Organic compound

Abstract

The invention relates to the use of a compound of formula (I), wherein R1 is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; and 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 wherein at least one of R2 or R3 is Me, as a fragrance; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2- methylbenzoate.

Description

[0001] ORGANIC COMPOUND

[0002] TECHNICAL FIELD

[0003] The present invention relates generally to the use of compounds in fragrance applications, and to fragrance compositions and fragrance applications comprising said compounds. It further relates to methods of modifying fragrance compositions and fragrance applications by the use of said compounds.

[0004] BACKGROUND

[0005] In the fragrance industry, perfumers are continually looking for new compounds possessing unique olfactory properties. For example, there is a need for ingredients that are suitable for the fragrance industry possessing green metallic notes.

[0006] The esters of orf o-methylbenzoic acid are well known compounds in the chemical industry. However, beside for the methyl ester (described by IFF in US 2005 / 0170998) and the ethyl ester (described by Symrise in WO 2023 / 232237) the odor characteristics of such compounds are not described to the best of our knowledge. Derivatives of esters of orf o-methylbenzoic acid with an alkyl substituent in a different position on the aromatic ring are also not known in this context.

[0007] It is therefore desirable to provide new compounds for the fragrance industry, having desired odour properties and raising no concerns in terms of safe use, as could be the case for some salicylates.

[0008] SUMMARY

[0009] In accordance with a first aspect of the present invention there is provided a use of at least one compound of formula (I) as fragrance wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; and

[0010] 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 wherein at least one of R2or R3is Me; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2- methylbenzoate.

[0011] In accordance with a second aspect of the present invention there is provided a fragrance composition comprising at least one compound of formula (I), as described above.

[0012] In accordance with a third aspect of the present invention there is provided a consumer product comprising at least one compound of formula (I), as described above.

[0013] In accordance with a fourth aspect of the present invention there is provided a method of improving, enhancing or modifying a fragrance composition through the addition of an olfactory acceptable amount of at least one compound of formula (I), as described above.

[0014] In accordance with a fifth aspect of the present invention there is provided a group of novel compounds which can be useful fragrance compounds.

[0015] Certain embodiments of any aspect of the present invention may provide one or more of the following advantages:

[0016] Fragrance compounds mimicking odour aspects of salicylates, in particular cyclohexyl salicylate, without the associated health risk. 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.

[0017] DETAILED DESCRIPTION

[0018] The present invention is based on the surprising finding that the esters of ortho- or mefa- methylbenzoic acid or esters of bismethylbenzoic acid, although at least partially known in the chemical industry for a long time, were now found to have interesting odor properties.

[0019] Therefore, there is provided herein the use of at least one compound of formula (I) wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; and

[0020] 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 wherein at least one of R2or R3is Me, as a fragrance; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2- methylbenzoate.

[0021] This means that the R1group is defined by a sum of C atoms. Said R1group consists of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic or aromatic moiety. The atoms of the cyclic are included in the counting of C atoms of the C1 to C6 hydrocarbon moiety. The R1group can also be outside of the C1 to C6 hydrocarbon range. For example, benzyl is defined as a phenyl-CH2 group and consists of 7 carbons. Phenethyl comprises 1 -phenylethyl and 2-phenylethyl groups. Both groups consist of 8 carbons.

[0022] The compounds of formula (I) have strong green metallic odours. Overall, they partially resemble salicylates, in particular cyclohexyl salicylate, which might be classified as CMR2 ingredients in the future. So the compounds of formula (I) could be used as replacer for salicylates, in particular as replacer for cyclohexyl salicylate.

[0023] By the use of the compound of formula (I) as defined above, fragrance notes with green metallic aspects resembling particular cyclohexyl salicylate can be provided. This is in contrast to the known methyl- and ethyl esters of orf o-methylbenzoic acid having different odour descriptions (ylang, orange flower, and grape for Me; harsh, medicinal, fresh after methyl salicylate for Et). This finding was discovered by threshold measurements carried out on GC and corroborated by comparing measured EC 50 values obtained by means of an in-vitro assay employing a novel olfactory receptor discovered by the applicant to be implicated in the human sensing of the cyclohexyl salicylate. This test and the novel olfactory receptors are more fully described in the examples below.

[0024] The compounds of formula (I) can be used as fragrance compounds, and in particular as cyclohexyl salicylate replacer. It is a surprising finding, that the methyl group in the compounds of the present invention mimics a hydroxyl group of certain salicylates.

[0025] The compounds of formula (I) can comprise one or more chiral centers and one or more CO double bonds, and as such may exist as a mixture of stereoisomers and / or double bond isomers, or they may be resolved as isomerically pure forms. If it is desired to prepare individual stereoisomers, 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.

[0026] For example, there is provided the use of the compound of formula (I) wherein R1is a linear C3 to C6 alkyl, like n-propyl, n-butyl, n-pentyl or n-hexyl.

[0027] For example, there is provided the use of the compound of formula (I) wherein R1is a branched C3 to C6 alkyl, like / -propyl, / -butyl, sec-butyl, f-butyl, / -pentyl, / -hexyl, or others.

[0028] For example, there is provided the use of the compound of formula (I) wherein R1is a cyclic C3 to C6 alkyl, like cyc / o-propyl, cyc / o-butyl, cyc / o-butyl, cyc / o-pentyl, or cyc / o-hexyl. Preferably, there is provided the use of the compound of formula (I) wherein R1is a cyclic C3 to C6 alkyl, like cyc / o-propyl, cyc / o-butyl, cyc / o-butyl, or cyc / o-hexyl.

[0029] For example, there is provided the use of the compound of formula (I) wherein R1is a C1 to C6 hydrocarbon moiety and contains one cyclic moiety, like cyc / o-propyl, cyc / o-propylmethyl, cyc / o-butyl, cyc / o-butyl, cyc / o-pentyl, or cyc / o-hexyl. Preferably, there is provided the use of the compound of formula (I) wherein R1is a cyclic C3 to C6 alkyl, like cyc / o-propyl, cyc / o-butyl, cyc / o-butyl, or cyc / o-hexyl.

[0030] For example, there is provided the use of the compound of formula (I) wherein R1is further containing saturated and unsaturated bonds like 1 -propenyl, 2-propenyl, 3-butenyl, 3- methylbut-2-en-1-yl, 3-hexenyl, or others.

[0031] For example, there is provided the use of the compound of formula (I) wherein R1is benzyl or phenethyl, preferably benzyl.

[0032] For example, in the compound of formula (I) R2is Me, and R3, R4, R5and R6are H.

[0033] For example, in the compound of formula (I) R3is Me, and R2, R4, R5and R6are H.

[0034] For example, in the compound of formula (I) R2and R3is Me, and R4, R5and R6are H.

[0035] For example, in the compound of formula (I) R2and R4is Me, and R3, R5and R6are H.

[0036] For example, in the compound of formula (I) R2and R5is Me, and R3, R4and R6are H.

[0037] For example, in the compound of formula (I) R2and R6is Me, and R3, R4and R5are H.

[0038] For example, in the compound of formula (I) R3and R4is Me, and R2, R5and R6are H.

[0039] For example, in the compound of formula (I) R3and R5is Me, and R2, R4and R6are H.

[0040] For example, there is provided the use of a compound of formula (I) wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; and

[0041] 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 wherein at least one of R2or R3is Me, as a fragrance; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2- methylbenzoate.

[0042] For example, there is provided the use as fragrance of the compound of formula (I) selected from the group consisting of methyl 3-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, cyclopropylmethyl 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, 2-phenylethyl 2-methylbenzoate, pentyl 3-methylbenzoate, pentyl 3,4-dimethylbenzoate, pentyl 2,5-dimethylbenzoate, pentyl 2,4-dimethylbenzoate, pentyl 2,3- dimethylbenzoate, 3-methylbut-3-en-1-yl 2-methylbenzoate and pentyl 2,6-dimethylbenzoate.

[0043] For example, there is provided the use as fragrance of the compound of formula (I) selected from the group consisting of allyl 2-methylbenzoate, propyl 2-methylbenzoate, isopropyl 2- methylbenzoate, but-3-en-1-yl 2-methylbenzoate, isobutyl 2-methylbenzoate, butyl 2- methylbenzoate, cyclopropylmethyl 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, 2-phenylethyl 2-methylbenzoate, and 3-methylbut-3-en-1-yl 2- methylbenzoate.

[0044] For example, there is provided the use as fragrance of the compound of formula (I) selected from the group consisting of methyl 3-methylbenzoate and pentyl 3-methylbenzoate.

[0045] For example, there is provided the use as fragrance of the compound of formula (I) selected from the group consisting of methyl 3,4-dimethylbenzoate, methyl 2,5-dimethylbenzoate, methyl 2,4-dimethylbenzoate, methyl 2,3-dimethylbenzoate, methyl 2,6-dimethylbenzoate, pentyl 3,4-dimethylbenzoate, pentyl 2,5-dimethylbenzoate, pentyl 2,4-dimethylbenzoate, pentyl 2,3-dimethylbenzoate, and pentyl 2,6-dimethylbenzoate.

[0046] In particular, there is provided the use as fragrance of the compound of formula (I) selected from the group consisting of propyl 2-methylbenzoate, isopropyl 2-methylbenzoate, cyclohexyl 2-methylbenzoate and butyl 2-methylbenzoate.

[0047] Thus, there is provided in a further aspect of the invention a fragrance composition comprising a compound of formula (I). There is further provided a fragrance composition comprising the compound of formula (I) as defined above and at least one further fragrance compound.

[0048] The compounds of formula (I) may be used alone, as mixture thereof, or in combination with known odorant molecules selected from the extensive range of natural products, and synthetic molecules currently available, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, fragrance precursors, and / or in a mixture with one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions, for example, carrier materials, and other auxiliary agents commonly used in the art.

[0049] As used herein, "carrier material" means a material which is practically neutral from an odorant point of view, i.e. a material that does not significantly alter the organoleptic properties of odorants.

[0050] The term “auxiliary agent" refers to ingredients that might be employed in a fragrance composition for reasons not specifically related to the olfactory performance of said composition. For example, an auxiliary agent may be an ingredient that acts as an aid to processing a fragrance ingredient or ingredients, ora composition containing said ingredient(s), or it may improve handling or storage of a fragrance ingredient or composition containing same. It might also be an ingredient that provides additional benefits such as imparting color or texture. It might also be an ingredient that imparts light resistance or chemical stability to one or more ingredients contained in a fragrance composition. A detailed description of the nature and type of adjuvants commonly used in fragrance compositions containing same cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art. As used herein, ‘fragrance composition’ means any composition comprising a compound of formula (I), or a mixture thereof and a base material, e.g. a diluent conventionally used in conjunction with odorants, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane-1 ,2-diol, triethyl citrate (TEC) and alcohol (e.g. ethanol).

[0051] Optionally, the composition may comprise an anti-oxidant, adjuvant / a stabilizing compound. Said adjuvant or compound may be selected from Tinogard® TT (BASF), Tinogard® Q (BASF), Tocopherol (including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78-2), 2,6- bis(1 ,1-dimethylethyl)-4-methylphenol (BHT, CAS 128-37-0) and related phenols, hydroquinones (CAS 121-31-9), EDTA, and ascorbic acid, or others. In some embodiments, said adjuvant or compound, for example, can be added to the compounds of formula (I) in 0.01- 1 % by weight,

[0052] The following list comprises examples of known odorant molecules, which may be combined with a compound of formula (I), or a mixture thereof:

[0053] • Essential oils and extracts, e.g. castoreum, costus root oil, oak moss absolute, geranium oil, tree moss absolute, basil oil, fruit oils, such as bergamot oil and mandarine oil, myrtle oil, palmarose oil, patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and / or ylang-ylang oil;

[0054] • Alcohols, e.g. cinnamic alcohol ((E)-3-phenylprop-2-en-1-ol); cis-3-hexenol ((Z)-hex-3- en-1-ol); Citronellol (3,7-dimethyloct-6-en-1-ol); dihydro myrcenol (2,6-dimethyloct-7- en-2-ol); Ebanol™ ((E)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); eugenol (4-allyl-2-methoxyphenol); ethyl linalool ((E)-3,7-dimethylnona-1 ,6-dien-3-ol); farnesol ((2E,6Z)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol); geraniol ((E)-3,7- dimethylocta-2,6-dien-1-ol); Super Muguet™ ((E)-6-ethyl-3-methyloct-6-en-1-ol); linalool (3,7-dimethylocta-1 ,6-dien-3-ol); menthol (2-isopropyl-5-methylcyclohexanol); Nerol (3,7-dimethyl-2,6-octadien-1-ol); phenyl ethyl alcohol (2-phenylethanol); Rhodinol™ (3,7-dimethyloct-6-en-1-ol); Sandalore™ (3-methyl-5-(2,2,3- trimethylcyclopent-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohex-3-en-1- yl)propan-2-ol); or Timberol™ (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); 2,4,7- trimethylocta-2,6-dien-1-ol, and / or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]- methanol;

[0055] • Aldehydes and ketones, e.g. anisaldehyde (4-methoxybenzaldehyde); alpha amyl cinnamic aldehyde (2-benzylideneheptanal); Georgywood™ (1-(1 ,2,8,8-tetramethyl- 1 ,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); Hydroxycitronellal (7-hydroxy- 3,7-dimethyloctanal); Iso E Super® (1-(2,3,8,8-tetramethyl-1 ,2,3,4,5,6,7,8- octahydronaphthalen-2-yl)ethanone); Isoraldeine® ((E)-3-methyl-4-(2,6,6- trimethylcyclohex-2-en-1-yl)but-3-en-2-one); Hedione® (methyl 3-oxo-2- pentylcyclopentaneacetate); Nympheal (3-(4-isobutyl-2-methylphenyl)propanal); Mahonial (5,9-dimethyl-9-hydroxy-decen-4-al); maltol; methyl cedryl ketone; methylionone; verbenone; and / or vanillin;

[0056] • Ether and acetals, e.g. Ambrox® (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro- 1 / 7-benzo[e][1]benzofuran); geranyl methyl ether ((2E)-1-methoxy-3,7-dimethylocta- 2,6-diene); rose oxide (4-methyl-2-(2-methylprop-1-en-1-yl)tetrahydro-2 / 7-pyran); and / or Spirambrene® (2',2',3,7,7-pentamethylspiro[bicyclo[4.1 ,0]heptane-2,5'- [1 ,3]dioxane]);

[0057] • Esters and lactones, e.g. benzyl acetate; cedryl acetate ((1 S,6 / ?,8a / ?)-1 ,4,4,6- tetramethyloctahydro-1 / 7-5,8a-methanoazulen-6-yl acetate); y-decalactone (6- pentyltetrahydro-2 / 7-pyran-2-one); Helvetolide® (2-(1-(3,3-dimethylcyclohexyl)ethoxy)- 2-methyl propyl propionate); y-undecalactone (5-heptyloxolan-2-one); and I or vetiveryl acetate ((4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1 / 7-azulen-6-yl) acetate

[0058] • Macrocycles, e.g. Ambrettolide ((Z)-oxacycloheptadec-10-en-2-one); ethylene brassylate (1 ,4-dioxacycloheptadecane-5, 17-dione); and I or Exaltolide® (16- oxacyclohexadecan-1-one); and

[0059] • Heterocycles, e.g. isobutylquinoline (2-isobutylquinoline).

[0060] Overall, the compounds of formula (I) can be used alone, as a mixture thereof, or in combination with other fragrance ingredients and / or precursors thereof. Such other fragrance ingredients are also described, for example, in "Perfume and Flavor Chemicals", S. Arctander, Ed., Vol. I & II, Allured Publishing Corporation, Carol Stream, USA, 2003 and include fragrance compounds of natural or synthetic origin and essential oils.

[0061] The compounds of formula (I) may be used in a broad range of fragranced articles or consumer products, e.g. in any field of fine and functional perfumery, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. The compound can be employed in widely varying amounts, depending upon the specific article and on the nature and quantity of other odorant ingredients. The proportion is typically from 0.00001 to 3 weight per cent of the article. In one embodiment, the compound may be employed in a fabric softener in an amount from 0.0001 to 3 weight per cent (e.g. 0.001 to 1 including 0.5, 0.3, and 0.05 weight %). In another embodiment, the compound may be used in fine perfumery in amounts from 0.01 to 30 weight per cent (e.g. up to about 10 or up to 20 weight per cent), more preferably between 0.01 and 5 weight per cent (e.g. 0.01 to 0.1 weight per cent).

[0062] For example, the compound of formula (I) is present from about 1 % to about 30% by weight in a fragrance composition. The perfume composition is then applied, for example, in fabric care compositions, for example in about 0.1% to 0.3% by weight in powder detergent, from 0.6% to 0.8% by weight in heavy duty liquid detergent (HDLD), and from 0.8% to 1.5% by weight in fabric softener. For example, the perfume composition can be applied in personal care compositions, for example in from 0.5% to 0.8% by weight in shampoo, from 0.3% to 1 % by weight in conditioner, from 0.3% to 1.5% by weight in body deodorant, from 0.5% to 1.5% by weight in soap. For example, the perfume composition can be applied in fine fragrance, or in home care applications, in similar levels, or in levels that are slightly higher or lower.

[0063] However, these values are given only by way of example, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations.

[0064] The compounds of formula (I) may be employed in a consumer product base simply by directly mixing the compound, or a fragrance composition comprising a compound of formula (I), or a mixture thereof, with the consumer product base, or it may, in an earlier step, be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base.

[0065] Thus, the invention additionally provides a method of manufacturing a consumer product, comprising the incorporation a compound of formula (I), or a mixture thereof as a fragrance ingredient, either by directly admixing to the consumer product base or by admixing a fragrance composition comprising a compound of formula (I), or a mixture thereof, which may then be mixed with a consumer product base, using conventional techniques and methods. Through the addition of an olfactory acceptable amount of a compound of formula (I), or a mixture thereof the odor notes of a consumer product base will be improved, enhanced, or modified.

[0066] Thus, the invention furthermore provides a method for improving, enhancing or modifying a consumer product base by means of the addition thereto of an olfactory acceptable amount of a compound of formula (I), or a mixture thereof. There is provided in a further aspect of the present invention a consumer product comprising: a) a compound of formula (I) wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; and

[0067] 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 wherein at least one of R2or R3is Me; and b) a consumer product base; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate, ethyl 2-methylbenzoate and 2-phenylethyl 2-methylbenzoate.

[0068] As used herein, ‘consumer product base’ means a composition for use as a consumer product to fulfill specific actions, such as cleaning, softening, and caring or the like. Examples of such products include fine perfumery, e.g. perfume and eau de toilette; fabric care, household products and personal care products such as cosmetics, laundry care detergents, rinse conditioner, personal cleansing composition, detergent for dishwasher, surface cleaner; laundry products, e.g. softener, bleach, detergent; body-care products, e.g. shampoo, shower gel; air care products (includes products that contain preferably volatile and usually pleasantsmelling compounds which advantageously can even in very small amounts mask unpleasant odors). Air fresheners for living areas contain, in particular, natural and synthetic essential oils such as pine needle oils, citrus oil, eucalyptus oil, lavender oil, and the like, in amounts for example of up to 50% by weight. As aerosols they tend to contain smaller amounts of such essential oils, by way of example less than 5% or less than 2% by weight, but additionally include compounds such as acetaldehyde (in particular, <0.5% by weight), isopropyl alcohol (in particular, <5% by weight), mineral oil (in particular, <5% by weight), and propellants.

[0069] This list of products is given by way of illustration and is not to be regarded as being in any way limiting.

[0070] In one particular embodiment the consumer product base is selected form fine perfumery, and personal care products, including deodorants, hair care products, soaps, and the like. In one particular embodiment the consumer product base is a hair care product.

[0071] In a further particular embodiment the consumer product base is selected from fabric care products, including fabric softener, and home care products, including air fresheners, dish washers and the like.

[0072] 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 C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; and

[0073] 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 wherein at least one of R2or R3is Me; 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. For example, 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.

[0074] For example, there is provided the compound of formula (I) selected from the group consisting of methyl 3-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, cyclopropylmethyl 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, pentyl 3-methylbenzoate, pentyl 3,4- dimethylbenzoate, pentyl 2,3-dimethylbenzoate, and pentyl 2,6-dimethylbenzoate.

[0075] For example, there is provided the compound of formula (I) selected from the group consisting of allyl 2-methylbenzoate, propyl 2-methylbenzoate, isopropyl 2-methylbenzoate, but-3-en-1-yl 2-methylbenzoate, isobutyl 2-methylbenzoate, butyl 2-methylbenzoate, cyclopropylmethyl 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, and benzyl 2-methylbenzoate.

[0076] For example, there is provided the compound of formula (I) selected from the group consisting of methyl 3-methylbenzoate and pentyl 3-methylbenzoate.

[0077] For example, there is provided the compound of formula (I) selected from the group consisting of methyl 3,4-dimethylbenzoate, methyl 2,5-dimethylbenzoate, methyl 2,4-dimethylbenzoate, methyl 2,3-dimethylbenzoate, methyl 2,6-dimethylbenzoate, pentyl 3,4-dimethylbenzoate, pentyl 2,3-dimethylbenzoate, and pentyl 2,6-dimethylbenzoate.

[0078] 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.

[0079] EXAMPLES

[0080] Example 1 : Methyl 3-methylbenzoate, methyl 3,4-dimethylbenzoate, methyl 2,5-dimethylbenzoate, methyl 2,4-dimethylbenzoate, methyl 2,3-dimethylbenzoate and methyl 2,6-dimethylbenzoate were purchased from commercial suppliers.

[0081] Methyl 3-methylbenzoate (CAS 99-36-5):

[0082] Odour description (10% solution in DPG): green (chemical), sweet, floral, medicinal (wintergreen, warm)

[0083] Methyl 3,4-dimethylbenzoate (CAS 38404-42-1):

[0084] Odour description (10% solution in DPG): green (sharp, thin, citrus peel), medicinal.

[0085] Methyl 2,5-dimethylbenzoate (CAS 13730-55-7):

[0086] Odour description (10% solution in DPG): green (chemical, leafy), medicinal (wintergreen, solvent).

[0087] Methyl 2,4-dimethylbenzoate (CAS 23617-71-2):

[0088] Odour description (10% solution in DPG): green (anisic), powdery (almondy), medicinal (wintergreen).

[0089] Methyl 2,3-dimethylbenzoate (CAS 15012-36-9):

[0090] Odour description (10% solution in DPG): warm, medicinal (wintergreen, orange flower aspect).

[0091] Methyl 2,6-dimethylbenzoate (CAS 14920-81-1):

[0092] Odour description (10% solution in DPG): green (leathery, dry, phenolic, chemical) medicinal (acetophenone).

[0093] Example 2: allyl 2-methylbenzoate

[0094] Allyl 2-methylbenzoate was prepared as described in the literature Tu, H.-Y. et al., J. Am. Chem. Soc. 2020, 142, 9604-9611.

[0095] 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, CDC , 5 / ppm): 167.2, 140.2, 132.3, 132.0, 131.6, 130.6, 129.5, 125.7, 118.1 , 65.3, 21.7.

[0096] Odour description (10% solution in DPG): green (metallic), medicinal (orange flower), fruity (peachy, juicy orange).

[0097] Example 3: propyl 2-methylbenzoate

[0098] 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.

[0099] 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, CDCI3, 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).

[0100] Odour description (10% solution in DPG): medicinal (ethyl salicylate), fruity (peachy, neroli).

[0101] Example 4: isopropyl 2-methylbenzoate

[0102] 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). Example 5: but-3-en-1-yl 2-methylbenzoate

[0103] 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.

[0104] 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.

[0105] Odour description (10% solution in DPG): green (metallic, mushroom).

[0106] Example 6: isobutyl 2-methylbenzoate

[0107] 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.

[0108] 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.

[0109] Odour description (10% solution in DPG): green (technical), medicinal.

[0110] Example 7: butyl 2-methylbenzoate

[0111] 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.

[0112] 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).

[0113] Odour description (10% solution in DPG): fruity, green (leathery, cyclohexyl salicylate), medicinal (wintergreen).

[0114] Example 8: cyclopentyl 2-methylbenzoate

[0115] 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.

[0116] 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.

[0117] Odour description (10% solution in DPG): green (leathery), medicinal.

[0118] Example 9: 3-methylbut-2-en-1-yl 2-methylbenzoate

[0119] 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.

[0120] 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, CDCh, 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.

[0121] Odour description (10% solution in DPG): weak, slightly medicinal, citrus, green (mushroom).

[0122] Example 10: pentyl 2-methylbenzoate

[0123] 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):

[0124] 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).

[0125] Odour description (10% solution in DPG): green (hexyl salicylate, cyclohexyl salicylate), medicinal, floral.

[0126] Example 11 : isopentyl 2-methylbenzoate

[0127] 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.

[0128] 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,

[0129] 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).

[0130] Odour description (10% solution in DPG): green (isoamyl salicylate), medicinal (wintergreen).

[0131] Example 12: (Z)-hex-3-en-1-yl 2-methylbenzoate

[0132] Adapting the procedure of example 2 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.

[0133] 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.

[0134] Odour description (10% solution in DPG): green (metallic, mushroom, bark), floral (salicylate). Example 13: cyclohexyl 2-methylbenzoate

[0135] 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.

[0136] Odour description (10% solution in DPG): green (leathery, rubbery), floral (salicylate).

[0137] Example 14: hexyl 2-methylbenzoate

[0138] 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.

[0139] Odour description (10% solution in DPG): weak, green (bark), soft, floral.

[0140] Example 15: benzyl 2-methylbenzoate

[0141] Benzyl 2-methylbenzoate was prepared according to a literature procedure: Sultane, Prakash R. et al., Tetrahedron Lett. 2015, 56, 2067-2070.

[0142] Odour description (10% solution in DPG): green (metallic, mushroom, medicinal) fruity, floral.

[0143] Example 16: 2-phenylethyl 2-methylbenzoate

[0144] 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.

[0145] Odour description (10% solution in DPG): green (metallic, dusty, bark), floral (rosy).

[0146] Example 17: pentyl 3-methylbenzoate

[0147] 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. Odour description (10% solution in DPG): green (leathery, dry, phenolic, chemical, peonile aspect).

[0148] Example 18: pentyl 3,4-dimethylbenzoate

[0149] 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.

[0150] 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, CDCI3, 5 / ppm): 166.9, 142.0, 136.6, 130.5, 129.5, 128.1,

[0151] 127.1. 64.8, 28.4, 28.2, 22.3, 19.9, 19.6, 13.9.

[0152] Odour description (10% solution in DPG): green (leathery, phenolic, chemical, harsh), powdery (peonile aspect).

[0153] Example 19: pentyl 2,5-dimethylbenzoate

[0154] 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.

[0155] 1H NMR (400 MHz, CDCI3, 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, CDCI3, 5 / ppm): 167.9, 136.8, 135.1 , 132.5, 131.5, 130.9,

[0156] 129.8, 64.8, 28.4, 28.2, 22.3, 21.2, 20.7, 13.9.

[0157] Odour description (10% solution in DPG): green (leathery, dry, phenolic), powdery (peonile aspect).

[0158] Example 20: pentyl 2,4-dimethylbenzoate

[0159] 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.

[0160] 1H NMR (400 MHz, CDCI3, 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.

[0161] Odour description (10% solution in DPG): green (anisic, apple peel, citrus peel), powdery (creamy, peonile aspect).

[0162] Example 21 : pentyl 2,3-dimethylbenzoate

[0163] 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.

[0164] 1H NMR (400 MHz, CDCh, 5 / 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, 5 / 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.

[0165] Odour description (10% solution in DPG): green (leathery, sharp), medicinal.

[0166] Example 22: pentyl 2,6-dimethylbenzoate

[0167] 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 K2COs (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.

[0168] 1H NMR (400 MHz, CDCh, 5 / 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, 5 / 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).

[0169] Example 23: 3-methylbut-3-en-1-yl 2-methylbenzoate

[0170] 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.

[0171] 1H NMR (400 MHz, CDCh, 5 / 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, 5 / 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.

[0172] Odour description (10% solution in DPG): floral medicinal, ethyl salicylate, slightly green, leathery.

[0173] Counterexample 1 : Methyl 2-methylbenzoate (CAS 89-71-4)

[0174] 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).

[0175] Counterexample 2: Ethyl 2-methylbenzoate (CAS 87-24-1)

[0176] 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).

[0177] Counterexample 3: pentyl 4-methylbenzoate

[0178] Adapting the procedure of example 2 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.

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

[0180] Counterexample 4: heptyl 2-methylbenzoate

[0181] 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.

[0182] 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),

[0183] Odour description (10% solution in DPG): green (anisic, estragol, citrus peel) floral (anisic, cyclene) medicinal(wintergreen, warm).

[0184] Example 24: Activation of OR8H1 by the compounds of the present invention

[0185] To create the expression plasmid for OR8H1 the human OR8H1 gene with an optimized C- terminus (DNA sequence SEQ ID NO: 1 and amino acid sequence SEQ ID NO: 2) was synthesized by a DNA synthesis service provider (BioCat GmbH, Germany) and inserted into pcDNA3.1 (+) (Invitrogen, MA, USA) downstream of the CMV promoter sequence (SEQ ID NO: 3) and before the bgh terminator sequence (SEQ ID NO: 4). The synthetic OR8H1 nucleotide sequence further contained at its 5’-end a nucleotide sequence encoding a signal peptide (mmLucy-FLAG-rho) (SEQ ID NO 5 and 6). This plasmid thus contains a constitutively expressed OR gene

[0186] Expression of the OR8H1 gene was performed in HEK293T cells that had been stably transfected with a DNA sequence coding for functional variants of the human RTP1S (V227I, SEQ ID NO: 7 and 8) and RTP2 (L220R, SEQ ID NO: 9 and 10). These cells were seeded into polyethyleneimine coated 96-well plates (100pl / well) at a density of 10,000 cells / well and grown at 37°C in presence of 5% CO2for 24 h.

[0187] 0.625 pg of the OR8H1 expression plasmid, 1 pg of the empty pcDNA3.1 (+) vector and 1 pg of pGL4.29 (Promega) harbouring the CRE-inducible luciferase were diluted in 0.25 ml OptiMEM medium (Gibco™, ThermoFisher Scientific, MA, USA). In parallel 15 pl Lipofectamine 2000 (Invitrogen) was diluted in 0.25 ml OptiMEM medium and after 5 min preincubation, the two mixtures were combined to prepare the transfection mixture, which was incubated for an additional 25 min.

[0188] 50 pl of growth medium was replaced with fresh DMEM containing 9% foetal bovine serum (FBS). The pre-incubated transfection mixture was diluted to 5.5 ml in OptiMEM medium and

[0189] 50 pl of the diluted mixture was added per well (total volume 150 pl). Cells were further incubated for 24 h at 37°C in presence of 5% CO2 to allow for DNA uptake and expression of OR8H1.

[0190] Activation of OR8H1 by the test substances was measured by removal of 100 pl growth medium and addition of 50 pl DMEM containing 9% FBS, 1 % DMSO, and different concentrations of the test substances. After incubation for 4.5 h, the cells were lysed using 20 pl passive lysis buffer (Promega) and the luciferase signal, which is induced based on OR- dependent cAMP production, was measured.

[0191] Potency of the tested OR8H1 ligands is expressed as the EC20% value, which is the concentration that leads to a 20 % increase of the luciferase activity relative to the positive control (cyclohexyl salicylate). Table x shows the potency of the test compounds.

[0192] OR8H1 with an optimized C-terminus DNA sequence (SEQ ID NO 1): ATGGGTAGAAGAAATAACACAAATGTGCCTGACTTCATCCTTACGGGACTGTCAGATTCT GAAGAGGTCCAGATGGCCCTCTTTATACTATTTCTCCTGATATACCTAATTACTATGCTG GGCAATGTGGGGATGATATTGATAATCCGCCTGGACCTCCAGCTTCACACTCCCATGTA TTTTTTCCTTACTCACTTGTCATTTATTGACCTCAGTTACTCAACTGTCATCACACCTAAA ACCTTAGCGAACTTACTGACTTCCAACTATATTTCCTTCATGGGCTGCTTTGCCCAGATG TTCTTTTTTGTCTTCTTGGGAGCTGCTGAATGTTTTCTTCTCTCATCAATGGCCTATGAT CGCTACGTAGCTATCTGCAGTCCTCTACGTTACCCAGTTATTATGTCCAAAAGGCTGTGT TGCGCTCTTGTCACTGGGCCCTATGTGATTAGCTTTATCAACTCCTTTGTCAATGTGGTT TGGATGAGCAGACTGCATTTCTGCGACTCAAATGTAGTTCGTCACTTTTTCTGCGACACG TCTCCAATTTTAGCTCTGTCCTGCATGGACACATACGACATTGAAATCATGATACACATT TTAGCTGGTTCCACCCTGATGGTGTCCCTTATCACAATATCTGCATCCTATGTGTCCATT CTCTCTACCATCCTGAAAATTAATTCCACTTCAGGAAAGCAGAAAGCTTTGTCTACTTGT GCCTCTCATCTCTTGGGAGTCACCATCTTTTATGGAACTATGATTTTTACTTATTTAAAA CCAAGAAAGTCTTATTCTTTGGGAAGGGATCAAGTGGCTTCTGTTTTTTATACTATTGTG ATTCCCATGCTGAATCCACTCATTTATAGTCTTAGGAACAAAGAAGTTAAAAAGGCCATA AAGAGGTTGTTCAAGAGAAAGTGCTGCAGGAGAAGGTGA

[0193] OR8H1 with an optimized C-terminus amino acid sequence (SEQ ID NO 2 ): MGRRNNTNVPDFILTGLSDSEEVQMALFILFLLIYLITMLGNVGMILIIRLDLQLHTPMY FFLTHLSFIDLSYSTVITPKTLANLLTSNYISFMGCFAQMFFFVFLGAAECFLLSSMAYD RYVAICSPLRYPVIMSKRLCCALVTGPYVISFINSFVNWWMSRLHFCDSNWRHFFCDT

[0194] SPILALSCMDTYDIEIMIHILAGSTLMVSLITISASYVSILSTILKINSTSGKQKALSTC

[0195] ASHLLGVTIFYGTMIFTYLKPRKSYSLGRDQVASVFYTIVIPMLNPLIYSLRNKEVKKAI KRLFKRKCCRRR

[0196] CMV Promoter DNA sequence (SEQ ID NO 3)

[0197] GTTGACATTGATTATTGACTAGTTATTAATAGTAATCAATTACGGGGTCATTAGTTCATA

[0198] GCCCATATATGGAGTTCCGCGTTACATAACTTACGGTAAATGGCCCGCCTGGCTGACCG

[0199] CCCAACGACCCCCGCCCATTGACGTCAATAATGACGTATGTTCCCATAGTAACGCCAAT

[0200] AGGGACTTTCCATTGACGTCAATGGGTGGAGTATTTACGGTAAACTGCCCACTTGGCAG

[0201] TACATCAAGTGTATCATATGCCAAGTACGCCCCCTATTGACGTCAATGACGGTAAATGGC

[0202] CCGCCTGGCATTATGCCCAGTACATGACCTTATGGGACTTTCCTACTTGGCAGTACATCT

[0203] ACGTATTAGTCATCGCTATTACCATGGTGATGCGGTTTTGGCAGTACATCAATGGGCGTG

[0204] GATAGCGGTTTGACTCACGGGGATTTCCAAGTCTCCACCCCATTGACGTCAATGGGAGT

[0205] TTGTTTTGGCACCAAAATCAACGGGACTTTCCAAAATGTCGTAACAACTCCGCCCCATTG

[0206] ACGCAAATGGGCGGTAGGCGTGTACGGTGGGAGGTCTATATAAGCAGAGCTC bgh terminator DNA sequence (SEQ ID NO 4)

[0207] CTGTGCCTTCTAGTTGCCAGCCATCTGTTGTTTGCCCCTCCCCCGTGCCTTCCTTGACC

[0208] CTGGAAGGTGCCACTCCCACTGTCCTTTCCTAATAAAATGAGGAAATTGCATCGCATTGT

[0209] CTGAGTAGGTGTCATTCTATTCTGGGGGGTGGGGTGGGGCAGGACAGCAAGGGGGAG

[0210] GATTGGGAAGACAATAGCAGGCATGCTGGGGATGCGGTGGGCTCTATGG mmLucy-FLAG-rho DNA sequence (SEQ ID NO 5)

[0211] ATGAGCCACCAGATCCTGCTGCTCCTGGCCCTGCTGACCCTAGGCCTGGCTGATTACAA

[0212] GGACGACGACGATAAGATCGAATTGATGAACGGGACCGAGGGCCCAAACTTCTACGTG

[0213] CCTTTCTCCAACAAGACGGGCGTGGTGGAATTC mmLucy-FLAG-rho amino acid sequence (SEQ ID NO 6)

[0214] MSHQILLLLALLTLGLAMDYKDDDDKMNGTEGPNFYVPFSNKTGWEF

[0215] RTP1S(V227I) DNA sequence (SEQ ID NO 7)

[0216] ATGTGTAAAAGCGTGACCACAGATGAGTGGAAGAAAGTCTTCTATGAGAAGATGGAGGA

[0217] GGCAAAGCCGGCTGACAGCTGGGACCTCATCATAGACCCCAACCTCAAGCACAATGTG CTGAGCCCTGGTTGGAAGCAGTACCTGGAATTGCATGCTTCAGGCAGGTTCCACTGCTC

[0218] CTGGTGCTGGCACACCTGGCAGTCGCCCTACGTGGTCATCCTCTTCCACATGTTCCTGG

[0219] ACCGCGCCCAGCGGGCGGGCTCGGTGCGCATGCGCGTCTTCAAGCAGCTGTGCTATG

[0220] AGTGCGGCACGGCGCGGCTGGACGAGTCCAGCATGCTGGAGGAGAACATCGAGGGCC

[0221] TGGTGGACAACCTCATCACCAGCCTGCGCGAGCAGTGCTACGGCGAGCGTGGCGGCC

[0222] AGTACCGCATCCACGTGGCCAGCCGCCAGGACAACCGGCGGCACCGCGGAGAGTTCT

[0223] GCGAGGCCTGCCAGGAGGGCATCGTGCACTGGAAGCCCAGCGAGAAGCTGCTGGAGG

[0224] AGGAGGCGACCACCTACACCTTCTCCCGGGCGCCCAGCCCCACCAAGTCGCAGGACCA

[0225] GACGGGCTCAGGCTGGAACTTCTGCTCTATCCCCTGGTGCTTGTTTTGGGCCACGGTCC TG CTG CTG ATCATCTACCTG CAGTTCTCTTTCCGTAGCTCCATCTAA

[0226] RTP1S(V227I) amino acid sequence (SEQ ID NO 8)

[0227] MCKSVTTDEWKKVFYEKMEEAKPADSWDLIIDPNLKHNVLSPGWKQYLELHASGRFHCSW

[0228] CWHTWQSPYWILFHMFLDRAQRAGSVRMRVFKQLCYECGTARLDESSMLEENIEGLVDN

[0229] LITSLREQCYGERGGQYRIHVASRQDNRRHRGEFCEACQEGIVHWKPSEKLLEEEATTYT

[0230] FSRAPSPTKSQDQTGSGWNFCSI PWCLFWATVLLLI I YLQFSFRSSI

[0231] RTP2(L220R) DNA sequence (SEQ ID NO 9)

[0232] ATGTGTACCAGCTTGACCACTTGTGAGTGGAAGAAAGTCTTCTATGAGAAGATGGAGGT

[0233] GGCAAAGCCAGCGGACAGCTGGGAGCTCATCATAGACCCCAACCTCAAGCCCAGTGAG

[0234] CTGGCCCCTGGCTGGAAGCAGTACCTGGAGCAGCACGCCTCAGGCAGGTTCCACTGCT

[0235] CCTGGTGCTGGCACACCTGGCAGTCTGCCCATGTGGTCATCCTCTTCCACATGTTCCTG

[0236] GACCGCGCCCAGCGGGCGGGCTCGGTGCGCATGCGCGTCTTCAAGCAGCTGTGCTAT

[0237] GAGTGCGGCACGGCGCGGCTGGACGAGTCCAGCATGCTGGAGGAGAACATCGAGGGC

[0238] CTGGTGGACAACCTCATCACCAGCCTGCGCGAGCAGTGCTACGAGGAGGATGGTGGCC

[0239] AGTACCGCATCCACGTGGCCAGCCGCCCGGACAGCGGGCCGCATCGTGCAGAGTTCT

[0240] GTGAGGCCTGCCAGGAGGGCATCGTTCACTGGAAGCCCAGCGAGAAGCTGCTGGAGG

[0241] AGGAGGTGACCACCTACACCTCTGAAGCCTCCAAGCCGAGGGCCCAGGCGGGATCCG

[0242] GCTACAACTTCTTGTCTCTTCGCTGGTGCCTCTTCTGGGCCTCTCTCTGCCTGCTCGTTG TTTACCTGCAGTTCTCCTTCCGCAGTCCTGCCTTCTTTTAG

[0243] RTP2(L220R) amino acid sequence (SEQ ID NO 10)

[0244] MCTSLTTCEWKKVFYEKMEVAKPADSWELIIDPNLKPSELAPGWKQYLEQHASGRFHCSW

[0245] CWHTWQSAHWILFHMFLDRAQRAGSVRMRVFKQLCYECGTARLDESSMLEENIEGLVDN LITSLREQCYEEDGGQYRIHVASRPDSGPHRAEFCEACQEGIVHWKPSEKLLEEEVTTYT

[0246] SEASKPRAQAGSGYNFLSLRWCLFWASLCLLWYLQFSFRSPAFF

[0247] Table 1 :

[0248] According the receptor activation data in the table above, it can be concluded that compounds with a linear and branched C3-C6 alkyl (examples 2, 3, 5, 6, 9, 10, 13) and cycloalkyl chain (example 13) do significantly activate the OR8H1 receptor in contrast to the prior art compounds methyl 2-methylbenzoate and ethyl 2-methylbenzoate, for which no EC20% values could be measured, or the value was significantly higher (EC20% values >40 pM). Compounds with a longer R1(counterexample 4), or compounds with the methyl substituent in para-position (counterexample 3), were not active.

[0249] Example 25: Fragrance composition

[0250] Mixing 72 parts of the fragrance composition mentioned above with 28 parts of DPG constitutes the reference. It is a floral accord to be applied @ 0.5% in shampoo. It develops a floral tropical accord around the Ashok Indian flower concept. When 28 parts DPG of the reference are replaced by a mixture of 10 parts propyl 2- methylbenzoate (example 3) + 18 parts DPG, the top note is much more floral medicinal (ylang, Wintergreen) with a slight fruity (banana) enhanced facet, and overall, this rendition is closer to the original natural flower olfactive profile.

[0251] When 28 parts DPG of the reference are replaced by a mixture of 20 parts butyl 2- methylbenzoate (example 7) + 8 parts DPG, the top note is slightly greener, more shampoo like. The benefit will appear in use, on bloom shampoo cabins and on dry hair, with an increased performance.

[0252] Example 26: cyclopropylmethyl 2-methylbenzoate

[0253] 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.

[0254] 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).

[0255] Odour description (10% solution in DPG): green, aromatic (medicinal, Wintergreen, thyme) floral (amyl salicylate).

Claims

wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; 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, and wherein at least one of R2or R3is Me, as a fragrance; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2-methylbenzoate.

2. The use according to claim 1 , wherein R1is n-propyl, / -propyl, cyc / o-propyl, cyclopropyl methyl, 1-propenyl, 2-propenyl, n-butyl, n-pentyl, / -pentyl, cyc / o-pentyl, n- hexyl, cyc / o-hexyl, benzyl, phenethyl; R2is Me, and R3, R4, R5and R6are H.A fragrance composition comprising at least one compound of formula (I)wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; 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, and wherein at least one of R2or R3is Me, and at least one further fragrance compound; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2-methylbenzoate.

4. Fragrance composition according to claim 3, wherein the weight ratio of the at least one compound of formula (I) as defined in claim 1 to the total amount of other fragrances is in the range of 1 :99 to 30 :

705. Fragrance composition according to claim 3 and / or 4, wherein the amount of the at least one compound of formula (I) as defined in claim 1 is in the range of 0.01 to 50% by weight, based on the total weight of the fragrance composition, for example in the range of 1 to 30% by weight.

6. A consumer product comprising at least one compound of formula (I)wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety;or is benzyl or phenethyl; 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, and wherein at least one of R2or R3is Me, or a fragrance composition as defined in any claims 3 to 5, and a consumer product base; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate, ethyl 2-methylbenzoate and 2-phenylethyl 2-methylbenzoate.

7. The consumer product according to claim 6 selected from the group consisting of perfume, a cologne, a toilet water, a cosmetic product, a personal care product, a fabric care product, a cleaning product, and an air freshener.

8. A method of improving, enhancing or modifying a fragrance composition through the addition of an olfactory acceptable amount of a compound of formula (I)wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; 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, and wherein at least one of R2or R3is Me; with the proviso that the compound of formula (I) is not methyl 2-methylbenzoate and ethyl 2-methylbenzoate.

9. The method of claim 8, wherein the fragrance composition is incorporated into a consumer product selected from the group consisting of a perfume, a cologne, a toilet water, a cosmetic product, a personal care product, a fabric care product, a cleaning product, and an air freshener.

10. The method of claim 8 or 9, wherein the amount of the compound of formula (I) is from about 0.01 to about 50 % by weight of the fragrance composition, for example from about 01 to about 30% by weight of the fragrance composition.11.wherein R1is selected from the group consisting of a C1 to C6 hydrocarbon moiety, which is straight or branched, and contains saturated and / or unsaturated bonds, and up to one cyclic moiety; or is benzyl or phenethyl; 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, and wherein at least one of R2or R3is Me; 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.

12. The compound according to claim 11 , 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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