylate and / or ethyl salicylate can be used in oral care compositions.

[0058] For example, methyl and / or ethyl 2-methylbenzoate provide stronger impact than the corresponding salicylates. It was surprisingly found that methyl 2-methylbenzoate is about 90- 100 times stronger than methyl salicylate.

[0059] The compound of formula (I) can be used along with further oral care flavor compounds. For example, the compound of formula (I) can be used in oral care composition having fresh notes, for example Wintergreen or peppermint notes. For example, it can be also used to impart medicinal notes to other flavour notes.

[0060] The compound of formula (I) can be used in oral care compositions along with one or more cooling compounds. So in a further embodiment, the oral composition further comprises at least one cooling compound selected from the group consisting of menthol (e.g., in form of peppermint oil, and I or spearmint oil), menthone, p-menthanecarboxamides, A / -2,3-trimethyl-

[0061] 2-isopropyl-butanamide, menthyl lactate (Frescolat® ML), menthone glycerol acetal (Frescolat® MGA), 3-(1-menthoxy)-propane-1 ,2-diol (TK-10), p-menthane-3,8-diol (Coolact 38D), isopulegol (Coolact P), monomenthyl succinate, monomenthyl glutarate, o-menthylglycerol, menthyl A / ,A / -dimethylsuccinamate, 2-(sec-butyl)cyclohexan-1-one (Freskomenthe), N- (pyrazol-3-yl)-A / -(thiophen-2-ylmethyl)-2-(p-tolyloxy)acetamide, 2-(4-ethylphenoxy)-A / -(pyrazol-

[0062] 3-yl)-A / -(thiophen-2-ylmethyl)acetamide, 3-(benzo[d][1 ,3]dioxol-5-yl)-A / ,A / -diphenylacrylamide,

[0063] 4-(2-(4-allyl-2,6-dimethoxyphenoxy)-1-ethoxypropyl)-2-methoxyphenol, 4-(2-(4-allyl-2,6- dimethoxyphenoxy)-1-((2-isopropyl-5-methylcyclohexyl)oxy)propyl)-2-methoxyphenol (including 4-(2-(4-allyl-2,6-dimethoxyphenoxy)-1-(((1 S,2 ?,5S)-2-isopropyl-5- methylcyclohexyl)oxy)propyl)-2-methoxyphenol) and 4-(2-(4-allyl-2,6-dimethoxyphenoxy)-1- (((1F?,2S,5F?)-2-isopropyl-5-methylcyclohexyl)oxy)propyl)-2-methoxyphenol), A / -(2-Hydroxy-2- phenylethyl)-2-isopropyl-5,5-dimethylcyclohexane-1-carboxamide, A / -(4-

[0064] (Cyanomethyl)phenyl)-2-isopropyl-5,5-dimethylcyclohexanecarboxamide, A / -(3-Hydroxy-4- methoxyphenyl)-2-isopropyl-5,5-dimethylcyclohexanecarboxamide, and 2-methyl-1-(2-(5-(p- tolyl)-1 / 7-imidazol-2-yl)piperidin-1-yl)butan-1-one.

[0065] Examples of p-methanecarboxamides include compounds such as N-ethyl-p-menthan-3- carboxamide (WS-3), N-ethoxycarbonylmethyl-p-menthan-3-carboxamide (WS-5), N-( 4- methoxyphenyl)-p-menthan-3-carboxamide (WS-12) and N-tert-butyl-p-menthan-3- carboxamide (WS-14), N-(4-(cyanomethyl)phenyl)-2-isopropyl-5-methylcyclohexane-1- carboxamide (Evercool 180), 2-isopropyl-5-methyl-N-(2-(pyridin-2-yl)ethyl)cyclohexane-1- carboxamide (Evercool 190), and (1 R,2S,5R)-N-((S)-2-((R)-2-aminopropanamido)-2- phenylethyl)-2-isopropyl-5-methylcyclohexane-1-carboxamide

[0066] In a further aspect of the present invention there is provided the use of the compound of formula (I), in an oral care composition. By the use of the compound of formula (I) fresh flavour notes with hygienic mouthfeel of like Wintergreen notes can be provided to oral care compositions.

[0067] For example, there is provided the use of the compound of formula (I) in an oral care composition to enhance, modify or replace salicylates, in particular methyl and / or ethyl salicylate.

[0068] In a further aspect of the present invention, there is provided a method of improving, enhancing, or modifying an oral care composition, comprising the step of adding thereto the compound of formula (I).

[0069] In particular, the method comprises the steps of a) providing oral care base, and b) admixing the compound of formula (I).

[0070] The compound of formula (I) can be admixed directly to the oral care base. Alternatively, it can be provided as solution, for example in benzyl alcohol, IPM (Isopropyl myristate), Triacetin, TEC (Triethyl Citrate), Castor Seed oil, PG (propylene glycol), or mixtures thereof, or others, which is then admixed to the oral care base.

[0071] While some of the compounds are already known in literature, others have not been described so far. In a further aspect of the present invention, there is provided a compound of formula (I) wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety;

[0072] R2, R3, R4, R5, and R6at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring, with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2- methylbenzoate, cyclopentyl 2-methylbenzoate, 2-phenylethyl 2-methylbenzoate, 3-methylbut- 3-en-1-yl 2-methylbenzoate, pentyl 2,4-dimethylbenzoate and pentyl 2,5-dimethylbenzoate..

[0073] In one specific embodiment, the compound of formula (I) is selected from the group consisting of 3-methylbut-2-en-1-yl 2-methylbenzoate, (Z)-hex-3-en-1-yl 2-methylbenzoate, cyclopropyl methyl 2-methylbenzoate, pentyl 2,3-dimethylbenzoate and pentyl 2,6- dimethylbenzoate.

[0074] The invention is now further described with reference to the following non-limiting examples. These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art.

[0075] EXAMPLES

[0076] General Protocol for sip and spit to obtain taste descriptions (@15 ppm dosage):

[0077] A 1 liter aqueous stock solution was prepared in an Erlenmeyer flask with strong magnetic stirring by weighting the solubilizers Poloxamer407 (Pluronic F-127, Sigma Aldrich, CAS 9003- 11-6) @0.5% wt / wt (5.0 grams) and Cremophor RH40 (Kolliphor RH 40, Sigma Aldrich, CAS 61788-85-0) @0.25% wt / wt (2.5 grams) and adding tap water to 1000 g (from the water dispenser). After 3 hours of stirring, the solution became homogeneous. 0.03 grams of a 1% propylene glycol solution of each substance was dosed to 20 grams of the aqueous stock solution in plastic cups. After manual stirring, each sample was tasted separately.

[0078] Example 1 :

[0079] Methyl 2-methylbenzoate (CAS 89-71-4), ethyl 2-methylbenzoate (CAS 87-24-1), methyl 3- methylbenzoate (CAS 99-36-5), methyl 4-methylbenzoate (CAS 99-75-2), methyl 3,4- dimethylbenzoate (CAS 38404-42-1), methyl 2,5-dimethylbenzoate (CAS 13730-55-7), methyl 2,4-dimethylbenzoate (CAS 23617-71-2), methyl 2,3-dimethylbenzoate (CAS 15012-36-9) and methyl 2,6-dimethylbenzoate (CAS 14920-81-1) were purchased from commercial suppliers.

[0080] Methyl 2-methylbenzoate (CAS 89-71-4)

[0081] GC-MS (El, 70 eV): 150 (43, [M]+*), 120 (9), 119 (100), 118 (60), 91 (73), 90 (22), 89 (18), 65 (26), 63 (15), 39 (14).

[0082] Taste description: medicinal, hygienic, Wintergreen, round, floral, orange flower, similar to methyl salicylate which has herbal, medicinal.

[0083] Ethyl 2-methylbenzoate (CAS 87-24-1)

[0084] GC-MS (El, 70 eV): 164 (36, [M]+*), 135 (23), 119 (100), 118 (70), 91 (61), 90 (22), 89 (16), 65 (28), 63 (11), 39 (11).

[0085] Taste description: similar as methyl 2-methylbenzoate, medicinal, hygienic, Wintergreen, slightly bitter, still sweet, anisic, orange flower.

[0086] Methyl 3-methylbenzoate (CAS 99-36-5):

[0087] Odour description (10% solution in DPG): green (chemical), sweet, floral, medicinal (wintergreen, warm)

[0088] Taste description: medicinal, almond, nutty, wintergreen, bitter.

[0089] Methyl 4-methylbenzoate (CAS 99-75-2):

[0090] Odour description (10% solution in DPG): green (anisic, estragol, citrus peel), floral (anisic, cyclene), medicinal (wintergreen, warm).

[0091] Taste description: anisic, hygienic, sweet, fruity, berry.

[0092] Methyl 3,4-dimethylbenzoate (CAS 38404-42-1): Odour description (10% solution in DPG): green (sharp, thin, citrus peel), medicinal.

[0093] Taste description: waxy, hesperidic, medicinal, weak.

[0094] Methyl 2,5-dimethylbenzoate (CAS 13730-55-7):

[0095] Odour description (10% solution in DPG): green (chemical, leafy), medicinal (wintergreen, solvent).

[0096] Taste description: medicinal, hygienic, wintergreen.

[0097] Methyl 2,4-dimethylbenzoate (CAS 23617-71-2):

[0098] Odour description (10% solution in DPG): green (anisic), powdery (almondy), medicinal, (wintergreen).

[0099] Taste description: sweet, fruity, almond, green.

[0100] Methyl 2,3-dimethylbenzoate (CAS 15012-36-9):

[0101] Odour description (10% solution in DPG): warm, medicinal, (wintergreen, orange flower aspect).

[0102] Taste description: medicinal, hygienic, sweet, wintergreen, floral.

[0103] Methyl 2,6-dimethylbenzoate (CAS 14920-81-1):

[0104] Odour description (10% solution in DPG): green (leathery, dry, phenolic, chemical), medicinal (acetophenone).

[0105] Taste description: phenolic, bitter, chemical.

[0106] Example 2: allyl 2-methylbenzoate

[0107] Allyl 2-methylbenzoate was prepared as described in the literature Tu, H.-Y. et al., J. Am. Chem. Soc. 2020, 142, 9604-9611.

[0108] GC-MS (El, 70 eV): 176 (5, [M]+*), 158 (13), 147 (22), 135 (100), 119 (81), 91 (71), 90 (12), 89 (15), 65 (29), 41 (16), 39 (28).1H NMR (400 MHz, CDCh, 5 / ppm): 7.94 (dd, J = 1.3, 8.2 Hz, 1 H), 7.39 (t, J = 7.3 Hz, 1 H), 7.26 - 7.22 (m, 2H), 6.09 - 5.99 (m, 1 H), 5.41 (qd, J = 1.5, 17.2 Hz, 1 H), 5.28 (qd, J = 1.3, 10.4 Hz, 1 H), 4.80 (td, J = 1.4, 5.7 Hz, 2H), 2.61 (s, 3H).13C NMR (101 MHz, CDCh, 5 / ppm): 167.2, 140.2, 132.3, 132.0, 131.6, 130.6, 129.5, 125.7, 118.1 , 65.3, 21.7.

[0109] Odour description (10% solution in DPG): green (metallic), medicinal (orange flower), fruity (peachy, juicy orange). Taste description: herbaceous, green, medicinal, less bitter than Wintergreen, slightly artificial.

[0110] Example 3: propyl 2-methylbenzoate

[0111] 2-Methylbenzoic acid (19.0 g, 140 mmol, 1.0 equiv), 1-bromopropane (18.9 g, 154 mmol, 1.1 equiv) and Na2CO3 (17.8 g, 168 mmol, 1.2 equiv) in DMF (150 mL) were placed in a 350mL- sulfonation flask and heated to 40°C for 3 hours and to 50°C for 2 hours. The reaction mixture was poured on 150 mL ice cold saturated Na2CO3solution and extracted with 2 x 150 mL MTBE. The organic layer was washed with 1 x 150 mL water and 1 x 150 mL brine. The combined organic layer was dried over MgSO4, filtered by suction and evaporated. The crude was purified by fractional distillation over a 10 cm Vigreux column under high vacuum (0.03 mbar) to afford propyl 2-methylbenzoate 17.6 g (71 % yield) as a colorless liquid.

[0112] GC-MS (El, 70 eV): 178 (20, [M]+*), 136 (37), 119 (100), 118 (100), 91 (68), 90 (20), 89 (15), 65 (28), 39 (15), 27 (14).1H NMR (400 MHz, CDCI3, 5 / ppm): 7.91 (dd, J = 1.5, 8.1 Hz, 1 H), 7.38 (t, J = 7.4 Hz, 1 H), 7.26 - 7.22 (m, 2H), 4.26 (t, J = 6.6 Hz, 2H), 2.60 (s, 3H), 1.83 - 1.74 (m, 2H), 1.03 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, CDCh, 5 / ppm): 167.8, 140.0, 131.8, 131.6, 130.5, 130.0, 125.6, 66.3, 22.1 , 21.7, 10.6. bp 58 °C (0.03 mbar).

[0113] Odour description (10% solution in DPG): medicinal (ethyl salicylate), fruity (peachy, neroli). Taste description: typical Wintergreen character but slightly more artificial. Similar to methyl salicylate, hygienic, herbal and medicinal, lacking sweetness.

[0114] Example 4: isopropyl 2-methylbenzoate

[0115] 2-Methylbenzoic acid (3.0 g, 22 mmol, 1.0 equiv), para-toluenesulfonic acid monohydrate (0.42 g, 2.2 mmol, 10 mol%) and isopropanol (40 mL) were placed in a 100mL-sulfonation flask and refluxed for 16 hours. According to GC the reaction mixture still contained starting material, more para-toluenesulfonic acid monohydrate (0.42 g, 2.2 mmol, 10 mol%) was added and the reaction was refluxed for 3 days. The reaction mixture was poured on 20 mL ice cold saturated Na2CO3solution and extracted with 30 mL MTBE. The organic layer was washed with 1 x 150 mL water and 1 x 150 mL brine. The combined organic layer was dried over MgSO4, filtered by suction and evaporated. The crude was purified by column chromatography (heptane / MTBE, 95:5) and Kugelrohr distilled under high vacuum to afford isopropyl 2-methylbenzoate (3.11 g, 80% yield) as a colorless liquid. The spectral data were identical to those reported previously (Majek, M.; Jacobi von Wangelin, A., Angew. Chem. Int. Ed. 2015, 54, 2270-2274.) Odour description (10% solution in DPG): green, fruity, medicinal (salicylate).

[0116] Taste description: medicinal, bitter, chemical. Example 5: but-3-en-1-yl 2-methylbenzoate

[0117] Adapting the procedure of example 3 using 2-methylbenzoic acid (2.0 g, 14.7 mmol, 1.0 equiv), 4-bromobut-1-ene (2.18 g, 16.2 mmol, 1.1 equiv) and Na2CO3(1.87 g, 17.6 mmol, 1.2 equiv) in DMF (20 mL) furnished but-3-en-1-yl 2-methylbenzoate (2.48 g, 89% yield) as a colorless oil.

[0118] GC-MS (El, 70 eV): 190 (3, [M]+*), 136 (32), 135 (8), 120 (9), 119 (100), 118 (23), 91 (42), 65 (14), 55 (10), 54 (8), 39 (9).1H NMR (400 MHz, CDCI3, 5 / ppm): 7.90 (dd, J = 1.3, 8.2 Hz, 1 H), 7.38 (dt, J = 1.3, 7.5 Hz, 1 H), 7.25 - 7.21 (m, 2H), 5.94 - 5.81 (m, 1 H), 5.19 (q, J = 1.6 Hz, 1 H), 5.11 (qd, J = 1.4, 10.1 Hz, 1 H), 4.36 (t, J = 6.6 Hz, 2H), 2.59 (s, 3H), 2.52 (tq, J = 1.3, 6.7 Hz, 2H).13C NMR (101 MHz, CDCI3, 5 / ppm): 167.6, 140.1 , 134.2, 131.9, 131.6, 130.5, 129.7, 125.6, 117.3, 63.8, 33.2, 21.7.

[0119] Odour description (10% solution in DPG): green (metallic, mushroom).

[0120] Example 6: isobutyl 2-methylbenzoate

[0121] Adapting the procedure of example 3 using 2-methylbenzoic acid (2.5 g, 18.4 mmol, 1.0 equiv), 1-bromo-2-methylpropane (2.77 g, 20.2 mmol, 1.1 equiv) and Na2CO3(2.34 g, 22.0 mmol, 1.2 equiv) in DMF (20 mL) afforded isobutyl 2-methylbenzoate (2.83 g, 80% yield) as a colorless oil.

[0122] GC-MS (El, 70 eV): 192 (6, [M]+*), 137 (16), 136 (40), 119 (100), 118 (63), 91 (55), 90 (11), 65 (22), 57 (16), 41 (17), 39 (12).1H NMR (400 MHz, CDCI3, 5 / ppm): 7.93 (dd, J = 1.5, 8.1 Hz, 1 H), 7.38 (t, J = 7.4 Hz, 1 H), 7.26 - 7.22 (m, 2H), 4.09 (d, J = 6.6 Hz, 2H), 2.61 (s, 3H), 2.08 (td, J = 6.6, 13.4 Hz, 1 H), 1.03 (d, J = 6.6 Hz, 6H).13C NMR (101 MHz, CDCI3, 5 / ppm): 167.7, 140.0, 131.8, 131.6, 130.5, 129.9, 125.6, 70.9, 27.8, 21.8, 19.3.

[0123] Odour description (10% solution in DPG): green (technical), medicinal.

[0124] Taste description: medicinal, hygienic, anisic, Wintergreen.

[0125] Example 7: butyl 2-methylbenzoate

[0126] Adapting the procedure of example 4 using 2-methylbenzoic acid (25.0 g, 184 mmol, 1.0 equiv), para-toluenesulfonic acid monohydrate (3.49 g, 18.4 mmol, 10 mol%) and 1-butanol (100 mL) furnished after fractional distillation over a 10 cm Vigeux column under high vaccum (0.03 mbar) butyl 2-methylbenzoate (19.7 g, 56% yield) as a colorless oil.

[0127] GC-MS (El, 70 eV): 192 (14, [M]+*), 137 (14), 136 (56), 119 (88), 118 (100), 91 (53), 90 (14), 89 (10), 65 (18), 41 (10).1H NMR (400 MHz, CDCI3, 5 / ppm): 7.90 (dd, J = 1.5, 8.1 Hz, 1 H), 7.40 - 7.36 (m, 1 H), 7.26 - 7.22 (m, 2H), 4.30 (t, J = 6.6 Hz, 2H), 2.60 (s, 3H), 1.78 - 1.71 (m, 2H), 1.53 - 1.43 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H).13C NMR (101 MHz, CDCI3, 5 / ppm): 167.7, 140.0, 131.8, 131.6, 130.5, 130.0, 125.6, 64.6, 30.8, 21.7, 19.3, 13.7. bp 65°C (0.03 mbar).

[0128] Odour description (10% solution in DPG): fruity, green (leathery, cyclohexyl salicylate), medicinal (wintergreen).

[0129] Taste description: medicinal, hygienic, green, wintergreen, slightly bitter, weaker.

[0130] Example 8: cyclopentyl 2-methylbenzoate

[0131] Adapting the procedure of example 4 using 2-methylbenzoic acid (3.0 g, 22 mmol, 1.0 equiv), para-toluenesulfonic acid monohydrate (0.42 g, 2.2 mmol, 10 mol%) and cyclopentanol (30 mL) afforded cyclopentyl 2-methylbenzoate (2.72 g, 60% yield) as a colorless oil.

[0132] GC-MS (EI, 70 eV): 204 (2, [M]+«), 137 (13), 136 (54), 120 (9), 119 (100), 118 (36), 91 (38), 90 (6), 65 (11), 41 (9), 39 (6).1H NMR (400 MHz, CDCI3, 5 / ppm): 7.88 - 7.85 (m, 1 H), 7.39 - 7.35 (m, 1 H), 7.25 - 7.21 (m, 2H), 5.40 (tt, J = 2.9, 5.9 Hz, 1 H), 2.58 (s, 3H), 1.99 - 1.91 (m, 2H), 1.88 - 1.75 (m, 4H), 1.69 - 1.63 (m, 2H).13C NMR (101 MHz, CDCI3, 5 / ppm): 167.5, 139.7, 131.6, 131.5, 130.4, 130.4, 125.6, 77.5, 32.8, 23.8, 21.7.

[0133] Odour description (10% solution in DPG): green (leathery), medicinal.

[0134] Example 9: 3-methylbut-2-en-1-yl 2-methylbenzoate

[0135] Adapting the procedure of example 3 using 2-methylbenzoic acid (2.0 g, 14.7 mmol, 1.0 equiv), 1-bromo-3-methylbut-2-ene (2.41 g, 16.2 mmol, 1.1 equiv) and Na2CO3(1.87 g, 17.6 mmol, 1.2 equiv) in DMF (20 mL) afforded 3-methylbut-2-en-1-yl 2-methylbenzoate (2.18 g, 73% yield) as a colorless oil.

[0136] GC-MS (El, 70 eV): 204 (4, [M]+*), 136 (15), 119 (100), 118 (15), 91 (39), 69 (61), 68 (25), 67 (13), 65 (17), 41 (32), 39 (13).1H NMR (400 MHz, CDCI3, 5 / ppm): 7.90 (dd, J = 1.5, 8.1 Hz, 1 H), 7.39 - 7.35 (m, 1 H), 7.25 - 7.20 (m, 2H), 5.49 - 5.45 (m, 1 H), 4.80 (d, J = 7.1 Hz, 2H), 2.59 (s, 3H), 1.79 - 1.76 (m, 6H).13C NMR (101 MHz, CDCI3, 5 / ppm): 167.7, 139.9, 139.0, 131.7, 131.5, 130.5, 129.9, 125.6, 118.7, 61.6, 25.7, 21.7, 18.1.

[0137] Odour description (10% solution in DPG): weak, slightly medicinal, citrus, green (mushroom).

[0138] Example 10: pentyl 2-methylbenzoate

[0139] Adapting the procedure of example 4 using 2-methylbenzoic acid (100 g, 735 mmol, 1.0 equiv), para-toluenesulfonic acid monohydrate (14.0 g, 73.5 mmol, 10 mol%) and pentan-1-ol (400 mL) furnished after fractional distillation over a 10 cm Vigeux column under high vaccum (0.06 mbar) pentyl 2-methylbenzoate (129 g, 85% yield) as a colorless oil. GC-MS (El, 70 eV): 206 (8, [M]+'), 137 (23), 136 (65), 119 (88), 118 (100), 91 (62), 90 (14), 65 (22), 43 (21), 41 (15), 29 (14).1H NMR (400 MHz, CDCh, 5 / ppm): 7.90 (dd, J = 1.2, 8.1 Hz, 1 H), 7.40 - 7.36 (m, 1 H), 7.24 (dd, J = 5.0, 7.5 Hz, 2H), 4.29 (t, J = 6.6 Hz, 2H), 2.60 (s, 3H), 1 .80 - 1 .73 (m, 2H), 1 .47 - 1.34 (m, 4H), 0.96 - 0.90 (m, 3H).13C NMR (101 MHz, CDCh, 5 / ppm):

[0140] 167.8, 140.0, 131.8, 131.6, 130.5, 130.0, 125.6, 64.9, 28.4, 28.3, 22.3, 21.7, 14.0. bp 86°C (0.06 mbar).

[0141] Odour description (10% solution in DPG): green (hexyl salicylate, cyclohexyl salicylate), medicinal, floral.

[0142] Taste description: green, leafy, slightly bitter, Wintergreen, hexylsalicylate.

[0143] Example 11 : isopentyl 2-methylbenzoate

[0144] Adapting the procedure of example 4 using 2-methylbenzoic acid (25 g, 184 mmol, 1.0 equiv), para-toluenesulfonic acid monohydrate (3.49 g, 18.4 mmol, 10 mol%) and 3-methylbutan-1-ol (100 mL) furnished after fractional distillation over a 10 cm Vigeux column under high vaccum (0.04 mbar) isopentyl 2-methylbenzoate (29.1 g, 77% yield) as a colorless oil.

[0145] GC-MS (El, 70 eV): 206 (5, [M]+*), 137 (27), 136 (48), 119 (100), 118 (72), 91 (57), 71 (19), 70 (30), 65 (20), 43 (32), 41 (13).1H NMR (400 MHz, CDCh, 5 / ppm): 7.91 - 7.88 (m, 1 H), 7.40 - 7.36 (m, 1 H), 7.26 - 7.21 (m, 2H), 4.33 (t, J = 6.7 Hz, 2H), 2.60 (s, 3H), 1.83 - 1.74 (m, 1 H), 1.68 - 1.61 (m, 2H), 0.97 (d, J = 6.6 Hz, 6H).13C NMR (101 MHz, CDCh, 5 / ppm): 167.7, 140.0,

[0146] 131.8, 131.6, 130.5, 129.9, 125.6, 63.4, 37.4, 25.2, 22.5, 21.7. bp 75-79°C (0.04 mbar).

[0147] Odour description (10% solution in DPG): green (isoamyl salicylate), medicinal (wintergreen).

[0148] Example 12: (Z)-hex-3-en-1-yl 2-methylbenzoate

[0149] Adapting the procedure of example 3 using 2-methylbenzoic acid (2.0 g, 14.7 mmol, 1.0 equiv), (Z)-1-bromohex-3-ene (2.63 g, 16.2 mmol, 1.1 equiv) and Na2CO3(1.87 g, 17.6 mmol, 1.2 equiv) in DMF (20 mL) afforded (Z)-hex-3-en-1-yl 2-methylbenzoate (2.43 g, 76% yield) as a colorless oil.

[0150] GC-MS (El, 70 eV): 218 ([M]+*), 137 (5, [M-C6H9]+), 120 (9), 119 (100), 91 (51), 89 (8), 82 (74), 67 (40), 65 (18), 55 (11), 41 (16), 39 (12).1H NMR (400 MHz, CDCh, 5 / ppm): 7.94 - 7.85 (m, 1 H), 7.42 - 7.34 (m, 1 H), 7.28 - 7.18 (m, 2H), 5.58 - 5.48 (m, 1 H), 5.44 - 5.36 (m, 1 H), 4.32 - 4.28 (m, 2H), 2.59 (s, 3H), 2.54 - 2.48 (m, 2H), 2.13 - 2.05 (m, 2H), 0.99 - 0.95 (m, 3H).13C NMR (101 MHz, CDCh, 5 / ppm): 167.6, 140.0, 134.5, 131.8, 131.6, 130.5, 129.8, 125.6, 123.9, 64.3, 26.8, 21.7, 20.6, 14.2.

[0151] Odour description (10% solution in DPG): green (metallic, mushroom, bark), floral (salicylate). Taste description: green, medicinal, floral, bitter.

[0152] Example 13: cyclohexyl 2-methylbenzoate

[0153] Cyclohexyl 2-methylbenzoate was prepared according to a literature procedure: Yang, C.-H. et al., RSC Advances 2015, 5, 61081-61093. The analytical data were identical to those reported in the reference.

[0154] Odour description (10% solution in DPG): green (leathery, rubbery), floral (salicylate).

[0155] Taste description: medicinal, green, leathery, bitter.

[0156] Example 14: hexyl 2-methylbenzoate

[0157] Adapting the procedure of example 3 using 2-methylbenzoic acid (2.0 g, 14.7 mmol, 1.0 equiv), 1-bromohexane (2.67 g, 16.2 mmol, 1.1 equiv) and Na2CO3(1.87 g, 17.6 mmol, 1.2 equiv) in DMF (20 mL) afforded hexyl 2-methylbenzoate (2.42 g, 69% yield) as a colorless oil. The analytical data were identical to those reported previously: Wu, H. et al., Chem. Eur. J. 2018, 24, 3444-3447.

[0158] Odour description (10% solution in DPG): weak, green (bark), soft, floral.

[0159] Example 15: benzyl 2-methylbenzoate

[0160] Benzyl 2-methylbenzoate was prepared according to a literature procedure: Sultane, Prakash R. et al., Tetrahedron Lett. 2015, 56, 2067-2070.

[0161] Odour description (10% solution in DPG): green (metallic, mushroom, medicinal), fruity, floral. Taste description: medicinal, earthy, green, floral, not very strong.

[0162] Example 16: heptyl 2-methylbenzoate

[0163] Adapting the procedure of example 3 using 2-methylbenzoic acid (2.0 g, 14.7 mmol, 1.0 equiv), 1 -bromoheptane (2.89 g, 16.2 mmol, 1.1 equiv) and Na2CO3(1.87 g, 17.6 mmol, 1.2 equiv) in DMF (20 mL) afforded heptyl 2-methylbenzoate (2.82 g, 82% yield) as a colorless oil.

[0164] GC-MS (El, 70 eV): 234 (7, [M]+*), 137 (49), 136 (100), 119 (87), 118 (96), 91 (52), 90 (10), 65 (15), 57 (21), 43 (12), 41 (16).1H NMR (400 MHz, CDCI3, 5 / ppm): 7.95 - 7.86 (m, 1 H), 7.42 - 7.34 (m, 1 H), 7.26 - 7.22 (m, 2H), 4.29 (t, J = 6.7 Hz, 2H), 2.60 (s, 3H), 1.79 - 1.72 (m, 2H), 1.46 - 1.28 (m, 8H), 0.91 - 0.87 (m, 3H).13C NMR (101 MHz, CDCI3, 5 / ppm): 167.8, 140.0, 131.8, 131.6, 130.5, 130.0, 125.6, 64.9, 31.7, 28.9, 28.7, 26.1 , 22.6, 21.7, 14.0.

[0165] Odour description (10% solution in DPG): weak, slightly green (hay, leathery). Example 17: 2-phenylethyl 2-methylbenzoate

[0166] Adapting the procedure of example 3 using 2-methylbenzoic acid (2.0 g, 14.7 mmol, 1.0 equiv), (2-bromoethyl)benzene (2.99 g, 16.2 mmol, 1.1 equiv) and Na2CO3(1.87 g, 17.6 mmol, 1.2 equiv) in DMF (20 mL) afforded 2-phenylethyl 2-methylbenzoate (2.57 g, 73% yield) as a colorless oil. The analytical data were identical to those reported previously: Zhang, C. et al., J. Am. Chem. Soc. 2013, 135, 15257-1526.

[0167] Odour description (10% solution in DPG): green (metallic, dusty, bark), floral (rosy).

[0168] Taste description: floral, woody, green, rosy.

[0169] Example 18: pentyl 3-methylbenzoate

[0170] Adapting the procedure of example 3 using 3-methylbenzoic acid (10 g, 73.4 mmol, 1 .0 equiv), 1-iodo pentane (14.6 g, 73.4 mmol, 1.0 equiv) and K2CO3(20.3 g, 147 mmol, 2.0 equiv) in DMF (100 mL) afforded pentyl 3-methylbenzoate (12 g, 78% yield) as a pale pink colored liquid. The analytical data were identical to those reported previously: Liu, J. et al., Org. Biomol. Chem. 2014, 12, 2637-2640.

[0171] Odour description (10% solution in DPG): green (leathery, dry, phenolic, chemical, peonile aspect).

[0172] Example 19: pentyl 4-methylbenzoate

[0173] Adapting the procedure of example 3 using 4-methylbenzoic acid (8 g, 58.8 mmol, 1.0 equiv), 1-iodo pentane (11.6 g, 58.8 mmol, 1.0 equiv) and K2CO3(16.2 g, 118 mmol, 2.0 equiv) in DMF (70 mL) afforded pentyl 4-methylbenzoate (5 g, 41 % yield) as a pale yellow liquid. The analytical data were identical to those reported previously: Liu, J. et al., Org. Biomol. Chem. 2014, 12, 2637-2640.

[0174] Odour description (10% solution in DPG): green (leathery, chemical, orange peel), powdery (peonile aspect).

[0175] Example 20: pentyl 3,4-dimethylbenzoate

[0176] Adapting the procedure of example 3 using 3,4-dimethyl benzoic acid (8 g, 53.3 mmol, 1.0 equiv), 1-iodo pentane (10.6 g, 53.3 mmol, 1.0 equiv) and K2CO3(14.7 g, 107 mmol, 2.0 equiv) in DMF (60 mL) afforded pentyl 3,4-dimethylbenzoate (8.8 g, 75% yield) as a pale yellow liquid.

[0177] 1H NMR (400 MHz, CDCI3, 5 / ppm): 7.81 (s, 1 H), 7.77 (dd, J = 1.7, 7.7 Hz, 1 H), 7.18 (d, J = 7.8 Hz, 1 H), 4.30 (t, J = 6.7 Hz, 2H), 2.31 (s, 6H), 1.81 - 1.71 (m, 2H), 1.64 - 1.19 (m, 4H), 0.99 - 0.88 (m, 3H).13C NMR (101 MHz, CDCh, 5 / ppm): 166.9, 142.0, 136.6, 130.5, 129.5, 128.1,

[0178] 127.1. 64.8, 28.4, 28.2, 22.3, 19.9, 19.6, 13.9.

[0179] Odour description (10% solution in DPG): green (leathery, phenolic, chemical, harsh), powdery (peonile aspect).

[0180] Example 21 : pentyl 2,5-dimethylbenzoate

[0181] Adapting the procedure of example 3 using 2,5-dimethyl benzoic acid (8 g, 53.3 mmol, 1.0 equiv), 1-iodo pentane (10.6 g, 53.3 mmol, 1.0 equiv) and K2CO3(14.7 g, 107 mmol, 2.0 equiv) in DMF (80 mL) afforded pentyl 2,5-dimethylbenzoate (10.4 g, 89% yield) as a colorless liquid.

[0182] 1H NMR (400 MHz, CDCh, 5 / ppm): 7.71 (s, 1 H), 7.21 - 7.18 (m, 1 H), 7.12 (d, J = 7.8 Hz, 1 H), 4.29 (t, J = 6.7 Hz, 2H), 2.55 (s, 3H), 2.35 (s, 3H), 1 .83 - 1 .71 (m, 2H), 1 .47 - 1 .34 (m, 4H), 1 .00 - 0.87 (m, 3H).13C NMR (101 MHz, CDCh, 5 / ppm): 167.9, 136.8, 135.1 , 132.5, 131.5, 130.9,

[0183] 129.8, 64.8, 28.4, 28.2, 22.3, 21.2, 20.7, 13.9. Odour description (10% solution in DPG): green (leathery, dry, phenolic), powdery (peonile aspect).

[0184] Example 22: pentyl 2,4-dimethylbenzoate

[0185] Adapting the procedure of example 3 using 2,4-dimethyl benzoic acid (8 g, 53.3 mmol, 1.0 equiv), 1-iodo pentane (10.6 g, 53.3 mmol, 1.0 equiv) and K2CO3 (14.7 g, 107 mmol, 2.0 equiv) in DMF (80 mL) afforded pentyl 2,4-dimethylbenzoate (8.5 g, 72% yield) as a pale yellow liquid.

[0186] 1H NMR (400 MHz, CDCh, 5 / ppm): 7.84 (d, J = 7.6 Hz, 1 H), 7.07 - 7.03 (m, 2H), 4.28 (t, J = 6.7 Hz, 2H), 2.58 (s, 3H), 2.35 (s, 3H), 1.82 - 1 .70 (m, 2H), 1.50 - 1.22 (m, 4H), 1.04 - 0.84 (m, 3H).13C NMR (101 MHz, CDCh, 5 / ppm): 167.6, 142.2, 140.1 , 132.4, 130.7, 127.0, 126.3, 64.6, 28.4, 28.2, 22.3, 21.7, 21.3, 13.9.

[0187] Odour description (10% solution in DPG): green (anisic, apple peel, citrus peel), powdery (creamy, peonile aspect).

[0188] Taste description: green, fruity, apple, medicinal, floral.

[0189] Example 23: pentyl 2,3-dimethylbenzoate

[0190] Adapting the procedure of example 4 using 2,3-dimethyl benzoic acid (10 g, 66.6 mmol, 1.0 equiv), para-toluenesulfonic acid monohydrate (3.80 g, 19.9 mmol, 30 mol%) and pentan- 1 -ol (5.87 g, 66.6 mmol, 1.0 equiv) furnished pentyl 2,3-dimethylbenzoate (9 g, 61% yield) as a pale yellow liquid.1H NMR (400 MHz, CDCh, 6 / ppm): 7.60 (d, J = 7.7 Hz, 1 H), 7.26 (d, J = 7.5 Hz, 1 H), 7.12 (t, J = 7.6 Hz, 1 H), 4.29 (t, J = 6.7 Hz, 2H), 2.45 (s, 3H), 2.31 (s, 3H), 1.81 - 1.69 (m, 2H), 1.61 - 1.18 (m, 4H), 0.96 - 0.89 (m, 3H).13C NMR (101 MHz, CDCh, 6 / ppm): 168.8, 137.8, 137.3, 132.9, 131.4, 127.5, 125.1 , 64.9, 28.4, 28.2, 22.3, 20.5, 16.6, 13.9.

[0191] Odour description (10% solution in DPG): green (leathery, sharp), medicinal.

[0192] Example 24: pentyl 2,6-dimethylbenzoate

[0193] Adapting the procedure of example 3 using 2,6-dimethyl benzoic acid (8 g, 53.3 mmol, 1.0 equiv), 1-iodo pentane (10.6 g, 53.3 mmol, 1.0 equiv) and K2CO3(14.7 g, 107 mmol, 2.0 equiv) in DMF (100 mL) afforded pentyl 2,6-dimethylbenzoate (8.1 g, 69% yield) as a pale yellow liquid.

[0194] 1H NMR (400 MHz, CDCh, 6 / ppm): 7.19 - 7.14 (m, 1 H), 7.02 (d, J = 7.8 Hz, 2H), 4.32 (t, J = 6.7 Hz, 2H), 2.32 (s, 6H), 1.81 - 1.66 (m, 2H), 1.48 - 1 .20 (m, 4H), 1 .01 - 0.82 (m, 3H).13C NMR (101 MHz, CDCh, 6 / ppm): 170.1 , 134.7, 134.2, 129.1 , 127.5, 65.1 , 28.3, 28.1 , 22.3, 19.6, 13.9. Odour description (10% solution in DPG): green (leathery, dry, styrene), powdery (chemical, acetophenone).

[0195] Example 25: 3-methylbut-3-en-1-yl 2-methylbenzoate

[0196] A solution of methyl 2-methylbenzoate (5.0 g, 33.3 mmol, 1.0 equiv), 3-methylbut-3-en-1-ol (8.6 g, 99.9 mmol, 3.0 equiv) and titanium tetraisopropoxide (38 mg, 0.4 mol%) was heated to 120°C for 16 hours, while distilling off methanol. The reaction mixture was added to ice cold water and extracted with MTBE. The organic layer was washed with brine and dried over MgSO4, filtered and concentrated under reduced pressure. The crude was purified by column chromatography to afford 3-methylbut-3-en-1-yl 2-methylbenzoate (5.70 g, 84%) as a colorless liquid.

[0197] 1H NMR (400 MHz, CDCh, 6 / ppm): 7.93 - 7.87 (m, 1 H), 7.45 - 7.31 (m, 1 H), 7.27 - 7.20 (m, 2H), 4.86 - 4.78 (m, 2H), 4.42 (t, J = 6.8 Hz, 2H), 2.61 - 2.57 (m, 3H), 2.48 (t, J = 6.8 Hz, 2H), 1.81 (s, 3H).13C NMR (101 MHz, CDCh, 6 / ppm): 167.6, 141.7, 140.1 , 131.8, 131.6, 130.5, 129.8, 125.6, 112.4, 62.8, 36.8, 22.4, 21.7.

[0198] Odour description (10% solution in DPG): floral medicinal, ethyl salicylate, slightly green, leathery.

[0199] Taste description: medicinal, clean, Wintergreen, slightly bitter, metallic.

[0200] Example 26: Toothpaste and mouthwash - comparison with methyl salicylate The compounds of the present invention have been assessed in the following reference flavor formula.

[0201] The toothpastes have been prepared by adding 1 % of the respective flavour and 0.2% saccharin in opacified silica: i. flavour comprising 2.0% of methyl 2-methylbenzoate solution (10% in PG) + 18% PG, ii. flavour comprising 2.0% of propyl 2-methylbenzoate solution (10% in PG) + 18% PG, iii. flavour comprising 2.0% of ethyl 2-methylbenzoate solution (10% in PG) + 18% PG, iv. flavour comprising 2.0% of methyl 2,3-dimethylbenzoate solution (10% in PG) + 18% PG, v. flavour comprising 2.0% of methyl 2,4-dimethylbenzoate solution (10% in PG) + 18% PG, vi. flavour comprising 20% methyl salicylate. The smell and taste of the toothpaste samples have been assessed in a randomized way: a) Smell: The toothpaste has been squeezed onto a paper pad, and smelled. b) Taste by licking: The toothpaste has been squeezed onto a spoon, and tasted. The toothpaste has been spitted, and there was a rest for 10 min between 2 samples. c) Taste by brushing: The toothpaste has been squeezed onto a toothbrush, and the teeth have been brushed for 1 min. The toothpaste has been spitted, and there was a rest for 30 min between 2 samples.

[0202] Methyl 2-methylbenzoate, ethyl 2-methylbenzoate, propyl 2-methylbenzoate and methyl salicylate have a similar organoleptic profile. All materials offer a salicylate, Wintergreen note and have a good performance in toothpaste.

[0203] Methyl 2-methylbenzoate and ethyl 2-methylbenzoate seem to have a lower taste threshold than methyl salicylate. They are about 90-100 times stronger than methyl salicylate.

[0204] Methyl 2,3-dimethylbenzoate and methyl 2,4-dimethylbenzoate also provide salicylate notes, however not Wintergreen specific. Their impact is less perceivable.

[0205] An oral care flavour as described above is typically employed in about 1-1.5% by weight in a toothpaste. However, a person skilled in the art will be able to modify the flavour composition and also the usage ranges.

[0206] Similar results as for the toothpaste have been obtained in a comparison of the compounds in a non-alcoholic mouthwash, comprising 0.2% by weight of the flavour.

[0207] Example 27: Gradual replacement of methyl salicylate

[0208] The oral flavor composition of example 26 was used to study partial replacement of methyl salicylate by methyl 2-methylbenzoate in toothpaste. The toothpastes have been prepared by adding 1 % of the respective flavour and 0.2% saccharin in opacified silica: i. flavour comprising 2.2% of methyl 2-methylbenzoate solution (10% in PG) + 17.8% PG, ii. flavour comprising 1.1 % of methyl 2-methylbenzoate solution (10% in PG) + 8.9% PG + 10% methyl salicylate, iii. flavour comprising 1.65% of methyl 2-methylbenzoate solution (10% in PG) + 13.35% PG + 5% methyl salicylate, iv. flavour comprising 20% methyl salicylate.

[0209] The four flavour compositions were perceived equivalent. This shows that it is possible to replace methyl salicylate fully or partially by methyl-2-methylbenzoate. For example, this might be useful for consumer products, in which stability of the salicylate is an issue due to compatibility with other ingredients or partial permeability of the packaging material.

[0210] Example 28: cyclopropylmethyl 2-methylbenzoate

[0211] A solution of 2-methylbenzoic acid (3.00 g, 22.0 mmol) in DMF (N,N-dimethyl formamide) (30 mL) was treated with sodium carbonate (2.80 g, 26.4 mmol, 1.2 equiv.) and (bromomethyl)cyclopropane (3.27 g, 24.2 mmol, 1.1 equiv.) and the resulting mixture heated to 40°C for 2 h. The reaction mixture was then added to ice cold aqueous saturated Na2CO3solution (30 ml) and extracted with MTBE (methyl tert-butyl ether) (40 ml). The organic layer was washed with water (40 ml) and brine (40 ml). The organic layer was dried over MgSO4, filtered, and evaporated. The resulting crude material was purified by flash chromatography on silica gel eluting with heptane / MTBE, followed by Kugelrohr distillation to give cyclopropylmethyl 2-methylbenzoate (2.72 g, 65 % yield) as a colorless liquid.

[0212] 1H NMR (400 MHz, CDCI3, 5 / ppm) = 7.96 (dd, J = 1.3, 8.2 Hz, 1 H), 7.45 - 7.38 (m, 1 H), 7.31 - 7.23 (m, 2H), 4.17 (d, J = 7.1 Hz, 2H), 2.64 (s, 3H), 1.35 - 1.22 (m, 1 H), 0.68 - 0.61 (m, 2H), 0.42 - 0.36 (m, 2H).13C NMR (101 MHz, CDCI3, 5 / ppm) = 167.9, 139.9, 131.8, 131.6, 130.5, 130.1 , 125.7, 69.5, 21.7, 9.9, 3.4. GC / MS (El, 70eV) m / z (rel. intens.) = 190 (5, [M]+*), 172 (1), 161 (1), 147 (6), 135 (7), 119 (100), 91 (38), 55 (25).

[0213] Odour description (10% solution in DPG): green, aromatic (medicinal, Wintergreen, thyme) floral (amyl salicylate).

[0214] Example 29: Stability studies of methyl 2-methylbenzoate vs. methyl salicylate in different toothpaste bases

[0215] Composition of toothpaste bases and dosages:

[0216] A typical silica base contains 8% wt / wt of precipitated silica and 8.5% wt / wt of synthetic amorphous silica. A typical chalk base contains 40% wt / wt of calcium carbonate and 4% of synthetic amorphous silica. A typical peroxide base contains 3% wt / wt of hydrogen peroxide and was used as received by the toothpaste manufacturer.

[0217] Methyl salicylate was dosed at 0.5% wt / wt and methyl 2-methylbenzoate at 0.05% wt / wt (added as a 10% solution in propylene glycol) in the silica base, chalk base and peroxide base, respectively. a) Silica base: As can be seen from the results above, the compound of the present invention, methyl 2- methylbenzoate, is significantly more stable at 40°C and 50°C after 2 months and 3 months in silica base than the benchmark methyl salicylate, in terms of taste (flavour) and color stability / appearance (much less discoloration occurs). Methyl 2-methylbenzoate can be dosed about 10 times lower than methyl salicylate. b) Chalk base: As can be seen from the table above, the compound of the present invention, methyl 2- methylbenzoate, is significantly more stable at 0°C, 40°C and 50°C after 2 months and 3 months in chalk base than the benchmark methyl salicylate, both in terms of taste (flavour) and color stability / appearance (much less discoloration occurs). Methyl salicylate is not stable at all at 50°C in chalk base. Methyl 2-methylbenzoate can be dosed about 10 times lower than methyl salicylate. c) Peroxide base:

[0218] As can be seen from the table above, the compound of the present invention, methyl 2- methylbenzoate, is comparably stable at 40°C and 50°C after 2 months and 3 months in peroxide base, compared to the benchmark methyl salicylate, both in terms of taste and color stability / appearance (much less discoloration occurs). Methyl 2-methylbenzoate can be dosed about 10 times lower than methyl salicylate.

[0219] The assessments in the tables above used the following grading system:

[0220] Example 30: Stability studies of the compounds of the present invention in a typical Wintergreen flavour applied in two toothpaste bases

[0221] A typical silica base contains 8% wt / wt of precipitated silica and 8.5% wt / wt of synthetic amorphous silica. A typical chalk base contains 40% wt / wt of calcium carbonate and 4% of synthetic amorphous silica.

[0222] A typical Wintergreen flavour was dosed at 1% wt / wt along with 0.25% saccharin in the toothpaste bases, which are silica base and chalk base, respectively.

[0223] This Wintergreen flavour formula contains 20% wt / wt methyl salicylate (formula A, reference), which was replaced with 0.22% wt / wt of methyl 2-methylbenzoate (formula B) or with a mixture of 10% wt / wt methyl salicylate and 0.11% wt / wt methyl 2-methylbenzoate (formula C). a) Silica base:

[0224] As shown above, the compound of the present invention, methyl 2-methylbenzoate incorporated in a Wintergreen flavour (formula B) is significantly more stable both at 40°C and 50°C up to 3 months than the benchmark methyl salicylate (formula A) in terms of taste and color stability / appearance (much less discoloration occurs). Methyl 2-methylbenzoate can be dosed 91 times lower (formula B) than methyl salicylate (formula A). Formula C (mixture of methyl salicylate and methyl 2-methylbenzoate) is comparably stable at 40°C and more stable at 50°C than formula A (methyl salicylate). b) Chalk base: As shown above, the compound of the present invention, methyl 2-methylbenzoate incorporated in a Wintergreen flavour (formula B) is more stable both at 40°C and 50°C up to 3 months than the benchmark methyl salicylate (formula A) in terms of taste and color stability / appearance (much less discoloration occurs). Methyl 2-methylbenzoate can be dosed 91 times lower (formula B) than methyl salicylate (formula A). Formula C (mixture of methyl salicylate and methyl 2-methylbenzoate) is comparably or slightly more stable both at 40°C and at 50°C than formula A (methyl salicylate).

[0225] The assessments in the tables above used the following grading system: Example 31 : Application in chewing gums

[0226] Methyl 2-methylbenzoate, a compound of the present invention, was tested in two types of reference flavours, a bubble gum and a mint chewing gum flavour, both of which containing a significant amount of methyl salicylate, which was replaced with the compound of the present invention or ethyl salicylate, respectively. The chewing gums were chewed and tasted. a) Bubble gum flavour:

[0227] The flavour was dosed at 1.4% wt / wt in the chewing gum base for formulas 1 to 3. Formula 1 contains 4.1 % methyl salicylate in a typical bubble gum flavour formula (=control). 4.1 % methyl salicylate in formula 1 was replaced with 4.0% ethyl salicylate in formula 2 and with 0.052% methyl 2-benzoate in formula 3, respectively.

[0228] Replacement of methyl salicylate (formula 1) and of ethyl salicylate (formula 2) by an about 80- times lower dosage of methyl 2-methylbenzoate (formula 3) resulted in a Wintergreen type character with additional sweetness (slightly anthranilate). b) Mint flavour:

[0229] The flavour was dosed at 1 .6% wt / wt in the chewing gum base for formula 4 and at 1.0% wt / wt in the chewing gum base for formula 5, respectively. Formula 4 contains 40% methyl salicylate in a typical mint flavour formula (=control). 40% methyl salicylate in formula 4 was replaced with 0.8% methyl 2-benzoate in formula 5. Replacement of methyl salicylate (formula 4) by an about 80-times lower dosage of methyl 2- methylbenzoate (formula 5) resulted in a mint, Wintergreen type character with additional sweetness (slightly anthranilate).

Claims

Claims1 . An oral care composition comprising a) at least one compound of formula (I)wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety;R2, R3, R4, R5, and R6at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring; and b) an oral care base.

2. The oral care composition according to claim 1 , wherein in the at least one compound of formula (I) R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety;R2is Me; andR3, R4, R5and R6are H.

3. The oral care composition according to claim 1 , wherein the at least one compound of formula (I) is selected from the group consisting of methyl 2-methylbenzoate, ethyl 2- methylbenzoate, methyl 3-methylbenzoate, methyl 4-methylbenzoate, methyl 3,4- dimethylbenzoate, methyl 2,5-dimethylbenzoate, methyl 2,4-dimethylbenzoate, methyl 2,3-dimethylbenzoate, methyl 2,6-dimethylbenzoate, allyl 2-methylbenzoate, propyl 2-methylbenzoate, isopropyl 2-methylbenzoate, but-3-en-1-yl 2-methylbenzoate, isobutyl 2-methylbenzoate, butyl 2-methylbenzoate, cyclopentyl 2-methylbenzoate, 3- methylbut-2-en-1-yl 2-methylbenzoate, pentyl 2-methylbenzoate, isopentyl 2- methylbenzoate, hex-3-en-1-yl 2-methylbenzoate, cyclohexyl 2-methylbenzoate, hexyl 2-methylbenzoate, benzyl 2-methylbenzoate, heptyl 2-methylbenzoate, 2-phenylethyl 2-methylbenzoate, cyclopropylmethyl 2-methylbenzoate, pentyl 3-methylbenzoate, pentyl 4-methylbenzoate, pentyl 3,4-dimethylbenzoate, pentyl 2,5-dimethylbenzoate, pentyl 2,4-dimethylbenzoate, pentyl 2,3-dimethylbenzoate and pentyl 2,6- dimethylbenzoate.

4. The oral care composition according to any previous claim selected from the group consisting of toothpastes, tooth gels, subgingival gels, denture adhesives, denture cleaner, mouthwashes, mouthrinses, mouth sprays, chewing gums, lozenges, flosses and breath mints.

5. The oral care composition according to any previous claim, wherein the at least one compound of formula (I) is comprised in an amount of at least 0.5 ppm or more, for example 1 ppm or more, for example 5 ppm or more, for example 10 ppm or more, 20 ppm or more, for example 50 ppm or more, for example 100 ppm or more, for example 250 ppm or more, for example 500 ppm or more.

6. The oral care composition according to any one of the previous claims which is essentially free of methyl and / or ethyl salicylate.

7. The oral care composition according to any one of the previous claims, further comprising at least one cooling compound.

8. The oral care composition according to any one of the previous claims, wherein the oral care base is selected from the group consisting of chalk base, hydrogen peroxide base, silica base, sodium carbonate base, sodium bicarbonate base and mixtures thereof.

9. Use of a compound of formula (I)wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety; andR2, R3, R4, R5, and R6at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring; in an oral care composition.

10. The use according to claim 9, wherein the at least one compound of formula (I) is replacing methyl and / or ethyl salicylate.

11. The use according to claim 9, wherein the compound of formula (I) enhances and modifies oral care formulations with Wintergreen flavour notes.

12. The use according to claim 9, wherein the oral care composition comprises an oral care base selected from the group consisting of chalk base, hydrogen peroxide base, silica base, sodium carbonate base or sodium bicarbonate base.

13. A method of improving, enhancing, or modifying an oral care composition, comprising the step of adding thereto at least one compound of formula (I)wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety; andR2, R3, R4, R5, and R6at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring.

14. The method of claim 13, wherein the at least one compound of formula (I) is added in an amount of at least 0.5 ppm or more, for example 1 ppm or more, for example 5 ppm or more, for example 10 ppm or more, 20 ppm or more, for example 50 ppm or more, for example 100 ppm or more, for example 250 ppm or more, for example 500 ppm or more.

15. A compound of formula (I)wherein R1is selected from the group consisting of a C1 to C9 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety;R2, R3, R4, R5, and R6at the phenyl ring are independently selected from H and Me, wherein the compound according to formula (I) has one or two methyl groups at said phenyl ring, with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2-methylbenzoate, cyclopentyl 2-methylbenzoate, 2-phenylethyl 2- methylbenzoate, 3-methylbut-3-en-1-yl 2-methylbenzoate, pentyl 2,4-dimethylbenzoate and pentyl 2,5-dimethylbenzoate.

16. The compound according to claim 15, wherein the compound is selected from the group consisting of 3-methylbut-2-en-1-yl 2-methylbenzoate, (Z)-hex-3-en-1-yl 2- methylbenzoate, cyclopropylmethyl 2-methylbenzoate, pentyl 2,3-dimethylbenzoate and pentyl 2,6-dimethylbenzoate.

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