CN114733575B - Palladium-supported molecular sieve catalyst and preparation method and application thereof - Google Patents

Palladium-supported molecular sieve catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114733575B
CN114733575B CN202210441807.3A CN202210441807A CN114733575B CN 114733575 B CN114733575 B CN 114733575B CN 202210441807 A CN202210441807 A CN 202210441807A CN 114733575 B CN114733575 B CN 114733575B
Authority
CN
China
Prior art keywords
molecular sieve
palladium
catalyst
mass
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210441807.3A
Other languages
Chinese (zh)
Other versions
CN114733575A (en
Inventor
朱国荣
屠勇军
李嵘嵘
陈先朗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LINHAI TIANYU PHARMACEUTICAL CO Ltd
Zhejiang Jingsheng Pharmaceutical Co ltd
Zhejiang Tianyu Pharmaceutical Co Ltd
Original Assignee
LINHAI TIANYU PHARMACEUTICAL CO Ltd
Zhejiang Jingsheng Pharmaceutical Co ltd
Zhejiang Tianyu Pharmaceutical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LINHAI TIANYU PHARMACEUTICAL CO Ltd, Zhejiang Jingsheng Pharmaceutical Co ltd, Zhejiang Tianyu Pharmaceutical Co Ltd filed Critical LINHAI TIANYU PHARMACEUTICAL CO Ltd
Priority to CN202210441807.3A priority Critical patent/CN114733575B/en
Publication of CN114733575A publication Critical patent/CN114733575A/en
Application granted granted Critical
Publication of CN114733575B publication Critical patent/CN114733575B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P9/00—Drugs for disorders of the cardiovascular system
    • A61P9/12—Antihypertensives
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Animal Behavior & Ethology (AREA)
  • Medicinal Chemistry (AREA)
  • Cardiology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)

Abstract

The invention provides a palladium-supported molecular sieve catalyst, which takes a molecular sieve as a carrier, and metal palladium and ionic liquid forming a complex with the metal palladium are supported on the carrier. The invention also provides a preparation method and application of the palladium-supported molecular sieve catalyst. The invention also provides a preparation method of the 2-cyano-4' -methyl biphenyl. The palladium-supported molecular sieve catalyst provided by the invention can be used as a heterogeneous catalyst for catalyzing various chemical reactions, in particular for catalyzing the synthesis of 2-cyano-4' -methyl biphenyl, and has high catalytic activity and convenient recycling. The preparation method of the 2-cyano-4' -methyl biphenyl provided by the invention can greatly improve the yield of target products, can recover and reuse the catalyst and the reaction solvent, is suitable for industrial production, has important economic and social values, and has a very good application prospect.

Description

Palladium-supported molecular sieve catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a palladium-supported molecular sieve catalyst, a preparation method and application thereof in catalytic preparation of 2-cyano-4 '-methyl biphenyl, and also relates to a preparation method of 2-cyano-4' -methyl biphenyl.
Background
Sartan drugs are novel antihypertensive drugs with small side effects, definite curative effects and novel action mechanisms, and occupy important positions in the markets of antihypertensive drugs, and the annual market sales can reach hundreds of billions of RMB.
The 2-cyano-4' -methyl biphenyl is a key intermediate for synthesizing angiotensin H antagonist drugs, and different sartan drugs such as candesartan, irbesartan, tasosartan and the like can be obtained through modification. The synthesis method of 2-cyano-4' -methyl biphenyl has a plurality of methods, wherein the catalytic one-step synthesis method is the most ideal industrialized production method at present, so great attention is paid to the method, and the method has the advantages of low equipment investment, low raw material cost, less pollutant, less byproducts, high efficiency, good selectivity and the like. There are reports of synthesizing 2-cyano-4' -methylbiphenyl using metals such as Ni (e.g., negishi, E.King, A.O.Okukado, N.Selective carbon-carbon bond formation via transition metal catalysis.3.A highly selective synthesis of unsymmetrical biaryls and diarylmethanes by the nickel-or paladium-catalyzed reaction of aryl-and benzylzinc derivatives with aryl halides [ J ]. J.org. chem.,1977, 42:1821-1823.), mn (e.g., kim, S.H.; rieke, R.D.A facile synthetic method for the preparation of benzylic manganese halides using highly active manganese and their coupling reactions [ J ]. J.org. chem.,1998, 63:6766-6767.; pd (e.g., torres, J.C.; pinto, A.C.; garden, S.J.application of a catalytic palladium biaryl synthesis reaction via C-H functionalization, to the total synthesis of amaryllidaceae alkaloids [ J ]. Tetrahedron,2004, 60:9889-9900.)) as catalysts. Some research groups in China have conducted intensive studies on it. However, because these catalysts are homogeneous catalysts, the catalysts are difficult to recycle and the yield of the target product is also difficult to further improve, thus limiting the scale-up research and industrial application of the catalytic one-step synthesis method.
In view of the above, there is an urgent need to design a novel catalyst which is environmentally friendly, convenient to recover and has higher catalytic activity, so as to improve the utilization efficiency of the catalyst and increase the yield of 2-cyano-4' -methyl biphenyl, which has important industrial and social significance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a palladium-supported molecular sieve catalyst which has excellent catalytic activity and is convenient to recycle, so that the service life and the utilization efficiency of the catalyst are prolonged.
It is another object of the present invention to provide a method for preparing the palladium supported molecular sieve catalyst and its use.
It is still another object of the present invention to provide a method for preparing 2-cyano-4' -methylbiphenyl.
The palladium-supported molecular sieve catalyst provided by the invention takes a molecular sieve as a carrier, and metal palladium and ionic liquid forming a complex with the metal palladium are supported on the molecular sieve.
In the palladium-supported molecular sieve catalyst provided by the invention, the ionic liquid is combined with the metal palladium to form a complex and wrap the metal palladium, so that the dispersibility of the metal palladium is improved, and the catalytic activity site is increased, and the catalytic activity of the catalyst can be obviously improved. Meanwhile, the molecular sieve serving as a carrier can provide a large specific surface area and also contributes to improving the dispersibility of the metallic palladium, so that the catalytic activity of the catalyst can be further improved. In addition, the molecular sieve catalyst of the invention has very good stability, and active sites are not easy to run off or inactivate in the reaction process, so that the catalyst can be repeatedly recycled and reused, and can keep higher level of catalytic activity.
In some embodiments according to the invention, the mass of the metallic palladium may be 1-6% of the mass of the support, including but not limited to mass percent values of 1%, 2%, 3%, 4%, 5%, 6%, etc., or any combination of mass percent intervals. In some preferred embodiments, the mass of the metallic palladium may be 3 to 5% of the mass of the support.
In some embodiments according to the present invention, the ionic liquid may be selected from ionic liquids of 1-butyl-3-methylimidazole cations, which have two N atoms in their molecular structure, to facilitate coordination with metallic palladium to form stable complexes.
In some preferred embodiments, the ionic liquid may be selected from one or more of 1-butyl-3-methylimidazole sulfate, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole dicyan amine salt.
In some embodiments according to the invention, the mass of the ionic liquid may be 20-90% of the mass of the support. In some preferred embodiments, the mass of the ionic liquid may be 30 to 70% of the mass of the support. In some more preferred embodiments, the mass of the ionic liquid may be 40 to 60% of the mass of the support.
In some embodiments according to the present invention, the molecular sieve may be selected from one or more of a ZSM-5 molecular sieve, a 10X molecular sieve, a 13X molecular sieve, a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve. In some preferred embodiments, the molecular sieve may be selected from ZSM-5 molecular sieves.
The invention also provides a preparation method of the palladium-supported molecular sieve catalyst according to any one of the technical schemes, which comprises the following steps:
s1: uniformly mixing the molecular sieve, the palladium precursor and the ionic liquid, and stirring for 5-8 hours at 70-130 ℃ to obtain a catalyst precursor; and
s2: and (2) reducing the catalyst precursor obtained in the step (S1) in reducing gas at 200-500 ℃ to obtain the palladium-supported molecular sieve catalyst.
In some embodiments according to the invention, the palladium precursor may be selected from one or more of potassium chloropalladate, palladium acetate, sodium chloropalladate, palladium nitrate, palladium acetylacetonate, ammonium tetrachloropalladate. In some preferred embodiments, the palladium precursor may be selected from potassium chloropalladate.
In some embodiments according to the present invention, the reducing gas may be selected from one or more of hydrogen, ammonia, carbon monoxide. In some preferred embodiments, the reducing gas may be selected from hydrogen.
In some embodiments according to the present invention, the step S1 may further be: and uniformly mixing the molecular sieve, the palladium precursor and the ionic liquid, and stirring for 6-8 hours at the temperature of 90-100 ℃ to obtain the catalyst precursor.
In some embodiments according to the present invention, the temperature at which the catalyst precursor is reduced in the reducing gas in the step S2 may be 250 to 350 ℃.
In some embodiments according to the present invention, the reduction time when the catalyst precursor is reduced in the reducing gas may be 1 to 6 hours in the step S2. In some preferred embodiments, the reduction time may be 1 to 3 hours.
The invention also provides the application of the palladium-supported molecular sieve catalyst in the technical scheme in the catalytic preparation of 2-cyano-4' -methyl biphenyl.
The invention also provides a preparation method of the 2-cyano-4 '-methyl biphenyl, which takes o-chlorobenzonitrile and p-chlorotoluene as raw materials to react in the presence of the palladium-supported molecular sieve catalyst in any one of the technical schemes, thereby preparing the 2-cyano-4' -methyl biphenyl.
In some embodiments according to the present invention, the preparation method may include the following processes: the catalyst, o-chlorobenzonitrile and p-chlorotoluene are reacted in a solvent at 50-80 deg.c, preferably 60-70 deg.c, to produce 2-cyano-4' -methylbiphenyl.
In some embodiments according to the invention, the preparation method may further comprise the following purification process: and removing the solvent after the reaction is finished to obtain a crude product, and carrying out negative pressure distillation on the crude product to obtain the purified 2-cyano-4' -methyl biphenyl. In some preferred embodiments, the fraction collected in the negative pressure distillation at 165-180 ℃/2000Pa is the purified 2-cyano-4' -methylbiphenyl.
In some embodiments according to the invention, the mass of the palladium-supported molecular sieve catalyst may be 5 to 10% of the mass of the o-chlorobenzonitrile.
In some embodiments according to the invention, the molar ratio of the o-chlorobenzonitrile to the p-chlorotoluene may be from 1:1.1 to 1.3.
In some embodiments according to the present invention, the solvent may be a common organic solvent used for preparing 2-cyano-4' -methylbiphenyl. In some preferred embodiments, the solvent may be N-methylpyrrolidone, which may be used in an amount of 2 to 6 times (volume/mass ratio) the raw material o-chlorobenzene.
The invention also provides the application of the 2-cyano-4 '-methyl biphenyl prepared by the preparation method in the preparation of the intermediate 5- [4' - (bromomethyl) biphenyl-2-yl ] -1-trityl-tetrazole of the sartan drug.
The reaction scheme for preparing 5- [4'- (bromomethyl) biphenyl-2-yl ] -1-trityl-tetrazole from 2-cyano-4' -methylbiphenyl as starting material is as follows:
the 2-cyano-4 '-Methyl Biphenyl (MB) is firstly reacted with sodium azide to obtain 5- (4' -methyl biphenyl-2-yl) -1H-tetrazole (MBA), then the 5-cyano-4 '-methyl biphenyl-2-yl) -tetrazole (MBB) is obtained after the substitution of triphenylchloromethane, and finally the 5- [4' - (bromomethyl) biphenyl-2-yl ] -1-trityl-tetrazole (MBB-Br) is obtained after the bromination.
The intermediate MBB-Br can be used for synthesizing sartan medicaments, such as valsartan, olmesartan medoxomil and the like. The synthetic route can be summarized as follows:
n-alkylating L-valine methyl ester and MBB-Br to obtain ((2 '- (1-trityl-1H-tetrazol-5-yl) - [1,1' -biphenyl ] -4-yl) methyl) -L-valine methyl ester; reacting the intermediate with pentanoyl chloride to obtain N-pentanoyl-N- ((2 '- (1-trityl-1H-tetrazol-5-yl) - [1,1' -biphenyl ] -4-yl) methyl) -L-valine methyl ester; deprotection to give N- ((2 '- (1H-tetrazol-5-yl) - [1,1' -biphenyl ] -4-yl) methyl) -N-pentanoyl-L-valine methyl ester; finally, the valsartan is obtained by hydrolysis.
MBB-Br is coupled with 4- (2-hydroxypropyl-2-yl) -2-propyl-1H-imidazole-5-carboxylic acid ethyl ester to obtain ethyl-4- (2-hydroxypropyl-2-yl) -2-propyl-1- ((2 '- (1-trityl-1H-tetrazol-5-yl) - [1,1' -biphenyl ] -4-yl) methyl) -1H-imidazole-5-carboxylic acid ester; after hydrolysis, reacting with 4- (bromomethyl) -5-methyl-1, 3-dioxole-2-one to obtain trityl olmesartan medoxomil; finally, the olmesartan medoxomil is obtained by deprotection.
Sartan drugs are antihypertensive drugs of angiotensin receptor antagonists, and mainly achieve the effect of reducing blood pressure by inhibiting excitatory distention of the RAS system. The medicine can not only stably reduce blood pressure for a long time, but also has the effects of reducing urine protein, delaying kidney damage, improving myocardial function and the like, and is a hypertension and cardiovascular disease treatment medicine with highest clinical safety and least side effect at present. Is especially suitable for patients with hypertension complicated with diabetes, coronary heart disease, heart failure, and albuminuria.
The palladium-supported molecular sieve catalyst provided by the invention has excellent catalytic activity, can be used as a heterogeneous catalyst for catalyzing various chemical reactions, is particularly used for catalyzing the synthesis of 2-cyano-4' -methyl biphenyl, has high catalytic activity, is convenient to recycle, can still keep higher catalytic activity after repeated recycling, improves the service life and the utilization efficiency of the catalyst, reduces the emission of waste catalyst, and is environment-friendly. In addition, the preparation process of the palladium-supported molecular sieve catalyst provided by the invention is simple and convenient, the condition is mild, and expensive reagents or raw materials are not required.
Compared with the preparation methods using other catalysts, the preparation method of the 2-cyano-4' -methyl biphenyl provided by the invention has the advantages that the yield of target products is greatly improved, the catalyst and the reaction solvent can be recycled, and the reaction condition is mild and easy to control, so that the production cost can be obviously reduced, the production efficiency is improved, the preparation method is suitable for industrial production, and the preparation method has important economic and social values, thereby having very good application prospects.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
The raw materials or reagents used in the examples and comparative examples of the present invention were commercially available products unless otherwise specified.
The percentages used in the examples and comparative examples of the present invention are mass percentages unless otherwise specified.
Example 1
1. Preparation of the catalyst
1) 4g of ZSM-5 molecular sieve, 456.2mg of potassium chloropalladate and 2g of 1-butyl-3-methylimidazole sulfate are taken and stirred and mixed uniformly to obtain a mixture.
2) The mixture obtained in the step 1) is heated and stirred for 7 hours at 95 ℃ to obtain a catalyst precursor.
3) And 2) reducing the catalyst precursor obtained in the step 2) under hydrogen at 300 ℃ for 2 hours to obtain the catalyst.
Preparation of 2, 2-cyano-4' -methylbiphenyl
Under the protection of nitrogen, adding 4g of self-made catalyst, 50g (0.36 mol) of o-chlorobenzonitrile, 200mL of N-methylpyrrolidone and 50.6g (0.4 mol) of p-chlorotoluene into a three-neck flask with a reflux condenser pipe and a constant pressure dropping funnel at one time, heating to 60-70 ℃ for about 30-40min, preserving heat for 4h, cooling to room temperature after the heat preservation, filtering, concentrating the mother solution until the solvent is clean, and obtaining a crude product. And (3) putting the obtained crude product into a distillation flask, heating, distilling under negative pressure, and collecting fractions of 165-180 ℃/2000Pa to obtain 65.4g of a high-purity target product with the yield of 93.4%.
The catalyst used in example 1 was recovered and reused. To make up for the catalyst loss, 10% of fresh catalyst was added for each reuse, and the reuse was repeated 4 times to prepare 2-cyano-4' -methylbiphenyl, the results of which are shown in table 1.
TABLE 1 results of recycling of catalyst of example 1
Number of times of repeated use Target product weight (g) Yield of target product (%)
1 65.6 93.7
2 65.3 93.3
3 64.9 92.7
4 65.1 93.0
Example 2
1. Preparation of the catalyst
1) 4g of ZSM-5 molecular sieve, 456.2mg of potassium chloropalladate and 2g of 1-butyl-3-methylimidazole chloride are taken and stirred and mixed uniformly to obtain a mixture.
2) The mixture obtained in the step 1) is heated and stirred for 7 hours at 95 ℃ to obtain a catalyst precursor.
3) And 2) reducing the catalyst precursor obtained in the step 2) under hydrogen at 300 ℃ for 2 hours to obtain the catalyst.
Preparation of 2, 2-cyano-4' -methylbiphenyl
The procedure was the same as in example 1 except that the catalyst prepared in example 1 was replaced with the same mass of the catalyst prepared in example 2, to obtain 63.7g of the aimed product in a yield of 91.0%.
Example 3
1. Preparation of the catalyst
1) 4g of ZSM-5 molecular sieve, 456.2mg of potassium chloropalladate and 2g of 1-butyl-3-methylimidazole acetate are taken and stirred and mixed uniformly to obtain a mixture.
2) The mixture obtained in the step 1) is heated and stirred for 7 hours at 95 ℃ to obtain a catalyst precursor.
3) And 2) reducing the catalyst precursor obtained in the step 2) under hydrogen at 300 ℃ for 2 hours to obtain the catalyst.
Preparation of 2, 2-cyano-4' -methylbiphenyl
The procedure was the same as in example 1 except that the catalyst prepared in example 1 was replaced with the catalyst prepared in example 3 in the same mass, to obtain 64.1g of the aimed product in a yield of 91.6%.
Example 4
1. Preparation of the catalyst
1) 4g of ZSM-5 molecular sieve, 456.2mg of potassium chloropalladate and 2g of 1-butyl-3-methylimidazole dicyandiamide salt are taken and stirred and mixed uniformly to obtain a mixture.
2) The mixture obtained in the step 1) is heated and stirred for 7 hours at 95 ℃ to obtain a catalyst precursor.
3) And 2) reducing the catalyst precursor obtained in the step 2) under hydrogen at 300 ℃ for 2 hours to obtain the catalyst.
Preparation of 2, 2-cyano-4' -methylbiphenyl
The procedure was the same as in example 1, except that the catalyst prepared in example 4 was used in place of the catalyst prepared in example 1, to obtain 67.8g of the aimed product in 96.9% yield.
Comparative example 1 2 preparation of cyano-4' -methylbiphenyl
Except that Pd (PPh) of the same mass was used 3 ) The procedure of example 1 was repeated except for replacing the catalyst prepared in example 1, to obtain 51.2g of the desired product in 73.1% yield.
Comparative example 2 2 preparation of cyano-4' -methylbiphenyl
The procedure was the same as in example 1, except that the catalyst prepared in example 1 was replaced with cobalt chloride of the same quality, to obtain 24.7g of the aimed product in a yield of 35.3%.
Comparative example 3 2 preparation of cyano-4' -methylbiphenyl
The procedure was the same as in example 1 except that the catalyst prepared in example 1 was replaced with nickel chloride of the same quality, to obtain 41.9g of the aimed product in 59.8% yield.
Comparative example 42 preparation of cyano-4' -methylbiphenyl
The procedure was the same as in example 1 except that the catalyst prepared in example 1 was replaced with copper chloride of the same quality, to obtain 27.6g of the aimed product in a yield of 39.4%.
Comparative example 5 2 preparation of cyano-4' -methylbiphenyl
The procedure was the same as in example 1 except that the catalyst prepared in example 1 was replaced with cadmium chloride of the same quality, to obtain 28.1g of the objective product in 40.2% yield.
The embodiment and the comparative example show that the palladium-supported molecular sieve catalyst provided by the invention has excellent catalytic activity, is obviously stronger than the conventional metal catalyst, and greatly improves the yield of the 2-cyano-4' -methyl biphenyl by more than 90%, even more than 95%.
In addition, the molecular sieve catalyst provided by the invention is a heterogeneous catalyst, is convenient to recycle, can still keep higher catalytic activity after being recycled for four times, and the yield of target products is kept at higher level, so that the reaction efficiency can be improved, and the manufacturing cost can be reduced.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.

Claims (8)

1. The preparation method of the 2-cyano-4 '-methyl biphenyl is characterized by taking o-chlorobenzonitrile and p-chlorotoluene as raw materials, and carrying out reaction in the presence of a palladium-supported molecular sieve catalyst to prepare the 2-cyano-4' -methyl biphenyl, wherein the palladium-supported molecular sieve catalyst takes a molecular sieve as a carrier, and metal palladium and an ionic liquid forming a complex with the metal palladium are supported on the molecular sieve catalyst, the mass of the metal palladium is 1-6% of the mass of the carrier, the ionic liquid is selected from ionic liquids of 1-butyl-3-methylimidazole cations, the mass of the ionic liquid is 20-90% of the mass of the carrier, and the preparation of the palladium-supported molecular sieve catalyst comprises the following steps:
s1: uniformly mixing the molecular sieve, the palladium precursor and the ionic liquid, and stirring for 5-8 hours at 70-130 ℃ to obtain a catalyst precursor; and
s2: and (2) reducing the catalyst precursor obtained in the step (S1) in reducing gas at 200-500 ℃ to obtain the palladium-supported molecular sieve catalyst.
2. The method according to claim 1, wherein the mass of the metallic palladium is 3 to 5% of the mass of the carrier.
3. The preparation method according to claim 1, wherein the ionic liquid is selected from one or more of 1-butyl-3-methylimidazole sulfate, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole acetate and 1-butyl-3-methylimidazole dicyan amine salt.
4. The preparation method according to claim 1, wherein the mass of the ionic liquid is 40 to 60% of the mass of the carrier.
5. The method of claim 1, wherein the molecular sieve is selected from one or more of ZSM-5 molecular sieve, 10X molecular sieve, 13X molecular sieve, 3A molecular sieve, 4A molecular sieve, 5A molecular sieve.
6. The method according to claim 1, wherein the palladium precursor is one or more selected from the group consisting of potassium chloropalladate, palladium acetate, sodium chloropalladate, palladium nitrate, palladium acetylacetonate and ammonium tetrachloropalladate.
7. The method according to claim 1, wherein the reducing gas is one or more selected from the group consisting of hydrogen, ammonia, and carbon monoxide.
8. The production method according to any one of claims 1 to 7, wherein the mass of the palladium-supported molecular sieve catalyst is 5 to 10% of the mass of the o-chlorobenzonitrile; and/or
The molar ratio of the o-chlorobenzene to the p-chlorotoluene is 1:1.1-1.3.
CN202210441807.3A 2022-04-25 2022-04-25 Palladium-supported molecular sieve catalyst and preparation method and application thereof Active CN114733575B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210441807.3A CN114733575B (en) 2022-04-25 2022-04-25 Palladium-supported molecular sieve catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210441807.3A CN114733575B (en) 2022-04-25 2022-04-25 Palladium-supported molecular sieve catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114733575A CN114733575A (en) 2022-07-12
CN114733575B true CN114733575B (en) 2024-04-09

Family

ID=82283281

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210441807.3A Active CN114733575B (en) 2022-04-25 2022-04-25 Palladium-supported molecular sieve catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114733575B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6407253B1 (en) * 1996-09-20 2002-06-18 Sanofi-Synthelabo Method for preparing 4-methyl-biphenyl derivatives
CN102295577A (en) * 2011-05-30 2011-12-28 复旦大学 Synthetic method of sartanbipheny and derivatives thereof
CN103012202A (en) * 2012-12-04 2013-04-03 山东鑫泉医药有限公司 Preparation method of sartanbiphenyl
CN107935957A (en) * 2017-12-02 2018-04-20 河南龙湖生物技术有限公司 A kind of method for synthesizing high-purity losartan side chain TTBB
CN114054061A (en) * 2020-08-06 2022-02-18 台州学院 Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6407253B1 (en) * 1996-09-20 2002-06-18 Sanofi-Synthelabo Method for preparing 4-methyl-biphenyl derivatives
CN102295577A (en) * 2011-05-30 2011-12-28 复旦大学 Synthetic method of sartanbipheny and derivatives thereof
CN103012202A (en) * 2012-12-04 2013-04-03 山东鑫泉医药有限公司 Preparation method of sartanbiphenyl
CN107935957A (en) * 2017-12-02 2018-04-20 河南龙湖生物技术有限公司 A kind of method for synthesizing high-purity losartan side chain TTBB
CN114054061A (en) * 2020-08-06 2022-02-18 台州学院 Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Highly active and stable supported Pd catalysts on ionic liquidfunctionalized SBA-15 for Suzuki–Miyaura cross-coupling and transfer hydrogenation reactions;Etty N. Kusumawati等;《Energy & Environment》;第4卷;第180-189页 *
谢如刚.《现代有机合成化学》.华东理工大学出版社,2007,第29页. *

Also Published As

Publication number Publication date
CN114733575A (en) 2022-07-12

Similar Documents

Publication Publication Date Title
JP4729779B2 (en) Method for producing xylylenediamine
CN101429139B (en) Process for producing dicyclohexyl methyl hydride diisocyanate and its midbody
CN101544535A (en) Method for preparing synthetic 1,1,1,3,3-pentachloro propane
EP1113001B1 (en) Process for producing nitrile compounds
CN101912779B (en) Catalyst for catalytic synthesis of N-methylpyrrolidine and application thereof
CN108409605B (en) Preparation method of 3, 4-difluorobenzonitrile
CN101239919B (en) Synthetic method of aromatic diamine monomer
CN114733575B (en) Palladium-supported molecular sieve catalyst and preparation method and application thereof
CN108623497B (en) Preparation method of 2-cyano-4' -methyl biphenyl
CN108409626A (en) The preparation method of ovarian cancer resistance medicament Rucaparib key intermediates
TW593229B (en) Process for preparing 6-aminocaproamide
JP2010024187A (en) Method for producing aromatic nitrile
CN101037393B (en) Synthetic process for preparing arylamine by reduction of aromatic nitro compound
CN114733526B (en) Nickel-supported porous carbon material catalyst and preparation method and application thereof
CN1680307A (en) Reduction of 4,4'-diamino-diphenylethylene-2,2' disulfonic acid
CN108129402B (en) Method for synthesizing 2-phenyl quinazolinone compound by taking tolane compound as raw material
CN114478533A (en) Preparation method of 4-aminopyrrolo [2,1-f ] [1,2,4] triazine
CN114436803B (en) Preparation method of 3- (4-chlorophenyl) -1, 5-diphenylpentane-1, 5-dione compound
JP2001348370A (en) Method for producing nitrile compound
CN112625015B (en) Preparation method of 2- (1, 3-dihydro-2-isobenzofuran) -1-acetophenone compound
CN112321451B (en) Method for preparing cinacalcet hydrochloride drug intermediate
CN1228331C (en) Method for synthesizing cis-2,6-dimethyl piperazine
CN115894182B (en) Method for efficiently synthesizing 1, 4-tetramethoxy-2-butene
CN113943249B (en) Preparation method of N-cyanomethyl-4- (trifluoromethyl) nicotinamide
CN108299236B (en) Synthetic method of alpha-cyanoacrylate compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant