CN111909003A - 一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂 - Google Patents
一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂 Download PDFInfo
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- CN111909003A CN111909003A CN202010084223.6A CN202010084223A CN111909003A CN 111909003 A CN111909003 A CN 111909003A CN 202010084223 A CN202010084223 A CN 202010084223A CN 111909003 A CN111909003 A CN 111909003A
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- Prior art keywords
- acid
- oxidative coupling
- potassium
- reaction
- catalyst
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- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002184 metal Chemical class 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000003929 acidic solution Substances 0.000 claims abstract description 5
- ABNCNKAEHACKMO-UHFFFAOYSA-N 1,1'-biphenyl phenol Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C1=CC=CC=C1 ABNCNKAEHACKMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 alkyl phenol Chemical compound 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000011651 chromium Substances 0.000 claims abstract 6
- 150000002736 metal compounds Chemical class 0.000 claims abstract 4
- 239000011734 sodium Substances 0.000 claims abstract 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract 3
- 239000011777 magnesium Substances 0.000 claims abstract 3
- 239000012670 alkaline solution Substances 0.000 claims abstract 2
- 150000005224 alkoxybenzenes Chemical class 0.000 claims abstract 2
- 229910052802 copper Inorganic materials 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 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 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 5
- 239000011572 manganese Substances 0.000 claims 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 4
- 229940045803 cuprous chloride Drugs 0.000 claims 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 4
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 claims 4
- 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 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims 3
- 239000002243 precursor Substances 0.000 claims 3
- 125000001424 substituent group Chemical group 0.000 claims 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 claims 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- 241000872931 Myoporum sandwicense Species 0.000 claims 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 2
- 229960000583 acetic acid Drugs 0.000 claims 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 2
- 150000007514 bases Chemical class 0.000 claims 2
- 229940090961 chromium dioxide Drugs 0.000 claims 2
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 claims 2
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 claims 2
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 claims 2
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 claims 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 239000012362 glacial acetic acid Substances 0.000 claims 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- RCBVKBFIWMOMHF-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1.O[Cr](=O)(=O)O[Cr](O)(=O)=O RCBVKBFIWMOMHF-UHFFFAOYSA-L 0.000 claims 2
- 239000013067 intermediate product Substances 0.000 claims 2
- 239000000395 magnesium oxide Substances 0.000 claims 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims 2
- 238000009987 spinning Methods 0.000 claims 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 2
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- VNNDVNZCGCCIPA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VNNDVNZCGCCIPA-FDGPNNRMSA-N 0.000 claims 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims 1
- HNPVERUJGFNNRV-UHFFFAOYSA-N 3-iodophthalic acid Chemical compound OC(=O)C1=CC=CC(I)=C1C(O)=O HNPVERUJGFNNRV-UHFFFAOYSA-N 0.000 claims 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 239000005708 Sodium hypochlorite Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000001361 adipic acid Substances 0.000 claims 1
- 235000011037 adipic acid Nutrition 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 235000013877 carbamide Nutrition 0.000 claims 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims 1
- 229940077239 chlorous acid Drugs 0.000 claims 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims 1
- 229940117975 chromium trioxide Drugs 0.000 claims 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims 1
- 239000011636 chromium(III) chloride Substances 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims 1
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229960002089 ferrous chloride Drugs 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 229940013688 formic acid Drugs 0.000 claims 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims 1
- UIYIJRAZCUWXTG-UHFFFAOYSA-N n',n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)N(C(C)(C)C)CCN UIYIJRAZCUWXTG-UHFFFAOYSA-N 0.000 claims 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 claims 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 claims 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 claims 1
- HDCAZTXEZQWTIJ-UHFFFAOYSA-N n,n',n'-triethylethane-1,2-diamine Chemical compound CCNCCN(CC)CC HDCAZTXEZQWTIJ-UHFFFAOYSA-N 0.000 claims 1
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 claims 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 claims 1
- MRHPUNCYMXRSMA-UHFFFAOYSA-N nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Ni++] MRHPUNCYMXRSMA-UHFFFAOYSA-N 0.000 claims 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229960002446 octanoic acid Drugs 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims 1
- 239000001230 potassium iodate Substances 0.000 claims 1
- 235000006666 potassium iodate Nutrition 0.000 claims 1
- 229940093930 potassium iodate Drugs 0.000 claims 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 claims 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims 1
- 229960002218 sodium chlorite Drugs 0.000 claims 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims 1
- 239000011697 sodium iodate Substances 0.000 claims 1
- 235000015281 sodium iodate Nutrition 0.000 claims 1
- 229940032753 sodium iodate Drugs 0.000 claims 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 claims 1
- 229940005605 valeric acid Drugs 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000012216 screening Methods 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052728 basic metal Inorganic materials 0.000 abstract 1
- 150000003818 basic metals Chemical class 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 8
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- KJFMXIXXYWHFAN-UHFFFAOYSA-N 4,6-ditert-butylbenzene-1,3-diol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C=C1O KJFMXIXXYWHFAN-UHFFFAOYSA-N 0.000 description 3
- LHZNRPXICKUFLX-UHFFFAOYSA-N CC(C)(C)c1cc(c(O)c(c1O)-c1c(O)c(cc(c1O)C(C)(C)C)C(C)(C)C)C(C)(C)C Chemical group CC(C)(C)c1cc(c(O)c(c1O)-c1c(O)c(cc(c1O)C(C)(C)C)C(C)(C)C)C(C)(C)C LHZNRPXICKUFLX-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CZGOYCFECJIDSU-UHFFFAOYSA-N 2-(3-tert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC=C(O)C(C(C)(C)C)=C1 CZGOYCFECJIDSU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
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Abstract
本发明公开了一种制备新型联苯四酚的氧化偶联合成方法及其催化剂。该类新型联苯四酚具有如通式I所示的结构。在铜、铁、镍、锰、钴、铬、镁、钠、钾等金属化合物、金属配合物或碱式金属配合物,以及酸性溶液或含氧的有机碱性溶液的作用下,用烷氧基苯、烷基苯酚或烷氧基苯酚碳碳键氧化偶联反应得到通式I。本发明公开了新型联苯四酚的氧化偶联制备方法以及催化剂筛选。
Description
技术领域
本发明涉及一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂,包括氧化偶联条件以及催化剂筛选。
背景技术
偶联反应,是由两个有机化学单位进行某种化学反应而得到一个有机分子的过程,其中包括自由基偶联反应,过渡金属催化偶联反应。经典的偶联反应如Suzuki、Heck、Sonogashira、Stille、Kumada、Negishi和Hiyama是有机金属试剂与预活化的卤代烃之间的偶联反应。而卤代烃则需要提前制备,增加了反应步骤和实验流程。此外,贵金属钯的配位化合物Pd(PPh3)4是此类反应最常用的催化剂,其他催化剂包括PdCl2(PPh3)2、PdCl2(MeCN)2等。
氧化偶联反应是指反应物中的低价态的碳原子转化为高价态的碳原子化合物的一类氧化反应,该反应必须在氧化剂的存在下,直接将两个亲核试剂(Nucleophile)进行偶联,能够对烯、炔和芳烃等的C-H键直接进行活化和官能团化。氧化偶联反应的核心部分是催化金属源与氧化剂,常见的氧化剂有氧气、活性二氧化锰、重铬酸钾、高锰酸钾、二价铜盐及其氧化物、双氧水、TBHP、臭氧等。相对于传统的偶联反应,氧化偶联反应具有缩短反应步骤和原子经济性等优点。氧化偶联反应在医药、农药、化工和材料等有机中间体的合成中发挥着日益重要的作用。
廉价金属催化的氧化偶联反应可以追溯到1869年,Glaser报道了可以利用末端炔烃自身氧化偶联制备共轭二炔烃。使用CuCl做为催化剂,在氨水和乙醇的混合溶剂中,在空气中以苯乙炔为原料得到了1,3-二炔。Albert于1953年研究了在K2Cr2O7/H2SO4催化下,各种3,4,6-三烷基苯酚类的氧化偶联反应,得到了不同类型的联苯二酚,产率介于23~76%。在不同氧化剂(K2Cr2O7、过氧化苯甲酰、MCPBA/FeCl3)与反应条件下,等人报道了对羟基苯丙酸酯、3-叔丁基-4-羟基苯丙酸酯等一系列市售化合物的氧化偶合,收率达到22~32%。1962年Hay以O2作为氧化剂用催化量的TMEDA和CuCl来催化端基炔的偶联。Noji用CuCl(OH)TMEDA作催化剂,在二氯甲烷溶液中空气氧化2-萘酚得到了联萘二酚,化学产率为90~96%;Deuβen将2-萘酚和FeCl3在四氢呋喃中回流,产率为54%。此外,还有大量专利文献如US3210384、US481589、WO99/46227A1、WO9946227、JP2002069022、US4101561、US4070383、J.Chem.Soc.C 1971,2967、J.Org.Chem.1983,48,4948等报道了Cu/O2配合物催化的各种烷基取代苯酚氧化偶联制备联苯二酚的反应,产率在35~95%左右。
本发明中发展的一种制备新型联苯四酚的氧化偶联方法以及催化剂具有反应步骤短、原子经济性高、操作简便易于放大合成、收率较高、催化剂价格低廉易得且容易制备等特点。本发明对比了KMnO4、K2Cr2O7、MnO2、CrO3、FeCl3等传统的金属氧化剂与Cu(TMEDA)Cl2/O2、Cu(Et3N)Cl/O2、K3[Fe(CN)6]/O2等金属配合物氧化剂催化下,间苯二酚氧化偶联制备公斤级新型联苯四酚反应结果,并对氧化偶联条件和催化剂进行了优化和筛选。
发明内容
本发明目的是为了开发一种新型联苯四酚及其衍生物骨架的高效氧化偶联合成方法。其特点是:金属廉价易得、金属氧化剂或配合物制备相对简单、后处理步骤少、四酚骨架偶联收率较高和可以放大合成。
本发明所述的新型联苯四酚是一种制备新型联苯四齿亚磷酸酯配体的重要中间体原料。该四酚化合物的其中一种结构表达式,即:2,2’,6,6’-四羟基-3,3’,5,5’-四叔丁基-1,1’-联苯(结构式2)表示如下:
合成结构式2的起始原料为:4,6-二叔丁基间苯二酚,分别使用酸性和碱性的氧化偶联方法,合成路线如下:
酸性体系制备方法
碱性体系制备方法
具体实施方式
下面通过实施例对本发明的以上路线进行具体的描述,有必要指出的是,本实施例只用于对本发明作进一步说明,但并不对本发明构成任何限制。该领域的技术人员可以根据本发明的内容作出一些非本质的改进和调整。
实施例1
酸性体系制备方法
在公斤级合成通风房内,向10L装有防爆式机械搅拌桨、滴液漏斗、防爆式高低温循环、温度探针、回流冷凝器和下泄放料阀门等装置的双层玻璃夹套反应釜中加入4,6-二叔丁基间苯二酚(4.5mol),酸性溶液(3.8L),搅拌至溶解后,向反应釜中滴入定量的金属氧化剂(0.45–6.75mol)和水的澄清溶液(2L)。滴加期间,反应釜有局部放热现象,需用防爆式高低温循环控制好釜内温度。滴加完后,在额定温度(-20–50℃)下搅拌反应1~12小时。反应完成后,当釜内有大量固体颗粒析出时,用布氏漏斗或离心机分批次过滤所得滤饼即为氧化偶联产物,即:2,2’,6,6’-四羟基-3,3’,5,5’-四叔丁基-1,1’-联苯(结构式2);当没有固体析出时,用防爆式旋转蒸发仪旋干溶剂得到粘稠状粗产品,往粗产品中加入一定比例的水或甲醇和水的混合溶液,用机械搅拌桨进行打浆直至析出固体颗粒,过滤后得到产品。两种后处理反应方法产率接近,介于15~75%之间。
表1
实施例2
碱性体系制备方法
在公斤级合成通风房内,向10L装有防爆式机械搅拌桨、滴液漏斗、防爆式高低温循环、温度探针、气体导管、回流冷凝器和下泄放料阀门等装置的双层玻璃夹套反应釜中依次加入部分反应溶剂(3L)、碱性化合物(0.0225–0.9mol)和定量的金属化合剂(0.0225–0.45mol),在室温下均匀搅拌0.5~1个小时;在搅拌期间,往反应液面以下不间断地通入氧气或压缩空气(可由鼓泡判别)。待金属-有机碱配合物形成后,用滴液漏斗往反应釜内缓慢滴加已溶解好的4,6-二叔丁基间苯二酚溶液(4.5mol,3.8L),并一直保持通入氧气或空气。滴加完后,反应溶液在额定温度(25~40℃)下搅拌反应24~48小时。在此期间,由气体所带出的溶剂损耗通过补充溶剂来补偿。反应完成后,当釜内有大量固体颗粒析出时,用布氏漏斗或离心机分批次过滤所得滤饼即为氧化偶联产物,即:2,2’,6,6’-四羟基-3,3’,5,5’-四叔丁基-1,1’-联苯(结构式2);当没有固体析出时,用防爆式旋转蒸发仪旋干溶剂得到粘稠状粗产品,往粗产品中加入一定比例的水或甲醇和水的混合溶液,用机械搅拌桨进行打浆直至析出固体颗粒,过滤后得到产品。两种后处理反应方法产率接近,介于55~92%之间。
表2
Claims (10)
1.一种新型联苯四酚,即通式I所示化学结构式的氧化偶联合成方法以及催化剂。其特征在于:在酸性溶液或含氧的碱性溶液中加入上述前体原料,并加入催化量、等当量或过量的金属化合物或金属配位化合物;其中,所述金属包括:Cu(I)、Cu(II)、Fe(II)、Fe(III)、Ni(II)、Ni(IV)、Mn(III)、Mn(IV)、Mn(VII)、Co(II)、Co(III)、Cr(III)、Cr(VI)、Mg(II)、Na(I)和K(I)。有机碱性化合物可以是:一元胺、二元胺、三元胺、吡啶等。碳碳键氧化偶联的前体原料可以是:烷氧基苯、烷基苯酚或烷氧基苯酚,其结构式如下:
其中,R1,R2,R3的取代基可以是氢;直链或支链(C1-C4)烷基选自甲基、乙基、异丙基、叔丁基;R7和R8的取代基可以是氢或者甲基。此外,当结构式1的取代基R7和R8均为甲基或一半为甲基时,氧化偶联完后,中间产物需要多一步脱甲基得到四酚,还原产率介于95~99%之间,其结构式如下:
2.如权利要求1中所述的酸性溶液可以为浓硫酸、浓盐酸、浓硝酸、膦酸、六氟膦酸、次氯酸、亚氯酸、甲酸、冰乙酸、过氧乙酸、间氯过氧苯甲酸(MCPBA)、乙酸酐、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、己二酸、乙二酸、丙二酸、丁二酸中的任意一种或多种。
3.如权利要求1所述的含氧的溶液中的氧源可以为氧气、空气、臭氧、二羧酸碘苯、过氧化氢、叔丁基过氧化氢(TBHP)、过氧化二苯甲酰、过氧化环己酮、对苯醌、二氯二氰基苯醌(DDQ)、中的任意一种或多种。
4.如权利要求1所述的金属化合物可以为氯化亚铜(CuCl)、氯化铜(CuCl2)、碘化亚铜(CuI)、碘化铜(CuI2)、溴化亚铜(CuBr)、溴化铜(CuBr2)、硫酸铜(CuSO4)、硝酸铜(Cu(NO3)2)、三氟甲磺酸铜(Cu(OTf)2)、氯化亚铁(FeCl2)、三氯化铁(FeCl3)、氧化镍(NiO)、二氧化镍(NiO2)、三氧化二锰(Mn2O3)、活性二氧化锰(MnO2)、高锰酸钾(KMnO4)、三氟化钴(CoF3)、三氧化二钴(Co2O3)、三氧化铬(CrO3)、二氧化铬(CrO2)、二氧化二铬(Cr2O3)、铬酸(H2CrO4)、重铬酸钾(K2Cr2O7)、重铬酸钠(Na2Cr2O7)、氧化镁(MgO)、碘酸钠(NaIO3)、高碘酸钠(NaIO4)、次氯酸钠(NaClO)、亚氯酸钠(NaClO2)、氯酸钠(NaClO3)、高氯酸钠(NaClO4)、碘酸钾(KIO3)、高碘酸钾(KIO4)、次氯酸钾(KClO)、亚氯酸钾(KClO2)、氯酸钾(KClO3)、高氯酸钾(KClO4)、过硫酸钾(K2S2O8)、过硫酸氢钾(KHSO5)中的任意一种或多种。
5.如权利要求1所述的金属配位化合物可以为CuOAc、Cu(OAc)2、Cu(OTf)2、[Cu(NH3)4]SO4、[Cu(NH3)4](OH)2、CuCl(OH)TMEDA、Cu(TMEDA)Cl、Cu(TMEDA)Cl2、Cu(Et3N)Cl2、Cu(DTEDA)Cl2、Cu(morpholine)2Cl2、Cu(PDA)2Cl2、Cu2(TEEDA)2Br2、[Cu(MeCN)4][PF6]、Cu(PPh3)2Cl2、K3[Fe(CN)6]、K4[Fe(CN)6]、K3[Fe(NCS)6]、Na3[Fe(CN)6]、Na4[Fe(CN)6]、Na3[Fe(NCS)6]、Fe(PPh3)Cl、Ni(acac)2、Ni(OAc)2、Ni(CO)4、Mn(acac)2、Mn(OAc)2、Co(acac)2、Co(acac)3、[Co(NH3)3]Cl3、[Co(NH3)6]Cl3、[Co(NO2)3(NH3)3]、Co(OAc)2、CrCl3·6H2O、[Cr(H2O)6]Cl3、[CrCl(H2O)5]Cl2、[CrCl2(H2O)4]Cl、[CrCl2(H2O)4]Cl.2H2O、氯铬酸吡啶盐(PCC)、重铬酸吡啶盐(PDC)、[Mg(ClO4)2]·6H2O中的任意一种或多种。
6.如权利要求1所述的碱性化合物可以为甲胺、乙胺、二甲胺、二乙胺、三甲胺、三乙胺、N,N’-二甲基苯胺、N-甲基苯胺、苯胺、二苯胺、乙二胺(EDA)、N-甲基乙二胺、N,N-二甲基乙二胺(DMAEA)、N,N’-二甲基乙二胺、N,N,N’-三甲基乙二胺、N,N,N’,N’-四甲基乙二胺(TMEDA)、N-乙基乙二胺(EAEA)、N,N’-二乙基乙二胺(DEEN)、N,N-二乙基乙二胺(DEAEA)、N,N,N’-三乙基乙二胺、N,N,N’,N’-四二乙基乙二胺(TEEDA)、N,N-二叔丁基乙二胺、N,N,N’,N’-四甲基丙二胺(TMPDA)、碳酰胺、四氢吡咯、咪唑、吡啶、哌啶、吗啉、氢氧化钾中的任意一种。
7.如权利要求1中所述的一种合成新型联苯四酚(通式I)的氧化偶联合成方法以及催化剂。该氧化偶联方法分为酸性体系制备方法和碱性体系制备方法,按照以下工艺步骤及参数实现:
酸性体系制备方法:
(1).在5~20L玻璃反应釜内,依次加入反应溶剂、酸性溶液和一定比例的金属化合物,催化剂与原料(结构式1)的摩尔比介于0.1~1.5左右,在室温下均匀搅拌0.5~1小时。
(2).随后,往反应釜内缓慢滴加事先溶解好的原料溶液,用高低温循环装置控制好反应釜内温度。滴加完后,在额定温度下搅拌反应1~12小时。
(3).反应完成后,当有大量固体颗粒析出时,过滤所得滤饼即为氧化偶联产品;当没有固体析出时,旋干溶剂得到粘稠状粗产品,使用1~2种以上的良溶剂或不良溶剂对粗产品进行打浆或重结晶,析出固体颗粒,过滤后得到产品。两种后处理方法产率接近,介于15~75%之间。
碱性体系制备方法:
(1).在5~20L玻璃反应釜内,依次加入反应溶剂、碱和一定比例的金属配合物,催化剂与有机碱的摩尔比介于1~10,催化剂与原料(结构式1)的摩尔比介于0.005~0.1左右,在额定温度下均匀搅拌0.5~1小时。
(2).用导气管插至反应液面以下,往釜内不间断地通入氧气或压缩空气。随后,往反应釜内缓慢滴加事先溶解好的原料溶液,用高低温循环装置控制好反应釜内温度。滴加完后,在室温下搅拌反应24~48小时。
(3).反应完成后,停止通入气体,当有大量固体颗粒析出时,过滤所得滤饼即为氧化偶联产品;当没有固体析出时,旋干溶剂得到粘稠状粗产品,使用1~2种以上的良溶剂或不良溶剂对粗产品进行打浆或重结晶,析出固体颗粒,过滤后得到产品。两种后处理方法产率接近,介于55~92%之间。
9.根据权利要求7所述的反应方法,其特征在于,所述溶剂为水、甲醇、乙醇、异丙醇、正丁醇、叔丁醇、二氯甲烷、二氯乙烷、三氯甲烷、苯、甲苯、二甲苯、1,2-二氯苯、乙酸乙酯、二氧六环、四氢呋喃、丙酮、冰乙酸、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的任意一种或多种。
10.根据权利要求7所述的反应方法,其特征在于,所述良溶剂和不良溶剂为水、甲醇、四氢呋喃、乙腈、石油醚、正己烷、正庚烷、乙醚、甲基叔丁基醚、异丙醚、乙二醇、乙二醇二甲醚中的任意一种或多种。
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