CN115521280B - Method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and obtained product - Google Patents
Method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and obtained product Download PDFInfo
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- CN115521280B CN115521280B CN202110709574.6A CN202110709574A CN115521280B CN 115521280 B CN115521280 B CN 115521280B CN 202110709574 A CN202110709574 A CN 202110709574A CN 115521280 B CN115521280 B CN 115521280B
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- reaction
- chloroprene
- weight ratio
- alkene
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 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 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 141
- 150000001336 alkenes Chemical class 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 239000013067 intermediate product Substances 0.000 claims abstract description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 24
- 239000011976 maleic acid Substances 0.000 claims abstract description 24
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 31
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000011592 zinc chloride Substances 0.000 claims description 15
- 235000005074 zinc chloride Nutrition 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 14
- -1 transition metal salt Chemical class 0.000 claims description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 12
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 12
- 239000007818 Grignard reagent Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-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
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 150000004795 grignard reagents Chemical class 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 4
- 239000000523 sample Substances 0.000 claims 3
- 239000005456 alcohol based solvent Substances 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 11
- 238000005899 aromatization reaction Methods 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 208000005156 Dehydration Diseases 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 238000010992 reflux Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 9
- 238000010791 quenching Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000008878 coupling Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 229960001826 dimethylphthalate Drugs 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical class [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- JZALIDSFNICAQX-UHFFFAOYSA-N dichloro-methyl-trimethylsilylsilane Chemical compound C[Si](C)(C)[Si](C)(Cl)Cl JZALIDSFNICAQX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/33—Polycyclic acids
- C07C63/331—Polycyclic acids with all carboxyl groups bound to non-condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and a product obtained by the method, wherein the method for preparing the 3,3', 4' -biphenyl tetracarboxylic acid comprises the following steps: mixing dendron [4] alkene, maleic acid and a solvent for reaction, and removing the solvent in the system after the reaction is finished to obtain an intermediate product I; the intermediate product I reacts in the presence of an alkaline substance and an oxidant to obtain an intermediate product II; and (3) carrying out post-treatment on the intermediate product II to obtain the 3,3', 4' -biphenyl tetracarboxylic acid. The 3,3', 4' -biphenyl tetracarboxylic dianhydride can be obtained by carrying out dehydration treatment on the 3,3', 4' -biphenyl tetracarboxylic dianhydride. The invention adopts branch [4] alkene and maleic acid as raw materials to carry out cycloaddition-oxidation aromatization reaction, the synthesis strategy is novel, noble metal catalyst is not used, and the total yield is higher.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to preparation of 3,3', 4' -biphenyl tetracarboxylic dianhydride, in particular to preparation of 3,3', 4' -biphenyl tetracarboxylic dianhydride through cycloaddition reaction.
Background
3,3', 4' -biphenyltetracarboxylic acid is a precursor for preparing 3,3', 4' -biphenyltetracarboxylic acid dianhydride (BPDA), and 3,3', 4' -biphenyltetracarboxylic acid dianhydride (BPDA) is an important anhydride precursor of high-performance polyimide, and polyimide materials obtained by taking the 3,3', 4' -biphenyltetracarboxylic acid dianhydride as a monomer show very good heat resistance, water resistance and mechanical properties, and are super heat-resistant resins with highest heat resistance temperature so far. And the dielectric constant of polyimide material prepared from BPDA is only about 2.5, and the dielectric strength is 100-300 KV.mm -1 These properties remain at a high level over a wide temperature and frequency range, and are therefore more suitable for use in the field of high frequency electronic communications. The main preparation methods of the 3,3', 4' -biphenyl tetracarboxylic dianhydride at present are as follows:
1) The dehalogenation coupling method of 4-chloro (bromo) -phthalate is first proposed in 80 s by Nippon Kogyo Co., ltd., dehalogenation coupling is carried out on halophthalate in the presence of palladium metal catalyst, alkali and reducing agent, 3', 4' -biphenyltetracarboxylic acid is obtained by acidification, and then BPDA is obtained by dehydration. The method is continuously perfected in recent years, and is the most main industrialized method at present. See CN110563678A, CN111620769a, etc., however, the use of noble metal catalysts increases the cost of preparation;
2) Dehalogenation coupling of 4-chloro (bromo) -phthalate by Changchun Condition Ding Mengxian et alThe method adopts 4-chloro/bromo-dimethyl phthalate as raw material, and uses bis (triphenylphosphine) nickel dichloride catalyst and zinc powder as reducing agent to implement dehalogenation coupling reaction, and said reaction requires no water and N 2 Protecting, hydrolyzing and acidifying the generated ester to obtain 3,3', 4' -biphenyl tetracarboxylic acid, and dehydrating to obtain BPDA (poly (lactic acid-co-glycolic acid)), see US5081281A; CN1021439C, etc.; however, the method has poor process stability and generates more metal salt waste residues;
) The oxidative coupling method of dimethyl phthalate comprises the steps of oxidizing and coupling dimethyl phthalate with oxygen in the presence of palladium acetate and ligand to obtain 3,3', 4' -biphenyl tetracarboxylic acid, and dehydrating to obtain BPDA. See US,4292435,1981; US,4581469, 1986, etc.;
4) The anhydrous trimellitic acid monoacyl chloride coupling method is characterized in that dichloro tetramethyl disilane is taken as a reducing agent for decarboxylation coupling under the condition of a palladium catalyst, so that the BPDA can be obtained. Although this process has a high conversion rate, the raw materials are expensive and not readily available. See EP 339,455, 1989.
In summary, the main methods for preparing 3,3', 4' -biphenyltetracarboxylic acid and BPDA all adopt palladium catalysts, and the use of noble metal palladium catalysts is one of the main reasons for the high cost of 3,3', 4' -biphenyltetracarboxylic acid and BPDA. Therefore, the development of a non-noble metal catalyzed, simple and efficient synthetic route has important significance for reducing the production cost of 3,3', 4' -biphenyl tetracarboxylic acid and BPDA.
Disclosure of Invention
The invention aims to solve the problem that noble metal catalysts are commonly used for preparing 3,3', 4' -biphenyltetracarboxylic acid and 3,3', 4' -biphenyltetracarboxylic dianhydride, and provides a method for preparing 3,3', 4' -biphenyltetracarboxylic acid and dianhydride thereof and a product obtained by the method, wherein the method comprises the following steps: the 3,3', 4' -biphenyl tetracarboxylic dianhydride is prepared by cycloaddition-oxidative aromatization reaction of branch [4] alkene and maleic acid, the branch [4] alkene and maleic acid are mixed, the serial cycloaddition-oxidative aromatization reaction is realized by a one-pot method to obtain 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the 3,3', 4' -biphenyl tetracarboxylic dianhydride is further obtained by dehydration of acetic anhydride, thereby realizing a novel preparation method of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 3,3', 4' -biphenyl tetracarboxylic dianhydride.
It is an object of the present invention to provide a process for preparing 3,3', 4' -biphenyltetracarboxylic acid comprising:
(1) Mixing dendron [4] alkene, maleic acid and a solvent for reaction, and removing the solvent in the system after the reaction is finished to obtain an intermediate product I;
(2) The intermediate product I reacts in the presence of an alkaline substance and an oxidant to obtain an intermediate product II;
(3) And (3) carrying out post-treatment on the intermediate product II to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.
Wherein the structure of the branch [4] alkene in the step (1) is shown as a formula (i). In the step (1), D-A cycloaddition reaction of dendritic [4] alkene and maleic acid is carried out, and the obtained intermediate product is bi-1, 2,5, 6-tetrahydrophthalic acid, and the structure of the intermediate product is shown as a formula (ii):
wherein in step (2) the intermediate I undergoes oxidative aromatization to form intermediate II.
In a preferred embodiment, in step (1), the solvent is selected from at least one of an alcoholic solvent, tetrahydrofuran, ethyl acetate, 1, 4-dioxane.
In a further preferred embodiment, in step (1), the alcoholic solvent is selected from alcoholic solvents having a boiling point below 150 ℃, preferably at least one from methanol, ethanol, n-propanol, isopropanol, n-butanol.
In a still further preferred embodiment, the solvent in the system is removed in step (1) by distillation.
In a preferred embodiment, in step (1), the weight ratio of dendron [4] ene to solvent is 1 (5-200); and/or the weight ratio of the dendron [4] alkene to the maleic acid is 1 (1-4).
Wherein, the excessive maleic acid in the system can be removed by washing.
In a further preferred embodiment, in step (1), the weight ratio of the dendron [4] ene to the solvent is 1 (10 to 100); and/or the weight ratio of the dendron [4] alkene to the maleic acid is 1 (2-2.5).
For example, in step (1), the weight ratio of the dendron [4] ene to the alcoholic solvent is 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, or 1:100; and/or the weight ratio of dendron [4] ene to maleic acid is 1:1, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:3, or 1:4.
In a preferred embodiment, in step (1), the temperature of the reaction is 45 to 105 ℃ and the time of the reaction is 4 to 12 hours.
In a further preferred embodiment, in step (1), the reaction is carried out below the boiling point of the solvent.
For example, in step (1), the temperature of the reaction is 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 95 ℃, 105 ℃ or 115 ℃, and the time of the reaction is 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.
In a preferred embodiment, the alkaline substance is an inorganic alkaline substance, preferably at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
In a preferred embodiment, the oxidizing agent is at least one selected from hydrogen peroxide, potassium persulfate, and ammonium persulfate.
In a further preferred embodiment, the oxidizing agent is hydrogen peroxide, for example 30% hydrogen peroxide by mass.
In a preferred embodiment, the weight ratio of alkaline substance to dendron [4] ene is (0.6-2): 1; and/or the weight ratio of the oxidant to the dendron [4] ene is (2-6): 1.
In a further preferred embodiment, the weight ratio of alkaline substance to dendron [4] ene is (0.9-1.5): 1; and/or the weight ratio of the oxidant to the dendron [4] alkene is (4-5): 1.
In a preferred embodiment, in step (2), the intermediate product I, the alkaline substance and water are mixed (preferably, water and alkaline substance are added to the intermediate product I) and then heated, then an oxidizing agent is slowly added dropwise to the system, and the reaction is continued while maintaining the temperature after the dropwise addition (preferably, the reaction is cooled to room temperature after the completion), thereby obtaining the intermediate product II.
In a further preferred embodiment, in step (2), the intermediate product I, the alkaline substance and water are mixed (preferably, water and alkaline substance are added to the intermediate product I) and heated to 30 to 80 ℃, then an oxidizing agent is slowly added dropwise to the system, and the reaction is continued for 1 to 3 hours (preferably, cooled to room temperature after the completion of the reaction) while maintaining the temperature after the completion of the dropwise addition, thereby obtaining the intermediate product II.
For example, the hydrogen peroxide is slowly added dropwise to the system at 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃ and the reaction is continued for 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours after the completion of the dropwise addition.
In a further preferred embodiment, the weight ratio of water to dendron [4] ene is from (5 to 40): 1, preferably from (10 to 30): 1.
In a preferred embodiment, in step (3), the post-treatment comprises:
(3.1) adding a reducing substance to the intermediate II (to neutralize excess oxidant);
(3.2) adjusting the pH of the system to 1-5, preferably 2-3;
(3.3) filtering and washing to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.
In a preferred embodiment, the reducing substance is selected from sodium bisulphite and/or sodium hydrosulfite, preferably sodium bisulphite.
In a further preferred embodiment, the weight ratio of the reducing substance to the oxidizing agent is 1: (50-500), for example 1:50, 1:80, 1:100, 1:120, 1:150, 1:180, 1:200, 1:220, 1:250, 1:280, 1:300, 1:320, 1:350, 1:400, 1:450 or 1:500.
In a preferred embodiment, in step (3.2), the pH is adjusted with concentrated hydrochloric acid, for example 36.5% by mass concentrated hydrochloric acid.
In a preferred embodiment, the method for preparing the dendron [4] ene comprises: 2-chloroprene is used as a starting material, and the dendron [4] alkene is obtained through a coupling reaction of a grignard reagent.
In a further preferred embodiment, the method for preparing the dendron [4] ene comprises: firstly, preparing a 2-chloroprene format reagent, wherein the structure of the reagent is shown as a formula (iii); the 2-chloroprene format reagent reacts with 2-chloroprene to obtain dendron [4] ene.
In a still further preferred embodiment, the method for preparing a dendron [4] ene comprises:
(I) Preparation of 2-chloroprene Format reagent: mixing the dried magnesium chips, an initiator and a solvent in a protective atmosphere, stirring, heating to a set temperature, and adding anhydrous zinc chloride and the solvent; then, dropwise adding a solution containing 2-chloroprene and the solvent into a reaction container, and reacting to obtain a 2-chloroprene format reagent solution;
Wherein, after the anhydrous zinc chloride is added, magnesium can reduce a small amount of the added anhydrous zinc chloride to form a primary cell effect to increase the reactivity of the magnesium.
(II) preparation of dendron [4] ene: 2-chloroprene is dripped into the reaction system in the step (I) at the temperature of minus 10 ℃ to 10 ℃, a cocatalyst and a transition metal catalyst are added in sequence after the dripping is finished, the temperature is increased for reaction, and post-treatment is carried out after the reaction is finished to obtain the dendron [4] alkene.
For example, in the step (II), 2-chloroprene is added dropwise to the reaction system of the step (1) at-8 ℃, -5 ℃, -2 ℃, 0 ℃, 2 ℃, 5 ℃ or 8 ℃.
In a preferred embodiment, in step (I), the initiator is selected from at least one of dibromoethane and/or elemental iodine.
In a preferred embodiment, in step (I), the solvent is selected from at least one of diglyme (DGDE), triglyme, hexamethylphosphoramide.
In the present invention, the dendron [4] ene is produced by a form coupling based on 2-chloroprene as starting material. Aiming at the problem that the reaction solvent (tetrahydrofuran with the normal pressure boiling point of 66 ℃) and the dendron [4] alkene (with the normal pressure boiling point of 72 ℃) are close to each other and are not easy to separate in the method for synthesizing the dendron [4] alkene, the invention improves the synthesis and separation efficiency of the dendron [4] alkene by adopting the high boiling point solvent, optimizing the reaction condition.
In a preferred embodiment, in step (I), the weight ratio of magnesium turnings to 2-chloroprene is 1 (1-4); and/or the weight ratio of the initiator to the 2-chloroprene is (0.01-0.2): 1; and/or the weight ratio of the anhydrous zinc chloride to the 2-chloroprene is (0.01-0.2): 1; and/or the molar volume ratio of 2-chloroprene to the total solvent added is (0.1 mol to 5 mol): 1L.
In a further preferred embodiment, in step (I), the weight ratio of magnesium turnings to 2-chloroprene is 1 (2-2.5); and/or the weight ratio of the initiator to the 2-chloroprene is (0.05-0.1): 1; and/or the weight ratio of the anhydrous zinc chloride to the 2-chloroprene is (0.02-0.08): 1; and/or the molar volume ratio of 2-chloroprene to the total DGDE added is (0.5 mol to 2.5 mol): 1L.
In a preferred embodiment, in step (I), heating to 30℃to 90 ℃; the heating is carried out for 5 to 50 minutes.
In a further preferred embodiment, in step (I), heating to 35 ℃ to 75 ℃; heating is carried out for 10 to 30 minutes.
Wherein the purpose of the heating is to activate magnesium turnings. For example, in step (I), heating to 35 ℃, 45 ℃, 55 ℃, 65 ℃, or 75 ℃; heating is performed for 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.
In a preferred embodiment, in step (I), the solution comprising 2-chloroprene and the solvent is added dropwise to the reaction vessel for a period of time ranging from 1 to 8 hours and the reaction temperature is controlled not to exceed 70 ℃.
In a further preferred embodiment, in step (I), the solution comprising 2-chloroprene and the solvent is added dropwise to the reaction vessel for a period of from 2 to 6 hours and the reaction temperature is controlled not to exceed 60 ℃.
In a preferred embodiment, in step (I), the protective atmosphere is selected from at least one of nitrogen, argon, helium, for example nitrogen.
In a preferred embodiment, in step (I), the 2-chloroprene grignard reagent solution is formed by refluxing for 1 to 2 hours after the reaction.
In a preferred embodiment, in step (II), the cocatalyst is selected from at least one of triphenylphosphine, bis-diphenylethane, bis-diphenylpropane, e.g. triphenylphosphine.
In a preferred embodiment, in step (II), the transition metal catalyst is selected from at least one of copper salts, nickel salts, iron salts, manganese salts.
In a further preferred embodiment, the copper salt is selected from one or a mixture of two or more of copper acetate, copper bromide, copper chloride, copper sulfate, copper nitrate, copper phosphate; the nickel salt is selected from one or a mixture of more than two of nickel acetate, nickel chloride, nickel bromide, nickel sulfate, nickel nitrate and nickel phosphate; the ferric salt is selected from one or more than two of ferrous bromide, ferric bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, ferrous nitrate, ferric nitrate, ferrous phosphate, ferric phosphate, ferrous ammonium sulfate, potassium ferrocyanide and potassium ferricyanide; the manganese salt is selected from one or a mixture of two or more of manganese acetate, manganese chloride, manganese bromide, manganese sulfate, manganese nitrate, manganese phosphate and manganese oxalate.
In a preferred embodiment, in step (II), the weight ratio of transition metal salt catalyst to 2-chloroprene added dropwise in step (I) is from 1 (20 to 2500), preferably from 1 (50 to 2000).
For example, the weight ratio of transition metal salt catalyst to 2-chloroprene added dropwise in step (I) is 1:20, 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:800, 1:1000, 1:1500, or 1:2000.
In a preferred embodiment, in step (II), the weight ratio of the 2-chloroprene used in step (II) to the 2-chloroprene used in step (I) is from 0.2 to 2:1, and the weight ratio of the cocatalyst to the 2-chloroprene used in step (I) is from 1 (10 to 1500).
In a further preferred embodiment, in step (II), the weight ratio of the 2-chloroprene used in step (II) to the 2-chloroprene used in step (I) is from 0.5 to 1.5:1, and the weight ratio of the cocatalyst to the 2-chloroprene used in step (I) is from 1:20 to 1000.
In a preferred embodiment, in step (II), the temperature is raised to 10 to 40 ℃, preferably 15 to 35 ℃ (e.g. 20 to 30 ℃, e.g. room temperature).
In a preferred embodiment, in step (II), the post-treatment comprises: adding acid to quench reaction and regulating pH value to 6-9, reducing reaction system to negative pressure state, cooling to collect volatile matter and rectifying to obtain dendron 4 alkene.
In a further preferred embodiment, the acid is selected from concentrated sulfuric acid and/or phosphoric acid; and/or adjusting the pH value to 7-8; and/or the vacuum degree of the reaction system is reduced to 10 to 100mmHg, preferably 20 to 30mmHg.
In a preferred embodiment, the solvent in the original reaction system is recovered by distillation under reduced pressure.
The second object of the present invention is to provide a method for preparing 3,3', 4' -biphenyltetracarboxylic dianhydride, comprising: the preparation method of the invention is adopted to prepare 3,3', 4' -biphenyl tetracarboxylic acid, and then the 3,3', 4' -biphenyl tetracarboxylic acid is dehydrated to obtain 3,3', 4' -biphenyl tetracarboxylic dianhydride.
In a preferred embodiment, dehydration is carried out with a dehydrating agent to give 3,3', 4' -biphenyltetracarboxylic dianhydride.
In a further preferred embodiment, the dehydrating agent is selected from at least one of acetic anhydride, propionic anhydride, di-tert-butyl dicarbonate.
The invention provides a method for preparing 3,3', 4' -biphenyl tetracarboxylic dianhydride by using 2-chloroprene as a starting material, generating dendron [4] alkene through lattice coupling and then performing cycloaddition-oxidation aromatization reaction on the dendron [4] alkene and maleic acid. The method aims at the problem that the boiling point of a reaction solvent (tetrahydrofuran with the normal pressure boiling point of 66 ℃) and the boiling point of dendro [4] alkene (with the normal pressure boiling point of 72 ℃) are close to each other and are not easy to separate in the method for synthesizing dendro [4] alkene by the former, improves the synthesis and separation efficiency of dendro [4] alkene by adopting a high boiling point solvent and optimizing the reaction condition, then mixes the dendro [4] alkene with maleic acid, realizes a novel method for preparing 3,3', 4' -biphenyl tetracarboxylic acid by a one-pot method, and further obtains 3,3', 4' -biphenyl tetracarboxylic dianhydride by dehydrating acetic anhydride.
The invention also aims to provide 3,3', 4' -biphenyl tetracarboxylic acid obtained by the preparation method.
The fourth object of the present invention is to provide a 3,3', 4' -biphenyltetracarboxylic dianhydride obtained by the second preparation method of the present invention.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and 3,3', 4' -biphenyl tetracarboxylic dianhydride by adopting branch [4] alkene and maleic acid as raw materials to carry out cycloaddition-oxidation aromatization reaction, the method has novel synthesis strategy, no noble metal catalyst is used, and the total yield is higher;
(2) The cycloaddition-oxidation aromatization reaction atoms have high economy, mild reaction conditions and potential industrialization prospect;
(3) The dendron [4] alkene is prepared from 2-chloroprene serving as a starting material through lattice coupling, and meanwhile, a high boiling point melting point is adopted, and the normal pressure boiling point of the dendron [4] alkene is 72 ℃, so that the preparation of corresponding lattice reagent and transition metal catalyzed coupling reaction in a high boiling point solvent avoids a complicated dendron [4] alkene separation method, and lays a foundation for a subsequent cycloaddition strategy.
Drawings
FIG. 1 shows a schematic diagram of the chemical reaction process of the invention for preparing 3,3', 4' -biphenyltetracarboxylic acid and dianhydride thereof;
FIG. 2 is a chart showing nuclear magnetic resonance hydrogen spectrum of dendron [4] ene prepared according to the present invention;
FIG. 3 is a chart showing the nuclear magnetic resonance hydrogen spectrum of 3,3'4,4' -biphenyltetracarboxylic acid prepared according to the present invention;
FIG. 4 is a high performance liquid chromatography of 3,3'4,4' -biphenyltetracarboxylic acid produced according to the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings and examples, it being understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, but rather as essential modifications and adaptations of the invention to those skilled in the art, based on the teachings herein, may be made without departing from the scope of the invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
[ example 1 ]
400g of dried magnesium turnings, 80g of dibromoethane and 200mL of diglyme (DGDE) are sequentially added into a reaction tank, stirring is carried out by introducing nitrogen, heating is stopped after the magnesium turnings are activated for 20 minutes at about 35 ℃, and 20g of anhydrous zinc chloride and 2800mL of DGDE are sequentially added. 2000mL of DGDE solution containing 900g of 2-chloroprene was then added dropwise to the reaction vessel for 2-3 hours at a reaction temperature of not more than 60℃and gas evolution during the reaction. Then reflux is carried out for 1-2 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dropwise adding 450g of 2-chloroprene, sequentially adding 45g of triphenylphosphine and 18g of copper chloride after the dropwise adding is finished, heating to room temperature for reaction for 28 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction to ensure that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected by cooling, 542.50g of intermediate product dendron [4] alkene is obtained by further rectification, the yield is 51%, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Adding all the dendron [4] alkene, 8kg of ethanol and 1200g of maleic acid obtained in the previous step into a reaction kettle in sequence, reacting for 8 hours at 75 ℃, and distilling to remove the ethanol; then 12kg of distilled water and 500g of potassium carbonate are added in sequence, after the mixture is heated to 75 ℃, 2.7kg of 30wt% hydrogen peroxide is slowly added into the system in a dropwise manner, after the dropwise addition is finished, the temperature is maintained for continuous reaction for 2 hours, then the mixture is cooled to room temperature, and sufficient sodium bisulphite is added to neutralize excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 73%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 2 ]
380g of dried magnesium turnings, 20g of dibromoethane and 180mL of diglyme (DGDE) are sequentially added into a reaction tank, stirring is carried out by introducing nitrogen, heating is stopped after the magnesium turnings are activated for 20 minutes at about 35 ℃, and 50g of anhydrous zinc chloride and 2700mL of DGDE are sequentially added. 1800mL of DGDE solution containing 660 g of 2-chloroprene was then added dropwise to the reaction tank over a period of 2-3 hours, with gas evolved during the reaction. Then reflux is carried out for 1-2 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dripping 1000g of 2-chloroprene, sequentially adding 20g of triphenylphosphine and 9g of copper bromide after dripping, heating to room temperature for reaction for 26 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction so that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected by cooling, 628.60g of intermediate product dendro [4] alkene is obtained by further rectification, the yield is 60 percent, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Sequentially adding dendron [4] alkene, 31.4kg of methanol and 1100g of maleic acid into a reaction kettle, reacting for 6 hours at 55 ℃, and distilling to remove methanol; then 15kg of distilled water and 565.7g of sodium hydroxide are sequentially added, after the mixture is heated to 30 ℃, 2.6kg of 30wt% hydrogen peroxide is slowly added into the system in a dropwise manner, after the dropwise addition is finished, the temperature is maintained for continuous reaction for 2 hours, then the mixture is cooled to room temperature, and sufficient sodium bisulphite is added to neutralize excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 79%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 3 ]
480g of dried magnesium turnings, 89g of dibromoethane and 163mL of diglyme (DGDE) are sequentially added into a reaction tank, stirring is carried out by introducing nitrogen, heating is stopped after activating the magnesium turnings to about 75 ℃ for 20 minutes, and 60g of anhydrous zinc chloride and 2260mL of DGDE are sequentially added. 1600mL of DGDE solution containing 780 g of 2-chloroprene was then added dropwise to the reaction tank for 2-3 hours, with gas evolved during the reaction. Then reflux is carried out for 1-2 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dropwise adding 1335g of 2-chloroprene, sequentially adding 27g of triphenylphosphine and 12g of copper nitrate after the dropwise adding, heating to room temperature for reaction for 30 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction to ensure that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected through cooling, 578.65g of intermediate product dendron [4] alkene is obtained through further rectification, the yield is 55%, and the solvent in the reaction tank is recovered through reduced pressure distillation to obtain DGDE.
Sequentially adding dendron [4] alkene, 12kg ethanol and 1150g maleic acid into a reaction kettle, reacting for 10 hours at 65 ℃, and distilling to remove ethanol; then 17.4kg of distilled water and 515g of sodium carbonate are added in sequence, after the mixture is heated to 50 ℃, 2.5kg of 30wt% hydrogen peroxide is slowly added into the system in a dropwise manner, after the dropwise addition is finished, the reaction is continued for 2 hours at the maintained temperature, then the mixture is cooled to the room temperature, and sufficient sodium bisulphite is added to neutralize the excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 80%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 4]
390g of dried magnesium turnings, 60g of dibromoethane and 600mL of diglyme (DGDE) are sequentially added into a reaction tank, stirring is carried out by introducing nitrogen, heating is stopped after the magnesium turnings are activated for 20 minutes at about 55 ℃, and 80g of anhydrous zinc chloride and 1000mL of DGDE are sequentially added. Then will 2200The solution of DGDE containing 1100g of 2-chloroprene is added dropwise into the reaction tank for 4-5 hours, and gas is released during the reaction. Then reflux is carried out for 1-2 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dropwise adding 1190g of 2-chloroprene, sequentially adding 50g of triphenylphosphine and 20g of copper phosphate after the dropwise adding, heating to room temperature for reaction for 32 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction to ensure that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected by cooling, 539.84g of intermediate product dendron [4] alkene is obtained by further rectification, the yield is 45%, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Adding dendron [4] alkene, 8.5kg of n-propanol and 1000g of maleic acid into a reaction kettle in sequence, reacting for 8 hours at 95 ℃, and distilling to remove the n-propanol; then adding 11kg of distilled water and 600g of potassium carbonate in turn, heating to 44 ℃, slowly dropwise adding 2.3kg of 30wt% hydrogen peroxide into the system, maintaining the temperature for continuous reaction for 2 hours after the dropwise adding is finished, cooling to room temperature, and adding sufficient sodium bisulphite to neutralize excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 73%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 5 ]
To the reaction vessel, 440g of dried magnesium turnings, 70g of dibromoethane and 240mL of diglyme (DGDE) were added in this order, and after stirring under nitrogen and heating to about 66℃to activate the magnesium turnings for 20 minutes, the heating was stopped, and 30g of anhydrous zinc chloride and 2900mL of DGDE were added in this order. 2100mL of DGDE solution containing 940g of 2-chloroprene was then added dropwise to the reaction tank over a period of 3-4 hours, with gas evolved during the reaction. Then reflux is carried out for 1-2 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dropwise adding 660g of 2-chloroprene, sequentially adding 16g of triphenylphosphine and 5g of nickel chloride after the dropwise adding is finished, heating to room temperature for reaction for 27 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction to ensure that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected by cooling, 517.55g of intermediate product dendro [4] alkene is obtained by further rectification, the yield is 46%, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Sequentially adding dendron [4] alkene, 9kg ethanol and 1200g maleic acid into a reaction kettle, reacting at 67 ℃ for 8 hours, and distilling to remove ethanol; then 12kg of distilled water and 545g of sodium carbonate are added in sequence, after the mixture is heated to 58 ℃, 2.2kg of 30wt% hydrogen peroxide is slowly added into the system in a dropwise manner, after the dropwise addition is finished, the temperature is maintained for continuous reaction for 2 hours, then the mixture is cooled to room temperature, and sufficient sodium bisulphite is added to neutralize excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 72%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 6 ]
420g of dried magnesium turnings, 60g of dibromoethane and 200mL of diglyme (DGDE) are sequentially added into a reaction tank, stirring is carried out by introducing nitrogen, heating is stopped after the magnesium turnings are activated for 20 minutes at about 55 ℃, and 40g of anhydrous zinc chloride and 2700mL of DGDE are sequentially added. 2000mL of DGDE solution containing 910g of 2-chloroprene was then added dropwise to the reaction vessel over a period of 2-3 hours, with gas evolved during the reaction. Then reflux is carried out for 1-2 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dropwise adding 950g of 2-chloroprene, sequentially adding 5g of triphenylphosphine and 2g of nickel bromide after the dropwise adding is finished, heating to room temperature for reaction for 30 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction to ensure that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected by cooling, 573.06g of intermediate product dendro [4] alkene is obtained by further rectification, the yield is 53 percent, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Sequentially adding dendron [4] alkene, 8kg methanol and 1280g maleic acid into a reaction kettle, reacting for 8 hours at 45 ℃, and distilling to remove the methanol; then 12kg of distilled water and 550g of sodium hydroxide are sequentially added, after the mixture is heated to 74 ℃, 2.8kg of 30wt% hydrogen peroxide is slowly added into the system in a dropwise manner, after the dropwise addition is finished, the temperature is maintained for continuous reaction for 2 hours, then the mixture is cooled to room temperature, and sufficient sodium bisulphite is added to neutralize excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 81%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 7 ]
430g of dried magnesium turnings, 46g of dibromoethane and 220mL of diglyme (DGDE) are sequentially added into a reaction tank, stirring is carried out by introducing nitrogen, heating is stopped after the magnesium turnings are activated for 20 minutes at about 55 ℃, and 40g of anhydrous zinc chloride and 2900mL of DGDE are sequentially added. 2000mL of DGDE solution containing 920g of 2-chloroprene was then added dropwise to the reaction vessel over a period of 3-4 hours, with gas evolved during the reaction. Then reflux is carried out for 1-2 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dropwise adding 670g of 2-chloroprene, sequentially adding 3g of triphenylphosphine and 1g of nickel sulfate after the dropwise adding is finished, heating to room temperature for reaction for 28 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction so that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected through cooling, 737.10g of intermediate product dendron [4] alkene is obtained through further rectification, the yield is 68%, and the solvent in the reaction tank is recovered through reduced pressure distillation to obtain DGDE.
Sequentially adding dendron [4] alkene, 7.5kg of n-butanol and 1501g of maleic acid into a reaction kettle, reacting for 6 hours at 105 ℃, and distilling to remove the n-butanol; then 7.5kg of distilled water and 1126g of potassium carbonate are added in sequence, 3.0kg of 30wt% hydrogen peroxide is slowly added into the system after the mixture is heated to 47 ℃, the mixture is kept at the temperature for continuous reaction for 2 hours after the addition is completed, then the mixture is cooled to the room temperature, and sufficient sodium bisulphite is added to neutralize the excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 74%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 8 ]
390g of dried magnesium turnings, 45g of dibromoethane and 150mL of diglyme (DGDE) are sequentially added into a reaction tank, stirring is carried out by introducing nitrogen, heating is stopped after the magnesium turnings are activated for 20 minutes at about 55 ℃, and 17g of anhydrous zinc chloride and 2500mL of DGDE are sequentially added. 2000mL of DGDE solution containing 850g of 2-chloroprene was then added dropwise to the reaction vessel over a period of 2-3 hours, with gas evolved during the reaction. Then reflux is carried out for 4 to 6 hours to generate the molar concentration of 1mol L -1 DGDE solution of 2-chloroprene grignard reagent.
Cooling the reaction tank to zero, dropwise adding 1030g of 2-chloroprene, sequentially adding 0.85g of triphenylphosphine and 0.43g of nickel sulfate after the dropwise adding is finished, heating to room temperature for reaction for 30 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction so that the pH value of the reaction solution is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20 mmHg to 30mmHg, volatile matters are collected by cooling, 518.06g of intermediate product dendron [4] alkene is obtained by further rectification, the yield is 51%, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Sequentially adding dendron [4] alkene, 12kg ethanol and 1080g maleic acid into a reaction kettle, reacting for 6 hours at 55 ℃, and distilling to remove ethanol; then 12kg of distilled water and 540g of sodium carbonate are added in sequence, after the mixture is heated to 38 ℃, 2.4kg of 30wt% hydrogen peroxide is slowly added into the system in a dropwise manner, after the dropwise addition is finished, the temperature is maintained for continuous reaction for 2 hours, then the mixture is cooled to room temperature, and sufficient sodium bisulphite is added to neutralize excessive hydrogen peroxide. Then dropwise adding 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is between 2 and 3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyl tetracarboxylic acid, wherein the yield is 88%, and the purity is more than 98.5%. And (3) refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain the product, namely the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ Experimental example ]
1. Nuclear magnetic resonance characterization
The chemical structures of the dendron [4] ene and 3,3', 4' -biphenyltetracarboxylic acid prepared in examples 1 to 8 were verified by nuclear magnetic resonance. Wherein,
taking nuclear magnetic resonance hydrogen spectrum of dendron [4] alkene prepared in example 1 as an example, as shown in fig. 2, in the nuclear magnetic resonance hydrogen spectrum, multiple peaks about delta=6.44 ppm are attributed to carbon No. 2 and carbon No. 5 in the main chain structure, and shift to a low field due to anisotropic effect of ortho double bond structure and de-shielding effect of pi electrons; two broad doublets at δ=5.19 ppm and δ=5.11 ppm are attributed to terminal carbons on the main chain, and split occurs under the influence of mono-hydrogen on adjacent carbons, respectively; the remaining two peaks at δ=5.25 ppm and δ=5.07 ppm are ascribed to carbons on the branches, δ=7.62 ppm being the solvent peak of deuterated chloroform; the single peak with delta=1.56 ppm is water peak, which indicates that the intermediate branch [4] alkene is prepared.
For the final product 3,3', 4' -biphenyltetracarboxylic acid, as shown in fig. 3, in the nuclear magnetic resonance hydrogen spectrum, the broad peaks of δ=12.3 ppm-13.7ppm are attributed to the hydrogen on carboxylic acid, which are shifted to low fields by carbonyl electron withdrawing effect; the double peak at δ=8.09 ppm is attributed to carbon No. 5 and carbon No. 5' on the benzene ring structure, the double peak at δ=8.54 ppm corresponds to carbon No. 2 and carbon No. 2' beside the carbonyl group in the benzene ring structure, the double peak at δ=8.16 ppm at lower chemical shift is attributed to carbon No. 6 and carbon No. 6' on the aromatic structure, δ=2.50 ppm is the solvent peak of deuterated dimethyl sulfoxide, and δ=3.33 ppm is the water peak, which collectively indicates that the final product 3,3', 4' -biphenyltetracarboxylic acid is prepared.
The analysis results of nuclear magnetic resonance hydrogen spectrum diagrams of the dendron [4] ene and the 3,3', 4' -biphenyltetracarboxylic acid prepared in examples 2 to 8 are the same as those of example 1, namely, 3', 4' -biphenyltetracarboxylic acid is synthesized effectively.
2. High performance liquid chromatography characterization
The 3,3', 4' -biphenyltetracarboxylic acid dianhydride prepared in example 1 was hydrolyzed to form 3,3', 4' -biphenyltetracarboxylic acid, and the chromatographic peak having a retention time of 5.5 minutes was analyzed by reverse phase chromatography to obtain 3,3', 4' -biphenyltetracarboxylic acid, and the result was shown in fig. 4. As can be seen in FIG. 4, the corresponding integration area is greater than 98.5%, which indicates that the purity of the 3,3', 4' -biphenyltetracarboxylic dianhydride prepared by the method is better.
The anhydride belongs to an active substance, and can react with a mobile phase and a stationary phase to cause inaccurate analysis results and even damage to a chromatographic column, so that the conventional anhydride purity analysis method is to analyze and confirm the purity of the anhydride by hydrolyzing the anhydride into acid, which is a general method in the industry at present.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (19)
1. A process for preparing 3,3', 4' -biphenyltetracarboxylic acid comprising:
(1) Mixing dendron [4] alkene, maleic acid and a solvent for reaction, and removing the solvent in the system after the reaction is finished to obtain an intermediate product I;
(2) The intermediate product I reacts in the presence of an alkaline substance and an oxidant to obtain an intermediate product II; the alkaline substance is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the oxidant is at least one of hydrogen peroxide, potassium persulfate and ammonium persulfate;
(3) And (3) carrying out post-treatment on the intermediate product II to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
in the step (1), the solvent is at least one selected from alcohol solvents, tetrahydrofuran, ethyl acetate and 1, 4-dioxane; and/or the number of the groups of groups,
in the step (1), the weight ratio of the branch [4] alkene to the solvent is 1 (5-200); and/or the number of the groups of groups,
in the step (1), the weight ratio of the dendron [4] alkene to the maleic acid is 1 (1-4); and/or the number of the groups of groups,
in the step (1), the temperature of the reaction is 45-105 ℃, and the time of the reaction is 4-12 hours.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
In step (1), the alcoholic solvent is selected from alcoholic solvents having a boiling point below 150 ℃; and/or the number of the groups of groups,
in the step (1), the weight ratio of the branch [4] alkene to the solvent is 1 (10-100); and/or the number of the groups of groups,
in the step (1), the weight ratio of the dendron [4] alkene to the maleic acid is 1 (2-2.5).
4. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the weight ratio of the alkaline substance to the branch [4] alkene is (0.6-2): 1; and/or the number of the groups of groups,
the weight ratio of the oxidant to the branch [4] alkene is (2-6): 1.
5. The method of claim 4, wherein the step of determining the position of the first electrode is performed,
the weight ratio of the alkaline substance to the branch [4] alkene is (0.9-1.5): 1; and/or the number of the groups of groups,
the weight ratio of the oxidant to the branch [4] alkene is (4-5): 1.
6. The method according to claim 1, wherein in the step (2), the intermediate product I, the alkaline substance and water are mixed and then subjected to heating treatment, then the oxidant is slowly added dropwise into the system, and the reaction is continued while maintaining the temperature after the dropwise addition is completed, so as to obtain the intermediate product II.
7. The method according to claim 6, wherein the weight ratio of water to dendron [4] ene is (5-40): 1.
8. The method according to claim 7, wherein the weight ratio of water to dendron [4] ene is (10-30): 1.
9. The method of claim 1, wherein in step (3), the post-processing comprises:
(3.1) adding a reducing substance to the intermediate II, the reducing substance being selected from sodium bisulphite and/or sodium hydrosulfite;
(3.2) regulating the pH value of the system to 1-5;
(3.3) filtering and washing to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.
10. The method of claim 9, wherein the step of determining the position of the substrate comprises,
the reducing substance is selected from sodium bisulphite; and/or the number of the groups of groups,
the weight ratio of the reducing substance to the oxidant is 1: (50-500).
11. The method according to any one of claims 1 to 10, wherein the preparation of the dendron [4] ene comprises: 2-chloroprene is used as a starting material, and the dendron [4] alkene is obtained through a coupling reaction of a grignard reagent.
12. The method of claim 11, wherein the method of preparing the dendron [4] ene comprises:
(I) Preparation of 2-chloroprene Format reagent: mixing the dried magnesium chips, an initiator and a solvent in a protective atmosphere, stirring, heating to a set temperature, and adding anhydrous zinc chloride and the solvent; then, dropwise adding a solution containing 2-chloroprene and the solvent into a reaction container, and reacting to obtain a 2-chloroprene format reagent solution;
(II) preparation of dendron [4] ene: dropwise adding 2-chloroprene into the reaction system in the step (I) at the temperature of minus 10 ℃ to 10 ℃, sequentially adding a cocatalyst and a transition metal catalyst after the dropwise adding, heating to react, and carrying out aftertreatment after the reaction is finished to obtain dendron [4] alkene; the catalyst promoter is at least one selected from triphenylphosphine, bis-diphenylethane and bis-diphenylpropane, and the transition metal catalyst is at least one selected from copper salt, nickel salt, iron salt and manganese salt.
13. The method of claim 12, wherein the step of determining the position of the probe is performed,
in step (I), the initiator is selected from at least one of dibromoethane and/or elemental iodine; and/or the number of the groups of groups,
in step (I), the solvent is selected from at least one of diglyme, triglyme, hexamethylphosphoramide; and/or the number of the groups of groups,
in the step (I), heating to 30-90 ℃; heating for 5-50 min; and/or the number of the groups of groups,
in the step (I), a solution containing 2-chloroprene and the solvent is dropwise added to the reaction vessel for 1 to 8 hours and the reaction temperature is controlled not to exceed 70 ℃.
14. The process according to claim 12, wherein in step (I), the weight ratio of magnesium turnings to 2-chloroprene is 1 (1-4); and/or the weight ratio of the initiator to the 2-chloroprene is (0.01-0.2): 1; and/or the weight ratio of the anhydrous zinc chloride to the 2-chloroprene is (0.01-0.2): 1; and/or the molar volume ratio of 2-chloroprene to the total solvent added is (0.1 mol to 5 mol): 1L.
15. The method of claim 12, wherein the step of determining the position of the probe is performed,
in the step (II), the weight ratio of the transition metal salt catalyst to the 2-chloroprene added dropwise in the step (I) is 1 (20-2500); and/or the number of the groups of groups,
in the step (II), the temperature is raised to 10-40 ℃.
16. The method of claim 15, wherein the step of determining the position of the probe is performed,
in the step (II), the weight ratio of the transition metal salt catalyst to the 2-chloroprene added dropwise in the step (I) is 1 (50-2000); and/or the number of the groups of groups,
in the step (II), the temperature is raised to 15-35 ℃.
17. A method for preparing 3,3', 4' -biphenyl tetracarboxylic dianhydride, comprising: the 3,3', 4' -biphenyltetracarboxylic acid is prepared by the preparation method according to any one of claims 1 to 16, and then the 3,3', 4' -biphenyltetracarboxylic acid is dehydrated to obtain the 3,3', 4' -biphenyltetracarboxylic dianhydride.
18. The process according to claim 17, wherein the 3,3', 4' -biphenyltetracarboxylic dianhydride is obtained by dehydration using a dehydrating agent.
19. The method according to claim 18, wherein the dehydrating agent is at least one selected from acetic anhydride, propionic anhydride, and di-tert-butyl dicarbonate.
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| CN101016284A (en) * | 2007-02-13 | 2007-08-15 | 北京益利精细化学品有限公司 | Preparing method of 3,4,3',4'-biphenyltetracarbosylic dianhydride |
| CN101659647A (en) * | 2008-08-26 | 2010-03-03 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
| CN102329289A (en) * | 2011-07-19 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing biphenyltetracarboxylic dianhydride (BPDA) |
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| CN101016284A (en) * | 2007-02-13 | 2007-08-15 | 北京益利精细化学品有限公司 | Preparing method of 3,4,3',4'-biphenyltetracarbosylic dianhydride |
| CN101659647A (en) * | 2008-08-26 | 2010-03-03 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
| CN102329289A (en) * | 2011-07-19 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing biphenyltetracarboxylic dianhydride (BPDA) |
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