This disclosure relates to fragrance compositions and to a method of enhancing them.

Fragrance compositions are usually blends of volatile individual ingredients, both natural and synthetic, carefully blended by skilled perfumers to bring out an overall desired hedonic character. The individual ingredients are selected to add to this particular desired character.

A very common class of fragrance ingredient is the ester. Esters are found in the essential oils of many plants and are known for their sweet, fruity odor. As a result, they are a popular choice for fragrance compositions. Typical examples of popular fragrance esters include benzyl acetate, bornyl acetate (1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-yl acetate), 2-tert-butyl-cyclohexylacetate (Agrumex™) and octahydro-4,7-methano-3aH- indene-3a-carboxylic acid, ethyl ester (Fruitate™), and 1 ,3-cyclohexadiene-1 -carboxylic acid, 2,6,6-trimethyl-, ethyl ester (Ethyl Safranate™). All of these are known to have pleasant, desirable odors.

It has now been found that the addition of certain alkyl cycloalkylcarboxylate derivatives can enhance the desirable characteristics of ester-containing fragrance compositions. There is therefore provided a fragrance composition comprising a blend of fragrance ingredients, at least one of which ingredients is an ester, the composition additionally comprising up to 1 % by weight of an alkyl cycloalkylcarboxylate derivatives of formula (I) or a mixture thereof

wherein R ₃ is Ci - C ₃ alkyl (e.g. ethyl, isopropyl),

R ₄ is selected from hydrogen and Ci - C ₅ alkyl (e.g. ethyl, propyl, isopropyl, tert-butyl, 1 -methylpropyl, isobutyl, isopentyl)

n is selected from 0, 1 , 2, 3 and 4, and

ring A is either saturated or unsaturated comprising one double bond .

Whereas some of the compounds are described in the literature as such, they have never been described to be suitable as fragrance ingredients. As one example one may cite ethyl cyclohexanoate (i.e. a compound of formula (I) wherein n is 1 , R ₃ is ethyl, R ₄ is hydrogen and A represents a saturated ring), sometimes referred to as ethyl cyclohexyl carboxylate (CAS 3289-28-9), has an odour described as "fruity, cheesy, winey" in the database of the Good Scents Company, a well-known flavour and fragrance resource. It is known to occur in various natural oils, for example, in virgin olive oil (see, for example, Reiners et al, J. Agric. Food Chem. 1998, 46, 2754-2763) and rum (see Franitza et al, J. Agric. Food Chem. 2016, 64, 637-645). However, although known and characterized, it has never been produced as a commercial fragrance material and there is no disclosure of fragrance compositions comprising said compound.

It has been found that the compounds of formula (I) enhance the odour characteristics of esters. Moreover, it has been found that, in order to achieve this desirable effect, the proportion of the compound of formula (I) or mixtures thereof should be used within strict limits - too little, and there will be no enhancing effect, too much and there might be some undesirable odor notes. The compounds of formula (I) should thus preferably be used at concentrations up to 1 % by weight, preferably from 0.000001 to 0.05% by weight, e.g., between 0.00001 - 0.1 % by weight, which includes 0.0001 - 0.02% by weight (e.g., 0.0005% or 0.001 %), based on the fragrance composition. However the amounts of the compound of formula (I) present in a fragrance composition may vary, depending on the other fragrance ingredients present. In a further aspect of the present invention, the ratio of the compound(s) of formula (I) to ester should preferably be used within strict limits to avoid that undesirable odor notes will be recognized. The compound(s) of formula (I) should therefore be used at a weight ratio of from 1 :

10Ό00Ό00 to 1 : 100 (such as 1 : 5Ό00Ό00 to 1 : 500, which includes 1 :

1 Ό00Ό00 to 1 : 1 Ό00) of the ester component of the fragrance composition

(compound(s) of formula (I) : ester(s)).

There is also provided a method of enhancing the fragrance quality of a fragrance composition containing at least one ester, comprising the addition thereto of up to 1 % by weight (e.g. 0.000001 , 0.00001 , 0.00005, 0.0001 , 0.0005, 0.001 , 0.01 , 0.02, 0.05, 0.1 , 0.2, 0.5 % by weight) of of a compound of formula (I) or a mixture thereof.

All percentages and ratios as used herein are by weight unless otherwise indicated. Particular examples of compounds of formula (I) are selected from methyl

cyclopentanecarboxylate, ethyl cyclopentanecarboxylate, ethyl cyclopent-2-ene-1 - carboxylate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, methyl cyclohex-2-ene-1 -carboxylate, methyl cyclohex-3-ene-1 -carboxylate, ethyl cyclohex-2- ene-1 -carboxylate, ethyl cyclohex-3-ene-1 -carboxylate, methyl 4-methylcyclohex-2-ene- 1 -carboxylate, ethyl 4-methylcyclohex-2-ene-1 -carboxylate, ethyl 4-ethylcyclohex-2- ene-1 -carboxylate, ethyl 4-ethylcyclohex-3-ene-1 -carboxylate, methyl cycloheptane- carboxylate, ethyl cycloheptanecarboxylate, methyl cyclohept-2-ene-1 -carboxylate, ethyl cyclohept-2-ene-1 -carboxylate, methyl 5-methylcyclohept-2-ene-1 -carboxylate, methyl 5-ethylcyclohept-2-ene-1 -carboxylate, methyl 5-methylcyclohept-3-ene-1 - carboxylate, ethyl cyclooctanecarboxylate, ethyl cyclooct-3-ene-1 -carboxylate, and ethyl cyclooct-4-ene-1 -carboxylate.

By "enhancing" is meant that the hedonic qualities of the ester, and of the fragrance composition in which the compound(s) of formula (I) is (are) incorporated, are improved from the point of view of being not only more pleasant, but also more balanced, more natural and/or more intense. The overall hedonic effect is much improved and more desirable, and in general more preferred compared to compositions which are free of a compound of formula (I) or mixtures thereof.

By "ester" is meant a hydrocarbon compound comprising at least one ester group (- C(O)O-), provided that it is not a compound of formula (I) as defined hereinabove. Lactones, such as γ-decalactone (6-pentyltetrahydro-2H-pyran-2-one); γ-undecalactone (5-heptyloxolan-2-one), which are cyclic esters are also included. Optionally, the hydrocarbon compound may comprise other (e.g., one, two or three) functional group(s), such as, alcohol (-OH), carbonyl (-C(O) -), and ether (-O-).The ester having a molecular weight of up to 300 MW, preferably between 130 and 250 MW.

In a preferred embodiment the ester is a compound of formula (II)

having a molecular weight of up to 300 (e.g. 130 to 250) and wherein i) R is selected from methyl, ethyl, C ₃ to C ₆ alkyl, and C ₂ to C ₆ alkenyl (for example, hexenyl, prop-2-enyl), and

R ² is a hydrocarbon radical containing up to 14 C-atoms (for example 5, 6, 7, 8, 9, 10 or 1 1 C-atoms) , optionally comprising one, two, or three functional groups selected from -OH (alcohol), -C(O) - (carbonyl), and ether (-0-); or

ii) R is a hydrocarbon radical containing up to 14 C-atoms (for example 5, 6, 7, 8, 9, 10 or 1 1 C-atoms) , optionally comprising one, two, or three functional groups selected from -OH (alcohol), -C(O) - (carbonyl), and ether (-0-), and

R ² is selected from methyl, ethyl, C ₃ to C ₆ alkyl, or C ₂ to C ₆ alkenyl (for example, hexenyl, prop-2-enyl); or

iii) R and R ² forming together with the atoms to which they are attached a cyclic ester containing 5 or 6 ring atoms, wherein the ring is optionally substituted with one, two or more groups selected from alkyl and alkenyl,

with the proviso that it is not a compound of formula (I).

As used in relation to compounds of formula (II) unless otherwise indicated

"hydrocarbon radical" includes linear, branched, mono-, bi- or tri-cyclic alkyl, linear, branched, mono-, bi- or tricyclic alkenyl (comprising one or more double bonds), and aryl, wherein the ring (such as cyclic alkyl, cyclic alkenyl, aryl) is optionally substituted with alkyl.

Non-limiting examples of esters are compounds of formula (II) wherein either R or R ² is not alkyl. Further, non-limiting examples of esters are compounds of formula (II) wherein the hydrocarbon radical comprises 5 to 10 C-atoms.

Further, non-limiting examples of esters are compounds of formula (I I) wherein R and R ² forming together with the atoms to which they are attached a cyclic ester containing 5 or 6 ring atoms, wherein the ring is substituted with one linear C Ci ₂ alkyl (e.g., C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ alkyl), or one linear C ₃ - Ci ₀ alkenyl (comprising on or more double bonds, e.g., C ₄ , C ₅ , C ₆ alkenyl).

Further, non-limiting examples of esters are compounds of formula (I I) wherein R and R ² forming together with the atoms to which they are attached a cyclic ester containing 5 or 6 ring atoms, wherein the ring is substituted with methyl and one linear C Ci ₂ alkyl (e.g., C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ alkyl), or with methyl and one linear C ₃ - Ci ₀ alkenyl (comprising on or more double bonds, e.g., C ₄ , C ₅ , C ₆ alkenyl). Further specific examples of known esters according to formula (II) are: cedryl acetate ((1 S,6fl,8afi)-1 ,4,4,6-tetramethyloctahydro-1 H-5,8a-methanoazulen-6-yl acetate);

Helvetolide ^® (2-(1 -(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl propionate); 4,8- dimethyl-2-(propan-2-ylidene)-1 ,2,3,3a,4,5,6,8a-octahydroazulen-6-yl acetate; 4-(tert- butyl)cyclohexyl acetate; ethyl 2-methylpentanoate (Manzanate); hexyl salicylate;

methyl 3-oxo-2-pentylcyclopentaneacetate (Hedione); 2-tert-butyl-cyclohexylacetate (Agrumex™); octahydro-4,7-methano-3aH-indene-3a-carboxylic acid, ethyl ester (Fruitate™); and 1 ,3-cyclohexadiene-1 -carboxylic acid, 2,6,6-trimethyl-, ethyl ester (Ethyl Safranate™). Further specific esters according to formula (I) are methyl 2,4- dihydroxy-3,6-dimethylbenzoate (CAS 4707-47-5); allyl heptanoate (CAS 142-19-8); dimethyl benzyl carbinyl acetate (CAS 151 -05-3); dimethyl benzyl carbinyl butyrate (CAS 10094-34-5); ethyl 2-methylbutanoate (CAS 7452-79-1 ); 3a,4,5,6,7,7a- hexahydro-1 H-4,7-methanoinden-6-yl propionate (CAS 68912-13-0); and (Z)-hex-3-en- 1 -yl acetate (CAS 3681 -71 -8). The esters may be synthetic ingredients or they may occur in natural fragrance oils. The individual esters present in a known natural fragrance oil can be found by reference to Journals commonly used by those skilled in the art such as "Perfume and Flavourist" or "Journal of Essential Oil Research", or listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA and more recently re-publisehd by Allured Publishing Corporation Illinois (1994).

A fragrance composition as hereinabove described may, in addition to at least one ester, contain any of the other natural or synthetic ingredients known to the art to be useful in fragrance compositions. Non-limiting examples of such compositions include

- 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; - alcohols, e.g. cinnamic alcohol ((£)-3-phenylprop-2-en-1 -ol); cis-3-hexenol ((∑)- hex-3-en-1 -ol); citronellol (3,7-dimethyloct-6-en-1 -ol); dihydro myrcenol (2,6- dimethyloct-7-en-2-ol); Ebanol™ ((£)-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-

1 - yl)pent-4-en-2-ol); eugenol (4-allyl-2-methoxyphenol); ethyl linalool ((£)-3,7- dimethylnona-1 ,6-dien-3-ol); farnesol ((2£,6Z)-3,7,1 1 -trimethyldodeca-2,6,10- trien-1 -ol); geraniol ((£)-3,7-dimethylocta-2,6-dien-1 -ol); Super Muguet™ ((£)-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;

- 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 ^® ((£)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1 -yl)but-3-en-2-one); 3-(4-isobutyl-

2- methylphenyl)propanal; maltol; methyl cedryl ketone; methylionone;

verbenone; and/or vanillin;

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

- macrocycles, e.g. Ambrettolide ((Z)-oxacycloheptadec-10-en-2-one); ethylene brassylate (1 ,4-dioxacycloheptadecane-5,17-dione); and / or Exaltolide ^® (16- oxacyclohexadecan-1 -one); and heterocycles, e.g. isobutylquinoline (2-isobutylquinoline). Fragrance composition comprising a compound of formula (I) or a mixture thereof and at least one ester, as hereinabove described, may be used in a broad range of fragranced articles, for example, in any field of fine and functional perfumery, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. The composition can be employed in widely varying amounts, depending upon the specific application and on the nature and quantity of other odorant ingredients. The proportion is typically from 0.1 to 20 weight percent of the application. In one embodiment, the composition of the present invention may be employed in a fabric softener or shampoo in an amount of from 0.2 to 1 .5 weight per cent (e.g. 0.8 - 1 weight %). In another embodiment, the fragrance composition comprising a compound of formula (I) or a mixture thereof and at least one ester may be used in fine perfumery in amounts of from 5 to 20 weight per cent (e.g. up to about 30 weight per cent).

However, these values are given only by way of example, as the experienced perfumer may also achieve effects or may create novel accords with lower or higher

concentrations.

Moreover it has been found, that the odor performance is enhanced when a fragranced article comprising a fragrance composition as hereinabove described, is diluted with water. Thus, there is provided as one specific embodiment, the use of a fragrance composition comprising a compound of formula (I) or a mixture thereof and at least one ester, as hereinabove described, in rinse-off products, such as shampoo, and shower gel, but also in high dilutions in water, like hand wash fabric detergents (liquid or powder) or multi-purpose floor cleaners. The fragrance composition as described hereinabove may be employed in a consumer product base simply by directly mixing the fragrance composition 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.

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. Example 1 : Synthesis of ethyl cvclohexanoate

Cyclohexanecarboxylic acid (64 g, 0.50 mol) and p-toluenesulfonic acid (1 .0 g, 0.01 mol) in cyclohexane (64 g) were heated to 73 °C. Ethanol (64 g, 1 .39 mol) was added over 90 min and the reaction mixture was stirred at reflux for an additional 90 min while the aq. phase was gradually eliminated over time. After cooling the reaction mixture to r.t., the org. phase was washed with H ₂ 0, 4% aq. Na ₂ C0 ₃ -solution and H ₂ 0. The org. phase was concentrated and distilled to yield 73 g (93%) of ethyl cyclohexanecarboxylate as a colorless oil. H NMR (CDCI ₃ , 400 MHz): δ = 4.09 (q, J = 7.1 Hz, 2H), 2.25 (tt, J = 1 1 .3, 3.7 Hz, 1 H), 1 .90-1 .83 (m, 2H), 1 .78-1 .70 (m, 2H), 1 .64-1 .58 (m, 1 H), 1 .46-1 .36 (m, 2H), 1 .31 -1 .17 (m, 3H), 1 .22 (t, J= 7.1 Hz, 3H) ppm.

3C-NMR (CDCI ₃ , 100 MHz): δ = 176.0 (s), 59.9 (t), 43.2 (d), 29.0 (2t), 25.7 (t), 25.4 (2t), 14.2 (q) ppm.

MS (El, tR = 4.89 min): 156 (43, [M] ^+' ), 128 (21 ), 1 15 (16), 1 1 1 (41 ), 1 10 (23), 101 (68), 88 (21 ), 83 (100), 82 (17), 81 (17), 73 (21 ), 68 (15), 67 (16), 55 (79), 54 (1 1 ), 41 (38), 39 (20), 29 (30), 27 (20). Example 2:

The following solutions were prepared.

A) 0.1 weight % of ethyl cyclohexanoate in ethanol

B) 10 weight % of fragrant ingredient in ethanol The two alcoholic solutions above were mixt at a ratio of 1 :1 .

Both, solution B alone and the mixture of A+B was olfactively evaluated in a triangular test on a blotter in a randomized order. The trained panel was asked to describe the olfactory difference, if any. The results are summarized in Table 1 below. Table 1 :

±: in the mixture, overall performance of the ester (B) is clearly enhanced, and its character was slightly modified (details given in brackets).

-/-: both ingredients are recognised as individuals, do not combine as such and tend to be less pleasant than the fragrant ingredient (B) alone.

As can be seen from the results above, the addition of ethyl cyclohexanoate to a fragrant ester results in a more pleasant, more balanced, more natural and/or more intense composition which is more preferred compared to the esters alone. On the other hand, such a benefit was not observed when ethyl cyclohexanoate was added to a fragrant aldehyde, ketone or alcohol.

Example 3:

Ethyl cyclohexanoate (A) was evaluated on blotter in combination with several odorant esters as indicated at different concentrations. The results are shown in Table 2 below.

Table 2:

- - : unpleasant, cheesy animalic

- : becomes cheesy animalic,

± : in the mixture, overall performance of the ester (B) is clearly enhanced, and its character was slightly modified

+ : overall character and performance of the ester (B) is mildly enhanced

++: overall character and performance of the ester (B) is clearly enhanced, and the mixture was preferred to (B) alone. Example 4: Fragrance accord suitable for shampoo

Compound / Ingredient parts by weight 1/1000

Agrumex 40 Allyl Heptanoate 25

Benzyl Acetate 20

Citronellol 20

Cyclohexal 24

Delta Damascone 1 Dihydro Myrcenol 50

Dimethyl benzyl carbinyl acetate 15

Dimethyl benzyl carbinyl butyrate 5

Dipropylene Glycol (DPG) 177

Ethyl 2-Methylbutanoate 7 Evernyl (methyl 2,4-dihydroxy-3,6-dimethylbenzoate) 8 Fixolide (1 -(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydro

naphthalen-2-yl)ethan-1 -one) 30 Florocyclene (3a,4,5,6,7,7a-hexahydro-1 H-4,7-methanoinden-6-yl propionate) 20 Galaxolide (4,6,6,7,8,8-hexamethyl-l ,3,4,6,7,8-hexahydro- cyclopenta[g]isochromene) 120 cis-3-Hexen-1 -ol 3

(Z)-Hex-3-en-1 -yl acetate 3

2-Benzylideneoctanal 50

Beta lonone ((E)-4-(2,6,6-trimethylcyclohex-1 -en-1 -yl)but-3-en-2-one) 60 Iso E Super 20

Lilial (3-(4-(tert-butyl)phenyl)-2-methylpropanal) 50

Linalool 30

Manzanate 3

Orange oil 60 Peach Pure (γ-undecalactone) 10

2-phenoxyethyl isobutyrate 140

Tricyclal (2,4-dimethylcyclohex-3-ene-1 -carbaldehyde) 6

Ethyl cvclohexanoate (at a dilution as indicated in Table 3 below) 3

Total: 1000 The fragrance accord comprising 29.6 weight % of esters according to formula (I) and a variable amount of ethyl cyclohexanoate (A) in DPG as indicated in Table 3, first column, was assessed by a trained panel neat (on a blotter), in a shampoo (fragrance accord @ 0.5 weight %), and in a shampoo (fragrance accord @ 0.5 weight %) diluted with water. The results are given in Table 3 below.

Table 3:

As can be seen from the summary of the olfactory description of the fragrance accord in Table 3 above, the positive effect of ethyl cyclohexanoate on esters is more effective than the findings with regard to alcohols, aldehydes and ketones taken alone, resulting in an hedonically more pleasant fragrance formulation.