CN106947022B - A kind of preparation and its application of N-heterocyclic carbine metal porous organic polymer - Google Patents
A kind of preparation and its application of N-heterocyclic carbine metal porous organic polymer Download PDFInfo
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- CN106947022B CN106947022B CN201710089184.7A CN201710089184A CN106947022B CN 106947022 B CN106947022 B CN 106947022B CN 201710089184 A CN201710089184 A CN 201710089184A CN 106947022 B CN106947022 B CN 106947022B
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 claims abstract description 14
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 10
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- -1 propargylamine class compound Chemical class 0.000 claims abstract description 7
- 125000003903 2-propenyl group Chemical class [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 239000005749 Copper compound Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229940100890 silver compound Drugs 0.000 claims description 3
- 150000003379 silver compounds Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical class NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 150000003335 secondary amines Chemical class 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- OTWSURXLBKIUNH-UHFFFAOYSA-N methylidenesilver Chemical compound [Ag]=C OTWSURXLBKIUNH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- 241001311547 Patina Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000002785 azepinyl group Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000006362 organocatalysis Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/17—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses the preparations and its application of a kind of N-heterocyclic carbine metal porous organic polymer, its main feature is that being coordinated with the azacyclo- imidazole salts of allyl functional and metal, form the N-heterocyclic carbine metal compound of allyl functional, then polymerization reaction is carried out with DVB, the porous organic polymer is used to synthesize propargylamine class compound as catalyst in three component coupling reactions of aldehyde, alkynes and secondary amine by synthesis of azacyclic carbine metal porous organic polymer.The present invention has method simple, reproducible compared with prior art, Template-free method, specific surface area, hole hold and N-heterocyclic carbine metal content is adjustable, and catalysis aldehyde, alkynes, three component coupling reactions of amine are high with catalytic activity, it is easily separated, the advantages that multiple can be recycled.
Description
Technical field
The present invention relates to porous organic polymer and applied technical field, especially one kind can be recycled in synthesis alkynes third
The preparation and its application of the N-heterocyclic carbine metal porous organic polymer of amine product.
Background technique
Currently, the inorganic silicon materials of the mostly classics of the heterogeneouss material therefor in relation to N-heterocyclic carbine metal complex are such as
MCM-41, SBA-15 etc. and macromolecule polymer material such as PS, PEG etc. (Catal.Sci.Technol., 2013,3,
2161).Recently, porous organic polymer as a kind of novel materials show go out relatively good stability and its it is powerful from
Ability of regulation and control causes the great interest of scientists (Chem.Soc.Rev., 2015,44,6018).Scientists expectation benefit
The porosity that is formed under conditions of Template-free method with this polymer and its molecular level level adjust itself specific surface area and
The ability of Kong Rong, the highly stable and recyclable heterogeneous catalysis system of synthesizing new.
N-heterocyclic carbine (NHCs) ligand has many advantages, such as that structure design, thermal stability is good, catalytic activity is high, while this is matched
Body good compatibility can be coordinated with different transition metal, can be widely applied to organocatalysis and asymmetry catalysis
Field shows excellent catalytic in many organic reactions such as carbon-to-carbon coupling, eneyne cycloisomerisation, eneyne priming reaction
Can, it is one of research hotspot of organic chemistry (Chem.Rev.2009,109,3612-3676) in recent years.Although N-heterocyclic carbine
Metallic compound has an excellent catalytic activity in homogeneous reaction, but that there is also product and catalyst purifies and separates is difficult, urges
The disadvantages of inconvenient is recycled in the recycling of agent difficulty.
The prior art is not high about the N-heterocyclic carbine metal compound utilization rate of solid-carrying type, and catalytic effect is bad, preparation
Complex process, at high cost, synthesis cycle is long, and activity is not able to maintain after recycling, and preparation process causes serious pollution to the environment.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art and provide a kind of N-heterocyclic carbine metal porous organo polysilica
The azacyclo- imidazole salts of allyl functional and metal are coordinated by the preparation and its application for closing object, form allyl functional
Polymerization reaction is carried out after N-heterocyclic carbine metal compound with DVB, it is porous organic with specific surface area that there is large hole to hold for preparation
Polymer, and by the ratio of regulation N-heterocyclic carbine metal compound and DVB, it is integrated into N-heterocyclic carbine metal compound
In the skeleton of porous organic polymer, with adjust the polymer specific surface area and hole hold etc. properties, synthesize a series of azepine
Ring carbine metal porous organic polymer catalyst, it is anti-that which can be applied to aldehyde, alkynes, the three components coupling of amine
Answer, there is excellent reactivity, the easily separated recycling of catalyst, be it is a kind of it is novel can be recycled efficiently prepare propargylamine
The N-heterocyclic carbine metal porous organic polymer catalyst of class compound.
Realizing the specific technical solution of the object of the invention is: a kind of system of N-heterocyclic carbine metal porous organic polymer
It is standby, its main feature is that by the N-heterocyclic carbine metal compound of allyl functional and divinylbenzene (DVB), azodiisobutyronitrile
(AIBN) and N,N-dimethylformamide (DMF) presses 0.1~0.5g:0.75~2.5g:0.015~0.025g:8~12ml matter
Volume ratio mixing is measured, at room temperature prepolymerization 2~5 hours, then polymerization reaction 20~28 hours at a temperature of 80~100 DEG C,
The porous organic polymer that N-heterocyclic carbine metal compound and DVB cross-linked polymeric are formed is made, reaction structure formula is as follows:
The N-heterocyclic carbine metal compound is 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination
Cabbeen copper compound, 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen patina is closed or 1,3- bis- -
(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen gold compound.
A kind of application of N-heterocyclic carbine metal porous organic polymer, its main feature is that the porous organic polymer alkynes,
Propargylamine class compound is synthesized as catalyst in three component coupling reactions of aldehyde and secondary amine, reaction structure formula is as follows:
Wherein: R is aryl or alkyl；R1For hydrogen, aryl or alkyl；R2、R3For aryl or alkyl.
The three components coupling reaction be aldehyde, alkynes, secondary amine, methylene chloride or acetonitrile and catalyst by 1mmol:1~
It is small to be stirred at room temperature 8~16 than mixing for 1.2mmol:1~1.2mmol:0.5~3ml:0.005~0.02mmol molal volume
The catalysis reaction of tri- component of Shi Jinhang coupling filters out catalyst after reaction and is washed for several times with anhydrous ether, merged organic
It is separated after phase with anhydrous sodium sulfate drying, concentration and silica gel column chromatography, obtains the propargylamine class compound that product is the coupling of three components,
The porous organic polymer catalyst filtered out is washed, it is dry after it is reusable.
The present invention has preparation process simple compared with prior art, and synthesis cycle is short, reproducible, Template-free method, nitrogen
Heterocyclic carbene metal compounds content is adjustable and is evenly distributed, the porous organic polymer specific surface area and Kong Rong great of formation and can
Regulation, aldehyde, alkynes, secondary amine three component coupling reactions in catalytic activity it is high, it is easily separated, can be recycled, be a kind of Novel ring
The heterogeneous N-heterocyclic carbine metal porous organic polymer catalyst for efficiently synthesizing propargylamine class compound of border friendly, is being urged
Change field is with a wide range of applications.
Detailed description of the invention
Fig. 1 is the SEM figure that embodiment 1 prepares N-heterocyclic carbine copper porous organic polymer；
Fig. 2 is the SEM figure that embodiment 2 prepares N-heterocyclic carbine copper porous organic polymer；
Fig. 3 is the nitrogen Adsorption and desorption isotherms and BJH that Examples 1 to 2 prepares N-heterocyclic carbine copper porous organic polymer
Graph of pore diameter distribution；
Fig. 4 is the SEM figure that embodiment 3 prepares nitrogen heterocyclic carbene silver porous organic polymer；
Fig. 5 is the SEM figure that embodiment 4 prepares nitrogen heterocyclic carbene silver porous organic polymer；
Fig. 6 is the nitrogen Adsorption and desorption isotherms and BJH that embodiment 3~4 prepares nitrogen heterocyclic carbene silver porous organic polymer
Graph of pore diameter distribution.
Specific embodiment
By following specific embodiments, the present invention is described in further detail.
Embodiment 1
Weigh 0.2g 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen copper compound with
The steamed divinylbenzene of 15mg azodiisobutyronitrile, 1g weight and 8mL DMF mixing, are stirred at room temperature 3 hours, then exist
Polymerization reaction 24 hours, are cooled to room temperature after reaction at a temperature of 100 DEG C, polymer washed with dehydrated alcohol after at 80 DEG C
At a temperature of be dried in vacuo, obtain product be N-heterocyclic carbine copper porous organic polymer.
It refering to attached drawing 1, characterizes and shows through scanning electron microscope, the pattern of 1 resulting polymers of embodiment is highly cross-linked
Amorphous porous material.
Refering to a curve in attached drawing 3,1 products therefrom of embodiment is measured through isothermal nitrogen adsorption desorption characterization, specific surface area
For 573m2/ g, pore volume 1.6cm3/g。
Embodiment 2
Weigh 0.5g 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen copper compound with
The steamed divinylbenzene of 25mg azodiisobutyronitrile, 1g weight and 10mL DMF mixing, are stirred at room temperature 4 hours, then exist
Polymerization reaction 28 hours, are cooled to room temperature after reaction at a temperature of 95 DEG C, polymer washed with dehydrated alcohol after at 80 DEG C
At a temperature of be dried in vacuo, obtain product be N-heterocyclic carbine copper porous organic polymer.
It refering to attached drawing 2, characterizes and shows through scanning electron microscope, the pattern of 2 resulting polymers of embodiment is highly cross-linked
Amorphous porous material.
Refering to the b curve in attached drawing 3,2 products therefrom of embodiment is measured through isothermal nitrogen adsorption desorption characterization, specific surface area
For 618m2/ g, pore volume 1.9cm3/g。
Embodiment 3
Weigh 0.3g 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen silver compound with
20mg azodiisobutyronitrile, the 0.9g steamed divinylbenzene of weight and 10mL DMF mixing, are stirred at room temperature 3 hours, then
Polymerization reaction 22 hours, is cooled to room temperature after reaction at a temperature of 80 DEG C, polymer washed with dehydrated alcohol after 80
It is dried in vacuo at a temperature of DEG C, obtaining product is nitrogen heterocyclic carbene silver porous organic polymer.
It refering to attached drawing 4, characterizes and shows through scanning electron microscope, the pattern of 3 resulting polymers of embodiment is highly cross-linked
Amorphous porous material.
Refering to a curve in attached drawing 6,3 products therefrom of embodiment is measured through isothermal nitrogen adsorption desorption characterization, specific surface area
For 674m2/ g, pore volume 1.9cm3/g。
Embodiment 4
Weigh 0.4g 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen silver compound with
15mg azodiisobutyronitrile, the 0.6g steamed divinylbenzene of weight and 12mL DMF mixing, are stirred at room temperature 3 hours, then
Polymerization reaction 25 hours, is cooled to room temperature after reaction at a temperature of 90 DEG C, polymer washed with dehydrated alcohol after 80
It is dried in vacuo at a temperature of DEG C, obtaining product is nitrogen heterocyclic carbene silver porous organic polymer.
It refering to attached drawing 5, characterizes and shows through scanning electron microscope, the pattern of 4 resulting polymers of embodiment is highly cross-linked
Amorphous porous material.
Refering to the b curve in attached drawing 6,4 products therefrom of embodiment is measured through isothermal nitrogen adsorption desorption characterization, specific surface area
For 667m2/ g, pore volume 2.2cm3/g。
Embodiment 5
Weigh the N-heterocyclic carbine copper porous organic polymer catalyst and 15mg poly first of the preparation of 12mg above-described embodiment 2
It is anti-that three components of progress coupling in 16 hours is stirred at room temperature in aldehyde, 56mg phenylacetylene, 40mg pyrrolidines and the mixing of 1mL methylene chloride
It answers, filter out catalyst after reaction and is washed three times with anhydrous ether, with anhydrous sodium sulfate drying, mistake after merging organic phase
Filter, concentration and silica gel column chromatography (petroleum ether: ethyl acetate=3:1) separation, obtaining product is 1- (3- phenyl -2- propargyl) pyrrole
Cough up, yield 98%, the catalyst filtered out is washed, it is dry after it is reusable.
Embodiment 6
Weigh the nitrogen heterocyclic carbene silver porous organic polymer catalyst and 112mg hexamethylene of the preparation of 27mg above-described embodiment 3
Base formaldehyde, 122mg phenylacetylene, 94mg piperidines and the mixing of 2mL acetonitrile, are stirred at room temperature 8 hours three component coupling reactions of progress,
Filter out catalyst after reaction and washed three times with anhydrous ether, merge after organic phase with anhydrous sodium sulfate is dry, concentration and
Silica gel column chromatography (petroleum ether: ethyl acetate=4:1) separation, obtaining product is 1- (1- cyclohexyl -3- phenyl -2- propargyl) piperazine
Pyridine, yield 97%, the catalyst filtered out is washed, it is dry after it is reusable.
Only the present invention will be further described for the above various embodiments, is not intended to limit the invention patent, all is this hair
Bright equivalence enforcement, is intended to be limited solely by within the scope of the claims of the invention patent.
Claims (2)
1. a kind of preparation method of N-heterocyclic carbine metal porous organic polymer, it is characterised in that by the nitrogen of allyl functional
Heterocyclic carbene metal compound and divinylbenzene (DVB), azodiisobutyronitrile (AIBN) and N,N-dimethylformamide (DMF)
It is mixed by 0.1~0.5g:0.75~2.5g:0.015~0.025g:8~12ml mass volume ratio, at room temperature prepolymerization 2
~5 hours, then polymerization reaction 20~28 hours at a temperature of 80~100 DEG C, N-heterocyclic carbine metal compound and two is made
The porous organic polymer that vinyl benzene cross-linked polymeric is formed, the N-heterocyclic carbine metal compound are 1,3- bis--(4- allyl
Base -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen copper compound, 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl)
Imidazoles chlorination Cabbeen silver compound or 1,3- bis--(4- allyl -2,6- Diisopropyl-phenyl) imidazoles chlorination Cabbeen aurification are closed
Object.
2. the application of N-heterocyclic carbine metal porous organic polymer prepared by a kind of claim 1, it is characterised in that this is more
Hole organic polymer synthesizes propargylamine class compound as catalyst in three component coupling reactions of alkynes, aldehyde and secondary amine, anti-
Answer structural formula as follows:
Wherein: R is aryl or alkyl；R1For hydrogen, aryl or alkyl；R2、R3For aryl or alkyl；
The three component coupling reactions be aldehyde, alkynes, secondary amine, methylene chloride or acetonitrile and catalyst by 1mmol:1~
It is small to be stirred at room temperature 8~16 than mixing for 1.2mmol:1~1.2mmol:0.5~3ml:0.005~0.02mmol molal volume
The catalysis reaction of tri- component of Shi Jinhang coupling filters out catalyst after reaction and is washed for several times with anhydrous ether, merged organic
It is separated after phase with anhydrous sodium sulfate drying, filtering, concentration and silica gel column chromatography, obtaining product is the propargylamine class that three components are coupled
Close object, the porous organic polymer catalyst filtered out is washed, it is dry after it is reusable.
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| CN107501564B (en) * | 2017-07-19 | 2019-05-31 | 复旦大学 | Three-dimensional N-heterocyclic carbine metal coordination polymer and preparation method thereof and and application |
| CN107519937A (en) * | 2017-09-06 | 2017-12-29 | 河南理工大学 | A kind of short immobilized azepine Cabbeen Ag composition catalysts of fibre and preparation method thereof |
| CN107935801A (en) * | 2017-11-09 | 2018-04-20 | 湖南大学 | A kind of new method for synthesizing propargylamine class compound |
| CN108822243A (en) * | 2018-06-08 | 2018-11-16 | 华东师范大学 | A kind of preparation and its application of N-heterocyclic carbine gold porous organic polymer |
| CN108929286B (en) * | 2018-07-02 | 2022-02-15 | 河南师范大学 | Method for synthesizing propargylamine compounds by using functionalized ionic liquid to promote multi-component reaction |
| CN109261209A (en) * | 2018-10-16 | 2019-01-25 | 广西师范大学 | It is a kind of using nitrogen heterocycle carbine ligand as the preparation method of the monatomic catalyst of carrier |
| CN109746043B (en) * | 2018-10-31 | 2021-07-13 | 六盘水师范学院 | N-heterocyclic carbene functionalized porous organic polymer supported copper catalyst and preparation method and application thereof |
| CN110743620B (en) * | 2019-12-03 | 2022-09-27 | 东华理工大学 | Magnetic polyazacyclo-carbene palladium catalyst, preparation method and application |
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