Organic compounds having taste-modifying properties

Abstract

This disclosure relates to flavour modification and to compounds of formula (I) ##STR00001## wherein R.sup.1 is selected from C.sub.6-C.sub.20 alkyl, and C.sub.9-C.sub.25 alkenyl, R.sup.5 is C.sub.1-C.sub.3 alkyl, and a) n is 1; and i) R.sup.3 and R.sup.4 are hydrogen and R.sup.2 is the residue of a proteinogenic amino acid; ii) R.sup.2 and R.sup.3 are methyl and R.sup.4 is hydrogen; or R.sup.4 is hydrogen and R.sup.2 and R.sup.3 form together with the carbon atom to which they are attached cyclopropyl; iii) R.sup.2 is hydrogen, and R.sup.3 and R.sup.4 together are CH.sub.2CH.sub.2CH.sub.2; b) n is 2 or 3 and R.sup.2, R.sup.3 and R.sup.4 are hydrogen, useful in modifying flavours.

Claims

1. A flavour composition comprising a flavour co-ingredient and a compound selected from: (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl 1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate; methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate; methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and, methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate, wherein the said compound imparts a flavour modifying characteristic when the compound is present in an edible composition in a concentration of 1 ppb-10 ppm.

2. A flavour composition according to claim 1 wherein the flavour co-ingredient is selected from: sugars, fats, salts, monosodium glutamate, calcium ions, phosphate ions, organic acids, proteins, purines, flavours, and mixtures thereof.

3. A comestible product comprising a compound selected from: (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl 1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate; methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate; methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and, methyl 2((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate, wherein the said compound is present in the comestible composition in a concentration of 1 ppb-10 ppm.

4. A method of modifying the taste of comestible composition comprising at least one flavour co-ingredient, the method comprising the step of adding to or including in said comestible composition a compound selected from: (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl 1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate; methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate; methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and, methyl 2((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate, wherein the said compound is present in a concentration of 1 ppb-10 ppm within the comestible composition.

5. A taste-modifying agent adapted for use in a consumable product, the said taste-modifying agent comprising a compound selected from: (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate; (E)-methyl 1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate; (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate; methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate; methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate; and, methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate, wherein said compund imparts a taste-modifying characteristic when the compound is present within the consumable product in a concentration of 1 ppb-10 ppm.

6. The comestible product according to claim 3, wherein the compound is present in an amount of 100 ppb to 500 ppb based on the weight of the comestible product.

7. The comestible product according to claim 3, wherein the comestible product is an alcoholic beverage containing 1 ppb to 1 ppm of a said compound.

8. The comestible product according to claim 3, wherein the comestible product is a baked good containing 1 ppb to 1 ppm of a said compound.

9. The comestible product according to claim 3, wherein the comestible product is a beverage containing a sweetener selected from carbohydrate sweeteners, a non-nutritive sweetener, and a stevia based sweetener, which comestible product further contains 1 ppb to 1 ppm of a said compound.

10. The comestible product according to claim 3, wherein the comestible product is a soy-based composition containing 1 ppb to 10 ppm of a said compound.

11. The method of claim 4, wherein a said compound is added to a comestible composition in an amount of 1 ppb to 10 ppm based on the weight of the comestible product.

12. The method of claim 11, wherein a said compound is added to a comestible composition in an amount of 100 ppb to 500 ppb based on the weight of the comestible product.

13. The method of claim 4, wherein the comestible product is an alcoholic beverage to which 1 ppb to 1 ppm of a said compound is added.

14. The method of claim 4, wherein the comestible product is a baked good to which has 1 ppb to 1 ppm of a said compound has been added.

15. The method of claim 4, wherein the comestible product is a beverage containing a sweetener selected from carbohydrate sweeteners, a non-nutritive sweetener, and a stevia based sweetener, to which 1 ppb to 1 ppm of a said compound has been added.

16. The method of claim 4, wherein the comestible product is a soy-based composition to which 1 ppb to 10 ppm of a said compound has been added.

17. The flavour composition according to claim 1, wherein said compound is present in the flavor composition in a concentration of 100 ppb to 500 ppm.

Description

EXAMPLE 1

Methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate

(1) In a 250 mL round-bottomed flask fitted with a stirrer, cooler and dropping funnel methyl 2-amino-4-methylpentanoate, HCl (3 g, 16.51 mmol) was dissolved in dichloromethane (DCM; 100 ml). Triethyl amine (1.519 g, 15.01 mmol) was added at minus 15 C. Linoleic acid (4.21 g, 15.01 mmol) was added while stirring.

(2) A solution of N,N-dicyclohexylcarbodiimide (DCC; 3.10 g, 15.01 mmol) in 10 mL of DCM was added dropwise at 0 C. The reaction mixture was stirred at 0 C. for 1 hour and stirring was continued at room temperature for 3 hours.

(3) The formed dicyclohexyl urea was removed by filtration from the reaction mixture. Filtrate was washed with a saturated sodium bicarbonate solution, diluted hydrochloric acid solution and water. Organic layer was separated, dried and evaporated to yield 3 g of an oil. This oil was purified by flash column chromatography, eluent DCM/methanol methyl 4-methyl-2-((9Z,12Z)-octadeca-9,12-dienamido)pentanoate was obtained in a purity of 95%, yield: 31%.

(4) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.87-0.92 (t, J=6.82 Hz, 3H, HC(18)) 0.93-0.97 (m, 6H, HC(23, 24)) 1.26-1.46 (m, 14H, HC(4, 5, 6, 7, 15, 16, 17) 1.45-1.70 (m, 5H, HC(3, 21, 22)) 2.13 (m, 4H, HC(8, 14)) 2.13-2.33 (m, 2H, HC(2)) 2.69-2.88 (m, 2H, HC(11)) 3.70-3.90 (s, 3H, HC(25)) 4.62-4.74 (m, 1H, HC(20)) 5.30-5.49 (m, 4H, HC(9, 10, 12, 13) 5.83 (d, J=7.56 Hz, 1H, HN(26))

(5) .sup.13C NMR (151 MHz, CHLOROFORM-d) ppm 14.08 (C(18)), 21.95 (C(24)), 22.77 C(23)), 24.85 C(22)) 25.53 C(3)), 25.58 C(11)) 27.10-27.31 (C(8, 14)), 29.02-29.69 C(4, 5, 6, 7, 15)) 31.48 C(16)), 36.54 C(2)), 41.76 C(21)), 41.76 C(21)), 50.47 C(20)), 52.22 C(25)), 127.79-128.08 C(9, 10, 12, 13), 172.83 C(19), 173.75 C(1))

EXAMPLE 2

(E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate

(6) According to the same procedure of Example 1, (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-4-methylpentanoate was prepared from leucine methyl ester and geranic acid in a yield of 13%.

(7) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.67-0.93 (m, 6H) 1.37-1.74 (m, 10H) 1.93-2.17 (m, 6H) 2.41-2.65 (m, 1H) 3.50-3.66 (m, 3H) 4.25 (ddd, J=10.05, 7.13, 5.15 Hz, 1H) 4.96-5.14 (m, 1H) 5.60-5.75 (m, 1H) 7.95-8.15 (m, 1H)

(8) .sup.13C NMR (151 MHz, DMSO-d.sub.6) ppm 17.46 (s, 1C) 17.51 (s, 1C) 17.74 (s, 1C) 21.22 (s, 1C) 22.73 (s, 1C) 24.27 (s, 1C) 24.29 (s, 1C) 24.56 (s, 1C) 25.43 (s, 1C) 25.45 (s, 1C) 25.65 (s, 1C) 26.34 (s, 1C) 32.20 (s, 1C) (s, 1C) 39.64 (s, 1C) 39.79 (s, 1C) 39.92 (s, 1C) 40.19 (s, 1C) 49.89 (s, 1C) 49.95 (s, 1C) 51.67 (s, 1C) 51.69 (s, 1C) 117.91 (s, 1C) 123.40 (s, 1C) 124.02 (s, 1C) 131.40 (s, 1C) 152.82 (s, 1C) 166.06 (s, 1C) 173.34 (s, 1C)

EXAMPLE 3

(E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate

(9) According to the same procedure of Example 1, (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)propanoate was prepared from alanine methyl ester and geranic acid in a yield of 13%.

(10) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 1.12-1.27 (m, 6H) 1.45-1.66 (m, 12H) 1.76 (d, J=1.37 Hz, 2H) 1.88-2.14 (m, 9H) 2.47 (s, 1H) 4.09-4.29 (m, 1H) 4.96-5.15 (m, 1H) 5.59-5.72 (m, 1H) 8.13 (d, J=6.87 Hz, 1H)

(11) .sup.13C NMR (151 MHz, DMSO-d.sub.6) ppm 16.95 (s, 1C) 17.49 (s, 1C) 17.53 (s, 1C) 17.72 (s, 1C) 24.60 (s, 1C) 25.46 (s, 1C) 25.65 (s, 1C) 26.38 (s, 1C) 32.25 (s, 1C) 40.18 (s, 1C) 47.24 (s, 1C) 47.27 (s, 1C) 51.71 (s, 1C) 51.73 (s, 1C) 117.90 (s, 1C) 118.66 (s, 1C) 123.39 (s, 1C) 124.06 (s, 1C) 131.41 (s, 1C) 152.86 (s, 1C) 165.80 (s, 1C) 173.41 (s, 1C)

EXAMPLE 4

(E)-methyl 1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate

(12) According to the same procedure of Example 1, (E)-methyl 1-(3,7-dimethylocta-2,6-dienoyl)pyrrolidine-2-carboxylate was prepared from proline methyl ester and geranic acid in a yield of 65%.

(13) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 1.43-1.58 (m, 3H) 1.58-1.67 (m, 3H) 1.69-1.97 (m, 6H) 1.97-2.19 (m, 4H) 3.12-3.38 (m, 2H) 3.38-3.52 (m, 2H) 3.52-3.71 (m, 3H) 4.26 (dd, J=8.59, 4.47Hz, 1H) 4.47-4.59 (m, 1H) 4.98-5.13 (m, 1H) 5.61 (s, 1H) 5.72 (d, J=0.69 Hz, 1H) 5.79-5.91 (m, 1H)

(14) .sup.13C NMR (151 MHz, DMSO-d.sub.6) ppm 17.51 (s, 1C) 17.59 (s, 1C) 18.02 (s, 1C) 24.50 (s, 1C) 25.44 (s, 1C) 25.47 (s, 1C) 25.65 (s, 1C) 28.75 (s, 1C) 46.85 (s, 1C) 51.66 (s, 1C) 58.07 (s, 1C) 117.17 (s, 1C) 123.52 (s, 1C) 131.37 (s, 1C) 165.14 (s, 1C) 172.67 (s, 1C)

EXAMPLE 5

(E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate

(15) According to the same procedure of Example 1, (E)-methyl 2-(3,7-dimethylocta-2,6-dienamido)-3-(1H-imidazol-4-yl)propanoate was prepared from histidine methyl ester and geranic acid in a yield of 13%.

(16) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 1.45-1.67 (m, 6H) 1.92-2.13 (m, 6H) 2.47 (s, 2H) 2.82 (d, J=12.37Hz, 2H) 3.55 (s, 2H) 4.34-4.48 (m, 1H) 4.94-5.08 (m, 1H) 5.53-5.71 (m, 1H) 6.50-6.89 (m, 1H) 7.49 (br. s., 1H) 7.96-8.22 (m, 1H) 11.70-11.87 (m, 1H)

(17) .sup.13C NMR (151 MHz, DMSO-d.sub.6) ppm 18.04 (s, 1C) 18.08 (s, 1C) 18.27 (s, 1C) 24.05 (s, 1C) 25.11 (s, 1C) 25.95 (s, 1C) 25.99 (s, 1C) 26.02 (s, 1C) 26.05 (s, 1C) 26.17 (s, 1C) 26.89 (s, 1C) 27.18 (s, 1C) 31.22 (s, 1C) 32.79 (s, 1C) 40.58 (s, 1C) 40.69 (s, 1C) 52.24 (s, 1C) 52.80 (s, 1C) 118.51 (s, 1C) 123.94 (s, 1C) 124.57 (s, 1C) 131.96 (s, 1C) 135.41 (s, 1C) 166.48 (s, 1C) 207.02 (s, 1C)

EXAMPLE 6

Methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate (N-linoleoyl proline methyl ester)

(18) According to the same procedure of Example 1, methyl 1-((9Z,12Z)-octadeca-9,12-dienoyl)pyrrolidine-2-carboxylate was prepared from proline methyl ester and linoleic acid in a yield of 25%.

(19) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.86-0.93 (t, J=6.87, 3H, HC(18)) 1.24-1.40 (m, 14H, HC(4, 5, 6, 7, 15, 16, 17)) 1.63-1.71 (m, 2H, HC(3)) 1.95-2.02 (m, 2H, HC(22) 2.02-2.12 (m, 5H, HC(8, 14, 21) 2.12-2.22 (m, 1H, HC(21)) 2.23-2.38 (m, 2H, HC2))) 4.49 (dd, J=8.59, 3.78Hz, 1H, HC20)) 5.22-5.49 (m, 4H, HC(9, 10, 12, 13)

(20) .sup.13C NMR (151 MHz, CHLOROFORM-d) ppm 14.07 (C(18)) 22.57 (C(17)) 24.57 (C(3)) 24.82 (C(22)) 25.61 (C(11)) 27.15-27.27 (C(8, 14) 29.07-29.72 (C(4, 5, 6, 7, 15, 21)) (C) 31.51 (C(16)) 34.47 (C(2)) 46.97 (C(23)) 52.15 (C(24)) 58.54 (C(20)) 127.84-128.03 (C(10, 12)) 130.03-130.25 (C(9, 13)) 172.08 (C(1, 19))

EXAMPLE 7

Methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate (N-linolenoyl Alanine Methyl Ester)

(21) According to the same procedure of Example 1, methyl 2-((9Z,12Z,15Z)-octadeca-9,12,15-trienamido)propanoate was prepared from alanine methyl ester and linolenic acid in a yield of 25%.

(22) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.92 (t, J=7.39Hz, 3H) 1.14-1.19 (m, 1H) 1.17-1.39 (m, 20H) 1.39-1.59 (m, 3H) 1.92-2.13 (m, 9H) 2.62-2.84 (m, 5H) 3.60 (s, 4H) 4.23 (t, J=7.22Hz, 1H) 5.22-5.40 (m, 7H) 8.20 (d, J=6.87 Hz, 1H)

(23) .sup.13C NMR (151 MHz, DMSO-d.sub.6) ppm 14.43 (s, 1C) 14.62 (s, 1C) 17.46 (s, 1C) 20.56 (s, 1C) 22.51 (s, 1C) 25.63 (s, 1C) 25.67 (s, 1C) 25.72 (s, 1C) 27.13 (s, 1C) 27.17 (s, 1C) 29.08 (s, 1C) 29.11 (s, 1C) 29.21 (s, 1C) 29.26 (s, 1C) 29.55 (s, 1C) 31.43 (s, 1C) 35.40 (s, 1C) 47.93 (s, 1C) 52.23 (s, 1C) 127.48 (s, 1C) 128.06 (s, 1C) 128.26 (s, 1C) 128.42 (s, 1C) 128.45 (s, 1C) 130.24 (s, 1C) 130.41 (s, 1C) 132.00 (s, 1C) 172.63 (s, 1C) 173.79 (s, 1C)

EXAMPLE 8

Mango Flavoured Beverage

(24) A mango-flavoured beverage was prepared using a standard mango flavour (0.05% w/w), mango juice (0.18% w/w), sugar (8% w/w) and citric acid (0.1% w/w). The drinks were evaluated by a panel of experienced tasters. a) When 0.5 ppm of N-linoleoyl proline methyl ester (Example 6) was dosed to the mango drink the panel agreed that this drink tasted more fruity and peach-like than the reference drink. b) When 0.5 ppm of N-linolenoyl alanine methyl ester (Example 7) was dosed to the mango drink the panel agreed that this drink tasted more fully, more fatty than the reference drink.