CN116621797A - Preparation method of 4,4' -diphenyl ether dianhydride - Google Patents
Preparation method of 4,4' -diphenyl ether dianhydride Download PDFInfo
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- CN116621797A CN116621797A CN202310592559.7A CN202310592559A CN116621797A CN 116621797 A CN116621797 A CN 116621797A CN 202310592559 A CN202310592559 A CN 202310592559A CN 116621797 A CN116621797 A CN 116621797A
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- ether dianhydride
- diphenyl ether
- organic solvent
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- bipheny
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 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 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- KDVZJKOYSOFXRV-UHFFFAOYSA-N (3,4-dimethylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1C KDVZJKOYSOFXRV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 3
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000001681 protective effect Effects 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229940078552 o-xylene Drugs 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- 238000005406 washing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RUXHWBMJNBBYNL-UHFFFAOYSA-N 3-hydroxy-1,2-dihydropyrrol-5-one Chemical compound OC1=CC(=O)NC1 RUXHWBMJNBBYNL-UHFFFAOYSA-N 0.000 description 2
- PXHIYFMTRHEUHZ-UHFFFAOYSA-N 5-hydroxy-2-benzofuran-1,3-dione Chemical compound OC1=CC=C2C(=O)OC(=O)C2=C1 PXHIYFMTRHEUHZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CCTOEAMRIIXGDJ-UHFFFAOYSA-N 4-hydroxy-2-benzofuran-1,3-dione Chemical compound OC1=CC=CC2=C1C(=O)OC2=O CCTOEAMRIIXGDJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- -1 imide amine Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In a protective gas, 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid react in an organic solvent A under the catalysis of a copper catalyst and alkali to obtain 3,3', 4' -tetramethyl diphenylether; s2:3,3', 4' -tetramethyl diphenyl ether is dissolved in sulfolane as organic solvent, and is added into aqueous solution of potassium permanganate and sodium hydroxide to obtain tetraacid through oxidation at certain temperature, and then 4,4' -diphenyl ether dianhydride is obtained through high temperature dehydration in organic solvent B. The invention has the beneficial effects that: the method has the advantages that 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid are used as main raw materials, a main carbon skeleton of diphenyl ether is constructed through copper catalytic coupling, the reaction steps are simple, the adopted coupling method utilizes 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid, the reaction selectivity is higher, and the reaction yield is high, so that the preparation method is novel, the reaction steps are short, the selectivity is good, the overall preparation cost is low, and the yield is high.
Description
Technical Field
The invention belongs to the technical field of synthesis of polyimide monomers, and particularly relates to a preparation method of 4,4' -biphenyl ether dianhydride.
Background
4,4 '-biphenylene ether dianhydride (ODPA), also known as 4,4' -oxydiphthalic anhydride, is an important monomer for the synthesis of polyimides. Polyimide (PI for short) is one of the types of thermoplastic engineering plastics with the best heat resistance at present, and is widely applied to the fields of aviation, aerospace, electromechanics, electronics and the like. ODPA can be polymerized with amine with multiple functional groups to form monoether anhydride type polyimide (PEI for short), for example, the soluble polyimide synthesized by polycondensation of ODPA, ethylenediamine, aniline and the like has excellent thermal stability, thermal oxidation resistance, good mechanical property and dielectric property, and flexible ether bond is introduced into polyimide main chain by ODPA, so that softening temperature is reduced, and molding processability of resin is remarkably improved. Therefore, the 4,4' -oxydiphthalic anhydride is efficiently and simply synthesized by molecular design, and has higher theoretical significance and practical application value.
The structural formula of the 4,4' -diphenyl ether dianhydride is as follows:
at present, the method for synthesizing 4,4' -diphenyl ether dianhydride mainly comprises the following steps: 1. phthalic anhydride process: the method is characterized in that phthalic anhydride is used as a raw material, imidization protection is carried out, mixed acid nitration is carried out, then bi-molecular etherification condensation is carried out to obtain monoether imide amine, hydrolysis and acidification are carried out, ODPA is obtained after dehydration, the synthetic route is long, the total yield is low, the cost is high, and a large amount of three wastes are generated by mixed acid nitration; 2. halophthalic anhydride and hydroxy phthalic anhydride process: the method is characterized in that 4-halophthalic anhydride and 4-hydroxy phthalic anhydride are respectively synthesized, and then ODPA is synthesized through Willianmson reaction, the raw material 4-halophthalic anhydride of the method is relatively expensive, the 4-hydroxy phthalic anhydride is obtained through sulfonation hydrolysis of phthalic anhydride, the reaction yield is low, and the cost of the whole route is high. (U.S. Pat. No. 5,172,72, chinese patent CN1324794A, CN111187240A, japanese patent JP80136246, european patent EP 0119576A)
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of 4,4' -diphenyl ether dianhydride, which has simple synthetic route and improves the reaction selectivity and the product yield.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a method for preparing 4,4' -diphenyl ether dianhydride, comprising the following steps:
s1: under the protection gas, 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid react in an organic solvent A under the catalysis of a copper catalyst and alkali to obtain 3,3', 4' -tetramethyl diphenylether shown in a formula I;
s2: dripping a mixed solution of a compound 3,3', 4' -tetramethyl diphenyl ether and sulfolane in a mixed solution of potassium permanganate, sodium hydroxide and water, oxidizing the mixed solution into tetramic acid at a high temperature, and dehydrating the tetramic acid into anhydride in an organic solvent B at a high temperature to obtain 4,4' -diphenyl ether dianhydride shown in a formula II; the synthetic route is as follows:
further, in the step S1, a copper catalyst and alkali are added into a mixed solution of 3, 4-dimethylphenol, 3, 4-dimethylbenzeneboronic acid and an organic solvent A under the protection of gas, the temperature is raised to 60 ℃ for reaction, and the system is kept at 60 ℃ for stirring for 5 hours. After the HPLC detection reaction is finished, cooling, filtering, adding water into filtrate to separate out solid, filtering, washing with water, and drying to obtain the compound 3,3', 4' -tetramethyl diphenyl ether shown in the formula I. By controlling the reaction temperature and excessive equivalent amount of 3, 4-dimethylbenzeneboronic acid, incomplete reaction of raw materials is avoided to the greatest extent.
Further, in the step S1, the molar ratio of the raw materials 3, 4-dimethylphenol, 3, 4-dimethylbenzeneboronic acid, copper catalyst and base is 1: (1.1-2): (0.01-0.1): (1.2-3). Within this range, 3, 4-dimethylphenol reacts most completely with 3, 4-dimethylbenzeneboronic acid, with the highest yield.
Further, in the step S1, the copper catalyst is one or more of dihydroxy-bis-tetramethyl ethylenediamine copper chloride, copper bromide, copper acetate, copper sulfate, and copper oxalate.
Further, in the step S1, the base is one or more of triethylamine, N-diisopropylethylamine, DBU, pyridine, DMAP, N-methylmorpholine, sodium acetate, potassium carbonate, and sodium carbonate.
Further, in the step S1, the solvent a is one or more of methanol, ethanol, tetrahydrofuran, acetone, acetonitrile, 1, 4-dioxane, NMP, DMF, DMSO.
Further, in the step S2, the compound 3,3', 4' -tetramethyl diphenyl ether shown in the I is dissolved in sulfolane, the solution is dripped into a mixed solution of potassium permanganate, sodium hydroxide and water, and the system temperature is controlled to be 70-90 ℃ and stirred for 2 hours. After the reaction is detected by HPLC, filtering, washing, controlling the temperature of the filtrate to adjust the pH value to be 1, filtering, washing, adding the filter cake into the organic solvent B, heating, refluxing and dehydrating until no water is generated, cooling, filtering, eluting by acetonitrile, and drying to obtain the compound 4,4' -biphenyl ether dianhydride shown in the formula II. The incomplete reaction of raw materials is avoided to the greatest extent by controlling the solution of the compound of the formula I and sulfolane and the reaction temperature.
Further, in the step S2, the molar ratio of 3,3', 4' -tetramethyl diphenyl ether to potassium permanganate is 1: (9-15).
Further, the organic solvent B in the step S2 is one or more of toluene, o-xylene, m-xylene, p-xylene, mesitylene, chlorobenzene and o-dichlorobenzene.
Further, the shielding gas is an inert gas, preferably nitrogen.
Compared with the prior art, the preparation method of the 4,4' -biphenyl ether dianhydride has the following advantages:
the invention takes 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid as main raw materials, and the main carbon skeleton of the diphenyl ether is constructed through copper catalytic coupling, the reaction steps are simple, the adopted coupling method utilizes 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid, the reaction selectivity is higher, and the reaction yield is high, so the preparation method is novel, the reaction steps are short, the selectivity is good, the overall preparation cost is low, and the yield is high.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail with reference to examples.
The synthetic route of 4,4' -diphenyl ether dianhydride is as follows:
example 1:
a preparation method of 4,4' -diphenyl ether dianhydride comprises the following steps:
step (1): 3, 4-dimethylphenol (100 g,1.0 eq) and methanol (500 mL) were added to a 2L four-necked flask at a molar ratio of 1:1.1 under nitrogen protection, and the mixture was stirred uniformly, followed by addition of copper (3.8 g,0.01 eq) and triethylamine (99.4 g,1.2 eq) to the flask, followed by stirring at 60℃for 5 hours. After the reaction is detected by HPLC, cooling to room temperature, filtering, adding 1000mL of water into the filtrate to precipitate solid, filtering, washing with water, and drying to obtain 170.4g of the compound shown in the formula I, namely 3,3', 4' -tetramethyl diphenyl ether, with the yield: 92.0%.
Among these, in the above reaction, in order to sufficiently dissolve the substrates 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid to participate in the reaction, a polar solvent should be selected as the solvent, so that methanol may be replaced with ethanol, tetrahydrofuran, acetone, acetonitrile, 1, 4-dioxane, NMP, DMF, DMSO.
The base plays a role of an acid-binding agent, and common organic base or inorganic base can be selected, so that the triethylamine can be replaced by N, N-diisopropylethylamine, DBU, pyridine, DMAP, N-methylmorpholine, sodium acetate, potassium carbonate and sodium carbonate.
The said; the copper catalyst has a catalytic effect and can be selected from common cupric salts, so that the dihydroxy-bis-tetramethyl ethylene diamine copper chloride can be replaced by copper chloride, copper bromide, copper acetate, copper sulfate and copper oxalate.
Step (2): the molar ratio of the compound shown in the formula I to potassium permanganate is 1:9, water (900 mL) is added into a 5L four-mouth bottle, potassium permanganate (628.4 g,9 eq) and sodium hydroxide (70.7 g,4 eq) are added under stirring, the temperature is raised to 80 ℃, mixed solution of the compound shown in the formula I (100 g,1 eq) and sulfolane (300 mL) is dropwise added, the dropwise addition is continued to keep the temperature at 80 ℃ for 2h after the completion of the dropwise addition, after the HPLC detection reaction, the filtration and the hot water washing are carried out, the pH=1 is carried out by adding hydrochloric acid into the filtrate at 10 ℃, the filtration and the water washing are carried out, toluene (300 mL) is added into the filter cake transferred into the 2L four-mouth bottle, the stirring and heating are carried out, the reflux water diversion is carried out until no water is generated, the stirring and the temperature is reduced to 5 ℃ after the HPLC detection reaction is completed, the acetonitrile is leached and dried, and 118.3g of the compound shown in the formula II is obtained, and the yield is obtained: 86.3%.
The organic solvent has the function of dehydration to form anhydride, and the benzene solvent with high boiling point can be selected, so that toluene can be replaced by o-xylene, m-xylene, p-xylene, mesitylene, chlorobenzene and o-dichlorobenzene.
Example 2:
a preparation method of 4,4' -diphenyl ether dianhydride comprises the following steps:
step (1): 3, 4-dimethylphenol (100 g,1.0 eq), 3, 4-dimethylbenzeneboronic acid (184.2 g,1.5 eq) and tetrahydrofuran (500 mL) are added to a 2L four-necked flask with a feed molar ratio of 1:1.5 under nitrogen protection, stirred uniformly, copper bromide (9.14 g,0.05 eq) and pyridine (142.5 g,2.2 eq) are added, and stirred for 5 hours at 60 ℃. After the reaction is detected by HPLC, cooling to room temperature, filtering, adding 1000mL of water into the filtrate to precipitate solid, filtering, washing with water, and drying to obtain 166.2g of the compound shown in the formula I, namely, 3', 4' -tetramethyl diphenyl ether, with the yield: 89.7%.
Step (2): the molar ratio of the compound shown in the formula I to potassium permanganate is 1:12, water (900 mL) is added into a 5L four-mouth bottle, potassium permanganate (837.9 g,12 eq) and sodium hydroxide (70.7 g,4 eq) are added under stirring, the temperature is raised to 80 ℃, mixed solution of the compound shown in the formula I (100 g,1 eq) and sulfolane (300 mL) is dropwise added, the dropwise addition is continued to keep the temperature at 80 ℃ for 2h, after HPLC detection reaction is finished, filtration and water washing are carried out, 500mL, hydrochloric acid is added into the filtrate at the temperature of 10 ℃ for regulating the pH value to be 1, filtration and water washing are carried out, the filter cake is transferred into a 2L four-mouth bottle, o-xylene (300 mL) is added into the 2L four-mouth bottle, stirring and heating are carried out, water is carried out until no water is generated after HPLC detection reaction is finished, the temperature is reduced to 5 ℃, the mixture is filtered, acetonitrile is leached and dried, the compound 4,4' -biphenyl ether dianhydride shown in the formula II is obtained, the yield is 123.6 g: 90.2%.
Example 3:
a preparation method of 4,4' -diphenyl ether dianhydride comprises the following steps:
step (1): the feeding mole ratio of 3, 4-dimethylphenol to 3, 4-dimethylbenzeneboronic acid is 1:2.0, 3, 4-dimethylphenol (100 g,1.0 eq), 3, 4-dimethylboronic acid (245.5 g,2.0 eq) and DMF (500 mL) were added to a 2L four-necked flask under nitrogen protection, stirred well, copper oxalate (12.4 g,0.1 eq) and potassium carbonate (339.4 g,3.0 eq) were added, and stirred at 60℃for 5h. After the reaction is detected by HPLC, cooling to room temperature, filtering, adding 1000mL of water into the filtrate to precipitate solid, filtering, washing with water, and drying to obtain 158.8g of the compound shown in the formula I, namely, the 3,3', 4' -tetramethyl diphenyl ether, with the yield: 85.7%.
Step (2): the molar ratio of the compound shown in the formula I to potassium permanganate is 1:15, water (900 mL) is added into a 5L four-mouth bottle, potassium permanganate (1047.4 g,15 eq) and sodium hydroxide (70.7 g,4 eq) are added under stirring, the temperature is raised to 80 ℃, a mixed solution of the compound shown in the formula I (100 g,1 eq) and sulfolane (300 mL) is dropwise added, the dropwise addition is continued to keep the temperature at 80 ℃ for 2h, after HPLC detection reaction is finished, filtration and water washing are carried out, 500mL, hydrochloric acid is added into the filtrate at the temperature of 10 ℃ for regulating the pH value to be 1, filtration and water washing are carried out, chlorobenzene (300 mL) is added into a 2L four-mouth bottle, stirring and heating are carried out, water diversion is carried out until no water is generated, after HPLC detection reaction is finished, the stirring and cooling to 5 ℃, the filtration and acetonitrile leaching are carried out, and drying are carried out, and the compound 4,4' -biphenyl ether dianhydride shown in the formula II is obtained, and the yield is 128.0 g: 93.4%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A preparation method of 4,4' -diphenyl ether dianhydride is characterized by comprising the following steps: the method comprises the following steps:
s1, in a protective gas, 3, 4-dimethylphenol and 3, 4-dimethylbenzeneboronic acid react in an organic solvent A under the catalysis of a copper catalyst and alkali to obtain 3,3', 4' -tetramethyl diphenyl ether;
s2:3,3', 4' -tetramethyl diphenyl ether is dissolved in sulfolane as organic solvent, and is added into aqueous solution of potassium permanganate and sodium hydroxide to obtain tetraacid through oxidation at certain temperature, and then 4,4' -diphenyl ether dianhydride is obtained through high temperature dehydration in organic solvent B.
2. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the molar ratio of 3, 4-dimethylphenol, 3, 4-dimethylbenzeneboronic acid, copper catalyst and alkali in the step S1 is 1: (1.1-2): (0.01-0.1): (1.2-3).
3. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the copper catalyst in the step S1 comprises one or more of dihydroxy-bis-tetramethyl ethylenediamine copper chloride, copper bromide, copper acetate, copper sulfate and copper oxalate.
4. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the shielding gas in the step S1 is an inert gas, preferably, the shielding gas is nitrogen.
5. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the organic solvent A in the step S1 comprises one or more of methanol, ethanol, tetrahydrofuran, acetone, acetonitrile, 1, 4-dioxane and NMP, DMF, DMSO.
6. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the base in the step S1 comprises one or more of triethylamine, N-diisopropylethylamine, DBU, pyridine, DMAP, N-methylmorpholine, sodium acetate, potassium carbonate and sodium carbonate.
7. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the sulfolane solution of 3,3', 4' -tetramethyl diphenyl ether in the step S2 is added into the aqueous solution of potassium permanganate and sodium hydroxide in a dropwise adding mode, and the system temperature is controlled at a certain temperature, and the certain temperature is 70-90 ℃;
preferably, the system temperature is controlled at 70-90 ℃ and stirred for 2 hours, after the reaction is detected by HPLC, the mixture is filtered, washed, the pH value of the filtrate is controlled to be 1, filtered, washed, the filter cake is added with an organic solvent B, heated, refluxed and dehydrated until no water is generated, and after the reaction is detected by HPLC, the mixture is cooled, filtered, rinsed by acetonitrile and dried to obtain the 4,4' -biphenyl ether dianhydride.
8. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the molar ratio of 3,3', 4' -tetramethyl diphenyl ether to potassium permanganate in the step S2 is 1: (9-15).
9. The process for producing 4,4' -bipheny ether dianhydride according to claim 1, wherein: the organic solvent B in the step S2 comprises one or more of toluene, o-xylene, m-xylene, p-xylene, mesitylene, chlorobenzene and o-dichlorobenzene.
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