N-acyl proline derivatives as food flavoring compounds

Abstract

A flavour composition comprising a compound of formula (I) corresponding to the formula ##STR00001## and edible salts thereof, wherein R.sub.1 is an alkyl residue containing 6 to 20 carbon atoms, or an alkene residue containing from 9 to 25 carbon atoms with 1 to 6 double bonds, R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid.

Claims

1. A flavour composition comprising a compound selected from the group consisting of: N-geranoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro, and, N-linolenoyl-Pro, wherein, the compound accentuates the existing flavour or existing mouth feel characteristics of edible foodstuff products further comprising at least one flavour co-ingredient, or of beverage products further comprising at least one flavour co-ingredient, when the said compound is incorporated in an amount of 1 ppb-10 ppm within the edible foodstuff product or beverage product.

2. A stock solution comprising 0.01 to 1% by weight of a compound of claim 1, wherein the compound accentuates the existing flavour or existing mouth feel characteristics of edible foodstuff products further comprising at least one flavour co-ingredient, or of beverage products further comprising at least one flavour co-ingredient when the compound is incorporated therein in an amount of 1 ppb-10 ppm within the edible foodstuff product or beverage product.

3. A stock solution according to claim 2 further comprising a solvent selected from the group consisting of: ethanol, triacetine, glycerol and miglyol or mixtures thereof.

4. A method of accentuating the flavour or mouthfeel characteristics of an edible foodstuff composition, the method comprising the step of incorporating the flavour composition of claim 1 in the edible composition such that a compound is present in a concentration of 1 ppb-10 ppm within the edible foodstuff composition.

5. The flavour composition according to claim 1 further comprising at least one flavour co-ingredient.

6. The flavour composition according to claim 1 further comprising an ingredient selected from the group consisting of: sugars, fats, salt, MSG, calcium ions, phosphate ions, organic acids, proteins, purines and mixtures thereof.

7. The flavour composition according to claim 1 further comprising a carrier material and an adjuvant.

8. The flavour composition according to claim 7 wherein the adjuvant is an anti-oxidant.

9. The flavour composition according to claim 1 in the form of an emulsion.

10. The flavour composition according to claim 1 in the form of a powder.

11. An edible foodstuff product or a beverage product comprising a flavour composition according to claim 1, comprising 1 ppb-10 ppm of a compound selected from the group consisting of N-geranoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro and N-linolenoyl-Pro.

12. A caloric or non-caloric beverage product comprising an edible composition according to claim 11 containing at least one carbohydrate sweetener selected from: sucrose, high fructose corn syrup, fructose and glucose, or at least one high intensity, non-nutritive sweetener selected from: aspartame, acesulfame K, sucralose, cyclamate, sodium saccharin, neotame, rebaudioside A, and/or Stevia-based sweeteners.

13. A soy-based edible composition comprising an edible foodstuff product according to claim 11.

14. An edible foodstuff product or a beverage product comprising a compound selected from the group consisting of N-geranoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro and N-linolenoyl-Pro as defined in claim 1, and a flavour co-ingredient.

15. An edible foodstuff product or a beverage product according to claim 14 wherein the compound imparts enhanced fat perception.

16. An edible foodstuff product or a beverage product according to claim 14 wherein the compound imparts enhanced umami taste.

17. An edible foodstuff product or a beverage product according to claim 14 wherein the compound imparts enhanced salt taste.

18. An edible foodstuff product or a beverage product according to claim 14 wherein the compound imparts enhanced fruit profiles.

19. An edible foodstuff product or a beverage product according to claim 14 wherein the compound imparts enhanced savoury character.

20. An edible foodstuff product or a beverage product according to claim 14 wherein the compound imparts improved flavour performance.

21. An edible foodstuff product according to claim 14 wherein the compound imparts enhanced salivation.

Description

SYNTHESIS EXAMPLES

1. General Structure

(1) ##STR00003##

(2) R.sup.1=is a straight chain hydrocarbon group having 9 to 21 carbon atoms and containing zero to three double bonds

(3) or

(4) R.sup.1 is a [(1E)-2,6-dimethylhepta-1,5-dien-1-yl]-group.

(5) Several compounds belonging to that general formula have been synthesised according to one of the 2 procedure described below.

2. Synthesis

(6) 2.1 Route A: (DCC Method)

(7) In a 250 mL round-bottomed flask was mixed fatty acid (3.93 mmol) with 1-hydroxypyrrolidine-2,5-dione (0.498 g, 4.32 mmol) in dioxane (50 ml) to give a colorless solution. The solution was cooled to 10 C. and DCC (0.892 g, 4.32 mmol) was added while stirring. Stirring was continued for three hours at room temperature. The formed solids were filtered (dicyclohexylurea) and the filtrate was added to a solution of amino acid (6.48 mmol) in a 2% solution of sodiumbicarbonate (0.363 g, 4.32 mmol) in water. The reaction mixture was stirred for 4 hours at 50 C. Dioxane was evaporated and the aqueous residue was further diluted with water, acidified with a diluted hydrochloric acid solution and extracted with ethylacetate. Organic layers were combined, washed with brine, dried and evaporated to yield 1.3 g of a white solid. Product was purified by flash column chromatography, eluent DCM/methanol.

(8) 1 g of 85-90% pure product could be obtained.

(9) 2.2 Route B (DCC Method with Protection Group)

(10) Step 1:

(11) To a solution of an O-methylated amino acid (16.51 mmol) in DCM (100 ml) was added triethylamine (1.519 g, 15.01 mmol) at minus 15 C. A fatty acid (0.01 mmol) was added while stirring. A solution of DCC (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. The dicyclohexylurea was removed by filtration from the reaction mixture. Filtrate was washed with a saturated sodiumbicarbonate 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 The intermediate ester compound could be isolated in a purity of 95%.

(12) Step 2:

(13) The O-methylated N-acyl-amino-acid (4.91 mmol) was dissolved in a mixture of Ethanol (8.00 ml) and water (8 ml). To this mixture was added a 32% solution of sodiumhydroxide (2.453 g, 19.63 mmol) and mixture was stirred at room temperature for three hours. Mixture stand over for 14 hours.

(14) After 14 hours the mixture was acidified with a concentrated hydrochloric acid solution (1.612 ml, 19.63 mmol), diluted with water and extracted with mtbe. Organic layer was separated, dried and evaporated. 1.3 g of a half solid yellow residue was obtained. NMR confirmed the structure of the title compound, purity 95%

(15) 2.3 Route C (Acid Chloride)

(16) An amino acid (20 mmol) was dissolved in a solution of sodiumhydroxide (54.5 mmol) in water (40 ml).

(17) Tetrahydrofuran (60 ml) was added. Fatty acid chloride (18.18 mmol) was added dropwise at room temperature. Stirring was continued for 2 hours. Mixture was diluted with water, acidified with a 37% solution of hydrochloric acid (2.99 ml, 36.4 mmol) and extracted with ethylacetate.

(18) Organic layers were combined, dried and evaporated.

(19) The residue contains about 20% free fatty acid according NMR. The solids were stirred with heptane for 30 minutes, filtered and dried. This resulted in 2.4 g of the title compound as a creamy colored solid. (purity 95%).

(20) 2.4 All Synthesized Compounds

(21) TABLE-US-00001 TABLE 1 List of synthesized compounds Amino Carboxylic Structure acid acid Structure Route 1 Proline C10:2 A 2 Proline C16:0 C 3 Proline C16:0 C 4 Proline C18:2 A

3. NMR Data (Example)

(22) 3.1 Structure 4 Proline-C18:2

(23) ##STR00008##

(24) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.78-0.85 (m, 3H, HC(18)) 1.18-1.33 (m, 14H, HC(4, 5, 6, 7, 15, 16, 17) 1.54-1.65 (m, 2H, HC(3)) 1.84-1.92 (m, 1H, H_C(22)) 1.92-2.03 (m, 6H, H_C(8, 14, 23)) 2.26-2.32 (m, 2H, HC(2)) 2.44 (ddd, J=12.29, 6.10, 2.92 Hz, 1H, HC(22)) 2.70 (t, J=6.70 Hz, 2H, HC(11)) 3.39 (td, J=9.62, 6.87 Hz, 1H, HC(24)) 3.47-3.53 (m, 1H, HC(24)) 4.53 (dd, J=8.08, 1.89 Hz, 1H, HC(21)) 5.16-5.36 (m, 4H, HC(9, 10, 12, 13)

(25) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.07 (C(18)) 22.57 (C(17)) 24.48 (C(3)) 24.79 C(23)) 25.62 (C11)) 27.05 (C(22)) 27.17 (C(8)) 27.19 (C(14)) 29.10 C(6)) 29.27 (C(4, 15)) 29.34 (C(5)) 29.60 C(7)) 31.51 C((16)) 34.45 C(2)) 47.98 C(24)) 60.25 (C(21)) 128.07 (C(12)) 128.07 (C(10)) 130.00 (C(9)) 130.24 C(13)) 171.87 (C(1)) 175.87 (C20))

Application Examples

(26) Testing Proline Derivatives

(27) Samples were evaluated by expert tasters. Tasters were asked to describe the samples focusing on authentic taste, mouthfeel, fullness, salty-ness, salivation, umami, sweetness, juiciness, richness, long lastingness and fattiness.

(28) Comparison in a Mango Juice Drink

(29) Base is water, 8% sucrose, 0.1% citric acid, 1% clear mango juice, proprietary mango flavour @ 0.05%

(30) Base: Fruity mango

(31) Base plus C16:0-pro at 1 ppm overripe, orange like, long lasting after taste

(32) Base plus C18:1-pro at 1 ppm sweet, orange albedo

(33) Test in Orange Beverage

(34) Base is water, 7% sugar, 0.1% citric acid, proprietary orange flavour @ 0.06%.

(35) Base: orange, fruity, slightly candy

(36) Base plus C18:2-pro at 1 ppm: very juicy, authentic orange

(37) Test in Lemon Beverage

(38) Basis water, 7% sucrose, 0.15% citric acid, proprietary lemon flavor

(39) Base: floral, citral, lemon

(40) Base plus C18:2-pro at 1 ppm: very juicy, more citral like, very authentic.

(41) Test in Bouillion

(42) Base is Maggi beef bouillon 1 tablet in 500 ml of hot water

(43) Base: salty, umami, powdery

(44) Base plus C16:0-pro at 1 ppm: more salty, full, darker, more meat-like

(45) Base plus C18:1-pro at 1 ppm: full, more umami, long lasting