CN113603664B - Method for preparing biphenyl dianhydride by microwave-assisted catalytic coupling - Google Patents
Method for preparing biphenyl dianhydride by microwave-assisted catalytic coupling Download PDFInfo
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000004305 biphenyl Substances 0.000 title claims abstract description 23
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 238000010168 coupling process Methods 0.000 title claims abstract description 15
- 230000008878 coupling Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- -1 zinc halide Chemical class 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims abstract 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VEVUXRAGKBRVMF-UHFFFAOYSA-N 3-phenylcyclohexa-3,5-diene-1,2-diimine Chemical compound N=C1C(=N)C=CC=C1C1=CC=CC=C1 VEVUXRAGKBRVMF-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- 239000007787 solid Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 8
- 230000000536 complexating effect Effects 0.000 abstract description 5
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 1
- GQBONCZDJQXPLV-UHFFFAOYSA-N 4-aminoisoindole-1,3-dione Chemical compound NC1=CC=CC2=C1C(=O)NC2=O GQBONCZDJQXPLV-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—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
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing biphenyl dianhydride by microwave-assisted catalytic coupling, which mainly comprises the steps of taking halogenated phthalimide with complexing coordination capability as a raw material, taking zinc as a reducing agent, taking nickel salt as a catalyst, reacting for 20-60 minutes in a green solvent 2-methyltetrahydrofuran (2-THF) system under the condition of microwave irradiation at the temperature of 60-95 ℃, preparing biphenyl derivatives by coupling, hydrolyzing and dehydrating to obtain biphenyl dianhydride. The invention is characterized in that the halogenated monomer with complexation is adopted to form an organic metal complex with the by-product zinc halide generated by the reaction, so that the reduction capability of the zinc halide is prevented from being reduced due to the deposition of the zinc halide on the surface of the metal of the reducing agent. Compared with the traditional preparation reaction of the similar biphenyl dianhydride, the method has the advantages of high reaction speed, near quantitative reaction of the reducing agent and lower cost.
Description
Technical Field
The invention relates to a method for preparing biphenyl dianhydride by microwave-assisted catalytic 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, the industrial production of biphenyl tetracarboxylic dianhydride is mainly prepared by a noble metal Pd catalytic oxidative coupling method, and related patents such as JP7352749, US5243067, US3636168, CN201310049837 and the like, the yield of the method is low, the recovery and regeneration process of a metal Pd catalyst is complex, and the cost is high, so that the application market of biphenyl polyimide materials is greatly limited. Therefore, the development of a green and low-cost catalytic coupling reaction system for preparing the biphenyl dianhydride has important significance.
Ni (0) or Pd (0) is used as a catalyst, organic phosphine or nitrogen compound ligand and zinc powder are used as a reducing agent, and the biphenyl dianhydride is prepared through a method of reducing and 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 quantity, and further the reduction coupling reaction is affected, so that the reaction system generally needs to use the reducing agent with the theoretical quantity of more than 4 times to obtain better conversion rate. After the reaction is finished, a large amount of residual metal reducing agent waste residues are easy to cause fire, the safe production is influenced, and the industrial value is not possessed, so that the problem of adsorption of inorganic byproducts on the surface of the reducing agent in the method is solved, and the method is a key factor for realizing industrial application of the method.
The microwaves can quickly polarize polar molecules to realize hot spot heating, and weak polar molecules insensitive to the microwaves are not clear to the microwave frequency. The complex of transition metal nickel is an organic metal salt catalyst and is extremely sensitive to a microwave field, so that fixed-point heating can be realized, the catalyst becomes a hot spot, the phenyl insertion and transposition processes in the catalytic cycle process are facilitated, the speed of the coupling reaction is accelerated, and the progress of the reaction is promoted. 2-THF is a green solvent which has been found in recent years, has a boiling point of 86 ℃, has excellent solubility, and is easy to recycle. It was found that 3-carbon or more fatty amine-protected biphenylbisimine isomers have excellent solubility in 2-THF, whereas aniline-protected biphenylbisimine is difficult to dissolve in 2-THF, the nature of the aliphatic phthalimide monomers, makes it possible to use 2-THF as a green solvent for the preparation of biphenylbisimine compounds. 2-THF as a solvent in the Grignard reaction has been shown to have a very strong ability to complex with organometallic compounds while having the ability to dissolve ZnCl 2 Therefore, the catalyst has the characteristics of stabilizing and promoting the organic nickel intermediate in the process of catalyzing and coupling the aromatic compound, and is favorable for the occurrence of coupling reaction.
Disclosure of Invention
In order to overcome the defects in the existing preparation method of the biphenyl dianhydride by using a catalytic coupling reaction system, the invention provides a method for preparing the biphenyl dianhydride by microwave-assisted catalytic coupling, which utilizes microwave irradiation heating and the environment-friendly solvent 2-THF to have the characteristic of complexing organic metal, and supplements an organic nickel intermediate formed in the catalytic coupling process, so that the stability of the intermediate is improved, and the occurrence of coupling reaction is accelerated. Amino halogen phthalimide is adopted as a monomer to realize complexing coordination of amino and byproduct metal halide in a reaction system, the generated metal organic complex is shown in the following formula 1,
complexing schematic of aminophthalimide and zinc halide
The organic complex in the formula 1 is easier to dissolve in a reaction system, and effectively relieves ZnCl 2 The catalyst is adsorbed on the surface of the active metal reducing agent, 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 60-95 ℃, the reaction time is 20-60 minutes, and the reaction speed is high;
2) Purifying the bis (aminobiphenyl) tetracarboximide: purifying by recrystallization, wherein the purity is 96-99%;
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 by microwave-assisted catalytic 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 saturated aliphatic hydrocarbon group with 3-5 carbons;
the catalyst is nickel salt;
the reducing agent is metallic zinc;
the additive is one or two of triphenylphosphine and 2,2' -bipyridine;
the preparation method comprises the following steps: under the protection of nitrogen, mixing an amino halogenated phthalimide monomer, a nickel salt catalyst, an aprotic solvent and an additive reducer, carrying out coupling reaction for 20-60 minutes under the irradiation of microwaves of 200-500 w and stirring at 60-95 ℃, filtering to remove insoluble matters, recovering solvent 2-THF, recrystallizing the obtained solid product by using a mixture of isopropanol and hexane, obtaining bis (aminobiphenyl) bisimine, carrying out reflux hydrolysis on the bis (aminobiphenyl) bisimine by using an aqueous solution (the concentration of which is 20 percent) of 10-20 percent of NaOH for 2-24 hours, filtering insoluble matters, acidifying pH=1 by concentrated hydrochloric acid to generate biphenyl tetracarboxylic acid precipitate, filtering and collecting biphenyl tetracarboxylic acid, and carrying out water by trimethyl benzene reflux to obtain 3,3', 4' -biphenyl dianhydride or 2,2', 3' -biphenyl dianhydride.
Further, the nickel salt is nickel chloride and nickel bromide, and the molar ratio of the nickel salt to the reactant amino halogenated phthalimide is 0.01-0.02: 1, a step of; the reducer is metallic zinc, 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 use amount of the solvent 2-THF used in the coupling reaction is 3-4 times of the mass of the reaction monomer; the volume ratio of the isopropanol and the hexane which are mixed solvents used for recrystallization is 1:0.3-2.
The invention has the advantages that: the invention is characterized in that a green complex catalytic coupling reaction system is adopted, a green solvent 2-THF is utilized to supplement the position of the catalytic coupling organic nickel intermediate, the stability of the intermediate is increased, the occurrence of coupling reaction is accelerated, and simultaneously, the coupling byproduct ZnCl is dissolved 2 The method comprises the steps of carrying out a first treatment on the surface of the Amino halophthalimide is adopted as a monomer, complexing coordination between amino and byproduct metal halide in a reaction system is realized, the amino contained in the amino is complexed with byproduct halogenated metal salt to increase the solubility of the amino and byproduct halogenated metal salt in an organic solvent, and the metal salt is prevented from being adsorbed on the surface of reduced metal to influence the catalytic reduction process, so that the catalytic coupling reaction efficiency of halogenated o-xylene derivatives can be improved, and the reduction is greatly reducedThe consumption of the catalyst is reduced by 4 times from the literature, the consumption of the reducing agent is reduced to be close to the quantitative reaction, and the difficulty of post-treatment is reduced, so that the preparation cost of the biphenyl dianhydride is reduced, and the method is 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 90mL anhydrous 2-THF were reacted under microwave irradiation at power 200w with stirring at 60℃for 60 min, and then filtered to recover 83mL of the solvent. The product was recrystallized from 70mL of isopropanol/hexane (1:1, v/v) to give 22.5g of 3,3', 4' -biphenylbisimine in 95% yield.
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 2.86g 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 80mL of anhydrous 2-THF were added, and the mixture was reacted at 500w under microwave irradiation at 95℃for 20 minutes, followed by filtration to recover 75mL of the solvent. The product was recrystallized from 60mL of isopropanol/hexane (1:2, v/v) to give 21g of 2,2', 3' -biphenylbisimine in 91% yield.
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, 2.80g of white 2,2', 3' -biphenylbisanhydride is obtained, the yield is 95%, and the melting point is 268-270 ℃.
Example 3
N- (2-N, N-dimethylaminoethyl) -4-chlorophthalimide (25.25 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 95mL anhydrous 2-THF were reacted under microwave irradiation at 450w with stirring at 85℃for 40 min, and then filtered to recover 88mL of the solvent. The product was recrystallized from 80mL of isopropanol/hexane (1:1, v/v) to give 20.8g of 3,3', 4' -biphenylbisimine in 96% yield.
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 14 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 90mL anhydrous 2-THF were reacted under microwave irradiation at 400w, 80℃for 50 minutes with stirring, and 83mL of the solvent was recovered. The product was recrystallized from 70mL of isopropanol/hexane (1:1, v/v) to give 21.9g of 3,3', 4' -biphenylbisimine in 95% yield.
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 12 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 method for preparing the biphenyl dianhydride by green complex catalytic coupling provided by the invention is described in detail, and specific examples are applied to illustrate the principle and the implementation mode of the invention, and the description of the examples is only used for helping to understand the method and the core idea of the invention, and it should be pointed out that, to those skilled in the art, several improvements and modifications can be made to the invention without departing from the principle of the invention, and the improvements and modifications also belong to the full scope of protection of the invention.
Claims (2)
1. A method for preparing biphenyl dianhydride by microwave-assisted catalytic 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 or bromine, the position of the substituent X can be 3-position of an aromatic ring or 4-position of the aromatic ring, and R is saturated aliphatic hydrocarbon group with 3-5 carbons;
the catalyst is nickel salt, the nickel salt is nickel chloride and nickel bromide, and the molar ratio of the nickel salt to the reactant amino halogenated phthalimide is 0.01-0.02: 1, a step of;
the reducing agent is metallic zinc, and the molar ratio of zinc to amino halogenated phthalimide is 0.5-0.7: 1, a step of;
the additive is one or a mixture of two of triphenylphosphine and 2,2' -bipyridine, 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, amino halogenated phthalimide monomer, nickel salt catalyst, additive, solvent 2-methyltetrahydrofuran and reducing agent are subjected to coupling reaction under the microwave irradiation with the power of 200-500 w and stirring at the temperature of 60-95 ℃ for 20-60 minutes, insoluble matters are filtered, solvent 2-methyltetrahydrofuran is recovered, the obtained solid is recrystallized by isopropanol and hexane mixture, the obtained biphenyl bisimine is hydrolyzed by refluxing with 10-20% excess NaOH aqueous solution with the concentration of 20% for 2-24 hours, the biphenyl bisimine is acidified to pH=1 by concentrated hydrochloric acid, biphenyl tetracarboxylic acid precipitate is generated, the biphenyl tetracarboxylic acid is collected by filtration, and 3,3', 4' -biphenyl dianhydride or 2,2', 3' -biphenyl dianhydride is obtained by carrying out water by trimethylbenzene reflux.
2. The method for preparing biphenyl dianhydride by microwave-assisted catalytic coupling according to claim 1, wherein the use amount of the solvent 2-methyltetrahydrofuran used in the coupling reaction is 3-4 times of the mass of the reaction raw materials; the volume ratio of the isopropanol and the hexane which are mixed solvents used for recrystallization is 1:0.3-2.
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| US5081281A (en) * | 1988-10-11 | 1992-01-14 | Changchun Institute Of Applied Chemistry | Process for the preparation of 3,3',4,4'-biphenyltetracarboxylic acid and its derivatives |
| RU2682170C1 (en) * | 2017-12-22 | 2019-03-15 | Федеральное государственное унитарное предприятие "Институт химических реактивов и особо чистых химических веществ Национального исследовательского центра "Курчатовский институт" | Method of obtaining dianhydrides of aromatic tetracarbonic acids |
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| JP4168473B2 (en) * | 1998-03-17 | 2008-10-22 | Ｊｓｒ株式会社 | Bis (N-substituted) phthalimide, method for producing the same, and method for producing biphenyltetracarboxylic acid |
| JP4427946B2 (en) * | 2001-10-23 | 2010-03-10 | 住友化学株式会社 | Method for producing coupling compound |
| 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 |
| CN101481366B (en) * | 2008-12-29 | 2012-07-04 | 中国科学院长春应用化学研究所 | Preparation of 2,3,3',4'-biphenyl-tetracarboxylic acid dianhydride and derivatives thereof |
| CN104262234A (en) * | 2014-09-18 | 2015-01-07 | 哈尔滨工业大学（威海） | Preparation method of biphenyl derivatives |
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| US5081281A (en) * | 1988-10-11 | 1992-01-14 | Changchun Institute Of Applied Chemistry | Process for the preparation of 3,3',4,4'-biphenyltetracarboxylic acid and its derivatives |
| RU2682170C1 (en) * | 2017-12-22 | 2019-03-15 | Федеральное государственное унитарное предприятие "Институт химических реактивов и особо чистых химических веществ Национального исследовательского центра "Курчатовский институт" | Method of obtaining dianhydrides of aromatic tetracarbonic acids |
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