CN106854159A - A kind of method of phenylacetylene carbonyl compound into unsaturated aromatic ester - Google Patents
A kind of method of phenylacetylene carbonyl compound into unsaturated aromatic ester Download PDFInfo
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- CN106854159A CN106854159A CN201510902729.2A CN201510902729A CN106854159A CN 106854159 A CN106854159 A CN 106854159A CN 201510902729 A CN201510902729 A CN 201510902729A CN 106854159 A CN106854159 A CN 106854159A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a kind of phenylacetylene carbonyl compound into unsaturated aromatic ester method, using phenylacetylene, methyl alcohol and carbon monoxide as reaction raw materials, it it is 30~90 DEG C in reaction temperature, initial pressure is under conditions of 2~6MPa, using the supported palladium-based catalyst of multifunctional polymer, phenylacetylene carbonyl compound into unsaturated aromatic ester is catalyzed.The present invention carries out hinge with p styrene sulfonic acid and is polymerized to form multifunctional polymer (POL-2V-P, the N-SO of solid under certain condition using vinyl 2- pyridyldiphenylphosphines3H), it is complexed with multifunctional polymer and immobilized palladium prepares the supported palladium-based catalyst of multifunctional polymer.One-step method of the present invention by phenylacetylene carbonyl compound into unsaturated aromatic ester, with high-activity high-selectivity, excellent properties that are low to equipment corrosion and being easily isolated recycling.
Description
Technical field
The present invention relates to a kind of phenylacetylene carbonyl compound into unsaturated aromatic ester method, and in particular to one kind with phenylacetylene, an oxygen
Change carbon and methyl alcohol as reaction raw materials, be 30~90 DEG C in reaction temperature, the initial pressure of carbon monoxide is the bar of 2~6MPa
Under part, using the supported palladium-based catalyst of multifunctional polymer, catalysis phenylacetylene carbonylation is obtained unsaturation aromatic ester.
Background technology
Unsaturated aromatic ester (methyl cinnamate and its isomers), be it is a kind of with taste cream in osmanthus is fragrant, hesperidium fragrance white crystal,
It is mainly used in food, daily use chemicals and medical industry and as organic synthesis raw material, there is very vast potential for future development.At present, Chinese cassia tree
The synthesis of sour methyl esters is the direct ester in the presence of inorganic acid catalyst (such as sulfuric acid, hydrochloric acid) with cinnamic acid and methyl alcohol as raw material
It is combined to.But the side reaction that this method is produced is more, and product yield is low and of poor quality, reaction unit seriously corroded, while producing useless
Water pollution, it is impossible to meet the requirement of current sustainable development.So the synthetic method of the new unsaturated aromatic ester of exploitation has
Important meaning.
Phenylacetylene carbonylation method prepares unsaturated aromatic ester has the advantages that Atom economy, and the catalyst used by it is by 2- pyridines
Base diphenylphosphine, palladium, the catalyst system and catalyzing of p-methyl benzenesulfonic acid composition.Catalyst system catalysis phenylacetylene carbonylation exists
Carried out under the temperate condition of low-temp low-pressure, there is high-activity high-selectivity.However, the homogeneous catalyst is difficult and product
Separation is recycled, and influences the industrial applications of the technique.Additionally, reaction needs to use the stronger Bronsted acid of corrosivity,
Reaction unit seriously corroded, considerably increases production cost.Immobilized organic ligand is not only excellent with homogeneous catalyst high activity
Point, the characteristics of it also has heterogeneous catalysis easily separated recovery.
The content of the invention
The invention provides a kind of phenylacetylene carbonyl compound into unsaturated aromatic ester method, specially with phenylacetylene, carbon monoxide
With methyl alcohol as reaction raw materials, it is catalyzed using the supported palladium-based catalyst of multifunctional polymer, a step carbonylation system
Obtain unsaturated aromatic ester accordingly.
React the process conditions for using：30~90 DEG C, the initial pressure of CO is 2~6MPa, phenylacetylene:Methyl alcohol=1:8~1:40
(mass ratio), phenylacetylene：Carbon monoxide=1:1~1:20 (mass ratioes), catalyst:Phenylacetylene=1:1~1:25 (mass ratioes).
Methyl alcohol both also served as reaction substrate as solvent.
The palladium-based catalyst that described catalyst is supported for multifunctional polymer.Multifunctional polymer is by 2- pyridine radicals hexichol
Base phosphine (2-PyPPh2) as organic ligand, vinyl is connected, vinyl 2- pyridyldiphenylphosphines are prepared, adding
Hinge is carried out with p styrene sulfonic acid at initiator azodiisobutyronitrile and 100 DEG C to be polymerized the multifunctional polymer to be formed
(POL-2V-P,N-SO3H).With multifunctional polymer POL-2V-P, N-SO3H is complexed and immobilized palladium prepares palladium base catalysis
Agent, the polymer is both the part of catalyst, is also the carrier of catalyst, while being also proton acid donors.Palladium is supported
Measure the 0.2wt%~2wt% for catalyst weight.
The reactor for preparing the catalytic reaction of unsaturated aromatic ester is pressure autoclave type reactor.
Concrete technical scheme of the present invention is realized in the following way：
First by multi-functional copolymer p OL-2V-P, N-SO3H is placed in tetrahydrofuran, after stirring, adds Pd (OAc)2.At room temperature
After stirring, required immobilized insoluble catalyst is vacuum dried to obtain.Pd(OAc)2Addition according to the loading of palladium to urge
0.2wt%~2wt% additions of agent weight, only appropriate loading can obtain preferable catalytic performance.
Solid-supported catalyst, phenylacetylene are placed in methyl alcohol, autoclave is put into, autoclave is closed.It is passed through argon gas displacement autoclave
Interior air 3~6 times.Then pass to the CO gas that pressure is 4.8MPa.Then 60 DEG C are warming up under agitation
Reacted, room temperature is cooled down to reactor cooling water after reaction, liquid-phase product is separated using centrifugation or filter method
Liquid phase analysis are carried out after catalyst again.The catalyst isolated can as previously described carry out reaction next time again.
The process conditions of use：30~90 DEG C, the initial pressure of CO is 2~6MPa, phenylacetylene:Methyl alcohol=1:8~1:40 (quality
Than), phenylacetylene：Carbon monoxide=1:1~1:20 (mass ratioes), catalyst:Phenylacetylene=1:1~1:25 (mass ratioes).
Brief description of the drawings：
Fig. 1 is POL-2V-P, N-SO3The SEM figures of H organic ligand polymer；
Fig. 2 is Pd/POL-2V-P, N-SO3The Electronic Speculum SEM phenograms of H catalyst patterns.
Fig. 3 is POL-2V-P, N-SO3The schematic diagram of H synthetic technology routes；
Specific embodiment
The following is embodiments of the invention：
Embodiment 1
POL-2V-P,N-SO3H preparation methods：Under liquid nitrogen bath and nitrogen atmosphere, burnt to the tri- mouthfuls of round bottoms of 1L with magnetic stick
In bottle, the tetrahydrofuran of 45ml is sequentially added, the n-BuLi of 0.12mol, the adjacent bromopyridine of 0.1mol, 0.135mol's
ZnCl2, then 45ml pyridines, 90ml tetrahydrofurans react 14h at room temperature.Liquid in bottle outlet is toppled under nitrogen protection,
Then 60ml pyridines are sequentially added under the conditions of liquid nitrogen bath, 180ml tetrahydrofurans, the PCl3 solution of 0.12mol (is dissolved in
60ml pyridines, in 60ml tetrahydrofurans), then reaction 26h (being named as reaction solution 1) at room temperature.In liquid nitrogen bath and blanket of nitrogen
Under enclosing, to another 1L three neck round bottom flask with magnetic stick in, sequentially add 0.22mol (5.4g) magnesium chips, 35ml
Tetrahydrofuran, 36.6g (0.2mol) to bromstyrol (being named as reaction solution 2).Reaction solution 1 filter after in liquid nitrogen bath
In addition reaction solution 2 under nitrogen atmosphere, at room temperature after two hours of stirring reaction, 200ml deionized waters are added.Then
With 3 extractive reaction mixtures of 500mL ethyl acetate solutions point, combined ethyl acetate extract, rotary evaporation takes off after filtering
Except solvent, obtained primary product are purified through silica gel column chromatography, i.e., make fixing phase with silica gel, and ethyl acetate-petroleum ether presses volume
Than 1:The mixed solvent of 6 compositions makees eluent, bluish yellow color viscous oil-like liquid is obtained and is vinylated 2-PyPPh2.In argon
During atmosphere is enclosed, to the 50ml single necked round bottom flask with magnetic stick in, sequentially add the vinylated 2-PyPPh of 1.17g2,
0.11g azodiisobutyronitriles, 15ml tetrahydrofurans, 1.2ml deionized waters, 0.3g sodium p styrene sulfonates, at room temperature
It is stirred vigorously 3h.It is transferred in polymeric kettles of the 100ml with polytetrafluoro liner, 24h is reacted at 100 DEG C.Then vacuum is done
It is dry to can obtain POL-2V-P, N-SO3Na.In argon atmosphere, to the 100ml single necked round bottom flask with magnetic stick in,
Sequentially add 0.5gPOL-2V-P, N-SO3The sulfuric acid solution of Na, 50ml1M, is stirred at room temperature 24h.Then it is vacuum dried and is
Can obtain POL-2V-P, N-SO3H.Fig. 3 is POL-2V-P, N-SO3The schematic diagram of H synthetic technology routes.Using SEM Electronic Speculum
Characterize the POL-2V-P, N-SO of synthesis3H-shaped looks, are shown in Fig. 1.Add 1.19g's in the single-necked flask of 50ml
POL-2V-P,N-SO3H, 16ml tetrahydrofuran, add the Pd (OAc) of 0.0046g after stirring 30min2, stir at room temperature
24h, vacuum drying is obtained supported Pd/POL-2V-P, N-SO3H palladium-based catalysts.Characterized using SEM Electronic Speculum obtained
Pd/POL-2V-P, N-SO3H catalyst patterns, are shown in Fig. 2.
0.1g phenylacetylenes, methyl alcohol 15ml, Pd/POL-2V-P, N-SO are added in the autoclave of 150mL3H catalyst
0.02g,.Sealed reactor, is passed through the air in 2MPa argon gas replacement reaction kettles, replaces 3 times.Then pass to carbon monoxide
It is 4.8MPa to reaction pressure (system stagnation pressure).It is brought rapidly up under stirring condition to 30 DEG C, it is anti-under 500r/min rotating speeds
Answer a hour.Reaction separates liquid product and catalyst after terminating using centrifugal method, analyzes liquid product.According to liquid phase point
Analysis result calculates catalytic perfomance.
Embodiment 2
Reaction temperature is 40 DEG C, and other conditions are with embodiment 1.
Embodiment 3
Reaction temperature is 50 DEG C, and other conditions are with embodiment 1.
Embodiment 4
Phenylacetylene addition is 0.5g, and catalyst loading is 0.1g, and other conditions are with embodiment 3.
Embodiment 5
Reaction temperature is 80 DEG C, and other conditions are with embodiment 1.
Embodiment 6
Reaction pressure is 2.0MPa, and other conditions are with embodiment 5.
Embodiment 7
Reaction pressure is 6.0MPa, and other conditions are with embodiment 5.
Embodiment 8
Catalyst loading is 0.1g, and phenylacetylene addition is 0.1g, and other conditions are with embodiment 3.
Embodiment 9
Fresh catalyst in embodiment 1 is replaced using the catalyst reclaimed in embodiment 8, other conditions with embodiment 8, so
To catalyst recycling 4 times, gained response data is listed in table 2.
Comparative example 3
Using homogeneous 2-PyPPh2 parts, p-methyl benzenesulfonic acid and palladium replace Pd/POL-2V-P, N-SO3H, is directly added into reaction
In kettle, other conditions are with embodiment 4.
Fig. 1 is POL-2V-P, N-SO3The SEM figures of the multi-functional copolymers of H, can significantly it was observed that this of synthesis is organic
Polymeric material has abundant duct.Fig. 2 is Pd/POL-2V-P, N-SO3The SEM figures of H catalyst, it is seen then that Pd is complexed
And be immobilized on the surface of N-PPOL organic ligand polymer, show that new Pd/POL-2V-P, N-SO has successfully been obtained3H
Immobilized palladium-based catalyst.
Table 1 is immobilized Pd/POL-2V-P, N-SO3Reactivity of the phenylacetylene carbonyl compound into unsaturated aromatic ester on H catalyst
Energy.Immobilized Pd/POL-2V-P, N-SO3Phenylacetylene carbonylation has activity and selectivity high on H catalyst, in example 4 not
The TON numerical value of saturation aromatic ester reaches 1241.9, selectively reaches 99%.Homogeneous catalyst prepared by comparative example 4
Pd-2-PyPPh2 catalysis phenylacetylene acetylene carbonylations, the TON numerical value of unsaturated aromatic ester is 955.4, and selectivity is 99%.
Show, multiphase immobilized Pd/POL-2V-P, N-SO3H catalyst and homogeneous catalyst Pd-2-PyPPh2 catalysis phenylacetylene carbonylations
Performance it is substantially suitable.
Table 2 is immobilized Pd/POL-2V-P, N-SO3The recycling performance of H catalyst.From table, catalyst is by 4
Secondary recycling, the activity of catalyst and the selectivity of the unsaturated aromatic ester of generation are held essentially constant, show catalyst have compared with
Good separation and recovery utility and preferable stability.
Table 1 immobilized Pd/POL-2V-P, N-SO3Reactivity worth of the phenylacetylene carbonyl compound into unsaturated aromatic ester on H catalyst
Table 2 immobilized Pd/POL-2V-P, N-SO3The recycling performance of H catalyst
One-step method of the present invention by phenylacetylene carbonyl compound into unsaturated aromatic ester, with high-activity high-selectivity, to equipment corrosion
The low one-level of property is easily isolated the excellent properties of recycling.
Claims (7)
1. method of a kind of phenylacetylene carbonyl compound into unsaturated aromatic ester, it is characterised in that with phenylacetylene, carbon monoxide and
Methyl alcohol is urged as reaction raw materials, the supported palladium base of multifunctional polymer formed using organic ligand and p styrene sulfonic acid copolymerization
Agent is catalyzed, and a step carbonylation is obtained corresponding unsaturation aromatic ester.
2. method according to claim 1, it is characterised in that the process conditions that reaction is used：Reaction temperature is
30~90 DEG C, the initial pressure of CO is 2~6MPa, phenylacetylene:Methyl alcohol=1:8~1:40 (mass ratioes), phenylacetylene：Carbon monoxide
=1:1~1:20 (mass ratioes), catalyst:Phenylacetylene=1:1~1:25 (mass ratioes).
3. method according to claim 1, it is characterised in that：Methyl alcohol both also served as reaction substrate as solvent.
4. method according to claim 1, it is characterised in that：Described catalyst is supported for multi-functional insoluble copolymer
Palladium-based catalyst；The loading of palladium is the 0.2wt%~2wt% of catalyst weight.
5. method according to claim 4, it is characterised in that：Described multi-functional insoluble copolymer is vinylated
Organophosphor ligand 2- pyridyldiphenylphosphines (2-PyPPh2) with p styrene sulfonic acid add initiator azodiisobutyronitrile and
Hinge is carried out under the conditions of 100 DEG C to be polymerized solid multifunctional polymer (POL-2V-P, the N-SO to be formed3H)。
6. method according to claim 4, it is characterised in that：With multifunctional polymer POL-2V-P, N-SO3H is complexed simultaneously
Immobilized acid chloride prepares palladium base heterogeneous catalysis, and the wherein polymer also serves as matching somebody with somebody for catalyst both as the carrier of catalyst
Body, while as the proton acid donors of catalyst.
7. method according to claim 1, it is characterised in that：The reactor of described catalytic reaction is that pressure autoclave type is anti-
Answer device.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620124A (en) * | 2018-05-24 | 2018-10-09 | 绍兴文理学院 | A kind of porous polymer solid acid catalyst for alkynes hydration reaction |
| CN109746045A (en) * | 2018-10-31 | 2019-05-14 | 六盘水师范学院 | A kind of organic porous polymer loaded palladium catalyst and its preparation method and application |
| CN109761811A (en) * | 2019-02-26 | 2019-05-17 | 浙江师范大学 | A kind of preparation method of carboxylate |
| CN112892605A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst with alkalinity for nitrogen formylation reaction, preparation and application |
| WO2022105199A1 (en) * | 2020-11-23 | 2022-05-27 | 中国科学院大连化学物理研究所 | Palladium-based catalyst, preparation method therefor and use thereof |
| CN114534794A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst and preparation and application thereof |
| RU2807280C1 (en) * | 2023-03-02 | 2023-11-13 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") | Resource-saving method of producing phenylacetylene |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108620124A (en) * | 2018-05-24 | 2018-10-09 | 绍兴文理学院 | A kind of porous polymer solid acid catalyst for alkynes hydration reaction |
| CN109746045A (en) * | 2018-10-31 | 2019-05-14 | 六盘水师范学院 | A kind of organic porous polymer loaded palladium catalyst and its preparation method and application |
| CN109761811A (en) * | 2019-02-26 | 2019-05-17 | 浙江师范大学 | A kind of preparation method of carboxylate |
| CN109761811B (en) * | 2019-02-26 | 2021-12-31 | 浙江师范大学 | Preparation method of carboxylic ester |
| CN112892605A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst with alkalinity for nitrogen formylation reaction, preparation and application |
| CN112892605B (en) * | 2019-12-03 | 2022-05-06 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst with alkalinity for nitrogen formylation reaction, preparation and application |
| WO2022105199A1 (en) * | 2020-11-23 | 2022-05-27 | 中国科学院大连化学物理研究所 | Palladium-based catalyst, preparation method therefor and use thereof |
| CN114534794A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst and preparation and application thereof |
| RU2807280C1 (en) * | 2023-03-02 | 2023-11-13 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") | Resource-saving method of producing phenylacetylene |
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