CN108586540A - Ruthenium（II）The catalytic reduction method of Lian oxazoline pyridine compounds and preparation method thereof and aromatic nitro compound - Google Patents
Ruthenium（II）The catalytic reduction method of Lian oxazoline pyridine compounds and preparation method thereof and aromatic nitro compound Download PDFInfo
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- CN108586540A CN108586540A CN201810441475.2A CN201810441475A CN108586540A CN 108586540 A CN108586540 A CN 108586540A CN 201810441475 A CN201810441475 A CN 201810441475A CN 108586540 A CN108586540 A CN 108586540A
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- Prior art keywords
- ruthenium
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- lian
- pyridine compounds
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- -1 aromatic nitro compound Chemical class 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 40
- PZVKSFBOPQYWGM-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;pyridine Chemical class C1CN=CO1.C1=CC=NC=C1 PZVKSFBOPQYWGM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 240000000233 Melia azedarach Species 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 241001025261 Neoraja caerulea Species 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000010668 complexation reaction Methods 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical class [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 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 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000012327 Ruthenium complex Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000003809 water extraction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical class NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 150000002918 oxazolines Chemical class 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- 235000004237 Crocus Nutrition 0.000 description 1
- 241000596148 Crocus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZBQZBWKNGDEDOA-UHFFFAOYSA-N eosin B Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC([N+]([O-])=O)=C(O)C(Br)=C1OC1=C2C=C([N+]([O-])=O)C(O)=C1Br ZBQZBWKNGDEDOA-UHFFFAOYSA-N 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- UMHSKYSHOIGDPE-UHFFFAOYSA-N pyridine;quinoline Chemical class C1=CC=NC=C1.N1=CC=CC2=CC=CC=C21 UMHSKYSHOIGDPE-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of rutheniums（II）The catalytic reduction method of Lian oxazoline pyridine compounds and preparation method thereof and aromatic nitro compound, the ruthenium is (shown in the structure such as formula (I) of II) Lian oxazoline pyridine compounds, (II) Lian oxazoline pyridine compounds have excellent stability and catalytic performance for the ruthenium, the preparation method of ruthenium (II) connection oxazoline pyridine compounds has the characteristics that easy to operate, equipment requirement is low and yield is high simultaneously, further enables the ruthenium (II) connection oxazoline pyridine compounds to be catalyzed aromatic nitro compound in large quantity and is converted to aromatic amine compound.
Description
Technical field
The present invention relates to ruthenium complexes, and in particular, to a kind of ruthenium (II) Lian oxazoline pyridine compounds preparation methods
And the catalytic reduction method of aromatic nitro compound.
Background technology
In recent years, it is seen that photocatalytic redox activation organic molecule method has been developed as Synthetic Organic Chemistry
Important means, since it utilizes sunlight, green, by the attention of numerous chemists the advantages that pollution-free and low consumption, and
It is developing progressively as important one of the Disciplinary Frontiers of organic chemistry.In general, it is seen that the principle of photocatalytic redox is logical
It is living under conditions of visible light to cross metal complex (the predominantly complex of ruthenium and iridium), organic dyestuff and photosensitizer
Change organic substrates, generates single electron reactive intermediate, and then oxidative coupling occurs with other substrates, form new chemical bond.
Due to cheap (price of complex of iridium is probably 12.6 times/mmol of ruthenium complex) of ruthenium, more changed
The favor of scholars.Ru-polypyridine complex is due to its unique optical physics and spectrochemical property, longer fluorescence lifetime
And quantum yield, while under the action of visible light excitation state than ground state ruthenium have higher oxidation-reduction potential and it is lower also
Former current potential can play stronger oxidation and reduction in catalytic cycle, thus it is anti-to be widely used in visible light catalytic
Ying Zhong；If it is used as photochemical catalyst in photocatalytic water, photosensitizer is made in solar cells, and photocatalysis is used as in organic synthesis
Agent etc..Therefore, the synthesis of more pyridines of ruthenium and the like becomes weight in inorganic chemistry, Coordinative Chemistry and organic chemistry with application
One of research direction wanted, developing the ruthenium base complex with high activity becomes the hot spot of research.
Aromatic amine compound is the intermediate of a kind of important starting material and aminated compounds, is mainly used to synthesize agriculture
Medicine, medical product etc..With gradually increasing the demand of aromatic amine compound in production, this makes research synthesis aromatic amine
Closing object becomes particularly important.Original aromatic nitro compound is gone back to synthesize aromatic amine compounds be Chemical Manufacture and reality by catalysis
Test common important synthetic method in research.Currently, the primary synthetic methods of aromatic amine compounds are to utilize fragrant nitration
It closes object to be made by restoring, but generally requires strong acid system and high temperature process, there are poor selectivities, consume energy the shortcomings of high.
Invention content
The object of the present invention is to provide a kind of ruthenium (II) Lian oxazoline pyridine compounds and preparation method thereof and fragrant nitre
The catalytic reduction method of based compound, the ruthenium (II) Lian oxazoline pyridine compounds have excellent stability and catalytic performance,
The preparation method of ruthenium (II) connection oxazoline pyridine compounds has the characteristics that easy to operate, equipment requirement is low and yield is high simultaneously,
Further enabling the ruthenium, (II) Lian oxazolines pyridine compounds are catalyzed aromatic nitro compound and are converted to virtue in large quantity
Fragrant amine compounds.
To achieve the goals above, the present invention provides a kind of ruthenium (II) Lian oxazoline pyridine compounds, the ruthenium (II) connection
Shown in the structure of oxazoline pyridine compounds such as formula (I),
Present invention provides a kind of preparation method joining oxazoline pyridine compounds such as above-mentioned ruthenium (II), the preparation sides
Method is：In the presence of protecting gas, by presoma Ru (L1)2X2, 2,2- bipyridyls complexation reaction is carried out in solvent, then plus
Enter excessive saturation hexafluorophosphoric acid salting liquid and carries out precipitation reaction so that ruthenium (II) connection oxazoline pyridine compounds are made；Wherein, L1
4,4,4', 4'- tetramethyl -2,2'- bisoxazolines are represented, X represents halogen.
It being used to prepare the ruthenium as above (presoma of II) Lian oxazoline pyridine compounds, before this present invention also provides a kind of
Drive body Ru (L1)2X2Structure such as formula (II) shown in,
Wherein, L14,4,4', 4'- tetramethyl -2,2'- bisoxazolines are represented, X represents halogen.
Invention further provides a kind of preparation methods such as above-mentioned presoma, which is characterized in that including：It is being catalyzed
In the presence of agent and protection gas, by L1、RuX3Complexation reaction is carried out in solvent, and acetone is then added and is recrystallized；Wherein,
Catalyst is made of lithium salts and zinc, L14,4,4', 4'- tetramethyl -2,2'- bisoxazolines are represented, X represents halogen.
Invention still further provides a kind of catalytic reduction methods of aromatic nitro compound, which is characterized in that catalysis
Restoring method is：It, will be fragrant using such as above-mentioned ruthenium (II) connection oxazoline pyridine compounds as catalyst in the presence of solvent and light
Aromatic nitro compounds and reducing agent carry out catalysis reaction to obtain aromatic amine compound.
Through the above technical solutions, the present invention is first by using lithium salts and zinc as catalyst, by L1、RuX3Be coordinated anti-
Presoma Ru (L should be made1)2X2；Then presoma Ru (L1)2X2, 2,2- bipyridyls, hexafluorophosphate carry out reacting obtained ruthenium
(II) Lian oxazolines pyridine compounds [Ru (L1)2(bpy)](PF6)2, bpy expression 2,2- bipyridyls.Ruthenium (the II) Lian oxazolines
The preparation process of pyridine compounds has the following advantages that：1) experimentation it is simple, it is low for equipment requirements and cost-effective, can carry out
Batch production；2) simple for process, have preferable yield；3) ruthenium (II) Lian oxazolines pyridine compounds in low temperature, be protected from light condition
Under can be stabilized.
In addition, in this application, using ruthenium, (II) Lian oxazolines pyridine compounds can be efficiently by fragrant nitre as catalyst
Based compound catalysis is reduced to aromatic amine chemical combination；The catalytic process has the characteristics that simple for process, easy to operate, condition temperature, into
And make it have excellent application prospect.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Attached drawing 1 is the mono-crystalline structures figure of product in embodiment 1；
Attached drawing 2 is the hydrogen nuclear magnetic resonance spectrogram of product in embodiment 1；
Attached drawing 3 is the carbon-13 nmr spectra figure of product in embodiment 1；
Attached drawing 4 is the uv absorption spectra of product in embodiment 1；
Attached drawing 5 is the mass spectrogram of product in embodiment 1；
Fig. 6 is a kind of ruthenium (reaction mechanism mechanism of reaction figure of preferred embodiment of II) Lian oxazoline pyridine compounds of the present invention.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of ruthenium, (II) Lian oxazoline pyridine compounds, the ruthenium be (II) Lian oxazoline pyridine compounds
Shown in structure such as formula (I),
Present invention provides a kind of preparation method joining oxazoline pyridine compounds such as above-mentioned ruthenium (II), the preparation sides
Method is：In the presence of protecting gas, by presoma Ru (L1)2X2, 2,2- bipyridyls complexation reaction is carried out in solvent, then plus
Enter excessive saturation hexafluorophosphoric acid salting liquid and carries out precipitation reaction so that ruthenium (II) connection oxazoline pyridine compounds are made；Wherein, L1
4,4,4', 4'- tetramethyl -2,2'- bisoxazolines are represented, X represents halogen.
In the above preparation method, the dosage of each material can select in a wide range, but in order to make ruthenium obtained
(II) Lian oxazolines pyridine compounds have superior yield, it is preferable that presoma, 2,2- bipyridyls, saturation hexafluorophosphoric acid
The amount ratio of salting liquid is 0.2mmol：0.2-0.25mmol：2-6mL.Wherein, the dosage of solvent can also be in a wide range
Selection, but in order to further increase yield, it is highly preferred that the amount ratio of presoma, solvent is 0.2mmol：2-10mL.
In the above preparation method, the actual conditions of complexation reaction can select in a wide range, but in order to make system
(II) Lian oxazoline pyridine compounds have superior yield to the ruthenium obtained, it is preferable that complexation reaction meets the following conditions：Reaction
Temperature is 140-180 DEG C, reaction time 4-10h.
In the present invention, hexafluorophosphate, solvent, protective gas type can select in a wide range, but examine
Consider yield, it is preferable that hexafluorophosphate is selected from least one of Potassium Hexafluorophosphate, ammonium hexafluorophosphate and sodium hexafluoro phosphate；It is molten
Agent is selected from least one of methanol, ethyl alcohol and ethylene glycol, and protective gas is nitrogen and/or argon gas；
In the present invention, X can be any one in halogen, it is contemplated that ruthenium (II) Lian oxazoline pyridine compounds
Yield, it is preferable that X is chlorine.
It being used to prepare the ruthenium as above (presoma of II) Lian oxazoline pyridine compounds, before this present invention also provides a kind of
Drive body Ru (L1)2X2Structure such as formula (II) shown in,
Wherein, L14,4,4', 4'- tetramethyl -2,2'- bisoxazolines are represented, X represents halogen.
In the above preparation method, X can be any one in halogen, it is contemplated that presoma is preparing ruthenium (II)
Yield during Lian oxazoline pyridine compounds, it is preferable that X is chlorine.
Invention further provides a kind of preparation methods such as above-mentioned presoma, which is characterized in that including：It is being catalyzed
In the presence of agent and protection gas, by L1、RuX3Complexation reaction is carried out in solvent, and acetone is then added and is recrystallized；Wherein,
Catalyst is made of lithium salts and zinc, L14,4,4', 4'- tetramethyl -2,2'- bisoxazolines are represented, X represents halogen.
In the above preparation method, the dosage of each material can select in a wide range, it is contemplated that presoma
Yield, it is preferable that L1、RuX3, lithium salts, zinc molar ratio be 6：3-3.5：7-9：1-2.Similarly, solvent, acetone dosage also may be used
To select in a wide range, but in order to further increase the yield of presoma, it is preferable that L1, solvent, acetone amount ratio
For 6mmol：20-30mL：100-200mL.
In the above preparation method, the actual conditions of complexation reaction can select in a wide range, it is contemplated that preceding
Drive the yield of body, it is preferable that complexation reaction meets the following conditions：Reaction temperature is 140-170 DEG C, reaction time 6-12h.
In the above preparation method, the actual conditions of recrystallization can select in a wide range, it is contemplated that forerunner
The yield of body, it is preferable that recrystallization meets the following conditions：Crystallization temperature is -5 DEG C~0 DEG C, crystallization time 12-24h.
In the preparation process of above-mentioned presoma, the specific type of lithium salts can select in a wide range, but from urging
Change and consider in effect and cost, it is preferable that lithium salts is at least one of lithium fluoride, lithium chloride or lithium bromide；It is highly preferred that
Lithium salts is lithium chloride.
In the preparation process of above-mentioned presoma, the specific type of protective gas and solvent can be selected in a wide range
It selects, but considers from catalytic effect and cost, it is preferable that protective gas is nitrogen and/or argon gas, and solvent is selected from N, N- bis-
At least one of methylformamide, ethyl alcohol and acetonitrile.
In the present invention, X can be any one in halogen, it is contemplated that presoma is preparing ruthenium (II) Lian oxazoles
Yield during quinoline pyridine compounds, it is preferable that X is chlorine.
Invention still further provides a kind of catalytic reduction methods of aromatic nitro compound, which is characterized in that catalysis
Restoring method is：It, will be fragrant using such as above-mentioned ruthenium (II) connection oxazoline pyridine compounds as catalyst in the presence of solvent and light
Aromatic nitro compounds and reducing agent carry out catalysis reaction to obtain aromatic amine compound.
In above-mentioned catalytic reduction method, the specific dosage of aromatic nitro compound, reducing agent, catalyst can be in wide model
Interior selection is enclosed, but in order to further increase the reduction efficiency of aromatic nitro compound, it is preferable that aromatic nitro compound is gone back
Former agent, catalyst molar ratio be 1：5-10：0.01-0.03.Similarly, the dosage of solvent can also select in a wide range,
But in order to further increase the reduction efficiency of aromatic nitro compound, it is highly preferred that the dosage of aromatic nitro compound, solvent
Than for 1mmol：5-10mL.
In above-mentioned catalytic reduction method, being catalyzed the condition of reaction can select in a wide range, but in order into one
Step improves the reduction efficiency of aromatic nitro compound, it is preferable that catalysis reaction meets the following conditions：Reaction temperature is 15-25 DEG C,
Reaction time is 1-5h.
In above-mentioned catalytic reduction method, in order to further increase the reduction efficiency of aromatic nitro compound, can have
It being carried out under conditions of light, the specific type of wherein light can select in a wide range, but in order to further increase fragrant nitre
The reduction efficiency of based compound, it is preferable that catalysis, which reacts under sunlight or blue light illumination, to be carried out.Wherein, it is blue light in light
In the case of, the actual conditions of blue light can select in a wide range, but in order to further improve aromatic nitro compound
The reduction efficiency of object, it is preferable that blue light meets the following conditions：Wavelength is 400-450nm, and the power of blue-ray light is 35-40W.
In above-mentioned catalytic reduction method, the specific type of reducing agent can select in a wide range, but in order into
One step improves the reduction efficiency of aromatic nitro compound, it is preferable that reducing agent is in sodium borohydride, lithium borohydride, hydrazine hydrate
At least one.
In above-mentioned catalytic reduction method, the specific type of substrate can select in a wide range, it is contemplated that fragrant
Fragrant amine prepares the common degree of raw material, it is preferable that aromatic nitro compound be selected from 4- bromo nitrobenzenes, nitrobenzene, p-nitrophenol,
At least one of o-chloronitrobenzene, paranitroanilinum, 4- nitrobenzonitriles.
In above-mentioned catalytic reduction method, the specific type of solvent can select in a wide range, it is contemplated that cost
And solute effect, it is preferable that solvent is selected from least one of methanol, ethyl alcohol and ethylene glycol.
The present invention will be described in detail by way of examples below.In following embodiment, nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum
It is to be measured by Switzerland's Bruker AV300 and Bruker AV 500MHz Nuclear Magnetic Resonance；Single crystal diffraction collection of illustrative plates passes through Bruker
AXS single crystal diffractometer SMART APEX II are measured；Mass spectrum is measured by German Brooker company micrOTOF-Q 10280.
RuCl3, ethyl alcohol be Shanghai company of Jing Chun biochemical technologies limited liability company product, the nitro compounds such as p-Nitrobromobenzene be it is upper
The product of company of Hai Jingchun biochemical technologies limited liability company, 4,4,4', 4'- tetramethyl -2,2'- bisoxazolines are according to document side
Method synthesizes (L1:Altenhoff,G；Goddard,R；Lehmann,CW；J.Am.Chem.Soc.,2004,126(46),15195–
15201)。
Embodiment 1
1) by the 4,4,4' of 6mmol, 4'- tetramethyl -2,2'- Lian oxazolines, 3mmol RuCl3, LiCl (8mmol), zinc
Powder 0.1g is added in the DMF of 20mL, and the back flow reaction 8h at nitrogen protection and 140 DEG C is cooled to 25 DEG C, adds 100ml
Acetone, overnight in 0 DEG C, filtering.Filter cake is washed with cold water and acetone successively, and residue can be obtained with recrystallizing methanol in reaction
Mesosome Ru (L1)2Cl2(L1For), yield 63%.
2) by reaction intermediate Ru (L1)2Cl2(0.20mmol), 2,2- bipyridyls (0.22mmol) are placed in 8mL ethylene glycol
160 DEG C are heated to, 6h is reacted, 25 DEG C is cooled to after the completion of reaction, excessive saturation KPF is added into reaction solution6Aqueous solution is (at least
2mL), you can obtain crocus precipitation, filtering with 10mL water washing filter cakes, filter cake is dissolved in 10mL acetonitriles, rotary evaporation is used
Instrument removes solvent, you can obtains ruthenium (II) Lian oxazoline pyridine compounds, yield 85%.
Above-mentioned product is characterized, characterization result is as follows：
Nucleus magnetic hydrogen spectrum figure is referring to Fig. 2, specific data：1H NMR(500MHz,DMSO-d6,ppm):δ=8.25 (m, 3H),
7.96 (d, J=10Hz, 1H), 7.75 (d, J=5Hz, 2H), 7.65 (d, J=10Hz, 1H), 7.37 (d, J=15Hz, 1H),
7.26 (d, J=15Hz, 1H), 6.99 (d, J=5Hz, 1H), 6.72 (d, J=5Hz, 1H), 5.59 (d, J=5Hz, 1H), 5.49
(d, J=5Hz, 1H), 5.30 (d, J=5Hz, 1H), 5.05 (d, J=5Hz, 1H), 2.50 (m, 1H), 2.28 (s, 3H), 0.98
(d, J=5Hz, 3H), 0.90 (d, J=5Hz, 3H)；
Nuclear-magnetism carbon spectrogram is referring to Fig. 3, specific data：13C NMR(125MHz,DMSO-d6,ppm):δ=169.08,
154.95,148.01,144.87,142.47,138.05,135.13,131.48,130.65,129.14,128.17,124.88,
120.15,116.35,111.05,102.12,100.61,85.96,81.39,81.12,80.91,31.24,22.53,22.41,
19.33；
Mass spectrogram is referring to Fig. 5, specific data：HR ESI-MS:M/z=795.1702 (M-PF6)+；
Uv absorption spectra is referring to Fig. 4；
Infrared spectrum characterization data are：IR(KBr cm-1):3450(b),2980(m),2941(m),2901(m),2280
(m),1647(m),1501(s),1462(m),1371(m),1361(m),1345(m),1267(m),1206(m),1168(m),
1025(m),991(m),936(m),844(s),628(m),559(m)；
Single crystal diffraction figure is as shown in Figure 1, by above-mentioned characterization it is known that the product of the present embodiment is really for such as formula (I)
The compound of shown structure.
Embodiment 2
Carry out obtaining ruthenium that (II) Lian oxazoline pyridine compounds, yield 88% are different according to the method for embodiment 1
The dosage for being 2,2- bipyridyls is 0.25mmol.
Embodiment 3
Carry out obtaining ruthenium that (II) Lian oxazoline pyridine compounds, yield 83% are different according to the method for embodiment 1
It is：Reaction intermediate Ru (L1)2Cl2(0.20mmol), 2,2- bipyridyls (0.22mmol) are placed in 8mL ethylene glycol and are heated to 140
DEG C, 10h is reacted, 25 DEG C are cooled to after the completion of reaction, excessive saturation KPF is added into reaction solution6Aqueous solution (at least 2mL).
Embodiment 4
Carry out obtaining ruthenium that (II) Lian oxazoline pyridine compounds, yield 88% are different according to the method for embodiment 1
It is：Reaction intermediate Ru (L1)2Cl2(0.20mmol), 2,2- bipyridyls (0.22mmol) are placed in 8mL ethylene glycol and are heated to 180
DEG C, 4h is reacted, 25 DEG C are cooled to after the completion of reaction, excessive saturation KPF is added into reaction solution6Aqueous solution (at least 2mL).
The product of embodiment 2-4 is also characterized according to the method described in embodiment 1, characterization result also confirms that：It is real
The product for applying a 2-4 is the compound of the structure as shown in formula (I) really.
Application examples 1
Photocatalysis 4- bromo nitrobenzenes obtain 4- bromanilines：
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in reaction tube, the ruthenium coordination prepared with embodiment 1 is added
It is shone under 36W blue-ray lights after compound (0.02mmol), 1mmol4- bromo nitrobenzenes, 5ml ethyl alcohol, the mixing of 10mmol sodium borohydrides
It penetrates, stirred 2 hours at 25 DEG C.After reaction, solvent is removed with Rotary Evaporators, is transferred in separatory funnel and dichloro is added
Methane and water extraction, after organic layer merges, column chromatography for separation obtains product, yield 98%.
Products therefrom characterization result is：1H NMR(300MHz,CDCl3):δ 7.24 (d, J=9.0Hz, 2H), 6.56 (d, J
=9.0Hz, 2H), 3.69 (br, 2H)
Application examples 2
Photocatalysis nitrobenzene obtains aniline：
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in reaction tube, the ruthenium coordination prepared with embodiment 1 is added
It is irradiated under 36W blue-ray lights after compound (0.02mmol), 1mmol nitrobenzenes, 5ml ethyl alcohol, the mixing of 10mmol sodium borohydrides, 25
It is stirred 2 hours at DEG C.After reaction, solvent is removed with Rotary Evaporators, is transferred in separatory funnel and dichloromethane is added
It is extracted with water, after organic layer merges, column chromatography for separation obtains product, yield 90%.
Products therefrom characterization result is：1H NMR(500MHz,CDCl3):δ7.35(m,2H),6.95(m,1H),6.79(m,
2H),3.67(br,2H).
Application examples 3
Photocatalysis p-nitrophenol obtains para-aminophenol：
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in reaction tube, the ruthenium coordination prepared with embodiment 1 is added
It is shone under 36W blue-ray lights after compound (0.02mmol), 1mmol p-nitrophenols, 5ml ethyl alcohol, the mixing of 10mmol sodium borohydrides
It penetrates, is stirred 2 hours at 25 DEG C.After reaction, solvent is removed with Rotary Evaporators, is transferred in separatory funnel and dichloro is added
Methane and water extraction, after organic layer merges, column chromatography for separation obtains product, yield 95%.
Products therefrom characterization result is：1H NMR(300MHz,CD3OD):δ6.62(t,4H),4.87(s,NH2).
Application examples 4
Photocatalysis o-chloronitrobenzene obtains o-chloraniline：
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in reaction tube, the ruthenium coordination prepared with embodiment 1 is added
It is shone under 36W blue-ray lights after compound (0.02mmol), 1mmol o-chloronitrobenzenes, 5ml ethyl alcohol, the mixing of 10mmol sodium borohydrides
It penetrates, is stirred 2 hours at 25 DEG C.After reaction, solvent is removed with Rotary Evaporators, is transferred in separatory funnel and dichloro is added
Methane and water extraction, after organic layer merges, column chromatography for separation obtains product, yield 95%.
Products therefrom characterization result is：1H NMR(300MHz,CDCl3):δ4.03(bs,NH2),6.77(1H),6.92(m,
1H),7.07(m,1H),7.24(m,1H).
Application examples 5
Photocatalysis paranitroanilinum obtains p-phenylenediamine：
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in reaction tube, the ruthenium coordination prepared with embodiment 1 is added
Compound (0.02mmol), 1mmol paranitroanilinum shine after 5ml ethyl alcohol, the mixing of 10mmol sodium borohydrides under 36W blue-ray lights
It penetrates, is stirred 2 hours at 25 DEG C.After reaction, solvent is removed with Rotary Evaporators, is transferred in separatory funnel and dichloro is added
Methane and water extraction, after organic layer merges, column chromatography for separation obtains product, yield 98%.
Products therefrom characterization result is：1H NMR(300MHz,CDCl3):δ6.56(s,4H),3.33(br,4H).
Application examples 6
Photocatalysis 4- nitrobenzonitriles obtain 4- anthranilo nitriles：
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in reaction tube, the ruthenium coordination prepared with embodiment 1 is added
After compound (0.02mmol), 1mmol 4- nitrobenzonitriles, 5ml ethyl alcohol, the mixing of 10mmol sodium borohydrides under 36W blue-ray lights
It irradiates, is stirred 2 hours at 25 DEG C.After reaction, solvent is removed with Rotary Evaporators, is transferred in separatory funnel and is added two
Chloromethanes and water extraction, after organic layer merges, column chromatography for separation obtains product, yield 98%.
Products therefrom characterization result is：1H NMR(300MHz,CDCl3) 7.43 (d, J=9.0Hz, 2H), 6.65 (d, J=
9.0Hz, 2H), 4.15 (br, 2H).
Application examples 7
It carries out, is irradiated the difference is that irradiation under 36W blue-ray lights is changed under daylight, yield according to the method for application examples 1
It is 60%.
Comparative example 1
It is carried out according to the method for application examples 1, the difference is that it is not added with the ruthenium complex of 1 method of embodiment preparation,
Have no the generation of 4- bromanilines after reaction by detecting display, i.e. 4- bromo nitrobenzenes do not carry out catalysis reduction.
Comparative example 2
It is carried out according to the method for application examples 1, the difference is that irradiation under 36W blue-ray lights is changed to dark condition, yield is
3%.
Comparative example 3
It is carried out according to the method for application examples 1, the difference is that ruthenium complex (0.02mmol) is changed to equimolar amounts
Eosin B, yield 30%.
Comparative example 4
It is carried out according to the method for application examples 1, the difference is that ruthenium complex (0.02mmol) is changed to equimolar amounts
Ru (bpy)3Cl2, bpy 2,2- bipyridyls, yield 33%.
Comparative example 5
It is carried out according to the method for application examples 1, the difference is that ruthenium complex (0.02mmol) is changed to equimolar amounts
Eosin Y, yield 28%.
Comparative example 6
It carries out according to the method for application examples 1, is shone the difference is that irradiation under 36W blue-ray lights is changed under 18W blue-ray lights
It penetrates, yield 49%.
Comparative example 7
It carries out according to the method for application examples 1, is irradiated the difference is that irradiation under 36W blue-ray lights is changed under 3W blue-ray lights,
Yield is 10%.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of ruthenium (II) Lian oxazoline pyridine compounds, which is characterized in that the ruthenium be (II) Lian oxazoline pyridine compounds
Shown in structure such as formula (I),
2. a kind of ruthenium as described in claim 1 (preparation method of II) Lian oxazoline pyridine compounds, which is characterized in that described
Preparation method is：In the presence of protecting gas, by presoma Ru (L1)2X2, 2,2- bipyridyls complexation reaction is carried out in solvent,
Then excessive saturation hexafluorophosphoric acid salting liquid is added and carries out precipitation reaction so that ruthenium (II) the connection oxazoline pyridine chemical combination is made
Object；Wherein, L14,4,4', 4'- tetramethyl -2,2'- bisoxazolines are represented, X represents halogen.
3. preparation method according to claim 2, wherein the presoma, 2,2- bipyridyls, saturation hexafluorophosphate are molten
The amount ratio of liquid is 0.2mmol：0.2-0.25mmol：2-6mL.
4. preparation method according to claim 2, wherein the presoma, solvent amount ratio be 0.2mmol：2-
10mL。
5. preparation method according to claim 2, wherein the complexation reaction meets the following conditions：Reaction temperature is
140-180 DEG C, reaction time 4-10h.
6. preparation method according to claim 2, wherein hexafluorophosphate be selected from Potassium Hexafluorophosphate, ammonium hexafluorophosphate and
At least one of sodium hexafluoro phosphate.
7. preparation method according to claim 2, wherein the solvent in methanol, ethyl alcohol and ethylene glycol at least
One；Preferably, the protective gas is nitrogen and/or argon gas；It is highly preferred that X is chlorine.
8. a kind of catalytic reduction method of aromatic nitro compound, which is characterized in that the catalytic reduction method is：In solvent and
In the presence of light, using ruthenium as described in claim 1 (II) Lian oxazolines pyridine compounds as catalyst, by aromatic nitro compound
Object and reducing agent carry out catalysis reaction to obtain aromatic amine compound.
9. catalytic reduction method according to claim 8, wherein the aromatic nitro compound, reducing agent, catalyst
Molar ratio is 1：5-10：0.01-0.03；
Preferably, the aromatic nitro compound, solvent amount ratio be 1mmol：5-10mL；
It is highly preferred that the catalysis reaction meets the following conditions：Reaction temperature is 15-25 DEG C, reaction time 1-5h；
It is further preferred that the catalysis is reacted under sunlight or blue light illumination and is carried out；
It is further preferred that the blue light meets the following conditions：Wavelength is 400-450nm, and the power of blue-ray light is 35-40W.
10. catalytic reduction method according to claim 8, wherein the reducing agent be selected from sodium borohydride, lithium borohydride,
At least one of hydrazine hydrate；
Preferably, the aromatic nitro compound be selected from 4- bromo nitrobenzenes, nitrobenzene, p-nitrophenol, o-chloronitrobenzene, to nitre
At least one of base aniline, 4- nitrobenzonitriles；
It is highly preferred that the solvent is selected from least one of methanol, ethyl alcohol and ethylene glycol.
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| CN110283215A (en) * | 2019-07-12 | 2019-09-27 | 安徽师范大学 | Ruthenium connection oxazoline Phen compound, intermediate with coordinated compound anion and its preparation method and application |
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| CN105153237A (en) * | 2015-07-28 | 2015-12-16 | 安徽师范大学 | Half-sandwich cyclometalated ruthenium coordination compound, and preparation method and application thereof |
| CN106046061A (en) * | 2016-06-29 | 2016-10-26 | 安徽师范大学 | Half-sandwich ruthenium complex and preparation method thereof, preparation method of ligand and reduction method of nitrobenzene compound |
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| CN105153237A (en) * | 2015-07-28 | 2015-12-16 | 安徽师范大学 | Half-sandwich cyclometalated ruthenium coordination compound, and preparation method and application thereof |
| CN106046061A (en) * | 2016-06-29 | 2016-10-26 | 安徽师范大学 | Half-sandwich ruthenium complex and preparation method thereof, preparation method of ligand and reduction method of nitrobenzene compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283215A (en) * | 2019-07-12 | 2019-09-27 | 安徽师范大学 | Ruthenium connection oxazoline Phen compound, intermediate with coordinated compound anion and its preparation method and application |
| CN110283215B (en) * | 2019-07-12 | 2021-06-08 | 安徽师范大学 | Ruthenium-bisoxazoline phenanthroline compound with decatungstate anion, intermediate, preparation method and application thereof |
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