Organic compounds

Abstract

The present invention relates to ethyl cyclooct-3/4-ene-1-carboxylates, and to a process of making the same. The invention further refers to flavour and fragrance compositions comprising them.

Claims

1. A method comprising utilizing a compound of formula (I) ##STR00003## wherein one of the dotted lines represents together with the carbon-carbon bond a single bond and the other dotted line represents together with the carbon-carbon bond a double bond; as flavor or fragrance, the method comprising mixing the compound of formula (I) with a consumer product base, or admixing a composition comprising the compound of formula (I) and mixing with a consumer product base.

2. Ethyl cyclooct-3-ene-1-carboxylate.

3. A fragrance composition comprising as odorant a compound of formula (I) as defined in claim 1, or a mixture thereof, and a base material.

4. A fragranced article comprising as odorant a compound of formula (I) as defined in claim 1, and a consumer product base.

5. The fragranced article according to claim 4, wherein the consumer product base is selected from the group consisting of fine fragrance, household products, laundry products, body care products, cosmetic products, air care products and combinations thereof.

6. A method of improving, enhancing or modifying a consumer product base comprising adding to the consumer product base an olfactory acceptable amount of a compound selected from the group consisting of ethyl cyclooct-3-ene-1-carboxylate, ethyl cyclooct-4-ene-1-carboxylate, and mixtures thereof.

7. The method according to claim 6, wherein the consumer product base is selected from the group consisting of fine fragrance, household products, laundry products, body care products, cosmetic products, air care products and combinations thereof.

Description

EXAMPLE 1

ethyl (Z)-cyclooct-4-ene-1-carboxylate

(1) An autoclave was charged with PdCl.sub.2 (319 mg, 2 mol %), PPh.sub.3 (1.42 g, 6 mol %), 1,5-cyclooctadiene (15.6 g, 144 mmol, 1.6 equiv) and EtOH (4.15 g, 90 mmol, 1.0 equiv). The reaction mixture was then sealed, flushed 3 times with CO and stirred at 100° C. under an atmosphere of CO (45 bar) for 5 h. The crude product was purified by Kugelrohr distillation (150° C./0.01 mbar) and fractional distillation over a 2 cm Vigreux column (bp 73° C. at 0.08 mbar) to afford ethyl (Z)-cyclooct-4-ene-1-carboxylate (7.5 g, 46% yield) as a colorless liquid.

(2) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 5.67 (dt, J=10.5, 7.3 Hz, 1H), 5.67-5.57 (m, 1H), 4.08 (q, J=7.1 Hz, 2H), 2.48-2.29 (m, 2H), 2.19-1.95 (m, 4H), 1.88-1.79 (m, 1H), 1.77-1.50 (m, 3H), 1.45-1.31 (m, 1H), 1.22 (t, J=7.2 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3): δ 177.6, 130.5, 129.5, 60.1, 43.3, 31.6, 29.4, 27.8, 25.8, 24.1, 14.2 ppm. GC-MS (El) m/z (%): 182 (20, [M].sup.+), 109 (87), 108 (66), 94 (26), 93 (27), 79 (44), 67 (100), 55 (48), 54 (31), 41 (43), 39 (30). bp 73° C. (0.08 mbar).

(3) Odor description: a very clean, natural, pleasant olfactive profile, where the “fruity over ripe” relates olfactively to real, natural, fresh berries, like raspberries in particular, but also kiwi, banana, apple and pineapple in general

EXAMPLE 2

ethyl (Z)-cyclooct-3-ene-1-carboxylate

(4) A solution of sodium hypobromite was prepared as follows: Bromine (23.3 mL, 3 equiv) was added at 5-10° C. to a solution of NaOH (79 g, 13 equiv) in water (230 mL). After stirring for 15 min, the solution was diluted with cold dioxane (92 mL). To a solution of (Z)-1-(cyclooct-3-en-1-yl)ethan-1-one (23.0 g, 151 mmol, 1.0 equiv, prepared according to Granier, T. et aL, WO 200403501) in dioxane (230 mL) and water (115 mL) was added dropwise at 0° C. a freshly prepared solution of NaOBr (prepared as described above) at such a rate that the reaction temperature did not exceed 15° C. After stirring at room temperature for 1 h, the reaction mixture was diluted with sat. aq. NaS.sub.2O.sub.3 (50 mL) and MTBE (70 mL). The layers were separated and the organic layer was extraced with 2M NaOH (2×). The organic layer was discarded. The aqueous layer was acidified with conc. HCl and extracted with MTBE (2×). The combined organic extracts were dried over MgSO.sub.4, filtered and concentrated under reduced pressure to give crude (Z)-cyclooct-3-ene-1-carboxylic acid (20 g).

(5) .sup.1H NMR (400 MHz, CDCl.sub.3): δ 10.7 (brs, 1H), 5.77 (dt, J=10.4, 8.0 Hz, 1H), 5.63 (dt, J=10.5, 7.9 Hz, 1H), 2.60-2.34 (m, 3H), 2.26-2.06 (m, 2H), 1.89-1.63 (m, 3H), 1.61-1.43 (m, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3): δ 182.4, 132.3, 127.1, 44.8, 29.2, 27.9, 26.8, 25.9, 24.5 ppm. GC-MS (El) m/z (%): 154 (17, [M].sup.+), 136 (33), 109 (63), 82 (29), 81 (35), 79 (43), 67 (100), 55 (52), 54 (49), 41 (64.0), 39 (48).

(6) A solution of crude (Z)-cyclooct-3-ene-1-carboxylic acid (2.0 g, 13.0 mmol, 1.0 equiv) and para-toluenesulfonic acid monohydrate (247 mg, 1.30 mmol, 10 mol %) in EtOH (15 mL) was refluxed for 14 h and concentrated under reduced pressure. The crude was purified by Kugelrohr distillation (140° C./0.04 mbar) to afford ethyl (Z)-cyclooct-3-ene-1-carboxylate (1.7 g, 72%, contains 7% of ethyl cyclooct-1-ene-1-carboxylate) as a colorless liquid.

(7) (Z)-cyclooct-3-ene-1-carboxylate: .sup.1H NMR (400 MHz, CDCl.sub.3): δ 5.71 (dt, J=10.5, 7.8 Hz, 1H), 5.59 (dt, J=10.4, 7.8 Hz, 1H), 4.09 (q, J=7.1 Hz, 2H), 2.51-2.39 (m, 2H), 2.36-2.12 (m, 2H), 2.12-2.01 (m, 1H), 1.84-1.59 (m, 3H), 1.59-1.38 (m, 3H), 1.22 (t, J=7.1 Hz, 3H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3): δ 175.8, 131.9, 127.4, 60.0, 45.0, 29.1, 28.2, 27.1, 25.8, 24.3, 14.2 ppm. GC-MS (El) m/z (%):182 (21, [M].sup.+), 109 (76), 108 (60), 94 (31), 93 (25), 79 (48), 67 (100), 55 (47), 41 (43), 39 (33), 29 (40).

(8) ethyl cyclooct-1-ene-1-carboxylate: GC-MS (El) m/z (%): 182 (39, [M].sup.+), 137 (47), 109 (72), 108 (55), 81 (35), 79 (46), 67 (100), 55 (47), 53 (37), 41 (48).

(9) Odor description (ethyl (4-cyclooct-3-ene-1-carboxylate): still a relatively natural, pleasant olfactive profile, but slightly unbalanced by the slight chemical, green, artificial facet

(10) Odor description (ethyl cyclooct-1-ene-1-carboxylate): mainly perceived as chemical, plastic, with some berry, aromatic, slightly green facets: about 400 times weaker than the main constituent (ethyl (Z)-cyclooct-3-ene-1-carboxylate)

EXAMPLE 3 (COMPARISON)

ethyl (Z)-cyclooct-2-ene-1-carboxylate

(11) A solution of (Z)-cyclooct-2-ene-1-carboxylic acid (8.64 g, 56.0 mmol, 1.0 equiv, prepared according to Li, M. et al., Macromolecules 2016, 49, 9415) and para-toluenesulfonic acid monohydrate (1.07 g, 5.60 mmol, 10 mol %) in EtOH (60 mL) was refluxed for 7 h using a Dean-Stark trap. Since the reaction mixture still contained some starting material, an additional amount of para-toluenesulfonic acid monohydrate (0.48 g, 2.52 mmol, 4.5 mol %) was added and refluxing was continued for 16 h. The reaction mixture was diluted with 2M aq. NaOH (60 mL), water and MTBE. The layers were separated and the aqueous layer was extracted with MTBE (2×80 mL). The combined organic extracts were dried over MgSO.sub.4, filtered and concentrated under reduced pressure to give a crude product (4.27 g). The crude was purified by column chromatography (pentane/MTBE 50:1) and Kugelrohr distillation (90° C./0.04 mbar) to afford ethyl (Z)-cyclooct-2-ene-1-carboxylate (2.03 g, 20% yield, contains 8% of ethyl cyclooct-1-ene-1-carboxylate) as a colorless liquid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ 5.80-5.71 (m, 1H), 5.67 (ddd, J=10.5, 8.6, 1.1 Hz, 1H), 4.14 (q, J=7.1 Hz, 2H), 3.48-3.37 (m, 1H), 2.23-2.03 (m, 2H), 1.97-1.84 (m, 1H), 1.75-1.62 (m, 2H), 1.62-1.51 (m, 3H), 1.49-1.28 (m, 2H), 1.25 (t, J=7.1 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3): δ 175.5, 131.0, 127.7, 60.4, 42.7, 33.3, 29.1, 26.5, 26.4, 25.2, 14.2 ppm. GC-MS (El) m/z (%): 182 (13, [M].sup.+), 109 (58), 108 (38), 94 (23), 81 (24), 79 (30), 67 (100), 55 (35), 41 (36), 39 (24), 29 (33).

(12) About 10 times weaker than ethyl (Z)-cyclooct-4-ene-1-carboxylate and ethyl (Z)-cyclooct-3-ene-1-carboxylate, both of which are similar not only with regard to the odor profile but also in odor strength.

(13) Odor description: mainly perceived as chemical, green, artificial with a green, coniferous aspect. Overall, this relates to chemical, artificial, and results as unpleasant and unwanted olfactive character.

EXAMPLE 4

Fruity Gourmand Fragrance Composition Suitable for Shower Gel

(14) TABLE-US-00001 parts by weight Compound/Ingredient 1/1000 CIS-3-HEXENYL ACETATE 9 ACETOPHENONE (1-PHENYL-ETHANONE) 5 DODECANAL @10% TEC 5 CINNAMIC ALDEHYDE (3-PHENYL-2-PROPENAL) 23 METHYL ANTHRANILATE (METHYL 2- 4 AMINOBENZOATE) ETHYLENE BRASSYLATE (1,4- 124 DIOXACYCLOHEPTADECANE-5-17-DIONE) BUCHU LEAF OIL 5 ETHYL BUTYRATE 20 ETHYL HEXANOATE 1 CARVONE LAEVO (L-2-METHYL-5-ISOPROPENYL-2- 40 CYCLOHEXENONE) CYCLAL C (2,4-DIMETHYL-3-CYCLOHEXENE-1- 20 CARBALDEHYDE) DAMASCENONE (1-(2,6,6-TRIMETHYL-1,3- 20 CYCLOHEXADIENE-1-YL)-2-BUTENE-1-ONE) DAMASCONE ALPHA (1-(2,6,6-TRIMETHYL-2- 20 CYCLOHEXEN-1-YL)-2-BUTEN-1-ONE) DAMASCONE BETA (1-(2,6,6-TRIMETHYL-1- 17 CYCLOHEXEN-1-YL)-2-BUTEN-1-ONE) ETHYL MALTOL (3-HYDROXY-2-ETHYL-4H- 50 PYRAN-4-ONE) STRAWBERRY PURE (ETHYL 3-PHENYL-2,3- 10 EPOXYBUTANOATE) FRUCTONE (ETHYL 2-METHYL-1,3-DIOXOLANE- 10 2-ACETATE) HEDIONE (METHYL 3-OXO-2- 100 PENTYLCYCLOPENTANEACETATE) HEXENOL-3-CIS 34 METHYL 2-METHYLBUTYRATE 2 METHYL OCTYNE CARBONATE (METHYL 2- 4 NONYNOATE) ORANGE OIL 200 PEACH PURE (4-UNDECANOLIDE) 20 ETHYL PELARGONATE (ETHYL NONANOATE) 1 ETHYL PROPIONATE 1 UNDECAVERTOL (4-METHYL-3-DECEN-5-OL) 10 VANILLIN (4-HYDROXY-3-METHOXYBENZALDEHYDE) 65 DIPROPYLEN GLYCOLE (DPG) 180 Total: 1000

(15) By replacing 18 parts of DPG of the accord above with ethyl (Z)-cyclooct-4-ene-1-carboxylate the overall top note character shifts towards a natural, juicy, over ripe, pleasant fruity, berry, strawberry character both on neat and in use (i.e. when accord is applied @ 0.1% in shower gel).

(16) By replacing 18 parts of DPG of the accord above with ethyl (Z)-cyclooct-3-ene-1-carboxylate the overall top note character shifts towards a juicy, over ripe, fruity, berry, strawberry character both on neat and in use (i.e. when accord is applied @ 0.1% in shower gel), with a slight green, artificial facet.