CN105732546A - Preparation method of 2,5-diacyl furan compound - Google Patents
Preparation method of 2,5-diacyl furan compound Download PDFInfo
- Publication number
- CN105732546A CN105732546A CN201410765238.3A CN201410765238A CN105732546A CN 105732546 A CN105732546 A CN 105732546A CN 201410765238 A CN201410765238 A CN 201410765238A CN 105732546 A CN105732546 A CN 105732546A
- Authority
- CN
- China
- Prior art keywords
- group
- furan
- anhydride
- preparation
- diacyl
- 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
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The application discloses a preparation method of a 2,5-diacyl furan compound, which simply and high efficiently prepares the 2,5-diacyl furan compound by carrying out acylation reaction on a 2,3-dicarboxylic anhydride-7-oxabicyclo[2.2.1]hepta-5-ene and/or a furan and an acylation agent. The preparation method is simple and high efficient, and has short flow and less by-products. The purity of the 2,5-diacyl furan compound prepared by the method is high. The 2,5-diacyl furan compound can satisfy requirements as raw materials of engineering plastics such as high-performance polyester, epoxy resin, polyamide, and polyurethane and as chemical raw materials and medical intermediate raw materials.
Description
Technical field
The preparation method that the application relates to a kind of 2,5-diacyl furan compounds, belongs to the technical field of the polymer monomer preparations such as high-performance polyester, epoxy resin, polyamide and polyurethane and chemical industry, medicine intermediate.
Background technology
At present, what synthesizing polyester, epoxy resin, polyamide, polyurethane contour performance engineering plastics adopted is single containing the alcohol of stiffening ring structure, acid, esters monomer raw material.Furan is a kind of important fragrant monomer, yet with active group without bifunctionality in its structure, therefore, it is impossible to be directly used in the preparation of high-performance polymer, also restrained in the application of medicine, chemical field.
2,5-diacyl furan compounds because of the diacyl structure of the furan nucleus containing rigidity and para-position, the furan diacid obtained through peroxidating, reduction and furan glycol, can be directly used for the preparation of polyester, epoxy resin, polyamide, the contour performance engineering plastics of polyurethane.Adopt polymer prepared by furan diacid and furan glycol to have excellent mechanical property in intensity, modulus, creep resistant etc., there is higher glass transition temperature and heat distortion temperature simultaneously.Additionally, 2,5-diacyl furan compounds itself can also use as industrial chemicals and medicine intermediate.At present about 2; the synthesis report of 5-diacyl furan compound is less; mainly UchiyamaM et al. is with 2-acetyl furan for raw material, has synthesized 2,5-diacyl furan compound [Tetrahedron:Asymmetry; 1997; 8 (20): 3467-3474.], but the method has complex synthetic route, and gross production rate is low; the shortcoming that cost is high, is difficulty with heavy industrialization application.
Summary of the invention
An aspect according to the application, it is provided that the preparation method of a kind of 2,5-diacyl furan compounds; by by 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene and/or furan and acylting agent generation acylation reaction, simple and effective prepare 2,5-diacyl furan compounds.Preparation method is simply efficiently, flow process is short, by-product is few; adopt the method prepare 2; 5-diacyl furan compound purity is high, can meet the raw material as engineering plastics such as high-performance polyester, epoxy resin, polyamide, polyurethane and the requirement as industrial chemicals and medicine intermediate raw material.
The preparation method of described 2,5-diacyl furan compounds, it is characterised in that 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene and/or furan and acylting agent generation acylation reaction, obtains described 2,5-diacyl furan compounds；
Described 2,5-diacyl furan compound at least one in the compound with chemical structural formula shown in Formulas I:
Wherein, R1It is methyl or R1It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number；R2It is methyl or R2It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number.
Preferably, described 2,5-diacyl furan compounds at least one in 2,5-diacetyl furan, 2,5-dihalo-acetyl furans.
Preferably, described 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene are that furan is obtained by Diels-Alder reaction (being abbreviated as D-A to react) with maleic anhydride.The mol ratio of furan and maleic anhydride is furan: maleic anhydride=1:0.1～2；The reaction temperature of Diels-Alder reaction is-10 DEG C～100 DEG C, and the response time is 0.1～48h.The chemical structural formula of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene is such as shown in Formulas I V:
Preferably, described acylting agent is anhydride and/or carboxylic acid halides.
The acylation reaction of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene and anhydride is such as shown in Formula V-1, and the acylation reaction of furan and anhydride is such as shown in Formula V-2:
The acylation reaction of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene and carboxylic acid halides is such as shown in Formula IV-1, and the acylation reaction of furan and carboxylic acid halides is such as shown in Formula IV-2:
Preferably, described anhydride at least one in the compound with chemical structural formula shown in Formula II:
Wherein, R4It is methyl or R4It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number；R4It is methyl or R4It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number.
Preferably, described carboxylic acid halides at least one in the compound with chemical structural formula shown in formula III:
Wherein, R5It is methyl or R5It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number；X one in fluorine, chlorine, bromine, iodine.
Described aryl and heteroaryl are lose the group formed after any one hydrogen atom on aromatic rings in aromatic compound molecule.When not comprising the hetero atoms such as N, O, S on aromatic rings, the group of formation is aryl；When comprising the hetero atoms such as N, O, S on aromatic rings, the group of formation is heteroaryl.Forming the aromatic compound of aryl or heteroaryl, aromatic rings can not have substituent group can also have substituent group, typical substituent group is alkyl, carboxyl, hydroxyl, halogeno-group etc. such as.
Containing the group of group at least one in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group, refer to group at least contains in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group at least one.If chloracetyl is the group comprising halogens chlorine and carbonyl simultaneously.
Preferably, R in Formulas I1, R in Formulas I2, R in Formula II3, R in Formula II4, R in formula III5Separately selected from-CH3、-CF3、-CCl3、-CBr3、-CI3、-CH2F、-CH2Cl、-CH2Br、-CH2I、-CHCl2、-CH2CH2F、-CH2CH2Cl、-CH2CH2Br、-CH2CH2I、-CH3CHBr、-CF3CF2、-CF3CF2CF2, furyl ,-COCl, CH3CH2OCO-、C6H5CH2-、-C6H5、CH3OCO-、C6H5CH2CH2-、(C6H5)2One in CH-.
Preferably, described anhydride at least one in acetic anhydride, monochloroacetic acid anhydride, benzoyl oxide, trifluoroacetic anhydride, Trichloroacetic anhydride, tribromoacetic acid acid anhydride, triiodoacetic acid acid anhydride, heptafluorobutyric anhydride, PFPA.
Preferably, formula III removes the group R of X5(CO)-at least one in 2-acetyl fluoride base, 2-chloracetyl, 2-acetyl bromide, 2-iodoacetyl, 3-fluorine propiono, 3-chlorine propiono, 3-bromine propiono, 3-propidium jodiole base, dichloro-acetyl, 2-bromine propiono, furoyl base, oxalyl group, oxalyl group mono ethyl ester, phenylacetyl group, isobutyryl, benzoyl, methyl oxalyl, hydrogen cinnamoyl, diphenylacetyl.
Preferably, described carboxylic acid halides at least one in 2-fluoracyl chloride, 2-chloracetyl chloride, 2-bromoacetyl chloride, 2-iodacetyl chloride, 3-fluorine propionyl chloride, 3-chlorpromazine chloride, 3-bromo propionyl chloro, 3-propidium jodiole chlorine, dichloroacetyl chloride, 2-bromo propionyl chloro, furoyl chloride, oxalyl chloride, ethyl oxalyl chloride, phenyllacetyl chloride, isobutyryl chloride, Benzenecarbonyl chloride., methyl oxalyl chloride, hydrogen cinnamoyl chloride, two phenyllacetyl chlorides.
Preferably, described acylting agent with the mol ratio of furan and/or 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene is:
Acylting agent: (molal quantity of the molal quantity+furan of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene)=1～20:1.
Preferably, to be the mol ratio of anhydride and/or carboxylic acid halides, anhydride and/or carboxylic acid halides and 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene and/or furan be described acylting agent:
(molal quantity of the molal quantity+carboxylic acid halides of anhydride): (molal quantity of the molal quantity+furan of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene)=1～20:1.
Preferably, in described acylation reaction, the mol ratio of use acidic catalyst, acidic catalyst and acylting agent is:
The molal quantity of acid catalyst: molal quantity=0.002%～20% of acylting agent.
Preferably, described acylting agent is anhydride and/or carboxylic acid halides, and in acylation reaction, the mol ratio of use acidic catalyst, acidic catalyst and anhydride and/or acyl chlorides is:
The molal quantity of acid catalyst: (molal quantity of the molal quantity+carboxylic acid halides of anhydride)=0.002%～20%.Described acid catalyst at least one in Louis (Lewis) acid or Bronsted acid.Preferably, described acid catalyst at least one in sulphuric acid, nitric acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, aluminum chloride, zinc chloride, stannic chloride, boron trifluoride etherate.
Preferably, the reaction temperature of described acylation reaction is 10 DEG C～200 DEG C, and the response time is 0.1～48h.It is further preferred that the temperature range upper limit of described acylation reaction is selected from 200 DEG C, 180 DEG C, 160 DEG C, 120 DEG C, 100 DEG C, lower limit is selected from 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C.
Preferably, the R in Formulas I1And R2, R in Formula II3And R4, R in formula III5It it is identical group.
The beneficial effect that the application can produce at least includes:
Herein described technical scheme effectively utilizes furan as raw material, construct a set of simple efficiently, flow process is short, by-product is few chemical transformation technology, furan is converted to 2,5-diacyl furan compounds, product total recovery 60%-90% by two steps.
Herein described technical scheme is medicine, chemical field provides outside raw material, important raw material basis is provided for engineering plastics such as synthesized high-performance polyester, epoxy resin, polyurethane, can the manufacture level of service hoisting high performance engineering plastics comprehensively, and can promote that bio-based Polymer Material Industry is broken away from the height to petroleum resources and relied on.
Accompanying drawing explanation
Fig. 1 is 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in the heptan alkene that embodiment 1 obtains1H-NMR collection of illustrative plates.
Fig. 2 is the 2,5-diacetyl furan that embodiment 1 obtains1H-NMR collection of illustrative plates.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.
In embodiment, in embodiment, proton nmr spectra1H-NMR adopts the upper mensuration of 400AVANCE III type spectroscope (Spectrometer) of Brooker company (Bruker), 400MHz, CDCl3。
Elementary analysis adopts the 2400 II CHN patterns of Perkinelmer Inc. (Perkin-Elmer) and O pattern to measure.
Product analysis adopts the 7890B-5977A type liquid chromatograph-mass spectrometer detection of Agilent company (Agilent).
The productivity of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene is calculated by below equation and obtains:
Productivity %=(2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene quality × 100)/(furan mole × 68)
The productivity of 2,5-diacyl furan compound is calculated by below equation and obtains:
Productivity %=(quality × 100 of 2,5-diacyl furan)/(mole × 166 of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene or and mole × 68 of furan)
Embodiment 1
In 500ml reactor, adding 68.0g furan, 78.5g maleic anhydride, 100ml toluene, 50 DEG C of reaction 10h, crystallisation by cooling precipitates out, and dries and obtains 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, and product is white crystal, productivity 92%.Obtaining through 1H-NMR (400MHz, CDCl3) test, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58), as shown in Figure 1.
Take 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g adds in 100ml reactor; add 20.4g acetic anhydride; 0.02mol concentrated sulphuric acid reacts 2h at 160 DEG C; room temperature it is down to after having reacted; decompression is distilled off acetic anhydride, and distillation obtains white crystal 2,5-diacetyl furan; productivity 86%; fusing point 135-136 DEG C, liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 152.1,1H-NMR (400MHz; CDCl3) test obtains; CH, 2H, δ (7.24) on furan nucleus；CH3,6H, δ (2.59), as shown in Figure 2.Elementary analysis C8H8O3 value of calculation C:63.15, H:5.30, O:31.55；Measured value C:62.8, H:5.27, O:31.57.
Embodiment 2
In 500ml reactor, adding 68.0g furan, 19.6g maleic anhydride, 20ml dichloromethane, 100 DEG C of reaction 1h, crystallisation by cooling precipitates out, and dries and obtains 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, and product is white crystal, productivity 90%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g adds in 250ml reactor; adding 102.6g monochloroacetic acid anhydride, 0.025mol concentrated nitric acid reacts 0.5h at 200 DEG C, is down to room temperature after having reacted; decompression is distilled off monochloroacetic acid anhydride; distillation obtains white crystal 2,5-dichloro-acetyl furan, productivity 93%; liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 221.01H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.24) on furan nucleus；CH2Cl, 4H, δ (4.83).
Embodiment 3
In 500ml reactor, adding 68.0g furan, 9.8g maleic anhydride, 10ml chloroform, 70 DEG C of reaction 2h, crystallisation by cooling precipitates out, and dries and obtains 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, and product is white crystal, productivity 96%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 8.3g adds in 250ml reactor; adding 57.8g trifluoroacetic anhydride, 0.005mol concentrated hydrochloric acid reacts 6h at 160 DEG C, is down to room temperature after having reacted; decompression is distilled off trifluoroacetic anhydride; distillation obtains white crystal 2,5-bis--(trifluoroacetyl group) furan, productivity 88%; liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 260.11H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (8.14) on furan nucleus.
Embodiment 4
In 500ml reactor, adding 68.0g furan, 24.5g maleic anhydride, 60ml petroleum ether, 30 DEG C of reaction 6h, crystallization, dry and obtain 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, product is white crystal, productivity 92%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g adds in 100ml reactor; adding 15.5g heptafluorobutyric anhydride, 0.005mol strong phosphoric acid reacts 12h at 100 DEG C, is down to room temperature after having reacted; decompression is distilled off heptafluorobutyric anhydride; distillation obtains crystal 2,5-bis--(seven fluorine bytyries) furan, productivity 83%; liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 360.11H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.34) on furan nucleus.
Embodiment 5
In 500ml reactor, adding 68.0g furan, 117.7g maleic anhydride, 10 DEG C of reaction 16h, crystallization, dry and obtain 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, product is white crystal, productivity 88%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g adds in 100ml reactor; adding 7.85g chloroacetic chloride, 0.01mol methanesulfonic acid reacts 40h at 10 DEG C, to room temperature after having reacted; decompression is distilled off chloroacetic chloride; distillation obtains white crystal 2,5-diacetyl furan, productivity 91%; liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 152.11H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.24) on furan nucleus；CH3, 6H, δ (2.59).Elementary analysis C8H8O3Value of calculation C:63.15, H:5.30, O:31.55；Measured value C:62.9, H:5.33, O:31.43.
Embodiment 6
In 1000ml reactor, adding 68.0g furan, 137.2g maleic anhydride, 400ml methanol, 0 DEG C of reaction 24h, crystallization, dry and obtain 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, product is white crystal, productivity 90%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g adds in 250ml reactor; adding 90.4g chloracetyl chloride, 0.0005mol benzene methanesulfonic acid reacts 24h at 40 DEG C, is down to room temperature after having reacted; decompression is distilled off chloracetyl chloride; distillation obtains white crystal 2,5-dichloro-acetyl furan, productivity 88%; liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 221.01H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.24) on furan nucleus；CH2Cl, 4H, δ (4.83).
Embodiment 7
In 2000ml reactor, adding 68.0g furan, 176.4g maleic anhydride, 1000ml ethanol ,-5 DEG C of reaction 48h, crystallization, dry and obtain 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, product is white crystal, productivity 92%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g and add in 250ml reactor, add 14.7g dichloroacetyl chloride, 0.012molAlCl3Reacting 12h at 80 DEG C, be down to room temperature after having reacted, decompression is distilled off dichloroacetyl chloride, and distillation obtains crystal 2,5-bis--(dichloro-acetyl) furan, productivity 84%, and liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 289.9,1H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.24) on furan nucleus；CHCl2, 2H, δ (6.32).
Embodiment 8
In 250ml reactor, adding 68.0g furan, 58.8g maleic anhydride, 5ml chloroform, 20 DEG C of reaction 12h, crystallization, dry and obtain 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, product is white crystal, productivity 89%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g and add in 250ml reactor, add 156.6g furoyl chloride, 0.005molZnCl2Reacting 1h at 180 DEG C, be down to room temperature after having reacted, decompression is distilled off furoyl chloride, and distillation obtains white crystal 2,5-difurfuroyl base furan, productivity 92%, and liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 256.2,1H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.54) on furan nucleus；CH, 2H；δ(7.23)；CH, 2H, δ (6.61)；CH, 2H, δ (7.72).
Embodiment 9
In 500ml reactor, adding 68.0g furan, 78.5g maleic anhydride, 100ml toluene, 50 DEG C of reaction 10h, crystallisation by cooling precipitates out, and dries and obtains 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, and product is white crystal, productivity 92%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g and add in 500ml reactor, add 204.8g ethyl oxalyl chloride, 0.001molSnCl4Reacting 8h at 100 DEG C, be down to room temperature after having reacted, decompression is distilled off ethyl oxalyl chloride; distillation obtains white crystal 2,5-bis--(mono ethyl ester acetyl group) furan, productivity 89%; liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 268.21H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.24) on furan nucleus；CH2, 4H, δ (4.20)；CH3, 6H, δ (1.30).
Embodiment 10
In 500ml reactor, adding 68.0g furan, 78.5g maleic anhydride, 100ml toluene, 50 DEG C of reaction 10h, crystallisation by cooling precipitates out, and dries and obtains 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomers, and product is white crystal, productivity 92%.Warp1H-NMR (400MHz, CDCl3) test obtain, on ring, CH, 2H have three peaks, respectively δ (3.18,5.46,6.58).
Take 2; 3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene monomer 16.6g adds in 250ml reactor; adding 56.2g Benzenecarbonyl chloride., 0.001mol boron trifluoride etherate reacts 4h at 140 DEG C, is down to room temperature after having reacted; decompression is distilled off Benzenecarbonyl chloride.; distillation obtains white crystal 2,5-dibenzoyl furan, productivity 92%; liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 276.31H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.24) on furan nucleus；Phenyl ring, 4H, δ (7.81)；Phenyl ring, 4H, δ (7.45)；Phenyl ring, 2H, δ (7.54).
Embodiment 11
Take 6.8g furan and add in 250ml reactor; add 102.6g monochloroacetic acid anhydride; 0.030mol concentrated nitric acid reacts 5h at 100 DEG C; being down to room temperature after having reacted, decompression is distilled off monochloroacetic acid anhydride, and distillation obtains white crystal 2; 5-dichloro-acetyl furan; productivity 62%, liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 221.01H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.24) on furan nucleus；CH2Cl, 4H, δ (4.83).
Embodiment 12
Take 6.8g furan and add in 250ml reactor; add 57.8g trifluoroacetic anhydride; 0.005mol concentrated hydrochloric acid reacts 2h at 80 DEG C; being down to room temperature after having reacted, decompression is distilled off trifluoroacetic anhydride, and distillation obtains white crystal 2; 5-bis--(trifluoroacetyl group) furan; productivity 66%, liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 260.11H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (8.14) on furan nucleus.
Embodiment 13
Take 6.8g furan and add in 100ml reactor; add 15.5g heptafluorobutyric anhydride; 0.005mol strong phosphoric acid reacts 2h at 140 DEG C; being down to room temperature after having reacted, decompression is distilled off heptafluorobutyric anhydride, and distillation obtains crystal 2; 5-bis--(seven fluorine bytyries) furan; productivity 67%, liquid chromatography mass spectrometric combined instrument (LC-MS) records molecular weight 360.11H-NMR (400MHz, CDCl3) test obtain, CH, 2H, δ (7.34) on furan nucleus.
Although the application is with preferred embodiment openly as above; but it is not for limiting claim; any those skilled in the art are under the premise conceived without departing from the application; can making some possible variations and amendment, therefore the protection domain of the application should be as the criterion with the scope that the application claim defines.
Claims (10)
1. the preparation method of a diacyl furan compound, it is characterised in that 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene and/or furan and acylting agent generation acylation reaction, obtains described 2,5-diacyl furan compounds；
Described 2,5-diacyl furan compound at least one in the compound with chemical structural formula shown in Formulas I:
Wherein, R1It is methyl or R1It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number；R2It is methyl or R2It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number.
2. preparation method according to claim 1, it is characterised in that described 2,5-diacyl furan compounds at least one in 2,5-diacetyl furan, 2,5-dihalo-acetyl furans.
3. preparation method according to claim 1, it is characterised in that described acylting agent is anhydride and/or carboxylic acid halides.
4. preparation method according to claim 3, it is characterised in that described anhydride at least one in the compound with chemical structural formula shown in Formula II:
Wherein, R3It is methyl or R3It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number；R4It is methyl or R4It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number；
Described carboxylic acid halides at least one in the compound with chemical structural formula shown in formula III:
Wherein, R5It is methyl or R5It is 1～20 and containing the group of at least one group in halogen, aryl, heteroaryl, carbonyl, aliphatic radical, itrile group selected from carbon number；X one in fluorine, chlorine, bromine, iodine.
5. preparation method according to claim 3, it is characterized in that, described anhydride at least one in acetic anhydride, monochloroacetic acid anhydride, benzoyl oxide, trifluoroacetic anhydride, Trichloroacetic anhydride, tribromoacetic acid acid anhydride, triiodoacetic acid acid anhydride, heptafluorobutyric anhydride, PFPA.
6. preparation method according to claim 4, it is characterised in that remove the group R of X in formula III5(CO)-at least one in acetyl group, 2-acetyl fluoride base, 2-chloracetyl, 2-acetyl bromide, 2-iodoacetyl, 3-fluorine propiono, 3-chlorine propiono, 3-bromine propiono, 3-propidium jodiole base, dichloro-acetyl, 2-bromine propiono, furoyl base, oxalyl group, oxalyl group mono ethyl ester, phenylacetyl group, isobutyryl, benzoyl, methyl oxalyl, hydrogen cinnamoyl, diphenylacetyl.
7. the preparation method according to any one of claim 1 to 6, it is characterised in that the mol ratio of described acylting agent and furan and/or 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene is:
Acylting agent: (molal quantity of the molal quantity+furan of 2,3-dicarboxylic acid anhydride-7-oxabicyclo [2.2.1]-5-in heptan alkene)=1～20:1.
8. the preparation method according to any one of claim 1 to 6, it is characterised in that in described acylation reaction, the mol ratio of use acidic catalyst, acidic catalyst and acylting agent is:
The molal quantity of acid catalyst: molal quantity=0.002%～20% of acylting agent.
9. the preparation method according to any one of claim 1 to 6, it is characterised in that the reaction temperature of described acylation reaction is 10 DEG C～200 DEG C, and the response time is 0.1～48h.
10. the preparation method according to claim 1 or 4, it is characterised in that R1, R2, R3, R4And R5It it is identical group.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410765238.3A CN105732546A (en) | 2014-12-11 | 2014-12-11 | Preparation method of 2,5-diacyl furan compound |
| CN202011380642.0A CN112409305A (en) | 2014-12-11 | 2014-12-11 | Preparation method of 2, 5-diacyl furan compound |
| PCT/CN2014/094066 WO2016090658A1 (en) | 2014-12-11 | 2014-12-17 | Method for preparing 2,5-disubstituted furan compound |
| EP14908044.2A EP3231795B1 (en) | 2014-12-11 | 2014-12-17 | Method for preparing 2,5-disubstituted furan compound |
| US15/535,075 US10125110B2 (en) | 2014-12-11 | 2014-12-17 | Method for preparing 2,5-disubstituted furan compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410765238.3A CN105732546A (en) | 2014-12-11 | 2014-12-11 | Preparation method of 2,5-diacyl furan compound |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011380642.0A Division CN112409305A (en) | 2014-12-11 | 2014-12-11 | Preparation method of 2, 5-diacyl furan compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105732546A true CN105732546A (en) | 2016-07-06 |
Family
ID=56240664
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011380642.0A Pending CN112409305A (en) | 2014-12-11 | 2014-12-11 | Preparation method of 2, 5-diacyl furan compound |
| CN201410765238.3A Pending CN105732546A (en) | 2014-12-11 | 2014-12-11 | Preparation method of 2,5-diacyl furan compound |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011380642.0A Pending CN112409305A (en) | 2014-12-11 | 2014-12-11 | Preparation method of 2, 5-diacyl furan compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN112409305A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120735A (en) * | 2011-01-20 | 2011-07-13 | 清华大学 | Method for preparing substituted furan containing 2,5-di-substituent |
-
2014
- 2014-12-11 CN CN202011380642.0A patent/CN112409305A/en active Pending
- 2014-12-11 CN CN201410765238.3A patent/CN105732546A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120735A (en) * | 2011-01-20 | 2011-07-13 | 清华大学 | Method for preparing substituted furan containing 2,5-di-substituent |
Non-Patent Citations (2)
| Title |
|---|
| BRUCE RICKBORN: "The Retro-Diels-Alder Reaction Part I.C-C Dienophiles", 《ORGANIC REACTIONS》 * |
| KATIA SNEGAROFF 等: "Deprotonative Metalation of Functionalized Aromatics Using Mixed Lithium–Cadmium, Lithium–Indium, and Lithium–Zinc Species", 《CHEM. EUR. J.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112409305A (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4856826B2 (en) | Production method of vinyl ether compounds | |
| US9527952B1 (en) | Amorphous polyester from bio-based bis-furan assembly | |
| JP2017179120A (en) | Thermosetting compound | |
| JP2014201545A (en) | METHOD OF MANUFACTURING 2-HYDROXYMETHYL-2,3-DIHYDRO-THIENO[3,4-b][1,4]DIOXIN-5,7-DICARBOXYLIC ACID DIALKYL ESTER | |
| KR102387362B1 (en) | Method for producing high-purity cyclohexenone long-chain alcohol | |
| CN105732546A (en) | Preparation method of 2,5-diacyl furan compound | |
| CN106554338A (en) | A kind of method that furancarboxylic acid prepares 2,5- furandicarboxylic acids | |
| JP5623835B2 (en) | Dicarbonyl compound, intermediate thereof and method for producing the same | |
| US8975365B2 (en) | Cage-shaped cyclopentanoic dianhydride, method for production thereof, and polyimide | |
| CN105732545A (en) | Method for preparing 2,5-diacyl-furan compound | |
| WO2016090658A1 (en) | Method for preparing 2,5-disubstituted furan compound | |
| CN109232479A (en) | A kind of synthetic method of trimellitic acid three-glycidyl ester | |
| US11964939B2 (en) | Aromatic tetracarboxylic acid compound | |
| US7388064B2 (en) | Stereoregular polymer and monomer thereof and process for production of both | |
| JP2009263605A (en) | Molecular capsule and its producing method | |
| JP4015097B2 (en) | Polycyclic compound | |
| CN105732544A (en) | Preparation method of 2,5-dialkyl furan compound | |
| CN108299352A (en) | A kind of preparation method of furan dicarboxylic acid ester compounds | |
| WO2016095122A1 (en) | Preparation method for 2,5-furandicarboxylic acid | |
| JP5417976B2 (en) | High-purity bisoxetane compound and production method thereof. | |
| JP4125263B2 (en) | Trioxymethylcarboxylic acids of trisphenols and their tertiary cyclopentyl esters | |
| JP5783371B2 (en) | 10-substituted-1,4-dihydro-1,4-methanoanthracen-9-yl- (meth) acrylate compound and method for producing the same | |
| JP2014088480A (en) | Polyether ketone and manufacturing method thereof | |
| JP2018104317A (en) | METHOD FOR PRODUCING α-OLEFIN HAVING FURAN RING | |
| JP5403280B2 (en) | Method for producing alicyclic tetracarboxylic acid compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160706 |