CN109867701B - Pyridyl bridged bistriazine metal complex and preparation and application thereof - Google Patents
Pyridyl bridged bistriazine metal complex and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a pyridyl bridged bistriazine metal complex and a preparation method and application thereof. The pyridyl bridged bistriazine compound and transition metal chloride are subjected to coordination reaction in an organic solvent, and after the reaction is finished, the transition metal complex obtained through simple post-treatment can be used for catalyzing the reactions such as transfer hydrogenation of ketone, alpha-alkylation of ketone and the like. The method has the advantages of simple and convenient operation, mild reaction conditions, high synthesis efficiency and the like.
Description
Technical Field
The invention relates to a pyridyl-bridged bistriazine metal complex, and a preparation method and application thereof. The method has the advantages of simple and convenient operation, mild reaction conditions, high synthesis efficiency and the like.
Technical Field
The nitrogen-containing ligand is an important compound and can be coordinated with transition metal to generate a metal complex with a stable structure. The formed metal complex has wide application range, and can be used for organic chemical reactions such as catalytic hydrogenation, cross coupling, cyclopropanation, Michael addition, allyl substitution and the like, and can also be used for preparing luminescent materials and the like. For example, the study group of Yunzhenkun reports a series of metal ruthenium complexes based on nitrogen-containing ligands, and the metal ruthenium complexes show excellent catalytic activity in the hydrogen transfer reaction of catalytic ketone; patent WO2006098505 reports the potential use of nitrogen-containing ligands in organic electroluminescent materials.
The pyridyl bridged bistriazine ligands are important organic synthetic compounds which can be used as ligands to form strong actinide metal-nitrogen coordination bonds with minor actinides, can be used as actinide metal extractants, and can also be used for effectively separating actinide-lanthanides an (III)/Ln (III). The ligands have better recognition and selectivity for minor actinides than for lanthanides (New J. chem.2009,33, 2437-2442; Dalton Trans.2006, 1645-1653; chem. Commun.2001,1512-1513), Japanese (JP 2003215292A) and Chinese (CN101483079A and CN101502790A) patents also disclose the use of related compounds in this respect. In addition, the pyridyl bridged bis-triazine ruthenium complex can well catalyze the transfer hydrogenation reaction of ketone (J.organomet.chem.2007,692, 2306-2313).
The invention mainly relates to a pyridyl bridged bistriazine metal complex and a preparation method and application thereof. The pyridyl bridged bistriazine compound is coordinated with the transition metal chloride to synthesize the metal complex with high catalytic activity, and the preparation method is simple and high in yield. The transition metal complex has stable property, is not sensitive to air and is easy to store.
Disclosure of Invention
The invention aims to provide a method for preparing a pyridyl bridged bistriazine transition metal complex, which is simple and convenient to operate, mild in reaction conditions and high in yield. The prepared metal complex has stable property, is insensitive to air, is easy to store, and can be used for catalyzing the transfer hydrogenation of ketone, the alpha-alkylation of ketone and other reactions.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the pyridyl bridged bistriazine compound 2 and the transition metal chloride 3 are subjected to a coordination reaction in an organic solvent to form a metal complex. After the reaction is finished, separating and characterizing according to a conventional separation and purification method to obtain the complex 1.
The technical scheme is characterized in that:
1. the pyridyl bridged bistriazine compound 2 is a synthon, and four Rs in the structural formula are alkyl CnH2n+1Wherein n is an integer of 0 to 10, preferably 1 to 6.
2. The chloride 3 of the transition metal being FeCl2、CoCl2、NiCl2Or MnCl2。
3. The reaction solvent is one or more of dichloromethane, methanol, ethanol and toluene.
4. The molar ratio of the pyridyl bridged bistriazine compound 2 to the transition metal chloride 3 is 1:1-1.1: 1.
5. The reaction temperature of the pyridyl bridged bistriazine compound 2 and the transition metal chloride 3 is 20-110 ℃.
6. The reaction time of the pyridyl bridged bistriazine compound 2 and the transition metal chloride 3 is 1-24 h.
7. The prepared pyridyl bridged bistriazine metal complex 1 can be used for catalyzing transfer hydrogenation of ketone, alpha-alkylation of ketone and other reactions. The ketone compound has a structural formula as follows:
r in the structural formula1Is alkyl, aryl, naphthyl, pyridyl, furyl or thienyl with 1-4 carbon atoms; r2Is hydrogen, alkyl or aryl with 1-5 carbon atoms.
The invention has the following advantages:
1) the metal complex has simple synthetic route and mild condition, and can conveniently and quickly synthesize the target product.
2) The prepared metal complex has stable property, is not sensitive to air and is easy to store.
3) The prepared metal complex has good catalytic activity in the reactions of ketone transfer hydrogenation, ketone alpha-alkylation and the like.
Detailed Description
The invention takes pyridyl bridging bistriazine compound 2 as a raw material, and carries out coordination reaction with transition metal chloride 3 in an organic solvent to synthesize a metal complex 1, and the complex 1 can be used for catalyzing the transfer hydrogenation of ketone, the alpha-alkylation of ketone and other reactions.
The following examples are provided to aid in the further understanding of the present invention, but the invention is not limited thereto.
The starting pyridyl-bridged bistriazine compound 2 (j.heterocyclic. chem.,1971,8,1043) is prepared according to literature procedures.
Example 1
Under the nitrogen condition, the pyridyl bridged bistriazine compound 2a (92mg,0.2mmol) and the ferrous chloride 3a (25mg,0.2mmol) are stirred in 3mL of ethanol at room temperature for reaction for 5 h. Volatile components were removed under reduced pressure to give the objective product 1aa (104mg, yield 88%) as a violet black solid. The target product is confirmed by high resolution mass spectrometry and element analysis and determination.
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。
Example 2
The reaction procedure and operation were the same as in example 1, except that the reaction time of the system was 24 hours, as compared with example 1. After the reaction was stopped, the reaction mixture was worked up to obtain 1aa (111mg, yield 94%) as a violet black solid as a target product. Indicating that extended reaction times can increase the yield of the desired product.
Example 3
The reaction procedure and operation were the same as in example 1, except that the reaction solvent was toluene and the reaction temperature was 110 ℃. After the reaction was stopped, the reaction mixture was worked up to obtain 1aa (102mg, yield 86%) as a violet black solid as a target product. It is stated that this reaction can also be carried out in aprotic solvents.
Example 4
The procedure was as in example 1, except that the reaction solvent was methylene chloride/ethanol (v/v, 1/1) and the reaction temperature was 28 ℃. After the reaction was stopped, the reaction mixture was worked up to obtain 1aa (100mg, yield 85%) as a violet black solid as a target product. It is stated that the reaction can also be carried out in a mixed solvent.
Example 5
The reaction procedure and operation were the same as in example 1, except that the reaction temperature of the system was 78 ℃. After the reaction was stopped, the reaction mixture was worked up to obtain 1aa (101mg, yield 86%) as a violet black solid as a target product.
Example 6
The reaction procedure was the same as in example 1, except that in example 1, pyridyl-bridged bistriazine compound 2b (121mg,0.21mmol) and manganese dichloride (25mg,0.2mmol) were added to the reaction system. After the reaction was stopped, the reaction was worked up to give 1bb (132mg, yield 94%) as an aimed product as a yellow solid. The target product is confirmed by high resolution mass spectrometry and element analysis and determination. For C HRMS calcd35H55Cl2MnN7:698.3276；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。
Example 7
A mixture of the substrate acetophenone 4a (2.0mmol), complex 1aa (40.0. mu. mol) and 16.0mL isopropanol was stirred at 82 ℃ for 5 minutes under nitrogen. 4.0mL of iPrOK in isopropanol (0.1M) was then added to the reaction. 0.1mL of the reaction was withdrawn over the indicated time period and immediately quenched with 0.5mL of cold isopropanol and analyzed by gas chromatography. After 6 hours of reaction, acetophenone was reduced to the corresponding alcohol product at 95% conversion, indicating that the complex of the present invention can be used as a potential ketone reduction catalyst.
Example 8
Under the protection of nitrogen, complex 1bb (4.0. mu. mol), potassium tert-butoxide (0.2mmol), acetophenone 4a (0.2mmol), benzyl alcohol (0.2mmol) and 1.0mL of toluene were added to a 25mL sealed tube, and the mixture was reacted at 140 ℃ in an oil bath with stirring sealed tube for 8 hours. After the reaction was completed, silica gel column chromatography (eluent: petroleum ether (60-90 ℃ C.)/dichloromethane, v/v ═ 2:1) was performed to obtain 1, 3-diphenyl-1-propanone (36mg, yield 86%) as a white solid product. It is demonstrated that the complexes of the present invention can be used as catalysts for alpha-alkylation of ketones.
Claims (8)
1. A pyridyl bridged bis-triazine metal complex has a structural formula shown as the following formula:
wherein four R in the structural formula are alkyl CnH2n+1N is an integer of 1 to 10;
m is Fe or Mn.
2. A process for preparing a pyridyl-bridged bistriazine metal complex according to claim 1, wherein: pyridyl bridged bistriazine compound 2 and transition metal chloride 3 are reacted to synthesize complex 1;
the structural formula of the pyridyl-bridged bistriazine compound 2 is as follows:
four R in the structural formula are alkyl CnH2n+1Wherein n is an integer of 1 to 10;
the chloride 3 of the transition metal being FeCl2Or MnCl2；
The synthesis route of the metal complex 1 is shown as the following reaction formula:
3. the method of claim 2, wherein: the reaction solvent of the pyridyl bridging bistriazine compound 2 and the transition metal chloride 3 is one or more of dichloromethane, methanol, ethanol and toluene.
4. The method of claim 2, wherein: the molar ratio of the pyridyl bridged bistriazine compound 2 to the transition metal chloride 3 is 1:1-1.1: 1.
5. The method of claim 2, wherein: the reaction temperature of the pyridyl bridged bistriazine compound 2 and the transition metal chloride 3 is 20-110oC。
6. The method of claim 2, wherein: the reaction time of the pyridyl bridged bistriazine compound 2 and the transition metal chloride 3 is 1-24 h.
7. Use of a pyridyl-bridged bistriazine metal complex according to claim 1 in the transfer hydrogenation of ketones, alpha-alkylation of ketones.
8. Use according to claim 7, characterized in that: the structure of the ketone is shown below:
r in the structural formula1Is alkyl, aryl, pyridyl, furyl or thienyl with 1-4 carbon atoms; r2Is hydrogen, alkyl or aryl with 1-5 carbon atoms.
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| CN103087049A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院大连化学物理研究所 | 2,6-bis[(5,6-dialkyl)-1,2,4-triazinyl-3-yl]-pyridine and preparation method thereof |
| CN103539775A (en) * | 2012-07-12 | 2014-01-29 | 中国科学院大连化学物理研究所 | Dipyridine bridged bis-triazine compounds and preparation method thereof |
| 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 |
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| CN103087049A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院大连化学物理研究所 | 2,6-bis[(5,6-dialkyl)-1,2,4-triazinyl-3-yl]-pyridine and preparation method thereof |
| CN102532174A (en) * | 2012-01-09 | 2012-07-04 | 内蒙古大学 | Rare earth 2, 4, 6-tripyridyl triazine complex and preparation method thereof |
| CN103539775A (en) * | 2012-07-12 | 2014-01-29 | 中国科学院大连化学物理研究所 | Dipyridine bridged bis-triazine compounds and preparation method thereof |
| 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 |
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