CN106854159B - A kind of phenylacetylene carbonyl compound at unsaturated aromatic ester method - Google Patents

A kind of phenylacetylene carbonyl compound at unsaturated aromatic ester method Download PDF

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CN106854159B
CN106854159B CN201510902729.2A CN201510902729A CN106854159B CN 106854159 B CN106854159 B CN 106854159B CN 201510902729 A CN201510902729 A CN 201510902729A CN 106854159 B CN106854159 B CN 106854159B
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phenylacetylene
catalyst
reaction
multifunctional polymer
aromatic ester
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CN106854159A (en
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丁云杰
陈兴坤
朱何俊
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a kind of phenylacetylene carbonyl compounds into the method for unsaturated aromatic ester, using phenylacetylene, methanol and carbon monoxide as reaction raw materials, it is 30~90 DEG C in reaction temperature, under conditions of initial pressure is 2~6MPa, using the supported palladium-based catalyst of multifunctional polymer, phenylacetylene carbonyl compound is catalyzed into unsaturated aromatic ester.The present invention carries out hinge using vinyl 2- pyridyldiphenylphosphine with p styrene sulfonic acid under certain condition and polymerize multifunctional polymer (POL-2V-P, the N-SO to form solid3H), it is complexed with multifunctional polymer and immobilized palladium acetate prepares the supported palladium-based catalyst of multifunctional polymer.Phenylacetylene carbonyl compound at unsaturated aromatic ester, is had a high-activity high-selectivity by one-step method of the present invention, low to equipment corrosion and be easily isolated and recycled the excellent properties utilized.

Description

A kind of phenylacetylene carbonyl compound at unsaturated aromatic ester method
Technical field
The present invention relates to a kind of phenylacetylene carbonyl compounds into the method for unsaturated aromatic ester, and in particular to one kind is with benzene second Alkynes, carbon monoxide and methanol are 30~90 DEG C in reaction temperature as reaction raw materials, the initial pressure of carbon monoxide is 2~ Under conditions of 6MPa, using the supported palladium-based catalyst of multifunctional polymer, it is catalyzed phenylacetylene carbonylation and unsaturated virtue is made Fragrant ester.
Background technique
Unsaturated aromatic ester (methyl cinnamate and its isomers) is a kind of white fragrant, hesperidium fragrance with osmanthus taste cream Crystal is mainly used for food, daily use chemicals and medical industry and as organic synthesis raw material, there is very vast potential for future development.Currently, The synthesis of methyl cinnamate is using cinnamic acid and methanol as raw material, under the action of inorganic acid catalyst (such as sulfuric acid, hydrochloric acid) directly Connect lactate synthesis.But the side reaction that this method generates is more, and product yield is low and of poor quality, and reaction unit seriously corroded produces simultaneously Raw contaminated wastewater, is not able to satisfy the requirement of current sustainable development.So developing the synthesis side of novel unsaturated aromatic ester Method has great importance.
Phenylacetylene carbonylation method, which prepares unsaturated aromatic ester, has the advantages that Atom economy, used in catalyst be by 2- pyridyldiphenylphosphine, palladium acetate, the catalyst system of p-methyl benzenesulfonic acid composition.The catalyst system is catalyzed phenylacetylene carbonylation Reaction carries out under the temperate condition of low-temp low-pressure, has the advantages that high-activity high-selectivity.However, the homogeneous catalyst is difficult It separates and is recycled with product, influence the industrial applications of the technique.In addition, reaction needs to use the stronger matter of corrosivity Sub- acid, reaction unit seriously corroded considerably increase production cost.Immobilized organic ligand not only has homogeneous catalyst height living The advantages of property, also has the characteristics that the easily separated recycling of heterogeneous catalysis.
Summary of the invention
The present invention provides a kind of phenylacetylene carbonyl compounds into the method for unsaturated aromatic ester, specially with phenylacetylene, one Carbonoxide and methanol are catalyzed, a step carbonyl as reaction raw materials using the supported palladium-based catalyst of multifunctional polymer Change reaction and corresponding unsaturated aromatic ester is made.
React the process conditions used: 30~90 DEG C, the initial pressure of CO is 2~6MPa, phenylacetylene: methanol=1:8~ 1:40 (mass ratio), phenylacetylene: carbon monoxide=1:1~1:20 (mass ratio), catalyst: phenylacetylene=1:1~1:25 (quality Than).
Methanol had both been used as solvent or had been used as reaction substrate.
The catalyst is the palladium-based catalyst that multifunctional polymer supports.Multifunctional polymer is by 2- pyridyl group two Phenylphosphine (2-PyPPh2) it is used as organic ligand, vinyl is connected, vinyl 2- pyridyldiphenylphosphine is prepared, is caused being added Carry out at agent azodiisobutyronitrile and 100 DEG C with p styrene sulfonic acid hinge polymerize the multifunctional polymer to be formed (POL-2V-P, N-SO3H).With multifunctional polymer POL-2V-P, N-SO3H is complexed and immobilized palladium acetate prepares palladium-based catalyst, and the polymer was both It is the ligand of catalyst and the carrier of catalyst, while is also proton acid donors.The loading of palladium is catalyst weight 0.2wt%~2wt%.
The reactor for preparing the catalysis reaction of unsaturated aromatic ester is pressure autoclave type reactor.
Specific technical solution 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, is added Pd (OAc)2.Room After the lower stirring of temperature, it is dried in vacuo to obtain required immobilized insoluble catalyst.Pd(OAc)2Additive amount supporting according to palladium Amount is that 0.2wt%~2wt% of catalyst weight is added, and loading only appropriate can obtain preferable catalytic performance.
Solid-supported catalyst, phenylacetylene are placed in methanol, autoclave is put into, closes autoclave.It is high to be passed through argon gas displacement Press air 3~6 times in kettle.Then pass to the CO gas that pressure is 4.8MPa.Then it is warming up under agitation 60 DEG C are reacted, and cool down to room temperature with cooling water to reaction kettle after reaction, to liquid-phase product using centrifugation or filtering side Liquid phase analysis is carried out after method separating catalyst again.The catalyst isolated can carry out reaction next time as previously described again.
The process conditions of use: 30~90 DEG C, the initial pressure of CO is 2~6MPa, phenylacetylene: methanol=1:8~1:40 (mass ratio), phenylacetylene: carbon monoxide=1:1~1:20 (mass ratio), catalyst: phenylacetylene=1:1~1:25 (mass ratio).
Detailed description of the invention:
Fig. 1 is POL-2V-P, N-SO3The SEM of H organic ligand polymer schemes；
Fig. 2 is Pd/POL-2V-P, N-SO3The Electronic Speculum SEM phenogram of H catalyst morphology.
Fig. 3 is POL-2V-P, N-SO3The schematic diagram of H synthetic technology route；
Specific embodiment
It is the embodiment of the present invention below:
Embodiment 1
POL-2V-P,N-SO3H preparation method: under liquid nitrogen bath and nitrogen atmosphere, to the tri- mouthfuls of circles of 1L for having magnetic stick In the flask of bottom, the tetrahydrofuran of 45ml is sequentially added, the n-BuLi of 0.12mol, the adjacent bromopyridine of 0.1mol, 0.135mol's ZnCl2, 45ml pyridine, then 90ml tetrahydrofuran reacts 14h at room temperature.Liquid in bottle outlet is toppled under nitrogen protection, then 60ml pyridine is sequentially added under the conditions of liquid nitrogen bath, the PCl3 solution of 180ml tetrahydrofuran, 0.12mol (is dissolved in 60ml pyrrole Pyridine, in 60ml tetrahydrofuran), then react 26h (being named as reaction solution 1) at room temperature.Under liquid nitrogen bath and nitrogen atmosphere, to band Have in another 1L three neck round bottom flask of magnetic stick, sequentially adds 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 under liquid nitrogen bath and nitrogen atmosphere It is added in reaction solution 2, is stirred to react after two hours at room temperature, 200ml deionized water is added.Then 500mL acetic acid second is used 3 extraction reaction mixtures of ester solution point, combined ethyl acetate extract liquor, rotary evaporation removes solvent after filtering, obtained first Grade product is purified through silica gel column chromatography, i.e., makees stationary phase, the mixing that 1:6 is formed by volume of ethyl acetate-petroleum ether with silica gel Solvent makees eluent, and it is vinylated 2-PyPPh that bluish yellow color viscous oil-like liquid, which is made,2.In argon atmosphere, to having In the 50ml single necked round bottom flask of magnetic stick, the vinylated 2-PyPPh of 1.17g is sequentially added2, two isobutyl of 0.11g azo Nitrile, 15ml tetrahydrofuran, 1.2ml deionized water, 0.3g sodium p styrene sulfonate are vigorously mixed at room temperature for 3h.It is transferred to 100ml reacts for 24 hours at 100 DEG C in the polymeric kettle of polytetrafluoro liner.Then POL-2V-P can be obtained in vacuum drying, N-SO3Na.In argon atmosphere, into the 100ml single necked round bottom flask with magnetic stick, 0.5gPOL-2V- is sequentially added P,N-SO3The sulfuric acid solution of Na, 50ml1M, are stirred at room temperature for 24 hours.Then POL-2V-P, N- can be obtained in vacuum drying SO3H.Fig. 3 is POL-2V-P, N-SO3The schematic diagram of H synthetic technology route.Using the POL-2V-P, N- of the characterization synthesis of SEM Electronic Speculum SO3H-shaped looks, are shown in Fig. 1.The POL-2V-P, N-SO of 1.19g are added in the single-necked flask of 50ml3H, 16ml tetrahydrofuran, stirring The Pd (OAc) of 0.0046g is added after 30min2, it stirring at room temperature for 24 hours, supported Pd/POL-2V-P is made in vacuum drying, N-SO3H palladium-based catalyst.Using SEM Electronic Speculum characterization Pd/POL-2V-P, N-SO obtained3H catalyst morphology, is shown in Fig. 2.
0.1g phenylacetylene, methanol 15ml, Pd/POL-2V-P, N-SO are added in the autoclave of 150mL3H catalyst 0.02g,.Reaction kettle is sealed, the air being passed through in 2MPa argon gas replacement reaction kettle is replaced 3 times.Carbon monoxide is then passed to anti- Answering pressure (system stagnation pressure) is 4.8MPa.It is brought rapidly up under stirring condition to 30 DEG C, reacts one small under 500r/min revolving speed When.After reaction using centrifugal method separation liquid product and catalyst, liquid product is analyzed.According to liquid phase analysis result meter Calculate catalytic perfomance.
Embodiment 2
Reaction temperature is 40 DEG C, and other conditions are the same as embodiment 1.
Embodiment 3
Reaction temperature is 50 DEG C, and other conditions are the same as embodiment 1.
Embodiment 4
Phenylacetylene additive amount is 0.5g, and catalyst loading 0.1g, other conditions are the same as embodiment 3.
Embodiment 5
Reaction temperature is 80 DEG C, and other conditions are the same as embodiment 1.
Embodiment 6
Reaction pressure is 2.0MPa, and other conditions are the same as embodiment 5.
Embodiment 7
Reaction pressure is 6.0MPa, and other conditions are the same as embodiment 5.
Embodiment 8
Catalyst loading is 0.1g, and phenylacetylene additive amount is 0.1g, and other conditions are the same as embodiment 3.
Embodiment 9
Fresh catalyst in embodiment 1 is replaced using the catalyst recycled 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 ligand, p-methyl benzenesulfonic acid and palladium acetate replace Pd/POL-2V-P, N-SO3H directly adds Enter in reaction kettle, other conditions are the same as embodiment 4.
Fig. 1 is POL-2V-P, N-SO3The SEM of the multi-functional copolymer of H schemes, this that can significantly observe synthesis is organic Polymer material has duct abundant.Fig. 2 is Pd/POL-2V-P, N-SO3The SEM of H catalyst schemes, it is seen then that Pd is complexed and consolidates It is loaded on the surface of N-PPOL organic ligand polymer, shows successfully to be made novel Pd/POL-2V-P, N-SO3H is immobilized Change palladium-based catalyst.
Table 1 is immobilized Pd/POL-2V-P, N-SO3Phenylacetylene carbonyl compound is at the anti-of unsaturated aromatic ester on H catalyst Answer performance.Immobilized Pd/POL-2V-P, N-SO3Phenylacetylene carbonylation has high activity and selectivity, example 4 on H catalyst The TON numerical value of middle unsaturation aromatic ester reaches 1241.9, selectively reaches 99%.Homogeneous catalyst Pd-2- prepared by comparative example 4 PyPPh2 is catalyzed phenylacetylene acetylene carbonylation, and the TON numerical value of unsaturated aromatic ester is 955.4, and selectivity is 99%.Show more Mutually immobilized Pd/POL-2V-P, N-SO3The performance of H catalyst and homogeneous catalyst Pd-2-PyPPh2 catalysis phenylacetylene carbonylation Substantially quite.
Table 2 is immobilized Pd/POL-2V-P, N-SO3The recycling performance of H catalyst.By table as it can be seen that catalyst passes through 4 recyclings, the activity of catalyst and the selectivity for generating unsaturated aromatic ester are held essentially constant, and show that catalyst has Preferable separation and recovery utility and preferable stability.
Table 1 immobilized Pd/POL-2V-P, N-SO3Phenylacetylene carbonyl compound is at the anti-of unsaturated aromatic ester on H catalyst Answer performance
Table 2 immobilized Pd/POL-2V-P, N-SO3The recycling performance of H catalyst
Phenylacetylene carbonyl compound at unsaturated aromatic ester, is had high-activity high-selectivity, to equipment by one-step method of the present invention The low level-one of corrosivity is easily isolated and recycled the excellent properties utilized.

Claims (7)

1. a kind of phenylacetylene carbonyl compound is at the method for unsaturated aromatic ester, which is characterized in that with phenylacetylene, carbon monoxide and first Alcohol is as reaction raw materials, using organophosphor ligand 2- pyridyldiphenylphosphine (2-PyPPh2) and p styrene sulfonic acid be copolymerized to be formed The supported palladium-based catalyst of multifunctional polymer be catalyzed, corresponding unsaturated fragrance is made in a step carbonylation Ester.
2. according to the method described in claim 1, it is characterized in that the process conditions that use of reaction: reaction temperature is 30 ~ 90 DEG C, the initial pressure of CO is 2 ~ 6 MPa, phenylacetylene: methanol quality ratio=1:8 ~ 1:40, phenylacetylene: carbon monoxide mass ratio= 1:1 ~ 1:20, catalyst: phenylacetylene mass ratio=1:1 ~ 1:25.
3. according to the method described in claim 1, it is characterized by: methanol had both been used as solvent or had been used as reaction substrate.
4. according to the method described in claim 1, it is characterized by: the loading of palladium is 0.2wt% ~ 2wt% of catalyst weight.
5. according to the method described in claim 4, it is characterized by: the multifunctional polymer is vinylated organic phosphorus Ligand 2- pyridyldiphenylphosphine (2-PyPPh2) and p styrene sulfonic acid initiator azodiisobutyronitrile and 100 DEG C of items are being added Hinge is carried out under part polymerize the solid multifunctional polymer i.e. POL-2V-P to be formed, N-SO3H。
6. according to the method described in claim 5, it is characterized by: with solid multifunctional polymer complex and immobilized acid chloride system Standby palladium base heterogeneous catalysis, wherein solid multifunctional polymer had both been used as the carrier of catalyst, also as the ligand of catalyst, Proton acid donors as catalyst simultaneously.
7. according to the method described in claim 1, it is characterized by: the reactor of the catalysis reaction is pressure autoclave type reaction Device.
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Publication number Priority date Publication date Assignee Title
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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
CN109761811B (en) * 2019-02-26 2021-12-31 浙江师范大学 Preparation method of carboxylic ester
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
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87107279A (en) * 1986-12-05 1988-06-15 国际壳牌研究有限公司 Process for the carbonylation of acetylenically unsaturated compounds
CN1127501A (en) * 1993-07-19 1996-07-24 国际壳牌研究有限公司 Process for the carbonylation of acetylenically unsaturated compounds
CN1382116A (en) * 1999-10-22 2002-11-27 国际壳牌研究有限公司 Process for carbonylation of acetylenically unsaturated compound
CN1538876A (en) * 2001-03-30 2004-10-20 科学与工业研究委员会 Novel catalytic formulation and its preparation method
CN101456801A (en) * 2007-12-13 2009-06-17 中国科学院兰州化学物理研究所 Method for synthesizing alpha-beta unsaturated acetyenic ketone compounds by carbonylation
CN102470356A (en) * 2010-03-31 2012-05-23 日本高度纸工业株式会社 Hybrid inorganic/organic polymer catalytic membrane materials comprising immobilized molecular catalysts and their preparation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87107279A (en) * 1986-12-05 1988-06-15 国际壳牌研究有限公司 Process for the carbonylation of acetylenically unsaturated compounds
CN1127501A (en) * 1993-07-19 1996-07-24 国际壳牌研究有限公司 Process for the carbonylation of acetylenically unsaturated compounds
CN1382116A (en) * 1999-10-22 2002-11-27 国际壳牌研究有限公司 Process for carbonylation of acetylenically unsaturated compound
CN1538876A (en) * 2001-03-30 2004-10-20 科学与工业研究委员会 Novel catalytic formulation and its preparation method
CN101456801A (en) * 2007-12-13 2009-06-17 中国科学院兰州化学物理研究所 Method for synthesizing alpha-beta unsaturated acetyenic ketone compounds by carbonylation
CN102470356A (en) * 2010-03-31 2012-05-23 日本高度纸工业株式会社 Hybrid inorganic/organic polymer catalytic membrane materials comprising immobilized molecular catalysts and their preparation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Chemoselective methoxycarbonylation of terminal alkynes catalyzed by Pd(II)-TROPP complexes;Lorenzo Bettucci等;《Dalton Trans.》;20100608(第39期);6509–6517 *
Highly selective formation of unsaturated esters or cascade reactions to a,u-diesters by the methoxycarbonylation of alkynes catalysed by palladium complexes of 1,2-bis(ditertbutylphosphinomethyl)benzene;A. Alberto Nunez Magro等;《Chem. Sci.》;20100904(第1期);723-730 *
Iminophosphine-palladium(0) complexes as catalysts in the alkoxycarbonylation of terminal alkynes;A. Scrivanti等;《Journal of Molecular Catalysis A: Chemical》;20010122(第170期);51-56 *

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