CN106046061A - Half-sandwich ruthenium complex and preparation method thereof, preparation method of ligand and reduction method of nitrobenzene compound - Google Patents
Half-sandwich ruthenium complex and preparation method thereof, preparation method of ligand and reduction method of nitrobenzene compound Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003446 ligand Substances 0.000 title claims abstract description 21
- -1 nitrobenzene compound Chemical class 0.000 title claims abstract description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 26
- 239000000460 chlorine Substances 0.000 claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 239000002585 base Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 22
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 19
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000002367 halogens Chemical group 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 125000000266 alpha-aminoacyl group Chemical group 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 6
- 229960001860 salicylate Drugs 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001448 anilines Chemical class 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940005667 ethyl salicylate Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZTCQFVRINYOPOH-UHFFFAOYSA-N n-(4-nitrophenyl)formamide Chemical compound [O-][N+](=O)C1=CC=C(NC=O)C=C1 ZTCQFVRINYOPOH-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
-
- 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
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide 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
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a half-sandwich ruthenium complex and a preparation method thereof, a preparation method of ligand and a reduction method of a nitrobenzene compound. The structure of the half-sandwich ruthenium complex is shown by formula (A), wherein in the formula (A), R1 and R2 are separately selected from H or C1-C7 alkyl, and X is halogen; preferentially, the C1-C7 alkyl is methyl, ethyl or phenyl, and X is chlorine; more preferentially, R1 is H, R2 is H or C1-C7 hydrocarbyl, and X is chlorine; and most preferentially, R1 is H, R2 is methyl, ethyl or phenyl, and X is chlorine. The half-sandwich ruthenium complex is prepared by an efficient preparation method; the half-sandwich ruthenium complex can efficiently and mildly catalyze a nitrobenzene compound to reduce the nitrobenzene compound into an aniline compound; and moreover, the conditions of the preparation method of ligand in the half-sandwich ruthenium complex are relatively mild, and the yield is relatively high.
Description
Technical field
The present invention relates to ruthenium complex, in particular it relates to half sandwich ruthenium complex and preparation method thereof, the preparation side of part
Method and the method for reducing of nitrobenzene compounds.
Background technology
There is the coordination compound of ruthenium with half-sandwich structure there is the chemical stability of uniqueness, excellent optical property and abundant
Redox property, is the primary study content of the subjects such as inorganic chemistry, materials chemistry and Coordinative Chemistry, and is increasingly becoming the modern times
A very active field in chemical research.There is the coordination compound of ruthenium with half-sandwich structure at photochemistry, organic catalysis, alkene
Hydrocarbon double decomposition, electrochemistry, fluorescent ion probe, the aspect such as gas sensing plays important application.Therefore, synthesize and explore series
The application of the coordination compound with ruthenium with half-sandwich structure is very important research contents；But existing have ruthenium with half-sandwich structure
The preparation method of coordination compound still suffer from some defects, such as: the response time is longer, productivity is relatively low.
Amino benzenes compounds is a kind of basic Organic Chemicals, is widely used in medicine, pesticide, printing and dyeing and rubber etc.
Industry, is important Organic Ingredients.At present, the most frequently used preparation method of amino benzenes compounds is iron powder reducing method, because it produces
During high to equipment requirements, pollute environment, the drawbacks such as energy expenditure is big, product separation trouble, the method for another kind of preparation is
Catalytic hydrogenation, the major defect of the method is that reaction needs higher pressure, and production cost is higher.
Summary of the invention
It is an object of the invention to provide a kind of half sandwich ruthenium complex and preparation method thereof, the preparation method of part and nitre
The method of reducing of base benzene-like compounds；Half sandwich ruthenium complex is prepared, this half sandwich ruthenium complex by efficient preparation method
Efficiently, leniently can be catalyzed nitrobenzene compounds and be reduced into amino benzenes compounds；It addition, part in half sandwich ruthenium complex
Preparation method condition the gentleest, productivity is higher.
To achieve these goals, the invention provides a kind of half sandwich ruthenium complex, the knot of this half sandwich ruthenium complex
Shown in structure such as formula (A),
Wherein, in formula (A), R1、R2Being each independently selected from the alkyl of H or C1-C7, X is halogen；Preferably, C1-C7
Alkyl be methyl, ethyl or phenyl, X is chlorine；It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, X is chlorine；The most excellent
Selection of land, R1For H, R2For methyl, ethyl or phenyl, X is chlorine.
Present invention provides the preparation method of a kind of half above-mentioned sandwich ruthenium complex, this preparation method is: in protection
In the presence of gas, organic solvent and alkali compounds, will as shown in formula (B) the 2-oxazoline base phenol ligands of structure with such as formula
(C) compound of structure shown in carries out haptoreaction to prepare half sandwich ruthenium complex as shown in formula (A),
In above formula, R1、R2Being each independently selected from the alkyl of H or C1-C7, X is halogen；Preferably, the alkyl of C1-C7
For methyl, ethyl or phenyl, X is chlorine；It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, X is chlorine；It is further preferred that R1
For H, R2For methyl, ethyl or phenyl, X is chlorine.
Invention further provides a kind of 2-oxazoline base phenol for preparing the sandwich ruthenium complex of above-mentioned half to join
The preparation method of body, this preparation method is: will as shown in formula (D) salicylate of structure with as shown in formula (E) amino of structure
Substituted alcohols carry out haptoreaction with prepare as shown in formula (B) the 2-oxazoline base phenol ligands of structure,
In above formula, R1、R2It is each independently selected from the alkyl of H or C1-C7, R3Alkyl for C1-C6；Preferably, C1-
The alkyl of C7 is methyl, ethyl or phenyl, R3Alkyl for C1-C3；It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, R3
For ethyl；It is further preferred that R1For H, R2For methyl, ethyl or phenyl, R3For ethyl.
Present invention also offers a kind of method that nitrobenzene compounds is reduced into amino benzenes compounds, the method is:
In the presence of oxygen, with half sandwich ruthenium complex as claimed in claim 1 as catalyst, at alkali compounds and organic solvent
In the presence of, the nitrobenzene compounds of structure as shown in formula (F) is carried out reduction reaction to prepare the benzene of structure as shown in formula (F)
Aminated compounds；
Wherein, R4For H, halogen, the alkyl of C1-C6 or aminoacyl, n is the positive integer of 1-5；Preferably, R4For halogen, C1-
The alkyl of C3 or aminoacyl, n is 1；It is highly preferred that R4For chlorine, bromine, iodine, methyl or aminoacyl, n is 1, and, R4It is positioned at nitro
Or in the ortho position of amino, meta or para-position.
By technique scheme, the present invention the most just as shown in formula (D) salicylate of structure with as shown in formula (E)
It is (concrete to prepare the 2-oxazoline base phenol ligands of structure as shown in formula (B) that the amino substituted alcohols of structure carries out haptoreaction
The reaction mechanism mechanism of reaction is shown in Fig. 1, replaces additive reaction before this, followed by replaces cyclization)；Then at protection gas, organic solvent and alkali
Property compound in the presence of, will as shown in formula (B) the 2-oxazoline base phenol ligands of structure with as shown in formula (C) chemical combination of structure
Thing carries out haptoreaction to prepare half sandwich ruthenium complex as shown in formula (A)；Finally, in the presence of oxygen, with such as right
Half sandwich ruthenium complex of requirement 1 is catalyst, in the presence of alkali compounds and organic solvent, will tie as shown in formula (F)
The nitrobenzene compounds of structure carries out reduction reaction to prepare the amino benzenes compounds of structure as shown in formula (F).In the present invention,
Each reaction method for preparing environment is the gentleest, and the productivity of product is higher simultaneously；Especially, the reduction of nitrobenzene compounds
During, it is possible to reduce nitrobenzene compounds efficiently, have broad application prospects.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not intended that limitation of the present invention.In the accompanying drawings:
Fig. 1 is the reaction mechanism mechanism of reaction figure of the 2-oxazoline base phenol ligands that the present invention provides；
Fig. 2 is the single crystal diffraction figure of the half sandwich ruthenium complex prepared in embodiment 4.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of half sandwich ruthenium complex, shown in the structure such as formula (A) of this half sandwich ruthenium complex,
Wherein, in formula (A), R1、R2Being each independently selected from the alkyl of H or C1-C7, X is halogen.In fact, each substituent group
Concrete kind can select in wide scope, it is contemplated that synthesis be difficult to degree and preparation cost, it is preferable that
The alkyl of C1-C7 is methyl, ethyl or phenyl, and X is chlorine；It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, X is chlorine；Enter one
Walk preferably, R1For H, R2For methyl, ethyl or phenyl, X is chlorine.
Present invention provides the preparation method of a kind of half above-mentioned sandwich ruthenium complex, this preparation method is: in protection
In the presence of gas, organic solvent and alkali compounds, will as shown in formula (B) the 2-oxazoline base phenol ligands of structure with such as formula
(C) compound of structure shown in carries out haptoreaction to prepare half sandwich ruthenium complex as shown in formula (A),
In above formula, R1、R2Being each independently selected from the alkyl of H or C1-C7, X is halogen.In fact, each substituent group is concrete
Kind can select in wide scope, it is contemplated that synthesize is difficult to degree and preparation cost, it is preferable that C1-C7's
Alkyl is methyl, ethyl or phenyl, and X is chlorine；It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, X is chlorine；Further preferably
Ground, R1For H, R2For methyl, ethyl or phenyl, X is chlorine.
In the preparation method of above-mentioned half sandwich ruthenium complex, the consumption of each material can select in wide scope, but
It is the productivity in order to improve product further, it is preferable that relative to the compound of structure as shown in formula (C) of 1mmol, such as formula
(B) consumption of the 2-oxazoline base phenol ligands of structure shown in is 1-3mmol, and the consumption of strong base-weak acid salt is 1-3mmol, organic
The consumption of solvent is 5-25mL.
Meanwhile, in the preparation method of above-mentioned half sandwich ruthenium complex, the concrete kind of alkali compounds can also be wide
In the range of select, but in order to improve the productivity of reaction rate and product further, it is preferable that alkali compounds be alkali and/
Or strong base-weak acid salt；It is highly preferred that alkali compounds is selected from sodium acetate, potassium acetate, potassium carbonate, in sodium carbonate and sodium hydroxide
One or more.
Additionally, in the preparation method of above-mentioned half sandwich ruthenium complex, the concrete kind of organic solvent can also be at wide model
Enclose interior selection, but in order to improve the productivity of reaction rate and product further, it is preferable that organic solvent is selected from methanol, second
One or more in alcohol and acetonitrile.
It addition, in the preparation method of above-mentioned half sandwich ruthenium complex, the concrete kind of protection gas can also be in wide scope
Interior selection, but in order to improve the productivity of product further, it is preferable that the one or many in protection gas nitrogen, argon and helium
Kind.
Further, in the preparation method of above-mentioned half sandwich ruthenium complex, catalytic concrete reaction condition can also be
Select in wide scope, but in order to improve the productivity of reaction rate and product further, it is preferable that haptoreaction is the fullest
Be enough to lower condition: reaction temperature is 80-110 DEG C, the response time is 2-6h.
Invention further provides a kind of 2-oxazoline base phenol for preparing the sandwich ruthenium complex of above-mentioned half to join
The preparation method of body, this preparation method is: will as shown in formula (D) salicylate of structure with as shown in formula (E) amino of structure
Substituted alcohols carry out haptoreaction with prepare as shown in formula (B) the 2-oxazoline base phenol ligands of structure,
In above formula, R1、R2It is each independently selected from the alkyl of H or C1-C7, R3Alkyl for C1-C6.In fact, respectively replace
The concrete kind of base can select in wide scope, it is contemplated that synthesize is difficult to degree and preparation cost, it is preferable that
The alkyl of C1-C7 is methyl, ethyl or phenyl, R3Alkyl for C1-C3；It is highly preferred that R1For H, R2For the alkyl of H, C1-C7,
R3For ethyl；It is further preferred that R1For H, R2For methyl, ethyl or phenyl, R3For ethyl.
In the preparation method of above-mentioned 2-oxazoline base phenol ligands, the consumption of each material can select in wide scope
Select, but in order to improve the productivity of product, it is preferable that salicylate is 1:0.5-1.5 with the mol ratio of amino substituted alcohols.
In the preparation method of above-mentioned 2-oxazoline base phenol ligands, catalytic actual conditions can be in wide scope
Interior selection, but in order to improve the productivity of product, it is preferable that haptoreaction at least meets following condition: reaction temperature is 100-
180 DEG C, the response time is 3-12h.
Present invention also offers a kind of method that nitrobenzene compounds is reduced into amino benzenes compounds, the method is:
In the presence of oxygen, with half sandwich ruthenium complex as claimed in claim 1 as catalyst, at alkali compounds and organic solvent
In the presence of, the nitrobenzene compounds of structure as shown in formula (F) is carried out reduction reaction to prepare the benzene of structure as shown in formula (F)
Aminated compounds；
Wherein, R4For H, halogen, the alkyl of C1-C6 or aminoacyl, n is the positive integer of 1-5.In fact, the tool of each substituent group
The concrete numerical value of body kind and n can select in wide scope, it is contemplated that synthesize is difficult to degree and is prepared as
This, it is preferable that R4For halogen, the alkyl of C1-C3 or aminoacyl, n is 1；It is highly preferred that R4For chlorine, bromine, iodine, methyl or aminoacyl
Base, n is 1, and, R4It is positioned in nitro or the ortho position of amino, meta or para-position.
It addition, in above-mentioned reduction system, the concrete consumption of each material can select in wide scope, but in order to enter
One step improves the productivity of product, it is preferable that relative to 1mmol nitrobenzene compounds, the consumption of half sandwich ruthenium complex is
0.01-0.03mmol, the consumption of organic solvent is 1-4mL, and the consumption of alkali compounds is 0.05-0.2mmol；It is highly preferred that
Relative to 1mmol nitrobenzene compounds, the consumption of half sandwich ruthenium complex is 0.015-0.025mmol, the use of organic solvent
Amount is 1.5-2.5mL, and the consumption of alkali compounds is 0.08-0.15mmol.
Additionally, in above-mentioned reduction system, the concrete kind of organic solvent can select in wide scope, but in order to
Improve the productivity of product further, it is preferable that one or more in isopropanol, ethanol and methanol of organic solvent.
Meanwhile, in above-mentioned reduction system, the concrete kind of alkali compounds can select in wide scope, but is
The productivity of further raising product, it is preferable that alkali compounds in potassium hydroxide, sodium hydroxide and potassium tert-butoxide one
Plant or multiple.
On the basis of the above, the actual conditions of reduction reaction can select in wide scope, but in order to enter
One step improves the productivity of product, it is preferable that reduction reaction at least meets following condition: reaction temperature is 80-100 DEG C, during reaction
Between be 2-10h.
Hereinafter will be described the present invention by embodiment.Nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum are to pass through Switzerland
Bruker AV300 and Bruker AV 500MHz nuclear magnetic resonance analyser record, and single crystal diffraction collection of illustrative plates is spread out by Bruker AXS monocrystalline
Penetrate instrument SMART APEX II to record.
[(CymeneRuCl2)2] (i.e. the compound of structure as shown in formula (C)) be that the brilliant pure biochemical technology share in Shanghai is limited
The product of company of company, potassium carbonate, isopropanol, nitro compound is the product of Shanghai Jing Chun biochemical technology limited company,
Acetonitrile is the product of Shanghai Jing Chun biochemical technology limited company.
Embodiment 1
Preparation:
Ethyl salicylate (4.4mL, 30mmol) and 2-amino-2-methyl-1-propanol is added in 100mL round-bottomed flask
(2.39mL, 30mmol) mixture is heated to 170 DEG C of backflow 10h, is spin-dried for Rotary Evaporators after being then cooled to room temperature, will be thick
Reactant mixture loads on silicagel column, crosses post with ethyl acetate and normal hexane, obtains the intermediate product of white oil, by product
Adding in 50mL reaction tube, add 10mL dichloromethane and 0.5mL thionyl chloride reacts 2 days under ice-water bath, sucking filtration also uses water
Obtaining white solid 2.97g after washing with dichloromethane, productivity is 56%.
Gained sign data result:1H NMR(300MHz,CDCl3)δ12.16(s,1H),7.39(s,1H),7.37(s,
1H), 6.97 (d, J=9.0Hz, 1H), 6.84 (t, 1H), 4.56 (s, 1H), 3.80 (m, 1H), 3.67 (m, 1H), 1.38 (d, J
=9.0Hz, 3H)；13C NMR(125MHz,CDCl3)δ170.68,161.65,134.65,126.34,119.24,118.78,
114.65,43.13,37.70,32.24.IR(KBr,cm-1):3203(s),2926(m),1639(vs),1465(s),1366
(m),1326(w),1255(s),1167(m),1089(m),1051(w),930(s),829(w),743(s),678(m).
Embodiment 2
Preparation:
Carrying out preparing white liquid 2.46g according to the method for embodiment 1, productivity is 43%.Except that, by 2-ammonia
Base-2-methyl isophthalic acid-propanol is changed to 2-amino-n-butyl alcohol, changes return time into 8h.
Gained sign data result:1H NMR(300MHz,CDCl3)δ12.17(s,1H),7.40(t,2H),6.99(d,J
=9.0Hz, 1H), 6.85 (t, 1H), 4.35 (t, 1H), 3.78 (m, 2H), 1.75 (m, 2H), 1.00 (t, 3H)；IR(KBr,cm-1):3081(s),2968(m),1626(vs),1546(vs),1494(s),1454(s),1372(s),1303(s),1240(s),
1156(m),1099(s),1041(m),980(m),888(m),755(s),688(s),653(w),593(m).
Embodiment 3
Preparation:
Carrying out preparing white liquid 0.56g according to the method for embodiment 1, productivity is 31%.Except that, by 2-ammonia
Base-2-methyl isophthalic acid-propanol (30nmmol) is changed to DL-benzene glycinol (7.5nmmol), is changed into by the consumption of ethyl salicylate
7.5nmmol, and counterflow condition is changed into 4h at 100 DEG C.
Gained sign data result:1H NMR(300MHz,CDCl3) δ 12.16 (s, 1H), 7.73 (d, J=9.0Hz, 1H),
7.33 (m, 6H), 7.05 (d, J=9.0Hz, 1H), 6.91 (t, 1H), 5.47 (t, 1H), 4.80 (t, 1H), 4.24 (t, 1H) .IR
(KBr cm-1):3069(s),2956(m),1637(vs),1540(s),1490(s),1450(s),1364(s),1303(m),
1230(s),1152(w),1091(m),1034(w),938(w),888(w),820(w),751(s),695(s),615(m),525
(m).
Embodiment 4
Preparation:
Under nitrogen protection, in 50mL reaction tube, [(CymeneRuCl is put into2)2] (612mg, 1mmol), in embodiment 1
2-oxazoline base phenol ligands (354mg, 2mmol), the K prepared2CO3(276mg, 2mmol) and 15mL acetonitrile are as solvent.Will
Mixture is heated and stirred the 3h that refluxes at 100 DEG C, is subsequently cooled to 25 DEG C.Solvent, gained solid is removed with Rotary Evaporators
Being dried rufous product 250mg by column chromatography chromatogram method isolated, productivity is 56%.
Gained sign data result:1H NMR(300MHz,CDCl3) δ 7.42 (d, J=9.0Hz, 1H), 7.12 (d, J=
9.0Hz, 1H), 6.94 (d, J=9.0Hz, 1H), 6.36 (d, J=9.0Hz, 1H), 5.44 (s, 2H), 5.34 (s, 1H), 5.02
(d, J=6.0Hz, 1H), 4.72 (d, J=6.0Hz, 1H), 4.61 (d, J=9.0Hz, 1H), 4.16 (d, J=6.0Hz, 1H),
2.77 (t, 1H), 2.27 (s, 2H), 2.15 (s, 1H), 1.69 (s, 1H), 1.59 (d, J=6.0Hz, 2H), 1.25 (d, J=
9.0Hz, 3H), 1.15 (d, J=6.0Hz, 6H)；13C NMR(125MHz,CDCl3)168.47,163.10,134.35,
129.57,123.45,114.07,109.05,101.49,97.90,86.15,83.63,80.57,79.88,73.57,66.94,
31.05,23.20,22.58,22.22,19.18.IR(KBr cm-1):2968(m),1624(vs),1540(s),1472(s),
1446(m),1393(m),1353(s),1240(s),1154(m),1108(w),1062(m),965(m),909(w),867(w),
776(m),762(m),690(w)；Single crystal diffraction figure is shown in Fig. 2.
Embodiment 5
Preparation:
Carrying out preparing rufous product 410mg according to the method for embodiment 4, productivity is 89%.Except that, will implement
The 2-oxazoline base phenol ligands prepared in example 1 is changed in embodiment 2 the 2-oxazoline base phenol ligands prepared.
Gained sign data result:1H NMR(300MHz,CDCl3) δ 7.40 (d, J=9.0Hz, 1H), 7.11 (s, 1H),
6.91 (d, J=9.0Hz, 1H), 6.86 (d, J=9.0Hz, 1H), 5.43 (s, 2H), 5.34 (d, J=6.0Hz, 1H), 4.98
(d, J=4.0Hz, 1H), 4.52 (s, 2H), 4.31 (s, 1H), 2.78 (t, 1H), 2.25 (s, 3H), 1.89 (s, 1H), 1.74
(s, 1H), 1.25 (d, J=6.0Hz, 3H), 1.16 (d, J=6.0Hz, 3H), 0.95 (s, 3H)；13C NMR(125MHz,
CDCl3)δ168.61,162.96,134.29,129.56,123.43,114.01,108.97,101.63,97.67,85.84,
83.67,80.80,79.95,72.75,71.43,31.02,28.49,23.16,22.20,19.11,10.40.IR(KBr cm-1):2968(m),1624(vs),1540(s),1469(s),1395(s),1343(s),1242(vs),1200(w),1152(m),
1164(m),1028(w),988(w),949(w),921(m),852(s),755(m),688(m).
Embodiment 6
Preparation:
Carrying out preparing rufous product 305mg according to the method for embodiment 4, productivity is 60%.Except that, will implement
The 2-oxazoline base phenol ligands prepared in example 1 is changed in embodiment 3 the 2-oxazoline base phenol ligands prepared.
Gained sign data result:1H NMR(300MHz,CDCl3)δ7.49(m,6H),7.17(t,1H),6.95(d,J
=9.0Hz, 1H), 6.44 (t, 1H), 5.52 (m, 1H), 5.05 (d, J=3.0Hz, 2H), 4.77 (t, 1H), 4.65 (d, J=
3.0Hz, 1H), 4.56 (d, J=3.0Hz, 1H), 4.40 (m, 6H), 2,70 (m, 1H), 2.05 (s, 3H), 1.15 (d, J=
6.0Hz, 3H), 1.01 (d, J=6.0Hz, 3H)；13C NMR(125MHz,CDCl3)δ169.33,166.31,142.71,
134.67,134.56,129.85,129.59,129.42,129.15,127.68,123.40,114.31,110.04,102.54,
95.30,83.79,83.48,81.22,78.81,75.44,73.75,30.75,22.85,22.04,18.70.IR(KBr cm-1):2956(m),1616(vs),1538(m),1467(s),1383(m),1345(m),1238(s),1150(w),1072(m),
951(w),925(w),850(m),747(s),701(m),659(w),571(w).
Embodiment 7
In air atmosphere, put into politef magneton one in the reactor, add with in embodiment 3 the half of preparation
Sandwich ruthenium complex 0.02mmol (2mol%), 1mmol parachloronitrobenzene, 2mL isopropanol and 0.1mmol potassium hydroxide,
In oil bath, it is heated to 90 DEG C, stirs 3h.After reaction terminates, remove solvent with Rotary Evaporators, then by ethyl acetate and just
The eluant of hexane crosses silica gel column chromatography, obtains parachloroanilinum (117mg, productivity 92%)；Characterization result is:1H NMR
(300MHz,CDCl3): δ 7.10 (d, J=9.0Hz, 2H), 6.60 (d, J=6.0Hz, 2H), 3.64 (br, 2H).
Embodiment 8
Carrying out preparing para-bromoaniline (158mg, productivity 91%) according to the method for embodiment 7, characterization result is:1H NMR
(300MHz,CDCl3): δ 7.24 (d, J=9.0Hz, 2H), 6.57 (d, J=9.0Hz, 2H), 3.65 (br, 2H)；Except for the difference that
Parachloronitrobenzene is changed to p-Nitrobromobenzene.
Embodiment 9
Carrying out preparing 4-amino iodobenzene (192mg, productivity 88%) according to the method for embodiment 7, characterization result is:1H NMR
(300MHz,CDCl3): δ 7.41 (d, J=9.0Hz, 2H), 6.47 (d, J=6.0Hz, 2H), 3.72 (br, 2H).；Except for the difference that
Parachloronitrobenzene is changed to iodonitrobenzene.
Embodiment 10
Carrying out preparing ortho-aminotoluene (87mg, productivity 87%) according to the method for embodiment 7, characterization result is:1H NMR
(300MHz,CDCl3): δ 7.24 (t, 2H), 6.92 (t, 1H), 6.80 (d, J=6.0Hz, 1H), 3.68 (br, 2H), 2.30 (s,
3H).；Except for the difference that parachloronitrobenzene is changed to ortho-methylnitrobenzene.
Embodiment 11
Amido toluene (89mg, productivity 88%) between carrying out preparing according to the method for embodiment 7.11H NMR(300MHz,
CDCl3): δ 7.27 (m, 1H), 6.80 (d, J=6.0Hz, 1H), 6.63 (s, 2H), 3.72 (br, 2H), 2.46 (s, 3H).；No
Same is that parachloronitrobenzene is changed to meta-methylnitrobenzene, and half sandwich ruthenium complex of preparation in embodiment 3 is changed to reality
Execute half sandwich ruthenium complex of preparation in example 1.
Embodiment 12
Carrying out preparing amido toluene (100mg, productivity 94%) according to the method for embodiment 7, characterization result is:1H NMR
(300MHz,CDCl3): δ 7.05 (d, J=9.0Hz, 2H), 6.67 (d, J=9.0Hz, 2H), 3.54 (br, 2H), 2.31 (s,
3H)；Except for the difference that parachloronitrobenzene is changed to para-methylnitrobenzene, by half sandwich ruthenium complex of preparation in embodiment 3
It is changed in embodiment 2 half sandwich ruthenium complex of preparation.
Embodiment 13
Carrying out preparing amido Benzoylamide (130mg, productivity 96%) according to the method for embodiment 7, characterization result is:1H
NMR(300MHz,CD3: δ 7.64 (d, J=9.0Hz, 2H), OD) 6.66 (d, J=9.0Hz, 2H), 4.86 (s, 2H)；Different
It is that parachloronitrobenzene is changed to p-nitrophenyl Methanamide.
Comparative example 1
Carry out preparing chloroaniline (0mg, productivity 0%) according to the method for embodiment 7, except for the difference that do not use half sandwich ruthenium to join
Position compound.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. one and half sandwich ruthenium complex, it is characterised in that shown in the structure such as formula (A) of described half sandwich ruthenium complex,
Wherein, in formula (A), R1、R2Being each independently selected from the alkyl of H or C1-C7, X is halogen；
Preferably, the alkyl of described C1-C7 is methyl, ethyl or phenyl, and X is chlorine；
It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, X is chlorine；
It is further preferred that R1For H, R2For methyl, ethyl or phenyl, X is chlorine.
2. the preparation method of a half sandwich ruthenium complex as claimed in claim 1, it is characterised in that described preparation method
For: in the presence of protection gas, organic solvent and alkali compounds, the 2-oxazoline base phenol of structure as shown in formula (B) is joined
Body and the compound of structure as shown in formula (C) carry out haptoreaction with prepare shown in formula (A) as described in half sandwich ruthenium complex,
In above formula, R1、R2Being each independently selected from the alkyl of H or C1-C7, X is halogen；
Preferably, the alkyl of described C1-C7 is methyl, ethyl or phenyl, and X is chlorine；
It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, X is chlorine；
It is further preferred that R1For H, R2For methyl, ethyl or phenyl, X is chlorine.
Preparation method the most according to claim 2, wherein, relative to described in 1mmol as shown in formula (C) chemical combination of structure
Thing, the described consumption of the 2-oxazoline base phenol ligands of structure as shown in formula (B) is 1-3mmol, the use of described strong base-weak acid salt
Amount is 1-3mmol, and the consumption of described organic solvent is 5-25mL；
Preferably, described alkali compounds is alkali and/or strong base-weak acid salt；
It is highly preferred that described alkali compounds is selected from sodium acetate, potassium acetate, potassium carbonate, the one in sodium carbonate and sodium hydroxide
Or it is multiple；
It is further preferred that described organic solvent is selected from methanol, one or more in ethanol and acetonitrile；
It is further preferred that one or more in described protection gas nitrogen, argon and helium.
4. according to the preparation method described in Claims 2 or 3, wherein, described haptoreaction at least meets following condition: reaction is warm
Degree is for 80-110 DEG C, and the response time is 2-6h.
5. the preparation side being used for preparing the 2-oxazoline base phenol ligands of half sandwich ruthenium complex as claimed in claim 1
Method, it is characterised in that described preparation method is: will as shown in formula (D) salicylate of structure with as shown in formula (E) ammonia of structure
Base substituted alcohols carry out haptoreaction with prepare as shown in formula (B) the 2-oxazoline base phenol ligands of structure,
In above formula, R1、R2It is each independently selected from the alkyl of H or C1-C7, R3Alkyl for C1-C6；
Preferably, the alkyl of described C1-C7 is methyl, ethyl or phenyl, R3Alkyl for C1-C3；
It is highly preferred that R1For H, R2For the alkyl of H, C1-C7, R3For ethyl；
It is further preferred that R1For H, R2For methyl, ethyl or phenyl, R3For ethyl.
Preparation method the most according to claim 5, wherein, described salicylate is 1 with the mol ratio of amino substituted alcohols:
0.5-1.5；
Preferably, described haptoreaction at least meets following condition: reaction temperature is 100-180 DEG C, and the response time is 3-12h.
7. the method that nitrobenzene compounds is reduced into amino benzenes compounds, it is characterised in that described method is: at oxygen
In the presence of gas, with half sandwich ruthenium complex as claimed in claim 1 as catalyst, at alkali compounds and organic solvent
In the presence of, the nitrobenzene compounds of structure as shown in formula (F) is carried out reduction reaction to prepare the benzene of structure as shown in formula (F)
Aminated compounds；
Wherein, R4For H, halogen, the alkyl of C1-C6 or aminoacyl, n is the positive integer of 1-5；
Preferably, R4For halogen, the alkyl of C1-C3 or aminoacyl, n is 1；
It is highly preferred that R4For chlorine, bromine, iodine, methyl or aminoacyl, n is 1, and, R4Be positioned at nitro or the ortho position of amino, meta or
In person's para-position.
Preparation method the most according to claim 7, wherein, relative to nitrobenzene compounds described in 1mmol, described half folder
The consumption of heart ruthenium complex is 0.01-0.03mmol, and the consumption of described organic solvent is 1-4mL, the use of described alkali compounds
Amount is 0.05-0.2mmol；
Preferably, relative to nitrobenzene compounds described in 1mmol, the consumption of described half sandwich ruthenium complex is 0.015-
0.025mmol, the consumption of described organic solvent is 1.5-2.5mL, and the consumption of described alkali compounds is 0.08-0.15mmol.
9. according to the preparation method described in claim 7 or 8, wherein, described organic solvent is in isopropanol, ethanol and methanol
One or more；
Preferably, one or more in potassium hydroxide, sodium hydroxide and potassium tert-butoxide of described alkali compounds.
Preparation method the most according to claim 9, wherein, described reduction reaction at least meets following condition: reaction temperature
For 80-100 DEG C, the response time is 2-10h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610488042.3A CN106046061B (en) | 2016-06-29 | 2016-06-29 | The restoring method of half sandwich ruthenium complex and preparation method thereof, the preparation method of ligand and nitrobenzene compounds |
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| CN106905373A (en) * | 2017-02-17 | 2017-06-30 | 安徽师范大学 | Ruthenium complex of half-sandwich and preparation method thereof, the method that o-nitrophenylethanol class compound is reduced to Benzazole compounds |
| CN108586540A (en) * | 2018-05-10 | 2018-09-28 | 安徽师范大学 | Ruthenium（II）The catalytic reduction method of Lian oxazoline pyridine compounds and preparation method thereof and aromatic nitro compound |
| CN110028530A (en) * | 2019-05-28 | 2019-07-19 | 安徽师范大学 | Half sandwich ruthenium (II) compound containing more tungsten acid anions and its preparation method and application |
| CN110938086A (en) * | 2019-11-20 | 2020-03-31 | 安徽师范大学 | Half-sandwich ruthenium-thione complex and preparation method thereof, ammonia borane hydrolysis method and nitrobenzene compound reduction method |
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| CN106905373A (en) * | 2017-02-17 | 2017-06-30 | 安徽师范大学 | Ruthenium complex of half-sandwich and preparation method thereof, the method that o-nitrophenylethanol class compound is reduced to Benzazole compounds |
| CN108586540A (en) * | 2018-05-10 | 2018-09-28 | 安徽师范大学 | Ruthenium（II）The catalytic reduction method of Lian oxazoline pyridine compounds and preparation method thereof and aromatic nitro compound |
| CN108586540B (en) * | 2018-05-10 | 2020-05-05 | 安徽师范大学 | Ruthenium (II) bisoxazoline pyridine compound, preparation method thereof and catalytic reduction method of aromatic nitro compound |
| CN110028530A (en) * | 2019-05-28 | 2019-07-19 | 安徽师范大学 | Half sandwich ruthenium (II) compound containing more tungsten acid anions and its preparation method and application |
| CN110028530B (en) * | 2019-05-28 | 2021-05-14 | 安徽师范大学 | Half-sandwich ruthenium (II) compound containing polytungstate anions as well as preparation method and application thereof |
| CN110938086A (en) * | 2019-11-20 | 2020-03-31 | 安徽师范大学 | Half-sandwich ruthenium-thione complex and preparation method thereof, ammonia borane hydrolysis method and nitrobenzene compound reduction method |
| CN110938086B (en) * | 2019-11-20 | 2023-04-18 | 安徽师范大学 | Half-sandwich ruthenium-thione complex and preparation method thereof, ammonia borane hydrolysis method and nitrobenzene compound reduction method |
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