CN109867697A - Pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex and preparation and application - Google Patents
Pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex and preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex and preparations and application.Complexation reaction occurs in organic solvent to be coordinated unsaturated pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex and bidentate pyridine ligand, is simply post-processed after reaction, obtains the transient metal complex with higher catalytic activity.The present invention has many advantages, such as that easy to operate, reaction condition is mild, combined coefficient is high.
Description
Technical field
The present invention relates to a kind of pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex and preparations and application.With tool
There is the pyridyl group bridged pyrazolate benzimidazole ruthenium complex of coordination unsaturation to occur in organic solvent with bidentate pyridine ligand
Complexation reaction synthesizes the ruthenium complex with higher catalytic activity.The present invention is with easy to operate, reaction condition is mild, synthesis
The advantages that high-efficient.And obtained ruthenium complex property is stablized, and it is insensitive to air, it is easy to save, can be applied to catalysis ketone
Hydrogen transfer reaction.
Technical background
Transient metal complex is related to multiple research fields such as Coordinative Chemistry, materials chemistry and homogeneous catalysis, with high-new
Technology it is increasingly developed, the metal complex with the performances such as specific physical, chemistry and biology achieves quick development.
In terms of catalytic chemistry, these metal complexs can be used for catalytic hydrogenation, cross-coupling, Cyclopropanated, Michael
In the organic chemical reactions such as addition and allyl substitution.As Yu Zhengkun study group has reported a series of metals based on containing n-donor ligand
Ruthenium complex shows excellent catalytic activity in the hydrogen transfer reaction of catalysis ketone.In terms of materials chemistry, these metals
Complex can be used for preparing luminous or conductive material etc. again.As patent WO2006098505 has reported containing n-donor ligand in organic electroluminescence
Potential application in luminescent material.
Although transient metal complex and its synthesis have been achieved for very big progress, it is complex-catalyzed activity,
There are still certain problems for stability etc..The present invention is mainly to utilize the pyridyl group bridging pyrrole with coordination unsaturation
Azoles benzimidazole ruthenium complex is reacted with bidentate pyridine ligand, pyridine synthesis base bridged pyrazolate benzimidazole-bis- pyridines ruthenium cooperation
Object.The ruthenium complex preparation method is simple, yield is high.Such complex property is stablized, insensitive to air, is easy to save, and
And it can be applied to the hydrogen transfer reaction of catalysis ketone.
Summary of the invention
The purpose of the present invention is to provide it is a kind of it is easy to operate, reaction condition is mild, high yield prepares pyridyl group bridging
Pyrazoles benzimidazole-bis- pyridines ruthenium complex method.The metal complex property being prepared is stablized, insensitive to air,
It is easy to save, and can be used for being catalyzed the hydrogen transfer reaction of ketone.
To achieve the goals above, technical scheme is as follows:
Pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex 2 is matched in organic solvent with bidentate pyridine ligand 3
Position reaction, forms metal complex.Routinely isolation and purification method is separated and is characterized after reaction, obtains metal combination
Object 1.
Technical solution is characterized in that:
1, bidentate pyridine ligand 3 is synthon, and the X in structural formula is CH2, NH or O.
2, reaction dissolvent is one of methylene chloride, methanol, ethyl alcohol, toluene or two or more.
3, the molar ratio of pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex 2 and bidentate pyridine ligand 3 is 1:1-1:
1.1。
4, the reaction temperature of pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex 2 and bidentate pyridine ligand 3 is 20-
110℃。
5, the reaction time of pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex 2 and bidentate pyridine ligand 3 is 1-
24h。
6, the hydrogen migration that the pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex obtained can be used for being catalyzed ketone is anti-
It answers.Its structural formula of the ketone compounds are as follows:
R in structural formula1Alkyl, aryl, naphthalene, pyridyl group, furyl or the thienyl for being 1-4 for carbon atom number；R2For
Carbon atom number is the alkyl or aryl of 1-10.
The invention has the following advantages that
1) metalcomplex sythesis route is simple, and mild condition can be convenient and efficiently synthesize target product.
2) the metal complex property being prepared is stablized, insensitive to air, is easy to save.
3) metal complex being prepared has good catalytic activity in the hydrogen transfer reaction of ketone.
Specific embodiment
The present invention is raw material to have the pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex 2 of coordination unsaturation,
Complexation reaction occurs in organic solvent with bidentate pyridine ligand 3, pyridine synthesis base bridged pyrazolate benzimidazole-bis- pyridines ruthenium is matched
Object 1 is closed, complex 1 can be used for being catalyzed the hydrogen transfer reaction of ketone.
Facilitate to further understand the present invention by following embodiments, but the contents of the present invention are not limited to that.
Raw material pyridyl group bridged pyrazolate benzimidazole metal ruthenium complex 2 (Organometallics 2008,27,2898)
It is prepared by literature method；Bidentate pyridine ligand 3 can be by being commercially available.
Embodiment 1
Under condition of nitrogen gas, pyridyl group bridged pyrazolate benzimidazole ruthenium complex 2 (27.4mg, 0.04mmol), two (2- pyrroles
Piperidinyl) amine 3a (6.8mg, 0.04mmol) be stirred at room temperature in 3mL methylene chloride/methanol (v/v=5/1) reaction 5h.Reaction knot
Depressurized after beam it is lower remove Volatile Colstituent, residual solid through silica gel column chromatography (leacheate: methylene chloride/methanol, v/v=20/1),
Obtaining red solid is target product 1a (16.2mg, yield 47%).Target product is surveyed by nuclear magnetic resoance spectrum and elemental analysis
Surely it is confirmed.1H NMR (400 MHz, CDCl3, 23 DEG C) and δ 12.14 (br, 1H), 8.79 (d, J=5.9Hz, 1 H), 8.38
(m, 2H), 7.78 (m, 2H), 7.69 (d, J=7.0Hz, 1H), 7.63 (t, J=8.1Hz, 1H), 7.21 (m, 4H), 7.11 (t,
J=7.4Hz, 1H), 6.98 (d, J=8.3Hz, 1H), 6.93 (m, 6H), 6.82 (t, J=7.5Hz, 1H), 6.64 (d, J=
8.3Hz, 1H), 6.58 (m, 6H), 6.51 (t, J=6.8Hz, 1H), 6.22 (t, J=6.4Hz, 1H), 5.98 (s, 1 H),
2.58(s,3H),2.48(s,3H).31P{1H } NMR (162MHz, CDCl3, 23℃)δ42.9.Anal.Calcd for
C45H38ClN8PRu:C,62.97；H,4.46；Cl,4.13；N,13.05；P,3.61；Ru,11.78.Found:C,62.94；H,
4.48；Cl,4.12；N,13.03；P,3.63；Ru,11.80.
Embodiment 2
With embodiment 1, difference from Example 1 is for reaction step and operation, and the system reaction time is for 24 hours.Stop
After reaction, the post-treated red solid that obtains is target product 1a (30.2mg, yield 88%).Illustrate that the extension reaction time can
To increase target product yield.
Embodiment 3
Reaction step and operation are with embodiment 1, and difference from Example 1 is, reaction dissolvent is toluene, reaction temperature
It is 110 DEG C.After stopping reaction, the post-treated red solid that obtains is target product 1a (25.3mg, yield 74%).Illustrate non-
Also it can be carried out this reaction in protonic solvent.
Embodiment 4
Reaction step and operation are with embodiment 1, and difference from Example 1 is, reaction dissolvent is ethyl alcohol, reaction temperature
It is 78 DEG C.After stopping reaction, the post-treated red solid that obtains is target product 1a (31.2mg, yield 91%).Illustrate in matter
It also can be carried out this reaction in sub- property solvent.
Embodiment 5
Reaction step and operation are with embodiment 1, and difference from Example 1 is, pyridyl group bridged pyrazolate benzimidazole
The molar ratio of ruthenium metal complex 2 and bidentate pyridine ligand 3 is 1:1.1.It is post-treated to obtain red solid after stopping reaction
For target product 1a (20.5mg, yield 60%).
Embodiment 6
Under nitrogen protection, by substrate acetophenone 4a (2.0mmol), complex 1a (40.0 μm of ol) and 16.0mL isopropyl
The mixture of alcohol is stirred to react 5 minutes at 82 DEG C.Then reaction system is added in the aqueous isopropanol (0.1M) of 4.0mL iPrOK
In.In at the appointed time, the reaction solution of 0.1mL is extracted, and does gas phase color after being quenched immediately with the dilution of 0.5mL cold isopropanol
Spectrum analysis.Reaction 6 hours, acetophenone is reduced to corresponding alcohol product with 95% conversion ratio, illustrates that complex of the invention can
It is used as potential ketone reducing catalyst.
Claims (9)
1. a kind of pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex, structural formula are as shown below:
X in structural formula is CH2, NH or O.
2. a kind of preparation method of pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex described in claim 1, special
Sign is: being carried out using unsaturated pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex 2 is coordinated with bidentate pyridine ligand 3
Reaction synthesis ruthenium complex 1；
The structural formula of bidentate pyridine ligand 3 is as follows:
X in structural formula is CH2, NH or O；
The synthetic route of ruthenium complex 1 is as shown in following reaction equations:
3. preparation method as claimed in claim 2, it is characterised in that: pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex
2 with the reaction dissolvent of bidentate pyridine ligand 3 be one of methylene chloride, methanol, ethyl alcohol, toluene or two or more.
4. preparation method as claimed in claim 2, it is characterised in that: pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex
2 with the molar ratio of bidentate pyridine ligand 3 be 1:1-1:1.1.
5. preparation method as claimed in claim 2, it is characterised in that: pyridyl group bridged pyrazolate benzimidazole ruthenium metal complex
2 with the reaction temperature of bidentate pyridine ligand 3 be 20-110 DEG C.
6. the preparation method as described in claim 2 or 5, it is characterised in that: pyridyl group bridged pyrazolate benzimidazole ruthenium metal is matched
The reaction time for closing object 2 and bidentate pyridine ligand 3 is 1-24h.
7. a kind of pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex described in claim 1 is as ketone compounds
The application of reducing catalyst.
8. applying according to claim 7, it is characterised in that: its structure of the ketone compounds is as shown below:
R in structural formula1Alkyl, aryl, naphthalene, pyridyl group, furyl or the thienyl for being 1-4 for carbon atom number；R2For carbon original
Subnumber is the alkyl or aryl of 1-10.
9. according to application described in claim 7 or 8, it is characterised in that: flow back in isopropanol under nitrogen atmosphere, deposited in catalyst
Under, ketone compounds can be converted to corresponding alcohol compound.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175019A (en) * | 2020-10-14 | 2021-01-05 | 青岛理工大学 | Pyridyl-bridged NNP cobalt complex and application thereof |
| CN114149451A (en) * | 2021-11-18 | 2022-03-08 | 辽宁大学 | CuIIBinuclear complex, preparation method thereof and application thereof in catalyzing C-S coupling reaction under mechanical force |
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| CN105601672A (en) * | 2014-11-25 | 2016-05-25 | 中国科学院大连化学物理研究所 | Binuclear ruthenium NNN complex and preparation method thereof |
| CN106749417A (en) * | 2015-11-23 | 2017-05-31 | 中国科学院大连化学物理研究所 | A kind of three core ruthenium NNN complexs and preparation method thereof |
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2017
- 2017-12-01 CN CN201711246793.5A patent/CN109867697A/en active Pending
Patent Citations (2)
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| CN105601672A (en) * | 2014-11-25 | 2016-05-25 | 中国科学院大连化学物理研究所 | Binuclear ruthenium NNN complex and preparation method thereof |
| CN106749417A (en) * | 2015-11-23 | 2017-05-31 | 中国科学院大连化学物理研究所 | A kind of three core ruthenium NNN complexs and preparation method thereof |
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| FANLONG ZENG 等: "Construction of Highly Active Ruthenium(II) NNN Complex Catalysts Bearing a Pyridyl-Supported Pyrazolyl-Imidazolyl Ligand for Transfer Hydrogenation of Ketones", 《ORGANOMETALLICS》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175019A (en) * | 2020-10-14 | 2021-01-05 | 青岛理工大学 | Pyridyl-bridged NNP cobalt complex and application thereof |
| CN112175019B (en) * | 2020-10-14 | 2022-11-25 | 青岛理工大学 | Pyridyl-bridged NNP cobalt complex and application thereof |
| CN114149451A (en) * | 2021-11-18 | 2022-03-08 | 辽宁大学 | CuIIBinuclear complex, preparation method thereof and application thereof in catalyzing C-S coupling reaction under mechanical force |
| CN114149451B (en) * | 2021-11-18 | 2023-05-30 | 辽宁大学 | Cu (copper) alloy II Binuclear complex, preparation method thereof and application of binuclear complex in catalyzing C-S coupling reaction under mechanical force |
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Application publication date: 20190611 |