N-acylated 1-aminocycloalkyl carboxylic acids as food flavouring compounds

Abstract

Compounds represented by the formula ##STR00001## and their edible salts, and edible compositions containing same 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, such that R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and the amino acid residue connected to the carbonyl carbon atom is a residue of a 1-amino cycloalkane carboxylic acid (ACCA), and n is 1, 2, 3 or 4.

Claims

1. A flavor composition adapted for use in an edible composition comprising: 1 ppb to 10 ppm by weight based upon the weight of the edible composition of a compound selected from the group consisting of: N-palmitoyl 1-amino-cyclopropyl carboxylic acid (C16:0-ACCA), N-stearoyl 1-amino-cyclopropyl carboxylic acid (C18:0-ACCA), N-linoleoyl 1-amino-cyclopropyl carboxylic acid (C18:2-ACCA), N-linolenoyl 1-amino-cyclopropyl carboxylic acid (C18:2-ACCA), N-oleoyl 1-amino-cyclopropyl carboxylic acid (C18:1-ACCA), N-(9-palmitenoyi) 1-amino-cyclopropyl carboxylic acid (C16:1-ACCA), N-decanoyl 1-amino-cyclopropyl carboxylic acid (C10:0-ACCA), and, N-geranoyl 1-amino-cyclopropyl carboxylic acid (C10:2-ACCA), wherein, one or more of the foregoing compounds accentuates the existing flavour or existing mouth feel characteristics of an edible foodstuff product which further comprises at least one flavour co-ingredient, or of a beverage product which further comprises at least one flavour co-ingredient , when one or more of the foregoing compounds are incorporated therein.

2. A stock solution comprising 0.01 to 1% by weight of a compound selected from the group consisting of: N-palmitoyl 1-amino-cyclopropyl carboxylic acid (C16:0-ACCA), N-stearoyl 1-amino-cyclopropyl carboxylic acid (C18:0-ACCA), N-linoleoyl 1-amino-cyclopropyl carboxylic acid (C18:2-ACCA), N-linolenoyl 1-amino-cyclopropyl carboxylic acid (C18:2-ACCA), N-oleoyl 1-amino-cyclopropyl carboxylic acid (C18:1-ACCA), N-(9-palmitenoyl) 1-amino-cyclopropyl carboxylic acid (C16:1-ACCA), N-decanoyl 1-amino-cyclopropyl carboxylic acid (C10:0-ACCA), and, N-geranoyl 1-amino-cyclopropyl carboxylic acid (C10:2-ACCA), wherein, one or more of the foregoing compounds accentuates the existing flavour or existing mouth feel characteristics of an edible foodstuff product which further comprises at least one flavour co-ingredient, or of a beverage product which further comprises at least one flavour co-ingredient , when one or more of the foregoing compounds are incorporated therein at concentrations of 1 ppb to 10 ppm by weight based on the weight of the edible foodstuff product or beverage product.

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

4. A 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.

5. A flavour composition according to claim 1 further comprising a carrier material and an adjuvant.

6. A flavour composition according to claim 5 wherein the adjuvant is an anti-oxidant.

7. A flavour composition according to claim 1 wherein the flavour composition is in the form of an emulsion.

8. A flavour composition according to claim 1 wherein the flavour composition is in the form of a powder.

9. A flavour composition according to claim 8 wherein the flavour composition is a spray dried powder.

10. A flavour composition adapted for use in an edible composition according to claim 1, which flavor composition is in the form of a powdered soft drink or a dry mix composition.

11. A flavour composition adapted for use in an edible composition according to claim 1 in the form of a snack food wherein the flavor composition is incorporated in the snack food or is applied topically to the snack food as a powder.

12. A flavour composition according to claim 1 in an alcoholic beverage.

13. A flavour composition according to claim 1 in an orally administrable tablet, capsule, powder or multiparticulate.

14. A flavour composition according to claim 1 in a caloric or non-caloric beverage further 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.

15. A flavour composition according to claim 1 in a soy-based edible composition.

16. A flavor composition according to claim 1, wherein the compound provides an organoleptic, fat booting effect flavor when included in an edible foodstuff product or beverage product.

17. A flavor composition according to claim 1, wherein the compound provides an organoleptic, alcohol boosting effect flavor when included in an edible foodstuff product or beverage product.

18. A flavor composition according to claim 1, wherein the compound provides an organoleptic, coolant boosting effect flavor when included in an edible foodstuff product or beverage product.

19. A flavor composition according to claim 1, wherein the compound provides an organoleptic, umami boosting effect flavor when included in an edible foodstuff product or beverage product.

20. A flavor composition according to claim 1, wherein the compound imparts sweetness and mouthfeel reminiscent of sugar when present in a beverage product.

21. A flavor composition according to claim 1, wherein the compound imparts stability in a clouded beverage composition.

22. A flavor composition according to claim 1 in the form of an emulsion.

Description

SYNTHESIS EXAMPLES

(1) 1. General Structure

(2) ##STR00003##

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

(4) or

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

(6) and n=1 to 4

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

(8) 2. Synthesis

(9) 2.1 Route A: (DCC method)

(10) 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.

(11) 1 g of 85-90% pure product could be obtained.

(12) 2.2 Route B (DCC method with protection group)

(13) Step 1:

(14) 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%.

(15) Step 2:

(16) 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.

(17) 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%

(18) 2.3 Route C (acid chloride)

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

(20) 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.

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

(22) 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%).

(23) 2.4All synthesized products Based on the above described methods a series of compounds have been synthesized. All these compounds are summarized in table 1.

(24) TABLE-US-00001 TABLE 1 List of synthesized compounds Struc- Amino Carboxylic ture acid acid Structure Route 1 ACC C10:0 C 2 ACC C10:2 A 3 ACC C16:0 C 4 ACC C18:0 C 5 ACC C18:1 C 6 ACC C18:2 A

(25) ACC=1-Amino-cyclopropane carboxylic acid

(26) ##STR00010##
3 NMR data (example)
3.1 Structure 5, ACC-C18:1

(27) .sup.1H NMR (600 MHz, CHLOROFORM-d) ppm 0.88 (t, J=7.05 Hz, 3 H, HC (18)) 1.09-1.21 (m, 2H HC (22, 23)) 1.21-1.1.39 (m, 20 H, HC (4, 5, 6, 7, 12, 13, 14, 15, 16, 17)) 1.54-1.68 (m, 4 H, HC (3, 22, 23)) 1.91-2.07 (m, 4H, HC (8, 11)) 2.18 (t, J=7.73 Hz, 2 H, HC (2)) 5.26-5.44 (m, 2 H, HC (9, 10)) 6.28 (s, 1 H, HN (19))

(28) .sup.13C NMR (150 MHz, CHLOROFORM-d) ppm 14.13 (C (18) 18.01 (C (22, 23)) 22.69 (C (17)), 25.45 (C (3)), 27.19 (C (11) 27.23 (C11)) 29.16 (C4)) 29.18 (C6)) 29.26 (C (5)) 29.33 (C (13, 15)) 29.45 (C (14)) 29.72 (C (7)) 29.78 (C (12)) 31.91 (C (16, 21)) 33.47 (C (2)) 129.76 (C (10)) 129.99 (C (9)) 175.15 (C (1)) 177.39 (C (20))

APPLICATION EXAMPLES

(29) Testing of C18 amino cyclopropanic acid (ACCA) derivative

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

(31) Test on Kikkoman soy sauce low salt

(32) Salt level pure product between 5-40%

(33) Salt level in application 0.3-1.0%

(34) C18:1-ACCA: 0.5 ppm Strong upfront saltiness lingering, very strong saltiness

(35) Test in fish sauce

(36) Salt level pure product between 5-40%

(37) Salt level in application 0.3-1.0%

(38) C18:1-ACCA 0.5 ppm, Strong saltiness lingering, strong body mouthfeel

(39) Test in mayonnaise

(40) Fat levels between 10-80%

(41) Low fat Mayonnaise (27% Fat)

(42) C18:1-ACCA 0.5 ppmNice balanced, full mouthfeel, increased eggyness

(43) Test in dressings

(44) Oil levels 0.5-50%

(45) Acidity PH 3-6

(46) Low fat salad dressing (13.6% Fat)

(47) C18:1-ACCA 0.5 ppmIncreased mouthfeel body less acidic

(48) Test in Soups and Bouillons

(49) Fat levels 0.1-10%

(50) Salt levels 0.3-1.4%

(51) Standard Chicken bouillon base

(52) 0.7% salt, 0.5% fat

(53) C18:1-ACCA 0.5 ppmMore body and fatty notes, salivating and good aftertaste

(54) C18:1-ACCA 0.2 ppmSaltier, Stronger and more umami

(55) Test in Jus and Fonds

(56) Beef jus

(57) C18:1-ACCA 40 ppbmore salty, fatty, total profile is enhanced

(58) Test in Cheese

(59) Fat level: 1-40%

(60) Salt: 0.3-2%

(61) Spreadable cheese ERU

(62) C18:1-ACCA 0.5 ppmStrong umami, lingering cheese bite

(63) Cheese sauce: 5% fat 1.6% salt

(64) C18:1-ACCA 0.5 ppmStrong umami, cheese bite, expanding