CN116332889A - Preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride - Google Patents
Preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride Download PDFInfo
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- CN116332889A CN116332889A CN202310569309.1A CN202310569309A CN116332889A CN 116332889 A CN116332889 A CN 116332889A CN 202310569309 A CN202310569309 A CN 202310569309A CN 116332889 A CN116332889 A CN 116332889A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 45
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical compound C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 claims abstract description 41
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 claims abstract description 13
- JLGIBEAVRQOEKK-UHFFFAOYSA-N 5-(1,3-dioxoindene-5-carbonyl)indene-1,3-dione Chemical compound C1=C2C(=O)CC(=O)C2=CC(C(C=2C=C3C(=O)CC(=O)C3=CC=2)=O)=C1 JLGIBEAVRQOEKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002841 Lewis acid Substances 0.000 claims abstract description 6
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 6
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000029936 alkylation Effects 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229940078552 o-xylene Drugs 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000004715 keto acids Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000011968 lewis acid catalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- -1 ketone anhydride Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
- 238000002061 vacuum sublimation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FKFVCCPWFITRSN-UHFFFAOYSA-N bis(3,4-dimethylphenyl)methanone Chemical compound C1=C(C)C(C)=CC=C1C(=O)C1=CC=C(C)C(C)=C1 FKFVCCPWFITRSN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of fluorine-containing fine chemical industry, and relates to a preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride, which comprises the following steps of (1) reacting benzene with malonyl chloride at 20-110 ℃ by taking Lewis acid as a catalyst to obtain 1, 3-indandione; (2) The 1, 3-indandione and carbon tetrachloride are subjected to alkylation reaction, and the alkylation product is further hydrolyzed to obtain 5,5' -carbonyl bis (1H-indene-1, 3 (2H) -dione); (3) Oxidizing 5,5' -carbonylbis (1H-indene-1, 3 (2H) -dione) to give 3,3',4' -benzophenone tetracarboxylic acid; (4) Dehydrating to obtain 3,3',4' -benzophenone tetracarboxylic dianhydride. The invention provides a new route for synthesizing 3,3',4' -benzophenone tetracarboxylic dianhydride, and the method has the advantages of simple process, low raw material price, mild reaction condition and high conversion rate and selectivity.
Description
Technical Field
The invention belongs to the field of fluorine-containing fine chemical industry, and particularly relates to a preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride.
Background
The 3,3',4' -benzophenone tetracarboxylic dianhydride is an important chemical raw material, is mostly used for preparing matrix resin and high-temperature-resistant polyester of advanced composite materials, has wide temperature-resistant range and excellent performances of corrosion resistance, radiation resistance, insulativity, impact resistance and the like, can be prepared into structural parts, laminated boards, films, adhesives, coatings, insulating materials, reinforcing materials and the like, and is widely used in the fields of aviation/aerospace, electric/electronic, ships, automobiles, precision machinery and the like, and has wide market prospect at home and abroad.
At present, the preparation of 3,3',4' -benzophenone tetracarboxylic dianhydride comprises the following methods:
the method comprises the following steps: synthesizing 3,3',4' -tetraalkyl benzophenone by using o-xylene and bis (trichloromethyl) carbonate as raw materials, preparing the 3,3 'by oxidation and dehydration reaction, for example, patent CN103626727A (CN 201310609922.8) takes o-xylene and bis (trichloromethyl) carbonate as raw materials, carrying out acylation reaction under the catalysis of anhydrous Lewis acid, 4,4' -tetraalkyl benzophenone, 3',4' -tetraalkyl benzophenone is fully oxidized in a potassium permanganate/hydrochloric acid system, and 3,3 'is obtained through steps of filtering, concentrating, crystallizing and the like, 4,4' -benzophenone tetracarboxylic acid, and carrying out vacuum high-temperature melting dehydration on the 3,3',4' -benzophenone tetracarboxylic acid to obtain a 3,3',4' -benzophenone tetracarboxylic dianhydride product. The preparation method has the advantages of simple process, high yield, less three wastes, better environment, easy industrialized implementation and the like. However, the cost of the raw material bis (trichloromethyl) carbonate used in the method is high, the loss of the anhydrous Lewis acid catalyst is large, the cyclic utilization rate of the catalyst is low, a large amount of isomers can be generated in the reaction, and the selectivity is poor.
The second method is as follows: by o-xylene andthe 3,3',4' -tetraalkyl benzophenone is synthesized from carbon tetrachloride and then subjected to oxidation and dehydration reactions, such as YEGOROV et al (Development and Optimization of Producing 3,3',4' -benzophenonetetracarboxylic dianhydride,Orient.J.Chem.,2016, Vol. 32 (6), 3063-3070.) The method comprises the steps of taking o-xylene and carbon tetrachloride as raw materials, synthesizing 3,3',4' -tetraalkyl benzophenone under the condition of a Lewis acid catalyst, obtaining 3,3',4' -benzophenone tetracarboxylic acid through oxygen oxidation, and dehydrating the 3,3',4' -benzophenone tetracarboxylic acid in a mixed solution of acetic acid and acetic anhydride to obtain a 3,3',4' -benzophenone tetracarboxylic dianhydride product. The anhydrous Lewis acid catalyst used in the method has large loss, higher isomer content and lower yield, and is not suitable for industrial production.
And a third method: the method comprises the steps of taking o-xylene and acetaldehyde as raw materials, carrying out condensation reaction under the action of a catalyst to obtain 3,3',4' -tetramethyl diphenylethane, preparing keto acid by oxidation, and dehydrating the keto acid to obtain ketone anhydride. In the condensation reaction of o-xylene and acetaldehyde, 3',4' -tetramethyl diphenylethane, 2, 3',4' -tetramethyl diphenylethane and 2,2',3,3' -tetramethyl diphenylethane and the like, wherein 3,3',4' -tetramethyl diphenylethane is only about 60 percent. The yield of the target product is too low and byproducts are more, so that the ketone anhydride is difficult to industrially produce and apply. Although the Chinese patent document CN101381275A (CN 200810137385.0) uses aluminum trichloride, boron trifluoride or a molecular sieve and the like as catalysts to catalyze and isomerize 2, 3',4' -tetramethyl diphenylethane and 2,2', 3' -tetramethyl diphenylethane into 3,3',4' -tetramethyl diphenylethane, the yield of the 3,3',4' -tetramethyl diphenylethane is improved, but the method still has the defects that acetaldehyde is easily oxidized by sulfuric acid, aldol condensation occurs per se, the reaction conversion rate is low, and isomer separation is difficult.
Disclosure of Invention
The invention provides a preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride, which aims to solve the problems of lower selectivity and yield of the existing preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride. The synthetic method can avoid the generation of isomers, and the selectivity and the yield of the product are greatly improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the 3,3',4' -benzophenone tetracarboxylic dianhydride comprises the following steps:
(1) Benzene reacts with malonyl chloride at 20-110 ℃ by taking Lewis acid as a catalyst to obtain 1, 3-indandione;
(2) In the presence of Lewis acid as catalyst, the 1, 3-indandione and carbon tetrachloride are alkylated, the alkylated product is further hydrolyzed to obtain 5,5' -carbonyl bis (1H-indene-1, 3 (2H) -dione),
(3) Oxidizing 5,5' -carbonylbis (1H-indene-1, 3 (2H) -dione) with an oxidizing agent to obtain 3,3',4' -benzophenone tetracarboxylic acid;
(4) The 3,3',4' -benzophenone tetracarboxylic dianhydride is prepared by dehydration of 3,3',4' -benzophenone tetracarboxylic dianhydride into anhydride.
Preferably, in step (1) or step (2), the catalyst comprises one or a combination of several of aluminum chloride, ferric bromide, zinc chloride or boron trifluoride, preferably ferric chloride or aluminum chloride.
Preferably, in the step (1), the molar ratio of benzene to the catalyst is 1:2-5. The molar ratio of benzene to malonyl chloride is 0.6-1.2:1, and more preferably 0.8-1:1.
Preferably, in the step (1), the reaction temperature is 40-90 ℃; the reaction time is 2-5 h.
Preferably, in the step (1), the reaction is carried out in a solvent, wherein the solvent is one or a combination of a plurality of chloroform, DMF (N, N-dimethylformamide), DMAC (dimethylacetamide) and DMSO (dimethyl sulfoxide); further preferred solvents are one of chloroform or DMF.
Preferably, after the reaction in the step (1) is finished, removing the solvent and the catalyst, and crystallizing to obtain the 1, 3-indandione; the solvent used for crystallization is a combination of several of dichloromethane, chloroform, petroleum ether, ethyl acetate, methanol, ethanol, n-hexane and n-pentane. Further preferably, the crystallization solvent is a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1:1, a mixed solvent of methylene chloride and n-hexane in a volume ratio of 1:1, or a mixed solvent of methanol and n-pentane in a volume ratio of 1:1.
Preferably, step (2) is carried out in a solvent which is dichloromethane or chloroform.
Preferably, in the step (2), the molar ratio of the 1, 3-indandione to the catalyst is 1:1-7, and more preferably 1:2-5. The molar ratio of the 1, 3-indandione to the carbon tetrachloride is 1.5-2.5:1, and more preferably 1.8-2:1.
Preferably, in the step (2), the alkylation reaction temperature is-20-50 ℃ and the reaction time is 1-3 h. And (2) hydrolyzing at room temperature for 1-2 hours.
Preferably, in the step (3), the oxidizing agent is one or a combination of several of potassium permanganate, nitric acid and potassium dichromate, preferably potassium permanganate. When potassium permanganate is used as the oxidizing agent, the molar amount of the oxidizing agent is 4 times or more, preferably 5 to 7 times, the molar amount of the 1, 3-indandione. The oxidation reaction temperature is 70-130 ℃, preferably 110-130 ℃. The oxidation reaction adopts acetic acid as a solvent. The solvent and catalyst of step (2) are removed prior to the oxidation reaction.
Preferably, in the step (4), the dehydration to anhydride method is vacuum sublimation method, the temperature is 120-240 ℃, the vacuum degree is 2-12 mmHg, and the reaction time is 2-8 hours. Preferably, the vacuum sublimation method is as follows: heating to 120-170 ℃, reacting for 1-3 hours at a vacuum degree of 8-12 mmHg, heating to 200-240 ℃ at a vacuum degree of 2-4 mmHg, and reacting for 2-5 hours.
The synthetic route for preparing 3,3',4' -benzophenone tetracarboxylic dianhydride is shown as follows:
the invention has the beneficial effects that:
compared with the prior art, the invention has at least the following beneficial effects:
(1) Compared with the existing preparation method, the preparation method provided by the invention provides a new synthesis idea and a new synthesis route. The method has the advantages of simple process, mild reaction conditions, high conversion rate, high yield of 1, 3-indandione up to more than 90%, total yield of final products more than 75%, and easy realization of large-scale industrialization.
(2) The invention adopts the reaction of 1, 3-indandione and carbon tetrachloride, and the reaction position of 1, 3-indandione and carbon tetrachloride is meta-position due to the positioning effect, the steric hindrance of 1, 3-indandione is larger, the ortho-isomer content is almost 0, the products are all main products, the reaction selectivity is greatly improved, the intermediate product selectivity is more than 98%, and the final product selectivity is high.
(3) The process route of the invention is more environment-friendly, has less three wastes and is easy to treat wastewater.
Drawings
FIG. 1 is a Fourier infrared spectrum of 3,3',4' -benzophenone tetracarboxylic dianhydride obtained in example 1;
FIG. 2 is a nuclear magnetic resonance H-spectrum of 3,3',4' -benzophenone tetracarboxylic dianhydride obtained in example 1;
FIG. 3 is a partial enlarged view of the nuclear magnetic resonance H spectrum of 3,3',4' -benzophenone tetracarboxylic dianhydride obtained in example 1.
Detailed Description
The invention is further described below with reference to examples.
Example 1
Preparation of 3,3',4' -benzophenone tetracarboxylic dianhydride:
(1) Preparation of 1, 3-indandione: a500 mL three-neck flask is provided with mechanical stirring and placed in a 65 ℃ water bath, 233.3g of aluminum trichloride is added into the three-neck flask containing chloroform, 39g of benzene and 78.3g of malonyl chloride are simultaneously added by a constant pressure dropping funnel, and the dropping speed is controlled to finish the simultaneous addition of the two materials. After the dripping is finished, the reaction is continued for 3 hours, after the reaction is finished, water is added to extract and kill the catalyst, the organic phase is separated, and the solvent is removed. Crystallization from a mixed solvent of ethyl acetate and petroleum ether (V/v=1:1) at 20 ℃, filtration, and drying gave 67.41g of 1, 3-indandione in 93.1% yield and 99.5% HPLC purity.
(2) Preparation of 3,3',4' -benzophenone tetracarboxylic acid: a500 mL three-neck flask is provided with mechanical stirring and placed in a water bath at the temperature of minus 20 ℃, 65g of 1, 3-indandione and 179.53g of aluminum trichloride are added into the three-neck flask containing dichloromethane, 36.3g of carbon tetrachloride is dropwise added by a constant pressure dropping funnel, and the dropping rate is 60-65 drops/min. After completion of the dropwise addition, the reaction was carried out for 2 hours, and after completion of the reaction, water was added at room temperature for further hydrolysis for 1 hour. The conversion of 1, 3-indandione was 100% and the selectivity of intermediate 5,5' -carbonylbis (1H-indene-1, 3 (2H) -dione) was 99.2% as measured by liquid chromatography.
(3) Separating the reaction liquid obtained in the step (2) to obtain an organic phase, removing a solvent to obtain a crude product of 5,5' -carbonyl bis (1H-indene-1, 3 (2H) -diketone), adding 100mL of acetic acid, adding 460.57g of potassium permanganate in three batches at 110 ℃, filtering out manganese dioxide solid after the solution does not fade in purple red, removing the solvent by rotary evaporation, and recrystallizing with acetonitrile to obtain 73.25g of white solid powder 3,3',4' -benzophenone tetracarboxylic acid, wherein the yield is 91.2 percent and the purity is 99.7 percent.
(4) Dehydration to anhydride: 70g of 3,3',4' -benzophenone tetracarboxylic acid was placed in a sublimation tube and heated to 150 ℃ (8 mmHg); after 2 hours of reaction, the temperature was raised to 220 ℃ (2 mmHg) and the reaction was continued for 5 hours. White crystals on the wall of the sublimated tube were collected to give 59.78g of 3,3',4' -benzophenone tetracarboxylic dianhydride in a yield of 94.9% and a purity of 99.0%. The total yield of the four-step reaction is 80.6%.
The obtained 3,3',4' -benzophenone tetracarboxylic dianhydride has a Fourier infrared spectrum shown in figure 1, and a nuclear magnetic resonance H spectrum shown in figure 2 and figure 3. 1667cm in FIG. 1 -1 The peak near the position is the vibration expansion peak of the ketocarbonyl, 1851cm -1 、1776cm -1 And 912cm -1 The peak near the site is the vibratable telescopic peak of the anhydride.
In FIGS. 2 and 3, H 1 The chemical shift delta value of (C) is about 8.24ppm, H 2 And H 2' The split is incomplete, the chemical shift delta value is near 8.28ppm, the peak integral area of two positions is approximately 1:2, and the chemical shift and integral area of active hydrogen of the 3,3',4' -benzophenone tetracarboxylic dianhydride obtained by the invention are consistent with the theoretical value.
Example 2
Preparation of 3,3',4' -benzophenone tetracarboxylic dianhydride:
(1) Preparation of 1, 3-indandione: a500 mL three-neck flask is provided with mechanical stirring and placed in a water bath at 40 ℃, 333.4g of aluminum trichloride is added into the three-neck flask containing DMF, 39g of benzene and 70.5g of malonyl chloride are simultaneously added dropwise through a constant pressure dropping funnel, and the dropping speed is controlled to ensure that the two materials are simultaneously added dropwise. After completion of the dropwise addition, the reaction was continued for 3 hours, after completion of the reaction, the catalyst was extracted, the organic phase was separated, the solvent was removed, and the mixture of methylene chloride and n-hexane (V/v=1:1) was crystallized at 20 ℃, filtered and dried to give 66.38g of 1, 3-indandione with a yield of 91.5% and an HPLC purity of 99.2%.
(2) Preparation of 3,3',4' -benzophenone tetracarboxylic acid: a500 mL three-neck flask is provided with mechanical stirring and placed in a water bath at 0 ℃, 65g of 1, 3-indandione and 120.2g of aluminum trichloride are added into the three-neck flask containing dichloromethane, 38.37g of carbon tetrachloride is dropwise added by a constant pressure dropping funnel, and the dropping rate is 60-65 drops/min. After completion of the dropwise addition, the reaction was carried out for 2 hours, and after completion of the reaction, water was added at room temperature for further hydrolysis for 1.5 hours. The conversion of 1, 3-indandione was 100% and the selectivity of intermediate 5,5' -carbonylbis (1H-indene-1, 3 (2H) -dione) was 98.7% as measured by liquid chromatography.
(3) Separating the reaction liquid obtained in the step (2) to obtain an organic phase, removing a solvent to obtain a crude product of 5,5' -carbonyl bis (1H-indene-1, 3 (2H) -diketone), adding 100mL of acetic acid, adding 354.12g of potassium permanganate in three batches at 130 ℃, filtering out manganese dioxide solid after the solution does not fade in purple red, removing the solvent by rotary evaporation, and recrystallizing with acetonitrile to obtain 72.55g of white solid powder 3,3',4' -benzophenone tetracarboxylic acid, wherein the yield is 90.4 percent and the purity is 99.0 percent.
(4) Dehydration to anhydride: placing 70g keto acid into a sublimation tube, and heating to 120 ℃ (10 mmHg); after 1 hour of reaction, the temperature was raised to 200 ℃ (3 mmHg) and the reaction was continued for 2 hours. White crystals are precipitated on the wall of the sublimated tube, 58.78g of 3,3',4' -benzophenone tetracarboxylic dianhydride is collected, the yield is 93.5%, and the purity is 99.0%. The total yield of the four-step reaction is 77.3 percent.
Example 3
Preparation of 3,3',4' -benzophenone tetracarboxylic dianhydride:
(1) Preparation of 1, 3-indandione: a500 mL three-neck flask is provided with mechanical stirring and placed in a water bath at 90 ℃, 162.2g of ferric chloride is added into the three-neck flask containing chloroform, 39g of benzene and 88.1g of malonyl chloride are simultaneously added by a constant pressure dropping funnel, and the dropping speed is controlled to ensure that the two materials are simultaneously added. After the completion of the dropwise addition, the reaction was continued for 3 hours, after the completion of the reaction, the catalyst was extracted, the organic phase was separated, the solvent was removed, and the mixture of methanol and n-pentane (V/v=1:1) was crystallized at 20 ℃, filtered and dried to give 67.14g of 1, 3-indandione with a yield of 92.6% and an HPLC purity of 99.1%.
(2) Preparation of 3,3',4' -benzophenone tetracarboxylic acid: a500 mL three-neck flask is provided with mechanical stirring and placed in a water bath at 50 ℃, 65g of 1, 3-indandione and 363.72g of ferric chloride are added into the three-neck flask containing chloroform, 34.54g of carbon tetrachloride is dropwise added by a constant pressure dropping funnel, and the dropping rate is 60-65 drops/min. After completion of the dropwise addition, the reaction was carried out for 2 hours, and after completion of the reaction, water was added at room temperature for further hydrolysis for 2 hours. The conversion of 1, 3-indandione was 99.9% and the selectivity of intermediate 5,5' -carbonylbis (1H-indene-1, 3 (2H) -dione) was 98.9% as measured by liquid chromatography.
(3) Separating the reaction liquid obtained in the step (2) to obtain an organic phase, removing the solvent to obtain a crude product of 5,5' -carbonyl bis (1H-indene-1, 3 (2H) -diketone), extracting the catalyst, separating the liquid to obtain the organic phase, removing the solvent, adding 100mL of acetic acid, adding 496.04g of potassium permanganate in three batches at 130 ℃, filtering out manganese dioxide solid after the mauve color of the solution does not fade, removing the solvent by rotary evaporation, and recrystallizing with acetonitrile to obtain 73.01g of white solid powder 3,3',4' -benzophenone tetracarboxylic acid, wherein the yield is 90.9% and the purity is 99.0%.
(4) Dehydration to anhydride: 70g of keto acid is placed in a sublimating tube and heated to 170 ℃ (12 mmHg); after 2 hours of reaction, the temperature was raised to 240 ℃ (4 mmHg) and the reaction was continued for 3.5 hours. White crystals are precipitated on the wall of the sublimated tube, 59.32g of 3,3',4' -benzophenone tetracarboxylic dianhydride is obtained after collection, the yield is 94.2%, and the purity is 99.0%. The total yield of the four-step reaction is 79.3%.
Example 4
Preparation of 1, 3-indandione: a500 mL three-neck flask is provided with mechanical stirring and placed in a water bath at 20 ℃, 233.3g of aluminum trichloride is added into the three-neck flask containing chloroform, 39g of benzene and 78.3g of malonyl chloride are simultaneously added by a constant pressure dropping funnel, and the dropping speed is controlled to finish the simultaneous addition of the two materials. After the completion of the dropwise addition, the reaction was continued for 3 hours, after the completion of the reaction, the catalyst was extracted, the organic phase was separated, the solvent was removed, and the mixture of ethyl acetate and petroleum ether (V/v=1:1) was crystallized at 20 ℃, filtered and dried to give 58.65g of 1, 3-indandione with a yield of 80.9% and an HPLC purity of 99.4%.
Example 5
Preparation of 1, 3-indandione: a500 mL three-neck flask is provided with mechanical stirring and placed in an oil bath at 110 ℃, 233.3g of aluminum trichloride is added into the three-neck flask containing DMF, 39g of benzene and 78.3g of malonyl chloride are simultaneously added dropwise by a constant pressure dropping funnel, and the dropping speed is controlled to finish the simultaneous addition of the two materials. After the completion of the dropwise addition, the reaction was continued for 3 hours, after the completion of the reaction, the catalyst was extracted, the organic phase was separated, the solvent was removed, and the mixture of ethyl acetate and petroleum ether (V/v=1:1) was crystallized at 20 ℃, filtered and dried to give 56.84g of 1, 3-indandione in a yield of 78.4% and an HPLC purity of 99.5%.
Example 6
Preparation of 1, 3-indandione: a500 mL three-neck flask is provided with mechanical stirring and placed in a 65 ℃ water bath, 233.3g of aluminum trichloride and 29g of sodium chloride are added into the three-neck flask containing DMF, 39g of benzene and 78.3g of malonyl chloride are simultaneously added dropwise by a constant pressure dropping funnel, and the dropping speed is controlled to ensure that the two materials are simultaneously added dropwise. After the dripping is finished, the reaction is continued for 3 hours, after the reaction is finished, the catalyst is extracted, the organic phase is separated, the organic phase is washed for 2 times, the residual sodium chloride in the organic phase is removed, and the solvent is removed. Crystallization from a mixed solvent of ethyl acetate and petroleum ether (V/v=1:1) at 20 ℃, filtration, and drying gave 64.21g of 1, 3-indandione in 88.5% yield and 98.7% HPLC purity. After the auxiliary sodium chloride is added, the synthesis of the 1, 3-indandione is not beneficial, but the yield is slightly reduced, and the post-treatment difficulty is increased.
The inventor of the present invention firstly uses benzene and malonyl chloride as raw materials to synthesize raw material 1, 3-indandione of 3,3',4' -benzophenone tetracarboxylic dianhydride, and during the preparation process, the inventor accidentally discovers that the too high temperature can affect the selectivity of the product, thereby affecting the yield of the product. The inventor obtains proper conditions of the reaction through a large number of researches, simplifies the reaction process of the step (1), and obtains the 1, 3-indandione with high yield, thereby improving the yield of the final product.
Comparative example 1
240g of aluminum trichloride is dispersed into 400mL of carbon tetrachloride and transferred into a 1000mL three-necked flask, 300g of o-xylene and 200mL of carbon tetrachloride solution are mixed and placed in a constant pressure dropping funnel, and the mixture is dropwise added into the three-necked flask and continuously stirred. After 3h reaction at-10 ℃, the conversion of o-xylene was 98.9% and the selectivity of intermediate was 65.3% as measured by liquid chromatography. Washing off excessive aluminum chloride with clear water, separating out an organic phase, removing part of solvent by rotary evaporation, adding ethanol for recrystallization, and obtaining 208.8g of white 3,3',4' -tetramethyl benzophenone solid with the yield of 62% and the purity of 98.1%.
To a 1L reactor, 174g of 3,3',4' -tetramethylbenzophenone, 1.8g of manganese acetate and cobalt acetate, 3.6g of sodium bromide were added, 500ml of acetic acid was added and reacted at 195℃and 2.5MPa for 10 hours to obtain a reddish-purple liquid, after the solvent was removed, 213.5g of 3,3',4' -benzophenone tetracarboxylic acid was obtained as a white solid by recrystallization from acetonitrile, and the yield was 81.8% and the purity was 99.0%.
200g of 3,3',4' -benzophenone tetracarboxylic acid is added into a mixed solution of 300g of acetic acid and 150g of acetic anhydride, reflux is carried out for 5 hours at 140 ℃, the solvent is removed after cooling, and 170.9g of 3,3',4' -benzophenone tetracarboxylic dianhydride is obtained after washing with acetone and diethyl ether, the yield is 95%, and the purity is 99.0%. The total yield of the three-step reaction is 48.2 percent.
Comparative example 2
62.37g of bis (trichloromethyl) carbonate and 253.5mL of o-xylene are added into a 1L three-neck flask with a mechanical stirrer and a thermometer, and the temperature is controlled to be 3-5 ℃ and stirred for 2 hours under the protection of nitrogen; then adding 86.91g of ground aluminum trichloride, stirring to be uniform, reacting at 0-5 ℃ for 4 hours, adding 500ml of water into a three-neck flask, stirring and heating to 40 ℃, and reacting at the temperature for 2 hours. After the reaction, the conversion of o-xylene was 99.3% and the selectivity of the intermediate was 63.7% as measured by liquid chromatography. The solid aluminum hydroxide was removed by filtration, the organic phase was separated from the filtrate by a separating funnel, the solvent was removed, and the mixture was recrystallized from a mixed solvent of methylene chloride and n-hexane (V/v=1:1) at 20 ℃, filtered and dried to obtain 89.05g of white 3,3',4' -tetramethyldimethyl ketone. The yield was 59.31% and the purity was 99.0% calculated as bis (trichloromethyl) carbonate.
40g of bis (3, 4-xylyl) methanone and 800ml of 0.10ml/L hydrochloric acid solution are added into a 1L three-neck flask, stirred and heated to 80+/-2 ℃, 106g of potassium permanganate is added in three batches in total, each batch is added after the previous color fading, the solution is finally oxidized to be the color of the solution for 3 hours without fading, manganese dioxide is filtered out while the solution is hot, the solvent is removed by rotary evaporation, and acetonitrile is used for recrystallization, thus obtaining 42.12g of 3,3',4' -benzophenone tetracarboxylic acid. The obtained 3,3',4' -benzophenone tetracarboxylic acid was heated to 215.+ -. 5 ℃ in a high temperature vacuum sintering furnace to be melt dehydrated for 1h, thus obtaining 34.09g of white solid 3,3',4' -benzophenone tetracarboxylic dianhydride. The yield was 63.01% based on 3,3',4' -tetramethyldimethyl ketone. The overall yield of the reaction was 22.16%.
Claims (11)
1. A method for preparing 3,3',4' -benzophenone tetracarboxylic dianhydride, which is characterized by comprising the following steps:
(1) Benzene reacts with malonyl chloride at 20-110 ℃ by taking Lewis acid as a catalyst to obtain 1, 3-indandione;
(2) In the presence of Lewis acid as a catalyst, carrying out alkylation reaction on 1, 3-indandione and carbon tetrachloride, and further hydrolyzing an alkylation product to obtain 5,5' -carbonyl bis (1H-indene-1, 3 (2H) -dione);
(3) Oxidizing 5,5' -carbonylbis (1H-indene-1, 3 (2H) -dione) with an oxidizing agent to obtain 3,3',4' -benzophenone tetracarboxylic acid;
(4) The 3,3',4' -benzophenone tetracarboxylic dianhydride is prepared by dehydration of 3,3',4' -benzophenone tetracarboxylic dianhydride into anhydride.
2. The preparation method according to claim 1, wherein in the step (1) or the step (2), the catalyst comprises one or a combination of several of aluminum chloride, ferric bromide, zinc chloride or boron trifluoride;
the molar ratio of benzene to the catalyst in the step (1) is 1:2-5; the molar ratio of benzene to malonyl chloride is 0.6-1.2:1.
3. The method according to claim 2, wherein in step (1) or step (2), the catalyst is ferric chloride or aluminum chloride.
4. The process according to claim 1, wherein in step (1), the molar ratio of benzene to malonyl chloride is 0.8 to 1:1.
5. The process according to claim 1, wherein in step (1), the reaction temperature is 40 to 90 ℃.
6. The method according to claim 1, wherein in the step (1), the reaction is performed in a solvent which is one or a combination of a plurality of chloroform, N-dimethylformamide, dimethylacetamide and dimethylsulfoxide;
after the reaction is finished, removing the solvent and the catalyst, and crystallizing to obtain 1, 3-indandione; the solvent used for crystallization is a combination of several solvents selected from dichloromethane, chloroform, petroleum ether, ethyl acetate, methanol, ethanol, n-hexane and n-pentane.
7. The method according to claim 6, wherein in the step (1), the solvent is chloroform or N, N-dimethylformamide;
the solvent used for crystallization is a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1:1, a mixed solvent of dichloromethane and n-hexane in a volume ratio of 1:1, or a mixed solvent of methanol and n-pentane in a volume ratio of 1:1.
8. The method of claim 1, wherein step (2) satisfies one of the following reaction conditions:
the molar ratio of the 1, 3-indandione to the catalyst is 1:1-7;
(ii) the molar ratio of 1, 3-indandione to carbon tetrachloride is 1.5-2.5:1;
(iii) the alkylation reaction temperature is-20 to 50 ℃.
9. The method of claim 1, wherein the molar ratio of 1, 3-indandione to catalyst in step (2) is 1:2-5; the molar ratio of the 1, 3-indandione to the carbon tetrachloride is 1.8-2:1.
10. The method of claim 1, wherein step (3) satisfies one of the following reaction conditions:
the oxidant is one or a combination of a plurality of potassium permanganate, nitric acid and potassium dichromate;
(ii) the temperature of the oxidation reaction is 70 ℃ to 130 ℃;
(iii) the molar ratio of the oxidizing agent to the 1, 3-indandione is 5-7:1.
11. The method according to claim 10, wherein the oxidizing agent in the step (3) is potassium permanganate, and the temperature of the oxidation reaction is 110-130 ℃.
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| WO2022073003A1 (en) * | 2020-09-29 | 2022-04-07 | New York Blood Center, Inc | Small molecule antagonists of pf4 |
| CN114605363A (en) * | 2022-03-11 | 2022-06-10 | 大连新阳光材料科技有限公司 | Preparation method of 3,3',4,4' -benzophenone tetracarboxylic dianhydride |
| CN115490657A (en) * | 2022-09-29 | 2022-12-20 | 天津众泰材料科技有限公司 | Preparation method of 3,3', 4' -benzophenone tetracarboxylic dianhydride |
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| WO2022073003A1 (en) * | 2020-09-29 | 2022-04-07 | New York Blood Center, Inc | Small molecule antagonists of pf4 |
| CN113651784A (en) * | 2021-08-30 | 2021-11-16 | 大连新阳光材料科技有限公司 | Synthetic method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
| CN114605363A (en) * | 2022-03-11 | 2022-06-10 | 大连新阳光材料科技有限公司 | Preparation method of 3,3',4,4' -benzophenone tetracarboxylic dianhydride |
| CN115490657A (en) * | 2022-09-29 | 2022-12-20 | 天津众泰材料科技有限公司 | Preparation method of 3,3', 4' -benzophenone tetracarboxylic dianhydride |
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