CN106749438A - A kind of Amadori compound synthesis method - Google Patents
A kind of Amadori compound synthesis method Download PDFInfo
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- CN106749438A CN106749438A CN201611087461.2A CN201611087461A CN106749438A CN 106749438 A CN106749438 A CN 106749438A CN 201611087461 A CN201611087461 A CN 201611087461A CN 106749438 A CN106749438 A CN 106749438A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H7/00—Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
- C07H7/02—Acyclic radicals
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/12—Acyclic radicals, not substituted by cyclic structures attached to a nitrogen atom of the saccharide radical
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
- C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H7/00—Compounds containing non-saccharide radicals linked to saccharide radicals by a carbon-to-carbon bond
- C07H7/06—Heterocyclic radicals
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Abstract
The present invention relates to a kind of Amadori compound synthesis method, the method uses fructose and amino acid modified Protection Code, including obtaining the steps such as Amadori compounds by monose and amino acid dehydration.Amadori compounds process for production thereof step of the present invention is simple, mild condition, and any pollutant or toxic waste are not discharged, is conducive to environmental protection, and up to more than 90%, product purity reaches more than 98% to the preparation method high income.
Description
【Technical field】
The invention belongs to technical field of tobacco processing.More particularly it relates to a kind of Amadori compound synthesis
Method.
【Background technology】
Recognize constantly deeply with to smoking and health problem, people require that cigarette product has sucking quality high, high
Suck security.Current study show that, cigarette comes from tar to harm main component, therefore, improve smoking security master
Concentrate on reduction tar content.Present tar reduction means for example have filter tip, high air permeability cigarette paper, reconstituted tobacoo, mix expansion cigarette
Silk and expanded cut stem etc., but these technologies still suffer from some technological deficiencies, such as lose perfume quantity, reduce suction quality, city
Field receptance is low, then restricts tobacco business development.Therefore, developing low-coke tar cigarette product, carried out using fragrance precursor material
Compensating aroma, improves suction quality.Wherein volatility is weak under field conditions (factors) for Amadori compounds, stable chemical nature, and it is originally
Body does not have fragrance, and generation Pyrazine flavor matter can be converted in result of combustion of tobacco, this aromatic style and taste to cigarette
Feature plays the role of important.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of Amadori compound synthesis method.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of Amadori compound synthesis method.
The step of synthetic method, is as follows：
A, at ambient temperature, 1 is compared according to the weight of D-Fructose and acetone：12~18, D-Fructose is dissolved in acetone, obtain
To a kind of D-Fructose acetone soln；Weight according still further to D-Fructose and the concentrated sulfuric acid compares 1：1~2, dripped toward D-Fructose acetone soln
Enriching sulfuric acid, stirs 1.2~1.8h, obtains double propylidene base fructose solns；Then
Described double propylidene base fructose soln sodium hydrate aqueous solutions are neutralized to pH7~8, then in 20~40 DEG C of temperature
Acetone is reclaimed with being concentrated under reduced pressure under conditions of 0.01~0.1MPa of pressure；The raffinate obtained after acetone is reclaimed to be extracted with ethyl acetate
Take, wherein raffinate and ethyl acetate volume ratio is 1：1~3；Then toward adding anhydrous sodium sulfate dehydration in ethyl acetate organic phase,
Filtering, rotates recycling design, obtains product as light yellow solid；
B, under condition of ice bath, the product as light yellow solid that step A is obtained with pyridine solvent dissolve, wherein solid product with
The weight ratio of pyridine is 1：10~15, the weight according still further to solid product and trifluoromethanesulfanhydride anhydride compares 1：3~5 toward in pyridine solution
Trifluoromethanesulfanhydride anhydride is added dropwise, 25~35min is then reacted at temperature -30~-10 DEG C, add 0.8~1.2mol/L hydrochloric acid
The aqueous solution is neutralized to pH6~7；The neutralization solution is extracted with ethyl acetate 2~4 times, and the body of solution and ethyl acetate is neutralized every time
Product is 1：1~3, the acetic acid ethyl acetate extract anhydrous sodium sulfate dehydration of merging, filtering rotates recycling design, and residue leads to again
Silicagel column purifying is crossed, with petroleum ether and ethyl acetate according to volume ratio 8~12：The mixture wash-out of 1 mixing, collects Amadori
Compound object cut, is recovered under reduced pressure solvent, obtains residual solids product；
C, amino-acid benzyl ester salt is added in flask, the ammonia methyl alcohol that concentration is by weight 5~10% is added dropwise in ice bath
Solution, stirs 12~18min, stands 12~18min, then subtract under conditions of 5~15 DEG C of temperature with 0.01~0.1MPa of pressure
Pressure concentration and recovery solvent, obtains activated amino acid benzyl ester salt；
D, compare 1 according to the weight of amino-acid benzyl ester salt and DMF solvent：1.5~2.5, the amino-acid benzyl ester that step D is obtained
Salt is dissolved in DMF solvent, is subsequently added into the residual solids product that step B is obtained, and is well mixed, in oil bath under temperature 70 C
1.0~2.5h of reaction is carried out, adds 80~120ml deionized waters that reaction is quenched, according to the body that reaction solution and ethyl acetate is quenched
Product 1：0.5~1.0, reaction solution is quenched and is extracted with ethyl acetate 2~4 times, the ethyl acetate organic phase of separation is washed with water, then
Washed with saturated sodium-chloride water solution, then with anhydrous sodium sulfate dehydration, filtering, recycling design, the crude product for obtaining passes through silicon again
Glue post is purified, and is eluted with petroleum ether and ethyl acetate mixture, and wherein petroleum ether and the volume ratio of ethyl acetate is 1.5~2.5：
1, object cut is collected, recycling design obtains object；
E, the object that step D is obtained is dissolved in 80~120mL tetrahydrofurans, add in terms of target weight 7~
9% palladium-carbon catalyst, 7~9h of hydrogenation reaction is carried out under conditions of 50~60 DEG C of temperature, allows reaction solution to pass through diatomite mistake
Filter, the filtrate for obtaining is concentrated under reduced pressure, and obtains a kind of concentrate；
F, that the concentrate that step E is obtained is dissolved in into the trifluoroacetic acid that 80~120mL concentration is by weight 8~12% is water-soluble
In liquid, it is placed in oil bath and 1~2h is reacted at 56~64 DEG C of temperature, then several times to adding absolute ethyl alcohol in the reaction solution,
Reaction solution and the weight ratio of absolute ethyl alcohol is set to reach 1：1~2, then be concentrated under reduced pressure, the concentrate for obtaining passes through C18 reverse-phase chromatographic columns
Purifying, is first eluted with pure water, then with concentration for 50~70% methanol aqueous solutions by weight are eluted, collects first paragraph cut work
It is object, it obtains described Amadori compounds by freeze-drying.
A preferred embodiment of the invention, in step, the concentration of the sodium hydrate aqueous solution is 1~
4N。
Another preferred embodiment of the invention, in step, the raffinate obtained after acetone is reclaimed uses second
Acetoacetic ester is extracted 2~4 times in the same way.
Another preferred embodiment of the invention, in stepb, silicon is carried out with dry method upper prop under normal temperature condition
Glue post is purified.
Another preferred embodiment of the invention, in stepb, subtracts under conditions of 0.01~0.1MPa of pressure
Push back the solvent received and be made up of petroleum ether and ethyl acetate.
Another preferred embodiment of the invention, in step C, amino-acid benzyl ester salt be proline benzyl ester salt,
Alanine benzyl ester salt or glycine benzyl ester salt.
Another preferred embodiment of the invention, in step D, ethyl acetate organic phase is according to organic phase and water
Volume ratio 1：1~2 washes with water 1~3 time, then according to organic phase and the volume ratio 1 of saturated sodium-chloride water solution：1.0~
1.5 are washed 1~3 time with saturated sodium-chloride water solution.
Another preferred embodiment of the invention, in step D, the crude product for obtaining is with dry method upper prop in normal temperature bar
Purified by silicagel column under part.
Another preferred embodiment of the invention, in step D, using method concentrated under reduced pressure be temperature 40~
Recycling design is carried out under conditions of 60 DEG C and 0.01~0.1MPa of pressure.
Another preferred embodiment of the invention, in step E and step F, using method concentrated under reduced pressure in temperature
Degree 50~75 DEG C with 0.01~0.1MPa of pressure under conditions of be concentrated under reduced pressure.
The present invention is described in more detail below.
The present invention relates to a kind of Amadori compound synthesis method.
The step of synthetic method, is as follows：
A, at ambient temperature, 1 is compared according to the weight of D-Fructose and acetone：12~18, D-Fructose is dissolved in acetone, obtain
To a kind of D-Fructose acetone soln；Weight according still further to D-Fructose and the concentrated sulfuric acid compares 1：1~2, dripped toward D-Fructose acetone soln
Enriching sulfuric acid, stirs 1.2~1.8h, obtains double propylidene base fructose solns；
Known according to document R.F.Brady, Carbohydr.Res.15,35 (1970), D-Fructose with acetone (urge by the concentrated sulfuric acid
Change) reaction obtains double propylidene base fructose.
In the present invention, if D-Fructose is more than 1 with the weight ratio of the concentrated sulfuric acid：1, then double propylidene base fructose be not exclusively catalyzed
Generation；If D-Fructose is less than 1 with the weight ratio of the concentrated sulfuric acid：2, then fructose may be too dehydrated；Therefore, D-Fructose and dense sulphur
The weight ratio of acid is 1：1~2 be it is appropriate, preferably 1：1.2~1.8, more preferably 1：1.4~1.6；
Described double propylidene base fructose soln sodium hydrate aqueous solutions are neutralized to pH7~8, then in 20~40 DEG C of temperature
Acetone is reclaimed with being concentrated under reduced pressure under conditions of 0.01~0.1MPa of pressure；The raffinate obtained after acetone is reclaimed to be extracted with ethyl acetate
Take, wherein raffinate and ethyl acetate volume ratio is 1：1~3；Then toward adding anhydrous sodium sulfate dehydration in ethyl acetate organic phase,
Filtering, rotates recycling design, obtains product as light yellow solid；
Preferably, the concentration of the sodium hydrate aqueous solution is 1~4N.
In this step, the raffinate for being obtained after acetone is reclaimed makes to be extracted with ethyl acetate at room temperature, and with same
The mode of sample is extracted 2~4 times, because intermediate product is soluble in organic phase, therefore will be produced using the organic solvent of middle polarity
Thing is extracted from water phase.
In the present invention, ethyl acetate organic phase anhydrous sodium sulfate dehydration is a kind of routine operation in the art
Method.
Filtering of the present invention is that the one kind in the art is generally separated method, and the equipment for using is also this skill
Conventional equipment in art field.
Revolving recycling design of the present invention is entered under normal conditions using common revolving equipment in the art
Row recycling design.
Therefore, no longer gone to live in the household of one's in-laws on getting married when the technology contents such as relevant anhydrous sodium sulfate dehydration, filtering, revolving recycling design are set forth below
State.
B, under condition of ice bath, the product as light yellow solid that step A is obtained with pyridine solvent dissolve, wherein solid product with
The weight ratio of pyridine is 1：10~15, the weight according still further to solid product and trifluoromethanesulfanhydride anhydride compares 1：3~5 toward in pyridine solution
Trifluoromethanesulfanhydride anhydride is added dropwise, 25~35min is then reacted at temperature -30~-10 DEG C, add 0.8~1.2mol/L hydrochloric acid
The aqueous solution is neutralized to pH6~7；The neutralization solution is extracted with ethyl acetate 2~4 times, and the body of solution and ethyl acetate is neutralized every time
Product is 1：1~3, the acetic acid ethyl acetate extract anhydrous sodium sulfate dehydration of merging, filtering rotates recycling design, and residue leads to again
Silicagel column purifying is crossed, with petroleum ether and ethyl acetate according to volume ratio 8~12：The mixture wash-out of 1 mixing, collects Amadori
Compound object cut, is recovered under reduced pressure solvent, obtains residual solids product；
In the present invention, product as light yellow solid carries out substitution reaction with trifluoromethanesulfanhydride anhydride.
Preferably, the silicagel column for using in this step is silicagel column usually used in the art, silicagel column
Pretreatment and its application method are all known to this those skilled in the art.Specifically, with dry method upper prop in normal temperature bar
Silicagel column purifying is carried out under part.
In this step, the Amadori compound object cuts of collection are under conditions of 0.01~0.1MPa of pressure
The solvent being made up of petroleum ether and ethyl acetate is recovered under reduced pressure.
C, amino-acid benzyl ester salt is added in flask, the ammonia methyl alcohol that concentration is by weight 5~10% is added dropwise in ice bath
Solution, stirs 12~18min, stands 12~18min, then subtract under conditions of 5~15 DEG C of temperature with 0.01~0.1MPa of pressure
Pressure concentration and recovery solvent, obtains activated amino acid benzyl ester salt；
In the present invention, the purpose that amino-acid benzyl ester salt is activated is using in ammonia-methanol reagent and sloughing amino
Hydrochloride in acid benzyl ester salt.
Described amino-acid benzyl ester salt is proline benzyl ester salt, alanine benzyl ester salt or glycine benzyl ester salt.The present invention makes
Amino-acid benzyl ester salt is all the product sold in the market, such as by Sigma-Aldarich. companies with trade name L-
Proline benzyl ester hydrochloride sale proline benzyl ester salt, by Sigma-Aldarich. companies with trade name ALANINE benzyl ester
Hydrochloride sale alanine benzyl ester salt, by Sigma-Aldarich. companies with trade name L- glycine benzyl hydrochlorides sell
Glycine benzyl ester salt.
D, compare 1 according to the weight of amino-acid benzyl ester salt and DMF solvent：1.5~2.5, the amino-acid benzyl ester that step D is obtained
Salt is dissolved in DMF solvent, is subsequently added into the residual solids product that step B is obtained, and is well mixed, in oil bath under temperature 70 C
1.0~2.5h of reaction is carried out, adds 80~120ml deionized waters that reaction is quenched, according to the body that reaction solution and ethyl acetate is quenched
Product 1：0.5~1.0, reaction solution is quenched and is extracted with ethyl acetate 2~4 times, the ethyl acetate organic phase of separation is washed with water, then
Washed with saturated sodium-chloride water solution, then with anhydrous sodium sulfate dehydration, filtering, recycling design, the crude product for obtaining passes through silicon again
Glue post is purified, and is eluted with petroleum ether and ethyl acetate mixture, and wherein petroleum ether and the volume ratio of ethyl acetate is 1.5~2.5：
1, object cut is collected, recycling design obtains object；
The reaction of the residual solids product that amino-acid benzyl ester salt is obtained with step B is the benzyl ester salt step of replacing B of amino acid
TFMS anhydride group in product.
In this step, ethyl acetate organic phase is according to organic phase and the volume ratio 1 of water：1~2 washes 1~3 with water
It is secondary, then according to organic phase and the volume ratio 1 of saturated sodium-chloride water solution：1.0~1.5 wash 1 with saturated sodium-chloride water solution
~3 times.
In this step, the crude product for obtaining is purified under normal temperature condition with dry method upper prop by silicagel column.
In this step, it is the condition in 40~60 DEG C of temperature with 0.01~0.1MPa of pressure using method concentrated under reduced pressure
Under carry out recycling design.
E, the object that step D is obtained is dissolved in 80~120mL tetrahydrofurans, add in terms of target weight 7~
9% palladium-carbon catalyst, 7~9h of hydrogenation reaction is carried out under conditions of 50~60 DEG C of temperature, allows reaction solution to pass through diatomite mistake
Filter, the filtrate for obtaining is concentrated under reduced pressure, and obtains a kind of concentrate；
The palladium-carbon catalyst that the present invention is used is the product sold in the market, such as by Sigma-Aldarich companies
With the palladium-carbon catalyst that trade name Palladium sells.
Described hydrogenation reaction be in autoclave, after being passed through the 2-3 hydrogen of atmospheric pressure, stirring reaction.
F, that the concentrate that step E is obtained is dissolved in into the trifluoroacetic acid that 80~120mL concentration is by weight 8~12% is water-soluble
In liquid, it is placed in oil bath and 1~2h is reacted at 56~64 DEG C of temperature, then several times to adding absolute ethyl alcohol in the reaction solution,
Reaction solution and the weight ratio of absolute ethyl alcohol is set to reach 1：1~2, then be concentrated under reduced pressure, the concentrate for obtaining passes through C18 reverse-phase chromatographic columns
Purifying, is first eluted with pure water, then with concentration for 50~70% methanol aqueous solutions by weight are eluted, collects first paragraph cut work
It is object, it obtains described Amadori compounds by freeze-drying.
The C18 reverse-phase chromatographic columns that the present invention is used are the products sold in the market, such as by Merck ＆ Co., Inc. with commodity
The product of name TLC Silica gel 60RP-18F254S sale.
In step E and step F, using method concentrated under reduced pressure 50~75 DEG C of temperature and 0.01~0.1MPa of pressure bar
It is concentrated under reduced pressure under part.
In the present invention, freeze-drying is the temperature described in its specification using the freeze drying box sold in the market
Carried out according to its mode of operation for illustrating under the conditions of degree.
In this step, using thin layer chromatography analysis method in solvent (methyl alcohol：Water volume ratio=1:1), dilute sulfuric acid
Analyzed under color condition and determined, first paragraph cut object is Amadori compounds, tool by the product obtained by freeze-drying
It is 1- deoxidations -1-L- glycine-D-Fructose, 1- deoxidations -1-L- proline-D-Fructose, 1- deoxidation -1-L- alanine-D- body
The Amadori compounds such as fructose.
[beneficial effect]
The beneficial effects of the invention are as follows：Amadori compounds process for production thereof step of the present invention is simple, mild condition, does not arrange
What pollutant or toxic waste are let alone, is conducive to environmental protection, up to more than 90%, product purity reaches the preparation method high income
More than 98%.
【Specific embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：Amadori compound synthesis of the present invention
The implementation steps of the embodiment are as follows：
A, at ambient temperature, 1 is compared according to the weight of D-Fructose and acetone：16, D-Fructose is dissolved in acetone, obtain one
Plant D-Fructose acetone soln；Weight according still further to D-Fructose and the concentrated sulfuric acid compares 1：1.4, dense sulphur is added dropwise toward D-Fructose acetone soln
Acid, stirs 1.4h, obtains double propylidene base fructose solns；Then
Described double propylidene base fructose soln concentration 1N sodium hydrate aqueous solutions are neutralized to pH7.2, then in temperature 20
DEG C with pressure 0.1MPa under conditions of be concentrated under reduced pressure reclaim acetone；The raffinate obtained after acetone is reclaimed to be extracted with ethyl acetate, its
Middle raffinate is 1 with ethyl acetate volume ratio：1；Ethyl acetate organic phase is washed with water 3 times, the volume of each ethyl acetate and water
Than being 1：2, then toward anhydrous sodium sulfate dehydration is added in ethyl acetate organic phase, filter, recycling design is rotated, obtain light yellow
Solid product；
B, under condition of ice bath, the product as light yellow solid that step A is obtained with pyridine solvent dissolve, wherein solid product with
The weight ratio of pyridine is 1：14, the weight according still further to solid product and trifluoromethanesulfanhydride anhydride compares 1：3 toward being added dropwise three in pyridine solution
Fluorine methanesulfonic acid acid anhydride, then reacts 25min at -30 DEG C of temperature, adds 0.8mol/L aqueous hydrochloric acid solutions and is neutralized to pH6.4；Should
Neutralize solution to be extracted with ethyl acetate 3 times, it is 1 that solution is neutralized every time with the volume of ethyl acetate：1, the ethyl acetate extraction of merging
Liquid anhydrous sodium sulfate dehydration is taken, is filtered, rotate recycling design, residue carries out silica gel with dry method upper prop under normal temperature condition again
Post is purified, with petroleum ether and ethyl acetate according to volume ratio 8：The mixture wash-out of 1 mixing, collects Amadori compound targets
Thing cut, is recovered under reduced pressure the solvent being made up of petroleum ether and ethyl acetate under conditions of pressure 0.01MPa, obtains residual solids
Product；
C, proline benzyl ester salt is added in flask, the methanolic ammonia solution that concentration is by weight 7% is added dropwise in ice bath,
Stirring 16min, stands 12min, then the recycling design that is concentrated under reduced pressure under conditions of 12 DEG C of temperature with pressure 0.01MPa, is lived
Change amino-acid benzyl ester salt；
D, compare 1 according to the weight of amino-acid benzyl ester salt and DMF solvent：2.2, the amino-acid benzyl ester salt that step D is obtained is molten
In DMF solvent, the residual solids product that step B is obtained is subsequently added into, be well mixed, carried out under temperature 70 C in oil bath
Reaction 1.0h, adds 80ml deionized waters that reaction is quenched, according to the volume 1 that reaction solution and ethyl acetate is quenched：0.5, it is quenched anti-
Liquid is answered to be extracted with ethyl acetate 3 times, the volume ratio 1 of the ethyl acetate organic phase according to organic phase and water of separation：1 washes with water
1 time, then according to organic phase and the volume ratio 1 of saturated sodium-chloride water solution：1.0 are washed 2 times with saturated sodium-chloride water solution, are connect
And use anhydrous sodium sulfate dehydration, filtering, recycling design, the crude product for obtaining passes through silicagel column with dry method upper prop under normal temperature condition again
Purified, eluted with petroleum ether and ethyl acetate mixture, wherein petroleum ether and the volume ratio of ethyl acetate is 1.5：1, receive
Collection object cut, is to carry out recycling design under conditions of 40 DEG C of temperature with pressure 0.08MPa using method concentrated under reduced pressure, is obtained
To object；
E, the object that step D is obtained is dissolved in 80mL tetrahydrofurans, adds in terms of target weight 7% palladium carbon and urge
Agent, carries out hydrogenation reaction 9h under conditions of temperature 50 C, allows reaction solution to be filtered by diatomite, and the filtrate for obtaining uses
Method concentrated under reduced pressure is concentrated under reduced pressure under conditions of 58 DEG C of temperature with pressure 0.01MPa, obtains a kind of concentrate；
F, the concentrate that step E is obtained is dissolved in 94mL concentration is by weight in 8% trifluoroacetic acid aqueous solution, to be placed in
React 1.0h at 56 DEG C of temperature in oil bath, then several times to absolute ethyl alcohol is added in the reaction solution, make reaction solution with it is anhydrous
The weight ratio of ethanol reaches 1：1, then depressurized under conditions of temperature 50 C with pressure 0.01MPa using method concentrated under reduced pressure
Concentration, the concentrate for obtaining purifies by C18 reverse-phase chromatographic columns, is first eluted with pure water, is then by weight 50% with concentration
Methanol aqueous solution is eluted, and collects first paragraph cut as object, and it obtains described Amadori chemical combination by freeze-drying
Thing.
The analysis method described using this specification determines that first paragraph cut object is by the product obtained by freeze-drying
Thing is 1- deoxidations -1-L- glycine-D-Fructose Amadori compounds.
The embodiment prepares the yield 92% of Amadori compounds, product purity 98.6%.
Embodiment 2：Amadori compound synthesis of the present invention
The implementation steps of the embodiment are as follows：
A, at ambient temperature, 1 is compared according to the weight of D-Fructose and acetone：12, D-Fructose is dissolved in acetone, obtain one
Plant D-Fructose acetone soln；Weight according still further to D-Fructose and the concentrated sulfuric acid compares 1：1.0, dense sulphur is added dropwise toward D-Fructose acetone soln
Acid, stirs 1.2h, obtains double propylidene base fructose solns；Then
Described double propylidene base fructose soln concentration 4N sodium hydrate aqueous solutions are neutralized to pH7.8, then in temperature 26
DEG C with pressure 0.06MPa under conditions of be concentrated under reduced pressure reclaim acetone；The raffinate obtained after acetone is reclaimed to be extracted with ethyl acetate, its
Middle raffinate is 1 with ethyl acetate volume ratio：2；Ethyl acetate organic phase is washed with water 2 times, the volume of each ethyl acetate and water
Than being 1：1, then toward anhydrous sodium sulfate dehydration is added in ethyl acetate organic phase, filter, recycling design is rotated, obtain light yellow
Solid product；
B, under condition of ice bath, the product as light yellow solid that step A is obtained with pyridine solvent dissolve, wherein solid product with
The weight ratio of pyridine is 1：10, the weight according still further to solid product and trifluoromethanesulfanhydride anhydride compares 1：5 toward being added dropwise three in pyridine solution
Fluorine methanesulfonic acid acid anhydride, then reacts 30min at -22 DEG C of temperature, adds 1.0mol/L aqueous hydrochloric acid solutions and is neutralized to pH6.0；Should
Neutralize solution to be extracted with ethyl acetate 2 times, it is 1 that solution is neutralized every time with the volume of ethyl acetate：2, the ethyl acetate extraction of merging
Liquid anhydrous sodium sulfate dehydration is taken, is filtered, rotate recycling design, residue carries out silica gel with dry method upper prop under normal temperature condition again
Post is purified, with petroleum ether and ethyl acetate according to volume ratio 10：The mixture wash-out of 1 mixing, collects Amadori compound targets
Thing cut, is recovered under reduced pressure the solvent being made up of petroleum ether and ethyl acetate under conditions of pressure 0.04MPa, obtains residual solids
Product；
C, alanine benzyl ester salt is added in flask, the methanolic ammonia solution that concentration is by weight 5% is added dropwise in ice bath,
Stirring 12min, stands 18min, then the recycling design that is concentrated under reduced pressure under conditions of 5 DEG C of temperature with pressure 0.1MPa, is activated
Amino-acid benzyl ester salt；
D, compare 1 according to the weight of amino-acid benzyl ester salt and DMF solvent：1.5, the amino-acid benzyl ester salt that step D is obtained is molten
In DMF solvent, the residual solids product that step B is obtained is subsequently added into, be well mixed, carried out under temperature 70 C in oil bath
Reaction 2.5h, adds 100ml deionized waters that reaction is quenched, according to the volume 1 that reaction solution and ethyl acetate is quenched：0.6, it is quenched anti-
Liquid is answered to be extracted with ethyl acetate 2 times, the volume ratio 1 of the ethyl acetate organic phase according to organic phase and water of separation：2 wash with water
3 times, then according to organic phase and the volume ratio 1 of saturated sodium-chloride water solution：1.5 are washed 1 time with saturated sodium-chloride water solution, are connect
And use anhydrous sodium sulfate dehydration, filtering, recycling design, the crude product for obtaining passes through silicagel column with dry method upper prop under normal temperature condition again
Purified, eluted with petroleum ether and ethyl acetate mixture, wherein petroleum ether and the volume ratio of ethyl acetate is 2.5：1, receive
Collection object cut, is to carry out recycling design under conditions of temperature 60 C and pressure 0.03MPa using method concentrated under reduced pressure, is obtained
To object；
E, the object that step D is obtained is dissolved in 95mL tetrahydrofurans, adds in terms of target weight 8% palladium carbon and urge
Agent, hydrogenation reaction 8.2h is carried out under conditions of 52 DEG C of temperature, allows reaction solution to be filtered by diatomite, and the filtrate for obtaining is adopted
It is concentrated under reduced pressure under conditions of temperature 50 C with pressure 0.02MPa with method concentrated under reduced pressure, is obtained a kind of concentrate；
F, the concentrate that step E is obtained is dissolved in 80mL concentration is by weight in 10% trifluoroacetic acid aqueous solution, to put
2.0h is reacted at 58 DEG C of temperature in oil bath, then makes reaction solution and nothing to absolute ethyl alcohol is added in the reaction solution several times
The weight ratio of water-ethanol reaches 1：2, then subtracted under conditions of temperature 60 C with pressure 0.1MPa using method concentrated under reduced pressure
Pressure concentration, the concentrate for obtaining is purified by C18 reverse-phase chromatographic columns, is first eluted with pure water, then with concentration for by weight
60% methanol aqueous solution is eluted, and collects first paragraph cut as object, and it obtains described Amadori by freeze-drying
Compound.
The analysis method described using this specification determines that first paragraph cut object is by the product obtained by freeze-drying
Thing is 1- deoxidations -1-L- proline-D-Fructose Amadori compounds.
The embodiment prepares the yield 93.2% of Amadori compounds, product purity 98.4%.
Embodiment 3：Amadori compound synthesis of the present invention
The implementation steps of the embodiment are as follows：
A, at ambient temperature, 1 is compared according to the weight of D-Fructose and acetone：18, D-Fructose is dissolved in acetone, obtain one
Plant D-Fructose acetone soln；Weight according still further to D-Fructose and the concentrated sulfuric acid compares 1：2.0, dense sulphur is added dropwise toward D-Fructose acetone soln
Acid, stirs 1.6h, obtains double propylidene base fructose solns；Then
Described double propylidene base fructose soln concentration 2N sodium hydrate aqueous solutions are neutralized to pH 8.0, then in temperature 34
DEG C with pressure 0.04MPa under conditions of be concentrated under reduced pressure reclaim acetone；The raffinate obtained after acetone is reclaimed to be extracted with ethyl acetate, its
Middle raffinate is 1 with ethyl acetate volume ratio：3；Ethyl acetate organic phase is washed with water 4 times, the volume of each ethyl acetate and water
Than being 1：2, then toward anhydrous sodium sulfate dehydration is added in ethyl acetate organic phase, filter, recycling design is rotated, obtain light yellow
Solid product；
B, under condition of ice bath, the product as light yellow solid that step A is obtained with pyridine solvent dissolve, wherein solid product with
The weight ratio of pyridine is 1：15, the weight according still further to solid product and trifluoromethanesulfanhydride anhydride compares 1：4 toward being added dropwise three in pyridine solution
Fluorine methanesulfonic acid acid anhydride, then reacts 35min at -16 DEG C of temperature, adds 1.2mol/L aqueous hydrochloric acid solutions and is neutralized to pH6.8；Should
Neutralize solution to be extracted with ethyl acetate 4 times, it is 1 that solution is neutralized every time with the volume of ethyl acetate：3, the ethyl acetate extraction of merging
Liquid anhydrous sodium sulfate dehydration is taken, is filtered, rotate recycling design, residue carries out silica gel with dry method upper prop under normal temperature condition again
Post is purified, with petroleum ether and ethyl acetate according to volume ratio 12：The mixture wash-out of 1 mixing, collects Amadori compound targets
Thing cut, is recovered under reduced pressure the solvent being made up of petroleum ether and ethyl acetate under conditions of pressure 0.1MPa, obtains residual solids
Product；
C, glycine benzyl ester salt is added in flask, the ammonia methyl alcohol that concentration is by weight 10% is added dropwise in ice bath molten
Liquid, stirs 14min, stands 14min, then the recycling design that is concentrated under reduced pressure under conditions of 15 DEG C of temperature with pressure 0.08MPa, obtains
Activated amino acid benzyl ester salt；
D, compare 1 according to the weight of amino-acid benzyl ester salt and DMF solvent：2.5, the amino-acid benzyl ester salt that step D is obtained is molten
In DMF solvent, the residual solids product that step B is obtained is subsequently added into, be well mixed, carried out under temperature 70 C in oil bath
Reaction 1.6h, adds 100ml deionized waters that reaction is quenched, according to the volume 1 that reaction solution and ethyl acetate is quenched：1.0, it is quenched anti-
Liquid is answered to be extracted with ethyl acetate 4 times, the volume ratio 1 of the ethyl acetate organic phase according to organic phase and water of separation：2 wash with water
2 times, then according to organic phase and the volume ratio 1 of saturated sodium-chloride water solution：1.2 are washed 3 times with saturated sodium-chloride water solution, are connect
And use anhydrous sodium sulfate dehydration, filtering, recycling design, the crude product for obtaining passes through silicagel column with dry method upper prop under normal temperature condition again
Purified, eluted with petroleum ether and ethyl acetate mixture, wherein petroleum ether and the volume ratio of ethyl acetate is 1.8：1, receive
Collection object cut, is to carry out recycling design under conditions of 48 DEG C of temperature with pressure 0.01MPa using method concentrated under reduced pressure, is obtained
To object；
E, the object that step D is obtained is dissolved in 120mL tetrahydrofurans, adds 9% palladium carbon in terms of target weight
Catalyst, hydrogenation reaction 7.6h is carried out under conditions of 56 DEG C of temperature, allows reaction solution to be filtered by diatomite, the filtrate for obtaining
It is concentrated under reduced pressure under conditions of 66 DEG C of temperature with pressure 0.1MPa using method concentrated under reduced pressure, is obtained a kind of concentrate；
F, the concentrate that step E is obtained is dissolved in 120mL concentration is by weight in 12% trifluoroacetic acid aqueous solution, to put
1.5h is reacted at 64 DEG C of temperature in oil bath, then makes reaction solution and nothing to absolute ethyl alcohol is added in the reaction solution several times
The weight ratio of water-ethanol reaches 1：1, then subtracted under conditions of 75 DEG C of temperature with pressure 0.04MPa using method concentrated under reduced pressure
Pressure concentration, the concentrate for obtaining is purified by C18 reverse-phase chromatographic columns, is first eluted with pure water, then with concentration for by weight
70% methanol aqueous solution is eluted, and collects first paragraph cut as object, and it obtains described Amadori by freeze-drying
Compound.
The analysis method described using this specification determines that first paragraph cut object is by the product obtained by freeze-drying
Thing is 1- deoxidations -1-L- alanine-D-Fructose Amadori compounds.
The embodiment prepares the yield 95.1% of Amadori compounds, product purity 99.2%.
Embodiment 4：Amadori compound synthesis of the present invention
The implementation steps of the embodiment are as follows：
A, at ambient temperature, 1 is compared according to the weight of D-Fructose and acetone：14, D-Fructose is dissolved in acetone, obtain one
Plant D-Fructose acetone soln；Weight according still further to D-Fructose and the concentrated sulfuric acid compares 1：1.6, dense sulphur is added dropwise toward D-Fructose acetone soln
Acid, stirs 1.8h, obtains double propylidene base fructose solns；Then
Described double propylidene base fructose soln concentration 3N sodium hydrate aqueous solutions are neutralized to pH 7.5, then in temperature 40
DEG C with pressure 0.01MPa under conditions of be concentrated under reduced pressure reclaim acetone；The raffinate obtained after acetone is reclaimed to be extracted with ethyl acetate, its
Middle raffinate is 1 with ethyl acetate volume ratio：2；Ethyl acetate organic phase is washed with water 3 times, the volume of each ethyl acetate and water
Than being 1：3, then toward anhydrous sodium sulfate dehydration is added in ethyl acetate organic phase, filter, recycling design is rotated, obtain light yellow
Solid product；
B, under condition of ice bath, the product as light yellow solid that step A is obtained with pyridine solvent dissolve, wherein solid product with
The weight ratio of pyridine is 1：12, the weight according still further to solid product and trifluoromethanesulfanhydride anhydride compares 1：4 toward being added dropwise three in pyridine solution
Fluorine methanesulfonic acid acid anhydride, then reacts 30min at -10 DEG C of temperature, adds 1.0mol/L aqueous hydrochloric acid solutions and is neutralized to pH7.0；Should
Neutralize solution to be extracted with ethyl acetate 3 times, it is 1 that solution is neutralized every time with the volume of ethyl acetate：2, the ethyl acetate extraction of merging
Liquid anhydrous sodium sulfate dehydration is taken, is filtered, rotate recycling design, residue carries out silica gel with dry method upper prop under normal temperature condition again
Post is purified, with petroleum ether and ethyl acetate according to volume ratio 10：The mixture wash-out of 1 mixing, collects Amadori compound targets
Thing cut, is recovered under reduced pressure the solvent being made up of petroleum ether and ethyl acetate under conditions of pressure 0.08MPa, obtains residual solids
Product；
C, proline benzyl ester salt is added in flask, the ammonia methyl alcohol that concentration is by weight 75109% is added dropwise in ice bath
Solution, stirs 18min, stands 16min, then the recycling design that is concentrated under reduced pressure under conditions of 8 DEG C of temperature with pressure 0.06MPa, obtains
To activated amino acid benzyl ester salt；
D, compare 1 according to the weight of amino-acid benzyl ester salt and DMF solvent：1.8, the amino-acid benzyl ester salt that step D is obtained is molten
In DMF solvent, the residual solids product that step B is obtained is subsequently added into, be well mixed, carried out under temperature 70 C in oil bath
Reaction 2.1h, adds 120ml deionized waters that reaction is quenched, according to the volume 1 that reaction solution and ethyl acetate is quenched：0.8, it is quenched anti-
Liquid is answered to be extracted with ethyl acetate 3 times, the volume ratio 1 of the ethyl acetate organic phase according to organic phase and water of separation：1 washes with water
2 times, then according to organic phase and the volume ratio 1 of saturated sodium-chloride water solution：1.4 are washed 2 times with saturated sodium-chloride water solution, are connect
And use anhydrous sodium sulfate dehydration, filtering, recycling design, the crude product for obtaining passes through silicagel column with dry method upper prop under normal temperature condition again
Purified, eluted with petroleum ether and ethyl acetate mixture, wherein petroleum ether and the volume ratio of ethyl acetate is 2.4：1, receive
Collection object cut, is to carry out recycling design under conditions of 55 DEG C of temperature with pressure 0.1MPa using method concentrated under reduced pressure, is obtained
To object；
E, the object that step D is obtained is dissolved in 110mL tetrahydrofurans, adds 8% palladium carbon in terms of target weight
Catalyst, carries out hydrogenation reaction 7.0h under conditions of temperature 60 C, allows reaction solution to be filtered by diatomite, the filtrate for obtaining
It is concentrated under reduced pressure under conditions of 75 DEG C of temperature with pressure 0.07MPa using method concentrated under reduced pressure, is obtained a kind of concentrate；
F, the concentrate that step E is obtained is dissolved in 108mL concentration is by weight in 9% trifluoroacetic acid aqueous solution, to put
1.7h is reacted at 62 DEG C of temperature in oil bath, then makes reaction solution and nothing to absolute ethyl alcohol is added in the reaction solution several times
The weight ratio of water-ethanol reaches 1：2, then subtracted under conditions of temperature 70 C with pressure 0.06MPa using method concentrated under reduced pressure
Pressure concentration, the concentrate for obtaining is purified by C18 reverse-phase chromatographic columns, is first eluted with pure water, then with concentration for by weight
60% methanol aqueous solution is eluted, and collects first paragraph cut as object, and it obtains described Amadori by freeze-drying
Compound.
The analysis method described using this specification determines that first paragraph cut object is by the product obtained by freeze-drying
Thing is 1- deoxidations -1-L- proline-D-Fructose Amadori compounds.
The embodiment prepares the yield 90.8% of Amadori compounds, product purity 98.6%.
Claims (10)
1. a kind of Amadori compound synthesis method, it is characterised in that as follows the step of the synthetic method：
A, at ambient temperature, 1 is compared according to the weight of D-Fructose and acetone：12~18, D-Fructose is dissolved in acetone, obtain one
Plant D-Fructose acetone soln；Weight according still further to D-Fructose and the concentrated sulfuric acid compares 1：1~2, it is added dropwise toward D-Fructose acetone soln dense
Sulfuric acid, stirs 1.2~1.8h, obtains double propylidene base fructose solns；Then
Described double propylidene base fructose soln sodium hydrate aqueous solutions are neutralized to pH7~8, then in 20~40 DEG C of temperature and pressure
It is concentrated under reduced pressure under conditions of 0.01~0.1MPa of power and reclaims acetone；The raffinate obtained after acetone is reclaimed to be extracted with ethyl acetate, its
Middle raffinate is 1 with ethyl acetate volume ratio：1~3；Then toward anhydrous sodium sulfate dehydration is added in ethyl acetate organic phase, filter,
Revolving recycling design, obtains product as light yellow solid；
B, under condition of ice bath, the product as light yellow solid that step A is obtained pyridine solvent dissolves, wherein solid product and pyridine
Weight ratio be 1：10~15, the weight according still further to solid product and trifluoromethanesulfanhydride anhydride compares 1：3~5 are added dropwise toward in pyridine solution
Trifluoromethanesulfanhydride anhydride, then reacts 25~35min at temperature -30~-10 DEG C, adds 0.8~1.2mol/L hydrochloric acid water-soluble
Liquid is neutralized to pH6~7；The neutralization solution is extracted with ethyl acetate 2~4 times, solution is neutralized every time and is with the volume of ethyl acetate
1：1~3, the acetic acid ethyl acetate extract anhydrous sodium sulfate dehydration of merging, filtering rotates recycling design, and residue passes through silicon again
Glue post is purified, with petroleum ether and ethyl acetate according to volume ratio 8~12：The mixture wash-out of 1 mixing, collects Amadori chemical combination
Thing object cut, is recovered under reduced pressure solvent, obtains residual solids product；
C, amino-acid benzyl ester salt is added in flask, the methanolic ammonia solution that concentration is by weight 5~10% is added dropwise in ice bath,
12~18min of stirring, stands 12~18min, then be concentrated under reduced pressure under conditions of 5~15 DEG C of temperature with 0.01~0.1MPa of pressure
Recycling design, obtains activated amino acid benzyl ester salt；
D, compare 1 according to the weight of amino-acid benzyl ester salt and DMF solvent：1.5~2.5, the amino-acid benzyl ester salt that step D is obtained is molten
In DMF solvent, the residual solids product that step B is obtained is subsequently added into, be well mixed, carried out under temperature 70 C in oil bath
1.0~2.5h of reaction, adds 80~120ml deionized waters that reaction is quenched, according to the volume 1 that reaction solution and ethyl acetate is quenched：
0.5~1.0, reaction solution is quenched and is extracted with ethyl acetate 2~4 times, the ethyl acetate organic phase of separation is washed with water, then uses full
With sodium-chloride water solution washing, then with anhydrous sodium sulfate dehydration, filtering, recycling design, the crude product for obtaining passes through silicagel column again
Purifying, is eluted with petroleum ether and ethyl acetate mixture, and wherein petroleum ether and the volume ratio of ethyl acetate is 1.5~2.5：1, receive
Collection object cut, recycling design obtains object；
E, the object that step D is obtained is dissolved in 80~120mL tetrahydrofurans, adds 7~9% palladium in terms of target weight
C catalyst, 7~9h of hydrogenation reaction is carried out under conditions of 50~60 DEG C of temperature, allows reaction solution to be filtered by diatomite, is obtained
To filtrate be concentrated under reduced pressure, obtain a kind of concentrate；
F, the concentrate that step E is obtained is dissolved in the trifluoroacetic acid aqueous solution that 80~120mL concentration is by weight 8~12%
In, it is placed in oil bath and 1~2h is reacted at 56~64 DEG C of temperature, then make to absolute ethyl alcohol is added in the reaction solution several times
Reaction solution reaches 1 with the weight ratio of absolute ethyl alcohol：1~2, then be concentrated under reduced pressure, the concentrate for obtaining is pure by C18 reverse-phase chromatographic columns
Change, first eluted with pure water, then with concentration for 50~70% methanol aqueous solutions by weight are eluted, collection first paragraph cut conduct
Object, it obtains described Amadori compounds by freeze-drying.
2. Amadori compound synthesis method according to claim 1, it is characterised in that in step, the NaOH
The concentration of the aqueous solution is 1~4N.
3. Amadori compound synthesis method according to claim 1, it is characterised in that in step, after acetone is reclaimed
The raffinate for obtaining is extracted 2~4 times in the same way using ethyl acetate.
4. Amadori compound synthesis method according to claim 1, it is characterised in that in stepb, existed with dry method upper prop
Silicagel column purifying is carried out under normal temperature condition.
5. Amadori compound synthesis method according to claim 1, it is characterised in that in stepb, pressure 0.01~
The solvent being made up of petroleum ether and ethyl acetate is recovered under reduced pressure under conditions of 0.1MPa.
6. Amadori compound synthesis method according to claim 1, it is characterised in that in step C, amino-acid benzyl ester salt
It is proline benzyl ester salt, alanine benzyl ester salt or glycine benzyl ester salt.
7. Amadori compound synthesis method according to claim 1, it is characterised in that in step D, ethyl acetate is organic
According to organic phase and the volume ratio 1 of water：1~2 washes with water 1~3 time, then according to organic phase and saturated sodium-chloride water solution
Volume ratio 1：1.0~1.5 are washed 1~3 time with saturated sodium-chloride water solution.
8. Amadori compound synthesis method according to claim 1, it is characterised in that in step D, the crude product for obtaining with
Dry method upper prop is purified under normal temperature condition by silicagel column.
9. Amadori compound synthesis method according to claim 1, it is characterised in that in step D, using concentrated under reduced pressure
Method is to carry out recycling design under conditions of 40~60 DEG C of temperature with 0.01~0.1MPa of pressure.
10. Amadori compound synthesis method according to claim 1, it is characterised in that in step E and step F, uses
Method concentrated under reduced pressure is concentrated under reduced pressure under conditions of 50~75 DEG C of temperature with 0.01~0.1MPa of pressure.
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| CN112920238A (en) * | 2021-01-27 | 2021-06-08 | 河南农业大学 | Sugar amine Amadori derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704850A (en) * | 2009-10-21 | 2010-05-12 | 安徽中烟工业公司 | Method for separating and extracting compound of Amadori of Maillard reaction midbody |
| CN103113428A (en) * | 2013-02-06 | 2013-05-22 | 宁波美康生物科技股份有限公司 | Fructoselysine preparation method |
-
2016
- 2016-12-01 CN CN201611087461.2A patent/CN106749438A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704850A (en) * | 2009-10-21 | 2010-05-12 | 安徽中烟工业公司 | Method for separating and extracting compound of Amadori of Maillard reaction midbody |
| CN103113428A (en) * | 2013-02-06 | 2013-05-22 | 宁波美康生物科技股份有限公司 | Fructoselysine preparation method |
Non-Patent Citations (3)
| Title |
|---|
| D. XENAKIS,等: "Organic Synthesis of Amadori Rearrangement Products", 《SYNTHESIS》 * |
| S.N. NOOMEN，等: "The synthesis of pure Amadori rearrangement products", 《RECL. TRAV. CHIM. PAYS-BAS》 * |
| 王军，等: "Amadori化合物合成方法综述", 《烟草化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920238A (en) * | 2021-01-27 | 2021-06-08 | 河南农业大学 | Sugar amine Amadori derivative and preparation method and application thereof |
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