Organic compounds having taste-modifying properties

Abstract

This disclosure relates to flavour modification and to compounds of formula (I) or edible salts thereof, ##STR00001## wherein R.sup.1 is selected from C.sub.6-C.sub.20 alkyl, and C.sub.9-C.sub.25 alkenyl, and i) R.sup.3 and R.sup.4 are hydrogen and R.sup.2 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.2—CH.sub.2—CH.sub.2— useful in modifying flavours.

Claims

1. A flavour composition comprising a flavor co-ingredient and a compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide, and edible salts thereof, wherein the compound exhibits an organoleptic benefit when present at a concentration of 1 ppb-10 ppm in a comestible composition, based on the weight of the comestible composition.

2. The flavour composition according to claim 1, wherein the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbatanamide, 1-amino-N-octadecylcylopropanecarboxamide, or edible salt thereof exhibits a salt, alcohol or coolant boosting effect when present at a concentration of 1 ppb-100 ppb in a comestible composition, based on the weight of the comestible composition and where said comestible composition contains salt, alcohol or coolant compounds.

3. The flavour composition according to claim 1, wherein the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbatanamide, 1-amino-N-octadecylcylopropanecarboxamide, or edible salt thereof exhibits umami boosting effects when present at a concentration of 100 ppb-250 ppb in a comestible composition, based on the weight of the comestible composition and where said comestible composition contains umami tastants.

4. The flavour composition according to claim 1, wherein the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide, or edible salt thereof exhibits mouthfeel boosting effects when present at a concentration of 250 ppb-500 ppb in a comestible composition, based on the weight of the comestible composition.

5. The flavour composition according to claim 1, wherein the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide, or edible salt thereof exhibits fat boosting effects when present at a concentration of 500 ppb-1000 ppb in a comestible composition, based on the weight of the comestible composition and where said comestible composition contains fats.

6. The flavour composition according to claim 1, wherein the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide, or edible salt thereof exhibits sweetness effects when present at a concentration of 1 ppb-10 ppm in a beverage composition.

7. The flavour composition according to claim 1, wherein the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide, or edible salt thereof is present at a concentration of 1 ppb-10 ppm in a soy based composition or a fish based composition.

8. A taste modifying agent comprising a compound selected from: 2-amino-4-(methylthio) -N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide, and edible salts thereof, present in a consumable product at a concentration of 1 ppb-10 ppm based on the weight of the consumable product.

9. The taste modifying agent of claim 8, wherein when the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide or edible salt thereof, present in the consumable product at a concentration of 1 ppb-100 ppb based on the weight of the consumable product exhibits a sale, alcohol or coolant boosting effect where said consumable product contains salt, alcohol or coolant compounds.

10. The taste modifying agent of claim 8, wherein when the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide or edible salt thereof, present in the consumable product at a concentration of 100 ppb-250 ppb in the consumable product based on the weight of the consumable product exhibits umami boosting effects where the consumable product contains umami tastants.

11. The taste modifying agent of claim 8, wherein when the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide or edible salt thereof, present in the consumable product at a concentration of 250 ppb-500 ppb in the consumable product based on the weight of the consumable product, exhibits mouthfeel boosting effects.

12. The taste modifying agent of claim 8, wherein when the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide or edible salt thereof, present in the consumable product at a concentration of 500 ppb-1000 ppb exhibits fat boosting effect where the consumable product contains fats.

13. The taste modifying agent of claim 8, wherein when the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide or edible sale thereof, present in a beverage composition at a concentration of 1 ppb-10 ppm based on the weight of a beverage composition exhibits sweetness effects.

14. The taste modifying agent of claim 8, wherein when the said compound selected from: 2-amino-4-(methylthio)-N-octadecylbutanamide, 1-amino-N-octadecylcyclopropanecarboxamide or edible salt thereof, is present at a concentration of 1 ppb-10 ppm in a soy based composition or a fish based composition.

Description

EXAMPLE 1

2-amino-4-(methylthio)-N-octadecylbutanamide

(1) a) tert-butyl (4-(methylthio)-1-(octadecylamino)-1-oxobutan-2-yl)carbamate

(2) In a 250 mL round-bottomed flask fitted with a stirrer, cooler and dropping funnel tert-butyloxycarbonyl methionine (3 g, 12.03 mmol) was dissolved in in dichloromethane (DCM; 50 ml). Solution was cooled with an ice/water bath and triethylamine (1.677 ml, 12.03 mmol) was added at a temperature of approx. 10° C.

(3) Ethyl chloroformiate (1.306 g, 12.03 mmol) was added dropwise at 10° C.

(4) Stirring was continued for 15 minutes while cooling. Octadecan-1-amine (3.24 g, 12.03 mmol) was added, cooling bath was removed and stirring was continued for 4 hours.

(5) Reaction mixture stand over during the night.

(6) Mixture was diluted with DCM, washed with a diluted aqueous solution of hydrochloric acid and with a sodiumcarbonate solution.

(7) Organic layer was separated, dried and evaporated to yield 5 g of the title product as a white solid (Purity >95%, yield: 79%).

(8) b) 2-amino-4-(methylthio)-N-octadecylbutanamide

(9) In a 250 mL erlenmeyer tert-butyl (4-(methylthio)-1-(octadecylamino)-1-oxobutan-2-yl)carbamate (1 g, 1.997 mmol) was dissolved in Methanol (Volume: 100 ml).

(10) Acetyl chloride (3.62 ml, 51.0 mmol) was added carefully while stirring.

(11) Solution stand over during the night.

(12) Solution was evaporated and the solid residue was washed with some acetone/ether to remove the remaining starting material.

(13) 0.4 g of title product was left with a purity >95%, yield: 45%

(14) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.85 (t, J=6.70 Hz, 3 H, H—C(18)) 1.23 (m, 30 H, H—C(3, 4, 8, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17)) 1.36-1.46 (m, 2 H, H—C(2)) 1.96 (d, J=7.22 Hz, 2 H, H—C(21) 2.05 (s, 3 H, H—C(23)) 2.47 (d, J=5.84 Hz, 2 H, H—C(22)) 3.00-3.07 (m, 1H, (H—C(1)) 3.13-3.20 (m, 1H, H—C(1)), 3.76 (t, J=6.19 Hz, 1H, H—C(20)) 8.51 (br. s., 1 H, H—N(24))

(15) .sup.13C NMR (150 MHz, DMSO-d.sub.6) ppm 13.93 C(18)), 14.46 C(23)), 22.06 C(17)), 26.32 (C(2)), 28.13-29.10 (C(3 4, 5, 6, 7, 8, 9, 10, 1, 12, 13, 14, 15, 22) 31.07 (C(16)) 31.27 C(21)) 38.65 (C(1)), 51.69 C(C20)) 168.03 C(19))

EXAMPLE 2

2-amino-4-methyl-N-octadecylpentanamide

(16) According to the same procedure of Example 1, 2-amino-4-methyl-N-octadecylpentanamide was prepared from leucine and octadecyl amine in a yield of 47%.

(17) .sup.1H NMR (600 MHz, DMSO-d.sub.6) δ ppm 0.63-0.95 (m, 9 H) 1.05-1.29 (m, 30 H) 1.40 (br. s., 2 H) 1.55 (d, J=6.87 Hz, 3 H) 2.82-3.09 (m, 1 H) 3.09-3.21 (m, 1 H) 3.52-3.77 (m, 1 H) 3.82 (br. s., 4 H) 8.68 (s, 1 H)

(18) .sup.13C NMR (151 MHz, DMSO-d.sub.6) δ ppm 13.90 (s, 1 C) 22.08 (s, 1 C) 22.28 (s, 1 C) 22.40 (s, 1 C) 23.72 (s, 1 C) 26.32 (s, 1 C) 28.70 (s, 1 C) 29.00 (s, 1 C) 29.04 (s, 1 C) 31.29 (s, 1 C) 38.57 (s, 1 C) 40.20 (s, 1 C) 50.97 (s, 1 C) 168.49 (s, 1 C)

EXAMPLE 3

N-octadecylpyrrolidine-2-carboxamide

(19) According to the same procedure of Example 1, N-octadecylpyrrolidine-2-carboxamide was prepared from proline and octadecyl amine in a yield of 78%.

(20) .sup.1H NMR (600 MHz, DMSO-d.sub.6) δ ppm 0.88 (t, J=6.87 Hz, 3 H) 1.05-1.40 (m, 31 H) 1.50 (d, J=6.87 Hz, 2 H) 1.89-2.13 (m, 3 H) 2.31-2.51 (m, 1 H) 2.85-3.28 (m, 5 H) 3.34 (t, J=6.87 Hz, 2 H) 4.34 (s, 1 H) 8.44-8.53 (m, 1H)

(21) .sup.13C NMR (151 MHz, DMSO-d.sub.6) δ ppm 13.08 (s, 1 C) 21.49 (s, 1 C) 23.14 (s, 1 C) 25.77 (s, 1 C) 28.12 (s, 1 C) 28.14 (s, 1 C) 28.39 (s, 1 C) 28.44 (s, 1 C) 28.48 (s, 1 C) 29.39 (s, 1 C) 30.72 (s, 1 C) 38.60 (s, 1 C) 38.74 (s, 1 C) 38.87 (s, 1 C) 39.02 (s, 1 C) 39.15 (s, 1 C) 39.29 (s, 1 C) 39.44 (s, 1 C) 45.06 (s, 1 C) 58.27 (s, 1 C) 166.96 (s, 1 C)

EXAMPLE 4

4-amino-N-octadecylbutanamide

(22) According to the same procedure of Example 1, 4-amino-N-octadecylbutanamide was prepared from Gamma amino-butyric acid and octadecyl amine in a yield of 23%.

(23) .sup.1H NMR (600 MHz, DMSO-d.sub.6) δ ppm 0.85 (t, J=6.70 Hz, 3 H) 1.16-1.31 (m, 27 H) 1.31-1.42 (m, 2 H) 1.73 (s, 2 H) 2.15 (t, J=7.22 Hz, 2 H) 2.69-2.82 (m, 2 H) 3.01 (d, J=6.19 Hz, 3 H) 7.84-7.94 (m, 1H)

(24) .sup.13C NMR (151 MHz, DMSO-d.sub.6) δ ppm 13.95 (s, 1 C) 22.08 (s, 1 C) 23.55 (s, 1 C) 26.43 (s, 1 C) 28.68 (s, 1 C) 28.76 (s, 1 C) 28.98 (s, 1 C) 29.01 (s, 1 C) 29.09 (s, 1 C) 31.28 (s, 1 C) 32.13 (s, 1 C) 38.49 (s, 1 C) 38.72 (s, 1 C) 171.05 (s, 1 C)

EXAMPLE 5

1-amino-N-octadecylcyclopropanecarboxamide

(25) According to the same procedure of Example 1, 1-amino-N-octadecylcyclopropanecarboxamide was prepared from 1-amino-cyclopronae carboxylic acid and octadecyl amine in a yield of 50%.

(26) .sup.1H NMR (600 MHz, DMSO-d.sub.6) ppm 0.85 (t, J=6.87 Hz, 3 H, H—C(18)) 1.18-1.29 (m, 32 H, H—C(3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 20, 21) 1.35 (m, 2 H, H—C(20, 21)) 3.05 (m, 2 H, H—C(1)) 7.73 (t, J=6.36 Hz 1 H, H—N(23))

(27) .sup.13C NMR (150 MHz, DMSO-d.sub.6) ppm 12.00 (C(21, 22)), 13.94 (C(18)) 22.07 C(17)), 26.27 C(3)), 28.63-29.09 C(2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15), 31.27 C(16)), 34.69 C(C20)) 39.03 C(1)), 168.61 C(19))

EXAMPLE 6

(Z)-4-amino-N-(octadec-9-en-1-yl)butanamide

(28) According to the same procedure of Example 1, (Z)-4-amino-N-(octadec-9-en-1-yl)butanamide was prepared from gamma butyric acid and and 9-octadecenyl amine in a yield of 38%.

(29) .sup.1HNMR (600 MHz, DMSO-d.sub.6) δ ppm 0.85 (t, J=6.87 Hz, 1 H) 1.12-1.28 (m, 10 H) 1.28- 1.42(m, 2 H) 1.76 (quin, J=7.39 Hz, 1 H) 1.84-2.04 (m, 2 H) 2.16 (t, J=7.22 Hz, 1 H) 2.64-2.81 (m, 1 H) 3.00 (q, J=6.76 Hz, 1 H) 5.25-5.38 (m, 1 H) 7.93-8.13 (m, 1 H)

(30) .sup.13C NMR (151 MHz, DMSO-d.sub.6) δ ppm 13.93 (s, 1 C) 22.07 (s, 1 C) 23.22 (s, 1 C) 26.45 (s, 1 C) 26.56 (s, 1 C) 26.60 (s, 1 C) 28.57 (s, 1 C) 28.61 (s, 1 C) 28.67 (s, 1 C) 28.76 (s, 1 C) 28.81 (s, 1 C) 28.84 (s, 1 C) 28.87 (s, 1 C) 29.02 (s, 1 C) 29.04 (s, 1 C) 29.07 (s, 1 C) 29.09 (s, 1 C) 29.13 (s, 1 C) 31.27 (s, 1 C) 31.92 (s, 1 C) 32.12 (s, 1 C) 38.41 (s, 1 C) 38.48 (s, 1 C) 129.62 (s, 1 C) 130.05 (s, 1 C) 170.99 (s, 1 C)

EXAMPLE 8

Mango Flavoured Beverage

(31) 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 1 ppm of 1-amino-N-octadecylcyclopropanecarboxamide (Ex 5) was dosed to the mango drink the panel agreed that the drink tasted more sweet, more ripe mango, more full and more long-lasting than the reference drink. b) When 1 ppm of N-octadecylpyrrolidine-2-carboxamide (Ex 3) was dosed to the mango drink the panel agreed that this drink tasted more over-ripe, more sweet, and more full and had an increased mouthfeel than the reference drink.

EXAMPLE 9

Beef Bouillon

(32) A beef bouillon was prepared using bouillon cubes obtained from a local supermarket. The drinks were evaluated by a panel of experienced tasters. a) When 1 ppm of 2-amino-4-(methylthio)-N-octadecylbutanamide (Ex 1) was dosed to the bouillon the panel agreed that this drink tasted more salty and more full than the reference. b) When 1 ppm of N-hexadecyl 4-aminobutyramide (Ex 7) was dosed to the bouillon the panel agreed that this drink tasted more salty and more umami and was more longlasting than the reference.