CN111848930B - Soluble polybenzfuran, preparation method thereof and application thereof in synthesizing 5-substituted benzofuran - Google Patents
Soluble polybenzfuran, preparation method thereof and application thereof in synthesizing 5-substituted benzofuran Download PDFInfo
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Abstract
The invention discloses soluble polybenzfuran, a preparation method thereof and application thereof in synthesizing 5-substituted benzofuran. The method uses benzofuran as a raw material, polyfluoro substituted alcohol as a solvent and Lewis acid as a polymerization initiator to prepare the polymer shown in the formula I. The polybenzfuran polymer prepared by the method is easy to dissolve in an organic solvent, the chemical reaction activity and the reaction sites of all structural units are the same, and the highly selective functionalized polymer formula III is obtained in the electrophilic substitution reaction of a polymer benzene ring. The thermal cleavage reaction of formula III produces a 5-substituted benzofuran of formula IV.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and relates to soluble polybenzfuran, a preparation method thereof and application thereof in synthesis of 5-substituted benzofuran.
Background
Highly crosslinked resinous polybenzfurans are a class of polymers with high glass transition temperatures and high transparency, and have been widely used in the research and application of novel optical materials. Such polymers can be obtained by polymerization of benzofuran in a solvent such as toluene or dichloromethane in the presence of an initiator such as tin chloride, alkylboron, alkylaluminum (Mizote et al. Polymer Chemistry,1966,4,869), perfluorophenylboron (Lian et al. Dalton Trans.2009,9033), perfluorophenylaluminum (Lin et al. macromolecules,2017,50,8449) at a reaction temperature of-100 to-80 ℃ (Natta.Et al. Makromol.Chem.1961,43, 68-75). The polymer prepared under the reaction system has the characteristics that the reaction temperature is required to be severe or a high molecular product is a highly crosslinked resin-shaped polymer and is insoluble in a common organic solvent, so that the benzene ring of the polymer cannot be effectively subjected to electrophilic substitution reaction so as to realize the modification of the polymer.
Disclosure of Invention
The invention aims to provide soluble polybenzfuran, a preparation method thereof and application thereof in synthesizing 5-substituted benzofuran.
The invention claims polymers of formula I;
in the formula I, n is 10-800.
In the polymer shown in the formula I, n can be specifically 100-800, 100-500, 100-400, 100-300, 20-200 or 20-100; more specifically M may benA polymer of formula I ═ 36426.
In the formula I, the repeating structural unit is benzofuranyl; a and b represent substituted bits;
the repeating structural unit repeats in a mode that the substitution positions a and b are repeated at intervals, namely, the substitution position connected with the substitution position a is the substitution position b.
The invention also provides a method for preparing the polymer shown in the formula I, which comprises the following steps: carrying out polymerization reaction on a compound shown as a formula II and an initiator in a solvent to obtain a polymer shown as a formula I after the reaction is finished;
the solvent is polyfluoro substituted alcohol or a mixed solvent containing polyfluoro substituted alcohol.
In the above method, the initiator is a lewis acid; specifically at least one selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, hydrobromic acid, hydroiodic acid, and boron trifluoride;
the dosage of the initiator is 0.0-5% of the feeding molar dosage of the compound shown in the formula II; specifically 0.2% or 0.4%;
the polyfluoro substituted alcohol is 1,1,1,3,3, 3-hexafluoroisopropanol or 2,2, 2-trifluoroethanol;
the mixed solvent containing the polyfluoro substituted alcohol is a mixed solvent a or a mixed solvent b;
the mixed solvent a is a mixed solution consisting of 1,1,1,3,3, 3-hexafluoroisopropanol and dichloromethane; the volume ratio of the 1,1,1,3,3, 3-hexafluoroisopropanol to the dichloromethane is specifically 10:1-1: 1; specifically 4: 1;
the mixed solvent b is a mixed solution consisting of 2,2, 2-trifluoroethanol and dichloromethane; the volume ratio of the 2,2, 2-trifluoroethanol to the dichloromethane is specifically 10:1-1: 1; in particular 8: 1;
in the step of polymerization reaction, the temperature is-10-50 ℃; specifically 0-25 deg.C; the time is 1-24 hours.
The invention provides a method for preparing polybenzfuran shown as a formula III, which comprises the following steps: uniformly mixing the polymer shown in the formula I, an electrophilic reagent and a catalyst in an organic solvent to perform electrophilic substitution reaction, and obtaining polybenzfuran shown in the formula III after the reaction is finished;
or, after the method, uniformly mixing the obtained reaction product, electrophilic reagents and catalysts in an organic solvent to carry out electrophilic substitution reaction, and obtaining the polybenzfuran shown in the formula III after the reaction is finished;
n is 10 to 800;
in the formula III, R is C1-C18 alkyl, acyl, C1-C18 alkoxy, nitro, aryl or halogen;
n is 10 to 800; n can be more specifically 100-800, 100-500, 100-400, 100-300, 20-200 or 20-100.
In particular, the C1-C18 alkyl is C1-C10 alkyl; more particularly C1-C6 alkyl;
the alkoxy of C1-C18 is C1-C10 in particular; more particularly-MeCO, -EtCO, -C5H11CO、-C7H15CO、-c-C6H11CO、-n-C17H25CO or-para-BrC6H4CO；
The aryl is substituted phenyl or substituted furyl; in particular to
or-PhCO;
the halogen is fluorine, chlorine or bromine;
r is F, Cl, Br or-NO2；
When R is polysubstituted, the substituted position is at least one of para position, ortho position and meta position;
when R is monosubstituted, the substitution position is para.
In the formula III, a and b represent substituted positions; the repeating structural units repeat in the same manner as in formula I.
In the above method, the electrophile is selected from at least one of halogen, iodine bromide, bromine chloride, N-bromosuccinimide, chlorine gas, N-chlorosuccinimide, alkyl acid chloride, aryl acid chloride, and nitric acid;
specifically, in the alkyl acyl chloride, the carbon atom number of the alkyl is specifically 1-20; more specifically acetyl chloride, propionyl chloride, n-hexanoyl chloride, n-octanoyl chloride, cyclohexylcarbonyl chloride or n-octadecanoyl chloride;
the aryl acyl chloride is benzoyl chloride, p-bromobenzoyl chloride or 2-furoyl chloride;
the mass percentage concentration of the nitric acid is specifically 95%;
the addition amount of the electrophilic reagent is 0.1-6.0 times of the feeding molar amount of the polymer shown in the formula I; specifically 1.1, 1.2 or 1.25 times;
the catalyst is Lewis acid; specifically at least one selected from the group consisting of aluminum trichloride, aluminum tribromide, boron trifluoride, ferric trichloride and trimethylsilylchloride;
the dosage of the catalyst is 0.1-1.1 times of the feeding molar dosage of the polymer shown in the formula I;
the organic solvent is at least one selected from dichloromethane, chloroform, carbon tetrachloride, carbon disulfide and tetrahydrofuran; the dosage of the organic solvent is as follows: controlling the concentration of the polymer to 0.1M in terms of monomer;
in the step of electrophilic substitution, the temperature is-10-60 ℃; specifically 0-40 ℃ or 25-40 ℃; the time is 1-24 hours; in particular 12-16 hours.
The electrophilic substitution reaction of the above-mentioned polybenzofuran of the formula I has the following characteristics: (1) the polybenzfuran (formula I) can be dissolved in an organic solvent to carry out electrophilic substitution reaction; (2) all structural units of the polymer have consistent reactivity, and the functionalization rate is high; (3) the electrophilic substitution reaction has high position selectivity, and only occurs at a specific position of a benzene ring.
The invention provides a method for preparing 5-substituted benzofuran shown in formula IV, which comprises the following steps: carrying out thermal cracking reaction on the polybenzfuran shown in the formula III obtained by the method, and obtaining the 5-substituted benzofuran shown in the formula IV after the reaction is finished;
in the formula IV, R is defined as the same as the definition of R.
In the thermal cracking reaction step of the method, the reaction condition is inert atmosphere or decompression condition with vacuum degree of 2-950 mbar;
the inert atmosphere is specifically selected from at least one of nitrogen and argon atmosphere;
the temperature of the thermal cracking reaction is lower than 400 ℃; particularly 280-380 ℃; in particular 280-340 ℃ or 300 ℃;
the time of the thermal cracking reaction is 0.2-8 hours; in particular 3-5 hours;
the thermal cracking is specifically any one of thermal cracking a-b;
the thermal cracking a is the cracking for 3 to 5 hours from the room temperature to 340 ℃ within 20 minutes
The thermal cracking b is that after the pre-cracking is carried out for 1 hour from the room temperature to 300 ℃ within 20 minutes, the temperature is raised to 340 ℃ within 20 minutes for cracking for 3 to 5 hours;
the thermal cracking reaction is carried out in thermal cracking equipment made of glass or metal materials.
The method further comprises the following steps: after the thermal cracking reaction step, fractionating the reaction system in a fractionating receiver to obtain the 5-substituted benzofuran represented by formula IV.
The thermal cracking method of the functionalized polybenzfuran has the following characteristics: (1) the cracking of the polymer has high uniformity, 5-substituted benzofuran single molecules are mainly generated, and the oligomer products are few; (2) the yield of thermal cracking monomer is high; (3) the thermal cracking reaction temperature can be controlled within 400 ℃.
The invention also claims polymers of formula III,
in the formula III, R is the same as the definition of the R;
n is 10 to 800;
the invention also claims compounds described by formula IV,
in the formula IV, R is defined as the same as the definition of R.
The invention provides a non-crosslinked polybenzfuran polymer shown as a formula I. The polybenzfuran polymer has the following new properties: (1) good solubility in common organic solvents; (2) each polymerized unit of the polymer dissolved in the organic solvent has the same reactive site; (3) a lower initiator dosage is used; (4) the polymer can not only be subjected to pyrolysis reaction at the temperature of below 350 ℃, but also be subjected to uniform polymerization unit decomposition reaction with high selectivity to generate the functionalized benzofuran monomer. The traditional electrophilic substitution reaction of the functionalized benzofuran compound based on benzofuran cannot be obtained.
Drawings
FIG. 1 shows a hydrogen spectrum of the polybenzfuran obtained in example 1 for the preparation of polybenzfuran.
FIG. 2 shows a carbon spectrum of the polybenzfuran obtained in example 1 for the preparation of polybenzfuran.
FIG. 3 shows a GPC chart of the polybenzfuran obtained in example 1 for preparing the polybenzfuran.
FIG. 4 is a thermogravimetric analysis of the polybenzfuran obtained in example 1 for the preparation of polybenzfuran.
FIG. 5 is a hydrogen spectrum of benzofuran obtained in example 1 by thermal cracking of polybenzfuran (formula III).
FIG. 6 is a spectrum of benzofuran obtained in example 1 by thermal cracking of polybenzfuran (formula III).
FIG. 7 shows the hydrogen spectrum of brominated polybenzfuran obtained in example 1 of electrophilic substitution reaction of polybenzfuran (formula I).
FIG. 8 shows the carbon spectrum of brominated polybenzfuran obtained in example 1 for electrophilic substitution of polybenzfuran (formula I).
FIG. 9 is a hydrogen spectrum of 5-bromobenzofuran obtained in example 3 for thermal cracking of polybenzfuran (formula III).
FIG. 10 is a carbon spectrum diagram of polybenzfuran (formula III) thermal cracking example 3 for the resulting 5-bromobenzofuran.
FIG. 11 shows the hydrogen spectrum of polybenzfuran (formula III) in example 4 for 5-chlorobenzofuran obtained.
FIG. 12 is a carbon spectrum diagram of polybenzfuran (formula III) thermal cracking example 4 is the resulting 5-chlorobenzofuran.
FIG. 13 shows the hydrogen spectrum of acetylated polybenzfuran obtained in example 5, which is electrophilic substitution reaction of polybenzfuran (formula I).
FIG. 14 shows a carbon spectrum of acetylated polybenzfuran obtained in example 5, which is electrophilic substitution reaction of polybenzfuran (formula I).
FIG. 15 shows a hydrogen spectrum of polybenzfuran (formula III) obtained in example 5 for thermal cracking of 5-acetylbenzofuran.
FIG. 16 is a carbon spectrum diagram of polybenzfuran (formula III) thermal cracking example 5 is the resulting 5-acetylbenzofuran.
FIG. 17 shows the hydrogen spectrum of benzoylated polybenzfuran obtained in example 11 for electrophilic substitution of polybenzfuran (formula I).
FIG. 18 shows a carbon spectrum of benzoylated polybenzfuran obtained in example 11 for electrophilic substitution of polybenzfuran (formula I).
FIG. 19 is a hydrogen spectrum of polybenzfuran (formula III) obtained in example 11 for thermal cracking of 5-benzoylbenzofuran.
FIG. 20 is a carbon spectrum diagram of thermal cracking of polybenzfuran (formula III) example 11 is the resulting 5-benzoylbenzofuran.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1 preparation of polybenzofuran example 1
Benzofuran (118.1 mg, 1.0mmol) and trifluoroacetic acid (0.15. mu.L, 2. mu. mol) were added to 1.0mL of 1,1,1,3,3, 3-hexafluoroisopropanol, and the reaction temperature was controlled at 0 ℃ and stirred for 24 hours. 5.0mL of methanol is added to be quenched for reaction, white precipitate is separated out, and then the white solid 110.3mg (93 percent of yield) is obtained after precipitation, suction filtration, washing and drying. The poly-benzofuran is identified and confirmed by the hydrogen spectrum and the carbon spectrum. Number average molecular weight M by GPCn36426 (fig. 3).
Preparation of polybenzofuran example 2
11.8135g (0.1mol) of benzofuran and 15.0. mu.L (0.2mmol) of trifluoroacetic acid were added to 100.0mL of 1,1,1,3,3, 3-hexafluoroisopropanol, and the reaction temperature was controlled at 0 ℃ and stirred for 24 hours. 1,1,1,3,3, 3-hexafluoroisopropanol in the reaction solution was removed and recovered using a vacuum concentrator (95mL, 95% recovery) to give a pale yellow solid. This solid was dissolved in 20.0mL of dichloromethane, reprecipitated in 500mL of methanol, washed, filtered with suction, and dried under reduced pressure to yield 11.2226g (95% yield) of a white solid.
Preparation of polybenzofuran example 3
Benzofuran (118.1 mg, 1.0mmol) and trifluoroacetic acid (0.15. mu.L, 2. mu. mol) were added to 0.8mL of 1,1,1,3,3, 3-hexafluoroisopropanol and 0.2mL of dichloromethane, and the reaction temperature was controlled at 0 ℃ and stirred for 24 hours. 5.0mL of methanol is added for quenching reaction, white precipitate is separated out, and then the white solid 106.1mg (yield 90%) is obtained after precipitation, suction filtration, washing and drying, and is identified as the polybenzfuran by the identification of a hydrogen spectrum and a carbon spectrum.
Preparation of polybenzofuran example 4
Benzofuran (118.1 mg, 1.0mmol) and trifluoroacetic acid (0.15. mu.L, 2. mu. mol) were added to 1.0mL of 1,1,1,3,3, 3-hexafluoroisopropanol, and the reaction temperature was controlled at 25 ℃ and stirred for 24 hours. 5.0mL of methanol is added for quenching reaction, white precipitate is separated out, and white solid 44.9mg (yield 38%) is obtained after precipitation, suction filtration, washing and drying, and is identified as the polybenzfuran by the identification of a hydrogen spectrum and a carbon spectrum.
Preparation of polybenzofuran example 5
Benzofuran (118.1 mg) (1.0mmol) was added to 1.0mL of 1,1,1,3,3, 3-hexafluoroisopropanol, and the reaction temperature was controlled at 25 deg.C, and stirred for 24 hours. 5.0mL of methanol is added for quenching reaction, white precipitate is separated out, and white solid 42.5mg (yield 36%) is obtained after precipitation, suction filtration, washing and drying, and is identified as the polybenzfuran by the identification of a hydrogen spectrum and a carbon spectrum.
Preparation of polybenzofuran example 6
Benzofuran (118.1 mg, 1.0mmol) and trifluoroacetic acid (0.30. mu.L, 4. mu. mol) were added to 1.0mL of 1,1,1,3,3, 3-hexafluoroisopropanol, and the reaction temperature was controlled at 0 ℃ and stirred for 24 hours. 5.0mL of methanol is added for quenching reaction, white precipitate is separated out, and 112.3mg of white solid (yield 95%) is obtained after precipitation, suction filtration, washing and drying, and is identified as the polybenzfuran by the identification of a hydrogen spectrum and a carbon spectrum.
Preparation of polybenzofuran comparative example 1
Benzofuran (118.1 mg, 1.0mmol) and trifluoroacetic acid (0.15. mu.L, 2. mu. mol) were added to 1.0mL of 1,1,1,3,3, 3-hexafluoroisopropanol, and the reaction temperature was controlled at 60 ℃ and stirred for 24 hours. 5.0mL of methanol was added to quench the reaction, and no precipitate was precipitated.
Preparation of polybenzofuran comparative example 2
118.1mg (1.0mmol) of benzofuran and 0.15. mu.L (2. mu. mol) of trifluoroacetic acid were added to 1.0mL of dichloromethane, and the reaction temperature was controlled at 0 ℃ and stirred for 24 hours. 5.0mL of methanol was added to quench the reaction, and no precipitate was precipitated.
Preparation of polybenzofuran comparative example 3
1.180g (10.0mmol) of benzofuran, 2.7mg (20 mu mol) of initiator aluminum trichloride and 3.0mL of toluene are stirred at 20 ℃ for 24 hours, 5.0mL of methanol is added to quench the reaction, a white precipitate is separated out, and then the white solid 365.8mg (31% yield) is obtained through precipitation, suction filtration, washing and drying. The white solid obtained by the method is difficult to dissolve in common organic solvents such as dichloromethane, chloroform, carbon tetrachloride, carbon disulfide, tetrahydrofuran and the like. The polybenzfuran obtained by the method is insoluble in the common organic solvent, so that electrophilic substitution reaction cannot be carried out on the benzene ring of the polymer, the compound shown in the formula III cannot be obtained, and the compound shown in the formula IV cannot be obtained in a thermal cracking mode.
Electrophilic substitution of polybenzfurans of formula I to functionalized polybenzfurans of formula III
Electrophilic substitution of polybenzfurans (formula I) example 1
Preparation of brominated polybenzofuran: 1.1810g (10.0mmol) of the polybenzfuran obtained in example 1 was dissolved in 40mL of dichloromethane, and then 1.760g (11.0mmol) of a solution of bromine dissolved in 10mL of dichloromethane was added dropwise to the solution of the polybenzfuran in dichloromethane. The reaction temperature was controlled at 25 ℃ and stirred for 12 hours, then 50mL of methanol was added to quench the reaction. A white precipitated solid was precipitated, which was filtered off with suction, washed and dried to obtain 1.941g of a white solid (bromination yield 98%). Identified as brominated polybenzfuran by the hydrogen spectrum and the carbon spectrum (formula III: R ═ Br).
Electrophilic substitution of polybenzfuran (formula I) example 2
Preparation of chlorinated polybenzfuran: polybenzfuran 236.0mg (2.0mmol), N-chlorosuccinimide 320.4mg (2.4mmol) and trimethylsilyl chloride 30. mu.L (0.20mmol) were dissolved in 5.0mL of N, N-dimethylformamide. The reaction temperature is controlled at 40 ℃, after stirring for 16 hours, 5.0mL of methanol is added to quench the reaction, and a white solid is precipitated and separated out. Filtration with suction, washing and drying gave 304.2mg of a white solid (99% chloro yield). Identified by hydrogen spectrum and carbon spectrum as chlorinated polybenzfuran (formula III: R ═ Cl).
Electrophilic substitution of polybenzfuran (formula I) example 5
Preparation of acetylated polybenzofuran: 236.0mg (2.0mmol) of polybenzofuran, 172.6mg (2.2mmol) of acetyl chloride and 293.3mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of dichloromethane. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to quench the reaction, and after the dichloromethane is removed by reduced pressure distillation, white precipitate solid is obtained and separated out. After filtration with suction, washing and drying, 291.8mg (acylation rate 65%) of a white solid was obtained. Identified by a hydrogen spectrum and a carbon spectrum as acetylpolybenzfuran (formula III: R ═ MeCO).
Electrophilic substitution of polybenzfuran (formula I) example 6
Preparation of propionylated polybenzofuran: 236.0mg (2.0mmol) of polybenzofuran, 203.5mg (2.2mmol) of propionyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of dichloromethane. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to quench the reaction, and the dichloromethane is removed by reduced pressure distillation, so that a white solid is precipitated and separated out. After filtration with suction, washing and drying, 308.1mg of a white solid was obtained (acylation rate 66%). Identified by hydrogen and carbon spectra as propionyl polybenzfuran (formula III: R ═ EtCO).
Electrophilic substitution of polybenzfuran (formula I) example 7
Preparation of n-hexanoylated polybenzfuran: 236.0mg (2.0mmol) of polybenzofuran, 296.2mg (2.2mmol) of n-hexanoyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of dichloromethane. Controlling the reaction temperature at 0 ℃, stirring for 12 hours, adding 10.0mL of 3.0M hydrochloric acid to quench the reaction, and distilling under reduced pressure to remove dichloromethane to obtain a white solid precipitateAnd (4) precipitating. After filtration with suction, washing and drying, 354.1mg (acylation rate 60%) of a white solid was obtained. Identified by hydrogen spectrum and carbon spectrum as n-caproylated polybenzfuran (formula III, R ═ C)5H11CO)。
Electrophilic substitution of polybenzfuran (formula I) example 8
Preparation of n-octanoylated polybenzfuran: 236.0mg (2.0mmol) of polybenzofuran, 357.8mg (2.2mmol) of n-octanoyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of methylene chloride. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to quench the reaction, and the dichloromethane is removed by reduced pressure distillation, so that a white solid is precipitated and separated out. After filtration with suction, washing and drying, 308.1mg of a white solid was obtained (acylation rate 66%). Identified by hydrogen spectrum and carbon spectrum as propionyl-substituted polybenzfuran (formula III, R ═ C)7H15CO)。
Electrophilic substitution of polybenzfuran (formula I) example 9
Preparation of Cyclohexylformylphenylated polybenzfuran: 236.0mg (2.0mmol) of polybenzofuran, 322.5mg (2.2mmol) of cyclohexylcarbonyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of methylene chloride. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to quench the reaction, and the dichloromethane is removed by reduced pressure distillation, so that a white solid is precipitated and separated out. After filtration with suction, washing and drying, 399.2mg of a white solid (acylation rate 75%) was obtained. Identified by hydrogen spectrum and carbon spectrum as cyclohexylformylphenylated polybenzfuran (formula III, R ═ C-C)6H11CO)。
Electrophilic substitution of polybenzfuran (formula I) example 10
Preparation of n-octadecylated polybenzfuran: 236.0mg (2.0mmol) of polybenzofuran, 666.4mg (2.2mmol) of n-octadecanoyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of dichloromethane. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to quench the reaction, and the dichloromethane is removed by reduced pressure distillation, so that a white solid is precipitated and separated out. After suction filtration, washing and drying 449.5mg (acylation rate 40%) of a white solid was obtained. Identified by its hydrogen and carbon spectraDefinitely identified as cyclohexylformylphenylated polybenzofuran (formula III, R ═ n-C)17H25CO)。
Electrophilic substitution of polybenzfuran (formula I) example 11
Preparation of benzoylated polybenzfuran: 236.0mg (2.0mmol) of polybenzofuran, 310.0mg (2.2mmol) of benzoyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of dichloromethane. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to quench the reaction, and the dichloromethane is removed by reduced pressure distillation, so that a white solid is precipitated and separated out. After filtration with suction, washing and drying, 401.1mg (acylation rate 79%) of a white solid was obtained. Identified by its hydrogen and carbon spectra as propionylated polybenzofuran (formula III, R ═ PhCO).
Electrophilic substitution of polybenzfuran (formula I) example 12
Preparation of 5- (p-bromobenzoyl) polybenzofuran: 236.0mg (2.0mmol) of polybenzofuran, 310.0mg (2.2mmol) of p-bromobenzoyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of dichloromethane. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to quench the reaction, and the dichloromethane is removed by reduced pressure distillation, so that a white solid is precipitated and separated out. After filtration with suction, washing and drying, 514.1mg (acylation rate 76%) of a white solid was obtained. Identified by their hydrogen and carbon spectra as 5- (p-bromobenzoyl) polybenzofuran (formula III, R ═ para-BrC6H4CO)。
Electrophilic substitution of polybenzfuran (formula I) example 13
Preparation of nitrated polybenzfuran: polybenzfuran 236.0mg (2.0mmol) and 95% nitric acid 157.5mg (2.5mmol) were dissolved in 10.0mL of dichloromethane. The reaction temperature was controlled at 0 ℃ and stirred for 12 hours, then 10.0mL of methanol was added to quench the reaction. After suction filtration, washing and drying, 294.7mg of brown yellow solid (nitration rate 65%) is obtained. Identified as nitrated polybenzfuran (formula III, R ═ NO) by hydrogen spectrum and carbon spectrum identification2)。
Electrophilic substitution of polybenzfuran (formula I) example 14
Preparation of furan-2-carbonylated polybenzfuran: 236.0mg (2.0mmol) of polybenzofuran, 287.1mg (2.2mmol) of 2-furoyl chloride and 294.0mg (2.2mmol) of aluminum trichloride were dissolved in 20.0mL of dichloromethane. The reaction temperature is controlled at 0 ℃, the mixture is stirred for 12 hours, 10.0mL of 3.0M hydrochloric acid is added to be quenched, and the dichloromethane is removed by reduced pressure distillation, so that a white solid is precipitated and separated out. After filtration with suction, washing and drying, 379.1mg of a white solid (acylation rate 76%) was obtained.
Identified as furan-2-carbonylation polybenzfuran by the hydrogen spectrum and the carbon spectrum
Thermal cracking reaction of functionalized polybenzfuran formula III to prepare 5-substituted benzofuran formula IV
Thermal cleavage of polybenzfuran (formula III) example 1
236.0mg (2.0mmol) of polybenzfuran (formula III, R ═ H) was placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere, and the temperature was raised to 300 ℃ in 20 minutes, and the temperature was maintained at 300 ℃ for cracking for 3 hours. 226.6mg of liquid (96% yield) was obtained in the receiver of the fractional distillation. The benzofuran (formula II) is identified and confirmed by the hydrogen spectrum and the carbon spectrum.
Thermal cleavage of polybenzfuran (formula III) example 2
1.1800g (10.0mmol) of polybenzfuran (formula III, R ═ H) was placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under a nitrogen atmosphere, and the temperature was raised to 340 ℃ over 20 minutes, and the temperature was maintained at 340 ℃ for cracking for 3 hours. The yield in the receiver was 1.0971g (93% yield) as a liquid. The benzofuran (formula II) is identified and confirmed by the hydrogen spectrum and the carbon spectrum.
Thermal cleavage of polybenzfuran (formula III) example 3
Preparation of 5-bromobenzofuran: 1.9410g of brominated polybenzfuran (formula III, R ═ Br) was placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under a nitrogen atmosphere, and the temperature was raised to 300 ℃ over 20 minutes, and the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar and 1.7929g of a pale yellow transparent liquid (91% yield) were obtained in the fractionation receiver. The compound is identified as 5-bromobenzofuran (formula IV, R ═ Br) by hydrogen spectrum and carbon spectrum.
Thermal cleavage of polybenzfuran (formula III) example 4
Preparation of 5-chlorobenzofuran: 304.2mg (2.0mmol) of chlorinated polybenzfuran (formula III, R ═ Cl) was placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under a nitrogen atmosphere, and the temperature was raised to 300 ℃ in 20 minutes, and the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. In the receiver, 268.4mg (88% yield) of a liquid was obtained. Identified by hydrogen spectrum and carbon spectrum, the compound is 5-chlorobenzofuran (formula IV, R ═ Cl).
Thermal cleavage of polybenzfuran (formula III) example 5
Preparation of 5-acetylbenzofuran: 291.8mg (2.0mmol) of acetylated polybenzfuran (formula III, R ═ MeCO) was placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere, and the temperature was raised to 300 ℃ in 20 minutes, and the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. In the receiver of the fractional distillation, 208.2mg of a solid were obtained (yield 65%). Identified by its hydrogen and carbon spectra as 5-acetylbenzofuran (formula IV, R ═ MeCO).
Thermal cleavage of polybenzfuran (formula III) example 6
Preparation of 5-propionyl benzofuran: 308.1mg of propionylated polybenzfuran (formula III, R ═ EtCO) was placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under a nitrogen atmosphere, and the temperature was raised to 300 ℃ within 20 minutes, and the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The solid obtained in the receiver was 222.9mg (64% yield). Identified by its hydrogen and carbon spectra as 5-propionylbenzofuran (formula IV, R ═ EtCO).
Thermal cleavage of polybenzfuran (formula III) example 7
Preparation of 5-hexanoyl benzofuran: subjecting n-hexanoylated polybenzfuran (formula III, R ═ C)5H11CO)354.1mg were placed in a thermal cracking reactor vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere, and the temperature was raised to 300 ℃ within 20 minutes, and the temperature was maintained at 300 ℃ for 1 hour of pre-cracking. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar, giving 246.7mg of solid in the fractional distillation receiver (57% yield). Identified by hydrogen spectrum and carbon spectrum, 5-n-hexanoyl polybenzfuran (formula IV, R ═ C)5H11CO)。
Thermal cleavage of polybenzfuran (formula III) example 8
Preparation of 5-n-octanoylbenzofuran: n-octanoylated polybenzfuran (formula III, R ═ C)7H15CO)308.1mg (2.0mmol) were placed in a thermal cracking reactor vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere and the temperature was raised to 300 ℃ within 20 minutes, the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar, giving 249.2mg (51% yield) of a solid in the fractionation receiver. Identified by hydrogen spectrum and carbon spectrum, 5-n-octanoyl benzofuran (formula IV, R ═ C)7H15CO)。
Thermal cleavage of polybenzfuran (formula III) example 9
Preparation of 5-Cyclohexylformylbenzofuran: cyclohexylformylated polybenzfuran (formula III, R ═ C-C6H11CO)399.2mg (2.0mmol) were placed in a thermal cracking reactor vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere and the temperature was raised to 300 ℃ within 20 minutes, the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar, giving 337.9mg of solid in the fractional distillation receiver (74% yield). Identified by hydrogen spectrum and carbon spectrum as 5-cyclohexylformyl benzofuran (formula IV, R ═ C-C)6H11CO)。
Thermal cleavage example 10 of polybenzfuran (formula III)
Preparation of 5-n-octadecylbenzofuran: poly (n-octadecylation)Benzofuran (formula III, R ═ n-C)17H25CO)449.5mg was placed in a thermal cracking reactor vessel and heated initially to 280 ℃ under nitrogen and then to 300 ℃ over 20 minutes, and the temperature was maintained at 300 ℃ for 1 hour of pre-cracking. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar, giving 276.9mg of solid in the fractional distillation receiver (36% yield). Identified by hydrogen spectrum and carbon spectrum, 5-n-octadecanoyl benzofuran (formula IV, R ═ n-C)17H25CO)。
Thermal cleavage example 11 of polybenzfuran (formula III)
Preparation of 5-benzoylbenzofuran: 401.1mg of benzoylated polybenzfuran (formula III, R ═ PhCO) was placed in a thermal cracking reactor vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere, and the temperature was raised to 300 ℃ over 20 minutes, and the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar, giving 339.4mg of solid in the fractionation receiver (76% yield). Identified by its hydrogen and carbon spectra as 5-benzoylbenzofuran (formula IV, R ═ PhCO).
Thermal cleavage example 12 of polybenzfuran (formula III)
Preparation of 5- (p-bromobenzoyl) benzofuran: 4-bromobenzoylated polybenzofuran (formula III, R ═ para-BrC6H4CO)514.1mg were placed in a thermal cracking reactor vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere, and the temperature was raised to 300 ℃ within 20 minutes, and the temperature was maintained at 300 ℃ for 1 hour of pre-cracking. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar, giving 439.9mg of solid in the fractional distillation receiver (73% yield). Identified by hydrogen and carbon spectra as 5- (p-bromobenzoyl) benzofuran (formula IV, R ═ para-BrC)6H4CO)。
Thermal cleavage example 13 of polybenzfuran (formula III)
Preparation of 5-nitrobenzofuran: reacting nitrated polybenzfuran (formula III, R ═ NO)2)294.7mg (2.0mmol) were placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere, and the temperature was raised to 300 ℃ within 20 minutes, and the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The solid was obtained in the receiver of the fractional distillation at 208.9mg (yield 64%). Identified by hydrogen spectrum and carbon spectrum as 5-nitrobenzofuran (formula IV, R ═ NO)2)。
Thermal cleavage example 14 of polybenzfuran (formula III)
Preparation of 5- (furan-2-carbonyl) benzofuran: carbonylation of furan-2-polyphenofuran
379.1mg were placed in a thermal cracking reaction vessel, the initial heating temperature was controlled at 280 ℃ under nitrogen atmosphere, and the temperature was raised to 300 ℃ within 20 minutes, and the temperature was maintained at 300 ℃ for pre-cracking for 1 hour. The temperature was raised to 340 ℃ over 20 minutes for lysis for 5 hours. The vacuum distillation unit was turned on to reduce the system pressure of the cracker to 20mbar, giving 309.6mg of solid in the fractional distillation receiver (73% yield). Identified as 5- (furan-2-carbonyl) benzofuran by hydrogen spectrum and carbon spectrum
Claims (15)
1. A method of making a polymer of formula I, comprising: carrying out polymerization reaction on benzofuran and an initiator in a solvent to obtain a polymer shown in the formula I after the reaction is finished;
in the formula I, n is 10-800;
the solvent is polyfluoro substituted alcohol or a mixed solvent containing polyfluoro substituted alcohol;
in the step of polymerization reaction, the temperature is-10-50 ℃; the time is 1-24 hours.
2. The method of claim 1, wherein: in the formula I, n is 100-800.
3. The method according to claim 1 or 2, characterized in that: the initiator is Lewis acid;
the amount of the initiator is 0.0-5% of the molar amount of the added benzofuran;
the polyfluoro substituted alcohol is 1,1,1,3,3, 3-hexafluoroisopropanol or 2,2, 2-trifluoroethanol;
the mixed solvent containing the polyfluoro substituted alcohol is a mixed solvent a or a mixed solvent b;
the mixed solvent a is a mixed solution consisting of 1,1,1,3,3, 3-hexafluoroisopropanol and dichloromethane;
the mixed solvent b is a mixed solution consisting of 2,2, 2-trifluoroethanol and dichloromethane;
in the polymerization step, the temperature is 0 to 25 ℃.
4. The method of claim 3, wherein: the Lewis acid is selected from at least one of hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, hydrobromic acid, hydroiodic acid and boron trifluoride;
the dosage of the initiator is 0.2 percent of the feeding molar dosage of the benzofuran;
the volume ratio of the 1,1,1,3,3, 3-hexafluoroisopropanol to the dichloromethane is 10:1-1: 1;
the volume ratio of the 2,2, 2-trifluoroethanol to the dichloromethane is 10:1-1: 1.
5. A method of preparing a polybenzfuran of formula III comprising: uniformly mixing a polymer shown in a formula I, an electrophilic reagent and a catalyst in an organic solvent for electrophilic substitution reaction, and obtaining polybenzfuran shown in a formula III after the reaction is finished;
or, after the method of any one of claims 1 to 4, mixing the obtained reaction product, an electrophilic reagent and a catalyst uniformly in an organic solvent to perform electrophilic substitution reaction, and obtaining the polybenzfuran shown in the formula III after the reaction is finished;
in the formula III, R is C1-C18 alkyl, acyl, C1-C18 alkoxy, nitro, aryl or halogen;
n is 10 to 800.
6. The method of claim 5, wherein: in the formula III, R is-MeCO, -EtCO and-C5H11CO、-C7H15CO、-c-C6H11CO、-n-C17H25CO、-para-BrC6H4CO, substituted phenyl, substituted furyl, fluoro, chloro, bromo or-NO2；
When R is polysubstituted, the substituted positions are at least two of para position, ortho position and meta position;
when R is monosubstituted, the substitution position is para.
7. The method of claim 6, wherein: the substituted furyl is
The substituted phenyl is PhCO.
8. The method according to any one of claims 5 to 7, wherein: the electrophilic reagent is selected from at least one of halogen, iodine bromide, bromine chloride, N-bromosuccinimide, chlorine, N-chlorosuccinimide, alkyl acyl chloride, aryl acyl chloride and nitric acid;
the addition amount of the electrophilic reagent is 0.1-6.0 times of the feeding molar amount of the polymer shown in the formula I;
the catalyst is Lewis acid;
the dosage of the catalyst is 0.1-1.1 times of the feeding molar dosage of the polymer shown in the formula I;
the organic solvent is at least one selected from dichloromethane, chloroform, carbon tetrachloride, carbon disulfide and tetrahydrofuran;
in the step of electrophilic substitution, the temperature is-10-60 ℃; the time is 1-24 hours.
9. The method of claim 8, wherein: in the alkyl acyl chloride, the carbon atom number of the alkyl is 1-20;
the aryl acyl chloride is benzoyl chloride, p-bromobenzoyl chloride or 2-furoyl chloride;
the Lewis acid is selected from at least one of aluminum trichloride, aluminum tribromide, boron trifluoride, ferric trichloride and trimethylsilyl chloride.
10. The method of claim 9, wherein: the alkyl acyl chloride is acetyl chloride, propionyl chloride, n-hexyl chloride, n-octanoyl chloride, cyclohexyl formyl chloride or n-octadecanoyl chloride.
11. A process for preparing a 5-substituted benzofuran of formula IV comprising: carrying out a thermal cracking reaction on the polybenzfuran shown in the formula III obtained by the method of any one of claims 5 to 10 to obtain the 5-substituted benzofuran shown in the formula IV after the reaction is finished;
in the formula IV, R is as defined in claim 5.
12. The method of claim 11, wherein: in the thermal cracking reaction step, the reaction condition is inert atmosphere or decompression condition with vacuum degree of 2-950 mbar;
the temperature of the thermal cracking reaction is lower than 400 ℃;
the time of the thermal cracking reaction is 0.2-8 hours;
the thermal cracking reaction is carried out in thermal cracking equipment made of glass or metal materials;
the method further comprises the following steps: after the thermal cracking reaction step, fractionating the reaction system in a fractionating receiver to obtain the 5-substituted benzofuran represented by formula IV.
13. The method of claim 12, wherein: the inert atmosphere is at least one of nitrogen and argon atmosphere;
the temperature of the thermal cracking reaction is 280-380 ℃;
the time of the thermal cracking reaction is 3-5 hours;
the thermal cracking is any one of thermal cracking a-b;
the thermal cracking a is the cracking for 3 to 5 hours from the room temperature to 340 ℃ within 20 minutes;
the thermal cracking b is that after the pre-cracking is carried out for 1 hour from the room temperature to 300 ℃ within 20 minutes, the temperature is increased to 340 ℃ within 20 minutes for cracking for 3 to 5 hours.
14. The method of claim 13, wherein: the temperature of the thermal cracking reaction is 280-340 ℃.
15. The method of claim 14, wherein: the temperature of the thermal cracking reaction was 300 ℃.
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