WO2012159957A1

WO2012159957A1 - Taste modifying compound

Info

Publication number: WO2012159957A1
Application number: PCT/EP2012/059142
Authority: WO
Inventors: Yvan Niclass; Christian Starkenmann
Original assignee: Firmenich SA
Current assignee: Firmenich SA
Priority date: 2011-05-24
Filing date: 2012-05-16
Publication date: 2012-11-29
Anticipated expiration: 2013-11-24

Abstract

The invention provides the use as a flavor precursor of a compound according to formula (I) wherein R₁ is a C₁ to C₅ alkyl or alkenyl group for the generation of certain highly valued onion notes.

Description

TASTE MODIFYING COMPOUND

Technical field

The present invention relates to the field of taste. More particularly, it relates to flavor precursors capable of retaining flavors upon storage and releasing them at a later stage.

The present invention also concerns compositions or articles containing at least one of the aforementioned compounds. Back2round and Prior art

Flavors are used to provide an olfactive and gustatory experience when consuming food. However, many foods require one or more processing steps which involve the use of heat to fulfil various needs, e.g. cooking, sterilization or pasteurization, generation of reaction flavors and so on. This can have adverse consequences upon volatile flavors which can be lost or even destroyed by such heating processes. For this reason, it is known to encapsulate flavors by such methods as extrusion, spray-drying, spray-chilling, coacervation and the like. Such methods can be effective but they can retard undesirably or interfere with the flavor itself, they add complexity to the flavor system and they can even be visible to the naked eye which may in certain circumstances be undesirable. Thus, it would be desirable to provide a flavor that, even if volatile, can survive storage and be released under certain conditions at a desired stage.

The principle of using flavor precursors is known. For instance, WO-A1- 2008/011744 describes precursors of these relate to mono or diglyceride-based lactone flavors.

Onions have been used in foodstuffs and cooking since time immemorial and onion flavor is highly desirable in many applications, such as snack foods. To date, the most usual onion flavor has been onion itself, usually in dried powder and flake form. While this is generally satisfactory, the onions from which the powders and flakes are made can vary in quality and availability, making the achievement of a satisfactory and consistent onion flavor sometimes difficult.

The provision of an onion flavor is described in EP-A-2165612 (Givaudan) where there is provided a flavoring composition comprising a compound selected from S-allyl cysteine and S-l-propenyl cysteine. However, these compounds are limited in that they are transformed primarily into l-sulfanyl-2-propene and 1-sulfanyl-l-propene, which are not fully representative of a rounded onion or garlic flavor insofar as only minute amounts of other important compounds, such as disulfides and poly sulfides, may be formed. It would be desirable to address this issue.

The cysteine propylsulphide conjugate is described in the publication "Cysteine and Glutathione Mixed-Disulfide Conjugates of Thiosulfinates: Chemical Synthesis and Biological Activities", Guodong Zhang, Bin Li, Chen-Hsien Lee, Kirk Parkin, Journal of Agriculture and Food Chemistry 2010, 58, 1564-1571. However, this article refers only to the capacity of various conjugates to induce quinine reductase (QR, a representative phase II enzyme) in murine hepatoma cells (Hepa lclc7) and to inhibit nitric oxide (NO) production in lipopolysaccharide (LPS)-stimulated macrophage cells (RAW 264.7), indicating they have potential cancer preventive and anti-inflammatory activities. Nowhere in this document is there any suggestion that one class of the compounds described therein is suitable for use as flavor precursors.

Thus, to the best of our knowledge no mention or suggestion of any of the compounds of formula (I) below for use as flavor precursors below is made in the prior art.

Summary of the invention

We have now surprisingly discovered that a compound having the formula

Formula (I) wherein Ri is a Ci to C5 alkyl or alkenyl group provides a new flavor precursor for the generation of certain highly valued onion notes.

Accordingly, the present invention provides the use as a flavor precursor of a compound according to formula (I).

The invention further provide the use of a compound according to formula (I) as a flavor precursor to release a flavor composition comprising two or more different compounds having the structure according to formula (II)

Formula (II) wherein R₂ represents H or a Ci to C3 alkyl or alkenyl chain, n represents an integer from 1 to 4 and each dotted line independently denotes that a single or double bond is present.

In a preferred aspect of the invention, there is provided a composition comprising the flavor precursor according to formula (I) in combination with at least one ingredient selected from the group consisting of a flavor carrier, flavor base and optionally at least one flavor adjuvant, the combination providing a flavored article.

In another aspect there is provided a flavor precursor according to formula (I) as part of or incorporated into a foodstuff.

In still a further aspect there is provided a method to enhance, improve or modify the flavor or taste of a flavoring composition or a flavored product, which comprises adding thereto a flavor precursor according to formula (I).

In the context of the present invention, the flavor precursor according to formula (I) includes all isomers and salts thereof as well as any mixture of the isomers and/or salts. Thus, although the R-enantiomer is shown above, the flavor precursor may comprise the S-enantiomer, the R-enantiomer or a mixture thereof. Nevertheless, the R-enantiomer is preferred.

Detailed Description of the Invention

The flavor precursor, as herein defined, is a compound according to the following formula

Formula (I) wherein Ri is a Q to C5 alkyl or alkenyl group. In a preferred aspect, Ri is a Q to C3 alkyl or alkenyl group. More preferably Ri is a C₂ to C₄ alkyl or alkenyl group. Even more preferably Ri is a C3 alkyl or alkenyl group. Most preferably Ri is a propenyl moiety.

The flavor precursor is preferably used for releasing at least two compounds having the structure according to formula (II)

Formula (II) wherein R₂ represents H or a Ci to C3 alkyl or alkenyl chain, n represents an integer from 1 to 4 and each dotted line independently denotes that a single or double bond is present and further wherein for the first compound, n is equal to 2 and for the second compound, n is not equal to 2.

It is particularly preferred that the flavor precursor releases a mixture of compounds comprising a disulfide and a disulfide according to formula (II).

Most preferably there is a large excess of the disulfide compound generated since it is this molecule that provides a key desirable onion flavor. This is achieved by the use of the precursor according to the invention. Indeed, it is found that the amount of disulfide generated is typically greater than 65% by weight based on the total weight of flavors generated by the precursors, and may even be greater than 70% by weight.

Flavor Precursor Mixture

The flavor precursor is preferably used in a food product requiring an onion or alliaceous character. For instance, savory foods, where a garlic or onion-like note is desired, can benefit from the presence of these flavor precursors according to the present invention.

A flavor composition according to the invention is a composition that comprises a flavor precursor according to formula (I) and an additional different flavor ("flavor co- ingredient") and/or a flavor adjuvant. Flavors for use as the flavor co-ingredient are described in numerous literature references such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or in other works of a similar nature, as well as in the abundant patent literature in the field of flavor and the skilled flavorist is readily capable of selecting suitable flavor co-ingredients based on his general knowledge and according to the intended application or desired organoleptic effect.

Flavor adjuvants are well known and may be selected from, for example, without limitation, solvents, binders, diluents, disintegrating agents, lubricants, coloring agents, preservatives, antioxidants, emulsifiers, stabilisers, flavor-enhancers, sweetening agents, anti-caking agents, enzymes, enzyme-containing preparations and the like. Examples of carriers or diluents for flavor or fragrance compounds can be found in, for instance, "Perfume and Flavor Chemicals", S. Arctander, Ed., Vol. I & II, "Perfume and Flavor Materials of Natural Origin, S. Arctander, 1960; in "Flavorings", E. Ziegler and H. Ziegler (ed), Wiley- VCH Weinheim, 1998, and "CTFA Cosmetic Ingredient Handbook".

In a preferred embodiment, a flavor composition comprises the flavor precursor according to formula (I) and an enzyme.

The flavor composition may be added in any suitable form, for example as a liquid, as a paste, or in encapsulated form bound to or coated onto carriers/particles or as a powder.

Foodstuffs

In the context of the present invention "foodstuffs" denotes any composition consumed for nutrition or pleasure. Typical examples include, but are not limited to soups, broths, bouillons, stews, gravies, meat and vegetable extracts, powdered soups, instant noodles, dried pesto mixes, dried savory dishes, stable in-dough flavoring for noodles, frozen foods and snack foods.

Since the present invention relates to a flavor precursor that is particularly suitable for releasing an onion flavor, especially desirable foodstuffs are snack foods, such as crisps and chips, based on potatoes, corn (maize), rice and tapioca.

The flavor precursor may be encapsulated. Suitable encapsulation systems for the flavor precursors of the present invention are described below.

The proportions in which the compounds according to the invention can be incorporated into the various aforementioned articles or products vary within a wide range of values. These values are dependent on the nature of the article to be flavored and on the desired organoleptic effect, as well as the nature of the co-ingredients in a given base, when the compounds according to the invention are mixed with flavoring co- ingredients, solvents or additives commonly used in the art.

In the case of flavored products, the minimum concentration of flavor precursor (I) is preferably at least 0.1 ppm, more preferably 0.2 ppm, even more preferably 0.5 ppm and most preferably 1 ppm. The maximum concentration is preferably 100 ppm, more preferably 80 ppm, even more preferably 70 ppm and most preferably 50 ppm.

Examples

The invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the NMR spectral data were recorded in CDCI₃, with a 400MHz machine for ¹³C, the chemical displacements, δ, are indicated in ppm with respect to TMS as standard, and the coupling constants, /, are expressed in Hz. Example 1

Synthesis of S-propyl-L-cysteine disulfide

3-[(Methoxycarbonyl)dithio]-L-alanine (0.5 g, 2.0 mmole) in anhydrous methanol (10 mL) was added to 1-propane thiol (2 mL, 22 mmole), triethylamine (0.7 mL, 5 mmole) and ethanol. The pH was maintained between 8 and 9 by adding triethylamine (3 x 0.3 mL), then the reaction was stirred over night. The resulting mixture was diluted with water 100 mL and the organic compounds were extracted with pentane. The water phase was loaded on a S1O₂-RPI8 column (internal diameter 4.5 cm, level of dry phase 10 cm). The column was rinsed with water (400 mL), then water with 10% EtOH (200 mL) and the product was eluted with water containing 30% EtOH (500 mL). The product was then lyophilized to provide powdered S-propyl-L-cysteine disulfide (750 mg, yield 69%).

HPLC-TOF High-Resolution MS: C₆H₁₄N0₂S₂, calculated mass 195.03877, measured 195.03709 (difference 8.6 ppm).

HPLC-ESr (BEH-C18, 150): 4.61 min. (MW+H) 196, for SRM fragments used: 107 (100%).

¹³C NMR : 15.2 (q), 24.6 (t), 39.6 (t), 42.7 (t), 54.6 (d), 173.4 (s) (5). Example 2

Preparation of S-allyl-L-cysteine disulfide

3-[(Methoxycarbonyl)dithio]-L-alanine (4.2 g, 16.9 mmole) in anhydrous methanol (30 mL) was added to 2-propene thiol (5.37 g, 74 mmole), triethylamine (2.61 g, 25.8 mmole) and ethanol 30 mL. The pH was maintained between 8 and 9 by adding triethylamine (3 x 0.3 mL), then the reaction was stirred over night. The resulting mixture was diluted with water (100 mL) and the organic compounds were extracted with pentane. The water phase was loaded on a Si0₂-RP18 column (internal diameter 4.5 cm, level of dry phase 10 cm). The column was rinsed with water (400 mL), then the product was eluted with water containing 10, 20, 30 and 40% EtOH (200 mL). The compound 8 was in fractions eluted with 30% aqueous EtOH. The product was then lyophilized to provide S-allyl-L-cysteine disulfide (1.6 g, yield 49%).

HPLC-TOF High-Resolution MS: C6H₁₂N0₂S2, calculated mass 193.0228, measured 193.02312 (difference 1.6 ppm).

HPLC-ESf (BEH-C18, 150): 2.70 min. (M+l) 194, for SRM fragments used: 152

(100%), 105 (30%).

1³C NMR : J39.7 (t), 43.5 (t), 54.6 (d), 122.2 (t), 136.2 (d), 173.6 (s). (5) Example 3

Preparation of 3 S-d-propenyD-L-cysteine disulfide

(E/Z)-l-Propenthiol was obtained after reduction of bis[(E/Z)-l-propenyl] disulfide (0.9 g, 6 mmole) (16) with LiAlH₄ (0.24 g, 6 mmole) in Et₂0 (20 mL) over night at room temperature. Salts and excess L1AIH₄ were removed after careful addition of ice water and HC1 2 M. The organic phase was separated and dried on Na₂S0₄. The volume of Et₂0 was reduced to 5 mL and the solution was added to 3-[(methoxycarbonyl)dithio]-L- alanine (5.5 mmole) in anhydrous methanol (10 mL). Triethylamine was added (0.7 mL, 5 mmole) until the pH was 3-4. After one hour an additional 0.2 mL of triethyl amine was added until the pH was 6-7, then the reaction was stirred over night. The resulting mixture was diluted with water (100 mL) and the organic compounds were extracted with pentane. The water phase was loaded on a Si0₂-RP18 column (internal diameter 4.5 cm, level of dry phase 10 cm). The column was rinsed with water (400 mL), then water with 10% EtOH (200 mL), water with 20% EtOH (200 mL) and the product was eluted with aqueous EtOH 30% (400 mL). The product was lyophilization to obtain 400 mg of a white powder which was further purified by chromatography under the same conditions and only the purest fraction, containing 7, was retained (60 mg, yield 9%).

HPLC-TOF High-Resolution MS: C6H₁₂N0₂S2, calculated mass 193.02101, measured 193.02312 (difference 10.9 ppm).

HPLC-ESf (BEH-C18, 150): 4.48 min. (M+l) 194, for SRM fragments used: 105

(100%), 131 (40%). No separation of (E/Z) isomers.

7-(Z): *H NMR: 6.19 (dq, J = 9.1, 1.6, 1H, H-4); 5.96 (dq, J = 9.1, 6.9, 1H, H-5); 4.26-4.21 (m, 1H, H-2); 3.34 (dd, J = 15.1, 4.0, 1H, H-3); 3.16 (dd, J = 15.1, 8.2, 1H, H-3'); 1-77 (dd, J = 6.9, 1.6, 3H, H-6). ¹³C NMR: δ ΠΑ.Ί (s), 134.5 (d), 129.0 (d), 55.4 (d), 39.6 (t), 16.8 (q);

7-(E) ^lU NMR: 6.17-6.14 (m, 2H, H-4 and H-5); 4.26-4.21 (m, 1H, H-2) ; 3.38 (dd, J = 15.1, 4.1, 1H, H-3); 3.17 (dd, J = 15.1, 7.8, 1H, H-3'); 1-79 (m, 3H, H-6);¹³C NMR : δ 174.6 (s), 137.8 (d), 125.1 (d), 55.5 (d), 40.6 (t), 20.4 (q). Example 4

Onion Soup Preparations

Two flavoring compositions, (A) and (B), for onion soup, are prepared by admixing the following ingredients:

Table 1

prepared as in example 1 To a portion of a standard unflavored canned onion soup are added 20 ppm, relative to the weight of the soup, of the flavoring composition (A).

To the other portion of the above unflavored canned onion soup are added 20 ppm, relative to the weight of the soup, of the flavoring composition (B).

There are thus obtained two flavored canned onion soups, one containing flavor compound from example 1 and the other not containing it.

The soup containing composition (A) has an aggressive, roasted onion and caramelized character.

The soup containing composition (B) has a flavor with a rounded alliaceous, oniony character.

Example 5

Garlic Flavor Preparations

A typical flavor having a garlic roast type flavor character is prepared by admixing the following ingredients in the amounts indicated:

Table 2

Ingredients Parts by weight

Acetylpyrazine at 1.00%* 30.000

Ethyl acrylate at 10.00%* 10.000

Heptanal at 10.00%* 15.000

Benzylmercaptan at 10.00%* 15.000

Caryophyllene at 10.00%* 10.000

Cis-3-hexenol formate at 1.00%* 20.000

2,3,5-Trimethylpyrazine at 10.00%* 70.000

2-Ethyl-3-methylpyrazine at 10.00%* 60.000

Thiol at 10.00%* 40.000

Decanoic acid redist. 5.000

Garlic essential oil 20.000

Isovalerianic aldehyde 5.000 3 -Propylidene- 1 -benzo(C)furanone 10.000

Benzothiazole 20.000

Furaneol^® 25.000

Methylfurfural 40.000

Methylnussol at 10.00%** 10.000

Mustard essential oil 30.000

(E)-2-hexenal 5.000

Diallyl sulfide 350.000

Dipropyl disulfide 50.000

5-Ethyl-3-hydroxy-4-methyl-2(5H)- 5.000

furanone at 1.00%*

Nussol extra 10.000

Propylmercaptan at 10.00%* 100.000

Sulfurobase 30.000

Dimethyl trisulfide at 10.00%* 15.000

Total 1000.000

* In triacetine

** In ethyl citrate

1) Origin: Firmenich SA, Geneva, Switzerland

To this flavor composition there is added the flavor precursor as defined in example 3 in an amount sufficient to provide a final concentration of 1 ppm of this extract in a tasting saline solution (salt 0.5%, MSG 0.05% w/w) where the flavor is used in an amount of 0.001 ppm. The flavor precursor of the invention increases the rounded alliaceous character of the flavor.

Example 6

Beef bouillon preparation A beef bouillon has the following ingredients in the amounts shown. The bouillon is prepared by thoroughly mixing the ingredients. Table 3

(1) ex Firmenich, ref. 967746

(2) ex Firmenich, ref. 927409

(3) ex Firmenich, ref. 946686

(4) ex Firmenich, ref. 992444

(5) ex Firmenich, ref. 909251 20 g of the bouillon is then added to 1 litre of hot water and stirring until dissolved. Next 20 ppm of the flavor precursor as defined in example 3 is added to provide a solution having an enhanced onion note.

Example 7

Instant vegetable cream soup

An instant vegetable cream soup has the following ingredients in the amounts shown. The soup is prepared by thoroughly mixing the ingredients. Table 4

Ingredient % by weight

Creaming agent (1) 22.0

Table Salt 7.5

Yeast extract (2) 3.0 Skimmed milk powder 12.0

Onion powder 2.7

Modified starch (3) 33.0

Beaded palm oil (4) 1.6

Monosodium glutamate 1.5

Garlic powder (5) 0.15

Tomato powder (6) 2.4

Carrot powder (7) 1.2

Leek powder (8) 2.0

Red bell pepper (9) 0.45

Rubbed parsley 0.25

Maltodextrin 10.25

(1) ref. 936110

(2) ref. 946686

(3) VA70T, ex Prejel.

(4) ref. 948082

(5) ref. 905113

(6) ref. 988136

(7) ref. 920511

(8) ref. 974504

(9) ref. 974548

(10) ref. 909251

The soup is prepared by mixing the ingredients thoroughly, and lOOg of the mixture is added to 1 liter of hot water and stirred until dissolved. The soup is then divided into 2 portions, to one of which is added 20ppm of the flavor precursor prepared in example 3. The soup containing the compound of example 1 has a more rounded onion note.

Claims

1. Use as a flavor precursor of a compound according to formula (I)

Formula (I)

2. Use according to claim 1 wherein the compound has the structure

Formula (Γ)

3. Use according to any one of the preceding claims wherein Ri is a Ci to C₃ alkyl or alkenyl group.

4. Use according to any one of the preceding claims wherein Ri is a C₂ to C₄ alkyl or alkenyl group.

5. Use according to any one of the preceding claims wherein Ri is a C₃ alkyl alkenyl group

6. Use according to any one of the preceding claims wherein Ri is a propenyl group.

7. Use according to any one of the preceding claims wherein the flavor precursor releases an onion or alliaceous flavor.

8. Use of the compound according to claim 1 or claim 2 as a flavor precursor to release a flavor composition comprising at least a first and a second compound having the structure according to formula (II)

Formula (II) wherein R₂ represents H or a Ci to C3 alkyl or alkenyl chain, n represents an integer from 1 to 4, each dotted line independently denotes that a single or double bond is present and further wherein for the first compound, n is equal to 2 and for the second compound, n is not equal to 2.

9. Use according to claim 8 wherein the two or more different compounds comprise a disulfide and a disulfide.

10. Use according to claim 8 wherein the content of disulfide generated is greater than 65% by weight based on the total weight of flavors generated by the flavor precursor(s).