CN108299354A - A kind of preparation method of 2,5- furandicarboxylic acids or its carboxylate - Google Patents
A kind of preparation method of 2,5- furandicarboxylic acids or its carboxylate Download PDFInfo
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- CN108299354A CN108299354A CN201710021911.6A CN201710021911A CN108299354A CN 108299354 A CN108299354 A CN 108299354A CN 201710021911 A CN201710021911 A CN 201710021911A CN 108299354 A CN108299354 A CN 108299354A
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- 0 *C(C1=CC=C(*(N*=I)=O)[U]C1)=O Chemical compound *C(C1=CC=C(*(N*=I)=O)[U]C1)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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Abstract
The present invention relates to the preparation methods of a kind of 2,5 furandicarboxylic acids or its carboxylate, specifically, the method includes the steps：(a) solution system containing 2 acetyl group, 5 furancarboxylic acid or its carboxylate and halogen is provided；(b) pH to 7 10 for adjusting the solution system, removes the solid generated in the solution system, obtains liquid reaction mixture；(c) pH to 04 for adjusting the liquid reaction mixture, obtains described 2,5 furandicarboxylic acids or its carboxylate；Wherein, the structure of 2 acetyl group, 5 furancarboxylic acid or its carboxylate and 2,5 furandicarboxylic acids or its carboxylate is as noted in the discussion.The method of the present invention has many advantages, such as high income, and it is convenient to prepare.
Description
Technical field
The invention belongs to high-performance polymer monomers to prepare the technical field with chemical industry, medicine intermediate, and in particular, to
A kind of preparation method of 2,5- furandicarboxylic acids or its carboxylate.
Background technology
2,5-furandicarboxylic acid because containing rigidity furan nucleus and contraposition diformyl structure, can be directly used for polyester,
The preparation of the high performance polymer such as epoxy resin, polyamide, polyurethane.The polymer prepared using furans diacid is in intensity, mould
Amount, creep resistant etc. have excellent mechanical property, while having higher glass transition temperature and heat distortion temperature.This
Outside, 2,5-furandicarboxylic acid or its carboxylate itself can also be used as industrial chemicals and medicine intermediate uses.2,5- furans at present
It mutters dioctyl phthalate or the main synthetic method of its carboxylate is with expensive 5 hydroxymethyl furfural (HMF) for raw material.This method
Disadvantage low with gross production rate, of high cost is difficult to realize the shortcomings that heavy industrialization is applied.
In conclusion the present invention still lacks the method for conveniently and efficiently preparing 2,5-furandicarboxylic acid or its carboxylate.
Invention content
The object of the present invention is to provide a kind of method conveniently and efficiently preparing 2,5-furandicarboxylic acid or its carboxylate,
The method includes the steps：
(a) solution system containing 2- acetyl group -5- furancarboxylic acids or its carboxylate and halogen is provided；
(b) pH to 7-10 for adjusting the solution system, removes the solid generated in the solution system, it is anti-to obtain liquid phase
Answer mixture；
(c) pH to 0-4 for adjusting the liquid reaction mixture, obtains the 2,5-furandicarboxylic acid or its carboxylate
(I)；
Wherein, the 2,5-furandicarboxylic acid or its carboxylate have Formulas I structure：
2- acetyl group -5- the furancarboxylic acids or its carboxylate have Formula II structure：
In formula,
R1' be selected from the group：H, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted phenyl, substitution
Or unsubstituted cyclopenta, substituted or unsubstituted cyclohexyl, wherein " substituted ", which refers to, has one or more (such as 1-5
A, preferably 1-3) substituent group is selected from the group：H、OCH3, F, Cl, Br, I, C1-C3 alkyl；
R1It is selected from the group：H, methyl；Or R1=R1’。
In another preferred example, in the step (a), solution system is prepared by the following method：By 2- acetyl group -5-
Furancarboxylic acid or its carboxylate and halogen are dissolved in atent solvent, obtain solution system.
In another preferred example, in the step (a), the atent solvent is the mixing of water or water and organic solvent
Solvent.
In another preferred example, in the step (a), solution system is prepared by the following method：By 2- acetyl group -5- chaffs
Acid or its esterification are dissolved in water and/or organic solvent A and obtain solution A 1, halogen is dissolved in water and/or organic solvent B obtain it is molten
Solution A 1 and B1 are mixed to get the solution system by liquid B1.
In another preferred example, the step (a), (b) and/or (c) under Elevated Temperature Conditions (such as 30-140 DEG C) into
Row.
In another preferred example, B1 is added in A1 under Elevated Temperature Conditions (such as 30-140 DEG C) and is mixed, to obtain
The solution system stated.
In another preferred example, in the A1, the volume ratio of organic solvent and water is 0-99:1.
In another preferred example, in the B1, the volume ratio of organic solvent and water is 0-20:1.
In another preferred example, in the step (a), the inertia is added in the halogen at 0-160 DEG C
Solvent.
In another preferred example, the upper limit of the range of reaction temperature is selected from 140 DEG C, 120 DEG C, 100 DEG C, and lower limit is selected from 20
℃、40℃、60℃、80℃。
In another preferred example, halogen described in the step (a) is selected from the group：Halogen simple substance, the chemical combination containing halogen
Object, or combinations thereof.
In another preferred example, the halogen in the step (a) includes：Halogen simple substance, halide ion, or contain halide ion
Group.
In another preferred example, the halogen is F, Cl, Br, I.
In another preferred example, the compound containing halogen is the inorganic compound containing halogen；Preferably contain
The salt (such as metal halide salt, secondary halide) of halogen.
In another preferred example, the compound containing halogen is selected from the group：Sodium hypochlorite, hypoiodous acid sodium, hypobromous acid
Sodium, potassium iodide, or combinations thereof.
In another preferred example, the 2- acetyl group -5- furancarboxylic acids or its carboxylate are selected from the group：2- acetyl group -5- furancarboxylic acids,
2- acetyl group -5- methylfuroates, 2- acetyl group -5- ethyl furoates, 2- acetyl group -5- furancarboxylic acids propyl ester, 2- acetyl group -5- furancarboxylic acid fourths
Ester, 2- acetyl group -5- amyl furoates, the own ester of 2- acetyl group -5- furancarboxylic acids, 2- acetyl group -5- furancarboxylic acids heptyl ester, 2- acetyl group -5- chaffs
Misery ester, 2- acetyl group -5- furancarboxylic acid nonyls ester, 2- acetyl group -5- furancarboxylic acid last of the ten Heavenly stems esters, or combinations thereof.
In another preferred example, the organic solvent is selected from the group：The ethers of C2-C10, the alcohols of C3-C10, C2-C10
Oxygen-containing cycloalkane, n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), or combinations thereof.
In another preferred example, the organic solvent is selected from the group：Ether, propylene glycol, 1,4- dioxane, N, N- diformazans
Yl acetamide, dimethyl sulfoxide (DMSO), or combinations thereof.
In another preferred example, the organic solvent is selected from the group：1,4- dioxane, DMAC N,N' dimethyl acetamide, two
Methyl sulfoxide, or combinations thereof.
In another preferred example, further include in the step (b)：The pH value that alkali adjusts solution system is added, wherein described
Alkali be selected from the group：The oxide of alkali or alkaline earth metal, the hydroxide of alkali or alkaline earth metal, alkali metal or alkaline earth
Carbonate, the ammonium hydroxide of metal, or combinations thereof.
In another preferred example, the alkali is solution form or pure substance.
In another preferred example, the alkali is selected from the group：Sodium hydroxide, potassium hydroxide, hydrogen-oxygen lithium, rubidium hydroxide, hydrogen-oxygen
Change caesium, barium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide, or combinations thereof.
In another preferred example, the solution of the alkali is the aqueous solution of alkali.
In another preferred example, in the solution of the alkali alkali a concentration of 0.01-10mol/L, preferably 0.1-10mol/
L, more preferably 1-5mol/L.
In another preferred example, the pH of solution system is 7-9 in the step (b).
In another preferred example, further include that acid selected from the group below is added to adjust the solution system in the step (c)
PH value：Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, methanesulfonic acid, boron trifluoride etherate, benzene methanesulfonic acid, or combinations thereof.
In another preferred example, the solution of the acid is the aqueous solution of acid.
In another preferred example, a concentration of 0.01-10mol/L, preferably 0.1-10mol/ sour in the solution of the acid
L, more preferably 1-5mol/L.
In another preferred example, in the step (c), the pH of the liquid reaction mixture is 1-3.
In another preferred example, 2- acetyl group -5- furancarboxylic acids or the molar ratio of its carboxylate and halogen are in the step (a)
1:1-60；Preferably 1:1-30；More preferably 1:1-20；Most preferably 1:1-10.
In another preferred example, 2- acetyl group -5- furancarboxylic acids or the molar ratio of its carboxylate and halogen are in the step (a)
1:1.5-60。
In another preferred example, in the step (a) 2- acetyl group -5- furancarboxylic acids or its carboxylate and halogen molar ratio
For：1:6.25、1:10、1:20、1:18、1:16、1:14.
In another preferred example, in the step (a) in solution system, the mass percentage of solvent is 10%-99%.
In another preferred example, in the step (a) in solution system solvent mass percentage be selected from 95%,
90%, 85%, 20%, 29%, 30%, 40%, 50%, 52%, 60%, 65%.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Description of the drawings
Fig. 1 is 1 gained 2,5- furandicarboxylic acids of embodiment1H-NMR collection of illustrative plates.
Specific implementation mode
The present inventor by depth studying extensively, it has unexpectedly been found that a kind of 2,5-furandicarboxylic acid or its carboxylate
Preparation method.Experiment shows that the preparation method is simple and efficient, by-product is few, yield is high, is suitble to large-scale industry metaplasia
Production.On this basis, the present invention is completed.
Term
As used herein, term " C1-C20 alkyl " refers to the alkyl of the linear chain or branched chain containing 1-10 C atom.
Term " C1-C3 alkyl " refers to the alkyl containing 1-3 C atom.
Term " ethers of C2-C10 " refers to the ether compound containing 2-10 C atom.
Term " alcohols of C3-C10 " refers to the alcohol compound containing 3-10 C atom.
Term " the oxygen-containing cycloalkane of C2-C10 " refers to the oxygen-containing naphthene-based compounds containing 2-10 C atom.
The preparation method of 2,5- furandicarboxylic acids or its carboxylate
The present invention provides a kind of method conveniently and efficiently preparing 2,5-furandicarboxylic acid or its carboxylate, the sides
Method includes step：
(a) solution system containing 2- acetyl group -5- furancarboxylic acids or its carboxylate and halogen is provided；
(b) pH to 7-10 for adjusting the solution system, removes the solid generated in the solution system, it is anti-to obtain liquid phase
Answer mixture；
(c) pH to 0-4 for adjusting the liquid reaction mixture, to obtain the 2,5-furandicarboxylic acid or its esterification
Object (I)；
Wherein, the 2,5-furandicarboxylic acid or its carboxylate have Formulas I structure：
2- acetyl group -5- the furancarboxylic acids or its carboxylate have Formula II structure：
In formula,
R1' be selected from the group：H, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted phenyl, substitution
Or unsubstituted cyclopenta, substituted or unsubstituted cyclohexyl, wherein " substituted ", which refers to, has one or more (such as 1-5
A, preferably 1-3) substituent group is selected from the group：H、OCH3, F, Cl, Br, I, C1-C3 alkyl；
R1It is selected from the group：H, methyl；Or R1=R1’。
In the step (a), solution system can be prepared by the following method：By 2- acetyl group -5- furancarboxylic acids or its ester
Compound and halogen are dissolved in atent solvent, obtain solution system.The atent solvent can be water or water and organic solvent
Mixed solvent.
In another preferred example, the solution system in the step (a) can also be prepared by the following method：By 2- acetyl
Base -5- furancarboxylic acids or its esterification are dissolved in water and/or organic solvent A and obtain solution A 1, and halogen is dissolved in water and/or organic solvent B
In obtain solution B 1, solution A 1 and B1 are mixed to get the solution system.Preferably, at Elevated Temperature Conditions (such as 30-140 DEG C)
Lower B1 is added in A1 mixes, to obtain the solution system.Wherein, in the A1, the volume of organic solvent and water
Than for 0-99:1；In the B1, the volume ratio of organic solvent and water is 0-20:1.
In general, the atent solvent is added in halogen at 0-160 DEG C.Preferably, the upper limit of the range of reaction temperature
Selected from 140 DEG C, 120 DEG C, 100 DEG C, lower limit is selected from 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C.Halogen described in the step (a) can be
Halogen simple substance, the compound containing halogen, or combinations thereof.Wherein, the halogen is F, Cl, Br, I；The change containing halogen
Conjunction object is the inorganic compound containing halogen, the salt (such as metal halide salt, secondary halide) preferably containing halogen；It is described containing
The compound of halogen can be sodium hypochlorite, hypoiodous acid sodium, sodium hypobromite, potassium iodide, or combinations thereof.
In another preferred example, the 2- acetyl group -5- furancarboxylic acids described in step (a) or its carboxylate can be selected from following
It is one or more：2- acetyl group -5- furancarboxylic acids, 2- acetyl group -5- methylfuroates, 2- acetyl group -5- ethyl furoates, 2- acetyl
Base -5- furancarboxylic acids propyl ester, 2- acetyl group -5- butyl pyromucates, 2- acetyl group -5- amyl furoates, the own ester of 2- acetyl group -5- furancarboxylic acids, 2-
Acetyl group -5- furancarboxylic acids heptyl ester, 2- acetyl group -5- furancarboxylic acids monooctyl ester, 2- acetyl group -5- furancarboxylic acid nonyls ester, the 2- acetyl group -5- furancarboxylic acid last of the ten Heavenly stems
Ester.
In another preferred example, organic solvent described in step (a) is selected from the group：The ethers of C2-C10, the alcohol of C3-C10
The oxygen-containing cycloalkane of class, C2-C10, n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), or combinations thereof.It is excellent
Selection of land, the organic solvent are selected from the group：Ether, propylene glycol, 1,4- dioxane, DMAC N,N' dimethyl acetamide, dimethyl are sub-
Sulfone, or combinations thereof.It is highly preferred that the organic solvent is selected from the group：1,4- dioxane, DMAC N,N' dimethyl acetamide, diformazan
Base sulfoxide, or combinations thereof.
In another preferred example, 2- acetyl group -5- furancarboxylic acids or the molar ratio of its carboxylate and halogen are in the step (a)
1:1-60；Preferably 1:1-30；More preferably 1:1-20；Most preferably 1:1-10.
In another preferred example, 2- acetyl group -5- furancarboxylic acids or the molar ratio of its carboxylate and halogen are in the step (a)
1:1.5-60、1:6.25、1:10、1:20、1:18、1:16、1:14。
In another preferred example, in the step (a) in solution system, the mass percentage of solvent can be 10%,
20%, 29%, 30%, 40%, 50%, 52%, 60%, 65%, 85%, 90%, 95%, 99%.
And in the step (b) further include the pH value that alkali is added and adjusts solution system, preferably 7-9.The alkali of addition can be with
For solution form or pure form.Preferably, the alkali is oxide, alkali metal or the alkaline earth of alkali or alkaline earth metal
The hydroxide of metal, the carbonate of alkali or alkaline earth metal, ammonium hydroxide, or combinations thereof.It is highly preferred that the alkali is selected from the group
In it is one or more：Sodium hydroxide, potassium hydroxide, hydrogen-oxygen lithium, rubidium hydroxide, cesium hydroxide, barium hydroxide, calcium hydroxide,
Magnesium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide.The solution of wherein alkali is preferably the aqueous solution of alkali, can also be water and other inertia
The mixed solution of the alkali of solvent.When aqueous slkali is added, a concentration of 0.01-10mol/L of alkali, preferably 0.1- in aqueous slkali
10mol/L, more preferably 1-5mol/L.
Further include the pH value that acid is added and adjusts the solution system, preferably 1-3 in the step (c).The acid choosing of addition
From one or more in the following group：Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, methanesulfonic acid, boron trifluoride etherate, benzene methanesulfonic acid.
The acid of addition can be solution form or pure form.
Wherein, sour solution is preferably the aqueous solution of acid, can also be the mixed solution of water and the acid of other atent solvents.
Sour concentration can be 0.01-10mol/L, preferably 0.1-10mol/L, more preferably 1-5mol/L in the solution of acid.
Main advantages of the present invention include：
The preparation method of a kind of 2,5-furandicarboxylic acid of the present invention or its carboxylate, with 2- acetyl group -5- furancarboxylic acids
Or its carboxylate is the 2,5-furandicarboxylic acid or its carboxylate that raw material prepares high-purity, to get through by furan starting material chemical combination
The technology path of object synthesized high-performance engineering material.Since furan starting material can drive biology base high score using biology base as source
The development of sub- material industry reduces Polymer Material Industry and relies on the height of petroleum resources, entire high molecular material is promoted to produce
The sustainable development of industry.
The method of the invention is simple and efficient, flow is short, by-product is few, and product total recovery is up to 70%-99%, purity
Height is suitble to large-scale industrial production, can meet as polymer such as high-performance polyester, epoxy resin, polyamide, polyurethane
Raw material and requirement as industrial chemicals and medicine intermediate raw material.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Embodiment 1
In 250ml reactors, 3.08g 2- acetyl group -5- furancarboxylic acids are dissolved in 20ml water, 30 DEG C of whens are added dropwise to
17.8g iodine and 100ml water, it is 7 that NaOH aqueous solutions (a concentration of 2mol/L), which are then added dropwise, and adjust pH, and filtering removal precipitation uses salt
Reacting solution pH value is adjusted to 1 by sour (a concentration of 0.5mol/L), is filtered the solid of precipitation and drying, is obtained 2,5- furans diformazans
Acid, yield 78%.
Through1H-NMR (400MHz, DMSO) tests obtain, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ
(13.60), liquid chromatography mass spectrometric combined instrument (LC-MS) measures molecular weight 156.1.
Embodiment 2
In 250ml reactors, 3.08g 2- acetyl group -5- furancarboxylic acids are dissolved in 100ml water, 40 DEG C of whens slowly lead to
Enter 0.1mol chlorine, while KOH aqueous solutions (a concentration of 1mol/L) are added dropwise, chlorine addition finishes (a concentration of with KOH solution
It is 7 1mol/L) to adjust pH, and reacting solution pH value with sulfuric acid (a concentration of 1.0mol/L), is adjusted to 1, mistake by filtering removal precipitation
The solid being precipitated and drying are filtered, 2,5-furandicarboxylic acid or its carboxylate, yield 85% are obtained.
It is obtained through 1H-NMR (400MHz, DMSO) tests, CH on furan nucleus, 2H, δ (7.28)；Carboxyl OH, 2H, δ
(13.60), liquid chromatography mass spectrometric combined instrument (LC-MS) measures molecular weight 156.1.
Embodiment 3
In 250ml reactors, 6.72g 2- acetyl group -5- methylfuroates are dissolved in 200ml water, 60 DEG C of whens add
Enter 10.0g bromines and 50ml water, LiOH aqueous solutions (a concentration of 4mol/L) are then added dropwise, it is 7 to adjust pH, and filtering removal precipitation is used
Phosphoric acid (a concentration of 2mol/L), is adjusted to 1 by reacting solution pH value, filters the solid of precipitation and drying, obtain 2- methyl formates
Base -5- furancarboxylic acids, yield 70%.It is obtained through 1H-NMR (400MHz, DMSO) tests, CH on furan nucleus, 1H, δ (7.29,7.30)；
CH, 1H, δ (7.37,7.38)；Carboxyl OH, 2H, δ (13.62), liquid chromatography mass spectrometric combined instrument (LC-MS) measure molecular weight 170.1.
Embodiment 4
In 250ml reactors, 6.72g 2- acetyl group -5- methylfuroates are dissolved in 100ml water, 80 DEG C of whens drip
Add the aqueous solution 400ml containing 0.28mol sodium hypochlorite, RaOH aqueous solutions (a concentration of 2mol/L) are then added dropwise, adjusting pH is
7, reacting solution pH value is adjusted to 1 with formic acid, filters the solid of precipitation and drying, obtains 2- formic acid first by filtering removal precipitation
Ester group -5- furancarboxylic acids, yield 84%.It is obtained through 1H-NMR (400MHz, DMSO) tests, CH on furan nucleus, 1H, δ (7.29,
7.30)；CH, 1H, δ (7.37,7.38)；Carboxyl OH, 2H, δ (13.62), liquid chromatography mass spectrometric combined instrument (LC-MS) measure molecular weight
170.1。
Embodiment 5
In 250ml reactors, by 3.08g 2- acetyl group -5- furancarboxylic acids, it is dissolved in 100ml water and 20ml Isosorbide-5-Nitraes-dioxy
In six rings, the aqueous solution 800ml containing 0.32mol hypoiodous acid sodium is added dropwise at 100 DEG C, it is (a concentration of that CsOH aqueous solutions are then added dropwise
4mol/L), it is 7 to adjust pH, and reacting solution pH value is adjusted to 1 with methanesulfonic acid, filters the solid of precipitation simultaneously by filtering removal precipitation
Drying, obtains 2,5-furandicarboxylic acid, yield 99%.It is obtained through 1H-NMR (400MHz, DMSO) tests, CH, 2H on furan nucleus,
δ(7.29)；Carboxyl OH, 2H, δ (13.62), liquid chromatography mass spectrometric combined instrument (LC-MS) measure molecular weight 156.1.
Embodiment 6
In 250ml reactors, by 7.28g 2- acetyl group -5- ethyl furoates, it is dissolved in 40ml water and 10ml N, N- bis-
In methylacetamide, the solution 1000ml containing 0.36mol sodium hypobromites is added dropwise at 140 DEG C, wet chemical is then added dropwise
(a concentration of 0.5mol/L), it is 7 to adjust pH, filtering removal precipitation, with boron trifluoride etherate by reacting solution pH value tune
Section filters the solid of precipitation and drying, obtains 2- group-4 ethyl formate -5- furancarboxylic acids, yield 91% to 2.Through 1H-NMR (400MHz,
DMSO) test obtains, CH on furan nucleus, 2H, δ (7.48,7.63)；CH2, 2H, δ (4.29)；CH3, 3H, δ (1.35), liquid phase matter
Spectrum combined instrument (LC-MS) measures molecular weight 184.1.
Embodiment 7
In 250ml reactors, by 4.21g 2- acetyl group -5- butyl pyromucates, it is dissolved in 60ml water and 10ml dimethyl
In sulfoxide, the aqueous solution 600ml containing 0.40mol iodine and 0.4mol potassium iodide is added dropwise at 120 DEG C, ammonia spirit tune is then added dropwise
It is 7 to save pH, and reacting solution pH value is adjusted to 3 with benzene methanesulfonic acid, filters the solid of precipitation and drying, obtain by filtering removal precipitation
To 2- butyl formate base -5- furancarboxylic acids, yield 96%.
It is obtained through 1H-NMR (400MHz, DMSO) tests, CH on furan nucleus, 2H, δ (7.45,7.58)；CH2, 2H, δ
(4.25)；CH2, 2H, δ (1.85)；CH2, 2H, δ (1.32)；CH3, 3H, δ (0.78), liquid chromatography mass spectrometric combined instrument (LC-MS) measures
Molecular weight 212.2.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. the preparation method of a kind of 2,5-furandicarboxylic acid or its carboxylate, which is characterized in that the method includes the steps：
(a) solution system containing 2- acetyl group -5- furancarboxylic acids or its carboxylate and halogen source is provided；
(b) pH to 7-10 for adjusting the solution system, removes the solid generated in the solution system, and it is mixed to obtain liquid phase reactor
Close object；
(c) pH to 0-4 for adjusting the liquid reaction mixture, obtains the 2,5-furandicarboxylic acid or its carboxylate (I)；
Wherein, the 2,5-furandicarboxylic acid or its carboxylate have Formulas I structure：
2- acetyl group -5- the furancarboxylic acids or its carboxylate have Formula II structure：
In formula,
R1' be selected from the group：H, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted phenyl, substitution or do not take
The cyclopenta in generation, substituted or unsubstituted cyclohexyl, wherein " substituted " refer to it is one or more (such as 1-5, preferably
Ground 1-3) substituent group is selected from the group：H、OCH3, F, Cl, Br, I, C1-C3 alkyl；
R1It is selected from the group：H, methyl；Or R1=R1’。
2. the method as described in claim 1, which is characterized in that in the step (a), the halogen source is selected from the group：Halogen
Simple substance, the compound containing halogen, or combinations thereof.
3. the method as described in claim 1, which is characterized in that the 2- acetyl group -5- furancarboxylic acids or its carboxylate are selected from the group：
2- acetyl group -5- furancarboxylic acids, 2- acetyl group -5- methylfuroates, 2- acetyl group -5- ethyl furoates, 2- acetyl group -5- furancarboxylic acids propyl ester,
2- acetyl group -5- butyl pyromucates, 2- acetyl group -5- amyl furoates, the own ester of 2- acetyl group -5- furancarboxylic acids, 2- acetyl group -5- furancarboxylic acid heptan
Ester, 2- acetyl group -5- furancarboxylic acids monooctyl ester, 2- acetyl group -5- furancarboxylic acid nonyls ester, 2- acetyl group -5- furancarboxylic acid last of the ten Heavenly stems esters, or combinations thereof.
4. the method as described in claim 1, which is characterized in that in the step (a), the atent solvent is water or water
With the mixed solvent of organic solvent；Preferably, the organic solvent is selected from the group：The ethers of C2-C10, the alcohols of C3-C10,
The oxygen-containing cycloalkane of C2-C10, n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), or combinations thereof.
5. the method as described in claim 1, which is characterized in that further include in the step (b)：Alkali is added and adjusts solution system
PH value, wherein the alkali is selected from the group：The oxide of alkali or alkaline earth metal, the hydrogen-oxygen of alkali or alkaline earth metal
Compound, the carbonate of alkali or alkaline earth metal, ammonium hydroxide, or combinations thereof.
6. the method as described in claim 1 or 5, which is characterized in that the pH of solution system is 7-9 in the step (b).
7. the method as described in claim 1, which is characterized in that further include that acid selected from the group below is added to adjust in the step (c)
Save the pH value of the solution system：Hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, methanesulfonic acid, boron trifluoride etherate, benzene methanesulfonic acid,
Or combinations thereof.
8. method as claimed in claim 1 or 7, which is characterized in that in the step (c), adjust the liquid phase reactor mixing
The pH to 1-3 of object.
9. the method as described in claim 1, which is characterized in that 2- acetyl group -5- furancarboxylic acids or its carboxylate in the step (a)
Molar ratio with halogen is 1:1-60；Preferably 1:1-30；More preferably 1:1-20；Most preferably 1:1-10.
10. the method as described in claim 1, which is characterized in that in the step (a) in solution system, the quality hundred of solvent
It is 10%-99% to divide content.
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| WO2022049384A1 (en) * | 2020-09-03 | 2022-03-10 | Imperial College Innovations Limited | Surfactants |
| CN114163407A (en) * | 2020-09-11 | 2022-03-11 | 中国科学院宁波材料技术与工程研究所 | Furan ring composition for inhibiting or killing microorganism, product containing furan ring composition and application of furan ring composition |
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