WO2013000595A1

WO2013000595A1 - Flavoring compound

Info

Publication number: WO2013000595A1
Application number: PCT/EP2012/056104
Authority: WO
Inventors: Estelle Delort; Erik Decorzant
Original assignee: Firmenich SA
Current assignee: Firmenich SA
Priority date: 2011-06-30
Filing date: 2012-04-03
Publication date: 2013-01-03
Anticipated expiration: 2013-12-30

Abstract

The present invention relates to the field of flavors. More particularly, it concerns the use as flavoring ingredient of a compound of formula (I) wherein R represents a C_1-3 alkyl group, and in particular a methyl or ethyl group. The inventions compound can be used to impart or reinforce the coumarine and/or vanilla notes of a flavoring composition or of a flavored food.

Description

FLAVORING COMPOUND

Technical field

The present invention relates to the field of flavors. More particularly, it concerns the use of an ester as a flavoring ingredient to impart or reinforce a coumarine and/or vanilla tonality.

Furthermore, the present invention concerns also the compositions or articles containing at least one of said compounds. Prior art

The ethyl ester, i.e. ethyl melilotate or ethyl 3-(2-hydroxyphenyl)propanoate, is known in the prior art. See for instance Z. Lebensm. Unters. Forsch. (1995) 201:278-82, HPLC Analysis of Tonka Bean Extracts; Ehlers D., Pfister M., Bork WR., Toffel- Nadolny P.

However, to the best of our knowledge, nowhere the prior art is it described or mentioned that such a compound has organoleptic properties that can be used to impart or reinforce coumarine or vanilla notes.

Description of the invention

We have now surprisingly discovered that a compound of formula

wherein R represents a C₁-3 alkyl group, and in particular a methyl or ethyl group;

can be used as flavoring ingredient, for instance to impart or reinforce the coumarine and/or vanilla notes of a flavoring composition or of a flavored food.

As specific examples of the invention's compounds, one may cite, as non-limiting example, the following ones in Table 1 : Table 1 : Invention's compounds and their flavor properties

The compound ethyl 3-(2-hydroxyphenyl)propanoate is particularly appreciated in flavor for the reconstitution of coumarine. Indeed, said compound brings sweetness, extends vanilla character, provides sweet-cream-vanilla character and complexity in the compositions wherein it is added.

According to a particular embodiment of the invention, the compound of formula (I) is ethyl melilotate (i.e. ethyl 3-(2-hydroxyphenyl)propanoate).

In other words it concerns a method to confer, enhance, improve or modify the flavor properties of a flavoring composition or of a flavored article, which method comprises adding to said composition or article an effective amount of at least a compound of formula (I). By "use of a compound of formula (I)" it has to be understood here also the use of any composition containing compound (I) and which can be advantageously employed in the flavor industry as active ingredients.

Said compositions, which in fact can be advantageously employed as flavoring ingredients, are also an object of the present invention.

Therefore, another object of the present invention is a flavoring composition comprising:

i) as flavoring ingredient, at least one invention's compound as defined above;

ii) at least one ingredient selected from the group consisting of a flavor carrier and a flavor base; and

iii) optionally at least one flavor adjuvant.

According to a particular embodiment of the invention, said flavoring composition comprises:

i) as flavoring ingredient, at least one invention's compound as defined above; ii) a flavor base of the savory, roast and/or caramel type; and

iii) optionally at least one ingredient selected from the group consisting of a flavor carrier and flavor adjuvant.

By "flavor carrier" we mean here a material which is practically neutral from a flavor point of view, i.e. that does not significantly alter the organoleptic properties of flavoring ingredients. Said carrier may be a liquid or a solid.

As liquid carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in flavors. A detailed description of the nature and type of solvents commonly used in flavor cannot be exhaustive. However, one can cite as non- limiting example solvents such as propylene glycol, triacetine, triethyl citrate, benzylic alcohol, ethanol, vegetal oils or terpenes.

As solid carrier one may cite, as non-limiting examples, absorbing gums or polymers, or yet encapsulating materials. Examples of such materials may comprise wall- forming and plasticizing materials, such as mono, di- or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins, or yet the materials cited in reference texts such as H. Scherz, Hydrokolloids : Stabilisatoren, Dickungs- und Gehermittel in Lebensmittel, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitat, Behr's VerlagGmbH & Co., Hamburg, 1996. The encapsulation is a well known process to a person skilled in the art, and may be performed, for instance, using techniques such as spray-drying, agglomeration or yet extrusion ; or consists of a coating encapsulation, including coacervation and complex coacervation techniques.

By "flavor base" we mean here a composition comprising at least one flavoring co-ingredient.

Said flavoring co-ingredient is not of the formula (I). Moreover, by "flavoring co- ingredient" it is meant here a compound, which is used in flavoring preparations or compositions to impart a hedonic effect. In other words such a co-ingredient, to be considered as being a flavoring one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the taste of a composition, and not just as having a taste.

The nature and type of the flavoring co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of its general knowledge and according to intended use or application and the desired organoleptic effect. In general terms, these flavoring co-ingredients belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of flavor. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of flavoring compounds.

However, according to a particular embodiment of the invention, said flavor base advantageously comprises Lactadione^® (3-hydroxy-3-methyl-2,4-nonanedione; origin : Firmenich SA) or Natactone^® ((6R)-perhydro-3,6-dimethyl-benzo[b]furan-2-one; origin : Firmenich SA).

Therefore a flavoring composition comprising at least a compound of formula (I) and at least a compound of formula (Π) is also an object of the present invention.

By "flavor adjuvant" we mean here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in flavoring bases cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.

An invention's composition consisting of at least one compound of formula (I) and at least one flavor carrier represents a particular embodiment of the invention as well as a flavoring composition comprising at least one compound of formula (I), at least one flavor carrier, at least one flavor base, and optionally at least one flavor adjuvant.

It is useful to mention here that the possibility to have, in the compositions mentioned above, more than one compound of formula (I) is important as it enables the flavorist to prepare accords, flavors, possessing the flavor tonality of various compounds of the invention, creating thus new tools for his work.

Preferably, any mixture resulting directly from a chemical synthesis, e.g. without an adequate purification, in which the compound of the invention would be involved as a starting, intermediate or end-product could not be considered as a flavoring composition according to the invention.

Moreover, a compound of formula (I) can be advantageously incorporated into flavored articles to positively impart, or modify, the taste of said articles. Consequently, a flavored article comprising:

i) as flavoring ingredient, at least one compound of formula (I), as defined above, or an invention's flavoring composition; and

ii) a foodstuff base;

is also an object of the present invention.

Suitable foodstuff bases, e.g. foods or beverages, include dairy and confectionary products where a vanilla tonality is desired, coffee, cocoa, chocolate and all applications where a coumarine tonality is desired, alcoholic beverages having molasses/caramelic notes such as rum and sugar cane derived beverages. Other suitable foodstuff bases could be snacks and biscuits.

For the sake of clarity, it has to be mentioned that, by "foodstuff base" we mean here an edible product, e.g. a food or a beverage. Therefore, a flavored article according to the invention comprises the functional formulation, as well as optionally additional benefit agents, corresponding to a desired edible product and a flavor effective amount of at least an invention' s compound.

The nature and type of the constituents of the foodstuffs or beverages do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature of said product.

The proportions in which the compounds according to the invention can be incorporated into the various aforementioned articles or compositions 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 flavoring compositions, typical concentrations are in the order of

0.01 % to 3 % by weight, or even more, of the compounds of the invention based on the weight of the consumer product into which they are incorporated. Concentrations lower than these, such as in the order of 0.0001% to 0.5% by weight, can be used when these compounds are incorporated into flavored articles, percentage being relative to the weight of the article. Examples

The invention will now be described in further detail by way of the following example, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade (°C); the NMR spectral data were recorded in CDCI₃ (if not stated otherwise) with a 360 or 400 MHz machine for H and ¹³C, the chemical shifts δ are indicated in ppm with respect to TMS as standard, the coupling constants J are expressed in Hz.

Example 1 Preparation of the Compound According to the Invention

A) Ethyl melilotate (ethyl 3-(2-hydroxyphenyl)propanoate)

Into a 2L reactor were charged 4.6g sodium ethylate (20% in ethanol) and 65g ethanol. The pot temperature was raised to 60°C and over the course of 1 hour a solution of 200g dihydrocoumarine in 122g ethanol was added. Stirring was continued for 20 minutes and the pot temperature was then set to 50°C. 7g of 10% w/w aqueous H₂SO₄ were added and after stirring for 10 minutes excess ethanol was distilled under reduced pressure. To the 259g of crude product was added 22g Emkapol. Wiped film distillation yielded 25 lg of product (GC: 99%, yield: 92%).

1³C NMR: 14.1 (q), 24.8 (t), 35.2 (t), 61.3 (t), 117.0 (d), 120.8 (d), 127.3 (s), 128.0 (d), 130.5 (d), 154.2 (s), 175.5 (s).

B) Methyl 3-(2-hydroxyphenyl)propanoate

In a 250mL flask, 3-(2-hydroxyphenyl)propanoic acid (lO.OOg, 98%), methanol (30.0 g, 15 molar equivalents) and H₂S0₄ (1.2 g, 0.2 molar equivalents) were refluxed for 3 hours, the methanol was concentrated and the mixture was poured onto ether, washed with water sat. NaHCC^ (3 times), brine (3 times), dried over MGSO₄ and concentrated, yielding a white slightly yellow solid (10.44 g, yield 96.0%, purity: GC/MS 99%). ^1JC NMR: 25.0 (t), 34.8 (t), 52.2 (q), 116.7 (d), 120.7 (d), 127.2 (s), 127.9 (d), 130.4 (d), 154.2 (s), 175.8 (s).

C) Propyl 3-(2-hydroxyphenyl)propanoate

Ethyl 3-(2-hydroxyphenyl)propanoate, prepared as described above, was dissolved in propanol (50 mL) at room temperature. KH, washed with pentane (3 times), slowly added, and the reaction mixture was heated at 80 °C during 1.5 hour. The mixture was poured onto diethyl ether and washed with brine (3 times) and deionised water (2 times), then dried over MgS0₄ and concentrated. The residue (2.59 g) was purified by bulk-to-bulk distillation (175°C under 0.059 mbar), yielding a colorless liquid (1.77 g, yield 82%, purity: GC/MS 99%).

¹³C NMR: 10.3 (q), 21.8 (t), 24.8 (t), 35.1 (t), 66.9 (t), 117.0 (d), 120.7 (d), 127.3 (s), 127.9 (d), 130.5 (d), 154.3 (s), 175.7 (s). D) Isopropyl 3-(2-hydroxyphenyl)propanoate

Ethyl 3-(2-hydroxyphenyl)propanoate, prepared as described above, was dissolved in propanol (50 mL) at room temperature. KH, washed with pentane (3 times), slowly added, and the reaction mixture was heated at 80 °C during 4 hours. The mixture was poured onto diethyl ether and washed with brine (3 times) and deionised water (2 times), then dried over MgS0₄ and concentrated. The residue (2.01 g) was purified by bulk-to-bulk distillation (180 °C under 0.042 mbar), yielding a colorless liquid (1.64 g, yield 76%, purity: GC/MS 99%).

¹³C NMR: 21.7 (q), 21.7 (q), 24.9 (t), 35.4 (t), 68.9 (d), 117.0 (d), 120.6 (d), 127.4 (s), 127.9 (d), 130.5 (d), 154.4 (s), 175.2 (s).

Example 2

Preparation of a flavouring composition and of a flavoured article comprising the invention's compound

A flavouring composition having a "tea character" was prepared by admixing the following ingredients : Ingredients Parts by weight

A) m

Ethyl melilotate 0.5 —

propylene glycol 85.0 85.5

Trimethyl cyclohexenone 1.5 1.5

Beta Ionone 1.0 1.0

Cis Jasmone 5.0 5.0

FEMA N° 3774* 2.0 2.0

Hexanal 5.0 5_

100.0 100.0

2,6,10,10-tetramethyl-l-oxaspiro[4.5]d( The addition of 0.14 part by weight of composition A) or B) to teas provided two new teas, respectively A') and B').

The flavour of tea A') in addition to the tea flavours presented a vanilla taste that was not present in tea B').

Claims

1. Use of a compound of formula (I),

as flavoring ingredient to impart or reinforce the coumarine and/or vanilla notes of a flavoring composition or of a flavored food.

2. Use according to claim 1, characterized in that said compound (I) is ethyl 3-(2-hydroxyphenyl)propanoate.

3. A flavoring composition comprising:

i) as flavoring ingredient, at least one compound of formula (I), as defined in claim 1 or 2;

iii) optionally at least one flavor adjuvant.

4. A flavoring composition according to claim 3, comprising at least one compound of formula (I), as defined in claim 1, and at least one compound selected from the group consisting of 3-hydroxy-3-methylnonane-2,4-dione and Natactone.

5. A flavoring composition according to claim 3 or 4, comprising

ii) a flavor base of the savory, roast and/or caramel type; and

6. A flavored article comprising:

i) at least one compound of formula (I), as defined in claim 1 or 2, or a composition as defined in any one of claims 3 to 5 ; and

ii) a foodstuff base.

7. A flavored article according to claim 6, characterized in that the foodstuff base is a savory cube, an instant soup, a canned soup, a preserved meat, instant noodles, a frozen dish or preparation, a sauce, a flavored oil and/or spread, a toffee, an alcoholic beverage having molasses/caramelic note, a snack or biscuit, or a pizza.