WO2012072630A1

WO2012072630A1 - Process for producing flavours

Info

Publication number: WO2012072630A1
Application number: PCT/EP2011/071286
Authority: WO
Inventors: David C. Bom; Gary Kleman; Yuangang Zhang
Original assignee: Givaudan SA
Current assignee: Givaudan SA
Priority date: 2010-11-29
Filing date: 2011-11-29
Publication date: 2012-06-07
Anticipated expiration: 2013-05-29

Abstract

Disclosed is a process for the preparation of flavor compositions with unique aroma profiles obtained by carrying out a reaction of 3,4,5-trihydroxypentan-2-one with an amino acid source.

Description

PROCESS FOR PRODUCING FLAVOURS

This disclosure refers to a process for the preparation of flavor compositions with unique flavor profiles obtained by carrying out a reaction of 3,4,5-trihydroxypentan-2- one with amino acids.

There is an ongoing demand in industry for compositions having unique natural flavoring properties and which are suitable for use in a variety of products. It has now been found that flavor compositions possessing unique flavor profiles can be obtained by carrying out a heat-induced reaction of 3 ,4,5-trihydroxypentan-2-one with an amino acid source in a liquid phase. The flavor compositions obtained by this process were found to have remarkable flavor characteristics and are particularly useful for imparting pleasant flavor notes to foodstuffs and beverages.

Thus there is provided in a first aspect, a process for preparing a flavoring composition comprising

a) admixing 3,4,5-trihydroxypentan-2-one with a liquid selected from the group consisting of water, oil and alcohol (e.g. methanol or ethanol), or a mixture thereof and an amino acid source;

b) adjusting the pH to 2-10, e.g., in a range of about 3 to about 8; and

c) heating the admixture to a treatment temperature of 50° C or higher, e.g. in a range from about 50 - about 180°C, such as about 80 - 140°C. The flavoring composition thus prepared may then optionally be cooled down to room temperature and then either be used as crude product or optionally further processed, e.g. by phase separation, or extraction, e.g. using solvents commonly used in the flavor industry, e.g. 1 ,2,3-triacetoxypropane (more generally known as triacetin) ortriethyl citrate. In a final step the products may be spray dried or encapsulated using techniques known to the skilled person.

Suitable oils are of any kind which are acceptable in the food industry, such as vegetable oils, e.g. sunflower oil, corn oil, soybean oil, palm oil, a medium chain triglyceride (MCT oil) oil, or mixtures thereof. 3,4,5-Trihydroxypentan-2-one, which exists naturally in an equilibrium with its cyclic form, comprises two chiral centers and as such may exist as two diastereomers (la known as 1 -deoxy-D-xylulose (DXX); lb known as 1 -deoxy-D-ribulose) as depicted below, each of which may exist as enantiomer pairs.

la lb

deoxyxylulose deoxyribulose

It is an aspect of certain embodiments to use 3,4,5-trihydroxypentan-2-one as isomeric mixture, as racemic mixture (3S/4R and 3R/4S) or, in a further aspect, to use 1-deoxy- D-xylulose (DXX; la) in its optically pure form.

DXX is commercially available (Carbosynth Limited, or Echelon Biosciences Inc.). It can be produced chemically following the general procedure as described, e.g. by Meyer O., J.F.Hoeffler, C.Grosdemange-Billiard, and M. Rohmer (Tetrahedron 2004 60:12153- 12162). Optionally DXX may be produced according to the following procedure, as depicted in Scheme 1 below, by treating the aldehyde 1 with the ylide 2 in

dichloromethane providing the olefin intermediate 3 as described by Giner et al.

(Tetrahedron Lett., 1998, pp. 2479-2482). Di hydroxy lation of 3 using catalytic osmium tetroxide and W-methylmorpholine-/V-oxide (NMO) in a 50:50 mixture of t-butanol and water provides the racemic diol 4. Finally, hydrogenolysis of the benzyl protecting group provides the desired racemic deoxyxylulose (DXX) as a mixture of its linear (5) and cyclic (6) forms.

Racemic Synthesis of deoxyxylulose

deoxyxylulose (DXX)

Optically pure DXX could be obtained by treatment of intermediate 3 with catalytic osmium tetroxide, 4-methylmorpholine-/V-oxide NMO and AD-mix β (e.g. offered by Sigma-Aldrich), followed by hydrogenolysis leading to 1-deoxy-D-xylulose with an ee of 98%, as depicted in Scheme 2. Instead of using methanol as solvent, as reported by Giner et al., one may use ethyl acetate, thus eliminating the problem of solvolysis of 6. In addition, high pressure (60 psi = 4.137 bar) of hydrogen along with Pearlman's catalyst (Pd(OH)2) led to a more efficient hydrogenolysis relative to the reported Pd/C.

Scheme 2: Asymmetric route to 1 -deoxy-D-xylulose

P

1-deoxy-D-xylulose (DXX) DXX from a microbial or botanical source may also be used. Non-phosphorylated DXX has been found, for example, in the broth of a Streptomyces species (Rohmer, . 2007. Pure Applied Chemistry. 79(4):739-751). It has also been made enzymatically with the enzyme 1-deoxyxylulose synthase. Both the phosphorylated and non-phosphorylated form may be produced depending upon the starting material (if the glyceraldehyde is phosphorylated) (Brammer and Meyers. 2009. Organic Letters. 1 1(20):4748-4751 ).

By an "amino acid source" is meant free amino acids, such as alanine, phenylalanine, glutamic acid, lysine, valine, proline, leucine, ornilhine, tyrosine, glycine and citrulllne, and salts thereof (e.g. lysine hydrochloride), or a mixture thereof, as well as peptides or hydrolyzed proteins, which may be selected from acidic or enzymatic hydrolyzates of materials rich in vegetable or animal proteins, such as oil seed cakes, soybeans, sugar extraction residues, cereal germs and the extracts or autolyzates of mocroorganisms rich in proteins, such as brewer's or baker's yeast, hydrolyzed dairy proteins such as enzyme modified cheeses or certain bacteria grown on hydrocarbon based substrates. Yeast extracts are commonly available from DSM Food Specialties, Bio-springer and Kerry Bio-science.

The molar ratio between 3,4,5-trihydroxypentan-2-one and the amino acid source may be preferably between about 3 :1 to about 1 :10, the ratio being calculated on the estimated free amino acid present. However, even much higher amounts of amino acid equivalents may be added.

In a further aspect one may add organic solvents such as triacetin (1 ,2,3- triacetoxypropane) ortriethylcitrate to the mixture before adjusting the pH. One may also add carbohydrates, in particular monosaccharides and oligosaccharides (e.g. di- and tri-saccharides) or mixtures thereof. The carbohydrates may be added in its pure form or in form of fruit juices or other food sources containing them. The pH range of the mixture may be adjusted with acid or base solutions, e.g. sodium hydroxide solution, sodium bicarbonate, sodium citrate, or sodium phosphate, to about 2 - 10, e.g., about pH 3 - 8. Controlling the pH during the reaction may maintain conditions to favor certain desired aroma chemicals. Particular treatment temperatures are about 100 - 140° C (e.g. up to 130° C) and the reaction mixture may be maintained at these temperatures for about 30 minutes to 48 hours, e.g., 1 to 16 hours. However even higher temperatures might be suitable, in particular when a continuous reactor is used for the process instead of a batch reactor. The appropriate time and temperature conditions may easily be evaluated by a person skilled in the art.

The flavoring composition obtainable through the process as hereinabove described may be used alone or in combination with a base material. As used herein, the "base material" includes all known flavor ingredients that will modify, enhance or create flavor to a food product or beverage to be flavored.

In addition to additional flavor ingredients the flavor composition may contain other ingredients useful as excipients such as carriers, diluents or bulking agents or the like, the purpose of which is to aid in the processing of a flavor composition or a product containing same, or otherwise impart a desirable property on the composition or product. Examples of such ingredients may include carbohydrates and carbohydrate polymers, e.g. polysaccharides, cyclodextrines, starches, starch hydrolysates, modified starches, modified celluloses, gums such as gum arabic, ghatti gum, traganth, karaya, carrageenan, guar, locust bean, alginates, pectin, inulin, or xanthan.

In a further aspect there is provided an aroma product comprising flavor compositions, obtainable through the process comprising

b) adjusting the pH to 2 -10, e.g., in a range of about 3 to about 8;

c) heating the admixture to a treatment temperature of 50° C or higher, e.g. in a range from about 50 - about 180°C, such as about 80 - 140°C;and

d) optionally cooling down to room temperature.

Instead of adding flavor compositions obtained through the process as herein above described to a product, one may add the admixture of 3,4,5-trihydroxypentan-2-one and the amino acid source in form of an emulsion or suspension to a consumable product first and the heating step (c) may take place when the consumable product is heated and thus generating the flavoring composition during the normal cooking process of the consumable product.

Thus there is provided in a further aspect a process for preparing a flavoring

composition comprising

a) admixing 3,4,5-trihydroxypentan-2-one with a liquid selected from the group consisting of water, oil, alcohol (e.g. methanol or ethanol), and mixtures thereof, and an amino acid source;

b) admixing the mixture of step a) to a consumable product; and

c) heating the admixture to a treatment temperature of 50° C or higher, e.g. in a range from about 50 - about 180°C, such as about 80 - 140°C.

The thus obtained consumable product may then either be consumed in its heated form or cooled down either to room temperature or may be frozen.

The flavor composition obtained through the process as hereinabove described may be used to impart unique aroma to consumable products. By "consumable product" is meant any product, whether natural or manufactured, intended for oral intake, either for ingestion, or for oral use only followed by spitting out. In general, this includes any foodstuff, beverage, confectionery, medicinal or cosmetic oral care composition, pharmaceutical and the like.

Typical non-limiting examples of consumable products include: Animal protein from any desired animal source, for example, beef, pork, poultry, lamb, kangaroo, shell fish, crustaceans, fish, and combinations thereof;

Vegetable protein from any vegetable source, for example, lupin protein, wheat protein, soy protein, and combinations thereof;

Fruit-derived products, for example, those derived from tomatoes, apples, avocado, pears, peaches, cherries, apricots, plums, grapes, oranges, grapefruit, lemons, limes, cranberries, raspberries, blueberries, watermelon, cantelope, muskmelon, honeydew melon, strawberries, banana, and combinations thereof; Vegetable-derived products, for example, those derived from peas, carrots, com, potatoes, beans, cabbage, tomatoes, celery, broccoli, cauliflower, and leeks, nuts and nut products, processed foods, vegetable products, and food compositions thereof; Cereals and cereal-derived products, for example, farinaceous matter including grains such as, rice, com, milo, sorghum, barley, and wheat, and the like, and products derived therefrom; tapioca products, sago products, and food compositions thereof; pasta (for example, ground pasta), breading, and food compositions, dough derived from any of a variety of dough sources, including wheat dough, corn dough, potato dough, soybean douyh, lice douyli, and combinations thereof, baker's products, biscuit products, pastry products, bread products, baking-powder, and food compositions thereof;

Confectionery and dessert products, for example, hard and soft candies, chocolate, ice creams, chewing gums, jellies and jams;

Milk and dairy products, for example, yoghurts, cheese products, butter and butter substitute products, milk and milk substitute products, milk powders, soy products, edible oils and fat products and food compositions thereof;

Beverages, for example, carbonated and non-carbonated beverages, alcoholic drinks such as beers, wines and spirits, non-alcoholic drinks such as soft drinks and sodas, including forms requiring reconstitution including, without limitation, beverage powder, milk-based beverage powder, sugar-free beverage powder, beverage syrup, beverage concentrate, coffee and tea, and food extracts;

Medicinal products, whether for ingestion or oral use only, for example,

pharmaceuticals and nutraceuticals, syrups, pastes, aerosols, emulsions, tablets and lozenges, and gums;

Oral care compositions, for example, mouthwashes, toothpastes and tooth gels, malodo counteractants and breath fresheners in solid, liquid and aerosol form;

Food additives and ingredients, for example, yeast products, salt and spice products, snack foods, savory products, mustard products, vinegar products, seasonings, plant extracts, meat extracts, condiments, and gelatins;

Prepared food products, including such products preserved by being, for example, dried, powdered, baked, refrigerated, frozen, fermented, pasteurized, sterilized, brined, for example, sauces (condiments), gravies, soups, prepared meat and vegetable products, pizzas, pre-cooked and oven-ready meals and microwave meals. The concentration of the flavor composition obtained through the process as hereinabove described required may vary over a wide range, depending on the desired taste and aroma effects, but as a general guide, they are employed in concentrations of from 1 to 2000 ppm by weight of the product in consumable form. Good results are obtained by using from 5 to 1000 ppm, e.g. about 10 - about 200 ppm in the final product. However, these values are given only by way of example, since the experienced flavorist may also achieve effects with lower or higher concentrations.

The compositions and methods are now further described with reference to the following non-limiting examples.

These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art without departing from the scope of the claims. It should be understood that the embodiments described are not only in the alternative, but can be combined.

Example 1. Reaction of 1 -deoxy-D-xylulose with amino acids

In a 25 ml microwave vial, DXX was added to deionized water at a final concentration as indicated in Table 1 below. The appropriate amino acid was added to a final concentration as shown in Table 1 below. After mixing, the pH was adjusted as indicated in Table 1 using either H3PO4 or NaOH. After capping the microwave vial, it was placed in the automated microwave (Emrys™ Optimizer from Biotage AB, Sweden), and heated (30 minutes for A - D, 1 hour for E and 2 hours for F) at the temperature as indicated in the table below. The vessels were removed from the device and allowed to cool overnight at room temperature. Samples were then tasted in warm water at 0.1% (w/w) by six trained panelists.

Table 1 : Reactions of DXX with an amino acid source

A B C D E F

Amino Acid source Proline Leucine Ornithine Tyrosine Mixture* Mixture^** (mM) 180 180 220 165 320 395

DXX (mM) 90 90 90 90 75 50 pH (before reaction) 3 3 6 3 8 10

Reaction temp. °C 140 140 140 110 150 150 ^*: Amino acid source was a mixture of Leucine, Alanine and Phenylalanine (2 :1 :1) ^**: Amino acid source was a mixture of Serine, Threonine, Proline and Cystine

(10 : 5 : 5 : 2)

The aroma descriptors for the reaction product thus obtained are as follows:

Composition A: Basmatic rice, tortilla note, roasted note.

Composition B: Strong roast brown note, burnt, chocolate.

Composition C: popcorn, nutty, chocolate.

Composition D: creamy, dairy, slight roasted.

Composition E: malty, chocolate-like, ashy, grilled

Composition F: ashy, coffee-like, seared meat

Example 2: comparison of DXX with other carbohydrates

Following the general procedure described in Example 1 , L-Tyrosine (165 mM) was admixed with a carbohydrate in a weight to weight ratio of approximately 3:1. The pH of the reaction mixture was adjusted to pH 3 prior to heating at 140°C for 30 minutes in a pressure reactor.

The thus obtained reaction product was tested in warm water at 1% (w/w) by a group of trained panelists. The results are shown below in Table 2.

Table 2:

Carbohydrate Concentration Taste description

DXX (racemic) 75 mM Dariy, creamy, metallic

DXX (D-form) 75 mM dairy, metallic, bloody, stronger

compared to DXX (racemic)

Xylose 67 mM Not perceivable

Glucose 56 mM Not perceivable

Fructose 56 mM Slightly roasted

Ribose 67 mM Earthy pyrazine-iike As can be seen from the table above the reaction product obtained from DXX compared to the reaction product obtained by using reducing sugars such as Xylose, Glucose, Fructose or Ribose is more intense and possesses superior flavor profiles i.e. dairy, and metallic, bioody notes which is desirable, for example, for savory and diary products.

Example 3: comparison of DXX with other carbohydrates

Following the general procedure described in Example 1 , L-Alanine (337 mM) was admixed with a carbohydrate In a weight to weight ratio of approximately 3:1. The pH of the reaction mixture was adjusted to pH 6 prior to heating at 140°C for 30 minutes in a pressure reactor.

The thus obtained reaction product was tested in warm water at 1% (w/w) by a group of trained panelists. The results are shown below in Table 3.

Table 3:

As can be seen from the table above the reaction product obtained from DXX compared to the reaction product obtained by using reducing sugars such as Xylose, Glucose, Fructose or Ribose is more intense with unique flavor profile such as bloody, metallic which is desirable for, for example for savory products.

Example 4: 3-in-1 Coffee Beverage

Sample 4A Sample 4B % by weight % by weight

Whole milk 50 50

Sucrose 8 8

Coffee extract 5 5

Sodium bicarbonate 0.04 0.04

Sugar Ester - P 1670 (Mitsubishi-Kagaku Foods Corp) 0.03 0.03

Sugar Ester- S 570 (Mitsubishi-Kagaku Foods Corp) 0.03 0.03

Water 36.9 36.8

Composition F of Example 1 0.1

Sample 4A and 4B were tested by a group of 9 trained panelists. Sample 6b was described to be creamier, burnt ending, less bitter, more rounded, slightly nutty, pleasant note, more chocolate aroma compared to sample 6A.

Example 5: Baked Cookie

Sample 5A Sample 5B

% by weight % by weight

All purpose flour 46.58 46.18

Table salt 0.29 0.29

Baking powder 0.48 0.48

Unsalted butter 18.52 18.52

Sugar 23.22 23.22

Egg 10.91 10.91

Composition C of Example 1 0.40

Sample 5a and 5B were tested by a group of 8 trained panelists. Sample 5B was described to be tastier (i.e. more flavor, more aroma, more buttery, more creamy, more nutty/tortilla).

Claims

1. A process comprising

a. admixing 3,4,5-irihydroxypentan-2-one with a liquid selected from the group consisting of water, oil, alcohol, and mixtures thereof and an amino acid source;

b. adjusting the pH to 2 -10; and

c. heating the admixture to a treatment temperature of 50°C or higher.

2. A process according to claim 1 wherein the admixture is heated for at least 30

minutes.

3. A process according to claim 1 wherein the admixture is heated for up to 48 hours.

4. A process according to claim 1 admixing (3S,4 )-3,4,5-trihydroxypentan-2-one

(=DXX) with the amino acid source.

5. A process according to claim 1 wherein 3,4,5-trihydroxypentan-2-one is obtained from a microbial source.

6. A process according to claim 1 wherein the amino acid source is selected from the group consisting of free amino acids, salts of amino acids, peptides, hydrolyzed proteins, autolyzates of microorganisms, hydrolyzed dairy proteins, and mixtures thereof.

7. A process according to claim 1 wherein the admixture resulting from step b) is added to a consumable product and the heating step c) takes place during the cooking process of the consumable product.

8. A product comprising a flavor composition obtainable through the process as defined in any one of the proceeding claims.

9. A product according to claim 8 wherein the product is a foodstuff or beverage.

10. A product according to claim 9 wherein the foodstuff comprises 1 to 2000 ppm of the flavor composition based on the weight of the foodstuff in consumable form.

11. A method of imparting an aroma comprising the step of adding a flavor composition obtained through the process as defined in claim 1 to foodstuff or beverages.