CN109867701A - A kind of double triazine metal complexs of pyridyl group bridging and its preparation and application - Google Patents
A kind of double triazine metal complexs of pyridyl group bridging and its preparation and application Download PDFInfo
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- CN109867701A CN109867701A CN201711246802.0A CN201711246802A CN109867701A CN 109867701 A CN109867701 A CN 109867701A CN 201711246802 A CN201711246802 A CN 201711246802A CN 109867701 A CN109867701 A CN 109867701A
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Abstract
The invention discloses a kind of double triazine metal complexs of pyridyl group bridging and its preparations and application.Complexation reaction occurs in organic solvent with the double triaizine compounds of pyridyl group bridging and transition metal chloride, is simply post-processed after reaction, obtained transient metal complex can be used for being catalyzed the transfer hydrogenation of ketone, alpha-alkyl of ketone etc. and react.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 double triazine metal complexs of pyridyl group bridging and its preparations and application, with pyridyl group bridging
Complexation reaction occurs in organic solvent for double triaizine compounds and transition metal chloride, and synthesizing has higher catalytic activity
Metal complex.The present invention has many advantages, such as that easy to operate, reaction condition is mild, combined coefficient is high.
Technical background
Containing n-donor ligand is a kind of important compound, and the metal combination of stable structure can be generated with transition-metal coordination
Object.It is formed by metal complex to have wide range of applications, such as can be used for catalytic hydrogenation, cross-coupling, Cyclopropanated, Michael
In the organic chemical reactions such as addition and allyl substitution, and can be used for preparing luminescent material etc..As Yu Zhengkun study group reports
It is living to show excellent catalysis in the hydrogen transfer reaction of catalysis ketone for a series of ruthenium complexes based on containing n-donor ligand
Property；Patent WO2006098505 has reported potential application of the containing n-donor ligand in electroluminescent organic material.
The double triazine ligands of pyridyl group bridging are a kind of important organic synthesis compounds, they can be as ligand and time actinium
Series elements form strong actinide metals-nitrogen coordinate bond, can be used as the extractant of actinide metals, can also efficiently separate actinium series-lanthanum
Series elements An (III)/Ln (III).Compared with separating lanthanide series, which has preferably identification energy to Minor actinides
Power and selectivity (New J.Chem.2009,33,2437-2442；Dalton Trans.2006,1645-1653；Chem.
Commun.2001,1512-1513), Japan Patent (JP 2003215292A) and Chinese patent (CN101483079A and
CN101502790A the application of related compound in this respect) is also disclosed.In addition, the double triazine ruthenium complexes of pyridyl group bridging
It can be very good the transfer hydrogenation (J.Organomet.Chem.2007,692,2306-2313) of catalysis ketone.
Present invention is primarily about a kind of double triazine metal complexs of pyridyl group bridging and its preparations and application.Utilize pyrrole
The double triaizine compounds of piperidinyl bridging and transition metal chloride are coordinated, and synthesize the metal complex with higher catalytic activity, system
Preparation Method is simple, yield is high.Such transient metal complex property is stablized, insensitive to air, is easy to save.
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
The method of double triazine transient metal complexes.The metal complex property being prepared is stablized, insensitive to air, is easy to protect
It deposits, and can be used for being catalyzed the reaction such as alpha-alkyl of the transfer hydrogenation of ketone, ketone.
To achieve the goals above, technical scheme is as follows:
With transition metal chloride 3 complexation reaction, shape occur in organic solvent for the double triaizine compounds 2 of pyridyl group bridging
At metal complex.Routinely isolation and purification method is separated and is characterized after reaction, obtains complex 1.
Technical solution is characterized in that:
1, the double triaizine compounds 2 of pyridyl group bridging are synthon, and four R in structural formula are alkyl CnH2n+1, wherein n be
The integer of 0-10 (preferably 1-6).
2, transition metal chloride 3 is FeCl2、CoCl2、NiCl2Or MnCl2。
3, reaction dissolvent is one of methylene chloride, methanol, ethyl alcohol, toluene or two or more.
4, the double triaizine compounds 2 of pyridyl group bridging and the molar ratio of transition metal chloride 3 are 1:1-1.1:1.
5, the double triaizine compounds 2 of pyridyl group bridging and the reaction temperature of transition metal chloride 3 are 20-110 DEG C.
6, the double triaizine compounds 2 of pyridyl group bridging and the reaction time of transition metal chloride 3 are 1-24h.
7, the double triazine metal complexs 1 of the pyridyl group bridging being prepared can be used for being catalyzed the α-of the transfer hydrogenation of ketone, ketone
The reaction such as alkylation.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；R2
The alkyl or aryl for being 1-5 for hydrogen, carbon atom number.
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 in the reaction such as the transfer hydrogenation of ketone, alpha-alkyl of ketone
Catalytic activity.
Specific embodiment
The present invention is raw material with the double triaizine compounds 2 of pyridyl group bridging, in organic solvent with transition metal chloride 3
Complexation reaction occurs, synthesizes metal complex 1, it is anti-that complex 1 can be used for being catalyzed the transfer hydrogenation of ketone, the alpha-alkyl etc. of ketone
It answers.
Facilitate to further understand the present invention by following embodiments, but the contents of the present invention are not limited to that.
The double triaizine compounds 2 (J.Heterocycl.Chem., 1971,8,1043) of raw material pyridyl group bridging press document side
Method preparation.
Embodiment 1
Under condition of nitrogen gas, the double triaizine compounds 2a (92mg, 0.2mmol) of pyridyl group bridging, frerrous chloride 3a (25mg,
Reaction 5h 0.2mmol) is stirred at room temperature in the ethyl alcohol of 3mL.Decompression is lower to remove Volatile Colstituent, and obtaining atropurpureus solid is target
Product 1aa (104mg, yield 88%).Target product is confirmed by high resolution mass spectrum and determination of elemental analysis. HRMS
calcd.for C27H39Cl2FeN7:587.1993；Found:587.1990.Anal. Calcd for C27H39Cl2FeN7:C,
55.11；H,6.68；Cl,12.05；Fe,9.49； N,16.66.Found:C,55.13；H,6.69；Cl,12.03；Fe,9.50；
N, 16.65。
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 atropurpureus solid that obtains is target product 1aa (111mg, yield 94%).Illustrate to extend the reaction time
Target product yield can be increased.
Embodiment 3
Reaction step and operation are with embodiment 1, and difference from Example 1 is, reaction dissolvent is toluene, reaction temperature
Degree is 110 DEG C.After stopping reaction, the post-treated atropurpureus solid that obtains is target product 1aa (102mg, yield 86%).It says
It is bright also to can be carried out this reaction in non-protonic solvent.
Embodiment 4
With embodiment 1, difference from Example 1 is for reaction step and operation, and reaction dissolvent is methylene chloride/second
Alcohol (v/v, 1/1), reaction temperature are 28 DEG C.After stopping reaction, the post-treated atropurpureus solid that obtains is target product 1aa
(100mg, yield 85%).Illustrate also to can be carried out this reaction in the mixed solvent.
Embodiment 5
With embodiment 1, difference from Example 1 is for reaction step and operation, and system reaction temperature is 78 DEG C.Stop
After only reacting, the post-treated atropurpureus solid that obtains is target product 1aa (101mg, yield 86%).
Embodiment 6
Reaction step and operation are with embodiment 1, and difference from Example 1 is, what is be added in reaction system is pyridine
The double triaizine compounds 2b (121mg, 0.21mmol) of base bridging, manganous chloride (25mg, 0.2mmol).After stopping reaction, after
It is target product 1bb (132mg, yield 94%) that processing, which obtains yellow solid,.Target product passes through high resolution mass spectrum and element
Analysis measurement is confirmed.HRMS calcd.for C35H55Cl2MnN7:698.3276； Found:698.3271.
Anal.Calcd for C35H55Cl2MnN7:C,60.08；H,7.92； Cl,10.13；Mn,7.85；N,14.01.Found:C,
60.07；H,7.94；Cl, 10.13；Mn,7.86；N,14.00.
Embodiment 7
Under nitrogen protection, by substrate acetophenone 4a (2.0mmol), complex 1aa (40.0 μm of ol) and 16.0mL isopropyl
The mixture of alcohol is stirred to react 5 minutes at 82 DEG C.Then reactant is added in the aqueous isopropanol (0.1M) of 4.0 mL iPrOK
In system.In at the appointed time, the reaction solution of 0.1mL is extracted, and does gas phase after being quenched immediately with the dilution of 0.5mL cold isopropanol
Chromatography.Reaction 6 hours, acetophenone is reduced to corresponding alcohol product with 95% conversion ratio, illustrates cooperation of the invention
Object can be used as potential ketone reducing catalyst and use.
Embodiment 8
Under nitrogen protection, complex 1bb (4.0 μm of ol) is added in a 25mL tube sealing, potassium tert-butoxide (0.2mmol), benzene
Ethyl ketone 4a (0.2mmol), benzyl alcohol (0.2mmol) and 1.0mL toluene, it is small that mixture in 140 DEG C of tube sealings of oil bath is stirred to react 8
When.After reaction, silica gel column chromatography (leacheate: petroleum ether (60-90 DEG C)/methylene chloride, v/v=2:1), obtains white
Solid product 1,3- diphenyl -1- acetone (36mg, yield 86%).Illustrate that complex of the invention can be used as the alpha-alkyl of ketone
Change catalysts to use.
Claims (8)
1. a kind of double triazine metal complexs of pyridyl group bridging, structural formula are shown below:
Wherein four R in structural formula are alkyl CnH2n+1, n is the integer of 0-10 (preferably 1-6)；
M is Fe, Co, Ni or Mn.
2. a kind of preparation method of the double triazine metal complexs of pyridyl group bridging described in claim 1, it is characterised in that: utilize
The double triaizine compounds 2 of pyridyl group bridging carry out reacting synthetic compound 1 with transition metal chloride 3；
The structural formula of the double triaizine compounds 2 of pyridyl group bridging is as follows:
Four R in structural formula are alkyl CnH2n+1, wherein n is the integer of 0-10 (preferably 1-6)；
Transition metal chloride 3 is FeCl2、CoCl2、NiCl2Or MnCl2；
The synthetic route of metal complex 1 is as shown in following reaction equations:
3. preparation method as claimed in claim 2, it is characterised in that: the double triaizine compounds 2 of pyridyl group bridging and transition metal
The reaction dissolvent of chloride 3 is 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: the double triaizine compounds 2 of pyridyl group bridging and transition metal
The molar ratio of chloride 3 is 1:1-1.1:1.
5. preparation method as claimed in claim 2, it is characterised in that: the double triaizine compounds 2 of pyridyl group bridging and transition metal
The reaction temperature of chloride 3 is 20-110 DEG C.
6. preparation method as claimed in claim 2, it is characterised in that: the double triaizine compounds 2 of pyridyl group bridging and transition metal
The reaction time of chloride 3 is 1-24h.
7. a kind of double triazine metal complexs of pyridyl group bridging described in claim 1 are in the transfer hydrogenation of ketone, the alpha-alkyl of ketone
Application in the reaction such as change.
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 hydrogen,
Carbon atom number is the alkyl or aryl of 1-5.
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| CN114436803A (en) * | 2020-10-30 | 2022-05-06 | 荆楚理工学院 | Preparation method of 3- (4-chlorphenyl) -1, 5-diphenyl pentane-1, 5-diketone compound |
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