CN102924366A - Carbazole ketone intermediate containing multi-functional group structure and preparation method for carbazole ketone intermediate - Google Patents
Carbazole ketone intermediate containing multi-functional group structure and preparation method for carbazole ketone intermediate Download PDFInfo
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Abstract
Carbazole ketone intermediate of the structure containing polyfunctional group and preparation method thereof, the technical issues of solving existing ketone-grouped resin limited thermostability, limit its application, the structural formula of the intermediate is
In formula, R is hydrogen, the straight chained alkyl of C1-C12, the branched alkyl of C1-C12, trifluoromethyl, propylene oxide base, allyl, propinyl, phenyl, 4- fluorophenyl, 4- trifluoromethyl, 4- ethenylphenyl, 4- ethynyl phenyl or 4- cyano-phenyl, X is same or different with Y, is F, Cl, NO2 or OH. Intermediate of the invention has multiple reactivity sites, carbazole ring can be introduced into polymer architecture, enhance the mechanical property and heat resistance of polymer, not only glass transition temperature is up to 293 DEG C to the ketone-grouped resin prepared using intermediate of the invention, and excellent in mechanical performance, intrinsic viscosity are moderate, it is good to dissolve processability, is widely used.
Description
Technical field
The present invention relates to a kind of carbazole ketone intermediate that contains the polyfunctional group structure and preparation method thereof, belong to the synthetic field of organic compound.
Background technology
The nitrogen-containing heterocycle compound carbazole is a kind of cheap industrial chemicals, the fragrant condensed ring structure of self makes it have good thermostability and chemical stability, 9 (N site) and 2 on the carbazole ring, 7 and 3,6 all is avtive spots, the number of chemical reaction can occur, and generates numerous compounds that contain carbazole ring structure.These carbazole intermediates demonstrate the performance of numerous excellences at aspects such as photoelectric material, dyestuff, medicine, resins, shown their potential using values, and along with the development of science and technology, the more multi-usage of carbazole raw material is developed gradually.
Polyaryletherketone has excellent mechanical mechanics property, the resist chemical of anti-solvent performance, radioresistance and flame retardant resistance etc. as a kind of thermoplastic engineering plastic with special construction.Since last century, the seventies ICI company released commercial PEEK resin, in order further to enlarge the Application Areas of ketone-grouped resin, investigator's many-sided trial of comforming carried out study on the modification to it, wherein, the high thermal resistance of ketone-grouped resin and solvability are one of more fields of research.
Chinese patent CN85108751 discloses with phenolphthalein biphenol monomer and 4, the unformed polyaryletherketone (PEK-C) that the polycondensation of 4 '-Diflurodiphenyketone monomer makes, and its structural formula is as follows:
In this patent, although large Cardo side group is given the certain rigidity of polymer molecular chain and good dissolving processing characteristics in the phenolphthalein biphenol monomer, second-order transition temperature is 228 ℃, and still along with the development of science and technology, people are in the urgent need to having the more polymkeric substance of high heat resistance.
Summary of the invention
The purpose of this invention is to provide a kind of carbazole ketone intermediate that contains the polyfunctional group structure and preparation method thereof, and prepare a kind of high thermal resistance ketone-grouped resin by this intermediate, solve existing ketone-grouped resin thermotolerance limited, limit the technical problem of its application.
The invention provides a kind of carbazole ketone intermediate that contains the polyfunctional group structure, the structural formula of this intermediate is as follows:
In the formula, R is hydrogen, C
1-C
12Straight chained alkyl, C
1-C
12Branched-chain alkyl, trifluoromethyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl;
X is identical from Y or different, and X, Y are F, Cl, NO
2Perhaps OH.
Described R is preferably hydrogen, methyl, sec.-propyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl.
The present invention also provides the preparation method of the carbazole ketone intermediate that contains the polyfunctional group structure,
(1) when R is H, the preparation method is:
1. when X is identical with Y
The Fu Shi acylation reaction occurs and obtains the compound VII in chemical compounds I and compound III, namely contains the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
The Fu Shi acylation reaction occurs with the compound III first and obtains the compound V in chemical compounds I, and compound V and compounds Ⅳ continue to occur the Fu Shi acylation reaction and obtain the compound VIII, namely contain the carbazole ketone intermediate of polyfunctional group structure;
(2) when R be trifluoromethyl, C
1-C
12Straight chained alkyl, C
1-C
12Branched-chain alkyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or during the 4-cyano-phenyl, the preparation method is:
1. when X is identical with Y
The Fu Shi acylation reaction occurs in chemical compounds I and compound III, obtains the compound VII;
Compound VII and bromo propylene, iodo propylene, bromo propine, epoxy chloropropane, iodobenzene, p-Fluoro bromo benzene, to fluorine iodobenzene, 4-trifluoromethyl iodobenzene, 4-methyl bromobenzene trifluoride, 4-bromstyrol, 4-bromobenzene acetylene, to the hydrogen atom on ioxynil, CF3I, the end carbon by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain the compound IX, namely contain the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
The Fu Shi acylation reaction occurs and obtains the compound V in chemical compounds I and compound III, and compound V and compounds Ⅳ continue the Fu Shi acylation reaction occurs, and obtain the compound VIII;
Compound VIII and bromo propylene, iodo propylene, bromo propine, epoxy chloropropane, iodobenzene, p-Fluoro bromo benzene, to fluorine iodobenzene, 4-trifluoromethyl iodobenzene, 4-methyl bromobenzene trifluoride, 4-bromstyrol, 4-bromobenzene acetylene, to the hydrogen atom on ioxynil, CF3I, the end carbon by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain the compound X, namely contain the carbazole ketone intermediate of polyfunctional group structure;
Chemical compounds I, the compound III, compounds Ⅳ, the compound V, the compound VII, the compound VIII, the compound IX, the compound X is the following compound of representative structure formula respectively:
When R is trifluoromethyl, C
1-C
12Straight chained alkyl or C
1-C
12Branched-chain alkyl the time, can also be in order to the standby carbazole ketone intermediate that contains the polyfunctional group structure of below legal system:
1. when X is identical with Y
Hydrogen atom on chemical compounds I and CF3I, the end carbon is by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain compound ii;
The Fu Shi acylation reaction occurs and obtains the compound IX in compound ii and compound III, namely contains the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
Hydrogen atom on chemical compounds I and CF3I, the end carbon is by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain compound ii;
The Fu Shi acylation reaction occurs with the compound III first and obtains the compound VI in compound ii, and compound VI and compounds Ⅳ continue to occur the Fu Shi acylation reaction and obtain the compound X, namely contain the carbazole ketone intermediate of polyfunctional group structure;
Chemical compounds I, compound ii, the compound III, compounds Ⅳ, the compound VI, the compound IX, the compound X is the following compound of representative structure formula respectively:
The present invention also provides the application of the carbazole ketone intermediate that contains the polyfunctional group structure in preparation high heat resistance ketone-grouped resin.
Beneficial effect of the present invention:
(1) the carbazole ketone intermediate that contains the polyfunctional group structure of the present invention preparation, this intermediate that exists for of carbazole ring structure has been introduced a N active reaction sites, can regulate the performances such as thermal property, stability, solvability of this intermediate by this site; The two carbonyls that exist in the molecular structure can with multiple nucleophilic reagent generation nucleophilic addition; Can carbazole structure be incorporated in some polymer architectures by X and two functional group's substituting groups of Y, such as in the polyester, polyetherketone, polyimide structures, thereby the high temperature resistant of polymkeric substance strengthened;
(2) utilize the carbazole ketone intermediate that contains the polyfunctional group structure of the present invention, carry out nucleophilic condensation polymerization with biphenol monomer and obtain ketone-grouped resin, this ketone-grouped resin has resistance to elevated temperatures, second-order transition temperature is up to 293 ℃, and have good dissolving processibility and mechanical property, under 25 ℃ of conditions, take NMP as solvent, change polymerization temperature and time, record the intrinsic viscosity of ketone-grouped resin at 0.3000-2.0000dl/g;
(3) preparation method's technique of the carbazole ketone intermediate that contains the polyfunctional group structure of the present invention's preparation is simple, and convenient operation is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is 3 of the embodiment of the invention 1, the NMR of 6-two (to fluoro benzoyl)-N (H) carbazole (
1H) figure.
Embodiment
The invention provides a kind of carbazole ketone intermediate that contains the polyfunctional group structure, the structural formula of this intermediate is as follows:
In the formula, R is hydrogen, C
1-C
12Straight chained alkyl, C
1-C
12Branched-chain alkyl, trifluoromethyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl;
X is identical from Y or different, and X, Y are F, Cl, NO
2Perhaps OH.
Described R is preferably hydrogen, methyl, sec.-propyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl.
The present invention also provides the preparation method of the carbazole ketone intermediate that contains the polyfunctional group structure,
(1) when R is H, the preparation method is:
1. when X is identical with Y
The Fu Shi acylation reaction occurs and obtains the compound VII in chemical compounds I and compound III, namely contains the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
The Fu Shi acylation reaction occurs with the compound III first and obtains the compound V in chemical compounds I, and compound V and compounds Ⅳ continue to occur the Fu Shi acylation reaction and obtain the compound VIII, namely contain the carbazole ketone intermediate of polyfunctional group structure;
Chemical compounds I, the compound III, compounds Ⅳ, the compound V, the compound VII, the compound VIII is the following compound of representative structure formula respectively:
(2) when R be trifluoromethyl, C
1-C
12Straight chained alkyl, C
1-C
12Branched-chain alkyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or during the 4-cyano-phenyl, the preparation method is:
1. when X is identical with Y
The Fu Shi acylation reaction occurs in chemical compounds I and compound III, obtains the compound VII;
Compound VII and bromo propylene, iodo propylene, bromo propine, epoxy chloropropane, iodobenzene, p-Fluoro bromo benzene, to fluorine iodobenzene, 4-trifluoromethyl iodobenzene, 4-methyl bromobenzene trifluoride, 4-bromstyrol, 4-bromobenzene acetylene, to the hydrogen atom on ioxynil, CF3I, the end carbon by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain the compound IX, namely contain the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
The Fu Shi acylation reaction occurs and obtains the compound V in chemical compounds I and compound III, and compound V and compounds Ⅳ continue the Fu Shi acylation reaction occurs, and obtain the compound VIII;
Compound VIII and bromo propylene, iodo propylene, bromo propine, epoxy chloropropane, iodobenzene, p-Fluoro bromo benzene, to fluorine iodobenzene, 4-trifluoromethyl iodobenzene, 4-methyl bromobenzene trifluoride, 4-bromstyrol, 4-bromobenzene acetylene, to the hydrogen atom on ioxynil, CF3I, the end carbon by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain the compound X, namely contain the carbazole ketone intermediate of polyfunctional group structure;
Chemical compounds I, the compound III, compounds Ⅳ, the compound V, the compound VII, the compound VIII, the compound IX, the compound X is the following compound of representative structure formula respectively:
Preparation process is:
When R is trifluoromethyl, C
1-C
12Straight chained alkyl or C
1-C
12Branched-chain alkyl the time, can also be standby in order to the below legal system:
1. when X is identical with Y
Hydrogen atom on chemical compounds I and CF3I, the end carbon is by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain compound ii;
The Fu Shi acylation reaction occurs and obtains the compound IX in compound ii and compound III, namely contains the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
Hydrogen atom on chemical compounds I and CF3I, the end carbon is by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain compound ii;
The Fu Shi acylation reaction occurs with the compound III first and obtains the compound VI in compound ii, and compound VI and compounds Ⅳ continue to occur the Fu Shi acylation reaction and obtain the compound X, namely contain the carbazole ketone intermediate of polyfunctional group structure;
Chemical compounds I, compound ii, the compound III, compounds Ⅳ, the compound VI, the compound IX, the compound X is the following compound of representative structure formula respectively:
Preparation process is:
Described substitution reaction and Fu Shi acylation reaction are prior art well known in the art, and used catalyzer is AlCl in the Fu Shi acylation reaction
3, solvent for use can be non-polar solvent, neutral solvent or polar solvent, such as dithiocarbonic anhydride, methylene dichloride, trichloromethane, oil of mirbane.Product contains the purification of the carbazole ketone intermediate of polyfunctional group structure and can select ethyl acetate, chloroform, acetone, tetrahydrofuran (THF) isopolarity solvent to carry out recrystallization purification or the purification of employing column chromatography method.
The method for preparing the high heat resistance ketone-grouped resin among the present invention with the carbazole ketone intermediate that contains the polyfunctional group structure: in the inert atmosphere, be the carbazole ketone intermediate and the biphenol monomer that contain the polyfunctional group structure of 1.0-1.1 with mol ratio, consumption is the 1.08-1.15 carbonate catalyzer doubly of biphenol monomer mole number, consumption is the 1.85-3.0 reaction solvent doubly of theoretical polymer quality, consumption is that the 0.50-1.5 band aqua doubly of reaction solvent volume joins in the reaction unit, 90 ℃-150 ℃ lower band water that reflux steamed the band aqua in 2-20 hour, then being warming up to 151 ℃-320 ℃ carried out polycondensation 3-50 hour, in polycondensation reaction system, add thinner dilution dissolving, leave standstill more than 6 minutes, in alcohols, settle in water or the alcohol-water mixture, repeatedly boil eccysis salt through deionized water, be dried to constant weight in the vacuum drying oven, namely obtain the ketone-grouped resin that main chain contains carbazole ring structure;
The structure of described biphenol monomer is
,
,
,
,
,
,
,
,
Perhaps
Described solvent is preferably tetramethylene sulfone, DMI, N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE or N, N '-dimethyl sulfoxide (DMSO).
Described catalyzer is preferably anhydrous alkali metal carbonate, more preferably Anhydrous potassium carbonate.
Described band aqua is preferably alkylbenzene or halogeno-benzene, more preferably dimethylbenzene or toluene.
Described thinner is preferably tetramethylene sulfone, DMI, dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc) or n-formyl sarcolysine base pyrrolidone (NMP).
Described backflow is preferably 2-10 hour with the time of water.
Described polycondensation temperature is preferably 151-220 ℃, and the time is preferably 3-30 hour.
The present invention prepares main chain, and to contain the chemical equation of reaction of ketone-grouped resin of carbazole ring structure as follows:
。
The weight-average molecular weight of the ketone-grouped resin that makes is 20000-75000, and repeated structural unit is as follows:
In the formula, R is hydrogen, allyl group, proyl, propylene oxide base, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl, 4-cyano-phenyl, trifluoromethyl, C
1-C
12Straight chained alkyl or C
1-C
12Branched-chain alkyl;
Ar is a kind of in the following structure:
The structure of the carbazole ketone intermediate that contains the polyfunctional group structure of the present invention's preparation is confirmed via nuclear magnetic resonance spectroscopy.
For making those skilled in the art better understand technical scheme of the present invention, further specify the present invention below in conjunction with specific embodiment and accompanying drawing.
Mention among the embodiment that material all can obtain by being purchased mode.
Embodiment 1
In conjunction with Fig. 1 embodiment 1 is described
The preparation of 3,6-two (to fluoro benzoyl)-N (H) carbazole
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches, add and drip fluorobenzoyl chloride 15.85mL (0.13mol) in the reaction flask again after complete, remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction revolves inspissation and contracts and use re-crystallizing in ethyl acetate, gets Powdered solid-state sterling.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test.
Fig. 1 is 3 of embodiment 1, the NMR of 6-two (to fluoro benzoyl)-N (H) carbazole (
1H) figure,
A, b, c, d, e, the hydrogen atom of different positions in the f difference representation compound
,
As can be seen from the figure δ 12.23 (s, 1H), 8.72 (s, 2H), 7.90 (d, 2H), 7.86 (t, 4H), 7.69 (d, 2H), 7.40 (t, 4H) have confirmed the structure of intermediate of the present invention.
Embodiment 2
The preparation of 3,6-two (to fluoro benzoyl)-N-methyl carbazole
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 15.36mL (0.13mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; fully dissolving in the tetrahydrofuran solvent of solid product crude product under the reflux condition of gained after filtering; filtered while hot is fallen silica-gel powder after adding silica-gel powder backflow 4h in the above-mentioned tetrahydrofuran solution afterwards; gained solution obtains 3,6-two (to fluoro benzoyl)-N (H) carbazole after crystallisation by cooling is purified.
With above-mentioned 3; 6-two (to fluoro benzoyl)-N (H) carbazole 6.2g (0.015mol) and 0.47g (0.0015mol) Tetrabutyl amonium bromide phase-transfer catalyst are added in the reaction flask that the 70mL toluene solvant is housed; add again stoichiometric ratio in the system and be 4 massfraction and be 50% potassium hydroxide solution; add and drip again 2.10g (0.0165mol) methyl-sulfate after complete; finish reaction behind the reaction 10h under 50 ℃ of conditions afterwards; gained crude product chloroform extraction; organic phase anhydrous sodium sulfate drying after the merging; also use Gossypol recrystallized from chloroform after revolving the inspissation contracting, obtain final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ CDCl
3) δ 8.56 (s, 2H), 8.05 (d, 2H), 7.87 (t, 4H), 7.52 (d, 2H), 7.19 (t, 4H), 3.98 (s, 1H).
Embodiment 3
The preparation of 3,6-two (to chlorobenzene formacyl)-N-sec.-propyl carbazole
20g (0.12mol) carbazole is joined in the reaction flask that the 120mL toluene solvant is housed, add afterwards 3.8g (0.012mol) Tetrabutyl amonium bromide and massfraction in the reaction flask and be 50% potassium hydroxide aqueous solution (45g potassium hydroxide is dissolved in the 45mL water), add and in above-mentioned system, drip 13.5mL (0.144mol) bromo sec.-propyl again after complete, behind 55 ℃ of reaction 10h, finish reaction after dropwising, crude product is filtered rear separation organic phase, and the washing organic phase is to neutral, with filtering and concentrated organic phase after the anhydrous sodium sulfate drying organic phase, mixed solvent with ethyl acetate and sherwood oil carries out the sedimentation purification to it afterwards, gets N-sec.-propyl carbazole.
Homemade N-sec.-propyl carbazole 16.12g (0.077mol) and dichloromethane solvent 100mL are added in the flask that magneton is housed, add aluminum trichloride (anhydrous) 25.75g (0.19mol) under the ice-water bath condition in batches, add and drip again parachlorobenzoyl chloride 20.5mL (0.17mol) in the reaction flask after complete, remove ice-water bath room temperature reaction (24 ℃) 10h after dropwising, then with aqueous hydrochloric acid with its cancellation, organic phase anhydrous sodium sulfate drying behind the chloroform extraction, revolve inspissation and contract and use Gossypol recrystallized from chloroform, obtain final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ CDCl
3) δ 8.53 (s, 2H), 7.84 (d, 2H), 7.66 (d, 4H), 7.49 (d, 2H), 7.37 (d, 4H), 4.13 (m, 1H), 1.53 (d, 6H).
Embodiment 4
The preparation of 3,6-two (to fluoro benzoyl)-N-allyl group carbazole
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 15.36mL (0.13mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; fully dissolving in the tetrahydrofuran solvent of solid product crude product under the reflux condition of gained after filtering; add in the above-mentioned tetrahydrofuran solution afterwards silica-gel powder refluxed four hours after filtered while hot fall silica-gel powder; gained solution obtains 3,6-two (to fluoro benzoyl)-N (H) carbazole after crystallisation by cooling is purified.
With 3; 6-two (to fluoro benzoyl)-N (H) carbazole 6g (0.015mol) and 0.47g (0.0015mol) Tetrabutyl amonium bromide phase-transfer catalyst are added in the reaction flask that the 70mL toluene solvant is housed; add again stoichiometric ratio in the system and be 4 massfraction and be 50% potassium hydroxide solution; add and drip again 2.00g (0.0165mol) bromopropylene after complete; finish afterwards reaction behind the reflux 10h; gained crude product chloroform extraction; organic phase anhydrous sodium sulfate drying after the merging; also use Gossypol recrystallized from chloroform after revolving the inspissation contracting, obtain final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ CDCl
3) δ 8.57 (s, 2H), 8.23 (d, 2H), 7.87 (t, 4H), 7.49 (d, 2H), 7.20 (t, 4H), 6.04 (m, 1H), 5.26 (d, 1H), 5.07 (s, 1H), 5.02 (d, 2H).
Embodiment 5
The preparation of 3,6-two (p-benzoyl base)-N-proyl carbazole
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 15.36mL (0.13mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; fully dissolving in the tetrahydrofuran solvent of solid product crude product under the reflux condition of gained after filtering; add in the above-mentioned tetrahydrofuran solution afterwards silica-gel powder refluxed four hours after filtered while hot fall silica-gel powder; gained solution obtains 3,6-two (p-benzoyl base)-N (H) carbazole after crystallisation by cooling is purified.
With 3; 6-two (p-benzoyl base)-N (H) carbazole 6g (0.015mol) and 0.47g (0.0015mol) Tetrabutyl amonium bromide phase-transfer catalyst are added in the reaction flask that the 70mL toluene solvant is housed; add again stoichiometric ratio in the system and be 4 massfraction and be 50% potassium hydroxide solution; add and drip again 1.98g (0.0165mol) bromopropylene after complete; finish afterwards reaction behind the reflux 10h; gained crude product chloroform extraction; organic phase anhydrous sodium sulfate drying after the merging; also use Gossypol recrystallized from chloroform after revolving the inspissation contracting, obtain final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (1H NMR 400MHZ CDCl3) δ 8.55 (s, 2H), (8.21 d, 2H), 7.84 (t, 4H), 7.46 (d, 2H), 7.17 (t, 4H), 4.81 (s, 2H), (2.02 s, 1H).
Embodiment 6
The preparation of 3,6-two (to fluoro benzoyl)-N-propylene oxide base carbazole
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 14.22mL (0.12mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction; revolving inspissation contracts and uses re-crystallizing in ethyl acetate; get product 3,6-two (to fluoro benzoyl)-N (H) carbazole.
With 3; 6-two (to fluoro benzoyl)-N (H) carbazole 6g (0.015mol) is dissolved in the 50mL acetone solvent; and then in mentioned solution, add 1.48 g (0.016) sodium cyanide catalyzer; slowly in above-mentioned system, add distilled water cancellation end reaction behind the heating reflux reaction 5h; gained crude product chloroform extraction; organic phase anhydrous sodium sulfate drying after the merging revolves and also uses Gossypol recrystallized from chloroform after inspissation contracts, and obtains final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, record the result as follows: (
1H NMR 400MHZ CDCl
3) δ 8.53 (s, 2H), 8.02 (d, 2H), 7.83 (t, 4H), 7.49 (d, 2H), 7.16 (t, 4H), 3.63 (s, 1H), 3.42 (s, 1H), (2.50 s, 1H), 2.37 (s, 1H), 2.20 (s, 1H).
Embodiment 7
The preparation of 3,6-two (to fluoro benzoyl)-N-phenyl carbazole
Carbazole 10g (0.061mol) and oil of mirbane solvent 80mL are added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 14.22mL (0.12mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction; revolving inspissation contracts and uses re-crystallizing in ethyl acetate; get product 3,6-two (to fluoro benzoyl)-N (H) carbazole.
Under the nitrogen atmosphere; with 7g (0.017mol) 3; 6-two (to fluoro benzoyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 30mLDMF solvent is housed; and then in reaction flask, add iodobenzene 3.81g (0.018mol); cuprous iodide 0.32g (0.0017mol); anhydrous phenanthroline 0.31g (0.0017mol); fill and finish reaction after being warming up to 100 ℃ of reaction 48h after the ventilation; first crude product is filtered; to strip with a large amount of chloroforms again after the washing of gained filtrate; collect organic phase and use anhydrous sodium sulfate drying; carry out column chromatography purification (ethyl acetate/petroleum ether=1:6), obtain final product after revolving the inspissation contracting.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, record the result as follows: (
1H NMR 400MHZ CDCl
3) δ 8.67 (s, 2H), 8.15 (d, 2H), 7.89 (t, 4H), 7.67 (d, 2H), 7.39 (d, 2H), 7.25 (t, 1H), 7.19 (t, 2H), 7.08 (t, 4H).
Embodiment 8
The preparation of 3,6-two (to fluoro benzoyl)-N-(4-fluorophenyl) carbazole
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 15.85mL (0.13mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction; revolving inspissation contracts and uses re-crystallizing in ethyl acetate; get 3,6-two (to fluoro benzoyl)-N (H) carbazole.
Under the nitrogen atmosphere; with above-mentioned synthesize 3; 6-two (to fluoro benzoyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 40mLNMP solvent is housed; and then in reaction flask, add fluorine iodobenzene 4.00g (0.018mol); cuprous iodide 0.32g (0.0017mol); anhydrous phenanthroline 0.31g (0.0017mol); fill and finish reaction after being warming up to 100 ℃ of reaction 48h after the ventilation; first crude product is filtered; to strip with a large amount of chloroforms again after the washing of gained filtrate; collect organic phase and use anhydrous sodium sulfate drying; carry out the recrystallization purification with methylene dichloride after revolving the inspissation contracting, obtain final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, record the result as follows: (
1H NMR 400MHZ DMSO) δ 8.69 (s, 2H), 8.19 (d, 2H), 7.89 (t, 4H), 7.69 (d, 2H), 7.43 (d, 2H), 7.29 (d, 2H), 7.18 (t, 4H).
Embodiment 9
The preparation of 3,6-two (to fluoro benzoyl)-N-(4-trifluoromethyl) carbazole
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 15.85mL (0.13mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction; revolving inspissation contracts and uses re-crystallizing in ethyl acetate; get 3,6-two (to fluoro benzoyl)-N (H) carbazole.
Under the nitrogen atmosphere; with above-mentioned synthesize 3; 6-two (to fluoro benzoyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 40mLNMP solvent is housed; and then in reaction flask, add iodine phenylfluoroform 4.90g (0.018mol); cuprous iodide 0.32g (0.0017mol); anhydrous phenanthroline 0.31g (0.0017mol); fill and finish reaction after being warming up to 80 ℃ of reaction 50h after the ventilation; first crude product is filtered; to strip with a large amount of chloroforms again after the washing of gained filtrate; collect organic phase and use anhydrous sodium sulfate drying; carry out the recrystallization purification with methylene dichloride after revolving the inspissation contracting, obtain final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ DMSO) δ 8.73 (s, 2H), 8.15 (d, 2H), 7.92 (t, 4H), 7.67 (d, 2H), 7.49 (d, 2H), 7.31 (d, 2H), 7.19 (t, 4H).
Embodiment 10
The preparation of 3,6-two (p-nitrophenyl formyl radical)-N-(4-ethenylphenyl) carbazole
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip again paranitrobenzoyl chloride 15.77mL (0.13mol) in the reaction flask after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction; revolving inspissation contracts and uses re-crystallizing in ethyl acetate; get 3,6-two (p-nitrophenyl formyl radical)-N (H) carbazole.
Under the nitrogen atmosphere; with above-mentioned synthesize 3; 6-two (p-nitrophenyl formyl radical)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 40mLDMSO solvent is housed; and then in reaction flask, add bromstyrol 3.30g (0.018mol); cuprous iodide 0.32g (0.0017mol); anhydrous phenanthroline 0.31g (0.0017mol); fill and finish reaction after being warming up to 100 ℃ of reaction 50h after the ventilation; first crude product is filtered; to strip with a large amount of chloroforms again after the washing of gained filtrate; collect organic phase and use anhydrous sodium sulfate drying; carry out column chromatography purification (chloroform/sherwood oil=1:4), obtain final product after revolving the inspissation contracting.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ DMSO) δ 8.99 (d, 4H), 8.79 (s, 2H), (8.64 d, 4H), 8.27 (d, 2H), (8.09 d, 2H), 7.45 (d, 2H), 7.39 (d, 2H), (6.94 s, 1H), 6.16 (s, 1H), 5.98 (s, 1H).
Embodiment 11
The preparation of 3,6-two (to fluoro benzoyl)-N-(4-ethynyl phenyl) carbazole
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip fluorobenzoyl chloride 15.85mL (0.13mol) in the reaction flask again after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction; revolving inspissation contracts and uses re-crystallizing in ethyl acetate; get 3,6-two (to fluoro benzoyl)-N (H) carbazole.
Under the nitrogen atmosphere; with above-mentioned synthesize 3; 6-two (to fluoro benzoyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 40mLDMSO solvent is housed; and then in reaction flask, add bromobenzene acetylene 3.26g (0.018mol); cuprous iodide 0.32g (0.0017mol); anhydrous phenanthroline 0.31g (0.0017mol); fill and finish reaction after being warming up to 100 ℃ of reaction 48h after the ventilation; first crude product is filtered; to strip with a large amount of chloroforms again after the washing of gained filtrate; collect organic phase and use anhydrous sodium sulfate drying; carry out column chromatography purification (chloroform/sherwood oil=1:5), obtain final product after revolving the inspissation contracting.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ DMSO) δ 8.66 (s, 2H), 8.13 (d, 2H), 7.91 (t, 4H), (7.66 d, 2H), 7.53 (d, 2H), 7.30 (d, 2H), 7.19 (t, 4H), 3.16 (s, 1H).
Embodiment 12
The preparation of 3,6-two (to chlorobenzene formacyl)-N-(4-cyano-phenyl) carbazole
With carbazole 10g (0.061mol) and CS
2Solvent 80mL is added in the flask that magneton is housed; add aluminum trichloride (anhydrous) 17.54g (0.13mol) under the ice-water bath condition in batches; add and drip again parachlorobenzoyl chloride 15.97mL (0.13mol) in the reaction flask after complete; remove ice-water bath room temperature reaction (24 ℃) 15h after dropwising; then with aqueous hydrochloric acid with its cancellation; organic phase anhydrous sodium sulfate drying behind the ethyl acetate extraction; revolving inspissation contracts and uses re-crystallizing in ethyl acetate; 3,6-two (to chlorobenzene formacyl)-N (H) carbazole.
Under the nitrogen atmosphere; with above-mentioned synthesize 3; 6-two (to chlorobenzene formacyl)-N (H) carbazole is added in the reaction flask of the drying that anhydrous 50mLNMP solvent is housed; and then in reaction flask, add ioxynil 4.12g (0.018mol); cuprous iodide 0.32g (0.0017mol); anhydrous phenanthroline 0.31g (0.0017mol); fill and finish reaction after being warming up to 80 ℃ of reaction 50h after the ventilation; first crude product is filtered; to strip with a large amount of chloroforms again after the washing of gained filtrate; collect organic phase and use anhydrous sodium sulfate drying; carry out the recrystallization purification with methylene dichloride after revolving the inspissation contracting, obtain final product.The structural formula of product is as follows:
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ DMSO) δ 8.69 (s, 2H), 8.15 (d, 2H), 7.69 (d, 4H), 7.50 (d, 2H), 7.48 (d, 2H), 7.42 (d, 2H), 7.35 (d, 4H).
Embodiment 13
3-is to the preparation of fluoro benzoyl-6-para hydroxybenzene formyl radical-N (H) carbazole
With carbazole 9.20g (0.055mol); to fluorobenzoyl chloride 7.15mL (0.061mmol); the dithiocarbonic anhydride solvent is added in the reaction flask that magneton is housed; add aluminum trichloride (anhydrous) 8.80g (0.066mol) in the ice-water bath condition downhill reaction bottle in batches; add and remove aqueous hydrochloric acid cancellation reaction on the rocks behind the ice-water bath room temperature reaction 7h after complete; filter to get filter cake; add silica dehydrator in the tetrahydrofuran (THF) of filter cake under reflux state and filter after two hours, and get 3-to fluoro benzoyl-N (H) carbazole with the tetrahydrofuran (THF) recrystallization.
Above-mentioned 3-is added in the reaction flask that is equipped with in the trichloromethane solvent fluoro benzoyl-N (H) carbazole 5g (0.017mol); then pass into boron trifluoride 1.41g (0.021mol); pass into complete after; in system, drip para hydroxybenzene formyl chloride 2.93g (0.019mol) under the ice-water bath condition; dropwise in the backward crude product of rear room temperature reaction 7h and slowly to drip the shrend reaction of going out; use afterwards chloroform extraction; organic phase is revolved the inspissation contracting after with anhydrous sodium sulfate drying; and carry out recrystallization with chloroform and purify, get the product shown in the following structure.
Product is carried out the nuclear magnetic resonance spectroscopy test, and test result is as follows: (
1H NMR 400MHZ DMSO) δ 12.19 (s, 1H), 11.92 (s, 1H), 8.71 (s, 2H), (7.89 d, 2H), 7.71 (t, 2H), 7.65 (d, 2H), (7.39 t, 2H), 7.28 (d, 2H), 6.99 (d, 2H).
Embodiment 14-17 is the Preparation Example that carbazole that the present invention contains the polyfunctional group structure prepares the high thermal resistance ketone-grouped resin.
Embodiment 14
In the nitrogen atmosphere; with phenolphthalein 3.1833 grams (0.01mol); the 3.6-two (to fluoro benzoyl) of embodiment 2 preparations-N-methyl carbazole 4.2543 grams (0.01mol); Anhydrous potassium carbonate 1.5899 grams (0.015mol); dimethylbenzene 15mL; tetramethylene sulfone 10.5mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 150 ℃ and after 2.5 hours, will react the water that generates and be taken out of by refluxing xylene and told by water trap; and then be warming up to when between 210 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; keep this temperature to reaction flask, rod climbing phenomenon to occur in 4 hours; cooling reaction solution and solubilizing agent N,N-DIMETHYLACETAMIDE (DMAc) dilution; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain clean ketone-grouped resin; yield is 98%, and the structural formula of resin is as follows.The second-order transition temperature of this resin is 283 ℃.
Embodiment 15
In the nitrogen atmosphere; with phenolphthalein 3.1833 grams (0.01mol); the 3.6-two (to fluoro benzoyl) of embodiment 7 preparations-N-phenyl carbazole 4.8714 grams (0.01mol); Anhydrous potassium carbonate 1.5899 grams (0.015mol); dimethylbenzene 15mL; tetramethylene sulfone 11.7mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 150 ℃ and after 2.5 hours, will react the water that generates and be taken out of by refluxing xylene and told by water trap; and then be warming up to when between 210 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; keep this temperature to reaction flask, rod climbing phenomenon to occur in 4 hours; cooling reaction solution and solubilizing agent N,N-DIMETHYLACETAMIDE (DMAc) dilution; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain clean ketone-grouped resin; yield is 98%, and the structural formula of resin is as follows.The second-order transition temperature of this resin is 285 ℃.
Embodiment 16
In the nitrogen atmosphere; with bisphenol fluorene 3.5041 grams (0.01mol); the 3.6-two (to fluoro benzoyl) of embodiment 6 preparations-N-propylene oxide base carbazole 4.6746 grams (0.01mol); Anhydrous potassium carbonate 1.5899 grams (0.015mol); dimethylbenzene 15mL; tetramethylene sulfone 11.46mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 150 ℃ and after 2.5 hours, will react the water that generates and be taken out of by refluxing xylene and told by water trap; and then be warming up to when between 190 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; keep this temperature to reaction flask, rod climbing phenomenon to occur in 4 hours; cooling reaction solution and solubilizing agent N,N-DIMETHYLACETAMIDE (DMAc) dilution; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain clean ketone-grouped resin; yield is 98%, and the structural formula of resin is as follows.The second-order transition temperature of this resin is 235 ℃.
Embodiment 17
In the nitrogen atmosphere; with bisphenol fluorene 3.5041 grams (0.01mol); the 3.6-two (to fluoro benzoyl) of embodiment 8 preparations-N-(4-fluorophenyl) carbazole 5.0549 grams (0.01mol); Anhydrous potassium carbonate 1.5899 grams (0.015mol); dimethylbenzene 15mL; tetramethylene sulfone 12.05mL join be equipped with mechanical stirring and water-taker there-necked flask in; under the nitrogen protection temperature is raised to 150 ℃ and after 2.5 hours, will react the water that generates and be taken out of by refluxing xylene and told by water trap; and then be warming up to when between 220 ℃ of assurance oligopolymer nucleophilic polycondensation occuring dimethylbenzene is steamed; keep this temperature to reaction flask, rod climbing phenomenon to occur in 4 hours; cooling reaction solution and solubilizing agent N-Methyl pyrrolidone (NMP) dilution; long period settles product in the mixing solutions of second alcohol and water after leaving standstill; boil with deionized water and to wash for several times; in 120 ℃ of lower vacuum-dryings to constant weight; obtain clean ketone-grouped resin; yield is 98%, and the structural formula of resin is as follows.The second-order transition temperature of this resin is 293 ℃.
Claims (4)
1. contain the carbazole ketone intermediate of polyfunctional group structure, it is characterized in that, the structural formula of this intermediate is as follows:
In the formula, R is hydrogen, C
1-C
12Straight chained alkyl, C
1-C
12Branched-chain alkyl, trifluoromethyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl;
X is identical from Y or different, and X, Y are F, Cl, NO
2Perhaps OH.
2. the carbazole ketone intermediate that contains the polyfunctional group structure according to claim 1, it is characterized in that, described R is hydrogen, methyl, sec.-propyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or 4-cyano-phenyl.
3. contain the preparation method of the carbazole ketone intermediate of polyfunctional group structure, it is characterized in that,
(1) when R is H, the preparation method is:
1. when X is identical with Y
The Fu Shi acylation reaction occurs and obtains the compound VII in chemical compounds I and compound III, namely contains the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
The Fu Shi acylation reaction occurs with the compound III first and obtains the compound V in chemical compounds I, and compound V and compounds Ⅳ continue to occur the Fu Shi acylation reaction and obtain the compound VIII, namely contain the carbazole ketone intermediate of polyfunctional group structure;
(2) when R be trifluoromethyl, C
1-C
12Straight chained alkyl, C
1-C
12Branched-chain alkyl, propylene oxide base, allyl group, proyl, phenyl, 4-fluorophenyl, 4-trifluoromethyl, 4-ethenylphenyl, 4-ethynyl phenyl or during the 4-cyano-phenyl, the preparation method is:
1. when X is identical with Y
The Fu Shi acylation reaction occurs in chemical compounds I and compound III, obtains the compound VII;
Compound VII and bromo propylene, iodo propylene, bromo propine, epoxy chloropropane, iodobenzene, p-Fluoro bromo benzene, to fluorine iodobenzene, 4-trifluoromethyl iodobenzene, 4-methyl bromobenzene trifluoride, 4-bromstyrol, 4-bromobenzene acetylene, to the hydrogen atom on ioxynil, CF3I, the end carbon by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain the compound IX, namely contain the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
The Fu Shi acylation reaction occurs and obtains the compound V in chemical compounds I and compound III, and compound V and compounds Ⅳ continue the Fu Shi acylation reaction occurs, and obtain the compound VIII;
Compound VIII and bromo propylene, iodo propylene, bromo propine, epoxy chloropropane, iodobenzene, p-Fluoro bromo benzene, to fluorine iodobenzene, 4-trifluoromethyl iodobenzene, 4-methyl bromobenzene trifluoride, 4-bromstyrol, 4-bromobenzene acetylene, to the hydrogen atom on ioxynil, CF3I, the end carbon by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain the compound X, namely contain the carbazole ketone intermediate of polyfunctional group structure;
When R is trifluoromethyl, C
1-C
12Straight chained alkyl or C
1-C
12Branched-chain alkyl the time, can also be standby in order to the below legal system:
1. when X is identical with Y
Hydrogen atom on chemical compounds I and CF3I, the end carbon is by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain compound ii;
The Fu Shi acylation reaction occurs and obtains the compound IX in compound ii and compound III, namely contains the carbazole ketone intermediate of polyfunctional group structure;
2. when X and Y are not identical
Hydrogen atom on chemical compounds I and CF3I, the end carbon is by iodine or the mono-substituted C of bromine
1-C
12Straight-chain paraffin or the hydrogen atom on the end carbon by iodine or the mono-substituted C of bromine
1-C
12Branched paraffin substitution reaction on the N position occurs, obtain compound ii;
The Fu Shi acylation reaction occurs with the compound III first and obtains the compound VI in compound ii, and compound VI and compounds Ⅳ continue to occur the Fu Shi acylation reaction and obtain the compound X, namely contain the carbazole ketone intermediate of polyfunctional group structure;
Chemical compounds I, compound ii, the compound III, compounds Ⅳ, the compound V, the compound VI, the compound VII, the compound VIII, the compound IX, the compound X is the following compound of representative structure formula respectively:
4. claim 1 or the 2 described application of carbazole ketone intermediate in preparation high heat resistance ketone-grouped resin that contain the polyfunctional group structure.
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| CN106674514A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Polyarylether with main chain containing carbazole, preparation method, nanocarbon modified material and composite |
| WO2020253283A1 (en) * | 2019-06-21 | 2020-12-24 | 江苏英力科技发展有限公司 | Novel diaroyl carbazole compound and use thereof as sensitising agent |
| CN115947936A (en) * | 2023-03-09 | 2023-04-11 | 中节能万润股份有限公司 | Preparation method of polyetherimide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674514A (en) * | 2017-01-09 | 2017-05-17 | 吉林大学 | Polyarylether with main chain containing carbazole, preparation method, nanocarbon modified material and composite |
| WO2020253283A1 (en) * | 2019-06-21 | 2020-12-24 | 江苏英力科技发展有限公司 | Novel diaroyl carbazole compound and use thereof as sensitising agent |
| CN113518774A (en) * | 2019-06-21 | 2021-10-19 | 艾坚蒙(安庆)科技发展有限公司 | Novel diarylacylcarbazole compound and application thereof as sensitizer |
| JP2022528738A (en) * | 2019-06-21 | 2022-06-15 | 艾▲堅▼蒙（安▲慶▼）科技▲発▼展有限公司 | New dialoylcarbazole compounds, and their use as sensitizers |
| TWI776133B (en) * | 2019-06-21 | 2022-09-01 | 中國大陸商艾堅蒙（安慶）科技發展有限公司 | Novel diaroylcarbazole compound and application thereof as sensitizer |
| CN115947936A (en) * | 2023-03-09 | 2023-04-11 | 中节能万润股份有限公司 | Preparation method of polyetherimide |
| CN115947936B (en) * | 2023-03-09 | 2023-05-16 | 中节能万润股份有限公司 | Preparation method of polyetherimide |
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Application publication date: 20130213 |