CN105622355B - A kind of method of synthesizing phenol class compound - Google Patents
A kind of method of synthesizing phenol class compound Download PDFInfo
- Publication number
- CN105622355B CN105622355B CN201410592980.9A CN201410592980A CN105622355B CN 105622355 B CN105622355 B CN 105622355B CN 201410592980 A CN201410592980 A CN 201410592980A CN 105622355 B CN105622355 B CN 105622355B
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- CN
- China
- Prior art keywords
- gold
- guaiacol
- catalyst
- golden
- chlorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 phenol class compound Chemical class 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 229960001867 guaiacol Drugs 0.000 claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000010931 gold Substances 0.000 claims description 82
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 63
- 229910052737 gold Inorganic materials 0.000 claims description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003003 phosphines Chemical class 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 3
- FYEHYMARPSSOBO-UHFFFAOYSA-N Aurin Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)=C1C=CC(=O)C=C1 FYEHYMARPSSOBO-UHFFFAOYSA-N 0.000 claims description 3
- 241001060848 Carapidae Species 0.000 claims description 3
- 229910003767 Gold(III) bromide Inorganic materials 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- OVWPJGBVJCTEBJ-UHFFFAOYSA-K gold tribromide Chemical compound Br[Au](Br)Br OVWPJGBVJCTEBJ-UHFFFAOYSA-K 0.000 claims description 3
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 description 3
- 238000007789 sealing Methods 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 2
- IJUJVDHUJHWQKP-UHFFFAOYSA-N 2-phenyl-1,3,5-tri(propan-2-yl)benzene Chemical group CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1 IJUJVDHUJHWQKP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- WHQSNFAZTUWRQI-UHFFFAOYSA-N CC(C)(C)[P]C(C)(C)C Chemical compound CC(C)(C)[P]C(C)(C)C WHQSNFAZTUWRQI-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- POZREVIEKHTOCE-UHFFFAOYSA-N [Au](=O)(=O)=O Chemical compound [Au](=O)(=O)=O POZREVIEKHTOCE-UHFFFAOYSA-N 0.000 claims description 2
- PMCCQGMSPIMKIE-UHFFFAOYSA-N [Au].C1(=CC=CC=C1)OP(OC1=CC=CC=C1)OC1=CC=CC=C1.[Cl] Chemical compound [Au].C1(=CC=CC=C1)OP(OC1=CC=CC=C1)OC1=CC=CC=C1.[Cl] PMCCQGMSPIMKIE-UHFFFAOYSA-N 0.000 claims description 2
- GVCNXMYLTJUSDA-UHFFFAOYSA-N [Cl].C1(CCCCC1)P(C1CCCCC1)C1CCCCC1 Chemical compound [Cl].C1(CCCCC1)P(C1CCCCC1)C1CCCCC1 GVCNXMYLTJUSDA-UHFFFAOYSA-N 0.000 claims description 2
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000006269 biphenyl-2-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C(*)C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 150000004074 biphenyls Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- SBOQCPPINFMCBH-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 SBOQCPPINFMCBH-UHFFFAOYSA-N 0.000 claims description 2
- VXIHRIQNJCRFQX-UHFFFAOYSA-K disodium aurothiomalate Chemical compound [Na+].[Na+].[O-]C(=O)CC(S[Au])C([O-])=O VXIHRIQNJCRFQX-UHFFFAOYSA-K 0.000 claims description 2
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 claims description 2
- 229940076131 gold trichloride Drugs 0.000 claims description 2
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 claims description 2
- YVIYNOINIIHOCG-UHFFFAOYSA-N gold(1+);sulfide Chemical compound [S-2].[Au+].[Au+] YVIYNOINIIHOCG-UHFFFAOYSA-N 0.000 claims description 2
- WRZZIMVMWOQUES-UHFFFAOYSA-N gold(1+);triphenylphosphane Chemical compound [Au+].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WRZZIMVMWOQUES-UHFFFAOYSA-N 0.000 claims description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 2
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims description 2
- VENHFCZBHVZHMO-UHFFFAOYSA-N gold;triphenylphosphane Chemical compound [Au].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VENHFCZBHVZHMO-UHFFFAOYSA-N 0.000 claims description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 2
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- MREOOEFUTWFQOC-UHFFFAOYSA-M potassium;5-chloro-4-hydroxy-1h-pyridin-2-one;4,6-dioxo-1h-1,3,5-triazine-2-carboxylate;5-fluoro-1-(oxolan-2-yl)pyrimidine-2,4-dione Chemical compound [K+].OC1=CC(=O)NC=C1Cl.[O-]C(=O)C1=NC(=O)NC(=O)N1.O=C1NC(=O)C(F)=CN1C1OCCC1 MREOOEFUTWFQOC-UHFFFAOYSA-M 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229960001315 sodium aurothiomalate Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 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
- 239000001509 sodium citrate Substances 0.000 claims 2
- HDPAFUGESXMLPZ-UHFFFAOYSA-N C(C)(C)C1(CC(=CC=C1)C(C)C)C=1NC=CN1 Chemical class C(C)(C)C1(CC(=CC=C1)C(C)C)C=1NC=CN1 HDPAFUGESXMLPZ-UHFFFAOYSA-N 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- YNTCPKKNJFIZQT-UHFFFAOYSA-N [Au].C(C)P(CC)CC.[Cl] Chemical compound [Au].C(C)P(CC)CC.[Cl] YNTCPKKNJFIZQT-UHFFFAOYSA-N 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 150000002344 gold compounds Chemical class 0.000 claims 1
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 150000001896 cresols Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- UYXMBPVOGLUKIV-UHFFFAOYSA-N (2-methoxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC=CC=C1OC UYXMBPVOGLUKIV-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- PBHROHRYFHKKSY-UHFFFAOYSA-N 2-[2,6-di(propan-2-yl)phenyl]-1h-imidazole Chemical class CC(C)C1=CC=CC(C(C)C)=C1C1=NC=CN1 PBHROHRYFHKKSY-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- SCJFMBCXOLDHCO-UHFFFAOYSA-N C(C)P(CC)CC.[Cl] Chemical compound C(C)P(CC)CC.[Cl] SCJFMBCXOLDHCO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 244000297179 Syringa vulgaris Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- IQARQEQNXROFNO-UHFFFAOYSA-N gold;pyridine Chemical compound [Au].C1=CC=NC=C1 IQARQEQNXROFNO-UHFFFAOYSA-N 0.000 description 1
- MZYVNHPNOJJEIY-UHFFFAOYSA-N hexan-2-ylphosphane Chemical compound CCCCC(C)P MZYVNHPNOJJEIY-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method of synthesizing phenol class compound, belongs to organic synthesis field.The present invention is used carries out hydrogenation deoxidation reaction containing Au catalyst to guaiacol or alkyl guaiacol, realizes the high selectivity of phenol compound, specially：Guaiacol or alkyl guaiacol solution are dissolved into organic solvent, Au catalyst will be contained to be added in guaiacol or alkyl guaiacol solution, it seals rear substitution and removes oxygen, finally it is passed through the hydrogen no more than 30MPa, range of reaction temperature is 473~873K, and the phenol compound is made in 1~12h of reaction.The invention has the advantages that having used Au catalyst, keep the selectivity of phenol compound in reaction product very high, and almost without phenyl ring saturated products.For reaction temperature in room temperature~873K, guaiacol or alkyl guaiacol can realize complete conversion, and all phenol of product and its alkyl derivative quickly.Catalyst repeat performance in batch still reaction is preferable, and can long-play on a fixed bed.
Description
Technical field
The present invention relates to organic synthesis field, more particularly to a kind of method of synthesizing phenol class compound.
Background technology
Lignin is the part in biomass lignocellulosic composition, and proportion is larger.Lignin is mainly by three
Kind structural unit is constituted：P-hydroxyphenyl class, guaiaci lignum base class and lilac base class.With the continuous depth to lignin Study on Cleavage
Enter, the post-processings such as lignin pyrolysis product hydro-upgrading also become a highly important part in current regenerative resource research.
Currently, in the research of lignin pyrolysis product after-treatment, people are usually using lignin structure unit chemical combination
Object adds the reactions such as hydrogen as model compound to study it.Guaiacol is exactly one of common several model compounds.
R.N.Olcese et al. carries out guaiacol hydrotreating in fixed bed using Fe/SiO2 catalyst with reaction temperature 673K,
Include phenol, benzene derivate and cresols in its obtained product, yield is respectively 34%, 38% and 12%.Junming
Sun etc. carries out hydrotreating at 723K using Pt/Fe/C catalyst to guaiacol, and the yield of phenol product is 80%.Van
Ngoc Bui et al. have studied and CoMoS/Al2O3Performance of the catalyst in guaiacol hydrogenation reaction.When using CoMoS/
ZrO2As catalyst, reaction temperature be 573K when, primary product be phenol and phenyl ring saturated products, yield is respectively 56% He
30%；When using CoMoS/Al2O3As catalyst, reaction temperature be 573K when, primary product be phenol, cresols, phenyl ring saturation
Product and catechol, yield are respectively 32%, 26%, 13% and 10%.Sin-Kuan Wu et al. are catalyzed using NiP/SiO2
Agent carries out hydrotreating to guaiacol, and primary product is benzene derivate, phenol and cresols, and yield is respectively 36%, 12%
With 6%.Cho Rim Lee et al. researchs Pt, Pd, Rh and Ru are supported on SiO2-Al2O3Supported catalyst is in guaiacol
Performance in hydrogenation reaction.When reaction temperature 523K, reaction product is hexamethylene and its derivative, selectivity 100%.
In studying at present the hydrogenation deoxidation of guaiacol, product distribution is mostly more dispersed, generally includes phenol
Close object, benzene derivate and phenyl ring saturated products.There is also the reaction time is long and the problems such as reaction temperature is high in terms of reaction condition.
The present invention uses nano catalyst to carry out hydrotreating to guaiacol for the first time, and product is phenol chemical combination
Object, selectivity of product are relatively simple.Simultaneous reactions temperature, reaction pressure and reaction time are more suitable.
Invention content
The present invention provides a kind of method preparing phenol compound with high selectivity by guaiacol, and feature exists
In：Using nano catalyst to guaiacol hydrotreating, the highly selective of phenol product is realized.
A kind of method of synthesizing phenol class compound of the present invention, using containing Au catalyst to guaiacol or alkyl guaiaci lignum
Phenol carries out hydrogenation deoxidation reaction, realizes the high selectivity of phenol compound, specially：
Guaiacol or alkyl guaiacol solution are dissolved into organic solvent, Au catalyst will be contained and be added to guaiaci lignum
In phenol or alkyl guaiacol solution, sealing rear substitution removes oxygen, is finally passed through the hydrogen no more than 30MPa, reaction temperature
The phenol compound is made in ranging from 473~873K, 1~12h of reaction；
The amount containing Au catalyst is the 0.1~40% of the quality of guaiacol or alkyl guaiacol；
The organic solvent is：Benzene, toluene, hexamethylene, n-tetradecane or hexadecane.
Described containing Au catalyst is that the load type gold catalyst that nanogold particle is loaded to carrier is loaded by aurosol,
Or the load type gold catalyst prepared by deposition-precipitation method or equi-volume impregnating using gold-containing solution；The load capacity of gold is to urge
Between 0.001wt%~5wt% of agent quality；
The carrier be titanium oxide, zirconium oxide, aluminium oxide, silica, activated carbon or TS-1 zeolite molecular sieves at least
It is a kind of.
It is the compound containing gold to prepare the golden raw material that catalyst uses：Tetra chlorauric acid, potassium chloroaurate, sodium aurothiomalate, gold
Smart tricarboxylic acids, aurin tricarboxyli acid (ATA) ammonium salt, phenolic aldehyde auramine, gold monochloride, gold trioxid, trichlorine (pyridine) gold, gold trichloride,
Two gold medal (I) of [bis- (diphenylphosphine) ethane of 1,2-] dichloro, bis- (chlorine gold (I)) bis- (diphenylphosphine) methane, tetrachloro golden (III) acid
The sour lithium of sodium, tetrachloro golden (III), tetra chlorauric acid ammonium, gold potassium bromide, gold hydroxide, chlorine (dimethyl vulcanization) golden (I), tetrabromo gold
Acid, gold bromide, aurous sulfide, aurous iodide, (dimethylphenylphosphine) chlorauride, 1- sulfydryls-(triethylene glycol) methyl ether function
Change solution of gold nanoparticles, three (triphenylphosphine gold) oxygen tetrafluoro boric acids, aurous cyanide, lauryl mercaptan and is functionalized Jenner's grain of rice
Son, n-octyl mercaptan functionalization gold nanoparticle, chlorine [bis- (2,4,6- trimethylphenyls) imidazoles -2- subunits of 1,3-] golden (I), chlorine [2-
(di-t-butyl phosphorus) diphenyl] gold, chlorine [three (p-trifluoromethyl phenyl) phosphines] golden (I), chloroformyl fund, chlorine [three (p-methylphenyls)
Phosphine] golden (I), chlorine [three (o-tolyl) phosphines] golden (I), chlorine (triethyl phosphine) golden (I), chlorine (tricyclohexyl phosphine) changes golden (I), chlorine
(triphenyl phosphorous acid) gold, (11- mercapto-undecanoics base) four (ethylene glycol) functionalization gold nanoparticle, (acetonitrile) [(2- biphenyl)
Di-t-butyl phosphine] hexafluoro-antimonic acid golden (I), 1,3- bis- (2,6- diisopropyl phenyl imidazoles -2- subunits) gold (I) acyl chlorides, bis- rings of 2-
Hexyl phosphine -2 ', bis- (fluoroform sulphonyl) imines of 4 ', 6 '-tri isopropyl biphenyls gold (I), [bis- (fluoroform sulphonyl) imines]
(triphenylphosphine) gold (I) (2:1) toluene adduct, chlorine [2- dicyclohexyls (2 ', 4 ', 6 '-tri isopropyl biphenyl base) phosphine] gold
(I), at least one of chlorine [three (2,4- di-tert-butyl-phenyls) phosphorous acid] gold and nanogold particle.
When preparing Au catalyst using deposition-precipitation method, the solution of gold-containing compound is added dropwise to containing carbonate, sulfuric acid
PH value is adjusted in root or solution hydroxy to keep in 1~13 range, then according to gold and the mass ratio 0.0001 of carrier~
20wt% is added carrier and adjusts pH value and be maintained in 1~13 range, mixture stirred at a temperature of room temperature is to 423K 1min~
It is filtered, washed after 72h to roasting 1min~10h between dry 1min~72h, 273K~773K between neutral, 273K~473K.
When preparing Au catalyst using the infusion process, by the gold-containing compound of a concentration of 0.0001wt%~50wt%
It is dissolved in water, formic acid, acetic acid, propionic acid, methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol and is configured to gold solution, according still further to gold and carrier
Mass ratio 0.0001wt%~20wt%, carrier is added in gold solution, stand or stirring 1min~72h after 273K~
Dry 1min~72h between 473K, and 1min~10h is roasted between 273K~773K.
When preparing nano gold sol load type gold catalyst, nano gold sol is adjusted into pH value in 1~13 range, then
Carrier is added in aurosol solution according to mass ratio 0.0001wt%~20wt% of gold and carrier and is adjusted to pH value
Then same range stirs 1min~72h, pH is adjusted again to 1~13 range after carrier can also be added in nano-Au solution
It is interior, it is filtered, washed to roasting 1min~10h between dry 1min~72h, 273K~773K between neutral, 273K~473K.
Gold-containing compound is dissolved when preparing nano gold sol, and into solution be added stabilizer, reducing agent, room temperature~
1min~12h is handled at a temperature of 423K.
When preparing nano gold sol, by the gold-containing compound of a concentration of 0.0001wt%~50wt% be dissolved in water, formic acid,
It is configured to gold solution in a kind of solvent in acetic acid, propionic acid, methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, according still further to gold and citric acid
The molar ratio 1 of sodium (reducing agent, stabilizer)：100:~2000, by citric acid under strong stirring condition between 273K~373K
Sodium (reducing agent) is added in gold solution, and solution boiling 1min~10min after reducing agent is added.
Advantages of the present invention：The present invention refers to a kind of by guaiacol, the preparation of alkyl guaiacol hydrogenation deoxidation
The method of phenol compound.Advantage is to have used Au catalyst, makes the selectivity of phenol compound in reaction product very
Height, and almost without phenyl ring saturated products.For reaction temperature in room temperature~873K, guaiacol or alkyl guaiacol can be very
It is fast to realize conversion, and all phenol of product and its alkyl derivative completely.Catalyst is reused in batch still reaction
Better performances, and can long-play on a fixed bed.
Specific implementation mode
Golden content can be measured by ICP or XRF in Au catalyst of the present invention, usual for load type gold catalyst
Golden carrying capacity can be obtained preferable effect within 20wt.%.Gold is set to have in Muffle kiln roasting Au catalyst first
Effect is attached to carrier surface.A certain amount of Au catalyst is added in reactant solution, sealing rear substitution removes oxygen, finally
It is passed through the hydrogen of certain pressure (within 30MPa).By temperature of reactor control in 373K between 873K, reaction a period of time with
After sample, calculate feed stock conversion and each product yield.
n0：Reflect the guaiacol mole (mol) in raw material；
n1：After reaction in reaction solution guaiacol mole (mol).
∑n2：The summation of phenol compound mole.
Embodiment 1
Deposition-precipitation method prepares Supported Gold Particle Catalysts：60ml chlorauric acid solutions are added in 1g titania supports
In, a concentration of 0.83mmol/L of gold chloride.The NaOH solution that 0.2mol/L is added dropwise in mixture in the state of stirring adjusts pH value
It 9.0, keeps pH value that 12h is stirred at room temperature, then stops stirring and stand 12h.Mixture is finally filtered, and uses deionization
Water washing filter cake to filtrate is neutrality.Filter cake dry 12h at 380K.The quality of Gold Samples is with carrier quality ratio
0.74wt%.Au catalyst is finally roasted to 2h in Muffle furnace, cooling is spare under 623K.
It takes 0.30g catalyst to be placed in high pressure intermittent kettle reactor, the guaiacol of 1.50g is then added into reaction kettle
With 25ml toluene.Reaction kettle is sealed, 3.0MPa hydrogen is passed through after being purged 3 times using nitrogen.Reaction kettle is warming up to 573K, is stirred
Mix rate 700rpm sustained responses 4h.
Embodiment 2
Reaction time is 7h, and method for preparing catalyst, feeding quantity and reaction condition are substantially the same manner as Example 1.
Embodiment 3
Reaction time 12h, method for preparing catalyst, feeding quantity and reaction condition are substantially the same manner as Example 1.
The reaction result of Examples 1 to 3 is shown in Table 1.
1. Examples 1 to 3 reaction result summary sheet of table
Embodiment 4
Reaction temperature is 523K, and method for preparing catalyst, feeding quantity and reaction condition are substantially the same manner as Example 1.
Embodiment 5
Reaction temperature is 673K, and method for preparing catalyst, feeding quantity and reaction condition are substantially the same manner as Example 1.
The reaction result of embodiment 4,5 is shown in Table 2.
The reaction result of 2. embodiment 4,5 of table summarizes
Embodiment 6
Reaction raw materials are to propyl guaiacol 2.02g, method for preparing catalyst, feeding quantity and the same embodiment of reaction condition
1.Reaction result is shown in Table 3.
3. embodiment of table, 6 reaction result
Embodiment 7
Catalyst amount 0.05g, method for preparing catalyst, feeding quantity and reaction condition are substantially the same manner as Example 1.
Embodiment 8
Catalyst amount 0.6g, method for preparing catalyst, feeding quantity and reaction condition are substantially the same manner as Example 1.
The reaction result of embodiment 7,8 is shown in Table 4.
The reaction result of 4. embodiment 7,8 of table summarizes
Embodiment 9
Equi-volume impregnating prepares Supported Gold Particle Catalysts：It is water-soluble that 0.8ml gold chlorides are added in 1g titanium dioxide carriers
In liquid, a concentration of 0.032mol/L of gold chloride.1h is stirred at room temperature, then mixture dry 12h at 380K.Gold Samples
Quality and carrier quality ratio be 0.5wt%.Au catalyst is finally roasted to 2h in Muffle furnace, cooling is spare under 623K.
Feeding quantity and reaction condition are same as Example 1.Reaction result is shown in Table 5.
The reaction result of 5. embodiment 9 of table summarizes
Embodiment 10
Golden supported catalyst is prepared using nano gold sol.
When preparing nano gold sol, solution 1 is the aqueous solution of chloraurate that 80ml is heated to a concentration of 0.32mmol/L of 333K.
Solution 2 is 5ml 1wt.% tannic acid aqueous solutions, 5ml 25mmol/L K2CO3Aqueous solution, 4ml 1wt.% trisodium citrate dihydrates
The mixture of aqueous solution and 6ml deionized waters.Solution 2 is also heated at 333K.Solution 2 is slowly added into the solution being vigorously stirred
Solution 3 is obtained in 1.Solution 3 is boiled into 2min postcoolings, solution is nano gold sol, and particle diameter is about 3nm.
When preparing nano gold sol load type titanium dioxide catalyst, it is molten to adjust 100ml nanogold using 1M salpeter solutions
Glue adjusts pH=2, and then 1g titanium dioxide is added in aurosol solution and pH value is adjusted to same range, is then stirred
2h.After being filtered, washed to neutrality 2h is roasted between 383K drying 12h and at 623K.
Catalyst, reactant addition and reaction condition are same as Example 1.Reaction result is shown in Table 6.
The reaction result of 6. embodiment 10 of table summarizes
Comparative example
Using the titanium oxide that catalyst is unsupported gold, feeding quantity and reaction condition are the same as embodiment 1.
7. comparative example reaction result of table
Guaiacol and alkyl guaiacol can be made efficiently to turn using Au catalyst it can be seen from the data of table 1~7
Phenol compound is turned to, product species are relatively simple, and phenyl ring is not saturated substantially.Temperature raising can improve reaction rate,
Guaiacol can be totally converted after 400oC reactions 4h, and the selectivity of phenol compound is 81% or more.
Embodiments of the present invention are not limited by above-mentioned fact Example, other any Spirit Essences without departing from the present invention
With under principle made by changes, modifications, substitutions, combinations, simplifications, should be equivalent substitute mode, be included in the present invention
Within protection domain.
Claims (6)
1. a kind of method of synthesizing phenol class compound, it is characterised in that more created to guaiacol or alkyl using containing Au catalyst
The wooden phenol carries out hydrogenation deoxidation reaction, realizes the synthesis of phenol compound, specially：
Guaiacol or alkyl guaiacol solution are dissolved into organic solvent, will contain Au catalyst be added to guaiacol or
In alkyl guaiacol solution, sealing rear substitution removes oxygen, is finally passed through the hydrogen no more than 30MPa, range of reaction temperature
The phenol compound is made for 473 ~ 873K, 1 ~ 12h of reaction；
The amount containing Au catalyst is the 0.1 ~ 40% of the quality of guaiacol or alkyl guaiacol；
The organic solvent is：Benzene, toluene, hexamethylene, n-tetradecane or hexadecane；
Described containing Au catalyst is that the load type gold catalyst that nanogold particle is loaded to carrier is loaded by aurosol, golden
Between load capacity is the wt% of 0.001 wt% ~ 5 of catalyst quality.
2. the method for synthesizing phenol class compound according to claim 1, it is characterised in that：The carrier is titanium oxide, oxygen
Change at least one of zirconium, aluminium oxide, silica, activated carbon or TS-1 zeolite molecular sieves.
3. the method for synthesizing phenol class compound according to claim 1, it is characterised in that：It is former to prepare the gold that catalyst uses
Material is the compound containing gold：Tetra chlorauric acid, potassium chloroaurate, sodium aurothiomalate, aurin tricarboxyli acid (ATA), aurin tricarboxyli acid (ATA) ammonium salt, phenolic aldehyde
Auramine, gold monochloride, gold trioxid, trichlorine（Pyridine）Gold, gold trichloride, two gold medal of [bis- (diphenylphosphine) ethane of 1,2-] dichloro
(I), bis- (chlorine gold (I)) bis- (diphenylphosphine) methane, the sour sodium of tetrachloro golden (III), the sour lithium of tetrachloro golden (III), tetra chlorauric acid ammonium, four
Potassium auric bromide, gold hydroxide, chlorine (dimethyl vulcanization) golden (I), four auribromohydric acids, gold bromide, aurous sulfide, aurous iodide, (diformazan
Base Phenylphosphine) chlorauride, 1- sulfydryls-(triethylene glycol) methyl ether functionalization solution of gold nanoparticles, three (triphenylphosphine gold) oxygen
Tetrafluoro boric acid, aurous cyanide, lauryl mercaptan functionalization gold nanoparticle, n-octyl mercaptan functionalization gold nanoparticle, chlorine [1,3-
Bis- (2,4,6- trimethylphenyls) imidazoles -2- subunits] golden (I), chlorine [2- (di-t-butyl phosphorus) diphenyl] gold, [three (to fluoroform for chlorine
Base phenyl) phosphine] golden (I), chloroformyl fund, chlorine [three (p-methylphenyl) phosphines] golden (I), chlorine [three (o-tolyl) phosphines] golden (I), chlorine
(triethyl phosphine) gold (I), chlorine (tricyclohexyl phosphine) change golden (I), chlorine (triphenyl phosphorous acid) gold, (11- mercapto-undecanoics base) four
(ethylene glycol) is functionalized gold nanoparticle, (acetonitrile) [(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid golden (I), the bis- (2,6- of 1,3-
Diisopropyl phenyl imidazoles -2- subunits) golden (I) acyl chlorides, 2- dicyclohexylphosphontetrafluoroborates -2 ', 4 ', 6 '-tri isopropyl biphenyls gold (I) is double
(fluoroform sulphonyl) imines, [bis- (fluoroform sulphonyl) imines] (triphenylphosphine) golden (I) and toluene adduct, chlorine [2- bis-
Cyclohexyl (2 ', 4 ', 6 '-tri isopropyl biphenyl base) phosphine] golden (I), chlorine [three (2,4- di-tert-butyl-phenyls) phosphorous acid] Jin Jina
At least one of rice gold particle；
In [bis- (fluoroform sulphonyl) imines] (triphenylphosphine) gold (I) and toluene adduct, [bis- (fluoroform sulphonyl)
Imines] (triphenylphosphine) golden (I) and toluene mole ratio be 2：1.
4. the method for synthesizing phenol class compound according to claim 1, it is characterised in that：Prepare nano gold sol support type
When Au catalyst, nano gold sol is adjusted into pH value in 1 ~ 13 range, then according to the mass ratio 0.0001 of gold and carrier
Carrier is added in aurosol solution and pH value is adjusted to same range by the wt% of wt% ~ 20, then stirs 1min ~ 72h, warp
It is filtered, washed to dry 1min ~ 72h between neutral, 273K ~ 473K, 1min ~ 10h is roasted between 273K ~ 773K.
5. the method for synthesizing phenol class compound according to claim 4, it is characterised in that：It will contain when preparing nano gold sol
Gold compound dissolves, and stabilizer, reducing agent are added into solution, and 1min ~ 12h is handled at a temperature of room temperature ~ 423K.
6. the method for synthesizing phenol class compound according to claim 5, it is characterised in that：It, will when preparing nano gold sol
The gold-containing compound of a concentration of wt% of 0.0001 wt% ~ 50 is dissolved in water, formic acid, acetic acid, propionic acid, methanol, ethyl alcohol, propyl alcohol, fourth
It is configured to gold solution in a kind of solvent in alcohol, amylalcohol, according still further to the molar ratio 1 of gold and sodium citrate：100:~ 2000,
Sodium citrate is added in gold solution under strong stirring condition between 273K ~ 373K, be added reducing agent after solution boiling 1min ~
10min。
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| CN109772333B (en) * | 2017-11-15 | 2022-03-18 | 中国科学院大连化学物理研究所 | Metal surface coating catalyst directly prepared from solid and application thereof |
| CN109772332B (en) * | 2017-11-15 | 2022-03-18 | 中国科学院大连化学物理研究所 | Supported metal catalyst directly prepared from solid and application thereof |
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