Natural vanillin composition

Abstract

This invention relates to natural vanillin compositions comprising at least one compound selected from 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde. The invention also relates to a method for obtaining the natural vanillin compositions according to the invention.

Description

[0001] This application claims priority to patent application No. 1908643, filed in France on July 30, 2019, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] This invention relates to natural vanillin compositions comprising at least one compound selected from 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde. The invention also relates to a method for obtaining the natural vanillin compositions according to the invention. Background Technology

[0003] Vanillin or 4-hydroxy-3-methoxybenzaldehyde can be obtained by various methods known to those skilled in the art, particularly through the following three pathways:

[0004] - A "natural" approach based on biotechnology methods, which specifically involves culturing microorganisms capable of biotransforming a fermentation substrate into vanillin. This method, in which the fermentation substrate is ferulic acid, is known in particular from application EP 0 885 968. The ferulic acid used can be from various sources, particularly derived from rice bran or corn bran.

[0005] - The "synthetic" route involves conventional chemical reactions starting with guaiacol without the involvement of microorganisms. The result of this method is the preparation of vanillin, known as synthetic vanillin.

[0006] Finally, vanillin can also be prepared via a pathway described as “bio-based,” in which vanillin is obtained from eugenol or lignin; specific references can be made to the literature US 2745796, DE 1132113, and the paper by Azadbakht et al. entitled “Preparation of lignin from wood dust as vanillin source and comparison of different extraction methods” in the International Journal of Biology and Biotechnology, 2004, Vol. 1, No. 4, pp. 535-537.

[0007] When the "natural route" is used for the industrial production of vanillin, several side reactions may occur, leading to the formation of numerous byproducts that can affect the sensory properties of natural vanillin. The chemical synthesis of one of these byproducts is specifically described in EP 2763947. Therefore, the preparation of natural vanillin compositions with the correct properties is complex, particularly regarding color or sensory characteristics. This invention aims to efficiently and controllably prepare natural vanillin compositions with known and controllable amounts of byproducts. Summary of the Invention

[0008] Therefore, the first subject of the present invention relates to a composition comprising natural vanillin, and further comprising at least one compound selected from 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde.

[0009] On the other hand, a method for preparing a natural vanillin composition according to the invention is provided, the method comprising a step (a) of fermenting ferulic acid and optionally a step (b) of purifying the natural vanillin composition obtained at the end of step (a).

[0010] Finally, the present invention relates to the use of natural vanillin compositions as flavorings in human food and animal feed, pharmaceuticals, or as fragrances in the cosmetics, perfumes and detergents industries. Detailed Implementation

[0011] In the context of this invention, and unless otherwise stated, the expression "between..." includes limit values. Unless otherwise stated, percentages and ppm are percentages and ppm by weight.

[0012] In the context of this invention, and unless otherwise stated, the term "ppm" means "parts per million". This unit represents a fraction by weight: 1 ppm = 1 mg / kg.

[0013] In the context of this invention, and unless otherwise stated, the term "natural vanillin" may refer to a flavoring substance according to Regulation (EC) No. 1334 / 2008, Section 9.2(c), namely, a flavoring substance obtained from material of plant, animal, or microbial origin by physical, enzymatic, or microbial methods, whether in the raw state of the material or after processing by one or more conventional food preparation methods for human consumption. Natural flavoring substances correspond to substances that are naturally occurring and have been identified in nature. Definitions given by current regulations of other countries or regions may also apply. Preferably, according to the invention, the term "natural vanillin" refers to vanillin obtained by a biotechnological method comprising culturing microorganisms capable of converting fermentation substrates into vanillin. According to the invention, the microorganisms may be wild or genetically modified, particularly for increasing vanillin yield or preventing the formation of byproducts. Very preferably, it may be a method of ferulic acid fermentation, as described in patent application EP 0 885 968. Ferulic acid can come from any source, particularly derived from rice bran, beet pulp, wheat bran, bagasse, sugarcane, or corn, especially corn bran or corn fiber, and especially from starch plants or nixtamalization units.

[0014] According to a first aspect, the present invention relates to a composition comprising natural vanillin and further comprising at least one compound selected from 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde.

[0015] [Chemical Formula 1]

[0016]

[0017] According to a specific aspect, the compositions according to the invention comprise 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde.

[0018] According to a preferred aspect, the composition according to the invention further comprises at least one compound selected from vanillin, vanillic acid, acetylvanillinone, guaiacol, and vinylguaiacol. For example, the composition according to the invention may comprise acetylvanillinone and / or vinylguaiacol.

[0019] [Chemical Formula 2]

[0020]

[0021] Preferably, the composition according to the invention may further comprise at least one compound selected from vanillin, vanillic acid and acetylvanillone.

[0022] Advantageously, the compositions according to the invention exhibit a natural vanillin titer of 90% or more, preferably 95%, and very preferably 99% or more. In particular, the natural vanillin titer is 99.5% or more.

[0023] According to a preferred aspect, the content of 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde by weight is less than or equal to 10,000 ppm, preferably less than or equal to 8,000 ppm, more preferably less than or equal to 7,000 ppm, and very preferably less than or equal to 5,000 ppm, relative to the total weight of the composition.

[0024] According to another preferred aspect, the content of 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde by weight is greater than or equal to 10 ppm, preferably greater than or equal to 200 ppm, more preferably greater than or equal to 500 ppm, and very preferably greater than or equal to 100 ppm, relative to the total weight of the composition.

[0025] Advantageously, the content of 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde by weight is between 600 ppm and 2500 ppm relative to the total weight of the composition.

[0026] According to a preferred aspect, the content of 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde by weight is less than or equal to 5000 ppm, preferably less than or equal to 2500 ppm, more preferably less than or equal to 1000 ppm, and very preferably less than or equal to 900 ppm, relative to the total weight of the composition.

[0027] According to another preferred aspect, the content of 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde by weight is greater than or equal to 10 ppm, preferably greater than or equal to 100 ppm, more preferably greater than or equal to 200 ppm, and very preferably greater than or equal to 300 ppm, relative to the total weight of the composition.

[0028] Advantageously, the content of 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde by weight is between 400 ppm and 800 ppm relative to the total weight of the composition.

[0029] According to the invention, the content of vanillin by weight, relative to the total weight of the composition, is less than or equal to 4000 ppm, preferably less than or equal to 2000 ppm, very preferably less than or equal to 1000 ppm, preferably less than or equal to 800 ppm, preferably less than or equal to 600 ppm, and very preferably less than or equal to 500 ppm. According to the invention, the content of vanillin by weight, relative to the total weight of the composition, is greater than or equal to 1 ppm, preferably greater than or equal to 5 ppm, preferably greater than or equal to 10 ppm, and very preferably greater than or equal to 20 ppm.

[0030] Advantageously, the content of vanillin alcohol by weight is between 50 ppm and 250 ppm relative to the total weight of the composition.

[0031] According to the invention, the content of vanillic acid by weight, relative to the total weight of the composition, is less than or equal to 1000 ppm, preferably less than or equal to 700 ppm, more preferably less than or equal to 500 ppm, and very preferably less than or equal to 200 ppm. According to the invention, the content of vanillic acid by weight, relative to the total weight of the composition, is greater than or equal to 1 ppm, preferably greater than or equal to 5 ppm, more preferably greater than or equal to 10 ppm, and very preferably greater than or equal to 20 ppm.

[0032] Advantageously, the content of vanillic acid by weight is between 50 ppm and 100 ppm relative to the total weight of the composition.

[0033] According to the invention, the content of acetylvanillin by weight relative to the total weight of the composition is less than or equal to 1000 ppm, preferably less than or equal to 800 ppm, more preferably less than or equal to 600 ppm, and very preferably less than or equal to 500 ppm. According to the invention, the content of acetylvanillin by weight relative to the total weight of the composition is greater than or equal to 0.1 ppm, preferably greater than or equal to 5 ppm, more preferably greater than or equal to 10 ppm, and very preferably greater than or equal to 20 ppm.

[0034] Advantageously, the content of acetylvanillin by weight is between 50 ppm and 400 ppm relative to the total weight of the composition.

[0035] According to the invention, the content of guaiacol by weight, relative to the total weight of the composition, is less than or equal to 100 ppm, preferably less than or equal to 50 ppm, more preferably less than or equal to 40 ppm, and very preferably less than or equal to 20 ppm. According to the invention, the content of guaiacol by weight, relative to the total weight of the composition, is greater than or equal to 0.01 ppm, preferably greater than or equal to 0.1 ppm, more preferably greater than or equal to 1 ppm, and very preferably greater than or equal to 10 ppm. According to another alternative of the invention, the vanillin composition does not contain guaiacol.

[0036] According to the invention, the content of vinyl guaiacol by weight, relative to the total weight of the composition, is less than or equal to 100 ppm, preferably less than or equal to 50 ppm, more preferably less than or equal to 40 ppm, and very preferably less than or equal to 20 ppm. According to the invention, the content of vinyl guaiacol by weight, relative to the total weight of the composition, is greater than or equal to 0.01 ppm, preferably greater than or equal to 0.1 ppm, more preferably greater than or equal to 1 ppm, and very preferably greater than or equal to 10 ppm. According to another alternative of the invention, the vanillin composition does not contain vinyl guaiacol, particularly if the vinyl guaiacol content is below the detection limit by liquid chromatography.

[0037] Advantageously, the compositions according to the invention are light-colored. Preferably, the natural vanillin compositions have a color of less than or equal to 400 Hassen, preferably less than or equal to 200 Hassen, more preferably less than or equal to 100 Hassen, very preferably less than or equal to 50 Hassen, and even more preferably less than or equal to 20 Hassen. The color was measured in a 10% by weight ethanol solution. Color measurements were performed using a Konica Minolta CM-5 spectrophotometer with a cuvette having a path length of 10 mm.

[0038] The natural vanillin composition according to the invention can be crystalline or amorphous, preferably crystalline. The natural vanillin composition can be formed as powder, crystals, beads, pellets or flakes.

[0039] Advantageously, the natural vanillin compositions according to the invention have consistent sensory characteristics, particularly in terms of visual appearance, texture, taste, or aroma. Advantageously, the compositions according to the invention do not exhibit false descriptions. In particular, the sensory characteristics of the compositions according to the invention are at least equivalent to those of natural vanillin extracted from pods.

[0040] The natural vanillin compositions according to the present invention can contain other compounds. These compounds present in the compositions are related to methods for preparing natural vanillin. 4-(3-hydroxy-4-methoxybenzyl)-2-methoxyphenol, 4,4'-methylenebis(2-methoxyphenol), ferulic acid, and vanillin dimers and / or trimers may be mentioned in particular, but not exhaustively.

[0041] On the other hand, a method for preparing a natural vanillin composition according to the invention is provided, characterized in that the method comprises a step (a) of fermenting ferulic acid and optionally a step (b) of purifying the crude natural vanillin composition obtained at the end of step (a).

[0042] Step (a): According to the present invention, step (a) of the method is the step of fermenting ferulic acid to produce crude natural vanillin composition.

[0043] Crude natural vanillin composition refers to the composition obtained at the end of the ferulic acid fermentation step. Specifically, crude vanillin composition can be obtained after treatment with an aqueous fermentation medium. For example, the fermentation medium can be separated from the biomass, and then the aqueous phase can be extracted with a suitable solvent. Thus, crude natural vanillin composition can be obtained indirectly at the end of the ferulic acid fermentation step. In particular, during the production of natural vanillin, a liquid composition containing natural vanillin, impurities, and a large amount of solvent (typically food-grade solvents, such as ethyl acetate) is usually recovered.

[0044] Fermentation can be carried out as shown in document EP 0 885 968. Fermentation is usually carried out in an aqueous medium.

[0045] Preferably, at the end of step (a), the weight concentration of natural vanillin relative to the weight of the crude natural vanillin composition is between 0.5% and 60%, preferably between 5% and 40%, and even more preferably between 10% and 35%.

[0046] The crude natural vanillin composition used in step (a) may contain at least one compound selected from 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde. The crude vanillin composition may further contain at least one compound selected from vanillyl alcohol, vanillic acid, acetylvanillinone, guaiacol, and vinylguaiacol.

[0047] Step (b): Step (b) is an optional step for purifying the composition obtained at the end of step (a). In one variant, step (b) is not optional.

[0048] Typically, step (b) may include liquid-liquid extraction as described in document EP 2 791 098; preferably, the liquid-liquid extraction is performed using a solvent compatible with food processing applications.

[0049] Step (b) may also include at least one crystallization step. Alternatively, the purification step may include extraction with supercritical CO2.

[0050] Finally, according to another alternative, step (b) may include the step of evaporating crude natural vanillin as described in document EP 2 948 424 or the stripping step as described in document WO 2018 / 146210.

[0051] According to a specific aspect of the invention, step (b) is an evaporation step in a rotating film evaporator or a falling film evaporator. Advantageously, this step removes compounds with lower volatility than vanillin present in the crude natural vanillin composition obtained at the end of step (a). The lower-volatility compounds are preferably selected from vanillyl alcohol, vanillic acid, acetylvanillinone, and heavy compounds.

[0052] The term "heavy compound" refers to a compound that is less volatile than vanillin under the temperature and pressure conditions under consideration. Among heavy impurities, vanillin dimers and trimers (i.e., compounds that exhibit a backbone with two or three phenyl groups, respectively) and ferulic acid may be mentioned.

[0053] A particular advantage of this embodiment is that it enables the purification of the crude natural vanillin composition obtained at the end of step (a) and allows for the preparation of the natural vanillin composition according to the invention. Impurity levels are well controlled, and the natural vanillin composition has a very light color.

[0054] The method according to the present invention can limit the content of 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde.

[0055] Furthermore, this embodiment makes it possible to avoid the stripping step in the presence of entrained gas and / or vaporized liquid. Therefore, from an industrial perspective, this method is of interest because it is economically feasible.

[0056] The temperature of the heat transfer fluid in step (b) is typically greater than or equal to 130°C, preferably greater than or equal to 145°C. Typically, the temperature of the heat transfer fluid is less than or equal to 230°C, preferably less than or equal to 180°C.

[0057] The pressure for step (b) is typically greater than or equal to 0.4 mbar, preferably greater than or equal to 1 mbar. Typically, the pressure is less than or equal to 75 mbar, preferably less than or equal to 8 mbar, and more preferably less than or equal to 4 mbar.

[0058] Advantageously, relative to the total weight of the crude natural vanillin composition, the weight concentration of natural vanillin in the crude natural vanillin composition used in step (b) is greater than or equal to 10%, preferably greater than or equal to 20%, more preferably greater than or equal to 30%, and even more preferably greater than or equal to 50%, and very preferably greater than or equal to 70%. The method may include the step of concentrating the crude natural vanillin composition.

[0059] According to a preferred aspect, step (b) is performed in the presence of at least one technical aid (e.g., a fluidizing agent). Therefore, according to a specific embodiment of the invention, a fluidizing agent authorized by food regulations can be added to natural vanillin. The fluidizing agent can be added before step (b), particularly between step (a) and step (b). According to another embodiment, the fluidizing agent can be added during step (b).

[0060] The fluidizing agent can be selected from white mineral oil (especially food-grade white mineral oil), polyethylene glycol (especially having an average molecular weight between 200 and 3000 g / mol, preferably between 600 and 1500 g / mol), or castor oil.

[0061] Preferably, step (b) is carried out under an inert atmosphere, particularly under argon, nitrogen, or a mixture thereof. Step (b) can also be carried out under oxygen-deficient air. Typically, the oxygen content is less than or equal to 1%.

[0062] The evaporator enables the recovery of gaseous effluent containing the evaporated natural vanillin composition, which is then condensed to recover the condensate of the natural vanillin composition according to the invention.

[0063] Advantageously, the titer of natural vanillin is greater than or equal to 90%, very preferably greater than 95%, and even more preferably greater than or equal to 99%. Depending on the specific aspect, the titer of vanillin is greater than or equal to 99.5%.

[0064] Advantageously, the natural vanillin condensate obtained at the end of step (b) of the natural vanillin purification process is light-colored. Advantageously, the natural vanillin condensate obtained at the end of step (b) is a natural vanillin composition according to the invention. Advantageously, this natural vanillin condensate obtained at the end of step (b) exhibits consistent sensory properties and is at least equivalent to those of natural vanillin extracted from pods or synthetic vanillin.

[0065] Depending on the specific aspect, purification step (b) does not include the stripping step.

[0066] According to a specific aspect, the method of the present invention does not include the step of melting the natural vanillin composition prior to the evaporation step in a falling film or transfer film evaporator. According to a specific aspect, the natural vanillin composition does not crystallize between step (a) and step (b).

[0067] The method may also include an optional step (c) to shape the natural vanillin composition obtained at the end of step (b), preferably by crystallization, and more preferably by FEMA GRAS. TM Crystallization occurs in a solvent identified by the procedure. In a preferred embodiment, the natural vanillin composition is crystallized or recrystallized from water or a mixture of water and alcohol (particularly ethanol).

[0068] The method according to the invention can be performed either continuously or in batches.

[0069] The present invention also relates to a natural vanillin composition that can be obtained by the method described in the present invention.

[0070] Finally, the present invention relates to the use of natural vanillin compositions as flavorings in human food and animal feed, pharmaceuticals, or as fragrances in the cosmetics, perfumes and detergents industries.

[0071] The following examples are intended to illustrate the invention, and not to limit it.

[0072] If any disclosure of patents, patent applications, and publications cited herein conflicts with the description of this application to the extent that it may lead to ambiguity in terminology, then this description shall prevail.

[0073] Example

[0074] Example 1: The crude natural vanillin composition was prepared by fermentation according to the procedure described in application EP 0 885 968. In addition to the solvent, the crude vanillin composition also contains the compounds listed in Table 1.

[0075] [Table 1]

[0076] Natural vanillin 21% by weight Vanillin 2.7% by weight vanillic acid 0.2% by weight Acetyl vanillin Not measured 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde Not detected 4-Hydroxy-3-(4-Hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde Not detected

[0077] Example 2: The crude natural vanillin composition obtained according to the method of application EP 0 885 968 was purified by vacuum evaporation in a transfer evaporator in the presence of castor oil.

[0078] The properties of the natural vanillin composition according to the present invention:

[0079] [Table 1]

[0080] Natural vanillin 99.7% by weight 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde 1000ppm 4-Hydroxy-3-(4-Hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde 400ppm Color (Hassen) (10% ethanol solution by weight) 20

Claims

1. A composition comprising natural vanillin and further comprising at least one compound selected from 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde and 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde, the composition exhibiting a natural vanillin titer greater than or equal to 99%, wherein, The content of 4-((4-hydroxy-3-methoxybenzyl)oxy)-3-methoxybenzaldehyde by weight is less than or equal to 5000 ppm and greater than or equal to 10 ppm by weight, relative to the total weight of the composition; the content of 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde by weight is less than or equal to 900 ppm and greater than or equal to 10 ppm by weight, relative to the total weight of the composition.

2. The composition of claim 1, further comprising: at least one compound selected from vanillin, vanillic acid, acetylvanillinone, guaiacol, and vinylguaiacol.

3. The composition of claim 1, further comprising: at least one compound selected from vanillin, vanillic acid and acetylvanillone.

4. The composition of claim 1, wherein, The natural vanillin titer is greater than or equal to 99.5%.

5. The composition according to any one of claims 1 to 3, characterized in that Colors less than or equal to 400 Hassen.

6. The composition according to claim 5, characterized in that Colors less than or equal to 200 Hassen.

7. The composition according to claim 5, characterized in that... Colors less than or equal to 100 Hassen.

8. The composition according to claim 5, characterized in that Color less than or equal to 50 Hassen.

9. The composition according to claim 5, characterized in that... Colors less than or equal to 20 Hassen.

10. A method for preparing the natural vanillin composition as described in claims 1 to 9, the method comprising: The fermentation of ferulic acid (a) and the purification of the natural vanillin composition obtained at the end of step (a) (b), wherein step (b) is an evaporation in a transfer film evaporator or a falling film evaporator, the step being carried out in the presence of a technical aid selected from white mineral oil, polyethylene glycol and castor oil.

11. The method of claim 10, wherein, Step (b) includes liquid / liquid extraction or extraction with supercritical CO2.

12. The use of the natural vanillin composition as described in any one of claims 1 to 9 as a flavoring agent in the fields of human food and animal feed, in pharmaceuticals, or as a fragrance in the cosmetics, perfumes and detergents industries.

Images