CN113845454A - Preparation method and application of ketomethionine and derivatives thereof - Google Patents
Preparation method and application of ketomethionine and derivatives thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and application of ketomethionine and derivatives thereof. The preparation method comprises the step of carrying out one-step reaction on pyruvic acid or pyruvic acid derivatives, formaldehyde and mercaptan under the action of a catalyst to generate ketomethionine or the derivatives thereof. The prepared ketomethionine or the derivative thereof can be further applied to the preparation of methionine and the derivative thereof, and hydroxymethionine and the derivative thereof. The ketomethionine and the derivative thereof synthesized by the inventive one-step method can react at normal temperature and normal pressure, have high conversion efficiency, avoid using hydrocyanic acid which is a highly toxic substance, are very suitable for industrial production and have great industrial value.
Description
Technical Field
The application relates to the technical field of biochemical synthesis, in particular to a preparation method and application of ketomethionine and derivatives thereof.
Background
Methionine, also known as methionine, and chemically 2-amino-4-methylthiobutanoic acid, is one of the basic units constituting proteins, and is the only amino acid containing sulfur among essential amino acids. Methionine is widely used in the fields of medicine, food, feed, cosmetics and the like, for example, methionine can maintain the growth and development of organisms and nitrogen balance, and promote human metabolism, so that methionine can be used for a plurality of medical purposes such as liver protection, myocardial protection, anti-depression, blood pressure reduction, poison prevention and poison elimination and the like. For another example, methionine is one of the most important amino acids necessary for animal protein synthesis of livestock and poultry, and can be used as a protein feed enhancer and a nutritional additive for compensating amino acid balance, and is used in the feed industry. Thus, there is a wide demand for methionine in the market.
The current methods for producing methionine include biological fermentation and chemical synthesis methods, such as cyanide method, hydantoin method, etc. The cyanide process is mainly used for producing liquid methionine, and utilizes the reaction of methyl mercaptan and acrolein to generate 3-methylthio propionaldehyde, which further reacts with hydrogen cyanide to generate methylthio butyl cyanide, and the methylthio butyl cyanide is hydrolyzed to prepare methionine or methionine hydroxy analogue. The hydantoin method is mainly used for producing solid methionine, and is characterized in that the hydantoin method is started by using sodium cyanide obtained from hydrogen cyanide and sodium hydroxide, and then a hydantoin derivative is further prepared, and then sodium methionine is further prepared, and finally methionine can be prepared. As can be seen from the two methods, the preparation method of the compound uses hydrocyanic acid which is a highly toxic substance.
Disclosure of Invention
The present application creatively proposes a one-step synthesis of ketomethionine and its derivatives, which can at least partially solve the above existing problems.
One of the objects of the present invention is to provide a method for producing ketomethionine or a derivative thereof, which comprises reacting pyruvic acid or a derivative thereof, formaldehyde and methyl mercaptan in the presence of a catalyst to produce ketomethionine or a derivative thereof.
Another object of the present invention is to provide a method for producing methionine or methionine derivatives, comprising the steps of: 1) reacting pyruvic acid or pyruvic acid derivative, formaldehyde and methyl mercaptan in the presence of a catalyst to produce ketomethionine or ketomethionine derivative; 2) and carrying out biotransformation or chemical reaction on the ketomethionine or the ketomethionine derivative to obtain the methionine or the derivative thereof.
The invention also provides a preparation method of hydroxymethionine or derivatives thereof, which comprises the following steps: 1) reacting pyruvic acid or pyruvic acid derivative, formaldehyde and methyl mercaptan in the presence of a catalyst to produce ketomethionine or ketomethionine derivative; 2) and carrying out chemical reaction or biotransformation on the ketomethionine or the derivative thereof to obtain the hydroxymethionine or the derivative thereof.
The ketomethionine and the derivative thereof synthesized by the inventive one-step method can react at normal temperature and normal pressure, have high conversion efficiency, avoid using hydrocyanic acid which is a highly toxic substance, are very suitable for industrial production and have great industrial value.
Drawings
FIG. 1 is an HPLC chromatogram of the reaction product of example 3.
Detailed Description
In the present disclosure, unless defined otherwise, scientific and technical terms used herein have the meanings that are commonly understood by those of skill in the art. Meanwhile, for better understanding of the present disclosure, definitions and explanations of related terms are provided below.
It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
As used herein and unless otherwise specified, the term "methionine" is meant to have
Structural compounds, methionine derivatives, include, but are not limited to, esters, amides, salts, and the like of methionine.
The term "ketomethionine" means methionine wherein the amino group is replaced by a carbonyl group, having
The compounds of structure, ketomethionine derivatives, include, but are not limited to, esters, amides, salts, and the like of ketomethionine.
The term "hydroxymethionine" means that the amino group of methionine is substituted by hydroxyl group, having
The compounds of structure (I), hydroxymethionine derivatives include, but are not limited to, esters, amides, salts, and the like of hydroxymethionine.
The term "pyruvic acid" is meant to have
Structural compounds, pyruvic acid derivatives include, but are not limited to, pyruvate salts, and the like.
The term "bio-based carbon" is intended to mean carbon obtained from biological sources other than petroleum-based sources. Fossil-based carbon is substantially free of14C, because fossil-based carbon is far older than14C's half-life of 5,730 years, and thus, in the composition14The presence and level of C provides a direct measure of the amount of carbon originating from sources other than fossil fuels, i.e., the level of biobased carbon in the composition.
The term "bioconversion" refers to a chemical reaction performed using living organisms (often microorganisms, such as bacteria and yeast).
Unless specifically stated otherwise, the terms "first," "second," and the like, do not denote any order or importance, but rather the terms first, second, and the like are used to distinguish one object from another.
As used herein and unless otherwise specified, the term "about" refers to a measurable value such as an amount, time period, or the like, and is meant to encompass a variation of ± 10%, more preferably ± 5%, even more preferably ± 1%, and still more preferably ± 0.1% from a given value, so long as such variation is suitable for practicing the disclosed methods.
As described above, an object of the present invention is to provide a method for synthesizing ketomethionine and its derivatives, which is safe, environmentally friendly and suitable for industrial production.
Some embodiments of the present invention disclose a one-step synthesis of ketomethionine and its derivatives by reacting pyruvic acid or a pyruvic acid derivative, formaldehyde and methyl mercaptan in the presence of a first catalyst to form ketomethionine or a ketomethionine derivative.
According to some embodiments of the invention, the molar ratio of pyruvic acid or pyruvic acid derivative, formaldehyde and thiol is 1: 1: 1-3, e.g. 1: 1: 2 or 1: 1: 3; optionally, the molar ratio of pyruvic acid or pyruvic acid derivative, formaldehyde, catalyst and thiol is 1: 1: 1-3: 1-3, e.g. 1: 1: 1: 2 or 1: 1: 3: 3
According to the preparation method provided by the invention, the first catalyst is mainly used for catalyzing Aldol reaction (Aldol reaction). According to some embodiments of the present invention, the first catalyst is selected from a basic catalyst or an amphoteric ligand catalyst, and the basic catalyst comprises an organic amine or an inorganic base.
According to some embodiments of the invention, organic amines include, but are not limited to, dimethylamine, diethylamine, triethylamine, and the like; inorganic bases, including but not limited to NaHCO3，Na2CO3，CaCO3NaOH, etc.; amphoteric ligand catalysts, including but not limited to amino acid type amphoteric phosphine ligands and the like.
According to some embodiments of the invention, wherein the first catalytic reaction is at a temperature of between 0 and 400 ℃ and at a pressure of between 0.5 and 100 atmospheres. The present invention is not critical to the reaction conditions and can be reacted between 0 and 400 deg.C, e.g., between about 400 deg.C, about 300 deg.C, about 200 deg.C, about 100 deg.C, about 70 deg.C, about 40 deg.C, about 25 deg.C, about 10 deg.C, or about 0 deg.C, 0.5 to 100 atmospheres. For example, the reaction can be carried out at normal temperature (about 25 ℃) and normal pressure (about one atmosphere).
According to some embodiments of the invention, wherein the pyruvic acid or pyruvic acid derivative is chemically or biologically produced.
According to some embodiments of the invention, wherein the pyruvic acid or pyruvic acid derivative is biologically produced, the pyruvic acid or pyruvic acid derivative is14C/12The ratio of C is greater than 0. When in use14C/12When the ratio of C is greater than 0, it means that pyruvic acid or a pyruvic acid derivative is present14C, having bio-based carbon.
According to some embodiments of the invention, wherein the pyruvic acid or pyruvic acid derivative is prepared by fermentation of glucose.
In another aspect, the present invention provides a method for producing methionine or methionine derivatives by biotransformation or chemical reaction of ketomethionine or ketomethionine derivatives. Wherein, the ketomethionine or the ketomethionine derivative can be prepared by the one-step synthesis method provided by the invention.
According to some embodiments of the invention, wherein the methionine or methionine derivative is produced by fermenting ketomethionine or ketomethionine derivative by a microorganism.
According to some embodiments of the invention, wherein the microorganism comprises yeast, bacteria, and the like. Microorganisms include, but are not limited to, Escherichia coli, Bacillus, Corynebacterium, or yeast; alternatively, the microorganism is selected from Escherichia coli (Escherichia coli), Bacillus subtilis (Bacillus subtilis), Bacillus megaterium (Bacillus megaterium), Bacillus amyloliquefaciens (Bacillus amyloliquefaciens), Corynebacterium glutamicum (Corynebacterium glutamicum), Saccharomyces cerevisiae (Saccharomyces cerevisiae), Candida utilis (Candida utilis), or Pichia pastoris (Pichia pastoris).
According to some embodiments of the invention, wherein the microbial fermentation temperature is 20-40 ℃.
According to some embodiments of the invention, wherein the methionine or methionine derivative is prepared by chemically reacting ketomethionine or ketomethionine derivative.
According to some embodiments of the invention, wherein the methionine or methionine derivative is produced by chemically reacting ketomethionine or ketomethionine derivative, hydrogen and ammonia gas in the presence of a second catalyst.
According to some embodiments of the present invention, wherein the second catalyst is selected from metal catalysts, including but not limited to palladium on carbon catalysts, nickel catalysts, copper catalysts, cobalt catalysts, platinum catalysts, and the like.
According to some embodiments of the invention, wherein the temperature of the second catalytic reaction is between 40-300 ℃, preferably between 60-200 ℃, such as about 40 ℃, about 60, about 100 ℃, about 200 ℃. The pressure of the second catalytic reaction is in the range of from 1 to 100 atmospheres, for example about 1 atmosphere, about 10 atmospheres, about 40 atmospheres, about 50 atmospheres, about 70 atmospheres, or about 100 atmospheres.
In another aspect, the present invention provides a method for producing hydroxymethionine or methionine derivative by subjecting ketomethionine or ketomethionine derivative to biotransformation or chemical reaction. Wherein, the ketomethionine or the ketomethionine derivative can be prepared by the one-step synthesis method provided by the invention.
According to some embodiments of the invention, the hydroxymethionine or methionine derivative is obtained by subjecting ketomethionine or a ketomethionine derivative to a reduction reaction. According to some embodiments of the invention, the reduction reaction comprises a hydrogenation reaction.
According to some embodiments of the invention, the hydrogenation is carried out under 1 to 100 atmospheres of hydrogen and with the addition of a third catalyst. For example, about 1 atmosphere, about 10 atmospheres, about 40 atmospheres, about 50 atmospheres, about 70 atmospheres, or about 100 atmospheres.
According to some embodiments of the invention, the third catalyst is selected from metal catalysts including, but not limited to, palladium on carbon catalysts, nickel catalysts, copper catalysts, cobalt catalysts, platinum catalysts, and the like.
According to some embodiments of the invention, the hydrogenation reaction temperature is between 40-300 ℃, such as about 40 ℃, about 60, about 100 ℃, about 200 ℃ or about 300 ℃, preferably between 60-200 ℃.
The starting reagents added or the equipment or procedures used in the examples below are those routinely determined by one of ordinary skill in the art.
EXAMPLE 1 one-step Synthesis of sodium Ketone methionine
The reaction formula of the synthesis is as follows:
300mg of sodium pyruvate was placed in the reactor and dissolved by adding 10mL of deionized water. The reactor was placed in an ice-water mixture and stirred, followed by addition of 0.212mL of 37% w/w formaldehyde solution, 0.282mL or 0.423mL of 98% methyl mercaptan, and 0.334mL or 1mL of base. The reaction was carried out at room temperature.
The base used herein is dimethylamine, and can also be used including, but not limited to: 3-hydroxypiperidine, diisopropylamine, and the like.
The reaction results were checked by HPLC-RID (Berkele Column 1250140Aminex HPX-87H Column 300X7.8 mm).
EXAMPLE 2 Tertiary amines as catalysts
300mg of sodium pyruvate was placed in the reactor and dissolved by adding 10mL of deionized water. The reactor was placed in an ice-water mixture and stirred, followed by the addition of 0.212mL of 37% w/w formaldehyde solution, 0.423mL of 98% methyl mercaptan, and 1.1mL of triethylamine.
The reaction results were measured by HPLC-RID (Berkele Column 1250140Aminex HPX-87H Column 300 X7.8mm).
Example 3 Secondary amine tetrahydropyrrole as catalyst under neutral conditions
The general scheme for this synthesis is as follows:
182mL of pyruvic acid was placed in the reactor, and 5mL of absolute ethanol was added. 0.212mL of 37% w/w formaldehyde solution, 0.195mL of ethanethiol, and 0.221mL of 99% tetrahydropyrrole were added in this order.
The mercaptan herein is ethanethiol, but may also include, but is not limited to: methyl mercaptan, and the like.
The reaction results were measured by HPLC-RID (Berkele Column 1250140Aminex HPX-87H Column 300X7.8mm), as shown in FIG. 1.
Claims (12)
1. A method for producing ketomethionine or a ketomethionine derivative, characterized by subjecting pyruvic acid or a pyruvic acid derivative, formaldehyde and thiol to a first catalytic reaction in the presence of a first catalyst to produce ketomethionine or a ketomethionine derivative.
2. The method according to claim 1, wherein the pyruvic acid derivative is selected from a salt or an ester of pyruvic acid; optionally, the pyruvic acid derivative is sodium pyruvate, potassium pyruvate, magnesium pyruvate, or calcium pyruvate; optionally, the pyruvic acid derivative is sodium pyruvate;
the mercaptan is selected from methyl mercaptan or ethyl mercaptan;
the first catalyst is selected from a base catalyst or an amphoteric catalystA bulk catalyst; alternatively, the amphoteric ligand catalyst is selected from amino acid type amphoteric phosphine ligands; optionally, the base catalyst is selected from an organic amine or an inorganic base, optionally, the organic amine is selected from a secondary amine or a tertiary amine; the inorganic base is selected from NaHCO3、Na2CO3、CaCO3Or NaOH; optionally, the organic amine is selected from dimethylamine, diethylamine, triethylamine, hydroxypiperidine, tetrahydropyrrole, diisopropylamine; optionally, the organic amine is selected from dimethylamine, triethylamine or tetrahydropyrrole.
3. The method of claim 1 or 2, wherein the molar ratio of pyruvic acid or a pyruvic acid derivative, formaldehyde and thiol is about 1: 1: 1-3, optionally the molar ratio of pyruvic acid or pyruvic acid derivative, formaldehyde and thiol is about 1: 1: 2 or about 1: 1: 3;
optionally, the pyruvic acid or pyruvic acid derivative, formaldehyde, catalyst and thiol are in a molar ratio of about 1: 1: 1-3: 1-3, optionally, the molar ratio of pyruvic acid or pyruvic acid derivative, formaldehyde, catalyst and thiol is about 1: 1: 1: 2 or 1: 1: 3: 3.
4. the production method according to any one of claims 1 to 3, wherein the temperature of the first catalytic reaction is 0 to 400 ℃; optionally, the temperature of the first catalytic reaction is about 400 ℃, about 300 ℃, about 200 ℃, about 100 ℃, about 70 ℃, about 40 ℃, about 25 ℃, about 10 ℃ or about 0 ℃;
optionally, the pressure of the first catalytic reaction is from 0.5 to 100 atmospheres; alternatively, the pressure of the first catalytic reaction is about 0.5 atmospheres, about 1 atmosphere, about 10 atmospheres, about 40 atmospheres, about 50 atmospheres, about 70 atmospheres, or about 100 atmospheres.
5. The production method according to any one of claims 1 to 4, wherein the pyruvic acid or pyruvic acid derivative is produced by a chemical or biological method; can be used forOptionally, among said pyruvic acid or pyruvic acid derivatives14C/12C is greater than 0, and optionally, the pyruvic acid or pyruvic acid derivative is produced by fermentation of glucose.
6. The production method according to any one of claims 1 to 5, wherein starting materials of sodium pyruvate, formaldehyde, methyl mercaptan and dimethylamine are reacted at 10 to 30 ℃ to produce ketomethionine sodium; alternatively, the molar ratio of sodium pyruvate, formaldehyde, methyl mercaptan, and dimethylamine is about 1: 1: 2: 1, optionally, in a molar ratio of 0.9 to 1.1: 0.9-1.1: 1.8-2.2: 0.9-1.1.
7. A process for producing methionine or methionine derivative, which comprises subjecting ketomethionine or ketomethionine derivative obtained by the process according to any one of claims 1 to 6 to biotransformation or chemical reaction.
8. The production method according to claim 7, wherein the bioconversion is microbial fermentation;
optionally, the microorganism is selected from yeast or bacteria; optionally, the microorganism is selected from escherichia coli, bacillus, corynebacterium or yeast; optionally, the microorganism is selected from Escherichia coli (Escherichia coli), Bacillus subtilis (Bacillus subtilis), Bacillus megaterium (Bacillus megaterium), Bacillus amyloliquefaciens (Bacillus amyloliquefaciens), Corynebacterium glutamicum (Corynebacterium glutamicum), Saccharomyces cerevisiae (Saccharomyces cerevisiae), Candida utilis (Candida utilis), or Pichia pastoris (Pichia pastoris); optionally, the fermentation temperature is 20-40 ℃.
9. The production method according to claim 7, wherein the chemical reaction is carried out by subjecting ketomethionine or a ketomethionine derivative, hydrogen gas and ammonia gas to a second catalytic reaction under a second catalyst;
optionally, the second catalyst is selected from metal catalysts; optionally, the second catalyst is selected from a palladium on carbon catalyst, a nickel catalyst, a copper catalyst, a cobalt catalyst, or a platinum catalyst;
optionally, the second catalytic reaction temperature is 40-300 ℃; optionally, the second catalytic reaction temperature is about 40 ℃, about 60, about 100 ℃, about 200 ℃, or about 300 ℃;
optionally, the second catalytic reaction pressure is from 1 to 100 atmospheres, optionally, the second catalytic reaction pressure is about 1 atmosphere, about 10 atmospheres, about 40 atmospheres, about 50 atmospheres, about 70 atmospheres, or about 100 atmospheres.
10. A process for producing hydroxymethionine or a derivative thereof, which comprises subjecting ketomethionine or a ketomethionine derivative obtained by the process according to any one of claims 1 to 6 to biotransformation or chemical reaction.
11. The production method according to claim 10, wherein the hydroxymethionine or methionine derivative is obtained by subjecting ketomethionine or a ketomethionine derivative to a reduction reaction; optionally, the reduction reaction comprises a hydrogenation reaction.
12. The production method according to claim 10, wherein the hydrogenation is carried out under hydrogen with addition of a third catalyst; optionally, the third catalyst is selected from metal catalysts; optionally, the third catalyst is selected from a palladium on carbon catalyst, a nickel catalyst, a copper catalyst, a cobalt catalyst, or a platinum catalyst;
alternatively, the hydrogenation reaction temperature is 40-300 ℃; alternatively, the hydrogenation reaction temperature is about 40 ℃, about 60, about 100 ℃, about 200 ℃, or about 300 ℃;
alternatively, the hydrogenation reaction pressure is from 1 to 100 atmospheres, alternatively, the hydrogenation reaction pressure is about 1 atmosphere, about 10 atmospheres, about 40 atmospheres, about 50 atmospheres, about 70 atmospheres, or about 100 atmospheres.
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