N-acylated methionine sulfoxides as food flavouring compounds
11319285 · 2022-05-03
Assignee
Inventors
Cpc classification
C07C317/50
CHEMISTRY; METALLURGY
A23V2002/00
HUMAN NECESSITIES
International classification
C07C317/50
CHEMISTRY; METALLURGY
Abstract
A flavour composition comprising a compound of formula (I) and edible salts thereof, wherein R.sub.1 is an alkyl residue containing 2 to 18 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 stock solution comprising 0.01 to 1% by weight of a compound of formula (I) corresponding to the formula ##STR00019## wherein R.sub.1 is an alkyl residue containing 2 to 18 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, wherein the Met-SO residue of the compound of formula (I) is selected from the group consisting of: N-geranoyl-Met, N-palmitoyl-Met, N-palmitenoyl-Met, N-oleoyl-Met, N-stearoyl-Met, N-linoleoyl-Met and N-linolenoyl-Met and wherein, the compound of formula (I) accentuates the taste or mouth feel characteristics of edible products in which it is incorporated when the sulfoxide compound is present at a level of from 1 part per billion to 10 parts per million in the edible product.
2. The stock solution of claim 1 further comprising a carrier material.
3. The stock solution of claim 2, wherein the carrier material comprises monosaccharides, disaccharides, trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteins, pectins, or mixtures thereof.
4. The stock solution of claim 2, wherein the carrier material comprises sucrose, glucose, lactose, levulose, fructose, maltose, ribose, dextrose, isomalt, sorbitol, mannitol, xylitol, lactitol, maltitol, pentatol, arabinose, pentose, xylose, galactose, maltodextrin, dextrin, chemically modified starch, hydrogenated starch hydrolysate, succinylated or hydrolysed starch, agar, carrageenan, gum arabic, gum accacia, tragacanth, alginates, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose derivatives or mixtures thereof.
5. The stock solution according to claim 1 further comprising an adjuvant.
6. The stock solution according to claim 5, wherein the adjuvant comprises a solvent, binder, diluent, disintegrating agent, lubricant, colouring agent, preservative, antioxidant, emulsifier, stabiliser, anti-caking agent or mixtures thereof.
7. The stock solution according to claim 6, wherein the solvent comprises water, alcohol, ethanol, triacetine, oils, fats, vegetable oil, miglyol, or mixtures thereof.
8. The stock solution of claim 1 further comprising a solvent, wherein the solvent is selected from the group consisting of ethanol, triacetine, glycerol, miglyol and mixtures thereof.
9. The stock solution according to claim 5, wherein the adjuvant comprises an antioxidant.
10. The stock solution according to claim 9, wherein the antioxidant is present in an amount of about 10 ppm to about 1,000 ppm based on the total weight of the stock solution.
11. The stock solution according to claim 9, wherein the antioxidant is selected from the group consisting of vitamin C, vitamin E, rosemary extract, antrancine, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and mixtures thereof.
Description
SYNTHESIS EXAMPLES
(1) 1. General Structure
(2) ##STR00002##
R.sup.1=is a straight chain hydrocarbon group having 2 to 18 carbon atoms and containing zero to three double bonds or
R.sup.1 is a [(1E)-2,6-dimethylhepta-1,5-dien-1-yl]-group.
Several compounds belonging to that general formula have been synthesized according to one of the 2 procedure described below.
2. Synthesis
2.1 Route A: (Acid Chloride Method)
General Procedure for Making Amide A:
(3) To a solution of methionine sulfoxide (0.6 g, 3.63 mmol) in 1:1 THF: 1N NaOH (20 ml:20 ml) at room temperature was added oleoyl chloride (1.1 g, 3.66 mmol) dropwise. The reaction was then stirred at room temperature for 7 hours. THF was removed under vacuum. Concentrated HCl was added to adjust the pH to 2. The aqueous layer was then extracted with EtOA.sub.c3X and the organic layers were combined. The combined organic layer was washed with water, brine, dried (Na.sub.2SO.sub.4) and concentrated. The residue was chromatographed on silica gel (5% MeOH/DCM, 0.1% formic acid) to give 0.56 g (34.1%) of the product as a white solid.
(4) 2.2 Route B (DCC Method)
(5) To a solution of (z)-dodec-5-enoic acid (5.04 mmol) with 1-hydroxypyrrolidine-2,5-dione (7.56 mmol) in THF (30 ml) was added DCC (7.77 mmol) at 0° C. The mixture was stirred at room temperature overnight. The formed solids (dicyclohexylurea) were removed by filtration and the filtrate was added to a solution of 2-amino-4-(methylsulfinyl) butanoic acid (6.05 mmol) and potassium carbonate (6.08 mmol) in water (30 ml) at room temperature. The mixture was stirred at room temperature for 7 hours. THF was evaporated under vacuum and the aqueous residue was acidified with conc. HCl to pH of 2. The aqueous layer was then extracted with EtOA.sub.c3X and the organic layers were combined. The combined organic layer was washed with water, brine, dried (Na.sub.2SO.sub.4) and concentrated. The residue was chromatographed on silica gel (5% MeOH/DCM, 0.1% formic acid) to give 0.81 g (36.8%) of clear oil as product.
(6) 2.3 All Synthesized Compounds
(7) TABLE-US-00001 TABLE 1 List of synthesized compounds Amino Carboxylic Structure acid acid Structure Route 1 Methionine sulfoxide C2:0
3. NMR Data (Examples)
3.1 Structure 3 Met-SO C12:1
(8) ##STR00015##
(9) (2S)-2-((Z)-dodec-5-enamido)-4-(methylsulfinyl)butanoic acid: 36.8% yield;
(10) .sup.1H NMR (300 MHz, CD.sub.3OD) δ ppm 0.90 (t, J=7.5 Hz, 3H), 1.24-1.40 (m, 8H), 1.61-1.73 (q, J=6.6 Hz, 2H), 2.01-2.17 (m, 5H), 2.27 (t, J=5.7 Hz, 2H), 2.30-2.44 (m, 1H), 2.65 (s, 3H), 2.75-2.99 (m, 2H), 4.50-4.58 (m, 1H), 5.32-5.45 (m, 2H).
(11) .sup.13C NMR (300 MHz, CD.sub.3OD) δ ppm 12.94, 22.19, 24.34, 24.49, 25.40, 25.42, 26.22, 26.70, 28.55, 29.31, 31.42, 34.87, 36.67, 49.71, 49.77, 50.88, 51.13, 128.26, 130.31, 172.58, 174.71, 174.77.
(12) 3.2 Structure 5 Met-SO C18:1
(13) ##STR00016##
(14) (2S)-4-(methylsulfinyl)-2-oleamidobutanoic acid: 34.1% yield;
(15) .sup.1H NMR (300 MHz, CD.sub.3OD) δ ppm 0.88 (t, J=8.1 Hz, 3H), 1.28-1.33 (m, 20H), 1.56-1.67 (q, J=8.7 Hz, 2H), 2.03-2.17 (m, 5H), 2.25 (t, J=6.3 Hz, 2H), 2.31-2.41 (m, 1H), 2.63 (s, 3H), 2.72-2.97 (m, 2H), 4.50-4.57 (m, 1H), 5.28-5.39 (m, 2H).
(16) .sup.13C NMR (300 MHz, CD.sub.3OD) δ ppm 12.96, 22.24, 24.37, 24.45, 25.34, 25.36, 26.64, 26.66, 28.76, 28.80, 28.85, 28.87, 28.94, 29.11, 29.35, 31.56, 35.34, 36.69, 49.75, 49.83, 50.89, 51.15, 129.32, 129.38, 172.66, 174.91, 174.97.
(17) In accordance with another embodiment, the applicant has now found that a S-Methylcysteine sulfoxide connected to a fatty acid residue through an amide bond may be employed as flavour ingredients that complement or accentuate the taste and mouthfeel characteristics of edible compositions into which they are incorporated across a wide category of flavour applications.
(18) The present disclosure provides in a first aspect compounds of formula (II)
(19) ##STR00017##
their edible salts, and their use in edible compositions wherein
R.sub.1 is an alkyl residue containing 2 to 18 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.
(20) In one embodiment, a compound of the formula (II) is (2S)-3-(methylsulfinyl)-2-oleamidopropanoic acid synthesized according to Route A described above and having the structure:
(21) ##STR00018##
(22) The sulfoxide compounds of formula (II) impart remarkable organoleptic properties to edible compositions to which they are added. In particular, they impart highly intense, authentic and harmonious flavour, and a roundness and fullness to edible compositions containing them.
(23) More particularly, the compounds can be incorporated into an edible product to impart a remarkable mouthfeel, body and enhanced fat perception; or an enhanced umami or salt taste. They are particularly useful in applications low in fat, salt and umami.
(24) This finding was all the more surprising considering that when applicant tasted the compounds in dilute aqueous solution, they were either tasteless or they exhibited a disappointing, faintly fatty taste profile. As such, they appeared to be quite unsuitable for use in flavour applications. Only their combination with flavour co-ingredients and the judicious selection of their usage levels was it possible to discover the remarkable organoleptic properties of these compounds. Their effect on edible compositions is quite unusual in that rather than exerting a characteristic flavour profile to a foodstuff or a beverage, they actually complement, lift or accentuate the essential or authentic flavour and mouth feel characteristics of the foods or beverages in which they are incorporated. Accordingly, the compounds of the present disclosure find utility in a broad spectrum of applications in the food and beverage industry, as well as in health and wellness.
(25) Accordingly, in one embodiment, a method of conferring flavour and/or mouthfeel to, or improving taste and/or mouthfeel of an edible composition, which method comprises adding to said composition a sulfoxide compound of formula (II) defined herein.
(26) The remarkable organoleptic effects are observed when the sulfoxide compounds of formula (II) are incorporated into an edible composition containing one or more flavour co-ingredients.
(27) The flavour co-ingredients may be sugars, fats, salt (e.g. sodium chloride), MSG, calcium ions, phosphate ions, organic acids, proteins, purines and mixtures thereof.
APPLICATION EXAMPLES
(28) Testing with Methionine Sulfoxide Derivatives
(29) 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
(30) Comparison in a Cheese Onion Crisp
(31) Base is a crisp with proprietary cheese onion powder flavoring @ 6%
(32) Base plus Met-SO C18:1 at 10 ppb: salt/taste level enhanced; onion character more fried
(33) Comparison in Onion Soup
(34) Base is Campbell's® French onion soup
(35) Base plus Met-SO C18:1 at 10 ppb: slightly stronger in salt; onion character slightly enhanced
(36) Comparison in Onion Soup
(37) Base is UNOX ‘Franse uiensoep’
(38) Base plus Met-SO C18:1 at 10 ppb: slightly stronger in salt; onion character increased
APPLICATION EXAMPLES
(39) Testing with S-Methylcysteine Sulfoxide Derivative
(40) 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.
(41) Comparison in a Cheese Sauce
(42) Base is a Maggie Saus Base with 0.05 g ethanol
(43) Base plus (2S)-3-(methylsulfinyl)-2-oleamidopropanoic acid at 0.5 ppm: salt/umami/fullness/cheesiness level enhanced.
(44) 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.
(45) The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.
(46) While particular embodiments have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.