CN105153237B - Half sandwich Cyclometalated ruthenium complex and its preparation method and application - Google Patents
Half sandwich Cyclometalated ruthenium complex and its preparation method and application Download PDFInfo
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- CN105153237B CN105153237B CN201510460424.0A CN201510460424A CN105153237B CN 105153237 B CN105153237 B CN 105153237B CN 201510460424 A CN201510460424 A CN 201510460424A CN 105153237 B CN105153237 B CN 105153237B
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000005181 nitrobenzenes Chemical class 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000002585 base Substances 0.000 claims abstract description 14
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 13
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical class [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 14
- -1 methyl isopropyl Chemical group 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 235000011056 potassium acetate Nutrition 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 235000019441 ethanol Nutrition 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 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 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims 1
- 239000003446 ligand Substances 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 239000003480 eluent Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OJSIAFVLLCPOKG-UHFFFAOYSA-N 5,5-dimethyl-2-propan-2-ylcyclohexa-1,3-diene Chemical compound CC(C)C1=CCC(C)(C)C=C1 OJSIAFVLLCPOKG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of half sandwich Cyclometalated ruthenium complex and its preparation method and application, shown in the structure such as formula (A) of the half sandwich Cyclometalated ruthenium complex:R1For Cl, Br or CH3.Under the conditions of preparation method includes: existing for the protective gas; it will be placed in such as formula (B) compound represented, dichloro (p -Methylisopropylbenzene base) ruthenium (II) dimer, alkali and solvent under conditions of temperature is 80-110 DEG C and mix 15-20h, half sandwich Cyclometalated ruthenium complex is made；R1For Cl, Br or CH3.The present invention will be by that will carry out single step reaction such as formula (B) compound represented and dichloro (p -Methylisopropylbenzene base) ruthenium (II) dimer, the Cyclometalated ruthenium complex with half-sandwich is made, and it is applied to catalysis reduction nitrobenzene compounds, aniline and its derivatives are made, it realizes at low cost, it is easy to operate, the small effect of environmental pollution.
Description
Technical field
The present invention relates to synthesising chemical technology fields, and in particular, to a kind of half sandwich Cyclometalated ruthenium complex
And its preparation method and application.
Background technique
Complex with ruthenium with half-sandwich structure has unique chemical stability, excellent optical property and abundant
Redox property, is the primary study content of the subjects such as inorganic chemistry, materials chemistry, and is increasingly becoming in modern chemistry research
One very active field.Have the complex of ruthenium with half-sandwich structure in photochemistry, organic catalysis, alkene subdivision simultaneously
Solution, electrochemistry, fluorescent ion probe, gas sensing etc. play important application.In comparison, ruthenium with half-sandwich structure is matched
Closing object has novel structure, and 1- methyl -4- isopropyl toluene can shield half of metal as class planar molecule, on the one hand
Be conducive to orient bonding；On the other hand the dissolubility that can improve ruthenium complex, is advantageously implemented its functionalized application.Therefore,
The synthesis and application for exploring the complex of ruthenium of the series with half-sandwich are very important.
Aniline and its derivatives are a kind of basic Organic Chemicals, are widely used in medicine, pesticide, printing and dyeing and rubber
Etc. industries, be important Organic Ingredients.Currently, the most common preparation method of aniline and its derivatives is iron powder reducing method, because of it
The high requirements on the equipment in production process pollutes environment, and energy consumption is big, the drawbacks such as product separation trouble, so that it actually makes
Used time has higher cost and pollution environment；And the method for another preparation is catalytic hydrogenation, the major defect of the method is
Reaction needs higher pressure, higher so as to cause production cost.
Therefore it provides a kind of half sandwich Cyclometalated ruthenium complex and preparation method thereof, and it is being applied to
Have at low cost when preparing aniline and its derivatives, easy to operate, the small effect of environmental pollution is urgent need to resolve of the present invention
Problem.
Summary of the invention
For the above-mentioned prior art, it is an object of the invention to overcome in the prior art aniline and its derivatives it is most common
Preparation method is iron powder reducing method, because of the high requirements on the equipment in its production process, pollutes environment, and energy consumption is big, product separation
The drawbacks such as trouble, so that it has higher cost and pollution environment in actual use；And the method for another preparation is catalysis
The problems such as hydrogenization method, the major defect of the method are the higher pressure of reaction needs, higher so as to cause production cost, to mention
For a kind of half sandwich Cyclometalated ruthenium complex and preparation method thereof, and it is made to be applied to prepare aniline and its derivative
There is at low cost, easy to operate, environmental pollution small effect when object.
To achieve the goals above, the present invention provides a kind of half sandwich Cyclometalated ruthenium complexes, wherein described
Shown in the structure such as formula (A) of half sandwich Cyclometalated ruthenium complex:
Wherein, R1For Cl, Br or CH3。
The present invention also provides a kind of preparation method according to half sandwich Cyclometalated ruthenium complex described above,
It wherein, will be if formula (B) compound represented, dichloro are (to first under the conditions of the preparation method includes: existing for the protective gas
Base isopropyl phenyl) ruthenium (II) dimer, alkali and solvent be placed under conditions of temperature is 80-110 DEG C and mix 15-20h, it is made half
Sandwich Cyclometalated ruthenium complex；
Wherein, R1For Cl, Br or CH3。
It is restored according to half sandwich Cyclometalated ruthenium complex described above in catalysis the present invention also provides a kind of
Application in nitrobenzene compounds, wherein the application method includes: by nitrobenzene compounds, reducing agent and according to upper
It states after the half sandwich Cyclometalated ruthenium complex mixes in the presence of a solvent and is reacted.
Through the above technical solutions, the present invention will be such as formula (B) compound represented and dichloro (p -Methylisopropylbenzene base)
Ruthenium (II) dimer carries out single step reaction, and synthesizing can the existing Cyclometalated ruthenium with half-sandwich stable in the air
Complex is then applied to catalysis reduction nitrobenzene compounds, aniline and its derivatives is made, to realize
It is at low cost, easy to operate, the small effect of environmental pollution.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is a kind of reaction mechanism figure provided by the invention；
Fig. 2 is a kind of reaction mechanism figure that embodiment 1 provides in the present invention；
Fig. 3 is the X-ray single crystal diffraction figure of 1a obtained in the embodiment of the present invention 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of half sandwich Cyclometalated ruthenium complexes, wherein the half sandwich Cyclometalated ruthenium
Shown in the structure of complex such as formula (A):
Wherein, R1For Cl, Br or CH3。
The present invention also provides a kind of preparation method according to half sandwich Cyclometalated ruthenium complex described above,
It wherein, will be if formula (B) compound represented, dichloro are (to first under the conditions of the preparation method includes: existing for the protective gas
Base isopropyl phenyl) ruthenium (II) dimer, alkali and solvent be placed under conditions of temperature is 80-110 DEG C and mix 15-20h, it is made half
Sandwich Cyclometalated ruthenium complex；
Wherein, R1For Cl, Br or CH3。
Through the above technical solutions, the present invention will be such as formula (B) compound represented and dichloro (p -Methylisopropylbenzene base)
It is reacted after the mixing of ruthenium (II) dimer, thus can be stable in the air existing with half with simple method one-step synthesis
The Cyclometalated ruthenium complex of interlayer structure.
Above-mentioned mixed method can be only simply to mix, and it is made to react in mixed process, certainly, in order to make
The yield of half sandwich Cyclometalated ruthenium complex obtained is higher, in a preferred embodiment of the invention, institute
Stating mixed process can also include stirring and carrying out back flow reaction.The whipping process and back flow reaction process can be according to abilities
The agitating mode of domain routine is operated, and different one is illustrated herein.
Dosage between each raw material can not be further qualified, and certainly, in order to keep yield higher, improve production effect
Rate reduces production cost, and in a preferred embodiment of the invention, the dichloro relative to 1mmol is (different to methyl
Propyl phenyl) ruthenium (II) dimer, the dosage such as formula (B) compound represented is 2.0-2.5mmol, the dosage of the alkali
For 4-5mmol, the dosage of the solvent is 25-30mL.
The alkali can be alkali commonly used in the art type, for example, can be highly basic, for example, potassium hydroxide or
Sodium hydroxide, or weak base, such as potassium carbonate, sodium oxalate etc., certainly, in a kind of more preferably embodiment party of the invention
In formula, the alkali can be further defined to one of sodium acetate, potassium acetate, potassium carbonate, sodium carbonate and sodium hydroxide or more
Kind.Certainly, the type of alkali here is not limited only to the type for the alkali that the example above illustrates, those skilled in the art can basis
Actual conditions are selected and are adjusted.In a kind of more preferably embodiment of the invention, in order to keep reaction efficiency higher,
Yield is higher, and the alkali can be further selected as potassium acetate.So that easy to operate and raising reaction efficiency.
Certainly, solvent here may be the type of solvent of those skilled in the art's conventional selection, as long as can dissolve above-mentioned
Raw material, for example, in a preferred embodiment of the invention, the solvent can be in methanol, ethyl alcohol and acetonitrile
It is one or more.Certainly, type of solvent those skilled in the art here can according to the actual situation and need carry out into one
The selection of step, the invention is not limited to the types of above-mentioned selected solvent.For example, it is of the invention it is a kind of more preferably
In embodiment, the solvent can be further selected as acetonitrile according to the actual situation by those skilled in the art.Using only one
The fussy degree that kind solvent can substantially reduce operation is still not limited only in the present invention using a kind of this solvent,
Those skilled in the art can be selected and be arranged in pairs or groups accordingly according to practical operation.
Similarly, as long as the protective gas can not be reacted with other raw materials, for example, can be indifferent gas
Body, in a preferred embodiment of the invention, the protective gas can be selected from nitrogen or argon gas.
It is restored according to half sandwich Cyclometalated ruthenium complex described above in catalysis the present invention also provides a kind of
Application in nitrobenzene compounds, wherein the application method includes: by nitrobenzene compounds, reducing agent and according to upper
It states after the half sandwich Cyclometalated ruthenium complex mixes in the presence of a solvent and is reacted.
Above-mentioned design is applied to catalysis reduction nitrobenzene as the half sandwich Cyclometalated ruthenium complex by made from
Aniline and its derivatives are made, to realize at low cost, easy to operate, the small effect of environmental pollution in compound.
Certainly, above-mentioned nitrobenzene compounds, reducing agent and half sandwich Cyclometalated ruthenium complex and solvent can
To be selected according to the actual situation, for example, in a preferred embodiment of the invention, in order in the base for saving cost
Yied of redution is greatly improved on plinth, relative to the nitrobenzene compounds of 1mmol, the dosage of the reducing agent is 3-5mmol, institute
The dosage for stating half sandwich Cyclometalated ruthenium complex is 0.02-0.10mmol, and the dosage of the solvent is 1-5mL.
Certainly, nitrobenzene compounds here can be conventional nitrobenzene and nitrobenzene derivative, art technology
The related compound that personnel are understood that can be used herein, for example, in a preferred embodiment of the invention, institute
Stating nitrobenzene compounds can be in nitrobenzene, 4- nitrophenol, 4- nitro-chlorobenzene, 4- nitrotoleune and 4- nitroaniline
It is one or more.Certainly, nitrobenzene compounds here are not limited thereto, and those skilled in the art can be according to reality
Situation is selected, and different one is illustrated herein.
Certainly, solvent here may be the type of solvent of those skilled in the art's conventional selection, as long as can dissolve above-mentioned
Raw material, for example, in a preferred embodiment of the invention, the solvent in water, methanol and ethyl alcohol one
Kind is a variety of.Certainly, type of solvent those skilled in the art here according to the actual situation and can need to carry out further
Selection, the invention is not limited to the types of above-mentioned selected solvent.For example, more preferably implementing in one kind of the invention
In mode, the solvent can be further selected as water according to the actual situation by those skilled in the art.
The reducing agent can be reducing agent type commonly used in the art, for example, preferred in one kind of the invention
In embodiment, the reducing agent can be selected from sodium borohydride and/or hydrazine.Certainly, in the present invention, the reducing agent not office
It is limited to this, those skilled in the art can select according to actual needs.Similarly, it is of the invention it is a kind of more preferably
In embodiment, the reducing agent can be further selected as sodium borohydride.Certainly, hydrazine here can choose as arbitrary form
Existing hydrazine, for example, in the present invention, in order to enable hydrazine is convenient for saving and using, the hydrazine can be further selected as by water
Hydrazine is closed to provide.
The reaction process can be adjusted according to actual needs, for example, in a kind of preferred embodiment party of the invention
In formula, it is 20-30 DEG C that the temperature of the reaction process, which can choose, and the reaction time can choose as 10-20h.
In order to keep product assay obtained after reduction higher, in a kind of more preferably embodiment of the invention, institute
Stating application method can also include extracting the mixture after reaction.
Certainly, extractant here can be selected according to the actual situation, for example, in a kind of preferred reality of the invention
It applies in mode, the extractant can choose as ethyl acetate.
The present invention will be described in detail by way of examples below.In following embodiment, the dichloro is (to methyl isopropyl
Base phenyl) ruthenium (II) dimer, the sodium acetate and the methanol be Shanghai Aladdin biochemical technology limited liability company production
Conventional commercial products, L1, L2 and L3 be according to P.Garg, S.Chaudhary and M.D.Milton publish in the 79th phase in 2014
" organic chemistry " the 8668-8677 pages (P.Garg, S.Chaudhary and M.D.Milton, The Journal of
Organic Chemistry, 2014,79,8668-8677) prepared by the method recorded in, wherein the knot of L1, L2 and L3
Structure formula difference is as follows.
L1:
L2:
L3:
Embodiment 1
Be put into 50mL reaction tube 1mmol dichloro (p -Methylisopropylbenzene base) ruthenium (II) dimer, 2.4mmolL1 and
4mmol potassium acetate takes 25mL acetonitrile as solvent.It by said mixture heating stirring and flows back 20 hours, is subsequently cooled to room
Temperature.Solvent then is removed with Rotary Evaporators, obtained solid is washed with ether.Product is tied again from ethyl acetate and methylene chloride
Crystalline substance is dried to obtain green product 1a811mg, show that its yield is 87%.Nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrum of product obtained
Parameter are as follows:1H NMR(500MHz,CDCl3, ppm): δ=8.09 (s, 1H), 7.26 (d, 1H), 6.96 (d, 1H) 5.54 (d, 1H),
5.45(d,1H),5.22(d,1H),5.00(d,1H),4.77-4.71(t,2H),4.19-4.12(t,2H),2.55(m,1H),
2.06(s,3H),1.09(d,3H),1.00(d,3H).13C NMR(125MHz,CDCl3, ppm): δ=184.59,174.07,
138.89,136.79,129.63,127.50,123.05,101.93,100.20,88.20,88.07,82.63,81.40,
71.19,54.72,31.49,22.95,22.49,19.31.Wherein, the structure of 1a is as follows:
Embodiment 2
Be put into 50mL reaction tube 1mmol dichloro (p -Methylisopropylbenzene base) ruthenium (II) dimer, 2.4mmolL2 and
4mmol potassium acetate takes 25mL acetonitrile as solvent.It by said mixture heating stirring and flows back 20 hours, is subsequently cooled to room
Temperature.Solvent then is removed with Rotary Evaporators, obtained solid is washed with ether.Product is tied again from ethyl acetate and methylene chloride
Crystalline substance is dried to obtain green product 1b869mg, show that its yield is 85%.Nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrum of product obtained
Parameter are as follows:1H NMR(500MHz,CDCl3, ppm): δ=8.26 (s, 1H), 7.20 (d, 1H), 7.12 (d, 1H) 5.54 (d, 1H),
5.46(d,1H),5.22(d,1H),4.50(d,1H),4.77-4.69(t,2H),4.18-4.10(t,2H),2.55(m,1H),
2.06(s,3H),1.09(d,3H),1.00(d,3H).13C NMR(500MHz,CDCl3, ppm): δ=185.15,174.21,
141.62,130.01,127.79,126.44,125.85,101.97,100.25,88.19,88.08,82.68,81.34,
71.20,54.74,31.49,22.94,22.51,19.31.Wherein, the structure of 1b is as follows:
Embodiment 3
Be put into 50mL reaction tube 1mmol dichloro (p -Methylisopropylbenzene base) ruthenium (II) dimer, 2.4mmolL3 and
4mmol potassium acetate takes 25mL acetonitrile as solvent.It by said mixture heating stirring and flows back 20 hours, is subsequently cooled to room
Temperature.Solvent then is removed with Rotary Evaporators, obtained solid is washed with ether.Product is tied again from ethyl acetate and methylene chloride
Crystalline substance is dried to obtain to obtain green product 1c731mg, show that its yield is 82%.The nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon of product obtained
The parameter of spectrum are as follows:1H NMR(300MHz,CDCl3, ppm): δ=7.95 (s, 1H), 7.24 (d, 1H), 6.79 (d, 1H) 5.53 (d,
1H),5.44(d,1H),5.20(d,1H),4.98(d,1H),4.76-4.67(t,2H),4.20-4.09(t,2H),2.55(m,
1H),2.39(s,3H),2.04(s,3H),1.09(d,3H),1.00(d,3H).13C NMR(500MHz,CDCl3, ppm): δ=
182.78(C-Ru),174.53,141.01,140.23,128.39,126.41,123.84,101.20,99.36,88.08,
87.88,82.38,81.09,70.93,54.57,31.48,22.95,22.53,19.30,15.63.Wherein, the structure of 1c is as follows
It is shown:
Application examples 1
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, is added in 0.1mmol embodiment 1 and is made
1a, 1mmol nitrobenzene, the sodium borohydride and 3mL water of 5mmol are as solvent, open stirring 15h at room temperature.Reaction
After, it is three times with the extraction of 3mL ethyl acetate, dry with anhydrous sodium sulfate after collected organic layer, then with ethyl acetate and just
The eluant, eluent of hexane crosses silica gel column chromatography, obtains 84mg aniline(yield 90%).The nucleus magnetic hydrogen spectrum of product obtained and
The parameter of nuclear-magnetism carbon spectrum are as follows:1H NMR(300MHz,CDCl3):7.16(m,2H),6.77(m,1H),6.69(m,2H),3.35
(br,2H)ppm；13C NMR(75MHz,CDCl3):146.41,129.41,118.73,115.26ppm。
Application examples 2
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, is added in 0.1mmol embodiment 2 and is made
1b, 1mmol nitrobenzene, the sodium borohydride and 3mL water of 5mmol are as solvent, open stirring 15h at room temperature.Reaction
After, it is three times with the extraction of 3mL ethyl acetate, dry with anhydrous sodium sulfate after collected organic layer, then with ethyl acetate and just
The eluant, eluent of hexane crosses silica gel column chromatography, obtains 82mg aniline(yield 88%).
Application examples 3
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, is added in 0.1mmol embodiment 3 and is made
1c, 1mmol nitrobenzene, the sodium borohydride and 3mL water of 5mmol are as solvent, open stirring 15h at room temperature.Reaction
After, it is three times with the extraction of 3mL ethyl acetate, dry with anhydrous sodium sulfate after collected organic layer, then with ethyl acetate and just
The eluant, eluent of hexane crosses silica gel column chromatography, obtains 78mg aniline(yield 83%).
Application examples 4
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, is added in 0.1mmol embodiment 1 and is made
1a, 1mmol4- nitrophenol, the sodium borohydride and 3mL water of 5mmol are as solvent, open stirring 15h at room temperature.
After reaction, three times with the extraction of 3mL ethyl acetate, dry with anhydrous sodium sulfate after collected organic layer, then use ethyl acetate
Silica gel column chromatography is crossed with the eluant, eluent of normal hexane, obtains 100mg4- amino-phenol(yield 92%).Product obtained
Nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum parameter are as follows:1H NMR(300MHz,CD3OD):6.59-6.67(m,4H)ppm；13C NMR
(75MHz,CD3OD):116.65,118.43,140.17,151.20ppm。
Application examples 5
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, is added in 0.1mmol embodiment 1 and is made
1a, 1mmol4- nitro-chlorobenzene, the sodium borohydride and 3mL water of 5mmol are as solvent, open stirring 15h at room temperature.
After reaction, three times with the extraction of 3mL ethyl acetate, dry with anhydrous sodium sulfate after collected organic layer, then use ethyl acetate
Silica gel column chromatography is crossed with the eluant, eluent of normal hexane, obtains 119mg4- amino-chloro-benzene(yield 93%).Product obtained
Nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum parameter are as follows:1H NMR(300MHz,CDCl3):3.62(s,2H),6.60-6.65(d,2H),
7.10-7.15(d,2H)；ppm；13C NMR(75MHz,CDCl3):116.63(2C),123.52,129.48(2C),
145.37ppm。
Application examples 6
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, is added in 0.1mmol embodiment 1 and is made
1a, 1mmol4- nitrotoleune, the sodium borohydride and 3mL water of 5mmol are as solvent, open stirring 15h at room temperature.
After reaction, three times with the extraction of 3mL ethyl acetate, dry with anhydrous sodium sulfate after collected organic layer, then use ethyl acetate
Silica gel column chromatography is crossed with the eluant, eluent of normal hexane, obtains 91mg4- amino toluene(yield 85%).Product obtained
The parameter of nucleus magnetic hydrogen spectrum and nuclear-magnetism carbon spectrum are as follows:1H NMR(300MHz,CDCl3):2.25(s,3H),3.54(br,2H),6.62(d,
2H),6.98(d,2H)；ppm；13C NMR(75MHz,CDCl3):20.34,115.13,127.66,129.63,143.69ppm。
Application examples 7
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, is added in 0.1mmol embodiment 1 and is made
1a, 1mmol4- nitroaniline, the sodium borohydride and 3mL water of 5mmol are as solvent, open stirring 15h at room temperature.
After reaction, three times with the extraction of 3mL ethyl acetate, dry with anhydrous sodium sulfate after collected organic layer, then use ethyl acetate
Silica gel column chromatography is crossed with the eluant, eluent of normal hexane, obtains 103mg1, bis- amido benzene of 4-(yield 95%).Production obtained
The parameter of nucleus magnetic hydrogen spectrum and the nuclear-magnetism carbon spectrum of object are as follows:1H NMR(300MHz,CD3OD):6.62-6.68(m,4H)；ppm；13C
NMR(75MHz,CD3OD):118.96,140.55ppm。
Comparative example
In air atmosphere, it is put into polytetrafluoroethylene (PTFE) magneton one in the reactor, 1mmol nitrobenzene, the boron of 5mmol is added
Sodium hydride and 3mL water are open at room temperature to stir 15h as solvent.After reaction, with 3mL ethyl acetate extraction three
It is secondary, it is dry with anhydrous sodium sulfate after collected organic layer, aniline is not obtained through detecting
Through the foregoing embodiment, application examples and comparative example can be seen that obtained half sandwich Cyclometalated through the invention
When restoring nitrobenzene compounds, its yield is high when ruthenium complex is as catalyst, and reaction condition requires low, reaction
Simply, and then as can be seen that it realizes at low cost, easy to operate, the small effect of environmental pollution.And it is not added with system of the present invention
When the catalyst obtained, then reducing agent reaction condition according to the invention can not restore nitrobenzene compounds.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (20)
1. a kind of half sandwich Cyclometalated ruthenium complex, which is characterized in that the half sandwich Cyclometalated ruthenium ligand compound
Shown in the structure of object such as formula (A):
Wherein, R1For Cl, Br or CH3。
2. a kind of preparation method of half sandwich Cyclometalated ruthenium complex according to claim 1, which is characterized in that
It, will be if formula (B) compound represented, dichloro are (to methyl isopropyl under the conditions of the preparation method includes: existing for the protective gas
Base phenyl) ruthenium (II) dimer, alkali and solvent be placed in temperature be 80-110 DEG C under conditions of mix 15-20h, be made half sandwich ring
Metallize ruthenium complex；
Wherein, R1For Cl, Br or CH3。
3. preparation method according to claim 2, wherein the mixed process includes stirring and carrying out back flow reaction.
4. preparation method according to claim 3, wherein the dichloro (p -Methylisopropylbenzene relative to 1mmol
Base) ruthenium (II) dimer, the dosage such as formula (B) compound represented is 2.0-2.5mmol, and the dosage of the alkali is 4-
5mmol, the dosage of the solvent are 25-30mL.
5. preparation method according to claim 2, wherein the alkali be sodium acetate, potassium acetate, potassium carbonate, sodium carbonate and
One of sodium hydroxide is a variety of.
6. preparation method according to claim 5, wherein the alkali is potassium acetate.
7. preparation method according to claim 5, wherein the solvent is one of methanol, ethyl alcohol and acetonitrile or more
Kind.
8. preparation method according to claim 5, wherein the solvent is acetonitrile.
9. preparation method according to claim 5, wherein the protective gas is selected from nitrogen or argon gas.
10. a kind of half sandwich Cyclometalated ruthenium complex according to claim 1 restores nitrobenzene in catalysis
Close the application in object, which is characterized in that the application method includes: to want by nitrobenzene compounds, reducing agent and according to right
Half sandwich Cyclometalated ruthenium complex described in asking 1 is reacted after mixing in the presence of a solvent.
11. application according to claim 10, wherein relative to the nitrobenzene compounds of 1mmol, the reducing agent
Dosage is 3-5mmol, and the dosage of the half sandwich Cyclometalated ruthenium complex is 0.02-0.10mmol, the solvent
Dosage is 1-5mL.
12. application according to claim 10, wherein the nitrobenzene compounds be selected from nitrobenzene, 4- nitrophenol,
One of 4- nitro-chlorobenzene, 4- nitrotoleune and 4- nitroaniline are a variety of.
13. application according to claim 10, wherein the solvent is selected from one of water, methanol and ethyl alcohol or a variety of.
14. application according to claim 13, wherein the solvent is water.
15. application according to claim 10, wherein the reducing agent is selected from sodium borohydride and/or hydrazine.
16. application according to claim 15, wherein the reducing agent is sodium borohydride.
17. application according to claim 15, wherein the hydrazine is provided by hydrazine hydrate.
18. application according to claim 10, wherein the temperature of the reaction process is 20-30 DEG C, and the reaction time is
10-20h。
19. application according to claim 10, wherein the application method further includes extracting the mixture after reaction
It takes.
20. application according to claim 19, wherein the extractant is ethyl acetate.
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-
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Non-Patent Citations (9)
| Title |
|---|
| Arene-Ruthenium(II)and -Iridium(III) Complexes with"Click"-Based Pyridyl-triazoles,Bis-triazoles,and Chelating Abnormal Carbenes:Applications in Catalytic Transfer Hydrogenation of Nitrobenzene;Stephan Hohloch 等;《Organometallics》;20131121(第32期);第7376-7385页 * |
| Autocatalytic Intermolecular versus Intramolecular Deprotonation in C-H Bond Activation of Functionalized Arenes by Ruthenium(II) or Palladium(II) Complexes;Indira Fabre 等;《Chem.Eur.J.》;20130417(第19期);7595-7604 * |
| Bin Li 等.Cycloruthenation of aryl imines and N-heteroaryl benzenes via C-H bond activation with Ru(II) and acetate partners.《Journal of Organometallic Chemistry》.2015,(第793期),第200-209页. * |
| Cycloruthenation of aryl imines and N-heteroaryl benzenes via C-H bond activation with Ru(II) and acetate partners;Bin Li 等;《Journal of Organometallic Chemistry》;20150327(第793期);第200-209页 * |
| Enantioselektive Katalysen.155 (Cymol)Ruthenium-Halbsandwich-Komplexe mit Pyrroloxazolin-Liganden-Synthese,Stereochemie,Katalyse;Henri Brunner 等;《Z.Anorg.Allg.Chem》;20041231(第630期);第91-96页 * |
| Ru(II)impregnated Al2O3,Fe3O4,SiO2 and N-coordinate ruthenium(II) arene complexes:Multifunctional catalysts in the hydrogenation of nitroarenes and the transfer hydrogenation of aryl ketones;Serkan Dayan 等;《Apolied Catalysis B:Environmental》;20140922(第164期);第305-315页 * |
| Synthesis and structural chemistry of arene-ruthenium half-sandwich complexes bearing an oxazolinyl-carbene ligand;Macarena Poyatos 等;《Journal of Organometallic Chemistry》;20060320(第691期);第2713-2720页 * |
| Synthesis,Structure,and Antiproliferative Activity of Ruthenium(II) Arene Complexes with N,O-Chelating Pyrazolone-Based b-Ketoamine Ligands;Riccardo Pettinari 等;《Inorganic Chemistry》;20141120(第53期);第13105-13111页 * |
| The Scope of Ambiphilic Acetate-Assisted Cyclometallation with Half-Sandwich Complexes of Iridium,Rhodium and Ruthenium;Youcef Boutadla 等;《Chem.Eur.J.》;20110214(第17期);第3438-3448页 * |
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