CN108299355A - A kind of preparation method of the disubstituted furan compounds of 2,5- - Google Patents
A kind of preparation method of the disubstituted furan compounds of 2,5- Download PDFInfo
- Publication number
- CN108299355A CN108299355A CN201710021916.9A CN201710021916A CN108299355A CN 108299355 A CN108299355 A CN 108299355A CN 201710021916 A CN201710021916 A CN 201710021916A CN 108299355 A CN108299355 A CN 108299355A
- Authority
- CN
- China
- Prior art keywords
- group
- furans
- alcohol
- substituted
- furan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application provides a kind of preparation methods of 2,5 disubstituted furan compounds, specifically, the method of the present invention is using 2 substituted furan compounds as raw material, the 2 of bifunctionality is prepared by simply chemically reacting, 5 disubstituted furan compounds make the furan compound of single functionality realize bifunctionality.This method raw material sources are abundant, cheap and easy to get, preparation method is simple and efficient, flow is short, by-product is few, 2 prepared using this method, 5 disubstituted furan compound purity are high, can meet the raw material as polymer such as high-performance polyester, epoxy resin, polyamide, polyurethane and the requirement as industrial chemicals and medicine intermediate raw material.
Description
Technical field
This application involves a kind of preparation methods of substituted furan compound, belong to high-performance polyester, epoxy resin, polyamide
The technical field with chemical industry, medicine intermediate is prepared with polymer monomers such as polyurethane.
Background technology
Furan compound 2- carboxaldehyde radicals furans, 2- formyls furans, 2- methyl formate bases furans, the 2- methylols of 2- substitutions
Furans, furans, 2- methylfurans, 2- methoxyl group furans etc. are obtained by the biomass resources catalyzed conversion such as stalk, rice husk, and raw material is honest and clean
Valence is easy to get, renewable.These furan compounds contain rigid furan nucleus, and the polymer high temperature resistant of preparation, strength modulus are good.But
Because these furan compounds only have the functional group of the positions 2- one, application for a long time is confined to the application of furane resins etc., adds
It is worth low, application range to be difficult to promote.
The present invention simply chemically reacts the 5- of 2- substituted furan compounds 2- substituted furans compound by a step
Position is Carboxylation, prepares 2- substitution -5- carboxylic acid group's furan compounds, becomes bifunctionality furan compound, poly- for high-performance
The preparations such as ester, epoxy resin, polyamide and polyurethane can both promote the high added value profit of the biomass resources such as agricultural wastes
With, and the rigidity of furan nucleus can be utilized to improve the high temperature resistant of polymer, creep-resistant property.
Currently, the carboxylic disubstituted furan compounds of 2,5- are mainly that raw material aoxidizes by 5 hydroxymethyl furfural (HMF)
It arrives, but raw material HMF prepares difficulty, it is of high cost, it is difficult to realize the shortcomings that heavy industrialization is applied.Even if HMF preparation processes change
Into yield improves, but the starting material for preparing HMF is fructose and glucose, is main raw-food material, if being used for extensive work
Industry produces, and certainly will break agri-food supply chains balance.And 2- carboxaldehyde radicals furans that cellulose converts, 2- formyls furans, 2-
Hydroxymethylfurans, 2- methyl formates furans, 2- methylfurans etc. are industrial biological base chemicals cheap and easy to get, if it is possible to
The disubstituted furan compounds of carboxylic 2,5- are prepared by this one kind biological-based chemicals, biology can be pushed well
The sustainable development of base chemical products and biology base high molecular material establishes key for the high value added utilization of agricultural wastes
Technical foundation.
In conclusion this field still lacks a kind of disubstituted furans of 2,5- preparing bifunctionality by biological-based chemicals
The method of compound.
Invention content
The object of the present invention is to provide a kind of disubstituted furans of 2,5- preparing bifunctionality by biological-based chemicals
The method for closing object.
The first aspect of the present invention provides the preparation method of the disubstituted furan compounds of 2,5- of one kind, including following step
Suddenly：
Haptoreaction is carried out with halogenated hydrocarbons, fatty alcohol and catalyst with 2 furan compounds with the substitution of R bases, obtains 2
Position has the substitution of R bases, and 5 substituted furan compounds with carboxyl；
Wherein, R is selected from the group：Substituted or unsubstituted C1-C4 aldehyde radicals, substituted or unsubstituted C1-C4 ester groups (R '-
OOC-), carboxyl, H, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxies；The substitution refers to base
One or more hydrogen atoms in group are replaced by substituent group selected from the group below：Hydroxyl, C1-C3 alkyl.
In another preferred example, the haptoreaction is carried out in the case where additionally not adding solvent.
In another preferred example, the molar ratio of the fatty alcohol and 2 furan compounds with the substitution of R bases is
0.1~8:1, preferably 2~6:1.
In another preferred example, the fatty alcohol and the molar ratio of 2- substituted furan compounds are 3~5:1
In another preferred example, the halogenated hydrocarbons rubs with described 2 the feeding intake for furan compound with the substitution of R bases
You are than being 1~20:1, preferably 1~10:1.
In another preferred example, the molar ratio of the catalyst and 2 furan compounds with the substitution of R bases is
0.005~0.1:1.
In another preferred example, described 2 furan compounds with the substitution of R bases are selected from the group：2- formyls furans, 2-
Carboxaldehyde radicals furans, 2- hydroxymethylfurans, furans, 2- methylfurans, 2- methoxyl groups furans, 2- methyl formate bases furans, 2- formic acid
Ethoxycarbonyl furans, 2- propyl formate base furans, or combinations thereof.
In another preferred example, described 2 furan compounds with the substitution of R bases are selected from the group：2- formyls furans, 2-
Carboxaldehyde radicals furans, 2- hydroxymethylfurans, furans, 2- methyl formate base furans, or combinations thereof.
In another preferred example, the disubstituted furan compounds of 2, the 5- are selected from the group：2- formyl -5- furancarboxylic acids, 2- first
Aldehyde radical -5- furancarboxylic acids, 2- methylol -5- furancarboxylic acids, 2- methyl -5- furancarboxylic acids, 2- methoxyl group -5- furancarboxylic acids, 2- methyl formate base -5- chaffs
Acid, 2- group-4 ethyl formate -5- furancarboxylic acids, 2- propyl formate base 5- furancarboxylic acids, or combinations thereof.
In another preferred example, the disubstituted furan compounds of 2, the 5- are selected from the group：2- formyl -5- furancarboxylic acids, 2- first
Aldehyde radical -5- furancarboxylic acids, 2- methyl formate base -5- furancarboxylic acids, 2- group-4 ethyl formate -5- furancarboxylic acids, or combinations thereof.
In another preferred example, the halogenated hydrocarbons is selected from the group：1- chloromethanes, dichloromethane, chloroform, four chlorinations
Carbon, dichloroethanes, tetrachloroethanes, 1- bromomethanes, methylene bromide, bromoform, carbon tetrabromide, Bromofume, tetrabromoethane,
Or combinations thereof.
In another preferred example, the halogenated hydrocarbons is selected from the group：Dichloromethane, tetrachloroethanes, chloroform, carbon tetrachloride,
Or combinations thereof.
In another preferred example, the fatty alcohol is selected from the group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutyl
Alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, or combinations thereof.
In another preferred example, the fatty alcohol is the linear chain or branched chain alcohol of C1-C10.
In another preferred example, the fatty alcohol is selected from the group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutyl
Alcohol, or combinations thereof.
In another preferred example, the catalyst is the compound of metal selected from the group below：Fe、Co、Ni、Cu、Zn、Mg、
Cr, Zr, Al, V, or combinations thereof.
In another preferred example, the catalyst is the compound of metal selected from the group below：Fe, Co, Ni, Cu or its group
It closes.
In another preferred example, the catalyst is selected from the group：Iron chloride, ferric iodide, ferric acetyl acetonade, ferric bromide, two
Ethyl iron, cobalt chloride, cobaltous iodide, acetylacetone cobalt, cobaltous bromide, diethyl cobalt, or combinations thereof.
In another preferred example, the catalytic reaction temperature is 60-250 DEG C.
In another preferred example, the catalytic reaction kettle is acid resistance reaction kettle.
The second aspect of the present invention provides a kind of method preparing the polymer with furan structure unit, the side
Method includes step：
Substituted furan compound is prepared with method as described in the first aspect of the invention；With
Polymerisation is carried out with the substituted furan compound, to obtain the polymer.
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.
Specific implementation mode
The present inventor's in-depth study by long-term, it has unexpectedly been found that, with 2- substituted furans compound and halogenated hydrocarbons, fat
Fat alcohol and catalyst reaction can obtain the 2 of the double official's degree for having different by the dosage of fatty alcohol in control reaction process,
The disubstituted furan compounds of 5-, and then in the preparation of the polymer of unit containing furan structure.Based on above-mentioned discovery, inventor is complete
At the present invention.
Term
As used herein, term " haptoreaction " contacts with each other between instigating reactant, concurrent biochemical reaction.Described
The method that this field routine may be used in haptoreaction, such as still reaction, the methods of streaming reaction.
Herein, " carboxaldehyde radicals " and " aldehyde radical " refers both to-CHO groups.
Term " 2 furan compounds with the substitution of R bases " and " 2- substituted furans compound " may be used interchangeably, at this
Under some preferable cases of text, the substituent group of the 2- substituted furans compound is R bases.
The preparation of substituted furan compound
In the present invention, a kind of preparation method of substituted furan compound is provided, the method includes：
Haptoreaction is carried out with halogenated hydrocarbons, fatty alcohol and catalyst with 2 furan compounds with the substitution of R bases, obtains 2
Position has the substitution of R bases, and 5 disubstituted furan compounds of 2,5- with carboxyl；
Wherein, the R can be selected from the group：Substituted or unsubstituted C1-C4 aldehyde radicals, substituted or unsubstituted C1-C4
Ester group (R'-OOC-), carboxyl, H, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxies；Described
The one or more hydrogen atoms referred on group are replaced to be replaced by substituent group selected from the group below：Hydroxyl, C1-C3 alkyl.
In another preferred example, the haptoreaction is carried out in the case where additionally not adding solvent.
In the present invention, by the dosage of control fatty alcohol, bifunctionality can be prepared and 5 have the 2 of carboxyl,
The disubstituted furan compounds of 5-.In the present invention, it is preferred to the fatty alcohol and 2- substituted furan compounds feed intake mole
Than being 0.1~8:1, preferably 2~6:1, further preferably 3~5:1.The molar ratio can be according to production process
In actual needs, be adjusted within the above range, such as 0.2:1、0.5:1、1:1、3:1、5:1、7:1 etc..
In the present invention, the rate of charge of halogenated hydrocarbons and 2 furan compounds with the substitution of R bases is not particularly limited,
In a preferred embodiment, the halogenated hydrocarbons and the molar ratio of 2- substituted furan compounds are 1~20:1, preferably
It is 1~10:1, further preferably 1~5:1.
In another preferred example, the molar ratio of the catalyst and 2- substituted furan compounds be 0.005~
0.1:1。
In another preferred example, the 2- substituted furans compound is selected from the group：2- formyls furans, 2- carboxaldehyde radicals furans
It mutters, 2- hydroxymethylfurans, furans, 2- methylfurans, 2- methoxyl groups furans, 2- methyl formate bases furans, 2- group-4 ethyl formate furans
It mutters, 2- propyl formate base furans, or combinations thereof.
In another preferred example, the 2- substituted furans compound is selected from the group：2- formyls furans, 2- carboxaldehyde radicals furans
It mutters, 2- hydroxymethylfurans, furans, 2- methyl formate base furans, or combinations thereof.
In the present invention, the disubstituted furan compounds of 2,5- being prepared are preferably the 5- chemical combination with carboxyl substituent
Object, such as the disubstituted furan compounds of 2,5- selected from the group below：2- formyl -5- furancarboxylic acids, 2- carboxaldehyde radicals -5- furancarboxylic acids, 2- hydroxyl first
Base -5- furancarboxylic acids, 2- methyl -5- furancarboxylic acids, 2- methoxyl group -5- furancarboxylic acids, 2- methyl formate base -5- furancarboxylic acids, 2- group-4 ethyl formate -5- chaffs
Acid, 2- propyl formate base 5- furancarboxylic acids, or combinations thereof.
In another preferred example, the substituted furan compound is selected from the group：2- formyl -5- furancarboxylic acids, 2- carboxaldehyde radicals -5-
Furancarboxylic acid, 2- methyl formate base -5- furancarboxylic acids, 2- group-4 ethyl formate -5- furancarboxylic acids, or combinations thereof.
In above-mentioned reaction, the halogenated hydrocarbons is not particularly limited, and the preferred halogenated hydrocarbons is selected from the group：1- chloros
Methane, dichloromethane, chloroform, carbon tetrachloride, dichloroethanes, tetrachloroethanes, 1- bromomethanes, methylene bromide, bromoform, four
Bromination carbon, Bromofume, tetrabromoethane, or combinations thereof.Preferred halogenated hydrocarbons is chlorohydrocarbon, such as selected from the group below halogenated
Hydrocarbon：Dichloromethane, tetrachloroethanes, chloroform, carbon tetrachloride, or combinations thereof.
The fatty alcohol is not particularly limited, and can be the linear chain or branched chain alcohol of C1-C10.Preferably, the fat
Fat alcohol is selected from the group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, just
Octanol, or combinations thereof；It is highly preferred that the fatty alcohol is selected from the group：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutyl
Alcohol, or combinations thereof.
The catalyst of the present invention is not particularly limited, and can be the compound of metal selected from the group below：Fe、Co、Ni、
Cu, Zn, Mg, Cr, Zr, Al, V, or combinations thereof.In another preferred example, the catalyst is the chemical combination of metal selected from the group below
Object：Fe, Co, Ni, or combinations thereof.
In another preferred example, the catalyst is selected from the group：Iron chloride, ferric iodide, ferric acetyl acetonade, ferric bromide, two
Ethyl iron, cobalt chloride, cobaltous iodide, acetylacetone cobalt, cobaltous bromide, diethyl cobalt, or combinations thereof.
The haptoreaction can carry out under arbitrary suitable reaction condition, the condition can according to reaction system,
Situations such as reaction unit, specifically considers.For example, in a preferred embodiment, the reaction temperature is 60-250 DEG C.
In another preferred example, the catalytic reaction kettle is acid resistance reaction kettle.
The advantageous effect that the application can generate includes at least：
(1) herein described method develops a new route for preparing the disubstituted furan compounds of 2,5-.Replaced with 2-
Furan compound is the disubstituted furan compounds of 2,5- for the bifunctionality that raw material prepares high-purity, to get through by raw material furan
It mutters the technology path of compound synthesis high-performance engineering material.
(2) due to raw material 2- substituted furans compound can with bio-based source, the application can drive biology base high score
The development of sub- material industry reduces current high molecular material to being depended on unduly to petroleum resources, promotes entire high molecular material
The sustainable development of industry, and reduce pollution of the existing fossil resources to environment.
(3) herein described method is simple and efficient, flow is short, by-product is few, product total recovery 70%-99%, is suitble to big
Technical scale metaplasia is produced.
(4) the disubstituted furan compound purity of 2,5- that prepared by herein described method is high, can meet poly- as high-performance
It the raw material of the polymer such as ester, epoxy resin, polyamide, polyurethane and is wanted as industrial chemicals and medicine intermediate raw material
It asks.
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.
In embodiment, nuclear magnetic resonance spectroscopy 1H-NMR is divided using III types of 400AVANCE of Brooker company (Bruker)
Instrument (Spectrometer) measures, 400MHz, dimethyl sulfoxide DMSO.
Product analysis is examined using the 7890B-5977A type liquid chromatograph-mass spectrometers of agilent company (Agilent)
It surveys.Density is not specified in embodiment, the reagent of the parameters such as concentration is commercially available pure reagent.
Embodiment 1
In 250ml reaction kettles, by 2- formyl furans 11.2g (0.1mol), it is dissolved in 12ml isopropanols and 32g tetrachloros
In ethane (0.19mol), cobalt chloride 0.35g (0.003mol), 60 DEG C of back flow reaction 2h are added, cool down, faint yellow solid is precipitated,
Re-crystallizing in ethyl acetate obtains 2- formyl -5- furancarboxylic acids, 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, and HPLC measures purity 99.0%.
Embodiment 2
In 250ml reaction kettles, by 2- formyl furans 11.2g (0.1mol), it is dissolved in 24ml isopropanols and 32g tetrachloros
In ethane (0.19mol), iron chloride 0.35g (0.002mol), 60 DEG C of back flow reaction 14h, cooling, faint yellow solid analysis is added
Go out, re-crystallizing in ethyl acetate, obtains 2- formyl -5- furancarboxylic acids, yield 98%.
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, and HPLC measures purity 99.5%.
Embodiment 3
In 250ml reaction kettles, by 2- formyl furans 11.2g (0.1mol), it is dissolved in 36ml isopropanols and 16g tetrachloros
In ethane (0.095mol), zinc chloride 0.70g (0.006mol), 120 DEG C of back flow reaction 2h, cooling, faint yellow solid analysis is added
Go out, re-crystallizing in ethyl acetate, obtains 2- formyl -5- furancarboxylic acids, yield 84%.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) measure molecular weight
156.1, HPLC measure purity 99.4%.
Embodiment 4
In 250ml reaction kettles, by 2- formyl furans 11.2g (0.1mol), it is dissolved in 12ml ethyl alcohol and 8g tetrabromo second
In alkane (0.024mol), cobalt chloride 1.6g (0.012mol), 160 DEG C of back flow reaction 0.5h, cooling, faint yellow solid analysis is added
Go out, re-crystallizing in ethyl acetate, obtains 2- formyl -5- furancarboxylic acids, yield 88%.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) measure molecular weight
156.1, HPLC measure purity 99.8%.
Embodiment 5
In 250ml reaction kettles, by 2- methyl formate base furans 12.6g (0.1mol), it is dissolved in 12ml n-butanols and 18g
In tetrachloroethanes (0.107mol), nickelous bromide 0.04g (0.0002mol), 200 DEG C of back flow reaction 1.0h are added, cool down, it is faint yellow
Solid is precipitated, and re-crystallizing in ethyl acetate obtains 2- formyl carbomethoxy -5- furancarboxylic acids, yield 96%.Through 1H-NMR (400MHz,
DMSO) test obtains, 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) measures molecular weight 170.1, and HPLC measures purity 98.7%.
Embodiment 6
In 250ml reaction kettles, by 2- methyl formate base furans 12.6g (0.1mol), it is dissolved in 20ml methanol and 18g tetra-
In chlorination carbon (0.117mol), cobalt chloride 0.08g (0.0006mol), 250 DEG C of back flow reaction 0.4h, cooling, pale yellow colored solid is added
Body is precipitated, and re-crystallizing in ethyl acetate obtains 2- formyl carbomethoxy -5- furancarboxylic acids, yield 96%.Through 1H-NMR (400MHz,
DMSO) test obtains, 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) measures molecular weight 170.1, and HPLC measures purity 99.1%.
Embodiment 7
In 250ml reaction kettles, by 2- carboxaldehyde radicals furans 10.6g (0.1mol), it is dissolved in 6ml isobutanols and 10g tribromos
In methane (0.04mol), manganese iodide 2g, 150 DEG C of back flow reaction 6h, cooling are added, faint yellow solid is precipitated, and ethyl acetate is tied again
Crystalline substance, obtains 2- carboxaldehyde radicals -5- furancarboxylic acids, yield 88%, and HPLC measures purity 98.5%.
Embodiment 8
In 250ml reaction kettles, by 2- formyl furans 11.2g (0.1mol), it is dissolved in tetra- chloroethene of 70ml ethyl alcohol and 32g
In alkane (0.19mol), iron chloride 0.35g (0.002mol), 120 DEG C of back flow reaction 4h are added, cool down, faint yellow solid is precipitated,
Re-crystallizing in ethyl acetate obtains 2- group-4 ethyl formate -5- ethyl furoates, yield 98%.
Through1H-NMR (400MHz, DMSO) tests obtain, CH on furan nucleus, 2H, δ (7.42)；CH3, 6H, δ (1.38),
CH2, 4H, δ (4.26), liquid chromatography mass spectrometric combined instrument (LC-MS) measures molecular weight 212.2, and HPLC measures purity 99.4%.
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. one kind 2, the preparation method of the disubstituted furan compounds of 5-, which is characterized in that include the following steps：
Haptoreaction is carried out with halogenated hydrocarbons, fatty alcohol and catalyst with 2 furan compounds with the substitution of R bases, obtains 2 tools
There are the substitution of R bases, and 5 substituted furan compounds with carboxyl；
Wherein, R is selected from the group：Substituted or unsubstituted C1-C4 aldehyde radicals, substituted or unsubstituted C1-C4 ester groups (R'-OOC-),
Carboxyl, H, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxies；The substitution refers on group
One or more hydrogen atoms are replaced by substituent group selected from the group below：Hydroxyl, C1-C3 alkyl.
2. the method as described in claim 1, which is characterized in that the fatty alcohol and 2 furans chemical combination with the substitution of R bases
The molar ratio of object is 0.1~8:1, preferably 2~6:1.
3. the method as described in claim 1, which is characterized in that the halogenated hydrocarbons and described 2 furans with the substitution of R bases
The molar ratio for compound of muttering is 1~20:1, preferably 1~10:1.
4. the method as described in claim 1, which is characterized in that described 2 furan compounds with the substitution of R bases are selected from down
Group：2- formyls furans, 2- carboxaldehyde radicals furans, 2- hydroxymethylfurans, furans, 2- methylfurans, 2- methoxyl groups furans, 2- formic acid
Carbomethoxy furans, 2- group-4 ethyl formates furans, 2- propyl formate base furans, or combinations thereof.
5. the method as described in claim 1, which is characterized in that the disubstituted furan compounds of 2,5- are selected from the group：2- first
Acidic group -5- furancarboxylic acids, 2- carboxaldehyde radicals -5- furancarboxylic acids, 2- methylol -5- furancarboxylic acids, 2- methyl -5- furancarboxylic acids, 2- methoxyl group -5- furancarboxylic acids, 2-
Methyl formate base -5- furancarboxylic acids, 2- group-4 ethyl formate -5- furancarboxylic acids, 2- propyl formate base 5- furancarboxylic acids, or combinations thereof.
6. the method as described in claim 1, which is characterized in that the halogenated hydrocarbons is selected from the group：1- chloromethanes, dichloromethane
Alkane, chloroform, carbon tetrachloride, dichloroethanes, tetrachloroethanes, 1- bromomethanes, methylene bromide, bromoform, carbon tetrabromide, dibromo
Ethane, tetrabromoethane, or combinations thereof.
7. the method as described in claim 1, which is characterized in that the fatty alcohol is selected from the group：It is methanol, ethyl alcohol, propyl alcohol, different
Propyl alcohol, butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, or combinations thereof.
8. according to the method described in claim 1, it is characterized in that, the catalyst is the compound of metal selected from the group below：
Fe, Co, Ni, Cu, Zn, Mg, Cr, Zr, Al, V, or combinations thereof.
9. according to the method described in claim 1, it is characterized in that, the catalytic reaction temperature is 60-250 DEG C.
10. a kind of method preparing the polymer with furan structure unit, which is characterized in that including step：
Substituted furan compound is prepared with the method as described in claim 1-9 is any；With
Polymerisation is carried out with the substituted furan compound, to obtain the polymer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210395944.8A CN114773298A (en) | 2017-01-12 | 2017-01-12 | Preparation method of 2, 5-disubstituted furan compound |
| CN201710021916.9A CN108299355A (en) | 2017-01-12 | 2017-01-12 | A kind of preparation method of the disubstituted furan compounds of 2,5- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710021916.9A CN108299355A (en) | 2017-01-12 | 2017-01-12 | A kind of preparation method of the disubstituted furan compounds of 2,5- |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210395944.8A Division CN114773298A (en) | 2017-01-12 | 2017-01-12 | Preparation method of 2, 5-disubstituted furan compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108299355A true CN108299355A (en) | 2018-07-20 |
Family
ID=62871724
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210395944.8A Pending CN114773298A (en) | 2017-01-12 | 2017-01-12 | Preparation method of 2, 5-disubstituted furan compound |
| CN201710021916.9A Pending CN108299355A (en) | 2017-01-12 | 2017-01-12 | A kind of preparation method of the disubstituted furan compounds of 2,5- |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210395944.8A Pending CN114773298A (en) | 2017-01-12 | 2017-01-12 | Preparation method of 2, 5-disubstituted furan compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN114773298A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845499A (en) * | 2021-10-26 | 2021-12-28 | 南京先进生物材料与过程装备研究院有限公司 | Method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2359968C2 (en) * | 2007-01-17 | 2009-06-27 | Институт нефтехимии и катализа РАН | Production method for methyl ethers of 2-thiophen carbonic acid and its derivatives |
| RU2402541C2 (en) * | 2008-10-06 | 2010-10-27 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Method of producing dimethyl ether of 2,5-thiophene dicarboxylic acid from 2-thiophene carboxylic acid |
| RU2404162C2 (en) * | 2008-11-10 | 2010-11-20 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | 5-acetylpyrrole-2-carboxylic acid methyl ether synthesis method |
-
2017
- 2017-01-12 CN CN202210395944.8A patent/CN114773298A/en active Pending
- 2017-01-12 CN CN201710021916.9A patent/CN108299355A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2359968C2 (en) * | 2007-01-17 | 2009-06-27 | Институт нефтехимии и катализа РАН | Production method for methyl ethers of 2-thiophen carbonic acid and its derivatives |
| RU2402541C2 (en) * | 2008-10-06 | 2010-10-27 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Method of producing dimethyl ether of 2,5-thiophene dicarboxylic acid from 2-thiophene carboxylic acid |
| RU2404162C2 (en) * | 2008-11-10 | 2010-11-20 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | 5-acetylpyrrole-2-carboxylic acid methyl ether synthesis method |
Non-Patent Citations (6)
| Title |
|---|
| R. I. KHUSNUTDINOV ET AL.: ""New Procedure for Synthesis Alkyl Esters of 5-Acetyl-2-Furan-Carboxylic Acid Alkyl Ester"", 《RUSSIAN JOURNAL OF APPLIED CHEMISTRY》 * |
| R. I. KHUSNUTDINOV ET AL.: ""New Synthesis of Pyrrole-2-carboxylic and Pyrrole-2,5-dicarboxylic Acid Esters in the Presence of Iron-Containing Catalysts"", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| R. I. KHUSNUTDINOV ET AL.: ""Synthesis of 2-Thiophenecarboxylic and 2,5-Thiophenedicarboxylic Acid Esters via the Reaction of Thiophenes with the CCl4–ROH Reagent in the Presence of Vanadium, Iron, and Molybdenum Catalysts"", 《PETROLEUM CHEMISTRY》 * |
| R. I. KHUSNUTDINOV ET AL.: ""Synthesis of methyl furan-2-carboxylate and dimethyl furan-2,5-dicarboxylate by copper-catalyzed reactions of furans with CCl4 and MeOH"", 《RUSSIAN CHEMICAL BULLETIN》 * |
| 李伟杰: ""噻吩-2,5-二甲酸及其酯的催化合成"", 《精细化工》 * |
| 李伟杰: ""氯化亚铁催化合成呋喃-2,5-二甲酸及其二甲酯"", 《化学试剂》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845499A (en) * | 2021-10-26 | 2021-12-28 | 南京先进生物材料与过程装备研究院有限公司 | Method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114773298A (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102666521B (en) | Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid | |
| Lilga et al. | Production of oxidized derivatives of 5-hydroxymethylfurfural (HMF) | |
| Xu et al. | KOH-mediated transition metal-free synthesis of imines from alcohols and amines | |
| CN108299353A (en) | A kind of preparation method of 5- formic acid ester group furan compound | |
| Jiang et al. | Zn-mediated decarboxylative carbagermatranation of aliphatic N-hydroxyphthalimide esters: evidence for an alkylzinc intermediate | |
| Hoffmeister et al. | Formal total synthesis of kendomycin by way of alkyne metathesis/gold catalysis | |
| CN110117282B (en) | Zinc ion fluorescent probe compound and preparation method and application thereof | |
| Kopylovich et al. | Copper (II) complexes with a new carboxylic-functionalized arylhydrazone of β-diketone as effective catalysts for acid-free oxidations | |
| WO2017076947A1 (en) | Process for preparing furan-2,5-dicarboxylic acid | |
| BR112012008164B1 (en) | method for the preparation of 2,5-furanedicarbloxylic acid and its esters | |
| CN108299351A (en) | A kind of preparation method of the disubstituted furan compounds of 2,5- | |
| Schade et al. | Direct catalytic route to biomass-derived 2, 5-furandicarboxylic acid and its use as monomer in a multicomponent polymerization | |
| CN104059037A (en) | Preparation method of 2,5-furandicarboxylic acid | |
| Zhang et al. | A facile and effective method for preparation of 2.5-furandicarboxylic acid via hydrogen peroxide direct oxidation of 5-hydroxymethylfurfural | |
| Deshpande et al. | Tuning molecular structure of tertiary amine catalysts for glucose isomerization | |
| Ma et al. | Conversion of cellulose to butyl levulinate in bio-butanol medium catalyzed by acidic ionic liquids | |
| AU2014390019A1 (en) | Synthesis of reduced sugar alcohols, furan derivatives | |
| CN108299355A (en) | A kind of preparation method of the disubstituted furan compounds of 2,5- | |
| Leonardi et al. | Pyrone synthesis from renewable sources: Easy preparation of 3‐Acetoxy‐2‐oxo‐2H‐pyran‐6‐carboxylic salts and their derivatives as 3‐Hydroxy‐2H‐pyran‐2‐one from C6 aldaric acids | |
| CN108299350A (en) | A kind of preparation method of furan dicarboxylic acid compound | |
| Li et al. | Palladium-Catalyzed Regiodivergent Decarboxylative Hydrothiocarbonylation of Vinylarenes Using Oxalic Acid Monothioesters | |
| Li et al. | Catalytic conversion of raw Dioscorea composita biomass to 5-hydroxymethylfurfural using a combination of metal chlorides in N, N-dimethylacetamide solvent containing lithium chloride | |
| Guo et al. | Palladium-catalyzed allylic C–H oxidation under simple operation and mild conditions | |
| CN108299352A (en) | A kind of preparation method of furan dicarboxylic acid ester compounds | |
| Li et al. | One-step assembly of alkoxypyrroloindolines via iodine-catalyzed alkoxycyclization of indole derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180720 |
|
| RJ01 | Rejection of invention patent application after publication |