Organic compounds

Abstract

Disclosed are fragrance compositions comprising ethyl cyclohexanoate.

Claims

1. A fragrance composition comprising ethyl cyclohexanecarboxylate and at least one odorant ester, wherein the weight ratio between the ethyl cyclohexanecarboxylate and the at least one odorant ester is from 1:10,000,000 to 1:100 (ethyl cyclohexanecarboxylate:ester).

2. The fragrance composition according to claim 1 wherein the odorant ester is a compound of formula (I) ##STR00002## having a molecular weight of up to 300 and wherein i) R.sup.1 is selected from methyl, ethyl, C.sub.3 to C.sub.6 alkyl, and C.sub.2 to C.sub.6 alkenyl, and R.sup.2 is a hydrocarbon radical containing up to 14 C-atoms, optionally comprising one, two, or three functional groups selected from OH, C(O), and O; or ii) R.sup.1 is a hydrocarbon radical containing up to 14 C-atoms, optionally comprising one, two, or three functional groups selected from OH, C(O), and O, and R.sup.2 is selected from methyl, ethyl, C.sub.3 to C.sub.6 alkyl, and C.sub.2 to C.sub.6 alkenyl; or iii) R.sup.1 and R.sup.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.

3. The fragrance composition according to claim 1 wherein the composition comprises up to 1 weight % of ethyl cyclohexanecarboxylate.

4. The fragrance composition according to claim 2 comprising at least one ester of formula (I) as defined in claim 2 with an enhanced odor profile obtained by admixing thereto ethyl cyclohexanecarboxylate.

5. The fragrance composition according to claim 4 obtained by admixing up to 1 weight % of ethyl cyclohexanecarboxylate.

6. A fragranced article comprising a fragrance composition as defined in claim 1.

7. A method of enhancing the fruity characteristics of esters, comprising the step of adding ethyl cyclohexanecarboxylate to a composition comprising at least one odorant ester, wherein the weight ratio between the ethyl cyclohexanecarboxylate and the at least one odorant ester is from 1:10,000,000 to 1:100 (ethyl cyclohexanecarboxylate:ester).

8. The method according to claim 7 wherein the odorant ester is a compound of formula (I) ##STR00003## having a molecular weight of up to 300 and wherein ii) R.sup.1 is selected from methyl, ethyl, C.sub.3 to C.sub.6 alkyl, and C.sub.2 to C.sub.6 alkenyl, and R.sup.2 is a hydrocarbon radical containing up to 14 C-atoms, optionally comprising one, two, or three functional groups selected from OH, C(O), and O; or ii) R.sup.1 is a hydrocarbon radical containing up to 14 C-atoms, optionally comprising one, two, or three functional groups selected from OH, C(O), and O, and R.sup.2 is selected from methyl, ethyl, C.sub.3 to C.sub.6 alkyl, and C.sub.2 to C.sub.6 alkenyl; or iii) R.sup.1 and R.sup.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.

9. The method according to claim 7, wherein up to 0.1 weight % of ethyl cyclohexanecarboxylate is added to the composition based on the total amount of the composition.

10. The method according to claim 8, wherein up to 0.1 weight % of ethyl cyclohexanecarboxylate is added to the composition based on the total amount of the composition.

11. The fragrance composition according to claim 2, wherein the composition comprises up to 1 weight % of ethyl cyclohexanecarboxylate.

12. A fragranced article having a fragrance composition comprising ethyl cyclohexanecarboxylate and at least one odorant ester, wherein the fragranced article consists of perfumes, air care products, household products, laundry products, body care products or cosmetics, and wherein the weight ratio between the ethyl cyclohexanecarboxylate and the at least one odorant ester is from 1:10,000,000 to 1:100 (ethyl cyclohexanecarboxylate:ester).

Description

EXAMPLE 1: SYNTHESIS OF ETHYL CYCLOHEXANOATE

(1) 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.sub.2O, 4% aq. Na.sub.2CO.sub.3-solution and H.sub.2O. The org. phase was concentrated and distilled to yield 73 g (93%) of ethyl cyclohexanecarboxylate as a colorless oil.

(2) .sup.1H NMR (CDCl.sub.3, 400 MHz): =4.09 (q, J=7.1 Hz, 2H), 2.25 (tt, J=11.3, 3.7 Hz, 1H), 1.90-1.83 (m, 2H), 1.78-1.70 (m, 2H), 1.64-1.58 (m, 1H), 1.46-1.36 (m, 2H), 1.31-1.17 (m, 3H), 1.22 (t, J=7.1 Hz, 3H) ppm.

(3) .sup.13C-NMR (CDCl.sub.3, 100 MHz): =176.0 (s), 59.9 (t), 43.2 (d), 29.0 (2t), 25.7 (t), 25.4 (2t), 14.2 (q) ppm. MS (EI, tR=4.89 min): 156 (43, [M].sup.+), 128 (21), 115 (16), 111 (41), 110 (23), 101 (68), 88 (21), 83 (100), 82 (17), 81 (17), 73 (21), 68 (15), 67 (16), 55 (79), 54 (11), 41 (38), 39 (20), 29 (30), 27 (20).

EXAMPLE 2

(4) The following solutions were prepared. A) 0.1 weight % of ethyl cyclohexanoate in ethanol B) 10 weight % of fragrant ingredient in ethanol

(5) The two alcoholic solutions above were mixt at a ratio of 1:1.

(6) 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.

(7) TABLE-US-00001 TABLE 1 B - compound odor description of the mixture Ester I-1 benzyl acetate (CAS 140-11-4) I-2 bornyl acetate (CAS 125-12-2) (more depth, more agrestic, more juicy fir needle) I-3 linalyl acetate (CAS 115-95-7) (bergamot candy) I-4 4-(tert-butyl)cyclohexyl acetate (CAS 32210-23-4) I-5 Argumex (CAS 88-41-5) (more juicy, natural fruity apple, less chemical fresh) I-6 Fruitate (CAS 80623-07-0) (natural, increases lift & juiciness I-7 Hedione (CAS 24851 -98-7) I-8 Manzanate (CAS 39255-32-8) (more natural, juicy, overripe apple flesh) I-9 Hexyle salicylate (CAS 6259-76-3) (fresh, minty winter green leaf association) I-10 Ethyl Safranate (CAS 35044-59-8) (more lift, more fruity juicy aromatic, more pleasant) Ketone/ II-1 2,6,10-trimethylundec-9-enal / Aldehyde (CAS 141-13-9) II-2 Delta Damascone / (CAS 57378-68-4) II-3 3-(3-isopropylphenyl)butanal / (CAS 125109-85-5) II-4 3-methyl-4-(2,6,6-trimethylcyclohex- / 2-en-1-yl)but-3-en-2-one (CAS 1335-46-2) II-5 Melonal / 2,6-dimethylhept-5-enal (CAS 106-72-9) II-6 4-(4-methoxyphenyl)butan-2-one / (CAS 104-20-1) II-7 3-(4-isobutyl-2- / methylphenyl)propanal (CAS 1637294-12-2) Alcohol II-8 (1-methyl-2-((1,2,2- / trimethylbicyclo[3.1.0]hexan-3- yl)methyl)cyclopropyl)methanol (CAS 198404-98-7) II-9 (1-methyl-2-(5-methylhex-4-en-2- / yl)cyclopropyl)methanol (CAS 1655500-83-6) : 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.

(8) 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

(9) 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.

(10) TABLE-US-00002 TABLE 2 B Ethyl Safranate Fruitate Argumex A [%] @10% Ethanol @10% Ethanol @10% Ethanol 1 0.5 0.2 0.1 0.01 ++ ++ ++ 0.001 ++ ++ ++ 0.0001 + ++ ++ : 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

(11) TABLE-US-00003 parts by weight Compound/Ingredient 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-(3,5,5,6,6,8,8-hexamethyl-5,6,7,8- 30 tetrahydro naphthalen-2-yl)ethan-1-one) Florocyclene (3a,4,5,6,7,7a-hexahydro-1H-4,7- 20 methanoinden-6-yl propionate) Galaxolide (4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8- 120 hexahydro-cyclopenta[g]isochromene) cis-3-Hexen-1-ol 3 (Z)-Hex-3-en-1-yl acetate 3 2-Benzylideneoctanal 50 Beta Ionone ((E)-4-(2,6,6-trimethylcyclohex-1-en-1- 60 yl)but-3-en-2-one) Iso E Super 20 Lilial (3-(4-(tert-butyl)phenyl)-2-methylpropanal) 50 Linalool 30 Manzanate 3 Orange oil 60 Peach Pure (-undecalactone) 10 2-phenoxyethyl isobutyrate 140 Tricyclal (2,4-dimethylcyclohex-3-ene-1-carbaldehyde) 6 Ethyl cyclohexanoate (at a dilution as indicated in 3 Table 3 below) Total: 1000

(12) 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.

(13) TABLE-US-00004 TABLE 3 (A) [%] on blotter in shampoo 2 ml shampoo in 50 ml water 4.1 10.0 Over ripe Over ripe, sweaty animalic, Over ripe, sweaty animalic, unpleasant unpleasant unpleasant, more lift, more intense, but unpleasant 4.2 1.0 more juicy intense juicy fruity apple, intense juicy fruity apple, more green starts to cover over all starts to cover over all more intense perfume character, still liked perfume character, still liked 4.3 0.1 push green already benefit, more natural, already benefit, more natural, pineapple more juicy, more pleasant, more juicy, more pleasant, esters, more more depth, more intensity, more depth, more intense, aggressive clear benefit, preferred to 4.2 clear benefit, preferred to 4.2 4.4 0.01 dear and good already benefit, more natural, already benefit, more natural, benefit, push more juicy, more pleasant, more juicy, more pleasant, juicy more depth, more intense, more depth, more intense, clear benefit, more lift, more clear benefit, more lift more freshness, effect even more freshness, effect even more noticeable noticeable, liked, preferred to 4.3 4.5 0.001 more juicy already benefit more natural already benefit, more natural, already benefit more juicy more pleasant more juicy, more pleasant, rounder, less green aggressive, more consumer appeal, more natural

(14) 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.