CN109678822B - Preparation method of 2, 5-furan diformic acid ester compound - Google Patents

Preparation method of 2, 5-furan diformic acid ester compound Download PDF

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CN109678822B
CN109678822B CN201811476801.XA CN201811476801A CN109678822B CN 109678822 B CN109678822 B CN 109678822B CN 201811476801 A CN201811476801 A CN 201811476801A CN 109678822 B CN109678822 B CN 109678822B
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chloroform
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furandicarboxylate
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furan
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CN109678822A (en
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尹标林
罗文坤
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South China University of Technology SCUT
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the field of fine chemical raw materials, and particularly relates to a preparation method of 2, 5-furan diformate. The method comprises the following steps
Figure DDA0001892370510000011
R2OH, an initiator and a catalyst are added into chloroform for reflux reaction to obtain the 2, 5-furan dicarboxylic acid ester compound. The method does not need to use expensive 5-hydroxymethylfurfural as a raw material, the used alcoxyl acylation reagent is chloroform, other solvents are not needed, strict anhydrous condition and low-temperature operation are not needed, expensive strong alkali such as butyl lithium and the like are not needed, the operation is simple, the cost is low, and the method has wide industrial application prospect.

Description

Preparation method of 2, 5-furan diformic acid ester compound
Technical Field
The invention belongs to the field of fine chemical raw materials, and particularly relates to a preparation method of a 2, 5-furan dicarboxylic acid ester compound.
Background
The transitional exploitation of fossil resources leads to the increasing exhaustion of limited fossil resources, and the refining process of fossil resources brings about the problems of environmental pollution and greenhouse effect, so that the preparation of various functional materials by utilizing platform compounds with biomass sources becomes an important research direction. Currently, governments and academic communities have invested extensive research into this direction. Among them, 5-Hydroxymethylfurfural (HMF) is an important biomass-derived chemical, which has attracted much attention in the field of biomass conversion, which can be converted into 2, 5-furandicarboxylic acid (FDCA) by oxidation. Because of containing rigid furan rings and 2, 5-site diformic acid group structures, FDCA is considered to be capable of replacing phthalic acid and can be directly used for high-performance engineering plastics such as polyester, epoxy resin, polyamide, polyurethane and the like. For example, because of the mechanical properties of poly FDCA such as good modulus and creep resistance, and higher glass transition temperature and heat distortion temperature, it is currently studied to replace conventional terephthalate (PET) with poly FDCA. In addition, poly FDCA has passed the european union food safety certification due to its biodegradable advantage. The method for synthesizing 2, 5-furan diformate reported in the literature at present mainly comprises the steps of preparing HMF by sequentially dehydrating cellulose, glucose and other raw materials, oxidizing the HMF into FDCA, and finally esterifying to obtain the HMF. However, the preparation efficiency of HMF is low in the past, and the market price of HMF is high due to the dependence on noble metal catalysts. Meanwhile, when cheap metal is used for oxidation, permanganate and dichromate are mostly used, and the defects of high toxicity, environmental pollution and the like are also caused.
Disclosure of Invention
In order to overcome the defects and shortcomings of the existing 2, 5-furan dicarboxylic acid ester synthesis technology, the invention aims to provide a preparation method of the 2, 5-furan dicarboxylic acid ester compound. The method does not need to use 5-Hydroxymethylfurfural (HMF) as a raw material, but adopts cheap 2-furoate as a raw material, and has the advantages of simple and convenient operation, low cost and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of 2, 5-furan dicarboxylic acid ester compounds comprises the following steps:
will be provided with
Figure BDA0001892370500000021
R2OH, an initiator and a catalyst are added into chloroform to obtain a reaction solution, and the 2, 5-furan dicarboxylic acid ester compound can be obtained after reflux reaction;
wherein, the 2, 5-furan dicarboxylate compound has the following structural general formula:
Figure BDA0001892370500000022
R1saturated aliphatic hydrocarbon and alicyclic hydrocarbon of C1-C17;
R2saturated aliphatic hydrocarbon and alicyclic hydrocarbon of C1-C17.
Preferably, the 2, 5-furan dicarboxylate compound has any one of the following structural formulas:
Figure BDA0001892370500000031
preferably, the initiator is one or more than two of azodiisobutyronitrile, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyhydrate, acetyl peroxide and di-tert-butyl peroxide.
Preferably, the catalyst is Cu (OAc)2、Cu(acac)2、CuCl2、CuCl、CuBr2、CuBr、CuI、Mn(OAc)2、Pd(OAc)2、Ni(acac)2、Fe(acac)3And Cu (OTf)2One or more than two of them.
Preferably, in the reaction solution
Figure BDA0001892370500000032
And R2The molar ratio of OH is 1: 1-1: 100.
Preferably, in the reaction solution
Figure BDA0001892370500000033
And the initiator in a molar ratio of 100:1 to 1: 100.
Preferably, in the reaction solution
Figure BDA0001892370500000034
And the molar ratio of the catalyst to the catalyst is 100: 1-1: 1.
Preferably, in said reaction solution
Figure BDA0001892370500000041
And the molar ratio of chloroform is 1: 1-1: 100.
Preferably, the reaction temperature of the reflux reaction is 0-160 ℃, and the reaction time is 1-60 hours.
Preferably, after the reflux reaction, the reaction product is further cooled to room temperature and then sequentially treated with saturated NaHCO3Extracting the solution, removing the solvent under reduced pressure, and finally carrying out chromatographic separation to obtain the 2, 5-furan dicarboxylic acid ester compound.
Compared with the prior art, the invention has the following advantages and effects:
(1) 5-hydroxymethylfurfural does not need to be used as a raw material, so that the method has the advantage of low cost;
(2) the used alcoxyl acylation reagent is chloroform, and other solvents are not needed;
(3) does not need strict anhydrous condition and low-temperature operation, does not need expensive strong alkali such as butyl lithium and the like, and has simple operation and low cost.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. But the embodiments of the present invention are not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000042
the preparation method comprises the following steps:
in a 10mL single-neck flask, 1mmol of chloroform was added, and 1mmol of methanol and 1mmol of chloroform were added
Figure BDA0001892370500000043
Adding 1mmol of benzoyl peroxide as an initiator and Cu (OAc) as a catalyst2Refluxing 0.01mmol at 100 deg.C for 12 hr, cooling to room temperature, adding saturated NaHCO3The solution was post-extracted, the solvent removed under reduced pressure to give a crude product which was then isolated by flash column chromatography to give 148.5mg (75% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.23–7.19(m,2H),4.40(q,J＝7.2Hz,2H),3.93(s,3H),1.40(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ158.55,158.11,147.10,146.66,118.55,118.34,61.72,52.42,14.33.
example 2
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000051
the preparation method comprises the following steps:
a100 mL single-neck flask was charged with 100mmol of chloroform, and 100mmol of methanol and 1mmol of chloroform were added
Figure BDA0001892370500000052
Adding 100mmol of tert-butyl peroxybenzoate as an initiator and Cu (acac) as a catalyst2Reacting 1mmol at 0 deg.C for 60 hr, returning to room temperature, adding saturated NaHCO3Solution back extractionThe solvent was removed under reduced pressure to give a crude product, which was then isolated by flash column chromatography to give 148.4mg (70% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.19(dd,J＝12.1,3.5Hz,2H),5.31–5.21(m,1H),3.93(s,3H),1.37(d,J＝6.3Hz,6H)；13C NMR(100MHz,CDCl3)δ158.63,157.75,147.50,146.61,118.54,118.11,69.65,52.41,21.91.
example 3
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000053
the preparation method comprises the following steps:
in a 100mL Schlenk bottle (sealable high pressure resistant) 25mmol of chloroform was added, followed by 25mmol of methanol and 1mmol of methanol
Figure BDA0001892370500000061
Adding initiator tert-butyl peroxybenzoate 10mmol and catalyst CuCl20.2mmol at 160 ℃ for 1 hour, cooling to room temperature, adding saturated NaHCO3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 124.3mg of a product (the yield is 55%). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.21(dd,J＝8.4,3.6Hz,2H),4.34(t,J＝6.7Hz,2H),3.93(s,3H),1.78–1.71(m,2H),1.51–1.40(m,2H),0.97(t,J＝7.4Hz,3H)；13C NMR(100MHz,CDCl3)δ158.58,158.21,147.13,146.72,118.54,118.27,65.54,52.41,30.72,19.17,13.75.
example 4
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000062
the preparation method comprises the following steps:
50mmol of chloroform, 50mmol of methanol and 1mmol of chloroform were added to a 100mL Schlenk flask (sealable high pressure resistant)
Figure BDA0001892370500000063
Adding 0.5mmol of tert-butyl peroxybenzoate as an initiator and CuBr as a catalyst20.5mmol reacted at 140 ℃ for 3 hours, cooled to room temperature and saturated NaHCO was added3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 146.6mg of a product (the yield is 52%). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.21(dd,J＝9.0,3.6Hz,2H),4.33(t,J＝6.8Hz,2H),3.93(s,3H),1.80–1.72(m,2H),1.43–1.26(m,11H),0.88(t,J＝6.3Hz,3H)；13C NMR(100MHz,CDCl3)δ158.62,158.24,147.17,146.75,118.57,118.30,65.89,52.45,31.88,29.30,29.26,28.72,25.96,22.74,14.18.
example 5
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000071
the preparation method comprises the following steps:
a40 mL single-neck flask was charged with 30mmol of chloroform, and 5mmol of methanol and 1mmol of chloroform were added
Figure BDA0001892370500000072
Adding 0.01mmol of initiator di-tert-butyl peroxide and 0.25mmol of catalyst CuCl, reacting at 50 deg.C for 30 hr, cooling to room temperature, adding saturated NaHCO3The solution was extracted, the solvent was removed under reduced pressure to give a crude product, which was then isolated by flash column chromatography to give 131.0mg (58% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.21(dd,J＝9.3,3.6Hz,2H),4.12(d,J＝6.7Hz,2H),3.93(s,3H),2.08(dp,J＝13.4,6.7Hz,1H),1.00(d,J＝6.7Hz,6H)；13C NMR(100MHz,CDCl3)δ158.63,158.01,147.51,146.62,118.53,118.06,78.79,52.41,32.76,23.86.
example 6
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000073
the preparation method comprises the following steps:
in a 10mL single-neck flask, 5mmol of chloroform was added, and 5mmol of methanol and 1mmol of methanol were added
Figure BDA0001892370500000074
Adding 0.1mmol of tert-butyl peroxybenzoate as an initiator and Cu (OAc) as a catalyst20.05mmol, refluxing at 80 deg.C for 24 hr, removing solvent under reduced pressure to obtain crude product, and separating by flash column chromatography to obtain 158.6mg (61% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.43(d,J＝7.1Hz,2H),7.40–7.33(m,3H),7.21(q,J＝3.6Hz,2H),5.37(s,2H),3.91(s,3H)；13C NMR(100MHz,CDCl3)δ158.52,157.93,146.92,146.76,135.29,128.73,128.65,128.62,118.74,118.55,67.21,52.45.
example 7
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000081
the preparation method comprises the following steps:
in a 10mL single-neck flask, 30mmol of chloroform was added, and 3mmol of methanol and1mmol of
Figure BDA0001892370500000082
Adding 2mmol of tert-butyl peroxybenzoate as an initiator and Cu (acac) as a catalyst20.2mmol of the compound is refluxed for 45 hours at 100 ℃, cooled to room temperature, and saturated NaHCO is added3The solution was extracted, the solvent was removed under reduced pressure to give a crude product, which was then isolated by flash column chromatography to give 156.6mg (56% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.20(dd,J＝10.5,3.5Hz,2H),4.37(t,J＝7.0Hz,2H),3.93(s,3H),1.69(dt,J＝13.8,9.7Hz,7H),1.42(ddd,J＝10.7,7.1,3.5Hz,1H),1.30–1.14(m,3H),1.03–0.91(m,2H)；13C NMR(100MHz,CDCl3)δ158.60,158.23,147.18,146.74,118.56,118.27,64.10,52.44,36.03,34.68,33.26,26.55,26.26.
example 8
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000091
the preparation method comprises the following steps:
a50 mL single-neck flask was charged with 20mmol of chloroform, and 60mmol of methanol and 1mmol of methanol were added
Figure BDA0001892370500000092
Adding 4mmol of azodiisobutyronitrile as initiator and 0.15mmol of CuBr as catalyst, reflux reacting at 120 deg.C for 8 hr, cooling to room temperature, adding saturated NaHCO3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 143.8mg of a product (the yield is 51%). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.20(dd,J＝15.6,3.5Hz,2H),4.26(d,J＝5.9Hz,2H),3.93(s,3H),1.72(dd,J＝12.1,6.0Hz,1H),1.39(ddd,J＝24.1,16.3,6.7Hz,8H),0.96–0.88(m,6H)；13C NMR(100MHz,CDCl3)δ158.55,158.24,147.09,146.77,118.49,118.13,68.10,52.35,38.89,30.45,28.97,23.87,22.99,14.05,11.02.
example 9
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000093
the preparation method comprises the following steps:
in a 10mL single-neck flask, 10mmol of chloroform was added, and further 2.5mmol of methanol and 1mmol of chloroform were added
Figure BDA0001892370500000094
Adding 2.5mmol of tert-butyl peroxy-phthalate as initiator and Mn (OAc) as catalyst20.25mmol of the product is refluxed for 12 hours at 100 ℃, cooled to room temperature, and saturated NaHCO is added3The solution was extracted, the solvent was removed under reduced pressure to give a crude product, which was then isolated by flash column chromatography to give 118.7mg (53% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.20(q,J＝3.6Hz,2H),5.28–5.15(m,1H),3.93(s,3H),2.44(ddd,J＝12.5,6.0,3.5Hz,2H),2.31–2.19(m,2H),1.92–1.81(m,1H),1.68(td,J＝10.4,2.3Hz,1H)；13C NMR(100MHz,CDCl3)δ158.60,157.49,147.13,146.72,118.57,118.38,70.14,52.46,30.43,13.63.
example 10
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000101
the preparation method comprises the following steps:
the preparation method comprises the following steps:
80mmol of chloroform and 15mmol of chloroform were added to a 100mL single-neck flaskAnd 1mmol of
Figure BDA0001892370500000102
Adding 50mmol of initiator acetyl peroxide and Pd (OAc) as catalyst20.5mmol reacted at 60 ℃ for 36 h, cooled to room temperature and saturated NaHCO was added3The solution was post-extracted, the solvent was removed under reduced pressure to give a crude product, which was then isolated by flash column chromatography to give 147.7mg (62% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.18(dd,J＝17.8,3.6Hz,2H),5.40(dt,J＝9.1,3.1Hz,1H),3.93(s,3H),2.02–1.92(m,2H),1.82(t,J＝13.9Hz,4H),1.70–1.59(m,2H)；13C NMR(100MHz,CDCl3)δ158.63,158.01,147.51,146.62,118.53,118.06,78.79,52.41,32.76,23.86.
example 11
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000111
the preparation method comprises the following steps:
in a 10mL single-neck flask, 20mmol of chloroform was added, and 2mmol of methanol and 1mmol of methanol were added
Figure BDA0001892370500000112
Adding 0.5mmol of tert-butyl peroxybenzoate as an initiator and Ni (acac) as a catalyst20.15mmol of NaHCO at 25 deg.C for 60 hours, cooling to room temperature and adding saturated NaHCO3The solution was extracted, the solvent was removed under reduced pressure to give a crude product, which was then isolated by flash column chromatography to give 158.8mg (63% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.20(dd,J＝12.1,3.6Hz,2H),5.05–4.97(m,1H),3.93(s,3H),2.00–1.91(m,2H),1.83–1.75(m,2H),1.62–1.53(m,3H),1.46–1.27(m,3H)；13C NMR(100MHz,CDCl3)δ158.61,157.60,147.51,146.60,118.51,118.05,74.40,52.37,31.64,25.37,23.82.
example 12
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000113
the preparation method comprises the following steps:
in a 10mL single-neck flask, 10mmol of chloroform was added, and further 7.5mmol of methanol and 1mmol of chloroform were added
Figure BDA0001892370500000114
Adding 10mmol of tert-butyl peroxybenzoate as an initiator and Fe (acac) as a catalyst30.75mmol of the product is refluxed for 12 hours at 100 ℃, cooled to room temperature, and saturated NaHCO is added3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 167.6mg of a product (the yield is 63%). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.18(dd,J＝15.1,3.6Hz,2H),5.25–5.09(m,1H),3.93(s,3H),2.01(ddd,J＝13.0,7.7,3.5Hz,2H),1.86–1.76(m,2H),1.72–1.50(m,8H)；13C NMR(100MHz,CDCl3)δ158.70,157.64,147.67,146.63,118.57,118.04,77.05,52.44,33.88,28.35,22.98.
example 13
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000121
the preparation method comprises the following steps:
in a 10mL single-neck flask, 10mmol of chloroform was added, and 6mmol of methanol and 1mmol of methanol were added
Figure BDA0001892370500000122
Adding 8mmol of tert-butyl peroxybenzoate as an initiator and Cu (OTf) as a catalyst20.2mmol of the compound is reacted at 120 ℃ for 24 hours under reflux, cooled to room temperature and added with saturated NaHCO3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 137.4mg (yield 49%). Structural characterization physical constants of the product1H NMR(400MHz,CDCl3)δ7.18(dd,J＝16.3,3.6Hz,2H),5.19(tt,J＝8.3,4.3Hz,1H),3.93(s,3H),1.97–1.71(m,6H),1.67–1.48(m,8H)；13C NMR(100MHz,CDCl3)δ158.66,157.61,147.69,146.59,118.54,117.99,77.06,52.39,31.63,27.15,25.49,23.02.
Example 14
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000131
the preparation method comprises the following steps:
in a 10mL single-neck flask, 10mmol of chloroform was added, and 3mmol of methanol and 1mmol of chloroform were further added
Figure BDA0001892370500000132
Adding 3mmol of tert-butyl peroxybenzoate as an initiator and Cu (OAc) as a catalyst20.3mmol of the compound is refluxed for 12 hours at 130 ℃, cooled to room temperature, and saturated NaHCO is added3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 150.9mg of a product (the yield is 82%). Structural characterization physical constants of the product1H NMR(400MHz,CDCl3)δ7.22(s,2H),3.94(s,6H)；13C NMR(100MHz,CDCl3)δ158.54,146.81,118.58,52.51.
Example 15
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000133
the preparation method comprises the following steps:
in a 100mL single-neck flask, 15mmol of chloroform was added, and 50mmol of ethanol and 1mmol of ethanol were added
Figure BDA0001892370500000134
Adding 4mmol of tert-butyl peroxybenzoate as an initiator and Cu (OAc) as a catalyst20.4mmol of the product is refluxed for 12 hours at 110 ℃, cooled to room temperature, and saturated NaHCO is added3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 150.5mg of a product (the yield is 71%). Structural characterization physical constants of the product1H NMR(400MHz,CDCl3)δ7.20(s,2H),4.40(q,J＝7.1Hz,4H),1.39(t,J＝7.1Hz,6H)；13C NMR(100MHz,CDCl3)δ158.18,147.04,118.33,61.68,14.34.
Example 16
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000141
the preparation method comprises the following steps:
in a 25mL single-neck flask, 20mmol of chloroform, 20mmol of isopropanol and 1mmol of isopropanol were added
Figure BDA0001892370500000142
Adding 2mmol of tert-butyl peroxybenzoate as an initiator and Cu (acac) as a catalyst20.2mmol of the compound is refluxed for 12 hours at the temperature of 100 ℃, cooled to room temperature, and saturated NaHCO is added3The solution was post-extracted, the solvent was removed under reduced pressure to give a crude product, which was then isolated by flash column chromatography to give 98.4mg (41% yield). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.16(s,2H),5.25(dt,J＝12.5,6.3Hz,2H),1.37(d,J＝6.3Hz,12H)；13C NMR(100MHz,CDCl3)δ157.81,147.28,118.07,69.53,21.89.
example 17
This example provides a method for preparing 2, 5-furandicarboxylate compounds.
The structural formula of the compound is as follows:
Figure BDA0001892370500000143
the preparation method comprises the following steps:
in a 10mL single-neck flask, 15mmol of chloroform was added, and 5mmol of n-butanol and 1mmol of chloroform were added
Figure BDA0001892370500000144
Adding 5mmol of tert-butyl peroxybenzoate as initiator and 1mmol of CuI as catalyst, reflux reacting at 100 deg.C for 12 hr, cooling to room temperature, adding saturated NaHCO3The solution is extracted, the solvent is removed under reduced pressure to obtain a crude product, and then the crude product is separated by flash column chromatography to obtain 134.0mg of a product (the yield is 50%). The structure of the product characterizes the physical constants:1H NMR(400MHz,CDCl3)δ7.19(s,2H),4.34(t,J＝6.7Hz,4H),1.80–1.68(m,4H),1.53–1.39(m,4H),0.97(t,J＝7.4Hz,6H)；13C NMR(100MHz,CDCl3)δ158.26,147.06,118.26,65.47,30.72,19.19,13.76.
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A preparation method of 2, 5-furan dicarboxylate compounds is characterized by comprising the following steps:
will be provided with
Figure FDA0003521827070000011
R2OH, an initiator and a catalyst are added into chloroform to obtain a reaction solution, and the 2, 5-furan dicarboxylic acid ester compound can be obtained after reaction;
wherein, the 2, 5-furan dicarboxylate compound has the following structural general formula:
Figure FDA0003521827070000012
specifically, the compound is selected from any one of the following structural general formulas:
Figure FDA0003521827070000013
the initiator is one or more than two of azodiisobutyronitrile, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyhydrate, acetyl peroxide and di-tert-butyl peroxide;
the catalyst is Cu (OAc)2、Cu(acac)2、CuCl2、CuCl、CuBr2、CuBr、CuI、Mn(OAc)2、Pd(OAc)2、Ni(acac)2、Fe(acac)3And Cu (OTf)2One or more than two of them.
2. The process for producing a 2, 5-furandicarboxylate compound according to claim 1, characterized in that: in the reaction solution
Figure FDA0003521827070000021
And R2The molar ratio of OH is 1: 1-1: 100.
3. The process for producing a 2, 5-furandicarboxylate compound according to claim 1, characterized in that: in the reaction solution
Figure FDA0003521827070000022
And the initiator in a molar ratio of 100:1 to 1: 100.
4. The process for producing a 2, 5-furandicarboxylate compound according to claim 1, characterized in that: in the reaction solution
Figure FDA0003521827070000023
And the molar ratio of the catalyst to the catalyst is 100: 1-1: 1.
5. The process for producing a 2, 5-furandicarboxylate compound according to claim 1, characterized in that: in the reaction solution
Figure FDA0003521827070000024
And the molar ratio of chloroform is 1: 1-1: 100.
6. The process for producing a 2, 5-furandicarboxylate compound according to claim 1, characterized in that: the reaction temperature is 0-160 ℃, and the reaction time is 1-60 hours.
7. The process for producing a 2, 5-furandicarboxylate compound according to claim 1, characterized in that: after the reaction, the reaction product is further cooled to room temperature and then sequentially treated with saturated NaHCO3Extracting the solution, removing the solvent under reduced pressure, and finally carrying out chromatographic separation to obtain the 2, 5-furan dicarboxylic acid ester compound.
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