Organic compounds

Abstract

A stock solution comprising a compound of formula (I) ##STR00001## Wherein R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR.sub.2R.sub.3, in which R.sub.3 is H or together with R.sub.2 and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid, in particular a proteinogenic amino acid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkyl carboxylic acid.

Claims

1. A method of isolating and recovering a compound according to the formula (I) which exhibits taste modifying properties when incorporated within an edible composition or within a flavour composition, ##STR00011## wherein R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR.sub.2R.sub.3, in which R.sub.3 is H or together with R.sub.2 and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid; from a reaction mixture comprising the compound in a reaction solvent, the method comprising the steps of: prior to removal of reaction solvent from the reaction mixture by evaporation, adding to the reaction mixture an extraction solvent for the compound, said extraction solvent having a higher boiling point than the reaction solvent, and subsequent to the evaporation of and removal of the reaction solvent from the reaction mixture containing the compound of formula (I), the reaction solvent and the extraction solvent, the compound of formula (I) is recovered in the form of a stock solution containing the compound of formula (I) in the extraction solvent.

2. A method of forming a stock solution comprising the steps of: isolating and recovering a compound which exhibits taste modifying properties when incorporated within an edible composition or within a flavour composition according to the formula (I) ##STR00012## wherein R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR.sub.2R.sub.3, in which R.sub.3 is H or together with R.sub.2 and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid; from a reaction mixture comprising the compound in a reaction solvent, the method comprising the steps of: prior to removal of the reaction solvent from the reaction mixture by evaporation, adding to the reaction mixture an extraction solvent for the compound which has a higher boiling point than the boiling point of the reaction solvent, and, subsequently, separating the compound according to formula (I) from the reaction solvent, and recovering from the reaction mixture a stock solution containing the compound and the extraction solvent.

3. A method according to claim 1 wherein the extraction solvent is selected from water-miscible alcohols and derivatives thereof.

4. A method according to claim 3 wherein the extraction solvent is selected from: ethanol, glycerol, propylene glycol, triacetine or miglyol, or mixtures thereof.

5. A method according to claim 3, wherein the extraction solvent is propylene glycol.

6. A stock solution comprising up to 25% by weight of a compound of formula (I) which exhibits taste modifying properties when incorporated within an edible composition or within a flavour composition ##STR00013## wherein R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR.sub.2R.sub.3, in which R.sub.3 is H or together with R.sub.2 and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid; in a solvent selected from water-miscible alcohols and/or derivatives thereof.

7. A stock solution according to claim 6 wherein the solvent is selected from: ethanol, glycerol, ethylene glycol, propylene glycol, triacetine or miglyol, or mixtures thereof.

8. A stock solution according to claim 6, wherein the solvent is propylene glycol.

9. A stock solution according to claim 6 wherein the compound of formula (I) is present in an amount of up to 15% by weight.

10. A spray dried powder comprising a compound according to formula (I) which exhibits taste modifying properties when incorporated within an edible composition or within a flavour composition ##STR00014## wherein R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR.sub.2R.sub.3, in which R.sub.3 is H or together with R.sub.2 and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid.

11. A spray dried powder according to claim 10, comprising a carrier material selected from a maltodextrin having a dextrose equivalent (DE) of 3 to 25, or gum Arabic.

12. A spray dried powder according to claim 10 wherein the compound of formula (I) is present in an amount of up to 1.5% by weight based on the total weight of the powder.

13. A spray dried powder according to claim 10 formed from a stock solution comprising up to 25% by weight of a compound of formula (I) ##STR00015## wherein R.sub.1 together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR.sub.2R.sub.3, in which R.sub.3 is H or together with R.sub.2 and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid.

14. The method according to claim 1, wherein: the residue of an amino acid is selected from: a proteinogenic amino acid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkyl carboxylic acid.

15. The method according to claim 2, wherein: the residue of an amino acid is selected from: a proteinogenic amino acid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkyl carboxylic acid.

16. The stock solution according to claim 6, wherein: the residue of an amino acid is selected from: a proteinogenic amino acid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkyl carboxylic acid.

17. The method according to claim 1, wherein the stock solution contains 5% to 30% by weight of the compound of formula (I).

18. The method according to claim 2, wherein the stock solution contains 5% to 30% by weight of the compound of formula (I).

19. The method according to claim 1, wherein the compound of formula (I) is represented by the following structure: ##STR00016## and wherein: n is 1, 2, 3 or 4.

20. The method according to claim 1, wherein the compound of formula (I) is represented by the following structure: ##STR00017## and wherein: m is 0 or 1.

21. The method according to claim 1, wherein the compound of formula (I) is represented by the following structure: ##STR00018## and wherein: R.sub.3 is hydrogen is methyl, and R.sub.4 is methyl, ethyl or iso-propyl.

22. The method according to claim 1, wherein the compound of formula (I) is represented by the following structure: ##STR00019##

23. The method according to claim 1, wherein the compound of formula (I) is represented by the following structure: ##STR00020## and wherein: X is OH or is NH.sub.2, and P is 0 or 1.

24. The method according to claim 1, wherein the compound of formula (I) is represented by the following structure: ##STR00021##

25. The method according to claim 1, wherein the compound of formula (I) is represented by the following structure: ##STR00022##

26. The stock solution according to claim 6, which is a flavour composition which in addition to the compound of formula (I) additionally comprises at least one flavour co-ingredient.

27. The spray dried powder of claim 10, wherein NR.sub.2R.sub.3 is a proteinogenic amino acid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkyl carboxylic acid.

28. The stock solution of claim 26, which further comprises a carrier material, or at least one adjuvant.

Description

EXAMPLE 1

Preparation

Linoleoyl Chloride

(1) 1026 grams (3.659 moles (assuming 100% purity), 1.0 equiv.) of linoleic acid (mixture of fatty acids, approximately 60% pure based on linoleic acid moiety) and 8210 grams of THF (0.13% water) were mixed together in a reaction vessel. While stirring and cooling (cooling water temperature 18.6 C.) 948 grams (7.32 moles, 2.0 equivalents) of oxalyl dichloride 98% (Sigma Aldrich) was dosed in 50 minutes. Thereafter, stirring was continued for 120 minutes at room temperature (22 C.).

(2) The reaction crude was concentrated in two steps. First distillation at 180 mbar\40 C. was carried out to obtain 5594 grams of distillate. This was removed and transferred to a rotary evaporator. Concentrating was continued till 55 C. and 30 mbar (reached in steps). The distillate (518 grams) was added to the earlier obtained solvent and excess oxalyl dichloride. The clear dark brown concentrate (1170 grams) will be used in the next step.

Preparation

4-((9Z,12Z)-octadeca-9,12-dienamido)butanoic Acid (C18:2-GABA or GABA Linoleic Acid Compound) Solution in Propylene Glycol

(3) A reaction vessel was charged with a mixture of 7016 grams of water and 280.7 grams (7.02 moles) of sodium hydroxide pellets. To the mixture was added 401.5 grams (3.89 moles, 1.247 equiv.) of gamma amino butyric acid (GABA) and 6244.6 grams of THF. While stirring the contents were cooled to 10 C. Over a period of 1 hour, 935.5 grams (3.13 moles (based on 100% purity, 1.0 equiv.) of linoleoyl chloride prepared in accordance with the aforementioned method added to the mixture. During the dosage the temperature range was 10 C.-6.5 C. While cooling stirring was continued for 1 hour, the temperature was 6.5 C. Cooling was stopped and stirring was continued for an additional hour, the temperature rose to 8.0 C.

(4) The crude product was acidified by dosing 579 grams (5.79 moles) of hydrochloric acid 36%. The pH was adapted from 12.17 to 2.0. After the addition of the acid, stirring was stopped and the mixture was allowed to separate.

(5) After the separation the light yellow lower aqueous phase was removed. The brown organic top phase was stored. The lower aqueous phase was extracted with 3898 grams of ethyl acetate. After stirring and separating the lower phase (8881 grams) was removed and stored. The ethyl acetate top phase (6375 grams) was added to the earlier obtained organic phase.

(6) The combined mixture was washed with a brine solution made out of 585 grams of sodium chloride and 5262 grams of water. After stirring and separating, the lower brine phase (6800 grams) was removed and the brown organic top phase was concentrated in two steps. Step 1 was concentrated at 40 C. and 170 mbar, whereas in step 2a rotary evaporator was employed to remove more solvent (and water) at 55 C. and 32 mbar. In total (steps 1 and 2) 6860 grams of distillate were obtained. 1,2-propylene glycol (PG) was added.

(7) To the product\PG mixture 3235 grams of heptane and 312 grams of water was added. The entire mixture was added to a 10 liter separatory funnel. After shaking and separating, two phases were visible. The lower PG\product phase (4385 grams) was removed and the top heptane phase (2115 grams) was stored.

(8) Residual solvents in the product/propylene glycol (PG) phase were removed in a rotaty evaporator at 55 C. and 22 mbar (reached in steps). As the solvents and water were removed the PG\product mixture became clear. In the end 762 grams of distillate were obtained.

EXAMPLE 2

(9) A spray dried powder of the GABA-Linoleic compound produced in Example 1 was prepared in the following manner:

(10) 400 grams of maltodextrin (DE12) was added to 600 grams of water and 26.7 grams of a propylene glycol solution (representing 1% of the GABA-linoleic acid compound after drying) to form a mixture. The mixture was stirred vigorously at 20 degrees centigrade in an equal volume of water to form a feed. The feed is homogenized using an Ultra Turrax T25 at 25,000 rpm for about 2 minutes. The homogenised feed is spray-dried in a NIRO MOBIL MINOR SPRAY DRYER using a rotary wheel atomiser at 20,000 rpm. Inlet air temperature is kept at 190 C., resulting in an outlet temperature in the range of 90 C.

(11) A dried powder containing 1% GABA-linoleic acid compound was obtained.

(12) The powder was equilibrated in a dessicator above a saturated salt solution for 2 weeks under conditions of 50% relative humidity. Thereafter, the Tg of the equilibrated powder was measured by DSC (Perkin Elmer Pyrus Diamond DSC) using a closed cup method, as follows: A stainless steel cup is filled with the equilibrated powder and closed such that no water can evaporate during measurement. DSC measurement is undertaken using the heat-cool-heat measurement wherein heating is carried out at 10 C./min; cooling at 40 C./min; and heating again at 10 C./min. The Tg measurement is calculate from the mid-point of a curve produced when heat flow is plotted against temperature on the second heat cycle.