CN108586540B - Ruthenium (II) bisoxazoline pyridine compound, preparation method thereof and catalytic reduction method of aromatic nitro compound - Google Patents
Ruthenium (II) bisoxazoline pyridine compound, preparation method thereof and catalytic reduction method of aromatic nitro compound Download PDFInfo
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- -1 Ruthenium (II) bisoxazoline pyridine compound Chemical class 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 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
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 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
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 4
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-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
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 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
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000012327 Ruthenium complex 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
- 230000009467 reduction Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000758 substrate Substances 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 compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- 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
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 238000005406 washing 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
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 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
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 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
- 230000005281 excited state Effects 0.000 description 1
- 238000001914 filtration Methods 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
- 229940127554 medical product Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a ruthenium (II) bioxazoline pyridine compound, a preparation method thereof and a catalytic reduction method of an aromatic nitro compound, wherein the structure of the ruthenium (II) bioxazoline pyridine compound is shown as a formula (I), the ruthenium (II) bioxazoline pyridine compound has excellent stability and catalytic performance, and meanwhile, the preparation method of the ruthenium (II) bioxazoline pyridine compound has the characteristics of simple operation, low equipment requirement and high yield, so that the ruthenium (II) bioxazoline pyridine compound can further catalyze the aromatic nitro compound to be converted into the aromatic amine compound in a large batch;
Description
Technical Field
The invention relates to a ruthenium complex, in particular to a ruthenium (II) bisoxazoline pyridine compound, a preparation method thereof and a catalytic reduction method of an aromatic nitro compound.
Background
In recent years, the visible light catalytic oxidation reduction activation method of organic small molecules has been developed to become an important means of organic synthetic chemistry, and has been paid attention by numerous chemists due to the advantages of sunlight utilization, greenness, no pollution, low consumption and the like, and has gradually developed to become one of the leading fields of organic chemistry. Generally, the principle of visible light catalytic oxidation reduction is that an organic substrate is activated by a metal coordination compound (mainly a coordination compound of ruthenium and iridium), an organic dye and a photosensitizer under the condition of visible light to generate a single-electron active intermediate, and then the single-electron active intermediate is subjected to oxidative coupling with other substrates to form a new chemical bond.
Because the price of ruthenium is low (the price of the iridium complex is about 12.6 times/mmol of the ruthenium complex), the ruthenium is favored by chemists. The ruthenium polypyridine coordination compound has longer fluorescence life and quantum yield due to unique photophysical and photochemical properties, and simultaneously has higher oxidation-reduction potential and lower reduction potential in an excited state under the action of visible light than that of ground-state ruthenium, and can play stronger oxidation and reduction roles in catalytic circulation, thereby being widely applied to visible light catalytic reaction; for example, it is used as a photocatalyst in photolysis water, as a photosensitizer in a solar cell, as a photocatalyst in organic synthesis, and the like. Therefore, the synthesis and application of ruthenium polypyridine and analogues thereof have become one of the important research directions in inorganic chemistry, coordination chemistry and organic chemistry, and the development of ruthenium-based complexes having high activity has become a hot point of research.
Aromatic amine compounds are important starting materials and intermediates of amine compounds, and are mainly used for synthesizing pesticides, medical products and the like. With the increasing demand for aromatic amine compounds in production, it becomes important to study the synthesis of aromatic amine compounds. The synthesis of aromatic amine compounds by catalytic reduction of aromatic nitro compounds is an important synthesis method commonly used in chemical production and experimental research. At present, the main synthetic method of aromatic amine compounds is to prepare aromatic nitro compounds by reduction, but generally needs a strong acid system and a high-temperature method, and has the defects of poor selectivity, high energy consumption and the like.
Disclosure of Invention
The invention aims to provide a ruthenium (II) bisoxazoline pyridine compound, a preparation method thereof and a catalytic reduction method of an aromatic nitro compound, wherein the ruthenium (II) bisoxazoline pyridine compound has excellent stability and catalytic performance, and the preparation method of the ruthenium (II) bisoxazoline pyridine compound has the characteristics of simple operation, low equipment requirement and high yield, so that the ruthenium (II) bisoxazoline pyridine compound can catalyze the aromatic nitro compound to be converted into the aromatic amine compound in a large batch.
In order to achieve the above object, the present invention provides a ruthenium (II) bisoxazoline pyridine compound, the structure of which is shown in formula (I),
the invention also provides a preparation method of the ruthenium (II) bisoxazoline pyridine compound, which comprises the following steps: in the presence of protective gas, the precursor Ru (L)1)2X2Carrying out coordination reaction on 2, 2-bipyridyl in a solvent, and then adding an excessive saturated hexafluorophosphate solution to carry out precipitation reaction to prepare a ruthenium (II) bisoxazoline pyridine compound; wherein L is1 Represents 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and X represents halogen.
The invention also provides a precursor for preparing the ruthenium (II) bisoxazoline pyridine compound, and the precursor Ru (L)1)2X2The structure of the compound is shown as a formula (II),
wherein L is1 Represents 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and X represents halogen.
The invention further provides a preparation method of the precursor, which is characterized by comprising the following steps: in the presence of a catalyst and a shielding gas, adding L1、RuX3Performing coordination reaction in a solvent, and then adding acetone for recrystallization; wherein the catalyst consists of lithium salt and zinc, L1Represents 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and X represents halogen.
The invention further provides a catalytic reduction method of the aromatic nitro compound, which is characterized by comprising the following steps: in the presence of a solvent and light, the aromatic nitro compound and a reducing agent are subjected to catalytic reaction by using the ruthenium (II) bisoxazoline pyridine compound as a catalyst to obtain the aromatic amine compound.
According to the technical scheme, firstly, lithium salt and zinc are used as catalysts, and L is1、RuX3Performing coordination reaction to prepare a precursor Ru (L)1)2X2(ii) a Then precursor Ru (L)1)2X2Reacting with 2, 2-bipyridyl and hexafluorophosphate to obtain ruthenium (II) bisoxazoline pyridine compound [ Ru (L)1)2(bpy)](PF6)2And bpy represents 2, 2-bipyridine. The preparation process of the ruthenium (II) bisoxazoline pyridine compound has the following advantages: 1) the experimental process is simple, the requirement on equipment is low, the cost performance is high, and batch production can be carried out; 2) the process is simple and has better yield; 3) the ruthenium (II) bisoxazoline pyridine compound can stably exist under the conditions of low temperature and light protection.
In addition, in the application, the ruthenium (II) bisoxazoline pyridine compound is used as a catalyst, so that the aromatic nitro compound can be efficiently catalytically reduced into the aromatic amine compound; the catalytic process has the characteristics of simple process, simple and convenient operation and mild conditions, and further has excellent application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a single crystal structure of the product of example 1;
FIG. 2 is a NMR chart of the product of example 1;
FIG. 3 is a NMR carbon spectrum of the product of example 1;
FIG. 4 is a UV absorption spectrum of the product of example 1;
FIG. 5 is a mass spectrum of the product of example 1;
FIG. 6 is a reaction scheme of a preferred embodiment of the ruthenium (II) bisoxazoline pyridine compound of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a ruthenium (II) bisoxazoline pyridine compound, the structure of the ruthenium (II) bisoxazoline pyridine compound is shown in a formula (I),
the invention also provides a preparation method of the ruthenium (II) bisoxazoline pyridine compound, which comprises the following steps: in the presence of protective gas, the precursor Ru (L)1)2X2Carrying out coordination reaction on 2, 2-bipyridyl in a solvent, and then adding an excessive saturated hexafluorophosphate solution to carry out precipitation reaction to prepare a ruthenium (II) bisoxazoline pyridine compound; wherein L is1 Represents 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and X represents halogen.
In the above production method, the amount of each material to be used may be selected within a wide range, but in order to obtain a ruthenium (II) bisoxazoline pyridine compound having a more excellent yield, it is preferable that the ratio of the amount of the precursor, 2-bipyridine, and saturated hexafluorophosphate solution is 0.2 mmol: 0.2-0.25 mmol: 2-6 mL. The amount of the solvent may be selected from a wide range, but in order to further improve the yield, it is more preferable that the ratio of the amount of the precursor to the amount of the solvent is 0.2 mmol: 2-10 mL.
In the above-mentioned production method, the specific conditions of the coordination reaction can be selected within a wide range, but in order to obtain a ruthenium (II) bisoxazoline pyridine compound having more excellent yield, it is preferable that the coordination reaction satisfies the following conditions: the reaction temperature is 140 ℃ and 180 ℃, and the reaction time is 4-10 h.
In the present invention, the kind of hexafluorophosphate, solvent, protective gas may be selected in a wide range, but in consideration of the yield, preferably, the hexafluorophosphate is selected from at least one of potassium hexafluorophosphate, ammonium hexafluorophosphate, and sodium hexafluorophosphate; the solvent is at least one selected from methanol, ethanol and glycol, and the protective gas is nitrogen and/or argon;
in the present invention, X may be any one of halogens, but preferably, X is chlorine in view of the yield of the ruthenium (II) bisoxazoline pyridine compound.
The invention also provides a precursor for preparing the ruthenium (II) bisoxazoline pyridine compound, and the precursor Ru (L)1)2X2The structure of the compound is shown as a formula (II),
wherein L is1 Represents 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and X represents halogen.
In the above preparation method, X may be any one of halogens, but preferably, X is chlorine in view of the yield of the precursor in the preparation of the ruthenium (II) bisoxazoline pyridine compound.
The invention further provides a preparation method of the precursor, which is characterized by comprising the following steps: in the presence of a catalyst and a shielding gas, adding L1、RuX3Performing coordination reaction in solvent, adding acetone for recombinationCrystallizing; wherein the catalyst consists of lithium salt and zinc, L1Represents 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and X represents halogen.
In the above production method, the amount of each material to be used may be selected within a wide range, but preferably, L is used in view of the yield of the precursor1、RuX3The molar ratio of the lithium salt to the zinc is 6: 3-3.5: 7-9: 1-2. Similarly, the amounts of the solvent and acetone can be selected from a wide range, but in order to further improve the yield of the precursor, it is preferable that L is used1And the dosage ratio of the solvent to the acetone is 6 mmol: 20-30 mL: 100 and 200 mL.
In the above-mentioned production method, the specific conditions of the coordination reaction can be selected within a wide range, but in view of the yield of the precursor, it is preferable that the coordination reaction satisfies the following conditions: the reaction temperature is 140 ℃ and 170 ℃, and the reaction time is 6-12 h.
In the above production method, specific conditions for recrystallization can be selected within a wide range, but in view of the yield of the precursor, it is preferable that recrystallization satisfies the following conditions: the crystallization temperature is-5 ℃ to 0 ℃, and the crystallization time is 12 to 24 hours.
In the preparation of the above precursor, the specific kind of the lithium salt may be selected within a wide range, but from the viewpoint of catalytic effect and cost, it is preferable that the lithium salt is at least one of lithium fluoride, lithium chloride or lithium bromide; more preferably, the lithium salt is lithium chloride.
In the preparation of the above precursor, specific kinds of the protective gas and the solvent may be selected from a wide range, but from the viewpoint of catalytic effect and cost, it is preferable that the protective gas is nitrogen and/or argon, and the solvent is at least one selected from N, N-dimethylformamide, ethanol, and acetonitrile.
In the present invention, X may be any one of halogens, but preferably, X is chlorine in view of the yield of the precursor in the preparation of the ruthenium (II) bisoxazoline pyridine compound.
The invention further provides a catalytic reduction method of the aromatic nitro compound, which is characterized by comprising the following steps: in the presence of a solvent and light, the aromatic nitro compound and a reducing agent are subjected to catalytic reaction by using the ruthenium (II) bisoxazoline pyridine compound as a catalyst to obtain the aromatic amine compound.
In the above catalytic reduction method, the specific amounts of the aromatic nitro compound, the reducing agent and the catalyst may be selected within wide ranges, but in order to further improve the reduction efficiency of the aromatic nitro compound, it is preferable that the molar ratio of the aromatic nitro compound, the reducing agent and the catalyst is 1: 5-10: 0.01-0.03. Similarly, the amount of the solvent may be selected from a wide range, but in order to further improve the reduction efficiency of the aromatic nitro compound, it is more preferable that the ratio of the amount of the aromatic nitro compound to the amount of the solvent is 1 mmol: 5-10 mL.
In the above catalytic reduction method, the conditions of the catalytic reaction may be selected within a wide range, but in order to further improve the reduction efficiency of the aromatic nitro compound, it is preferable that the catalytic reaction satisfies the following conditions: the reaction temperature is 15-25 ℃, and the reaction time is 1-5 h.
In the above catalytic reduction method, in order to further improve the reduction efficiency of the aromatic nitro compound, it may be carried out under the presence of light, wherein the specific kind of light may be selected within a wide range, but in order to further improve the reduction efficiency of the aromatic nitro compound, it is preferable that the catalytic reaction is carried out under irradiation of sunlight or blue light. Among them, in the case where the light is blue light, the specific condition of the blue light may be selected within a wide range, but in order to further improve the reduction efficiency of the aromatic nitro compound, it is preferable that the blue light satisfies the following condition: the wavelength is 400-450nm, and the power of the blue light lamp is 35-40W.
In the above catalytic reduction method, a specific kind of the reducing agent may be selected within a wide range, but in order to further improve the reduction efficiency of the aromatic nitro compound, it is preferable that the reducing agent is selected from at least one of sodium borohydride, lithium borohydride, and hydrazine hydrate.
In the above catalytic reduction method, the specific kind of the substrate may be selected within a wide range, but in consideration of the degree of the usual production of the aromatic amine raw material, it is preferable that the aromatic nitro compound is selected from at least one of 4-bromonitrobenzene, nitrobenzene, p-nitrophenol, o-chloronitrobenzene, p-nitroaniline, 4-nitrobenzonitrile.
In the above catalytic reduction method, the specific kind of the solvent may be selected within a wide range, but preferably, the solvent is selected from at least one of methanol, ethanol, and ethylene glycol in view of cost and dissolution effect.
The present invention will be described in detail below by way of examples. In the following examples, nuclear magnetic hydrogen and carbon spectra were measured by Bruker AV300 and Bruker AV 500MHz NMR spectrometer, Switzerland; the single crystal diffraction pattern is measured by a Bruker AXS single crystal diffractometer SMART APEX II; the mass spectrum was measured by microOTOF-Q10280, Bruker, Germany. RuCl3Ethanol is a product of Shanghai crystal purificationscience and technology Co., Ltd, a nitro compound such as p-bromonitrobenzene is a product of Shanghai crystal purificationscience and technology Co., Ltd, and 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline is synthesized according to a literature method (L1: Altenhoff, G; Goddard, R; Lehmann, CW; J.Am.Chem.Soc.,2004, 126(46), 15195-.
Example 1
1) Mixing 6mmol of 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and 3mmol of RuCl3LiCl (8mmol) and zinc powder 0.1g are added into DMF 20mL, the mixture is refluxed for 8h under the protection of nitrogen and at the temperature of 140 ℃, cooled to 25 ℃, added with acetone 100mL, and filtered at the temperature of 0 ℃ overnight. Washing the filter cake with cold water and acetone in turn, and recrystallizing the residue with methanol to obtain Ru (L) as a reaction intermediate1)2Cl2(L1Is composed of
) The yield was 63%.
2) Reacting intermediate Ru (L)1)2Cl2(0.20mmol) and 2, 2-bipyridine (0.22mmol) are put into 8mL of glycol and heated to 160 ℃, reacted for 6 hours, cooled to 25 ℃ after the reaction is finished, and excess saturated KPF is added into the reaction solution6An aqueous solution (at least 2mL) to give an orange precipitate, filtering, washing the filter cake with 10mL of water, and dryingDissolving the filter cake in 10mL of acetonitrile, and removing the solvent by using a rotary evaporator to obtain the ruthenium (II) bisoxazoline pyridine compound with the yield of 85 percent.
The above products were characterized as follows:
referring to fig. 2, the nuclear magnetic hydrogen spectrum diagram shows the following 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)；
referring to fig. 3, the nuclear magnetic carbon spectrum shows the following 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；
referring to fig. 5, the mass spectrum is shown as follows: HR ESI-MS: M/z 795.1702 (M-PF)6)+；
The ultraviolet absorption spectrogram is shown in FIG. 4;
the infrared spectrum characterization data is as follows: 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)；
The single crystal diffraction pattern is shown in fig. 1, and it can be known from the above characterization that the product of this example is indeed a compound having the structure shown in formula (I).
Example 2
Ruthenium (II) bisoxazoline pyridine compound was obtained in a yield of 88% by following the procedure of example 1, except that 2, 2-bipyridine was used in an amount of 0.25 mmol.
Example 3
A ruthenium (II) bisoxazoline pyridine compound was obtained in a yield of 83% by following the procedure of example 1, except that: reaction intermediate Ru (L)1)2Cl2(0.20mmol) and 2, 2-bipyridine (0.22mmol) are put into 8mL of glycol and heated to 140 ℃, reacted for 10 hours, cooled to 25 ℃ after the reaction is finished, and excess saturated KPF is added into the reaction solution6Aqueous solution (at least 2 mL).
Example 4
A ruthenium (II) bisoxazoline pyridine compound was obtained in a yield of 88% by following the procedure of example 1, except that: reaction intermediate Ru (L)1)2Cl2(0.20mmol) and 2, 2-bipyridine (0.22mmol) are put into 8mL of glycol and heated to 180 ℃ to react for 4h, the reaction solution is cooled to 25 ℃ after the reaction is finished, and excess saturated KPF is added into the reaction solution6Aqueous solution (at least 2 mL).
The products of examples 2-4 were also characterized as described in example 1, and the characterization results also confirmed: the products of examples 2-4 were indeed compounds of the structure shown in formula (I).
Application example 1
Photocatalytic 4-bromonitrobenzene to give 4-bromoaniline:
in an air atmosphere, a polytetrafluoroethylene magnetosphere was placed in a reaction tube, and the ruthenium complex (0.02mmol) prepared in example 1, 1mmol of 4-bromonitrobenzene, 5ml of ethanol, and 10mmol of sodium borohydride were mixed and irradiated under a 36W blue light lamp, followed by stirring at 25 ℃ for 2 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator, the mixture is transferred to a separating funnel, dichloromethane and water are added for extraction, organic layers are combined, and the product is obtained by column chromatography separation, wherein the yield is 98%.
The product obtained is characterized by:1H NMR(300MHz,CDCl3):δ7.24(d,J＝9.0Hz, 2H),6.56(d,J＝9.0Hz,2H),3.69(br,2H).
application example 2
Photocatalytic nitrobenzene to aniline:
in an air atmosphere, a polytetrafluoroethylene magnetosphere was placed in a reaction tube, and the ruthenium complex (0.02mmol) prepared in example 1, 1mmol of nitrobenzene, 5ml of ethanol, and 10mmol of sodium borohydride were mixed and irradiated under a 36W blue light lamp, followed by stirring at 25 ℃ for 2 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator, the mixture is transferred to a separating funnel, dichloromethane and water are added for extraction, organic layers are combined, and the product is obtained by column chromatography separation, wherein the yield is 90%.
The product obtained is characterized by:1H NMR(500MHz,CDCl3):δ7.35(m,2H),6.95(m, 1H),6.79(m,2H),3.67(br,2H).
application example 3
Photocatalytic p-nitrophenol to p-aminophenol:
in an air atmosphere, a polytetrafluoroethylene magnetosphere was placed in a reaction tube, and the ruthenium complex (0.02mmol) prepared in example 1, 1mmol of p-nitrophenol, 5ml of ethanol, and 10mmol of sodium borohydride were mixed and irradiated under a 36W blue light lamp, followed by stirring at 25 ℃ for 2 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator, the mixture is transferred to a separating funnel, dichloromethane and water are added for extraction, organic layers are combined, and the product is obtained by column chromatography separation, wherein the yield is 95%.
The product obtained is characterized by:1H NMR(300MHz,CD3OD):δ6.62(t,4H),4.87(s, NH2).
application example 4
Photocatalytic o-chloronitrobenzene to obtain o-chloroaniline:
in an air atmosphere, a polytetrafluoroethylene magnetosphere was placed in a reaction tube, and the ruthenium complex (0.02mmol) prepared in example 1, 1mmol of o-chloronitrobenzene, 5ml of ethanol, and 10mmol of sodium borohydride were mixed and irradiated under a 36W blue light lamp, followed by stirring at 25 ℃ for 2 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator, the mixture is transferred to a separating funnel, dichloromethane and water are added for extraction, organic layers are combined, and the product is obtained by column chromatography separation, wherein the yield is 95%.
The product obtained is characterized by:1H NMR(300MHz,CDCl3):δ4.03(bs,NH2), 6.77(1H),6.92(m,1H),7.07(m,1H),7.24(m,1H).
application example 5
Photocatalytic p-nitroaniline to p-phenylenediamine:
in an air atmosphere, a polytetrafluoroethylene magnetosphere was placed in a reaction tube, and the ruthenium complex (0.02mmol) prepared in example 1, 1mmol of p-nitroaniline, 5ml of ethanol, and 10mmol of sodium borohydride were mixed and irradiated under a 36W blue light lamp, followed by stirring at 25 ℃ for 2 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator, the mixture is transferred to a separating funnel, dichloromethane and water are added for extraction, organic layers are combined, and the product is obtained by column chromatography separation, wherein the yield is 98%.
The product obtained is characterized by:1H NMR(300MHz,CDCl3):δ6.56(s,4H),3.33 (br,4H).
application example 6
Photocatalytic 4-nitrobenzonitrile to give 4-aminobenzonitrile:
in an air atmosphere, a polytetrafluoroethylene magnetosphere was placed in a reaction tube, and the ruthenium complex (0.02mmol) prepared in example 1, 1mmol of 4-nitrobenzonitrile, 5ml of ethanol, and 10mmol of sodium borohydride were added and mixed, followed by irradiation with a 36W blue light lamp and stirring at 25 ℃ for 2 hours. After the reaction is finished, the solvent is removed by using a rotary evaporator, the mixture is transferred to a separating funnel, dichloromethane and water are added for extraction, organic layers are combined, and the product is obtained by column chromatography separation, wherein the yield is 98%.
The product obtained is characterized by:1H NMR(300MHz,CDCl3)7.43(d,J＝9.0Hz,2H), 6.65(d,J＝9.0Hz，2H),4.15(br,2H)。
application example 7
The procedure was carried out as in application example 1, except that irradiation under a 36W blue lamp was changed to irradiation under sunlight, and the yield was 60%.
Comparative example 1
The procedure was followed as in application example 1, except that the ruthenium complex prepared in example 1 was not added, and it was confirmed by detection that no 4-bromoaniline was produced after the reaction, i.e., 4-bromonitrobenzene was not catalytically reduced.
Comparative example 2
The procedure was carried out as in application example 1, except that the irradiation under a 36W blue lamp was changed to dark conditions, and the yield was 3%.
Comparative example 3
The procedure was carried out as in application example 1, except that the ruthenium complex (0.02mmol) was replaced by an equimolar amount of eosin B, giving a yield of 30%.
Comparative example 4
The procedure was as in application example 1, except that the ruthenium complex (0.02mmol) was changed to an equimolar amount of Ru (bpy)3Cl2Bpy is 2, 2-bipyridine, 33% yield.
Comparative example 5
The procedure was carried out as in application example 1, except that the ruthenium complex (0.02mmol) was changed to an equimolar amount of eosin Y, and the yield was 28%.
Comparative example 6
The procedure was carried out as in application example 1, except that the irradiation under a 36W blue lamp was changed to the irradiation under an 18W blue lamp, and the yield was 49%.
Comparative example 7
The procedure was carried out as in application example 1, except that the irradiation under a 36W blue lamp was changed to the irradiation under a 3W blue lamp, and the yield was 10%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (18)
1. A ruthenium (II) bisoxazoline pyridine compound is characterized in that the structure of the ruthenium (II) bisoxazoline pyridine compound is shown in a formula I,
2. a method for producing the ruthenium (II) bisoxazoline pyridine compound according to claim 1, which comprises: in the presence of protective gas, the precursor Ru (L)1)2X2Carrying out coordination reaction on 2, 2-bipyridyl in a solvent, and then adding an excessive saturated hexafluorophosphate solution to carry out precipitation reaction to prepare the ruthenium (II) bisoxazoline pyridine compound; wherein L is1Represents 4,4,4',4' -tetramethyl-2, 2' -bisoxazoline and X represents halogen.
3. The production method according to claim 2, wherein the precursor, 2-bipyridine and saturated hexafluorophosphate solution are used in a ratio of 0.2 mmol: 0.2-0.25 mmol: 2-6 mL.
4. The preparation method according to claim 2, wherein the ratio of the precursor to the solvent is 0.2 mmol: 2-10 mL.
5. The production method according to claim 2, wherein the coordination reaction satisfies the following condition: the reaction temperature is 140 ℃ and 180 ℃, and the reaction time is 4-10 h.
6. The production method according to claim 2, wherein the hexafluorophosphate salt is at least one selected from the group consisting of potassium hexafluorophosphate, ammonium hexafluorophosphate and sodium hexafluorophosphate.
7. The production method according to claim 2, wherein the solvent is selected from at least one of methanol, ethanol, and ethylene glycol.
8. The production method according to claim 2, wherein the shielding gas is nitrogen and/or argon.
9. The production method according to claim 2, wherein X is chlorine.
10. A catalytic reduction method of an aromatic nitro compound is characterized by comprising the following steps: in the presence of a solvent and light, the ruthenium (II) bisoxazoline pyridine compound as claimed in claim 1 is used as a catalyst, and an aromatic nitro compound and a reducing agent are subjected to catalytic reaction to obtain an aromatic amine compound.
11. A catalytic reduction process according to claim 10, wherein the molar ratio of the aromatic nitro compound, the reducing agent and the catalyst is 1: 5-10: 0.01-0.03.
12. A catalytic reduction process according to claim 10, wherein the aromatic nitro compound and the solvent are used in a ratio of 1 mmol: 5-10 mL.
13. A catalytic reduction process according to claim 10, wherein the catalytic reaction satisfies the following condition: the reaction temperature is 15-25 ℃, and the reaction time is 1-5 h.
14. A catalytic reduction process according to claim 10, wherein the catalytic reaction is carried out under irradiation of sunlight or blue light.
15. A catalytic reduction process according to claim 14, wherein the blue light satisfies the following condition: the wavelength is 400-450nm, and the power of the blue light lamp is 35-40W.
16. A catalytic reduction process according to claim 10, wherein the reducing agent is selected from at least one of sodium borohydride, lithium borohydride, hydrazine hydrate.
17. Catalytic reduction process according to claim 10, wherein the aromatic nitro compound is selected from at least one of 4-bromonitrobenzene, nitrobenzene, p-nitrophenol, o-chloronitrobenzene, p-nitroaniline, 4-nitrobenzonitrile.
18. A catalytic reduction process according to claim 10, wherein the solvent is selected from at least one of methanol, ethanol and ethylene glycol.
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