CN114950570A - Catalyst and preparation method of phenylpropanoic acid - Google Patents
Catalyst and preparation method of phenylpropanoic acid Download PDFInfo
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- CN114950570A CN114950570A CN202210762902.3A CN202210762902A CN114950570A CN 114950570 A CN114950570 A CN 114950570A CN 202210762902 A CN202210762902 A CN 202210762902A CN 114950570 A CN114950570 A CN 114950570A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000007787 solid Substances 0.000 claims abstract description 64
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 30
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 239000004332 silver Substances 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 229960000583 acetic acid Drugs 0.000 claims description 18
- 239000012362 glacial acetic acid Substances 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 17
- FDXVLBJUFHQDRV-UHFFFAOYSA-N 6-pyridin-2-yl-4h-pyridine-3,3-dicarboxylic acid Chemical compound N1=CC(C(=O)O)(C(O)=O)CC=C1C1=CC=CC=N1 FDXVLBJUFHQDRV-UHFFFAOYSA-N 0.000 claims description 11
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- 150000001345 alkine derivatives Chemical group 0.000 description 10
- 239000013110 organic ligand Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- -1 phenylpropargyl Chemical group 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst, and belongs to the technical field of preparation of phenylpropanoic acid. The catalyst is prepared by the following steps: 1) dissolving zirconium chloride powder and ligand organic acid in N, N-dimethylformamide, adding a regulator into the solution, and reacting to obtain a solid A; 2) dissolving a certain amount of the solid A in N, N-dimethylformamide, then adding zirconium chloride powder and ligand organic acid into the solution again, adding a regulator, and reacting to obtain a solid B; 3) dissolving silver nitrate in methanol, adding the solid B into the solution for reaction, and finally centrifuging, filtering and washing to obtain the catalyst. The invention also provides a method for preparing the phenylpropanoic acid by adopting the catalyst, and the catalyst can enable phenylacetylene and carbon dioxide to react and be converted into the phenylpropanoic acid under the conditions of relatively less loaded active metals and relatively mild reaction conditions.
Description
Technical Field
The invention belongs to the technical field of preparation of phenylpropanoic acid, and particularly relates to a catalyst and a preparation method of phenylpropanoic acid.
Background
The phenylpropanoic acid is used as an important intermediate of fine chemicals, medical molecules and the like, and has higher application value in the fields of pharmacy and the like, so the synthesis of the phenylpropanoic acid compounds is always concerned. In the prior art, the synthesis method of the phenylpropanoic acid compounds is mainly oxidation and carboxylation reaction of phenylacetylene, formaldehyde or carbon monoxide is used as a carboxylation reagent, but the method is limited due to the fact that the formaldehyde or the carbon monoxide is expensive, high in toxicity, inconvenient to operate and the like.
In recent years, the carboxylation of terminal alkyne and carbon dioxide can synthesize phenylpropionic acid under the action of a catalyst, and the method becomes a novel method for industrially synthesizing the phenylpropionic acid with low cost. The research finds that silver has good catalytic performance as the metal for activating alkyne. However, in the prior art, such reactions either require high-temperature and high-pressure reaction conditions or the dosage of active metal silver in the catalyst is relatively high, so that the preparation cost of the catalyst is relatively high, and the operability and the economical efficiency of the reactions are severely restricted. Therefore, how to design a catalyst which is efficient, cheap and easily available, and has mild reaction conditions is a problem to be solved.
Disclosure of Invention
The invention provides a catalyst and a preparation method of phenylpropargyl acid, and the catalyst can enable phenylacetylene and carbon dioxide to react and be converted into the phenylpropargyl acid under the conditions of relatively less loaded active metal and relatively mild reaction conditions.
In order to achieve the above purpose, the invention provides a catalyst, which is prepared by the following steps:
1) dissolving zirconium chloride powder and ligand organic acid in N, N-dimethylformamide, adding a regulator into the solution, and reacting to obtain a solid A;
2) dissolving a certain amount of the solid A in N, N-dimethylformamide, then adding zirconium chloride powder and ligand organic acid into the solution again, adding a regulator, and reacting to obtain a solid B;
3) dissolving silver nitrate in methanol, adding the solid B into the solution for reaction, and finally centrifuging, filtering and washing to obtain the catalyst.
Preferably, in the step 1) or the step 2), the ligand organic acid is dicarboxylic acid, and the regulator is glacial acetic acid;
the ligand organic acid is 1, 4-benzene dicarboxylic acid or 2, 2-bipyridine-5, 5-dicarboxylic acid.
Preferably, in the step 1) or the step 2), the mass ratio of the zirconium chloride powder to the ligand organic acid is 1: (0.5 to 1.5).
Preferably, in the step 2), the mass ratio of the solid a to the zirconium chloride powder is 1: (0.30-0.75).
Preferably, in the step 2), the mass ratio of the solid B to the silver nitrate is 1: (2.0-6.0).
Preferably, in the step 1) or the step 2), the reaction temperature is 60-180 ℃, and the reaction time is 2-30 h.
Preferably, in the step 3), the reaction temperature is 25-70 ℃, and the reaction time is 5-55 h.
The invention provides application of the catalyst in synthesizing phenylpropanoic acid.
Preferably, the raw materials for synthesizing the phenylpropanoic acid comprise phenylacetylene and carbon dioxide;
the mass ratio of the silver to the phenylacetylene in the catalyst is 1: (70-600);
the invention also provides a preparation method of the phenylpropanoic acid, which comprises the following steps:
under the condition of carbon dioxide, phenylacetylene, cesium carbonate, N-dimethylformamide and an activated catalyst are reacted to obtain 3-phenylpropionic acid;
the catalyst comprises the catalyst of any one of claims 1 to 7;
the pressure of the carbon dioxide is 0.01-0.2 MPa;
the reaction temperature is as follows: 25-60 ℃;
the reaction time is as follows: 2-30 h.
Compared with the prior art, the invention has the advantages and positive effects that:
according to the catalyst provided by the invention, the active metal silver is loaded on the composite material with the core-shell structure, which is obtained by taking the zirconium cluster as a metal node and connecting the zirconium cluster with the organic ligand, and the active metal silver is more uniformly dispersed on the surface of the composite material, so that a reactant can be effectively contacted with a catalytic active site, and the active metal silver and the organic ligand of the composite material generate a coordination effect, so that the catalytic active site has better stability, and the catalyst has higher catalytic performance, and therefore, phenylacetylene and carbon dioxide can be reacted and converted into phenylpropargyl acid under the conditions of relatively less active metal and relatively mild reaction conditions.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
All starting materials for the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art. All the raw materials of the invention are not particularly limited in purity, all the noun expressions, acronyms and designations of the invention belong to the conventional noun expressions, acronyms and designations in the field, each noun expression, acronyms and designation is clear and definite in the relevant application field, and a person skilled in the art can clearly, accurately and uniquely understand according to the noun expressions, acronyms and designations.
The invention provides a catalyst, which is prepared by the following steps:
1) dissolving zirconium chloride powder and ligand organic acid in N, N-dimethylformamide, adding a regulator into the solution, and reacting to obtain a solid A;
2) dissolving a certain amount of the solid A in N, N-dimethylformamide, then adding zirconium chloride powder and ligand organic acid into the solution again, adding a regulator, and reacting to obtain a solid B;
3) dissolving silver nitrate in methanol, adding the solid B into the solution for reaction, and finally centrifuging, filtering and washing to obtain the catalyst.
In the invention, in the step 1) or the step 2), the ligand organic acid is dicarboxylic acid, and the regulator is glacial acetic acid;
the ligand organic acid is 1, 4-benzene dicarboxylic acid or 2, 2-bipyridyl-5, 5-dicarboxylic acid.
In the present invention, in the step 1) or the step 2), the mass ratio of the zirconium chloride powder to the ligand organic acid is 1: (0.5 to 1.5).
In the present invention, in the step 2), the mass ratio of the solid a to the zirconium chloride powder is 1: (0.30-0.75).
In the present invention, in the step 2), the mass ratio of the solid B to the silver nitrate is 1: (2.0-6.0).
In the invention, in the step 1) or the step 2), the reaction temperature is 60-180 ℃, and the reaction time is 2-30 h.
In the invention, in the step 3), the reaction temperature is 25-70 ℃, and the reaction time is 5-55 h.
Specifically, firstly, adding zirconium tetrachloride solid powder into N, N-Dimethylformamide (DMF), completely dissolving the zirconium tetrachloride solid powder by ultrasonic, then adding an organic ligand 1, 4-benzenedicarboxylic acid and glacial acetic acid serving as a regulator, continuing to perform ultrasonic assisted dissolution, transferring the finally obtained uniform solution into a reaction kettle, sealing, and reacting at the temperature of 60-180 ℃ for 2-30 hours. After the reaction was complete, the temperature was cooled to room temperature and the white product was separated by centrifugation. The white product was then rinsed with DMF, which was then replaced with methanol, and finally the product was soaked in methanol solvent for three days. After the soaking, the white solid is obtained by centrifugation and then dried under vacuum to obtain a solid A.
Weighing a certain amount of solid A, adding the solid A into a DMF solvent, carrying out ultrasonic treatment, adding zirconium tetrachloride, 2, 2-bipyridyl-5, 5-dicarboxylic acid and glacial acetic acid serving as a regulator into the DMF solvent, continuing carrying out ultrasonic treatment, transferring the obtained suspension into a reaction kettle, and reacting the reaction kettle at the temperature of 60-180 ℃ for 2-30 hours. After the reaction is finished, the temperature is cooled to room temperature, and then a white product is obtained by centrifugation. The product was then washed with DMF and soaked in methanol solvent for three days. After the soaking, the white solid was dried under vacuum to give solid B.
Adding silver nitrate into a reaction container, completely dissolving the silver nitrate into a methanol solvent through ultrasound, then adding solid B into the silver solution, uniformly mixing the solid B through ultrasound, and finally stirring the obtained suspension at 25-70 ℃ for reaction for 5-55 h. After the reaction is finished, centrifuging to obtain a brown substance, washing the brown product by using methanol, soaking the brown product in the methanol for three days, and finally drying under vacuum to obtain the catalyst.
The invention provides application of the catalyst in synthesizing phenylpropanoic acid.
In the invention, the raw materials for synthesizing the phenylpropanoic acid comprise phenylacetylene and carbon dioxide;
the mass ratio of the silver to the phenylacetylene in the catalyst is 1: (70-600);
the invention also provides a preparation method of the phenylpropanoic acid, which comprises the following steps:
under the condition of carbon dioxide, phenylacetylene, cesium carbonate, N-dimethylformamide and an activated catalyst are reacted to obtain 3-phenylpropionic acid;
the catalyst comprises the catalyst of any one of claims 1 to 7;
the pressure of the carbon dioxide is as follows: 0.01 to 0.2 MPa;
the reaction temperature is as follows: 25-60 ℃;
the reaction time is as follows: 2-30 h.
Specifically, alkyne, cesium carbonate, DMF and activated catalyst were added to a reaction vessel under an inert atmosphere. Then, the reaction system is quickly ventilated with carbon dioxide for five times to remove air in the tube, tin foil is wrapped on the surface of the reaction container, and finally, the reaction is carried out under the condition of introducing carbon dioxide. Wherein the pressure of the carbon dioxide is controlled to be 0.01-0.2 MPa, and the reaction temperature is controlled to be: and (3) controlling the reaction time to be 2-30 h at 25-60 ℃, separating the reaction mixture after the reaction is finished, purifying the liquid phase, and recovering the solid catalyst for recycling.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
In addition, the preparation processes in the following examples are conventional means in the prior art unless otherwise specified, and therefore, detailed descriptions thereof are omitted; the parts in the following embodiments are all parts by weight.
Example 1
Preparation of the catalyst:
firstly, 1 part of zirconium tetrachloride solid powder is added into N, N-Dimethylformamide (DMF), then 0.68 part of 1, 4-benzene dicarboxylic acid and glacial acetic acid serving as organic ligands are added, and the mixture reacts for 15 hours at the temperature of 60 ℃, so that solid A is obtained.
1 part of the solid A was weighed and added to a DMF solvent, and then 0.45 part of zirconium tetrachloride, 0.50 part of 2, 2-bipyridine-5, 5-dicarboxylic acid and glacial acetic acid were added and reacted at 60 ℃ for 15 hours to obtain a solid B.
Adding 3.5 parts of silver nitrate into a reaction container, completely dissolving the silver nitrate in a methanol solvent by ultrasound, then adding 1 part of solid B into the silver solution, stirring and reacting for 40 hours at 35 ℃, and finally centrifuging, filtering and washing to obtain the catalyst.
Preparation of phenylpropionic acid:
120 parts of alkyne and the activated catalyst containing 1 part of silver are introduced into a reaction vessel under an inert atmosphere. Then carbon dioxide is introduced for reaction. Wherein the pressure of the carbon dioxide is controlled to be 0.05MPa, the reaction temperature is controlled to be 48 ℃, and the reaction time is controlled to be 20 h. After the reaction was completed, the reaction mixture was separated, and the yield of propiolic acid was calculated as 40.5% by purifying the liquid phase.
Example 2
Preparation of the catalyst:
firstly, 1 part of zirconium tetrachloride solid powder is added into N, N-Dimethylformamide (DMF), then 0.72 part of 1, 4-benzene dicarboxylic acid and glacial acetic acid serving as organic ligands are added, and the mixture reacts for 20 hours at the temperature of 120 ℃, so that solid A is obtained.
1 part of solid A was weighed and added to a DMF solvent, and then 0.55 part of zirconium tetrachloride, 0.59 part of 2, 2-bipyridine-5, 5-dicarboxylic acid and glacial acetic acid were added and reacted at 120 ℃ for 20 hours to obtain solid B.
Adding 4.3 parts of silver nitrate into a reaction container, completely dissolving the silver nitrate in a methanol solvent by ultrasound, then adding 1 part of solid B into the silver solution, stirring and reacting for 40 hours at 45 ℃, and finally centrifuging, filtering and washing to obtain the catalyst.
Preparation of phenylpropionic acid:
120 parts of alkyne and the activated catalyst containing 1 part of silver are introduced into a reaction vessel under an inert atmosphere. Then carbon dioxide is introduced for reaction. Wherein the pressure of the carbon dioxide is controlled to be 0.1MPa, the reaction temperature is controlled to be 48 ℃, and the reaction time is controlled to be 20 h. After the reaction was completed, the reaction mixture was separated, and the yield of propiolic acid was calculated to be 96.5% by purifying the liquid phase.
Example 3
Preparation of the catalyst:
firstly, 1 part of zirconium tetrachloride solid powder is added into N, N-Dimethylformamide (DMF), 1 part of 1, 4-benzene dicarboxylic acid and glacial acetic acid serving as organic ligands are added, and the mixture reacts for 10 hours at the temperature of 90 ℃ to obtain a solid A.
1 part of the solid A was weighed and added to a DMF solvent, and then 0.35 part of zirconium tetrachloride, 0.4 part of 2, 2-bipyridine-5, 5-dicarboxylic acid and glacial acetic acid were added and reacted at 90 ℃ for 10 hours to obtain a solid B.
Adding 5.3 parts of silver nitrate into a reaction container, completely dissolving the silver nitrate in a methanol solvent by ultrasonic waves, then adding 1 part of solid B into the silver solution, stirring and reacting for 40 hours at 40 ℃, and finally centrifuging, filtering and washing to obtain the catalyst.
Preparation of phenylpropionic acid:
300 parts of alkyne and the activated catalyst containing 1 part of silver are introduced into a reaction vessel under an inert atmosphere. Then carbon dioxide is introduced for reaction. Wherein the pressure of the carbon dioxide is controlled to be 0.1MPa, the reaction temperature is controlled to be 48 ℃, and the reaction time is controlled to be 20 h. After the reaction was completed, the reaction mixture was separated, and the yield of propiolic acid was calculated to be 75.9% by purifying the liquid phase.
Example 4
Preparation of the catalyst:
firstly, 1 part of zirconium tetrachloride solid powder is added into N, N-Dimethylformamide (DMF), then 0.5 part of 1, 4-benzene dicarboxylic acid and glacial acetic acid serving as organic ligands are added, and the mixture reacts for 15 hours at the temperature of 150 ℃, so that solid A is obtained.
1 part of solid A was weighed and added to a DMF solvent, and then 0.55 part of zirconium tetrachloride, 0.59 part of 2, 2-bipyridine-5, 5-dicarboxylic acid and glacial acetic acid were added and reacted at 150 ℃ for 15 hours to obtain solid B.
Adding 4.3 parts of silver nitrate into a reaction container, completely dissolving the silver nitrate in a methanol solvent by ultrasound, then adding 1 part of solid B into the silver solution, stirring and reacting for 40 hours at 45 ℃, and finally centrifuging, filtering and washing to obtain the catalyst.
Preparation of phenylpropanoic acid:
120 parts of alkyne and the activated catalyst containing 1 part of silver are introduced into a reaction vessel under an inert atmosphere. Then carbon dioxide is introduced for reaction. Wherein the pressure of the carbon dioxide is controlled to be 0.05MPa, the reaction temperature is controlled to be 48 ℃, and the reaction time is controlled to be 20 h. After the reaction was completed, the reaction mixture was separated, and the yield of propiolic acid was calculated to be 63.6% by purifying the liquid phase.
Example 5
Preparation of the catalyst:
firstly, 1 part of zirconium tetrachloride solid powder is added into N, N-Dimethylformamide (DMF), then 0.72 part of 1, 4-benzene dicarboxylic acid and glacial acetic acid serving as organic ligands are added, and the mixture reacts for 20 hours at the temperature of 180 ℃, so that solid A is obtained.
1 part of the solid A was weighed and added to a DMF solvent, and then 0.55 part of zirconium tetrachloride, 0.59 part of 2, 2-bipyridine-5, 5-dicarboxylic acid and glacial acetic acid were added and reacted at 180 ℃ for 20 hours to obtain a solid B.
Adding 4.3 parts of silver nitrate into a reaction container, completely dissolving the silver nitrate in a methanol solvent by ultrasound, then adding 1 part of solid B into the silver solution, stirring and reacting for 40 hours at 45 ℃, and finally centrifuging, filtering and washing to obtain the catalyst.
Preparation of phenylpropanoic acid:
120 parts of alkyne and the activated catalyst containing 1 part of silver are introduced into a reaction vessel under an inert atmosphere. Then carbon dioxide is introduced for reaction. Wherein the pressure of the carbon dioxide is controlled to be 0.01MPa, the reaction temperature is controlled to be 48 ℃, and the reaction time is controlled to be 20 h. After the reaction was completed, the reaction mixture was separated, and the yield of propiolic acid was calculated as 42.5% by purifying the liquid phase.
Comparative example 1
Preparation of the catalyst:
firstly, 1 part of zirconium tetrachloride solid powder is added into N, N-dimethylformamide, then 0.9 part of 2, 2-bipyridine-5, 5-dicarboxylic acid and glacial acetic acid serving as organic ligands are added, and the mixture reacts for 20 hours at the temperature of 120 ℃ to obtain solid C.
Adding 4.3 parts of silver nitrate into a reaction container, completely dissolving the silver nitrate into a methanol solvent by ultrasonic waves, then adding 1 part of solid C into the silver solution, stirring and reacting for 40 hours at 45 ℃, and finally centrifuging, filtering and washing to obtain the catalyst.
Preparation of phenylpropanoic acid:
120 parts of alkyne and the activated catalyst containing 1 part of silver are introduced into a reaction vessel under an inert atmosphere. Then carbon dioxide is introduced for reaction. Wherein the pressure of the carbon dioxide is controlled to be 0.1MPa, the reaction temperature is controlled to be 48 ℃, and the reaction time is controlled to be 20 h. After the reaction was completed, the reaction mixture was separated, and the yield of propiolic acid was calculated as 70% by purifying the liquid phase.
Comparative example 2
Preparation of the catalyst:
firstly, 1 part of zirconium tetrachloride solid powder is added into N, N-dimethylformamide, then 0.72 part of 1, 4-benzene dicarboxylic acid and glacial acetic acid serving as organic ligands are added, and the mixture reacts for 20 hours at the temperature of 120 ℃ to obtain a solid A.
Weighing 1 part of solid A, adding the solid A into a DMF solvent, adding 0.55 part of zirconium tetrachloride, 0.59 part of 2, 2-bipyridine-5, 5-dicarboxylic acid and glacial acetic acid, and reacting at the temperature of 120 ℃ for 20 hours to obtain the catalyst.
Preparation of phenylpropanoic acid:
6 parts of alkyne and 1 part of activated catalyst are introduced into a reaction vessel under an inert atmosphere. Then carbon dioxide is introduced for reaction. Wherein the pressure of the carbon dioxide is controlled to be 0.1MPa, the reaction temperature is controlled to be 48 ℃, and the reaction time is controlled to be 20 h. After the reaction was completed, the reaction mixture was separated, and the yield of propiolic acid was calculated as 5% by purifying the liquid phase.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The catalyst is characterized by being prepared by the following steps:
1) dissolving zirconium chloride powder and ligand organic acid in N, N-dimethylformamide, adding a regulator into the solution, and reacting to obtain a solid A;
2) dissolving a certain amount of the solid A in N, N-dimethylformamide, then adding zirconium chloride powder and ligand organic acid into the solution again, adding a regulator, and reacting to obtain a solid B;
3) dissolving silver nitrate in methanol, adding the solid B into the solution for reaction, and finally centrifuging, filtering and washing to obtain the catalyst.
2. The catalyst according to claim 1, wherein in the step 1) or the step 2), the ligand organic acid is dicarboxylic acid, and the regulator is glacial acetic acid;
the ligand organic acid is 1, 4-benzene dicarboxylic acid or 2, 2-bipyridyl-5, 5-dicarboxylic acid.
3. The catalyst according to claim 1, wherein in the step 1) or the step 2), the mass ratio of the zirconium chloride powder to the ligand organic acid is 1: (0.5 to 1.5).
4. The catalyst according to claim 1, wherein in the step 2), the mass ratio of the solid a to the zirconium chloride powder is 1: (0.30-0.75).
5. The catalyst according to claim 1, wherein in the step 3), the mass ratio of the solid B to the silver nitrate is 1: (2.0-6.0).
6. The catalyst according to claim 1, wherein in the step 1) or the step 2), the reaction temperature is 60-180 ℃ and the reaction time is 2-30 h.
7. The catalyst of claim 1, wherein in the step 3), the reaction temperature is 25-70 ℃ and the reaction time is 5-55 h.
8. Use of a catalyst according to any one of claims 1 to 7 in the synthesis of phenylpropanoic acid.
9. The use according to claim 8, wherein the starting material for the synthesis of phenylpropanoic acid comprises phenylacetylene and carbon dioxide;
the mass ratio of the silver to the phenylacetylene in the catalyst is 1: (70-600).
10. A preparation method of phenylpropanoic acid is characterized by comprising the following steps:
under the condition of carbon dioxide, phenylacetylene, cesium carbonate, N-dimethylformamide and an activated catalyst are reacted to obtain 3-phenylpropionic acid;
the catalyst comprises the catalyst of any one of claims 1 to 7;
the pressure of the carbon dioxide is 0.01-0.2 MPa;
the reaction temperature is as follows: 25-60 ℃;
the reaction time is as follows: 2-30 h.
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