CN116478114A - Synthesis method of 2, 3',4' -biphenyl tetracarboxylic dianhydride - Google Patents
Synthesis method of 2, 3',4' -biphenyl tetracarboxylic dianhydride Download PDFInfo
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- CN116478114A CN116478114A CN202310394819.XA CN202310394819A CN116478114A CN 116478114 A CN116478114 A CN 116478114A CN 202310394819 A CN202310394819 A CN 202310394819A CN 116478114 A CN116478114 A CN 116478114A
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- 238000001308 synthesis method Methods 0.000 title description 4
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- 229910052763 palladium Inorganic materials 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical group CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-UHFFFAOYSA-N 0.000 claims description 5
- HNQLMBJUMVLFCF-UHFFFAOYSA-N 4-chloro-1,2-dimethylbenzene Chemical group CC1=CC=C(Cl)C=C1C HNQLMBJUMVLFCF-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 3
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 claims description 3
- DANMWBNOPFBJSZ-UHFFFAOYSA-N 1-iodo-2,3-dimethylbenzene Chemical group CC1=CC=CC(I)=C1C DANMWBNOPFBJSZ-UHFFFAOYSA-N 0.000 claims description 3
- QOGHRLGTXVMRLM-UHFFFAOYSA-N 4-bromo-1,2-dimethylbenzene Chemical group CC1=CC=C(Br)C=C1C QOGHRLGTXVMRLM-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- CSFRCLYFVINMBZ-UHFFFAOYSA-N 4-iodo-1,2-dimethylbenzene Chemical group CC1=CC=C(I)C=C1C CSFRCLYFVINMBZ-UHFFFAOYSA-N 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
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- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- 238000001816 cooling Methods 0.000 description 3
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- 150000004795 grignard reagents Chemical class 0.000 description 3
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- 230000000171 quenching effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZYYANAWVBDFAHY-UHFFFAOYSA-N (2,3-dimethylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1C ZYYANAWVBDFAHY-UHFFFAOYSA-N 0.000 description 1
- LNBYLWMCLPBTEH-UHFFFAOYSA-N 5-(2,3-dimethylphenyl)-2-methylisoindole-1,3-dione Chemical compound C1=C2C(=O)N(C)C(=O)C2=CC=C1C1=CC=CC(C)=C1C LNBYLWMCLPBTEH-UHFFFAOYSA-N 0.000 description 1
- DCFSQEWFDPNDPQ-UHFFFAOYSA-N 5-chloro-2-methylisoindole-1,3-dione Chemical compound C1=C(Cl)C=C2C(=O)N(C)C(=O)C2=C1 DCFSQEWFDPNDPQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 2, 3',4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps: (1) the 3-halogenated o-xylene is subjected to lithiation reaction with a lithiation reagent to obtain 3-lithium o-xylene, and then is subjected to coupling reaction with 4-halogenated o-xylene to obtain 2, 3',4' -tetramethyl biphenyl; (2) 2, 3',4' -biphenyl tetracarboxylic acid is obtained from 2, 3',4' -tetramethyl biphenyl through oxidation reaction; (3) 2, 3',4' -biphenyl tetracarboxylic dianhydride is obtained by dehydrating 2, 3',4' -biphenyl tetracarboxylic dianhydride. The invention firstly adopts the lithiation reagent to prepare the 3-halogenated o-xylene, then the 3-halogenated o-xylene is coupled with the 4-halogenated o-xylene to prepare the 2, 3', 4-tetramethylbiphenyl, the coupling reaction has higher selectivity, the products are basically the 2, 3',4' -tetramethylbiphenyl obtained by cross coupling, the reaction yield is higher, and the product purity is higher.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of 2, 3',4' -biphenyl tetracarboxylic dianhydride.
Background
2, 3',4' -biphenyl tetracarboxylic dianhydride, alpha-BPDA for short, white solid with melting point of 195-205 ℃ and molecular formula of C 16 H 6 O 6 The relative molecular weight is 294.22, the CAS number is 36978-41-3, and the structural formula is as follows:
。
polyimide material is one of the polymer materials with highest comprehensive performance at present. Due to its excellent heat resistance and mechanical properties, good chemical stability and radiation resistance, and low dielectric constant, it is widely used in various fields such as films, plastics, paints, fibers, liquid crystals, photoresists, etc. Among them, biphenyl type polyimide is regarded as having excellent high temperature resistance and corrosion resistance.
The biphenyl tetracarboxylic dianhydride is a biphenyl polyimide monomer with wider application at present, and comprises three structures of 2,2', 3' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride and 3,3',4' -biphenyl tetracarboxylic dianhydride. Among them, 2, 3',4' -biphenyltetracarboxylic dianhydride has a better processability as polyimide synthesized from it as a monomer because it contains an asymmetric structure.
The halo-ortho-xylene process is one of the main processes for the synthesis of 2, 3',4' -biphenyltetracarboxylic dianhydride.
1. The Chinese patent document CN102020622A discloses a preparation method of 2, 3',4' -biphenyl tetracarboxylic dianhydride, which is characterized in that 3-halogenated o-xylene and 4-halogenated o-xylene are subjected to catalytic coupling in the presence of catalyst nickel halide, catalyst ligand triphenylphosphine and reducing agent zinc powder to obtain 2, 3',4' -tetramethyl biphenyl, and then the 2, 3',4' -biphenyl tetracarboxylic dianhydride is obtained by oxidizing and dehydrating the 2, 3',4' -biphenyl tetracarboxylic dianhydride.
The method has the following defects: (1) The coupling reaction has poor selectivity, and the total yield of the three-step reaction is less than 50%; (2) The catalyst system has higher price and higher dosage, thus leading to higher production cost and being not suitable for industrialized mass production.
2. Chinese patent document CN114230540a discloses a method for synthesizing α -BPDA, which comprises reacting 2, 3-dimethylbromobenzene (i.e. 3-bromo-o-xylene) in a format to obtain a format reagent 2, 3-dimethylbenzeneboronic acid, then reacting with N-methyl-4-chlorophthalimide in the presence of a palladium catalyst to obtain 5- (2, 3-dimethylphenyl) -2-methylisoindole-1, 3-dione, then oxidizing to obtain 2, 3',4' -biphenyltetracarboxylic acid, and finally dehydrating to obtain anhydride to obtain 2, 3',4' -biphenyltetracarboxylic dianhydride.
The method has the following defects: (1) The synthesis route is longer, the operation is more complicated, and the method is not suitable for industrial mass production; the total yield of (2) is only about 50%.
3. Chinese patent document CN103288583A, CN104211559A, CN104370685A, etc. discloses a preparation method of 2, 3', 4-tetramethylbiphenyl, wherein a Grignard reagent is prepared from 3 (4) -halogenated o-xylene, and then the Grignard reagent is coupled with 4 (3) -halogenated o-xylene to obtain 2, 3', 4-tetramethylbiphenyl.
The method has the following defects: (1) The Grignard reaction has higher temperature, longer time and lower safety, and has higher requirement on the quality of raw materials, thus being not suitable for industrialized mass production; (2) The coupling reaction temperature is also higher, so that the energy consumption is higher; (3) The grignard reagent has the self-coupling problem, and byproducts are not easy to separate and purify, so that the purity of the product is low, and only a crude product can be obtained generally.
Disclosure of Invention
The invention aims to solve the problems and provide a synthesis method of 2, 3',4' -biphenyl tetracarboxylic dianhydride, which has high coupling reaction selectivity and high coupling reaction yield.
The technical scheme for realizing the aim of the invention is as follows: a method for synthesizing 2, 3',4' -biphenyl tetracarboxylic dianhydride comprises the following steps:
(1) the 3-halogenated o-xylene is subjected to lithiation reaction with a lithiation reagent to obtain 3-lithium o-xylene, and then is subjected to coupling reaction with 4-halogenated o-xylene to obtain 2, 3',4' -tetramethyl biphenyl;
(2) 2, 3',4' -biphenyl tetracarboxylic acid is obtained from 2, 3',4' -tetramethyl biphenyl through oxidation reaction;
(3) 2, 3',4' -biphenyl tetracarboxylic dianhydride is obtained by dehydrating 2, 3',4' -biphenyl tetracarboxylic dianhydride.
The specific synthetic route is as follows:
。
in the step (1), the molar ratio of the 3-halo-ortho-xylene to the 4-halo-ortho-xylene is 1:0.5 to 1:2, preferably 1:0.8 to 1:1.5.
The 3-halogenated o-xylene is 3-chloro-o-xylene, 3-bromo-o-xylene or 3-iodo-o-xylene.
The 4-halogenated o-xylene is 4-chloro-o-xylene, 4-bromo-o-xylene or 4-iodo-o-xylene.
In the step (1), the lithiation reagent is metallic lithium, n-butyllithium or tert-butyllithium, preferably n-butyllithium.
In the step (1), the molar ratio of the 3-halogenated o-xylene to the lithiation reagent is 1:1-1:1.2.
In the step (1), the lithiation reaction is performed in the presence of an organic solvent; the organic solvent is one or two of tetrahydrofuran, toluene and n-hexane.
In the step (1), the lithiation reaction temperature is-70 ℃ to 10 ℃.
In the step (1), the coupling reaction is performed in the presence of a palladium catalyst+phosphine compound; the phosphine compound is 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (X-Phos for short) or tri-tert-butylphosphine (P (t-Bu for short) 3 】。
The molar dosage of the phosphine compound is 0.5-3.0% of the 3-halogenated o-xylene.
The palladium catalyst is tris (dibenzylideneacetone) dipalladium (Pd for short) 2 (dba) 3 Palladium acetate (abbreviated as Pd (OAc)) 2 Palladium dichloride (abbreviated as PdCl) 2 [1,1' -bis (diphenylphosphine) ferrocene]Palladium dichloride [ abbreviated as Pd (dppf) Cl ] 2 Bis (triphenylphosphine) palladium dichloride [ abbreviated as Pd (PPh) 3 ) 2 Cl 2 One of the above, preferably Pd 2 (dba) 3 。
The molar usage of the palladium catalyst is 0.3% -2.5% of the 3-halogenated o-xylene.
In the step (1), the coupling reaction temperature is 10 to 60℃and preferably room temperature (15 to 25 ℃).
In the step (2), the oxidant adopted in the oxidation reaction is dilute nitric acid; the mass fraction of the dilute nitric acid is 10% -50%; the molar ratio of the 2, 3',4' -tetramethyl biphenyl to the dilute nitric acid is 1:10-1:20.
In the step (2), the reaction temperature of the oxidation reaction is 100 to 200 ℃.
In the step (2), the reaction pressure of the oxidation reaction is 0.8 to 1.8MPa.
In the step (3), the dehydration to the anhydride is a conventional method in the art, such as heating and dehydration of acetic anhydride to the anhydride, solvent-free high temperature dehydration to the anhydride, and refluxing and dehydration of xylene to the anhydride.
Wherein the reaction temperature of acetic anhydride for dehydration by heating to form anhydride is 60-140 ℃, and the reaction temperature of solvent-free high-temperature dehydration to form anhydride is 90-160 ℃.
Wherein, in the process of heating and dehydrating acetic anhydride to form anhydride, the mol ratio of the 2, 3', 4-biphenyl tetracarboxylic acid to the acetic anhydride is 1:2-1:20.
The invention has the positive effects that:
(1) The invention firstly adopts the lithiation reagent to prepare the 3-halogenated o-xylene, then carries out the coupling reaction with the 4-halogenated o-xylene in the presence of the palladium catalyst and the phosphine compound to prepare the 2, 3', 4-tetramethylbiphenyl, the coupling reaction has higher selectivity, and the products are basically the 2, 3',4' -tetramethylbiphenyl obtained by cross coupling, the reaction yield is higher, and the product purity is higher.
(2) The invention has the advantages of mild coupling reaction condition, low energy consumption, low catalyst consumption and low production cost.
Drawings
FIG. 1 is an HPLC chart of 2, 3',4' -tetramethylbiphenyl obtained in example 1.
FIG. 2 is a DSC chart of 2, 3',4' -biphenyltetracarboxylic dianhydride prepared in example 9.
Detailed Description
Example 1
This example is a process for preparing 2, 3',4' -tetramethylbiphenyl, the reaction formula is as follows:
。
the specific method comprises the following steps:
(1) 80.0g (0.432 mol) of 3-bromo-o-xylene and 540mL of tetrahydrofuran are added into a 1L three-necked flask, nitrogen is replaced for 3 times, the temperature is reduced to-60 ℃, 284mL of n-butyllithium (0.454 mol) n-hexane solution (1.6M) is slowly added dropwise, the temperature is controlled to be not more than-50 ℃ in the dropwise process, the dropwise is completed in about 30 minutes, and then the solution containing 3-lithium-o-xylene is obtained by heat preservation and stirring for 30 minutes.
(2) 60.8g (0.432 mol) of 4-chloro-o-xylene, 3.96g (4.32 mmol) of Pd as a palladium catalyst 2 (dba) 3 3.09g (6.48 mmol) of phosphine X-Phos and 320mL of tetrahydrofuran are added into a 2L three-necked flask, the mixture is replaced by nitrogen for 3 times, the temperature is reduced to 0 ℃, the solution obtained in the step (1) is slowly pressed in, and then stirred at room temperature for 40min, and the reaction is completely controlled by HPLC.
(3) Quenching the solution obtained in the step (2) by using saturated ammonium chloride aqueous solution, extracting for 2-3 times by using ethyl acetate, combining organic phases, removing the organic solvent by reduced pressure distillation at 50-60 ℃, distilling at 180-200 ℃ under reduced pressure, and cooling to obtain 81.2g of white solid 2, 3',4' -tetramethyl biphenyl, wherein the yield is 89.4%, and the HPLC purity is 99.72%.
The HPLC spectrum of the 2, 3',4' -tetramethyl biphenyl prepared in this example is shown in FIG. 1.
Example 2 to example 5
Each example is a process for the preparation of 2, 3',4' -tetramethylbiphenyl, which differs from example 1 in the catalytic system, as shown in Table 1.
Comparative examples 1 to 5
The preparation of 2, 3',4' -tetramethylbiphenyl was carried out in each comparative example, and the catalytic system was different from that of example 1, specifically shown in Table 1.
TABLE 1
| Palladium catalyst | Phosphonates | Yield is good | |
| Example 1 | Pd 2 (dba) 3 | X-Phos | 89.4% |
| Example 2 | Pd 2 (dba) 3 | P(t-Bu) 3 | 83.7% |
| Example 3 | Pd(OAc) 2 | X-Phos | 78.1% |
| Example 4 | Pd(OAc) 2 | P(t-Bu) 3 | 77.3% |
| Example 5 | PdCl 2 | X-Phos | 74.2% |
| Comparative example 1 | Pd 2 (dba) 3 | PPh 3 | 41.5% |
| Comparative example 2 | Pd(OAc) 2 | PPh 3 | 35.8% |
| Comparative example 3 | Pd 2 (dba) 3 | / | 38.8% |
| Comparative example 4 | Pd(dppf)Cl 2 | / | 49.1% |
| Comparative example 5 | Pd(PPh 3 ) 2 Cl 2 | / | 25.4% |
Example 6
The preparation method of the 2, 3',4' -tetramethyl biphenyl is still provided in the embodiment, and the reaction formula is as follows:
。
the specific method comprises the following steps:
(1) 85.0g (0.366 mol) of 3-iodo-o-xylene and 510mL of tetrahydrofuran are added into a 1L three-necked flask, nitrogen is replaced for 3 times, the temperature is reduced to minus 60 ℃, 240mL of n-butyllithium (0.384 mol) n-hexane solution (1.6M) is slowly added dropwise, the temperature is controlled to be not more than minus 50 ℃ in the dropwise process, the dropwise is completed for about 30 minutes, and then the solution containing 3-lithium-o-xylene is obtained by heat preservation and stirring for 30 minutes.
(2) 74.6g (0.403 mol) of 4-bromoo-xylene, 1.98g (2.16 mmol) of Pd as a palladium catalyst 2 (dba) 3 1.55g (3.24 mmol) of phosphine X-Phos and 320mL of tetrahydrofuran are added into a 2L three-necked flask, nitrogen is replaced for 3 times, the temperature is reduced to 0 ℃, the solution obtained in the step (1) is slowly pressed in, then stirred at room temperature for 40min, and the reaction is completely controlled by HPLC.
(3) Quenching the solution obtained in the step (2) by using saturated ammonium chloride aqueous solution, extracting for 2-3 times by using ethyl acetate, combining organic phases, removing the organic solvent by reduced pressure distillation at 50-60 ℃, distilling at 180-200 ℃ under reduced pressure, and cooling to obtain 67.3g of white solid 2, 3',4' -tetramethyl biphenyl, wherein the yield is 87.5%, and the HPLC purity is 99.65%.
Example 7
The preparation method of the 2, 3',4' -tetramethyl biphenyl is still provided in the embodiment, and the reaction formula is as follows:
。
the specific method comprises the following steps:
(1) 2.71g (0.39 mol) of metallic lithium and 500mL of anhydrous tetrahydrofuran are added into a 1L three-necked flask, nitrogen is replaced for 3 times, the temperature is reduced to-20 ℃, 50.0g (0.356 mol) of 3-chloro-o-xylene is slowly added dropwise, the dropwise is completed for about 30min, and then the mixture is stirred for 5h under heat preservation, thereby obtaining a solution containing 3-lithium-o-xylene.
(2) 60.0g (0.427 mol) of 4-chloro-o-xylene, 3.26g (3.56 mmol) of Pd as a palladium catalyst 2 (dba) 3 2.04g (4.28 mmol) of phosphine X-Phos and 300mL of tetrahydrofuran are added into a 2L three-necked flask, nitrogen is replaced for 3 times, the temperature is reduced to 0 ℃, the solution obtained in the step (1) is slowly pressed in, then stirred at room temperature for 40min, and the reaction is completely controlled by HPLC.
(3) Quenching the solution obtained in the step (2) by using saturated ammonium chloride aqueous solution, extracting for 2-3 times by using ethyl acetate, combining organic phases, removing the organic solvent by reduced pressure distillation at 50-60 ℃, distilling at 180-200 ℃ under reduced pressure, and cooling to obtain 61.4g of white solid 2, 3',4' -tetramethyl biphenyl, wherein the yield is 82.1%, and the HPLC purity is 99.62%.
Example 8
The embodiment is a preparation method of 2, 3',4' -biphenyl tetracarboxylic acid, which comprises the following specific steps:
20.0g of 2, 3',4' -tetramethylbiphenyl (0.095 mmol) obtained in example 1 and 225.0g of 32% by mass of dilute nitric acid (1.14 mol) were charged into a 500mL autoclave, and reacted at a reaction temperature of 120.+ -. 5 ℃ and a reaction pressure of 1.0.+ -. 0.1MPa under stirring for 4 hours.
After the reaction is finished, the reaction solution is cooled to room temperature and decompressed, white solid is separated out from the reaction solution, the reaction solution is filtered, filter cakes are rinsed by purified water, and then the filter cakes are dried in vacuum at 60 ℃ for 12 hours, so that 25.6g of white solid 2, 3',4' -biphenyl tetracarboxylic acid is obtained, the yield is 81.5%, and the HPLC purity is 99.5%.
Example 9
The embodiment is a preparation method of 2, 3',4' -biphenyl tetracarboxylic dianhydride, which comprises the following specific steps:
20.0g of 2, 3',4' -biphenyltetracarboxylic acid (0.06 mol) obtained in example 9, 40g of acetic anhydride (0.39 mol) and 40mL of toluene were charged into a 250mL three-necked flask, and the temperature was raised to 110.+ -. 5 ℃ and the reaction was stirred for 3 hours.
After the reaction, the reaction mixture is cooled to room temperature, filtered and dried in vacuum at 60 ℃ for 12 hours to obtain 17.3g of white solid 2, 3',4' -biphenyl tetracarboxylic dianhydride, wherein the yield is 97.1%, the HPLC purity is 99.7%, and the melting point is 200.3-201.7 ℃.
The DSC spectrum of the 2, 3',4' -biphenyl tetracarboxylic dianhydride prepared in the example is shown in figure 2.
The three-step reaction yield was 70% based on examples 1, 8 and 9.
Claims (10)
1. A method for synthesizing 2, 3',4' -biphenyl tetracarboxylic dianhydride comprises the following steps:
(1) the 3-halogenated o-xylene is subjected to lithiation reaction with a lithiation reagent to obtain 3-lithium o-xylene, and then is subjected to coupling reaction with 4-halogenated o-xylene to obtain 2, 3',4' -tetramethyl biphenyl;
(2) 2, 3',4' -biphenyl tetracarboxylic acid is obtained from 2, 3',4' -tetramethyl biphenyl through oxidation reaction;
(3) 2, 3',4' -biphenyl tetracarboxylic dianhydride is obtained by dehydrating 2, 3',4' -biphenyl tetracarboxylic dianhydride.
2. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: in the step (1), the molar ratio of the 3-halogenated o-xylene to the 4-halogenated o-xylene is 1:0.5-1:2; the 3-halogenated o-xylene is 3-chloro-o-xylene, 3-bromo-o-xylene or 3-iodo-o-xylene; the 4-halogenated o-xylene is 4-chloro-o-xylene, 4-bromo-o-xylene or 4-iodo-o-xylene.
3. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: in the step (1), the lithiation reagent is metallic lithium, n-butyllithium or tert-butyllithium; the molar ratio of the 3-halogenated o-xylene to the lithiation reagent is 1:1-1:1.2.
4. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: in the step (1), the lithiation reaction is performed in the presence of an organic solvent; the organic solvent is one or two of tetrahydrofuran, toluene and n-hexane.
5. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: in the step (1), the lithiation reaction temperature is-70-10 ℃, and the coupling reaction temperature is 10-60 ℃.
6. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: in the step (2), the oxidant adopted in the oxidation reaction is dilute nitric acid; the mass fraction of the dilute nitric acid is 10% -50%; the molar ratio of the 2, 3',4' -tetramethyl biphenyl to the dilute nitric acid is 1:10-1:20; the reaction temperature of the oxidation reaction is 100-200 ℃; the reaction pressure of the oxidation reaction is 0.8-1.8 MPa.
7. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to any one of claims 1 to 6, wherein: in the step (1), the coupling reaction is performed in the presence of a palladium catalyst+phosphine compound; the phosphine compound is 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl or tri-tert-butylphosphine.
8. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 7, wherein: the palladium catalyst is one of tris (dibenzylideneacetone) dipalladium, palladium acetate, palladium dichloride, [1,1' -bis (diphenylphosphine) ferrocene ] palladium dichloride and bis (triphenylphosphine) palladium dichloride.
9. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 8, wherein: the palladium catalyst is tris (dibenzylideneacetone) dipalladium.
10. The method for synthesizing 2, 3',4' -biphenyltetracarboxylic dianhydride according to claim 7, wherein: the molar usage of the palladium catalyst is 0.3% -2.5% of the 3-halogenated o-xylene; the molar dosage of the phosphine compound is 0.5-3.0% of the 3-halogenated o-xylene.
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