CN109225339A - A kind of high activity cooperates with classification assemble method and the application of MOF catalyst - Google Patents
A kind of high activity cooperates with classification assemble method and the application of MOF catalyst Download PDFInfo
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Abstract
The invention discloses a kind of classification assemble method of high activity collaboration MOF catalyst and applications, selection tri- tooth schiff bases of ONO are skeleton, design has synthesized the tri- tooth schiff bases bridge ligand of ONO containing terminal carboxyl group first, and then has synthesized a kind of porous two dimension MOF catalyst 2 using the method for classification assembling；Secondly, the catalyst is acted on by the immobilized and confinement of MOF structure, the molecular catalyst with unique coordination environment and steric configuration is immobilized in the cellular structure of MOF；Again, similar catalytic active center copper ion can activate two kinds of reaction substrates in F-C reaction or Henry reaction simultaneously in MOF catalyst, so that catalysis reaction is more efficient, is easier to carry out, compared with containing only the mononuclear copper complex catalyst of an active catalyst sites, its catalytic activity significantly increases, it is used as different-phase catalyst simultaneously, the MOF catalyst circulation is constant using catalytic activity is still able to maintain after 5 times.
Description
Technical field
The invention belongs to organic chemistry and material chemistry technical fields more particularly to a kind of high activity to cooperate with MOF catalyst
Classification assemble method and application.
Background technique
Enzymatic is the main process in nature, because it has excellent conversion ratio, specificity, efficiency and conversion
Range, this usually requires the cooperation between metal center and residue of protein to activate substrate.Therefore, in the past few decades
In, people are dedicated to synthesizing the mimetic enzyme catalyst at mononuclear center or multi-nuclear metal center.Many homogeneous imitative enzyme collaborations
Catalyst, the especially catalyst containing bimetallic catalytic center, due to its design and synthesis simplicity and be widely studied,
But they are restricted in terms of stability and recycling.The shortcomings that in order to overcome homogeneous catalysis, inorganic or organic
Supported on carriers molecular catalyst, so design synthesize heterogeneous synergistic catalyst method receive chemist be absorbed in.
For example, Li Can and its colleague have been recently developed a series of high-performance out-phase solid catalysts with multiple active sites, they
It is by being urged with realizing that efficient asymmetry cooperates with using inorganic microporous/mesoporous material or porous organic frame as carrier
Change.Even if the research of this out-phase synergistic catalyst makes some progress, but these solid catalyst activity centers
Structure is still mysterious.It is well known that the configuration and space length of active site are very big on the influence of the efficiency of catalyst, therefore
It rationally designs, accurately there is the solid-phase catalyst of concerted catalysis performance still to face certain challenge, while also getting over for composite structure
More to attract attention.
Metal-organic framework (MOFs) is as a kind of crystalline material, and due to its high porosity, high stability, composition is adjustable
Property and specific reaction microenvironment so that it has very big application potential in heterocatalysis.The especially Structural Engineering of MOF
Considerable progress is achieved in recent years with modulation synthetic method, and the control that steric configuration is carried out to catalytic active center may be implemented
System, so that MOF becomes the ideal platform of design high-performance synergistic catalyst.For example, Cui Yong seminar is recently reported and is
The MOF catalyst containing metal salen is arranged, by utilizing bimetallic synergic catalytic effect, the asymmetry of catalysis aldehyde may be implemented
The high efficiency and selectivity of silicon cyanogenation and Kinetic Resolution epoxide.The refined seminar of Lin Wen divides cobalt (III) porphyrin
Muonic catalysis agent is supported in the MOF of interpenetrating structure, to realize the efficient hydration reaction of catalysis terminal alkyne.Although these grind
Study carefully progress impressive, but the report of the synergistic catalyst based on MOF is still very rare, therefore designs in organic catalysis
There is efficient novel synergistic catalyst in reaction, become current research hotspot.
In order to obtain the synergistic catalyst based on MOF with double activated or more active metal centres it may first have to wise
Ground selects a kind of suitable organic functional ligand as skeleton and the metal ion with specific coordination configuration and catalytic performance
Respectively as catalytic center and metal node.The present invention is considered first using tri- tooth schiff bases of ONO as skeleton, because of its ONO tri-
Tooth position point can be bonded with metal ion securely by coordination, and can be centrally formed complex with various metals, thus
With potential catalytic performance；And by the modification to three tooth schiff bases, terminal carboxyl groups are introduced, chelate center in view of ONO
Different binding abilities is shown to metal with carboxylic group, thus Schiff base metal complexes can be further integrated into
In MOF structure, to obtain the MOF catalyst with specific structure and function.
Summary of the invention
For the technical difficulty that there is the MOF catalyst of bimetallic collaboration activity function to be faced for current preparation, the present invention
The MOF catalyst with bimetallic concerted catalysis performance is successfully constructed by classification assemble method from bottom to top.At this
Invention, we will prepare a kind of while there is terminal carboxyl group and tri- tooth of ONO to chelate the uncommon of site by organic synthesis first
Husband's alkali bridge ligand, and then it is prepared for by solvent-thermal method and metal copper ion the complex (1) of an example schiff bases monokaryon copper, then
It is secondary to be connect mononuclear copper complex 1 and the cadmium oxygen cluster of 4- connection effect connects with having 2- using solvent-thermal method, thus group
Dress obtains a kind of porous two dimension MOF (2).Different from mononuclear copper complex 1, MOF 2 has to be connected by bridging oxygen atom
The double-core copper metal center got up, unique metal coordination environment and Molecular Geometries, so that the dinuclear metal center exists
Friedel-Crafts between catalyzing indole and nitrostyrolene react the Henry between aromatic aldehyde and nitromethane react in all
It is demonstrated by out synergic catalytic effect, thus the MOF catalyst shows to live compared with the catalysis of 1 superelevation of mononuclear copper complex catalyst
Property.As far as we know, MOF catalyst 2 be currently first it is based on three tooth Schiff base ligand skeletons and possess double-core copper collaboration
The example of the heterogeneous MOF catalyst of catalytic center.
In order to achieve the above purpose, the present invention the following technical schemes are provided:
A kind of high activity collaboration MOF catalyst, 1 He of compound including the homogeneous catalyst with monokaryon copper catalytic center
The compound 2 of MOF catalyst with bimetallic concerted catalysis reaction effect, chemical structure is as follows:
The structure of compound 1 and 2 is as shown in Figure 1.
The synthetic method of the compound 1, comprises the following steps:
(1) (1S, 2R)-(-) -1- amino -2- indanol and 3'- tert-butyl -5'- formoxyl -4'- xenol-will be contained
The mixture of 4- carboxylic acid is dissolved in methanol solvate, after reacting 12 hours under the conditions of 60 DEG C, organic solvent is removed in vacuum, uses methanol
Washing, obtains the three tooth Schiff base ligand H containing ONO electron donor3L；
(2) Cu (OAc) will be contained2·H2O and ligand H3The mixture of L is put into containing DMF, the mixed solvent of MeOH and water
In, sealing, and heated 24 hours at 60 DEG C, obtain the compound 1 of blue acicular crystal, methanol washing, drying at room temperature.
The synthetic method of the compound 2, comprises the following steps:
CdBr will be contained2It is put into the mixture of compound 1 containing DMF, the in the mixed solvent of MeOH and water are sealed in nothing
In color vial, and continuous heating reacts 36 hours at 80 DEG C, and cold filtration, the blue for obtaining compound 2 are blocky brilliant later
Body, methanol washing, drying at room temperature.
The structure of compound 1 and compound 2 is confirmed by single crystal X diffraction, infrared spectroscopy and TGA.It is worth noting that, chemical combination
Object 1 and 2 is all highly stable in air, and wherein compound 2 is not soluble in water and common organic solvent.
Single-crystal X-ray diffraction analysis shows the crystallization of compound 1 in P21Space group, asymmetric cell is containing there are two crystal phases
Independent copper ion, two HL molecules, two coordination methanol molecules and a free methanol molecules.In 1 structure, match
Body H3L chelates center as three teeth by the ONO electron donor that imido grpup and two hydroxyls provide.As shown in Fig. 2, each gold
Belong to copper center and 1 ligand H3The ONO electron donor of L and a MeOH molecular complexes, therefore Cu2+Ion takes the plane of distortion
Quadrangle coordination configuration, wherein Cu-O bond distance's range be 1.884 (3) extremelyCu-N bond distance's range is respectively 1.905
(3) extremely It is worth noting that, the carboxyl in compound 1 is protonation, in 1700cm-1The protonation at place
COOH has vC=O stretching vibration, this with do not generate the ligand H before complex3The characteristic peak of L is consistent.Therefore, of the invention
Compound 1 can be used as substructural unit to prepare porous MOF material.
By above-mentioned mononuclear copper complex 1 and Cd2+Ion carries out solvent thermal reaction, obtains the monocrystalline of compound 2, and monocrystalline X is penetrated
Line diffraction shows that compound 2 is porous two dimension MOF structure, and crystallizes in orthorhombic space group P21212.CuL structure in compound 2
Copper ion in unit and compound 1 in Cu (HL) structural unit has similar quadrangle coordination mode, wherein Cu-O bond distance
Range isCu-N bond distance's range respectively fromWith chemical combination
Object 1 is different, in compound 2 as the CuL of molecule construction unit by with two bridging oxygen atom bridges, form cis-structure
Dimer (CuL)2(as shown in Figure 3).It include two independent Cd of crystallography in compound 22+Ion, the center Cd1 with come from four
8 oxygen atom ligands of a ligand terminal carboxylic acid group, form double cap triangular prism coordination configurations of distortion, and Cd-O bond distance's range isAnd Cd2 and 1 DMF molecule, 4 of two hydrones and two ligand terminal carboxylic acid groups
Oxygen atom is coordinated, and the pentagonal bipyramid coordination configuration of distortion is formed, and Cd-O bond distance's range is
As shown in figure 4, (CuL) of dimer in the present invention2Unit can be used as organic structural unit of 2- connection, it connects with 4- respectively
The Cd connect1O8The Cd that cluster is connected with 2-2O7Cluster is coupled to form two-dimensional network architecture, is respectively provided with about along a axis Peace treatyOpen channel, and have about along c-axisOpen channel (figure
5).Using PLATON software, calculation shows that, the porosity in compound 2 is 41.8%, can be used for accommodating guest molecule.Thermogravimetric point
Guest molecule in analysis display 2 frame structure of compound, such as methanol, water and DMF molecule can be in 25-220 DEG C of temperature ranges
Interior removing, and the thermal stability of the frame structure of compound is up to~315 DEG C (Fig. 6).Powder x-ray diffraction experimental result
Show after removing guest molecule, the frame structure and crystallinity of compound 2 still maintain complete (Fig. 7).
It is catalyzed and reacts in Friedel-Crafts respectively as catalyst the present invention also provides a kind of compound 1 and 2
In application:
Wherein R is selected from phenyl, 4- aminomethyl phenyl, 4- trifluoromethyl, 3- methoxyphenyl, the 4- chlorobenzene optionally replaced
Base, 4- nitrobenzophenone；R1Selected from H, methyl；R2Selected from H, phenyl, methyl；R3Selected from H, 5- methyl, 5- methoxyl group, 5- chlorine, 6- first
Base.
The catalysis reaction comprises the following steps:
(1) activation of catalyst
As the compound 1 and 2 of catalyst, guest molecule is carried out with anhydrous super dry solvent first and is exchanged, then at 100 DEG C
Lower activation is verified activation by thermogravimetric analysis and is completed；
(2) catalysis Friedel-Crafts reaction
The activated catalyst of 1.0mol% equivalent is added to 10mmol β-nitroolefin derivative and 12mmol indoles
In dichloromethane solution, mixture is stirred at room temperature 12 hours, mixture is then centrifuged 10 with the speed of 14000rpm
Minute, and supernatant is concentrated in vacuo,1HNMR monitors reaction result and yield.
(3) catalysis comparison reaction
The ratio of catalyst and nitrostyrolene or 4- methyl nitrostyrolene is controlled by 1:100 to 1:1000 and 1:
10000, keeping the amount of nitrostyrolene or 4- methyl nitrostyrolene is 10mmol, and the amount of indoles is 12mmol, and mixture exists
It is centrifuged 10 minutes after stirring 12 hours at room temperature with the speed of 14000rpm, and supernatant is concentrated in vacuo,1HNMR monitoring reaction
And yield as a result.
As the result is shown: under identical F-C reaction condition, the compound 1 of monokaryon copper only shows that very general catalysis is lived
Property, and the catalytic activity of superelevation is shown as the MOF catalyst 2 with dinuclear metal copper catalytic center.And it this urges
Change active difference to become readily apparent under the ratio of low-down catalyst and reaction substrate.
Again, the present invention also provides a kind of compounds 1 and 2 is catalyzed in reaction respectively as catalyst in Henry
Using:
The catalysis reaction comprises the following steps:
(1) activation of catalyst
As the compound 1 and 2 of catalyst, guest molecule is carried out with anhydrous super dry solvent first and is exchanged, then at 100 DEG C
Lower activation is verified activation by thermogravimetric analysis and is completed；
(2) catalysis Henry reaction
The activated catalyst of 1.0mol% equivalent is added to 10mmol benzaldehyde derivative and 100mmol nitromethane
In methanol solution, reaction mixture is stirred 12 hours at 60 DEG C, mixture is then centrifuged 10 with the speed of 14000rpm
Minute, take supernatant to be concentrated in vacuo,1HNMR monitors reaction result and yield.
(3) catalysis comparison reaction
The ratio of catalyst and paranitrobenzaldehyde is controlled by 1:100 to 1:1000 and 1:10000, keeps p-nitrophenyl first
Aldehyde is 10mmol, nitromethane 100mmol, and mixture is stirred 12 hours at 60 DEG C, then by mixture with
The speed of 14000rpm is centrifuged 10 minutes, and supernatant is concentrated in vacuo,1HNMR monitors reaction result and yield.
As the result is shown: under identical Henry reaction condition, MOF catalyst 2 and list with bimetallic copper catalytic center
The catalytic activity of the compound 1 of core copper is compared, and catalytic activity dramatically increases, and the difference of this catalytic activity is very low
Catalyst and reaction substrate ratio under become readily apparent from.
The invention has the advantages that
It is skeleton that the present invention, which selects tri- tooth schiff bases of ONO, and design first has synthesized the tri- tooth Schiff of ONO containing terminal carboxyl group
Alkali bridge ligand, and then a kind of porous two dimension MOF catalyst 2 has been synthesized using the method for classification assembling；Secondly, the catalyst
It is acted on by the immobilized and confinement of MOF structure, the molecular catalyst with unique coordination environment and steric configuration is immobilized on MOF
Cellular structure in；Again, in MOF catalyst similar catalytic active center copper ion can activate simultaneously F-C reaction or
Two kinds of reaction substrates in Henry reaction, so that catalysis reaction is more efficient, is easier to carry out, and containing only an active catalyst sites
Mononuclear copper complex catalyst compare, catalytic activity significantly increases, while as different-phase catalyst, which is followed
Ring is constant using catalytic activity is still able to maintain after 5 times.
Detailed description of the invention
Fig. 1 show the compound 1 of the homogeneous catalyst with monokaryon copper catalytic center and has bimetallic concerted catalysis
The structure of the compound 2 of the MOF catalyst of reaction effect.
Fig. 2 show the molecular structure map of compound 1.
Fig. 3 show (CuL) Unit 2 of double-core in compound 2 and the connection mode of two kinds of cadmium oxygen clusters.
Fig. 4 show the frame structure of compound 2 along a axis direction accumulation graph.
Fig. 5 show the frame structure of compound 2 along c-axis direction accumulation graph.
Fig. 6 show the TGA curve of compound 1 and 2.
Fig. 7 show the PXRD map of compound 2.
Specific embodiment
Below by way of specific embodiment, above content of the invention is described in further detail, but should not be incited somebody to action
This is interpreted as any restrictions to present invention protection theme.All technical solutions realized based on above content of the present invention are belonged to
The scope of the present invention.The present invention to used in test to material and test method carry out general and/or specifically retouch
It states.
Embodiment 1
Compound H3The preparation of L
(1S, 2R)-(-) -1- amino -2- indanol and 3'- tert-butyl -5'- formoxyl -4'- xenol -4- carboxylic will be contained
In the mixture dissolution methanol solvate of acid, after being reacted 12 hours under the conditions of 60 DEG C, organic solvent is removed in vacuum, is washed with methanol
It washs, obtains the three tooth Schiff base ligand H containing ONO electron donor3L, yield 92%.FT-IR data (KBr pellet, cm-1): 3480 (w), 2952 (s), 2910 (s), 2867 (m), 1700 (w), 1670 (w), 1630 (s), 1605 (s), 1533 (s),
1480 (m), 1460 (m), 1440 (m), 1386 (s), 1268 (m), 1251 (m), 1224 (w), 1169 (m), 1095 (w), 1052
(w), 1016 (w), 993 (w), 952 (w), 888 (w), 860 (m), 790 (m), 775 (w), 750 (s), 712 (w), 651 (w)
634 (w), 620 (w), 564 (w), 527 (m), 500 (w), 449 (w).
Embodiment 2
The preparation of compound 1
Cu (OAc) will be contained2·H2O (10mmol) and ligand H3The mixture of L (10mmol) is put into containing DMF, MeOH and
In the vial of the mixed solvent of water.Bottle is sealed and is heated 24 hours at 60 DEG C.Collect the compound of blue acicular crystal
1, it is washed with methanol, and dry at room temperature.Based on H3The yield of L is about 75.0%.FT-IR data (KBr pellet, cm-1):
3480 (s), 2950 (s), 2910 (s), 2870 (m), 2360 (w), 1700 (w), 1620 (s), 1604 (s), 1533 (s), 1478
(w), 1458 (w), 1420 (m), 1386 (s), 1328 (m), 1275 (s), 1258 (m), 1228 (m), 1166 (s), 1107 (s)
1072 (m), 1053 (w), 1013 (w), 980 (w), 950 (w), 895 (w), 857 (m), 805 (w), 788 (m), 774 (m), 751
(m), 731 (w), 711 (w), 680 (w), 640 (w), 605 (w), 548 (w), 521 (m), 491 (w), 448 (w).
Embodiment 3
The preparation of compound 2
CdBr will be contained2The mixture of (0.2mmol) and compound 1 (0.2mmol) is put into containing DMF, and MeOH and water are mixed
In the vial of bonding solvent.Bottle is sealed and is heated 36 hours at 80 DEG C, blue bulk crystals 2 is obtained, is washed with methanol, room
Temperature is dry.Based on CdBr2Yield be about 60.0%.FT-IR data (KBr pellet, cm-1): 3450 (s), 2951 (s),
2908 (s), 1660 (s), 1620 (s), 1603 (s), 1529 (s), 1478 (w), 1457 (m), 1393 (s), 1324 (m), 1277
(s), 1257 (s), 1230 (m), 1199 (w), 1163 (s), 1099 (m), 1010 (w), 892 (w), 860 (s), 806 (w), 788
(s), 776 (s), 752 (s), 712 (m), 662 (m), 607 (m), 544 (m), 519 (w), 464 (m).
It is detected below for the catalytic activity of two kinds of catalyst compounds 1 and 2 of present invention design synthesis.
1, catalytic performance of the different catalysts in Frededl-Crafts reaction
The catalyst of 1.0mol% is added to the two of beta-nitrostyrene derivative (10mmol) and indoles (12mmol)
In chloromethanes solution, mixture is stirred at room temperature 12 hours.Then mixture is centrifuged 10 minutes with 14000rpm speed,
And be concentrated in vacuo supernatant,1HNMR measures yield, as follows:
As the result is shown: under best catalytic reaction condition of the invention, catalyst 2 can effectively catalyze indoles and β-nitre
Base styrene, 4- methyl-nitrostyrene and 4- trifluoromethyl-beta-nitrostyrene F-C reaction, wherein only having
The catalyst of 1.0mol% equivalent can obtain respectively 95%, 92% and 95% yield (entry 1,3,5) in 12 hours.
On the contrary, reaction yield is significant when using mononuclear copper complex 1 as catalyst (load capacity of CuL unit in 2 is identical)
It reduces, respectively only 39%, 31% and 42% (entry 2,4,6).This is the result shows that the compound 1 as reference substance is only shown
Very general catalytic activity out.It can be seen that unique bimetallic copper center is to F-C contained in 2 structure of the compounds of this invention
The catalytic activity of reaction plays an important role.
2, the catalytic activity of 2 pairs of compound different substrates
The catalyst of 1.0mol% is added to beta-nitrostyrene derivative (10mmol) and indole derivatives
In the dichloromethane solution of (12mmol), mixture is stirred at room temperature 12 hours.Then by mixture with 14000rpm's
Speed is centrifuged 10 minutes, and supernatant is concentrated in vacuo,1HNMR measures yield, as follows:
By F-C reaction of the various different betas-between nitroolefin derivative and indole derivatives, chemical combination of the present invention is investigated
The substrate tolerance of object 2.As a result, it has been found that compound 2 all there is wider substrate to be resistant to indoles and β-nitroolefin derivative
Property.
In the presence of catalyst 2 of the invention, be found to have different supplied for electronic or electron-withdrawing substituent it is various it is trans--
Beta-nitrostyrene derivative can effectively be reacted with indoles, generate corresponding product, yield (item between 89-96%
Mesh 1,3,5,6-9).In addition, under the action of catalyst 2, trans-nitrostyrene and various indole derivatives (including list
Replace or disubstituted group) between F-C reaction also obtained corresponding product, yield not equal (entry 10-17) from 89 to 97%.
These results again show that containing bimetallic active center 2 can be used as F-C reaction in effective catalyst, and have it is wider
Substrate tolerance.
3, concertedness of the compound 2 in catalysis F-C reaction
On the basis of to 2 reactivity Primary Study of catalyst, the present invention also further studies compound 2 and is being catalyzed
Concertedness in F-C reaction process.
The catalytic reaction condition being consistent, but control catalyst and reaction substrate nitrostyrolene or 4- methyl nitrobenzene
The ratio of ethylene drops to 1:1000 and 1:10000 by 1:100 respectively.Mixture is stirred at room temperature 12 hours.Then it will mix
Object is closed with 14000rpm centrifugation 10 minutes, and supernatant is concentrated in vacuo,1HNMR measures yield, as follows:
Immobilized dinuclear metal copper center can cooperate with priming reaction substrate Yin in channel in order to determine MOF catalyst 2
Diindyl and nitrostyrolene further have detected and are catalyzed under low-down C/S ratio (molar ratio of catalyst and nitrostyrolene)
The catalytic activity of agent 1 and 2.Experimental result is shown when being reduced to 1:1000 and 1:10000 from 1:100 with C/S ratio, indoles with
In the F-C reaction of beta-nitrostyrene, 1 catalytic activity drops sharply to 14% and 0% from 39% and compares with catalyst 1,
When C/S ratio is 1:1000 and 1:10000, MOF catalyst 2 still is able to be catalyzed the reaction, and obtains 52% and 17% relatively high yield
Rate.When under identical reaction conditions, using 4- methyl-nitrostyrene as substrate, it was similarly observed that similar situation.
These results indicate that homogeneous reactivity in the case where lower C/S ratio of monokaryon copper catalyst 1 is relatively low, it may be possible to due to two
The distance between a CuL is longer, and which prevent synergistic effect of the CuL unit in catalytic process.With 1 low reaction activity phase
Instead, the immobilized double-core copper (CuL) of MOF structure2Unit can activate indoles and nitrostyrolene simultaneously, this concerted catalysis
Journey makes catalyst 2 of the invention show the catalytic activity that opposite monokaryon copper catalyst is remarkably reinforced.
4, the stability and recuperability of compound 2
On the Research foundation to 2 reactivity of catalyst, the present invention also further studies compound 2 in catalysis nitro
Stability and recycling between styrene and indoles in F-C reaction process.
The catalyst of 1.0mol% is added to beta-nitrostyrene derivative (10mmol) and indole derivatives
In the dichloromethane solution of (12mmol), mixture is stirred at room temperature 12 hours.Then by mixture with 14000rpm's
Speed is centrifuged 10 minutes, by be centrifuged from reaction mixture can easily quantitative recovery catalyst 2, with fresh solvent
After washing, catalyst 2 can continue to reuse.Catalyst circulation uses 5 times, and the yield of reaction is respectively 97,95,94,93
With 93%, catalytic activity is almost without loss；Furthermore the PXRD characterization of the catalyst 2 after 5 recyclings, the results showed that although
There is slight malformation, catalyst still maintains high-crystallinity (Fig. 7).Furthermore it is noted that if being removed by centrifugation
Catalyst is removed, reaction will stop immediately.Thus it firmly believes, the compound of the present invention 2 is strictly a kind of efficient and stable F-C reaction
Catalyst.
5, catalytic performance of the different catalysts in Henry reaction
Compound 1 and 2 as catalyst is then living at 100 DEG C respectively with anhydrous super dry exchange of solvent guest molecule
Change, the activated catalyst of 1.0mol% equivalent is added to benzaldehyde derivative (10mmol) and nitromethane (100mmol)
In methanol solution, by with the speed of 14000rpm centrifugation 10 minutes after mixture is stirred 12 hours at 60 DEG C, supernatant is true
Sky concentration,1HNMR monitors reaction result and yield, as follows:
As the result is shown: under optimum reaction condition, catalyst 2 of the invention can efficiently be catalyzed benzaldehyde and its derivative
Henry between object and nitromethane reacts, wherein only the catalyst loadings of 1.0mol% can be distinguished in 12 hours
The reaction yield (entry 1,3,5-7) of 86-97% is provided.By taking benzaldehyde and 4- nitrobenzaldehyde as an example, when use monokaryon copper
When closing object 1 as catalyst (identical as 2 load capacity of CuL unit), reaction yield is significantly reduced, respectively only 48% He
53% (entry 2,4).This result shows that: catalyst 2 of the invention can also serve as Henry reaction effective catalyst,
And the catalyst 1 of the invention as reference substance only shows very general catalytic activity.It can be seen that the compounds of this invention 2
Unique bimetallic copper center contained in structure equally plays an important role to the catalytic activity that Henry reacts.
6, the concertedness in catalysis Henry reaction process of compound 2
On the basis of being catalyzed the research of Henry reactivity to compound 2, the present invention also demonstrates compound 2 again
Concertedness is equally existed in catalysis Henry reaction process.
The catalytic reaction condition being consistent, but the ratio of catalyst and reaction substrate paranitrobenzaldehyde is controlled, by 1:
100 drop to 1:1000 and 1:10000 respectively.By mixture with the speed of 14000rpm after mixture is stirred 12 hours at 60 DEG C
Degree centrifugation 10 minutes, supernatant vacuum concentration,1HNMR measures yield, as follows:
Experimental result is shown when being reduced to 1:1000 and 1:10000 from 1:100 with the ratio of C/S, paranitrobenzaldehyde
In Henry reaction between nitromethane, the catalytic activity of the compounds of this invention 1 as a comparison is dropped sharply to from 53%
20% and 3% compares with 1, and when C/S ratio is 1:1000 and 1:10000, MOF catalyst 2 of the invention still is able to the reaction simultaneously
Obtain 68% and 33% higher yields.In view of nitro can be urged by lewis acid in aldehyde compound carbonyl and nitromethane
Agent is activated, and combines the contrast and experiment, is shown under identical Henry reaction condition, has bimetallic copper center
The higher catalytic performance that is showed of MOF catalyst 2 be attributable to the concerted catalysis process of reaction, both aldehyde and nitro first
Alkane is all fixed on bimetallic (CuL) on 2 conduit wall of MOF2Unit collaboration activation.However, for 1 body of homogeneous catalyst
System, especially under the CuL catalyst of low concentration, due to activated nucleopilic reagent and electrophilic reagent collision probability very
It is low, it is therefore less likely to that the mode of concerted catalysis occurs.Equally, this invention preferably illustrates the load by MOF structure
The preparation of collaboration bimetallic catalyst is realized in effect in which can be convenient.Thus it firmly believes, using three tooth schiff bases skeletons as platform, leads to
Cross strictly a kind of stabilization of MOF catalyst 2 of the invention, efficient concerted reaction that bottom-to-top method classification assembling obtains
Catalyst.
Claims (8)
1. a kind of high activity cooperates with MOF catalyst, which is characterized in that including the homogeneous catalyst chemical combination as mononuclear copper complex
Object 1 and as the MOF catalyst compounds 2 with bimetallic copper synergic catalytic effect, chemical structure is as follows:
2. high activity according to claim 1 cooperates with MOF catalyst, which is characterized in that the synthesis side of the compound 1
Method comprises the following steps:
(1) (1S, 2R)-(-) -1- amino -2- indanol and 3'- tert-butyl -5'- formoxyl -4'- xenol -4- carboxylic will be contained
The mixture of acid is dissolved in methanol solvate, after reacting 12 hours under the conditions of 60 DEG C, organic solvent is removed in vacuum, is washed with methanol
It washs, obtains the three tooth Schiff base ligand H containing ONO electron donor3L；
(2) Cu (OAc) will be contained2·H2O and ligand H3The mixture of L is put into containing DMF, the in the mixed solvent of MeOH and water, close
Envelope, and heated 24 hours at 60 DEG C, obtain the compound 1 of blue acicular crystal, methanol washing, drying at room temperature.
3. high activity according to claim 1 cooperates with MOF catalyst, which is characterized in that the synthesis side of the compound 2
Method comprises the following steps:
CdBr will be contained2It is put into the mixture of compound 1 containing DMF, the in the mixed solvent of MeOH and water are sealed in colourless glass
In glass bottle, and continuous heating reacts 36 hours at 80 DEG C, and cold filtration, obtains the blue bulk crystals of compound 2, first later
Alcohol washing, drying at room temperature.
4. high activity according to claim 1 cooperates with MOF catalyst, which is characterized in that in following Friedel-Crafts
Application in catalysis reaction:
Wherein R be selected from optionally replace phenyl, 4- aminomethyl phenyl, 4- trifluoromethyl, 3- methoxyphenyl, 4- chlorphenyl,
4- nitrobenzophenone；R1Selected from H, methyl；R2Selected from H, phenyl, methyl；R3Selected from H, 5- methyl, 5- methoxyl group, 5- chlorine, 6- methyl.
5. application of the high activity collaboration MOF catalyst according to claim 4 in Friedel-Crafts catalysis reaction,
It is characterized in that, the catalysis reaction comprises the following steps:
(1) activation of catalyst
As the compound 1 and 2 of catalyst, guest molecule is carried out with anhydrous super dry solvent first and is exchanged, it is then living at 100 DEG C
Change, activation is verified by thermogravimetric analysis and is completed；
(2) catalysis Friedel-Crafts reaction
The activated catalyst of 1.0mol% equivalent is added to 10mmol β-nitroolefin derivative and 12mmol indoles dichloro
In dichloromethane, mixture is stirred at room temperature 12 hours, is then centrifuged mixture 10 minutes with the speed of 14000rpm,
And supernatant is concentrated in vacuo.
6. high activity according to claim 1 cooperates with MOF catalyst, which is characterized in that in following Henry catalysis reaction
Application:
7. application of the high activity collaboration MOF catalyst according to claim 6 in Henry catalysis reaction, feature exist
In the catalysis reaction comprises the following steps:
(1) activation of catalyst
As the compound 1 and 2 of catalyst, guest molecule is carried out with anhydrous super dry solvent first and is exchanged, it is then living at 100 DEG C
Change, activation is verified by thermogravimetric analysis and is completed；
(2) catalysis Henry reaction
The activated catalyst of 1.0mol% equivalent is added to the methanol of 10mmol benzaldehyde derivative and 100mmol nitromethane
In solution, reaction mixture is stirred 12 hours at 60 DEG C, is then centrifuged mixture 10 minutes with the speed of 14000rpm,
Supernatant is taken to be concentrated in vacuo.
8. high activity according to claim 1 cooperates with MOF catalyst, which is characterized in that the compound 1 is catalyst 2
The application of product is compared in Friedel-Crafts and Henry reaction.
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