CN108822243A - A kind of preparation and its application of N-heterocyclic carbine gold porous organic polymer - Google Patents
A kind of preparation and its application of N-heterocyclic carbine gold porous organic polymer Download PDFInfo
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- CN108822243A CN108822243A CN201810587060.6A CN201810587060A CN108822243A CN 108822243 A CN108822243 A CN 108822243A CN 201810587060 A CN201810587060 A CN 201810587060A CN 108822243 A CN108822243 A CN 108822243A
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/36—One oxygen atom
- C07D263/38—One oxygen atom attached in position 2
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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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses the preparations and its application of a kind of N-heterocyclic carbine gold porous organic polymer, its main feature is that with the 1 of alkenyl functional dough, bis- (to vinyl benzyl) the imidazole carbenes aurous chlorides (I) of 3- and divinylbenzene, azodiisobutyronitrile and N, dinethylformamide polymerization reaction at a temperature of 70~100 DEG C, N-heterocyclic carbine gold porous organic polymer is obtained, by the porous organic polymer in CO2Be used as catalyst synthesize 2- oxazolidinone compounds with the cyclization of propargylamine class compound, the catalyst filtered out is washed, dry after it is reusable.The present invention has simple process compared with prior art, synthesis cycle is short, reaction process low toxicity, it is reproducible, the N-heterocyclic carbine gold porous organic polymer specific surface area of formation and hole hold adjustable, catalytic activity height, easily separated, the advantages that can be recycled has huge development potentiality and application prospect in heterogeneous catalysis field.
Description
Technical field
The present invention relates to the preparation of porous organic polymer and applied technical field, especially one kind can be recycled in
CO2Synthesize the preparation and its application of the N-heterocyclic carbine gold porous organic polymer of 2- oxazolidinone product.
Background technique
In recent years, N-heterocyclic carbine Au catalyst is quickly grown, and important role is play in organic catalysis, still
Homogeneous metallic catalyst has the shortcomings that be difficult to recycle, metal residual, these all limit the application of Au catalyst, prepare
Heterogeneous catalyst becomes a kind of important solution.Existing N-heterocyclic carbine gold heterogeneous catalyst mainly consolidates catalyst
It is loaded in silicon substrate, high molecular material.
Li Fu in 2013 big et al. (ACS Catalysis, 2013,4 (1):321-327.) report and utilize Halofunctional
Dough N-heterocyclic carbine gold and three tooth alkynes are coupled by sonogashira is prepared N-heterocyclic carbine metal/polymer, and answers
For alkynes water and reaction.Asensio in 2017 et al. (ACS Catalysis, 2017,7 (10):7146-7155.) report
It is immobilized on silicon materials using the N-heterocyclic carbine Au catalyst of alkenyl functional dough, and realize under conditions of continuous flowing batch
Amount catalysis alkynes function dough.
The prior art is long and complicated there are preparation route about N-heterocyclic carbine gold heterogeneous catalyst, complex process, cost
Height, synthesis cycle is long, and activity is not able to maintain after recycling, and preparation process will use some high toxicity reagents and environment is caused to endanger
Evil.
Summary of the invention
The purpose of the present invention is a kind of N-heterocyclic carbine gold porous organo polysilica conjunctions of offer in view of the deficiencies of the prior art
The preparation and its application of object are reacted using the N-heterocyclic carbine gold complex of alkenyl functional dough with divinyl benzene crosslinked, system
The standby porous organic polymer held with large hole with specific surface area, and pass through regulation N-heterocyclic carbine gold complex and divinyl
The ratio of base benzene obtains a series of porous organic polymers with different size specific surface area and Kong Rong, the porous organo polysilica
Object is closed in CO2It is used as catalyst to synthesize 2- oxazolidinone compounds with the cyclization of propargylamine class compound, has excellent
The advantages that different reactivity, separation and recovery is easy to operate, can be with recycled for multiple times, which is that one kind is novel, can be recycled
Efficiently prepare the N-heterocyclic carbine metal porous organic polymer catalyst of 2- oxazolidinone compounds.
Realizing the specific technical solution of the object of the invention is：A kind of preparation of N-heterocyclic carbine gold porous organic polymer,
Its main feature is that by bis- (to vinyl benzyl) the imidazole carbenes aurous chlorides (I) of the 1,3- of alkenyl functional dough and divinylbenzene
(DVB), azodiisobutyronitrile (AIBN) and N,N-dimethylformamide (DMF) press 0.27 g:0.06~2.60g:0.10~
0.94g:The mass volume ratio of 2~20mL mixes, and 0.25~1h of prepolymerization hours at room temperature, then in 70~100 DEG C of temperature
The lower polymerization reaction for carrying out following reaction structure formula：
After reaction, DMF and acetone washing is successively used to be dried in vacuo afterwards three times much filtrate, obtaining product is azacyclo-
Cabbeen gold porous organic polymer, the polymerization reaction time are 12~30 hours.
A kind of application of N-heterocyclic carbine gold porous organic polymer, its main feature is that the porous organic polymer is in CO2With
2- oxazolidinone compounds are synthesized as catalyst in the cyclization of propargylamine class compound, reaction structure formula is as follows：
Wherein：R1For alkyl or aryl, R2For alkyl or aryl；
The cyclization of the propargylamine class compound is by N-heterocyclic carbine gold porous organic polymer and propargylamine class
Compound is dissolved in methanol solvate, then passes to the CO of 0.1~1MPa2The polarity synthesis for carrying out 2- oxazolidinone compounds is anti-
It answers, reaction temperature is 25~80 DEG C, and the reaction time is 12~48 hours, filters out catalyst after reaction and uses anhydrous ether
Washing for several times, is separated after merging organic phase with anhydrous sodium sulfate drying, filtering, concentration and silica gel column chromatography, obtaining product is 2- Evil
Oxazolidinones, the catalyst filtered out is washed, it is dry after reusable, the N-heterocyclic carbine gold porous organo polysilica
The mass volume ratio for closing object and propargylamine class compound and methanol is 0.01~1g:0.1~0.5g:1~10mL；The propargylamine
Class compound is N- benzyl -2- butyneamine, N- methyl -2- butyneamine, N- methyl-propargyl amine, N- isopropyl propargyl amine, N-
Cyclohexyl alkyne propyl amine, N- tert-butyl propargyl amine, N- isopropyl -2- butyneamine, N- cyclohexyl -2- butyneamine or the tertiary fourth of N-
Base -2- butyneamine.
The present invention has preparation process simple compared with prior art, and synthesis cycle is short, reaction process low toxicity, repeatability
Good, the N-heterocyclic carbine gold porous organic polymer specific surface area of formation and hole appearance are adjustable, in CO2With propargylamine class
It is high to close catalytic activity in object cyclization, it is easily separated, it is a kind of environmentally friendly heterogeneous catalyst the advantages that can be recycled,
There are huge development potentiality and application prospect in heterogeneous catalysis field.
Detailed description of the invention
Fig. 1 is the SEM figure that embodiment 1 prepares N-heterocyclic carbine gold porous organic polymer；
Fig. 2 is the N that embodiment 1 prepares N-heterocyclic carbine gold porous organic polymer2Adsorption-desorption isothermal curve.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail.
Embodiment 1
Weigh bis- (to vinyl benzyl) the imidazole carbenes aurous chlorides (I) of 0.27g 1,3- and 0.65g divinylbenzene
(DVB) it is dissolved in 27mg azodiisobutyronitrile (AIBN), adds 5mL DMF, 30min is stirred in prepolymerization at room temperature, is then existed
It is reacted at a temperature of 80 DEG C for 24 hours, after reaction, much filtrate is successively dried in vacuo with DMF and acetone washing afterwards three times, is obtained
0.83g product is N-heterocyclic carbine gold porous organic polymer.
Refering to attached drawing 1, above-mentioned product is characterized through scanning electron microscope, and resulting polymers are particle packing material.
Refering to attached drawing 2, above-mentioned product is measured through nitrogen adsorption-desorption isothermal characterization, specific surface area 572m2·g-1, hole
Holding is 0.54cm3·g-1。
Embodiment 2
Weigh bis- (to vinyl benzyl) the imidazole carbenes aurous chlorides (I) of 0.27g 1,3- and 0.33g divinylbenzene
(DVB) it is dissolved in 27mg azodiisobutyronitrile (AIBN), adds 10mL DMF, 30min is stirred in prepolymerization at room temperature, is then existed
20h is reacted at a temperature of 80 DEG C, after reaction, much filtrate is successively dried in vacuo with DMF and acetone washing afterwards three times, is obtained
0.55g product is N-heterocyclic carbine gold porous organic polymer.
Embodiment 3
Weigh bis- (to vinyl benzyl) the imidazole carbenes aurous chlorides (I) of 0.27g 1,3- and 1.30g divinylbenzene
(DVB) it is dissolved in 50mg azodiisobutyronitrile (AIBN), adds 15mL DMF, 30min is stirred in prepolymerization at room temperature, is then existed
It is reacted at a temperature of 80 DEG C for 24 hours, after reaction, much filtrate is successively dried in vacuo with DMF and acetone washing afterwards three times, is obtained
1.46g product is N-heterocyclic carbine gold porous organic polymer.
Embodiment 4
The N-heterocyclic carbine gold porous organic polymer for weighing the preparation of 0.2g above-described embodiment 1 is catalyst and 0.16g
N- benzyl -2- butyneamine is dissolved in 2mL methanol (MeOH), then passes to the CO of 1bar2, 2- oxazolidone is carried out at a temperature of 40 DEG C
The catalysis reaction of class compound polarity synthesis for 24 hours, filters out catalyst after reaction and is washed three times with anhydrous ether, is associated with
It is separated after machine phase with anhydrous sodium sulfate drying, filtering, concentration and silica gel column chromatography, obtaining product is 2- oxazolidinone compounds,
1,3,5- trimethoxy-benzene of internal standard is added, nuclear-magnetism yield is 99%, the catalyst filtered out is washed, it is dry after it is reusable.
Embodiment 5
The N-heterocyclic carbine gold porous organic polymer for weighing the preparation of 0.1g above-described embodiment 2 is catalyst and 0.16g
N- benzyl -2- butyneamine is dissolved in 1mL methanol (MeOH), then passes to the CO of 1bar2, 2- oxazolidone is carried out at a temperature of 40 DEG C
The catalysis reaction of class compound polarity synthesis for 24 hours, filters out catalyst after reaction and is washed three times with anhydrous ether, is associated with
It is separated after machine phase with anhydrous sodium sulfate drying, filtering, concentration and silica gel column chromatography, obtaining product is 2- oxazolidinone compounds,
1,3,5- trimethoxy-benzene of internal standard is added, nuclear-magnetism yield is 99%, the catalyst filtered out is washed, it is dry after it is reusable.
Embodiment 6
The N-heterocyclic carbine gold porous organic polymer for weighing the preparation of 0.5g above-described embodiment 3 is catalyst and 0.16g
N- benzyl -2- butyneamine is dissolved in 4mL methanol (MeOH), then passes to the CO of 1bar2, 2- oxazolidone is carried out at a temperature of 40 DEG C
The catalysis reaction of class compound polarity synthesis for 24 hours, filters out catalyst after reaction and is washed three times with anhydrous ether, is associated with
It is separated after machine phase with anhydrous sodium sulfate drying, filtering, concentration and silica gel column chromatography, obtaining product is 2- oxazolidinone compounds,
1,3,5- trimethoxy-benzene of internal standard is added, nuclear-magnetism yield is 99%, 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 of N-heterocyclic carbine gold porous organic polymer, it is characterised in that 1,3- of alkenyl functional dough is bis-
(to vinyl benzyl) imidazole carbenes aurous chloride is pressed with divinylbenzene, azodiisobutyronitrile and N,N-dimethylformamide
0.27g:0.06~2.60g:0.10~0.94g:The mass volume ratio of 2~20mL mixes, at room temperature 0.25~1h of prepolymerization
Hour, the polymerization reaction of following reaction structure formula is then carried out at a temperature of 70~100 DEG C：
After reaction, DMF and acetone washing is successively used to be dried in vacuo afterwards three times much filtrate, obtaining product is N-heterocyclic carbine
Golden porous organic polymer, the polymerization reaction time are 12~30 hours.
2. the application of N-heterocyclic carbine gold porous organic polymer described in a kind of claim 1, it is characterised in that this is porous organic
Polymer is in CO2It is used as catalyst to synthesize 2- oxazolidinone compounds with the cyclization of propargylamine class compound, it is anti-
Answer structural formula as follows：
Wherein：R1For alkyl or aryl, R2For alkyl or aryl；
The cyclization of the propargylamine class compound is by N-heterocyclic carbine gold porous organic polymer and propargylamine class chemical combination
Object is dissolved in methanol solvate, then passes to the CO of 0.1~1MPa2The polarity synthetic reaction of 2- oxazolidinone compounds is carried out,
Its reaction temperature is 25~80 DEG C, and the reaction time is 12~48 hours, filters out catalyst after reaction and is washed with anhydrous ether
It washs for several times, is separated after merging organic phase with anhydrous sodium sulfate drying, filtering, concentration and silica gel column chromatography, obtaining product is 2- oxazole
Alkane ketone compounds, the catalyst filtered out is washed, it is dry after it is reusable, the N-heterocyclic carbine gold porous organo polysilica closes
The mass volume ratio of object and propargylamine class compound and methanol is 0.01~1g:0.1~0.5g:1~10mL；The propargylamine class
Compound is N- benzyl -2- butyneamine, N- methyl -2- butyneamine, N- methyl-propargyl amine, N- isopropyl propargyl amine, N- ring
Hexyl propargyl amine, N- tert-butyl propargyl amine, N- isopropyl -2- butyneamine, N- cyclohexyl -2- butyneamine or N- tert-butyl -
2- butyneamine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057199A (en) * | 2019-12-09 | 2020-04-24 | 盐城工学院 | Aza-carbene-based nanogold surface polymer modification method |
| CN111205198A (en) * | 2020-01-24 | 2020-05-29 | 复旦大学 | Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material |
| CN112961110A (en) * | 2021-02-10 | 2021-06-15 | 浙江工业大学 | Olefin functionalized IPr HCl monomer and preparation method and application thereof |
| CN115260390A (en) * | 2022-07-26 | 2022-11-01 | 合肥工业大学 | Preparation of novel polymerized N-heterocyclic carbene catalyst and application of catalyst in furoic acid synthesis process |
| CN116037076A (en) * | 2022-12-07 | 2023-05-02 | 东华大学 | Efficient selective gold adsorption 1,2, 4-triazole polyelectrolyte adsorbent and preparation method and application thereof |
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| JP2016088893A (en) * | 2014-11-05 | 2016-05-23 | 国立研究開発法人産業技術総合研究所 | 2-oxazolones and manufacturing method of 2-oxazolones |
| CN106947022A (en) * | 2017-02-20 | 2017-07-14 | 华东师范大学 | A kind of preparation and its application of N-heterocyclic carbine metal porous organic polymer |
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| JP2016088893A (en) * | 2014-11-05 | 2016-05-23 | 国立研究開発法人産業技術総合研究所 | 2-oxazolones and manufacturing method of 2-oxazolones |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057199A (en) * | 2019-12-09 | 2020-04-24 | 盐城工学院 | Aza-carbene-based nanogold surface polymer modification method |
| CN111057199B (en) * | 2019-12-09 | 2022-11-11 | 青岛石控科技有限公司 | Aza-carbene-based nanogold surface polymer modification method |
| CN111205198A (en) * | 2020-01-24 | 2020-05-29 | 复旦大学 | Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material |
| WO2021147622A1 (en) * | 2020-01-24 | 2021-07-29 | 复旦大学 | Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material |
| CN111205198B (en) * | 2020-01-24 | 2023-08-01 | 复旦大学 | Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation through porous material |
| CN112961110A (en) * | 2021-02-10 | 2021-06-15 | 浙江工业大学 | Olefin functionalized IPr HCl monomer and preparation method and application thereof |
| CN112961110B (en) * | 2021-02-10 | 2022-05-24 | 浙江工业大学 | Olefin functionalized IPr HCl monomer and preparation method and application thereof |
| CN115260390A (en) * | 2022-07-26 | 2022-11-01 | 合肥工业大学 | Preparation of novel polymerized N-heterocyclic carbene catalyst and application of catalyst in furoic acid synthesis process |
| CN116037076A (en) * | 2022-12-07 | 2023-05-02 | 东华大学 | Efficient selective gold adsorption 1,2, 4-triazole polyelectrolyte adsorbent and preparation method and application thereof |
| CN116037076B (en) * | 2022-12-07 | 2024-07-12 | 东华大学 | Efficient selective gold adsorption 1,2, 4-triazole polyelectrolyte adsorbent and preparation method and application thereof |
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Application publication date: 20181116 |