CN113582954B - Method for preparing biphenyl dianhydride based on coupling of metal coordination halogenated phthalimide monomer - Google Patents
Method for preparing biphenyl dianhydride based on coupling of metal coordination halogenated phthalimide monomer Download PDFInfo
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- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
The invention discloses a method for preparing biphenyl dianhydride based on coupling of halogenated phthalimide monomers with metal coordination. The main content includes taking halogenated phthalimide with complexing coordination ability as raw material, zinc or magnesium as reducer, nickel salt as catalyst, coupling reaction in aprotic solvent system to generate biphenyl derivative, hydrolyzing, dewatering to obtain anhydride. The invention adopts halogenated monomer with coordination function, forms organic metal complex with by-product zinc halide generated by reaction, dissolves in the reaction system, and avoids reduction capability reduction caused by deposition on the metal surface of the reducer. Compared with the traditional similar biphenyl dianhydride preparation reaction, the reducing agent disclosed by the invention is close to a quantitative reaction, and is more suitable for industrialization.
Description
Technical Field
The invention relates to a method for preparing biphenyl dianhydride based on metal coordination halogenated phthalimide monomer coupling, belonging to the technical field of synthetic chemistry.
Background
The biphenyl tetracarboxylic dianhydride is called BPDA for short, and is one of the polyimide material mark dianhydride monomers with heat resistance, insulation, high strength and stable size. At present, biphenyl tetracarboxylic dianhydride is mainly prepared by a noble metal catalytic coupling method, and the cost is high, so that the application market of biphenyl polyimide materials is greatly limited. Therefore, the development of a cheap catalytic coupling reaction system for preparing the biphenyl dianhydride has important significance.
The metal palladium (Pd) and the salt thereof are mainly used as catalysts for producing the biphenyl dianhydride in industry, and the catalysts in the synthetic route are expensive and have large dosage, high-pressure reaction, low yield and high cost. Related studies are reported in patent JP7352749, US5243067, US3636168, CN201310049837, etc.
The biphenyl dianhydride can be prepared by using Ni (0) or Pd (0) as a catalyst, using organic phosphine or nitrogen compound ligand and zinc powder as a reducing agent through a method of coupling halogenated phthalic acid derivatives and then through hydrolysis, acidification, dehydration and other reactions, and the related research reports are more, including patents US 5081281, CN1189597, CN101481366, CN102020622B, CN201110202366 and the like. Inorganic salt byproducts such as zinc halide and the like generated in the reaction process of the method are adsorbed on the surface of the metal zinc serving as a reducing agent in a large amount, so that the sufficient contact between the catalyst and the zinc powder serving as a solid active reducing agent is influenced, and the reduction coupling reaction is further influenced, and therefore, the reaction system generally needs to use more than 5% of the catalyst with the raw material mole number and 400% of the feeding amount of the reducing agent to generate a large amount of solid waste residues; after the reaction is finished, the waste residue mixed with the excessive activated metal reducing agent is extremely easy to cause fire when encountering oxygen, affects the safe production, does not have industrial value, so how to solve the problem of the adsorption of inorganic byproducts on the surface of the reducing agent in the method is a key factor for realizing the industrial application of the method.
Patents US7893306, US7425650, JP61-22045, CN201310234457, CN201310302428, CN201310050630 and the like use tetrahydrofuran or diethyl ether with low boiling point and high toxicity as solvents to prepare grignard reagents, aromatic halides are prepared into grignard reagents, then a coupling method is used for preparing polymethyl biphenyl, and then biphenyl dianhydride is prepared through oxidation. Tetrahydrofuran or diethyl ether is known to be a highly flammable and explosive organic solvent, is difficult to recover, easily causes safety accidents, and is disadvantageous for industrial production.
Disclosure of Invention
In order to overcome the defects in the preparation method of the biphenyl dianhydride, the invention provides a novel preparation technology of the biphenyl dianhydride, namely, amino halogenide phthalimide is adopted as a monomer for the first time, the complexation coordination of amino and byproduct metal halide in a reaction system is realized, the generated metal organic complex is shown in the following formula 1,
the organic complex in the formula 1 is dissolved in the reaction system, thereby effectively relieving ZnCl 2 The catalyst is adsorbed on the surface of the active metal reducing agent to influence the reaction efficiency, so that the use efficiency of the reducing agent is improved, the use amount of the catalyst is reduced, and the efficiency of preparing the biphenyl dianhydride derivative through the coupling reaction is improved.
The invention provides a preparation method of biphenyl dianhydride, which comprises the following preparation reactions:
1) Coupling reaction: the amino halogenated phthalimide is catalyzed and coupled to generate biphenyl compound, the reaction temperature is 50-100 ℃, and the reaction time is 1-24 hours;
2) Purifying the bis (aminobiphenyl) tetracarboximide: purifying by recrystallization, the yield is 90-95%, and the purity is 95-99%;
3) Hydrolysis to anhydride: the bis-aminobiphenyl tetracarboxylic acid dianhydride is obtained by hydrolysis and dehydration, and the yield is 90-98%.
In order to realize the task of the invention, the invention adopts the following technical scheme:
a method for preparing biphenyl dianhydride based on metal coordination halogenated phthalimide monomer coupling is characterized in that the reaction process is as follows:
wherein the reaction raw material adopted is amino halogenated phthalimide in the following formula:
the halogen atom in the raw material is chlorine or bromine, the position of the halogen atom can be 3-position of an aromatic ring or 4-position of the aromatic ring, and R is a saturated aliphatic group with 2-5 carbons or a group containing aromatic hydrocarbon with more than 6 carbons;
the catalyst is nickel salt;
the reducing agent is metallic zinc or magnesium;
the additive is one or a mixture of more of triphenylphosphine, 2' -bipyridine or sodium bromide;
the preparation method comprises the following steps: under the protection of nitrogen, amino halogenated phthalimide monomer, nickel salt, aprotic solvent and additive reducer are mixed in a catalytic way, the mixture is stirred at 50-100 ℃ for carrying out coupling reaction for 1-24 hours, the solvent is recovered under reduced pressure, toluene or xylene with 3-4 times of the mass of the reaction monomer is added into the system, the mixture is heated and refluxed until organic matters are dissolved, the mixture is filtered while hot, the filtrate is cooled and collected to obtain precipitated bis-aminobiphenyl bisimine, then the bis-biphenyl bisimine is refluxed and hydrolyzed for 2-24 hours with 10-20% of NaOH aqueous solution (with the concentration of 20%) excess, insoluble matters are filtered and acidified with concentrated hydrochloric acid to generate biphenyl tetraacid precipitate, the biphenyl tetraacid is filtered and collected, and 3,3', 4' -biphenyl dianhydride or 2,2', 3' -biphenyl dianhydride is obtained through water carrying by trimethylbenzene reflux.
Further, the nickel salt is one or a mixture of a plurality of nickel chloride, nickel bromide, nickel acetate and nickel sulfate, and the molar ratio of the nickel salt to the reactant amino halogenated phthalimide is 0.005-0.02: 1, a step of; the reducer is metallic zinc or magnesium, and the mol ratio of the reducer to the amino halogenated phthalimide is 0.5-0.7: 1, a step of; the additive is one or a mixture of more of triphenylphosphine, 2'-' dipyridine and sodium bromide, and the mol ratio of the additive to the nickel salt is 1-7: 1.
further, the solvent used in the coupling reaction comprises one or a mixture of more of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMF) and dimethyl sulfoxide (DMSO), and the use amount of the solvent is 2.5-4 times of the mass of the reaction monomers.
The invention has the advantages that: the invention is characterized in that amino halogenated phthalimide with complexation with metal ions is adopted as a raw material, and the contained amino is complexed with by-product halogenated metal salt to increase the solubility of the amino halogenated phthalimide in an organic solvent, so that the metal salt is prevented from being adsorbed on the surface of reduced metal to influence the catalytic reduction process, the catalytic coupling reaction efficiency of halogenated o-xylene derivatives can be improved, the using amount of a catalyst is greatly reduced, the using amount of a reducing agent is 4 times that of a literature formula, the reducing agent is reduced to be close to a quantitative reaction, and the post-treatment difficulty is reduced, thereby reducing the preparation cost of biphenyl dianhydride, and being suitable for industrial production.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be specifically described with reference to examples, but the present invention is not limited to the scope of the examples.
Example 1
N- (3-N, N-dimethylaminopropyl) -4-chlorophthalimide (26.65 g,0.1 mOL), zinc powder (3.25 g,0.05 mol), anhydrous NiCl were added to a 500mL reaction flask under a nitrogen atmosphere 2 (127.5 mg,1 mmol), triphenylphosphine (250 mg,1 mmol) and 70mL of anhydrous DMAc were reacted at 50℃for 24 hours with stirring, and 55mL of the solvent DMAc was recovered under reduced pressure. Into the system80g of xylene is added for refluxing (recrystallization), inorganic matters are filtered off, the clarified filtrate is cooled to generate precipitate, the precipitate is filtered and dried in vacuum for 10 hours, and 21.8g of 3,3', 4' -biphenylbisimine is obtained, and the yield is 94%.
In a 100mL reaction flask, 4.62g (0.01 mol) of 3,3', 4' -biphenylbisimine and 9g of 20% sodium hydroxide aqueous solution are added, heated and refluxed for 24 hours, filtered, and pH=1 is adjusted by concentrated hydrochloric acid to obtain 3,3', 4' -biphenyltetracarboxylic acid, the filtered solution is washed with water for three times, and 20mL of trimethylbenzene is used for carrying water, so that 2.85g of white 3,3', 4' -biphenylbisanhydride is obtained, the yield is 97%, and the melting point is 298-300 ℃.
Example 2
N- (3-N, N-dimethylaminopropyl) -3-chlorophthalimide (26.65 g,0.1 mOL), zinc powder (3.25 g,0.05 mol), anhydrous NiBr were added to a 500mL reaction flask under a nitrogen atmosphere 2 (216 mg,1 mmol), triphenylphosphine (1.75 g,7 mmoL) and 110mL of anhydrous DMAc were added thereto, and the reaction was stirred at 100℃for 12 hours, whereby 99mL of the solvent DMAc was recovered under reduced pressure. 106g of toluene (recrystalization) was added to the system and refluxed, inorganic matters were filtered off, and the clarified filtrate was cooled to form a precipitate, which was then dried under vacuum for 10 hours, to obtain 21.2g of 2,2', 3' -biphenylbisimine, with a yield of 92%.
In a 100mL reaction flask, 4.62g (0.01 mol) of the 2,2', 3' -biphenylbisimine is added, 9.9g of 20% sodium hydroxide aqueous solution is added, heating reflux is carried out for 12 hours, filtration is carried out, pH=1 is regulated by concentrated hydrochloric acid, 2', 3' -biphenyltetracarboxylic acid is obtained, cold water washing is carried out three times after filtration, 20mL of trimethylbenzene is carried out, 2.79g of white 2,2', 3' -biphenylbisanhydride is obtained, the yield is 95%, and the melting point is 268-270 ℃.
Example 3
N- (3-N, N-dimethylaminopentyl) -4-chlorophthalimide (28.05 g,0.1 mOL), zinc powder (4.55 g,0.07 mol), anhydrous NiCl were added to a 500mL reaction flask under a nitrogen atmosphere 2 (255 mg,2 mmol), triphenylphosphine (3.5 g,14 mmoL) and 70mL anhydrous DMF were reacted for 4 hours at 85℃with stirring, and the solvent DMAc 55mL was recovered under reduced pressure. Adding 80g of dimethylbenzene (recrystallization) into the system, refluxing, filtering inorganic matters, cooling the clarified filtrate to generate precipitate, filtering and vacuum drying for 10 hours to obtain 3,3'25.4g of 4,4' -biphenylbisimine with a yield of 98 percent.
5.18g (0.01 mol) of 3,3', 4' -biphenylbisimine is added into a 100mL reaction bottle, 9g of 20% sodium hydroxide aqueous solution is added, heating reflux is carried out for 24 hours, filtration is carried out, pH=1 is regulated by concentrated hydrochloric acid, 3', 4' -biphenyltetracarboxylic acid is obtained, water washing is carried out for three times after filtration, 20mL of trimethylbenzene is carried out, and 2.82g of white 3,3', 4' -biphenyldianhydride is obtained, the yield is 96%, and the melting point is 298-300 ℃.
Example 4
N- (3-N, N-dimethylaminopropyl) -4-chlorophthalimide (26.65 g,0.1 mOL), zinc powder (4.55 g,0.07 mol), anhydrous NiCl were added to a 500mL reaction flask under a nitrogen atmosphere 2 (255 mg,2 mmol), 2-bipyridine (2.18 g,7 mmoL) and 70mL anhydrous NMP were reacted at 85℃for 4 hours under stirring, and 55mL of DMAc solvent was recovered under reduced pressure. 80g of xylene (recrystalization) is added into the system for reflux, inorganic matters are filtered, the clarified filtrate is cooled to generate precipitate, and the precipitate is filtered and dried in vacuum for 10 hours to obtain 21.9g of 3,3', 4' -biphenylbisimine with the yield of 95 percent.
In a 100mL reaction flask, 4.62g (0.01 mol) of 3,3', 4' -biphenylbisimine is added, 9g of 20% sodium hydroxide aqueous solution is added, heating reflux is carried out for 15 hours, filtration is carried out, pH=1 is regulated by concentrated hydrochloric acid, 3', 4' -biphenyltetracarboxylic acid is obtained, water washing is carried out for three times after filtration, and 20mL of trimethylbenzene is used for carrying water, thus obtaining 2.82g of white 3,3', 4' -biphenylbisanhydride, the yield is 96%, and the melting point is 298-300 ℃.
The above description has been given in detail to the preparation method of biphenyl derivative and biphenyl dianhydride isomer, and specific examples are applied to the description of the principle and the implementation of the present invention, and the above examples are only used to help understand the method and the core idea of the present invention, and it should be pointed out that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also belong to the scope of the full protection of the present invention.
Claims (2)
1. A method for preparing biphenyl dianhydride based on metal coordination halogenated phthalimide monomer coupling is characterized in that the reaction process is as follows:
wherein the reaction raw material adopted is amino halogenated phthalimide in the following formula:
the substituent X in the reaction raw material is chlorine, and R is a saturated aliphatic group with 2-5 carbons;
the catalyst is nickel salt, and the nickel salt is one or a mixture of a plurality of nickel chloride, nickel bromide, nickel acetate and nickel sulfate; the molar ratio of the nickel salt to the reactant amino halogenated phthalimide is 0.005-0.02: 1, a step of;
the reducing agent is metallic zinc, and the mol ratio of the reducing agent to the amino halophthalimide is 0.5-0.7: 1, a step of;
the additive is one or a mixture of more of triphenylphosphine, 2' -bipyridine and sodium bromide, and the mol ratio of the additive to the nickel salt is 1-7: 1, a step of;
the preparation method specifically comprises the following steps: under the protection of nitrogen, mixing an amino halogenated phthalimide monomer, a nickel salt catalyst, an aprotic solvent, an additive and a reducing agent, stirring at 50-100 ℃ for carrying out a coupling reaction for 1-24 hours, recovering the solvent under reduced pressure, adding toluene or xylene which is 3-4 times of the mass of the reaction monomer into the system, heating and refluxing until the organic matter is dissolved, filtering while the organic matter is hot, cooling the filtrate, collecting precipitated bis-aminobiphenyl bisimine, refluxing and hydrolyzing the bis-aminobiphenyl bisimine with an aqueous solution of NaOH with the concentration of 20% for 2-24 hours in excess of 10-20%, filtering insoluble matters, acidifying with concentrated hydrochloric acid to generate biphenyl tetraacid precipitate, filtering and collecting biphenyl tetraacid, and carrying out water by a trimethylbenzene reflux to obtain 3,3', 4' -biphenyl dianhydride or 2,2', 3' -biphenyl dianhydride.
2. The method for preparing biphenyl dianhydride based on metal coordination halogenated phthalimide monomer coupling according to claim 1, wherein the solvent used in the coupling reaction is one or a mixture of several of N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide and dimethyl sulfoxide, and the use amount of the solvent is 2.5-4 times of the mass of the reaction monomer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269145A (en) * | 1998-03-17 | 1999-10-05 | Jsr Corp | Bis(n-substituted) phthalimide, its production and production of biphenyltetracarboxylic acid |
| US7425650B1 (en) * | 2004-07-23 | 2008-09-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides |
| JP2009079008A (en) * | 2007-09-26 | 2009-04-16 | Tamio Hayashi | Method for producing biphenyl-3, 4, 3', 4'-tetracarboxylic acid |
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| CN1215068C (en) * | 2003-03-03 | 2005-08-17 | 中国科学院长春应用化学研究所 | Prepn process of 2,3,3',4'-diphenyl tetraformic dianhydride and its derivative |
| US7417108B2 (en) * | 2005-04-28 | 2008-08-26 | Ube Industries Ltd. | Process for production of 2,3,3′,4′-biphenyltetracarboxylic dianhydride |
| CN104262234A (en) * | 2014-09-18 | 2015-01-07 | 哈尔滨工业大学（威海） | Preparation method of biphenyl derivatives |
| CN104341256A (en) * | 2014-10-20 | 2015-02-11 | 哈尔滨工业大学（威海） | Low-cost and environment-friendly synthesis method of biphenyl derivatives |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269145A (en) * | 1998-03-17 | 1999-10-05 | Jsr Corp | Bis(n-substituted) phthalimide, its production and production of biphenyltetracarboxylic acid |
| US7425650B1 (en) * | 2004-07-23 | 2008-09-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides |
| JP2009079008A (en) * | 2007-09-26 | 2009-04-16 | Tamio Hayashi | Method for producing biphenyl-3, 4, 3', 4'-tetracarboxylic acid |
Non-Patent Citations (1)
| Title |
|---|
| 3,3′,4,4′-联苯四甲酸二酐的合成工艺;谢开林,王晓钟,戴立言,陈英奇;化工学报(第09期);第 1805-180 8 页 * |
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