WO2021019005A1 - Procede de traitement d'une composition comprenant de la vanilline naturelle - Google Patents
Procede de traitement d'une composition comprenant de la vanilline naturelle Download PDFInfo
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- WO2021019005A1 WO2021019005A1 PCT/EP2020/071489 EP2020071489W WO2021019005A1 WO 2021019005 A1 WO2021019005 A1 WO 2021019005A1 EP 2020071489 W EP2020071489 W EP 2020071489W WO 2021019005 A1 WO2021019005 A1 WO 2021019005A1
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- 0 **C(*(OCc1ccc(*)c(O)c1)=C)O Chemical compound **C(*(OCc1ccc(*)c(O)c1)=C)O 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/204—Aromatic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
- A61K47/14—Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
- C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
- C07C69/157—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/30—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with trihydroxylic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
Definitions
- the present invention relates to a method of treating a composition comprising natural vanillin by separating a compound of formula (I).
- PRIOR ART Vanillin or 4-hydroxy-3-methoxybenzaldehyde, can be obtained by various methods known to those skilled in the art, and in particular by the following three routes:
- vanillin can also be prepared according to a route described as “biobased” in which the vanillin is obtained from lignin, one can cite in particular the documents US Pat. No. 2745796, DE 1132113 and the article entitled “Preparation of lignin from wood dust as vanillin. source and comparison of different extraction method ”by Azadbakht et al. in International Journal of Biology and Biotechnology, 2004, vol 1, No 4, pp 535-537 or from eugenol.
- natural vanillin can be purified.
- document WO 2018/146210 describes a process for purifying natural vanillin comprising at least one step of stripping a liquid stream comprising natural vanillin with an entrainment gas and / or a vaporized liquid. Although this process allows the natural vanillin to be purified satisfactorily, the vanillic alcohol is not removed satisfactorily.
- the present invention aims to provide an effective solution making it possible to avoid side reactions with natural vanillin so as to improve the overall yield of the purification of natural vanillin, while maintaining or even improving its organoleptic properties.
- a first object of the present invention relates to a process for treating a composition (C) resulting from a process for the production of natural vanillin comprising natural vanillin and vanillic alcohol comprising:
- n is equal to 0 or 1
- R is chosen from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group, or R is a group of formula - (WO ) mX, in which W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and the average molecular weight of the group - (W-0) m- is between 200 and 3000 g / mol and X is chosen between H and a unit of formula (II)
- step (i) is carried out in the presence of natural vanillin and allows the formation of a composition (Cl) or (C2);
- Another aspect relates to a process for purifying a composition comprising natural vanillin and vanillic alcohol by separating a compound of formula (I).
- the present invention also relates to a process for preparing a compound of formula (I) in the presence of natural vanillin.
- the present invention relates to the use of a natural vanillin composition as a flavoring in the field of human and animal food, pharmaceuticals, or as a perfume in the cosmetics industry, perfumery and detergency.
- natural vanillin can designate a flavoring substance according to article 9.2c) of the CEI 334/2008 regulation, that is to say obtained by physical processes. , enzymatic or microbiological from materials of plant, animal or microbiological origin taken as is or after their transformation for human consumption by one or more of the traditional methods of preparation of foodstuffs.
- a natural flavoring substance is a substance that is naturally present and has been identified in nature. The definitions given by the regulations in force in other countries or zones may also apply.
- the term “natural vanillin” according to the present invention denotes vanillin obtained by a biotechnological process.
- the term “natural vanillin” designates the vanillin obtained by a microbiological process, in particular comprising the culture of a microorganism capable of allowing the transformation of a fermentation substrate into vanillin.
- the microorganism can be wild or be genetically modified, in particular in order to improve performance, for example to improve the yield of vanillin, to limit or avoid the formation of by-products or to increase productivity.
- it may be a ferulic acid fermentation process, as described in patent application EP 0885968.
- Ferulic acid can be of any origin, in particular derived from rice bran or pulp of beet, wheat bran, bagasse, sugar cane or maize, in particular maize bran or maize fibers, in particular obtained from starches or nixtamalization units.
- alkyl represents a linear or branched, saturated or unsaturated chain.
- an alkyl group comprises from 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms, even more preferably from 1 to 6 carbon atoms.
- An alkyl group may preferably be chosen from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, tert-butyl.
- the alkyl group can be substituted by at least one hydroxyl group.
- the alkyl group substituted by at least one hydroxyl group can be -CH2-CH (OH) - CH2-OH.
- a first object of the present invention relates to a process for treating a composition (C) resulting from a process for the production of natural vanillin comprising natural vanillin and vanillic alcohol, said treatment process comprising:
- n is equal to 0 or 1
- R is chosen from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group, or a group of formula - (WO) mX , in which W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and the average molecular weight of the group - (W-0) m- is between 200 and 3000 g / mol and X is chosen between H and a unit of formula (II)
- n is equal to 0 and / or R is a butyl group.
- the invention relates in particular to a process for treating a composition (C) comprising natural vanillin and vanillic alcohol in which - composition (C) is obtained from a process for producing natural vanillin - l Vanillic alcohol is converted to the compound of formula I above, and in which a natural vanilla composition is purified.
- the mass concentration of natural vanillin in composition (C) is between 0.50 and 99%, preferably between 0.50% and 60%, preferably between 5% and 40% and even more preferably between 10% and 35% relative to the mass of the natural vanillin composition resulting from a process for the production of natural vanillin.
- composition (C) resulting from a process for the production of natural vanillin comprises vanillic alcohol.
- the mass concentration of vanillic alcohol is between 0.1% and 5%, preferably between 0.5% and 4% and even more preferably between 1% and 2.5% relative to the mass of the composition (C ) natural vanillin from a natural vanillin production process.
- composition (C) can also comprise at least one compound chosen from vanillic acid, acetovanillone, guaiacol and vinyl guaiacol.
- composition (C) comprises G acetovanillone, guaiacol is also present.
- the present invention may further comprise a preliminary stage of fermentation of a substrate, preferably ferulic acid, for the production of a composition resulting from a process for the production of natural vanillin comprising vanillic alcohol.
- the fermentation can be carried out as indicated in document EP 0885968.
- the fermentation is generally carried out in an aqueous medium.
- Composition (C) can be obtained from the fermentation medium or after treatment of the aqueous medium obtained directly at the end of the fermentation, making it possible in particular to remove the fermentation biomass.
- Composition (C) used according to the treatment process of the present invention is generally obtained at the end of the fermentation step and optionally of the treatment of the aqueous medium directly obtained at the end of the fermentation.
- Composition (C) can be in aqueous solution, or in a water / solvent mixture, preferably water / organic solvent.
- the organic solvent is generally a food solvent, in particular a solvent registered on the FEMA GRAS list.
- ethanol isopropanol, butanol, isobutylalcohol, glycols, acetates, such as ethyl acetate, propyl.
- step (i) is a step of forming a compound of formula (I) according to the following formula:
- n is equal to 0 or 1
- R is chosen from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group, or a group of formula - (WO) mX , in which W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and and the average molecular weight of the group - (W-0) m- is between 200 and 3000 g / mol and X is chosen between H and a unit of formula (II)
- the average molecular weight of the - (W-0) m- group is between 200 and 3000 g / mol, preferably greater than or equal to 300 g / mol, more preferably greater than or equal to 350 g / mol.
- the average molecular weight of the - (W-0) m- group is generally less than or equal to 2000 g / mol, preferably less than or equal to 1500 g / mol.
- the average molecular weight of the - (W-0) m- group can be 400 g / mol or 600 g / mol.
- step (i) is a step of forming a compound of formula (Ia) according to the following formula:
- R is chosen from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group, or a group of formula - (W-0) m- X, in which W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and the average molecular weight of the group - (W-0) m- is between 200 and 3000 g / mol and X is chosen between H and a unit of formula (II)
- step (i) is a step of forming a compound of formula (Ib) according to the following formula:
- R is chosen from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group, or a group of formula - (W-0) m- X, in which W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and the average molecular weight of the - (WO) m- group is between 200 and 3000 g / mol and X is chosen between H and a unit of formula (II)
- the group R is preferably chosen from ethyl, n-butyl, n-propyl, i-propyl, i-butyl, optionally substituted with a hydroxyl group.
- the group R can be chosen from ethyl, n-butyl, OH-CH2-CH2-, OH-CH2- CH (CH3) -.
- the R group is chosen from the above groups further comprising -CH2-CH (OH) -CH2-OH.
- the compound of formula (Ia) is chosen from the group consisting of the compounds of formulas A to D:
- the compound of formula (Ib) is chosen from the group consisting of the compounds of formulas E to H:
- step (i) is an etherification or esterification reaction of the vanillic alcohol present in composition (C).
- the etherification or esterification reaction is carried out in the presence of natural vanillin.
- the etherification or esterification reaction is selective with respect to vanillic alcohol.
- the etherification or esterification reaction is advantageously carried out without degradation of the natural vanillin.
- less than 10% by weight of the natural vanillin present in composition (C) is degraded, preferably less than 5%, more preferably less than 1%, even more preferably less than 0.1%.
- the amount of degraded natural vanillin can be calculated according to the following formula: (amount of natural vanillin initially in the composition (C) - amount of natural vanillin remaining after step (i)) / (amount of natural vanillin initially in the composition (VS)).
- the etherification or esterification reaction is carried out in the presence of a compound selected from the group consisting of ROH, RCOOH, and HO- (W-0) m -H, in which R is selected from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group, and W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and the average molecular weight of the compound HO- (W-0) m -H is between 200 and 3000 g / mol.
- R is selected from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group
- W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and the average molecular weight of the compound HO- (W-0) m -H is between 200 and 3000 g
- the etherification reaction can comprise bringing the vanillic alcohol present in composition (C) into contact with a compound of formula ROH, R being defined above.
- the esterification reaction can comprise bringing the vanillic alcohol into contact with a compound of formula RCOOH, R being as defined above.
- the primary alcohol group of the vanillic alcohol reacts selectively with the compound of formula ROH or RCOOH to form the corresponding ether or ester of formula (I).
- the invention relates in particular to a process for treating a composition (C) in which a composition C1 is formed, the composition (C) comprising natural vanillin and vanillic alcohol, said treatment process comprising:
- the average molecular weight of the compound HO - (WO) m- H is between 200 and 3000 g / mol, preferably greater than or equal to 300 g / mol, more preferably greater than or equal to 350 g / mol.
- the average molecular weight of the HO - (WO) mH group is generally less than or equal to 2000 g / mol, preferably less than or equal to 1500 g / mol.
- the average molecular weight of the HO - (WO) m- H group can be 400 g / mol or 600 g / mol.
- the etherification or esterification reaction is carried out in the presence of a compound which can be used in the food industry.
- the reaction is carried out in the presence of an acid.
- the acid can be a strong acid.
- the acid is selected from the group consisting of HCl, H2SO4, para-toluenesulfonic acid (p-TsOH).
- the acid can also be a Lewis acid.
- the sulfuric acid makes it possible to avoid the chlorination reaction of vanillin which can be observed with HCl.
- the reaction can be carried out in the presence of an inorganic compound in solid form and exhibiting acidic properties, such as a zeolite, in particular titanosilicalite, silicalite or oxides of silica, aluminum, titanium or zirconium.
- the reaction can be carried out in the presence of the zeolites described in the document Angew. Chem. Int. Ed. 2007, 46, 298-300.
- reaction can also be carried out in the presence of a cation exchange resin, in particular of the Amberlite type as described in document CN101165038.
- a cation exchange resin in particular of the Amberlite type as described in document CN101165038.
- the etherification or esterification reaction can be carried out enzymatically.
- the acid is generally used in a catalytic amount.
- the amount of acid used is between 0.001 equivalent and 0.9 equivalent relative to the amount of vanillic alcohol present in composition (C).
- the reaction can be carried out at a temperature between 10 ° C and 100 ° C, preferably between 20 ° C and 80 ° C, preferably at a temperature less than or equal to 50 ° C, and more preferably at a temperature between 25 ° C and 40 ° C.
- the reaction is generally carried out at atmospheric pressure.
- a composition (Cl) is obtained comprising natural vanillin and a compound of formula (I).
- the composition (C1) can also comprise at least one compound chosen from vanillic acid, vanillic alcohol, acetovanillone, guaiacol and vinyl guaiacol.
- the composition (Cl) comprises between 0.1 ppm and 500 ppm of vanillic alcohol, preferably the composition comprises less than 200 ppm of vanillic alcohol, more preferably less than 100 ppm and even more preferably less than 50 ppm.
- the mass ratio between the vanillic alcohol and the vanillin in the composition (Cl) is less than or equal to 0.5, preferably less than or equal to 0.2, very preferably less than or equal to 0.1 and even more preferably less than or equal to 0.01.
- step (i) also allows the formation of a compound of formula (III), according to the following formula, from vanillic acid present in composition (C):
- n is equal to 0 or 1
- R is chosen from an alkyl group, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl, alkoxy or amine group, or a group of formula - (WO) mX , in which W is an alkyl chain, linear or branched, comprising from 1 to 4 carbon atoms and and the average molecular weight of the group - (W-0) m- is between 200 and 3000 g / mol and X is chosen between H and a unit of formula (IV)
- the formation of the compound of formula (III) is carried out in the presence of natural vanillin.
- the formation of the compound of formula (III) can be simultaneous with the formation of the compound of formula (I).
- a composition (C2) is obtained comprising natural vanillin, a compound of formula (I) and / or a compound of formula (PI).
- the composition (C2) can also comprise at least one compound chosen from vanillic acid, vanillic alcohol, acetovanillone, guaiacol and vinyl guaiacol.
- the composition (C2) comprises between 0.1 ppm and 500 ppm of vanillic alcohol, preferably the composition comprises less than 200 ppm of vanillic alcohol, more preferably less than 100 ppm and even more preferably less than 50 ppm.
- the composition (C2) comprises between 0.1 ppm and 500 ppm of vanillic acid, preferably the composition comprises less than 200 ppm of vanillic acid, more preferably less than 100 ppm and even more preferably less than 50 ppm.
- the mass ratio between vanillic alcohol and vanillin in composition (C2) is less than or equal to 0.5, preferably less than or equal to 0.2, very preferably less than or equal to 0.1 and even more preferably less than or equal to 0.01.
- the mass ratio between vanillic acid and vanillin in composition (C2) is less than or equal to 0.5, preferably less than or equal to 0.2, very preferably less than or equal to 0.1 and even more preferably less than or equal to 0.01.
- step (ii) is a step of recovering natural vanillin and / or recovering a compound of formula (I), present in composition (Cl) or (C2).
- step (ii) allows the recovery of the natural vanillin.
- the natural vanillin obtained from step (ii) is purified natural vanillin.
- the natural vanillin obtained at the end of step (ii) is a composition comprising purified natural vanillin.
- the natural vanillin obtained at the end of step (ii) comprises between 0.1 ppm and 500 ppm of vanillic alcohol, preferably the composition comprises less than 200 ppm of vanillic alcohol, more preferably less than 100 ppm and even more preferably less than 50 ppm.
- the natural vanillin obtained at the end of step (ii) comprises between 0 and 200 ppm of 4 - ((4-hydroxy-3-methoxybenzyl) oxy) -3 -methoxybenzaldehyde or 4-hydroxy- 3- (4-hydroxy-3-methoxybenzyl) -5 -methoxybenzaldehyde.
- the content of 4 - ((4- hydroxy-3 -methoxybenzyl) oxy) -3 -methoxybenzaldehyde or 4-hydroxy-3 - (4-hydroxy-3 - methoxybenzyl) -5-methoxybenzaldehyde is less than or equal to 100 ppm , preferably less than or equal to 50 ppm and more preferably less than or equal to 20 ppm.
- the content of 4 - ((4-hydroxy-3-methoxybenzyl) oxy) -3 -methoxybenzaldehyde or 4-hydroxy-3- (4-hydroxy-3-methoxybenzyl) -5-methoxybenzaldehyde is greater than or equal to 0, 01 ppm, and more preferably greater than or equal to 0.1 ppm.
- the treatment process according to the present invention also makes it possible to improve the overall yield of the treatment process compared with conventional purification methods.
- the method may comprise an additional step (iii) in which the natural vanillin obtained at the end of step (ii) is shaped, preferably in the form of crystals, powder, beads, pearls.
- the titer of natural vanillin at the end of step (ii) or (iii) is greater than or equal to 95%, preferably greater than or equal to 97%, very preferably greater than or equal to 99% , and even more preferably greater than or equal to 99.5%.
- the titer of natural vanillin at the end of step (ii) or (iii) is greater than or equal to 99.95%.
- the natural vanillin at the end of step (ii) or (iii) is weakly colored.
- the natural vanillin at the end of step (ii) or (iii) has a color less than or equal to 400 Hazen, preferably less than or equal to 200 Hazen, more preferably less than or equal to 100 Hazen, very preferably less than or equal to 50 Hazen and even more preferably less than or equal to 20 Hazen.
- the coloring is measured in an ethanolic solution at 10% by weight. Color measurements are performed with a Konica Minolta CM-5 spectrophotometer using a cuvette with an optical path of 10 mm.
- the natural vanillin at the end of step (ii) or (iii) exhibits compliant organoleptic properties, in particular in terms of visual appearance, texture, taste or fragrance.
- the composition according to the present invention does not exhibit false notes.
- the organoleptic profile of the composition according to the present invention is at least equivalent to the organoleptic profile of the natural vanillin extracted from pods.
- step (ii) allows the recovery of the compound of formula (I).
- the natural vanillin content in the compound of formula (I) is less than or equal to 200 ppm, preferably less than or equal to 100 ppm.
- the natural vanillin content in the compound of formula (I) is greater than or equal to 0.1 ppm.
- step (ii) allows the recovery of the natural vanillin and the compound of formula (I) is not recovered.
- the compound of formula (I) can be degraded during step (ii).
- step (ii) comprises the recovery of the natural vanillin and the recovery of a compound of formula (I).
- the steps for recovering the natural vanillin and the compound of formula (I) can be carried out simultaneously or successively in any order.
- the purification yield of natural vanillin is greater than or equal to 75%, preferably greater than or equal to 80%, preferably greater than or equal to 90%, even more preferably greater than or equal to 95%, and very preferably greater than or equal to 99%.
- the purification yield of natural vanillin corresponds to the ratio between the amount of natural vanillin isolated at the end of step (ii) and the amount of natural vanillin in composition (C).
- Step (ii) can be carried out by vacuum distillation, in particular in a falling film evaporator or a scraped film evaporator in order to prevent thermal degradation phenomena.
- Step (ii) can in particular be carried out under the conditions described in document WO 2018/146210 or WO2014 / 114590.
- step (ii) can be carried out under the conditions described in EP 2791098.
- step (i) when step (i) is carried out in the presence of an acid, the process according to the present invention can comprise an optional neutralization step, at the end of step (i) and before step ( ii).
- the neutralization step is not optional and / or can be carried out during step (ii).
- Neutralization can be carried out in the presence of a weak base or of a strong base.
- the neutralization can be carried out with NaOH, KOH, in solid form or in aqueous solution.
- the neutralization can be carried out in the presence of NaHCCb, KHCO 3 , Na 2 C0 3 , in solid form or in aqueous solution.
- the present invention relates to a process for purifying a composition comprising natural vanillin and vanillic alcohol by separating a compound of formula (I).
- the present invention also relates to a process for preparing a compound of formula (I) in the presence of natural vanillin.
- the natural vanillin that can be obtained according to the process of the present invention is also an object of the present invention.
- the compound of formula (I) obtainable according to the process of the present invention is also an object of the present invention.
- a compound is considered to be natural with regard to the legislation, in particular in the United States.
- natural compound is meant a compound meeting the definition provided by legislation, for example in the United States this means that the compound must be obtained by physical, enzymatic or microbiological processes and only from original materials. plant or animal.
- the invention also relates to a composition
- the composition comprises between 0 and 200 ppm of 4 - ((4- hydroxy-3 -methoxybenzyl) oxy) -3 -methoxybenzaldehyde or 4-hydroxy-3 - (4-hydroxy-3 - methoxybenzyl) -5-methoxybenzaldehyde .
- the content of 4 - ((4-hydroxy-3- methoxybenzyl) oxy) -3-methoxybenzaldehyde or 4-hydroxy-3- (4-hydroxy-3-methoxybenzyl) -5-methoxybenzaldehyde is less than or equal to 100 ppm , preferably less than or equal to 50 ppm and more preferably less than or equal to 20 ppm.
- the content of 4 - ((4- hydroxy-3 -methoxybenzyl) oxy) -3 -methoxybenzaldehyde or 4-hydroxy-3 - (4-hydroxy-3 - methoxybenzyl) -5-methoxybenzaldehyde is greater than or equal to 0, 01 ppm, and more preferably greater than or equal to 0.1 ppm.
- the present invention relates to the use of a natural vanillin composition as a flavoring in the field of human and animal food, pharmaceuticals, or as a perfume in the cosmetics industry, perfumery and detergency.
- a natural vanillin composition as a flavoring in the field of human and animal food, pharmaceuticals, or as a perfume in the cosmetics industry, perfumery and detergency.
- the method according to the invention will be better understood on reading the following example which is a particular embodiment of the method. This example is given purely by way of illustration and cannot be interpreted as limiting the invention. If the disclosure of patents, patent applications and publications cited herein by reference conflicts with the description of the present application to the extent that it may make a term uncertain, this description shall prevail.
- the ethanol, sulfuric acid, sodium hydroxide solution and the solvents used for the analyzes were obtained from Merck and were used without prior purification.
- High performance liquid chromatography (HPLC) is performed using an Agilent 1260 analytical chain with a Cl 8 column.
- composition (C) comprising natural vanillin, vanillic alcohol and an SI solvent was obtained following the treatment of the aqueous phase resulting from the fermentation of ferulic acid by a microorganism.
- the culture of the microorganism was carried out under the conditions described in EP 0885968 and the SI solvent corresponded to ethyl acetate.
- Composition (C) was analyzed by HPLC and the results are shown in Table 1.
- Composition C1 also included solvent SI and so-called heavy impurities, that is to say the relative volatility of which is lower than that of natural vanillin under the pressure and temperature conditions considered.
- solvent SI solvent SI
- heavy impurities that is to say the relative volatility of which is lower than that of natural vanillin under the pressure and temperature conditions considered.
- the identification of vanillin and vanillic alcohol was carried out by comparison with commercial standards.
- vanillic alcohol has been selectively converted to ether.
- the content in composition (C) was the same as the content in composition (Cl) and only the vanillic alcohol was transformed into ether, namely in vanillyl ethyl ether.
- a step (ii) the composition (Cl) was concentrated by evaporation of part of the solvent S1. There was thus obtained a concentrated composition (Cl) of about 270 g.
- the concentrated Cl medium was brought to pH 7 with a sodium hydroxide solution.
- the resulting mixture was washed with water.
- the organic phase was then removed with a rotary evaporator and the residue obtained was purified in a scraped-off evaporator in order to obtain natural vanillin with a titer greater than 99% and a coloration of 19 Hz.
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- General Health & Medical Sciences (AREA)
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- Veterinary Medicine (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Birds (AREA)
- Wood Science & Technology (AREA)
- Nutrition Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202080055051.8A CN114174252A (zh) | 2019-07-30 | 2020-07-30 | 用于处理包含天然香草醛的组合物的方法 |
US17/627,153 US20230183159A1 (en) | 2019-07-30 | 2020-07-30 | Method for the treatment of a composition comprising natural vanillin |
MX2022001167A MX2022001167A (es) | 2019-07-30 | 2020-07-30 | Metodo para el tratamiento de una composicion que comprende vainillina natural. |
BR112021026061A BR112021026061A2 (pt) | 2019-07-30 | 2020-07-30 | Método para o tratamento de uma composição que compreende vanilina natural |
EP20746224.3A EP4003949A1 (fr) | 2019-07-30 | 2020-07-30 | Procede de traitement d'une composition comprenant de la vanilline naturelle |
JP2022505513A JP2022542934A (ja) | 2019-07-30 | 2020-07-30 | 天然バニリンを含有する組成物の処理方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FRFR1908644 | 2019-07-30 | ||
FR1908644A FR3099478B1 (fr) | 2019-07-30 | 2019-07-30 | Procédé de traitement d’une composition comprenant de la vanilline naturelle |
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WO2021019005A1 true WO2021019005A1 (fr) | 2021-02-04 |
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PCT/EP2020/071489 WO2021019005A1 (fr) | 2019-07-30 | 2020-07-30 | Procede de traitement d'une composition comprenant de la vanilline naturelle |
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US (1) | US20230183159A1 (fr) |
EP (1) | EP4003949A1 (fr) |
JP (1) | JP2022542934A (fr) |
CN (1) | CN114174252A (fr) |
BR (1) | BR112021026061A2 (fr) |
FR (1) | FR3099478B1 (fr) |
MX (1) | MX2022001167A (fr) |
WO (1) | WO2021019005A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023198898A1 (fr) | 2022-04-15 | 2023-10-19 | Specialty Operations France | Procédé continu de croissance d' un microorganisme |
WO2023198897A1 (fr) | 2022-04-15 | 2023-10-19 | Specialty Operations France | Procédé de préparation d'un composé de formule (i) par fermentation |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2745796A (en) | 1953-10-21 | 1956-05-15 | Aschaffenburger Zellstoffwerke | Method of recovering vanillin |
DE1132113B (de) | 1959-07-09 | 1962-06-28 | Aschaffenburger Zellstoffwerke | Verfahren zur Reinigung von Vanillin |
EP0885968A1 (fr) | 1997-06-19 | 1998-12-23 | Givaudan-Roure (International) S.A. | Procédé pour la préparation de vanilline |
FR2765870A1 (fr) * | 1997-07-09 | 1999-01-15 | Rhodia Chimie Sa | Procede d'etherification d'un alcool de type benzylique |
CN101165038A (zh) | 2006-10-20 | 2008-04-23 | 上海香料研究所 | 香兰醇基乙基醚的合成方法 |
WO2014114590A1 (fr) | 2013-01-24 | 2014-07-31 | Rhodia Operations | Procédé de purification de la vanilline naturelle |
EP2791098A1 (fr) | 2011-12-15 | 2014-10-22 | Rhodia Operations | Procede de purification de la vanilline par extraction liquide-liquide |
EP2810564A1 (fr) * | 2005-08-12 | 2014-12-10 | Takasago International Corporation (USA) | Composition de masquage de sensation |
WO2018146210A1 (fr) | 2017-02-08 | 2018-08-16 | Rhodia Operations | Procede de purification de la vanilline naturelle |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2788269B1 (fr) * | 1999-01-08 | 2001-02-09 | Rhodia Chimie Sa | Procede de preparation d'un ether de type benzylique |
CN105622363B (zh) * | 2014-11-04 | 2017-12-08 | 南京工业大学 | 一步法制备香草醇醚的工艺 |
-
2019
- 2019-07-30 FR FR1908644A patent/FR3099478B1/fr active Active
-
2020
- 2020-07-30 MX MX2022001167A patent/MX2022001167A/es unknown
- 2020-07-30 CN CN202080055051.8A patent/CN114174252A/zh active Pending
- 2020-07-30 WO PCT/EP2020/071489 patent/WO2021019005A1/fr unknown
- 2020-07-30 JP JP2022505513A patent/JP2022542934A/ja active Pending
- 2020-07-30 EP EP20746224.3A patent/EP4003949A1/fr active Pending
- 2020-07-30 BR BR112021026061A patent/BR112021026061A2/pt unknown
- 2020-07-30 US US17/627,153 patent/US20230183159A1/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2745796A (en) | 1953-10-21 | 1956-05-15 | Aschaffenburger Zellstoffwerke | Method of recovering vanillin |
DE1132113B (de) | 1959-07-09 | 1962-06-28 | Aschaffenburger Zellstoffwerke | Verfahren zur Reinigung von Vanillin |
EP0885968A1 (fr) | 1997-06-19 | 1998-12-23 | Givaudan-Roure (International) S.A. | Procédé pour la préparation de vanilline |
FR2765870A1 (fr) * | 1997-07-09 | 1999-01-15 | Rhodia Chimie Sa | Procede d'etherification d'un alcool de type benzylique |
EP2810564A1 (fr) * | 2005-08-12 | 2014-12-10 | Takasago International Corporation (USA) | Composition de masquage de sensation |
CN101165038A (zh) | 2006-10-20 | 2008-04-23 | 上海香料研究所 | 香兰醇基乙基醚的合成方法 |
EP2791098A1 (fr) | 2011-12-15 | 2014-10-22 | Rhodia Operations | Procede de purification de la vanilline par extraction liquide-liquide |
WO2014114590A1 (fr) | 2013-01-24 | 2014-07-31 | Rhodia Operations | Procédé de purification de la vanilline naturelle |
WO2018146210A1 (fr) | 2017-02-08 | 2018-08-16 | Rhodia Operations | Procede de purification de la vanilline naturelle |
Non-Patent Citations (3)
Title |
---|
ANGEW. CHEM. INT. ED., vol. 46, 2007, pages 298 - 300 |
AZADBAKHT ET AL.: "Preparation of lignin from wood dust as vanillin source and comparison of différent extraction method", INTERNATIONAL JOURNAL OF BIOLOGY AND BIOTECHNOLOGY, vol. 1, no. 4, 2004, pages 535 - 537, XP009501182 |
SUHAS SHINDE ET AL: "Cascade Reductive Etherification of Bioderived Aldehydes over Zr-Based Catalysts", CHEMSUSCHEM, vol. 10, no. 20, 9 October 2017 (2017-10-09), DE, pages 4090 - 4101, XP055736107, ISSN: 1864-5631, DOI: 10.1002/cssc.201701275 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023198898A1 (fr) | 2022-04-15 | 2023-10-19 | Specialty Operations France | Procédé continu de croissance d' un microorganisme |
WO2023198897A1 (fr) | 2022-04-15 | 2023-10-19 | Specialty Operations France | Procédé de préparation d'un composé de formule (i) par fermentation |
FR3134583A1 (fr) | 2022-04-15 | 2023-10-20 | Rhodia Operations | Procédé continu de croissance d’un microorganisme |
FR3134582A1 (fr) | 2022-04-15 | 2023-10-20 | Rhodia Operations | Procédé de préparation d’un composé de formule (I) par fermentation |
Also Published As
Publication number | Publication date |
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MX2022001167A (es) | 2022-02-23 |
US20230183159A1 (en) | 2023-06-15 |
FR3099478A1 (fr) | 2021-02-05 |
EP4003949A1 (fr) | 2022-06-01 |
FR3099478B1 (fr) | 2021-07-09 |
BR112021026061A2 (pt) | 2022-02-08 |
CN114174252A (zh) | 2022-03-11 |
JP2022542934A (ja) | 2022-10-07 |
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