CN110950778A - Process and catalyst system for preparing aromatic malononitrile - Google Patents

Process and catalyst system for preparing aromatic malononitrile Download PDF

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CN110950778A
CN110950778A CN201911343850.0A CN201911343850A CN110950778A CN 110950778 A CN110950778 A CN 110950778A CN 201911343850 A CN201911343850 A CN 201911343850A CN 110950778 A CN110950778 A CN 110950778A
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malononitrile
aromatic
cuprous
catalyst system
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王福祥
曹泳
申雁
梅丽芸
靳文
徐守明
樊真
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Anhui research institute of chemical industry
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    • 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
    • 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
    • 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
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

Abstract

The present invention provides a process and catalyst system for the preparation of aromatic malononitrile. The process for the preparation of aromatic malononitrile comprises the step of reacting at least one aromatic iodine compound with malononitrile in a solvent in the presence of a coupling catalyst system comprising: an effective amount of a cuprous halide complex formed from cuprous halide and a ligand; an alkalinized compound. The preparation method of the aromatic malononitrile provided by the invention has the advantages of simple reaction process, high synthesis yield, low production cost and higher industrial application prospect.

Description

Process and catalyst system for preparing aromatic malononitrile
Technical Field
The invention relates to the technical field of synthesis, in particular to a method and a catalyst system for preparing aromatic malononitrile.
Background
Aromatic malononitrile compounds are important herbicide technical intermediates, and the aromatic malononitrile compounds are prepared by two steps of Sundall bromination of aromatic amine compounds and then coupling reaction of the aromatic amine compounds and malononitrile under palladium catalysis at present, but the method has a plurality of defects: firstly, when preparing bromobenzene from arylamine through diazo bromination, hydrobromic acid is used as a bromine source, bromine is currently lacked in China, the main source of bromine is a byproduct of salt chemical engineering, the price is expensive, and the hydrobromic acid needs to be recovered due to the requirement of environmental protection, so the production cost is increased; secondly, when bromobenzene and malononitrile are subjected to coupling reaction, palladium catalyst is needed for coupling reaction, palladium is expensive, and catalyst recovery is needed, so that operation is complex, and production cost is increased. Therefore, it is important to provide a safer, more convenient, more efficient and more environmentally friendly process for the preparation of aromatic malononitrile.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of aromatic malononitrile, wherein the total reaction yield in the preparation process is more than 65%, the purity of a target product is more than 95%, the reaction condition is mild, the raw materials are cheap and easy to obtain, the reaction temperature is low, the energy consumption is low, the requirement on reaction equipment is low, the production cost is low, the method is environment-friendly and safe, and the method is suitable for industrial production.
It is another object of the present invention to provide a catalyst system.
To achieve the above and related objects, the present invention is achieved by a process for preparing aromatic malononitrile, which comprises: a step of reacting at least one aromatic iodine compound and malononitrile in a solvent in the presence of a coupling catalyst system comprising the following components, wherein said components comprise: an effective amount of a cuprous halide complex formed from cuprous halide and a ligand; an alkalinized compound.
In one embodiment of the present disclosure, the aryl iodide compound has the following structure:
Figure BDA0002332818510000011
wherein R is1、R2、R3Independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, acetamido ethyl, acetamido propyl, propargyl, vinyl, allyl, methoxy, ethoxy and combination thereof.
In a specific embodiment disclosed by the invention, the aryl iodide compound is prepared by diazo and de-iodination reactions.
In a specific embodiment disclosed by the invention, the effective amount is that the mass ratio of the cuprous halide complex to the aromatic iodine compound is 3-15 wt%.
In a specific embodiment of the present disclosure, the cuprous halide is selected from any one of cuprous chloride, cuprous bromide, cuprous iodide, and combinations thereof.
In a specific embodiment of the present disclosure, the ligand is selected from any one of L-proline, bipyridine, triphenylphosphine, tributylphosphine, oxazoline, and combinations thereof.
In one embodiment of the present disclosure, the alkali compound is selected from any one of sodium hydroxide, sodium hydride, cesium carbonate, sodium tert-butoxide, sodium methoxide, and a combination thereof.
In one embodiment of the present disclosure, the catalytic temperature of the coupling catalyst system is 50-100 ℃.
The present invention also provides a coupling catalyst system comprising the following components: an effective amount of a cuprous halide complex formed from cuprous halide and a ligand; an alkalinized compound.
In a specific embodiment disclosed in the present invention, the cuprous halide is selected from any one of cuprous chloride, cuprous bromide, cuprous iodide, and a combination thereof; the ligand is selected from any one of L-proline, bipyridyl, triphenylphosphine, tributylphosphine, oxazoline and a combination thereof.
As described above, the present invention provides a method and catalyst system for preparing aromatic malononitrile. According to the preparation method, the aromatic iodine compound and the malononitrile are subjected to coupling reaction by using the coupling catalyst system comprising the effective amount of the cuprous halide complex formed by the cuprous halide and the ligand and the alkalide, so that the aromatic malononitrile is prepared, and the problems of expensive price and difficult recovery caused by using a palladium catalyst are solved. In addition, the invention avoids adopting aromatic bromine compound, and prepares the aromatic malononitrile by using raw materials comprising aromatic iodine compound and the like, and the raw materials of the aromatic iodine compound and the like have wide sources, are cheap and easy to obtain, and have stable reaction. Other features, benefits and advantages will be apparent from the disclosure including the description and claims detailed herein.
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Fig. 1 shows a schematic flow diagram of one embodiment of the method for preparing aromatic malononitrile according to the present invention.
FIG. 2 is a schematic flow diagram showing one embodiment of a process for producing an aromatic iodine compound as a raw material component in an aromatic malononitrile according to the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The term "effective amount" as used herein, unless otherwise specified, includes an amount of a component that is capable of increasing (directly or indirectly) the product of an aromatic malononitrile product or is capable of increasing the selectivity of an aromatic carbonate. The optimum amount of a given component may vary depending on the reaction conditions and the nature of the other components, but can readily be determined on an individual basis for a given application.
The term "complex" as used herein includes coordination or complexes comprising a central ion or atom. Depending on the charge of the central atom and coordinating group, the complex may be nonionic, cationic or anionic.
Referring to fig. 1, the present invention provides a method for preparing aromatic malononitrile, which includes, but is not limited to,
-S101, providing a coupling catalyst system, wherein the coupling catalyst system comprises the following components: an effective amount of a cuprous halide complex formed from cuprous halide and a ligand; an alkalinized compound;
-S102, reacting at least one aryl iodide compound and malononitrile in a solvent in the presence of a coupling catalyst system.
The aromatic malononitrile in the present invention includes mono-substituted aromatic malononitrile and poly-substituted aromatic malononitrile, such as 2, 6-diethyl-4-methylphenyl malononitrile, 4-methyl-phenyl malononitrile, 2-methylphenyl malononitrile, 2-hydroxyethyl-4-ethylphenyl malononitrile.
Referring next to fig. 1, in step S1, suitable cuprous halides include cuprous chloride, cuprous bromide, and cuprous iodide, such as cuprous chloride and cuprous iodide, within the coupling catalyst system. Suitable ligands are selected from L-proline, bipyridine, triphenylphosphine, tributylphosphine, oxazoline, for example L-proline. The cuprous halide and the ligand form a cuprous halide complex, and the effective amount of the cuprous halide complex is, for example, 3 to 15 wt%, such as 3 wt%, 5 wt%, 10 wt%, 15 wt%, of the cuprous halide complex in the mass ratio of the cuprous halide complex to the aromatic iodine compound. The molar ratio of the cuprous halide to the ligand is 1:2-5 based on obtaining an effective amount within the above range.
In step S1, suitable alkalides within the coupling catalyst system include sodium hydroxide, sodium hydride, cesium carbonate, potassium tert-butoxide, e.g., sodium hydroxide. The concentration of the alkalinization compound is 2-7 times of the aromatic iodine amount, and the alkalinization compound has the functions of forming metal salt of malononitrile by the malononitrile and alkali, then transferring the malononitrile to a copper catalyst through transmetallization, and further obtaining the final aromatic malononitrile product through reduction elimination.
Referring next to fig. 1, in step S2, the aryl iodide compound as a raw material component for preparing the aromatic malononitrile may, for example, have the following structural formula,
Figure BDA0002332818510000041
wherein R is1、R2、R3Independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, acetamido ethyl, acetamido propyl, propargyl, vinyl, allyl, methoxy, ethoxy and combination thereof.
Suitable examples may include mono-substituted and poly-substituted aryl-iodo compounds, such as 2, 6-diethyl-4-methyliodobenzene, 4-methyl-iodobenzene, 2-methylphenyliodobenzene, 2-hydroxyethyl-4-ethyliodobenzene. From the viewpoint of improving the reaction yield and purity of the aromatic malononitrile, the aromatic iodine, for example, 2, 6-diethyl-4-methyliodobenzene, can be obtained by a preparation comprising a preparation process in which the 2, 6-diethyl-4-methylaniline is prepared to obtain the 2, 6-diethyl-4-methyliodobenzene by diazotization, deammonification reaction, specifically, referring to fig. 2, comprising steps S201 to S206,
s201, adding 2, 6-diethyl-4-methylaniline into concentrated hydrochloric acid, raising the temperature to 80-90 ℃ for reaction for 15 minutes, and then reducing the temperature to-10 to-5 ℃ to obtain a white suspension;
s202, adding sodium nitrite into water to prepare a sodium nitrite aqueous solution, and controlling the temperature to be-5-0 ℃;
s203, dripping the sodium nitrite aqueous solution into the white suspension, controlling the temperature to be less than 0 ℃, and performing diazotization reaction on the white suspension and the sodium nitrite aqueous solution to obtain a diazotization reaction solution; after the addition, sulfamic acid or urea is added to quench the redundant generated nitrous acid;
s204, adding an iodo reagent into concentrated hydrochloric acid, stirring and heating to 80-90 ℃ for reaction to obtain a denitrification iodination solution;
s205, adding the diazotization reaction solution into the denitrification iodination solution to perform denitrification reaction to obtain a denitrification iodination product;
s206, performing post-treatment processes on the iodo product of the denitrification reaction, such as distillation, extraction, washing, drying and the like to obtain the 2, 6-diethyl-4-methyl iodobenzene.
In the above process, the iodinating agent may be sodium iodide, potassium iodide, or the like. The extractant may be ethyl acetate, chloroform, dichloromethane, methyl tert-butyl ether, etc. After extraction, the iodo product of the denitrification reaction can be further washed by sodium bisulfite, sodium hydroxide and water, so that the purity of the 2, 6-diethyl-4-methyl iodobenzene product is improved. It is to be understood that the present invention is only illustrative of one specific example of the method for producing the above-mentioned aryl iodide compound, and is not limited thereto. The molar ratio of the aromatic iodine to the malononitrile is 1: 1.05-2.
Referring back to fig. 1, in step S2, the solvent is used to provide a reaction site for the aryl iodide compound and malononitrile, and for the coupling catalyst system, and suitable solvents may include N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Dimethylsulfoxide (DMSO), such as DMF.
In step S2, the catalytic temperature of the coupling catalyst system is 50 to 100 ℃, further, 65 to 90 ℃, for example, 65 ℃, 75 ℃, 80 ℃, 90 ℃ from the viewpoint of enhancing the reaction activity. At a temperature within the above range, the catalytic efficiency, and the coupling reaction activity between the aromatic iodine and the malononitrile can be sufficiently improved effectively.
In step S2, the reaction time is 8-26h, for example 8h, 12h, 24 h. The stirring rate is, for example, 100-1000r/min, such as 100r/min, 150r/min, 350r/min, 500 r/min. Further, the product obtained after the reaction of the aromatic iodine compound and malononitrile can be, for example, sequentially subjected to filtration, extraction, acid washing and concentration to obtain the aromatic malononitrile. Suitable extractants may include ethyl acetate, chloroform, methylene chloride, methyl tert-butyl ether, and the acid may include hydrochloric acid and/or sulfuric acid.
The invention will now be illustrated in more detail by means of specific examples, in which experimental methods without specifying specific conditions, according to conventional methods and conditions, or according to commercial specifications, are selected unless otherwise specified.
In one embodiment of the invention, the 2, 6-diethyl-4-methylphenyl malononitrile is prepared:
under the nitrogen atmosphere, 0.32mol of 2, 6-diethyl-4-methyl iodobenzene, 0.4mol of malononitrile, 5mol of cuprous iodide, 10 mol of L-proline, 1.2mol of sodium hydride and 700ml of DMSO are sequentially added into a reactor with a stirrer, a thermometer and a reflux condenser tube, the reactor is heated to 70 ℃ for reacting for 18 hours, after the reaction is completed, 10% of ammonium chloride aqueous solution is added for quenching, chloroform is used for extraction, sodium hydroxide and water are used for washing, and concentrated acid is dried to obtain yellow solid 2, 6-diethyl-4-methyl phenyl malononitrile, wherein the yield is 87%, and the purity is 96.7%.
In the present example, 2, 6-diethyl-4-methyliodobenzene was prepared by a process including sequentially adding 0.4mol of 2, 6-diethyl-4-methylaniline and 200ml of concentrated hydrochloric acid to a reactor equipped with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and heating to 80 to 90 ℃, reacting for 15 to 20 minutes to obtain a white suspension, and cooling to-10 ℃. Meanwhile, 0.48mol of sodium nitrite is added into 100mL of water to obtain a sodium nitrite aqueous solution, the temperature is controlled to be-5-0 ℃, the sodium nitrite aqueous solution is slowly dripped into the white suspension, and a light yellow solution is obtained after the dripping is finished. Subsequently, 320mg of sulfamic acid or 1000mg of urea was added to the pale yellow solution, and the mixture was further stirred for 5 to 10 minutes to quench off excess nitrous acid generated in the reaction in step S3, thereby obtaining a diazotization reaction solution. Meanwhile, 1.6mol of sodium iodide and 200ml of concentrated hydrochloric acid are sequentially added into another reactor with a stirrer, a condenser, a thermometer and a constant pressure dropping funnel, stirred and heated to 80-90 ℃ to obtain a denitrification iodination solution. And then, adding the diazotization reaction solution into the iodination solution for denitrification reaction, and continuing to stir and react for 16 hours at the temperature of 80-90 ℃ after the addition is finished to obtain an iodo product for denitrification reaction. Then, carrying out reduced pressure distillation on the iodo product of the denitrification reaction, and completely evaporating at 150-; the black distilled solution was extracted three times with 500ml of chloroform, the organic phases were combined, washed with sodium bisulfite, sodium hydroxide and water, and the resulting organic phase was concentrated by drying to give a yellow oily liquid, i.e., 2, 6-diethyl-4-methyliodobenzene, in 83% yield and 95.7% purity.
In another embodiment of the present invention, the 2, 6-diethyl-4-methylphenyl malononitrile is prepared:
under the nitrogen atmosphere, 0.17mol of 2, 6-diethyl-4-methyl iodobenzene, 0.2mol of malononitrile, 5% mol of cuprous iodide, 10% mol of bipyridine, 0.64mol of cesium carbonate and 350ml of DMF are sequentially added into a reactor with a stirrer, a thermometer and a reflux condenser tube, then the mixture is heated to 70 ℃ for reaction for 24 hours, after the reaction is completed, 10% aqueous ammonium chloride solution is added for quenching, then ethyl acetate is used for extraction, sodium hydroxide and water are used for washing, and the yellow solid 2, 6-diethyl-4-methyl phenyl malononitrile is obtained after drying and concentration, wherein the yield is 85% and the purity is 96.1%.
The 2, 6-diethyl-4-methyliodobenzene in this example is prepared from 2, 6-diethyl-4-methylaniline by diazotization and de-iodination in sequence.
In another embodiment of the present invention, the 2, 6-diethyl-4-methylphenyl malononitrile is prepared:
under the nitrogen atmosphere, 0.16mol of 2, 6-diethyl-4-methyl iodobenzene, 0.2mol of malononitrile, 5mol of cuprous iodide, 10 mol of L-proline, 0.64mol of potassium tert-butoxide and 350ml of NMP are sequentially added into a reactor with a stirrer, a thermometer and a reflux condenser, then the mixture is heated to 100 ℃ and reacted for 17 hours, after the reaction is completed, 10% ammonium chloride aqueous solution is added for quenching, chloroform is used for extraction, sodium hydroxide and water are used for washing, and the yellow solid 2, 6-diethyl-4-methyl phenyl malononitrile is obtained through drying and concentration, wherein the yield is 88% and the purity is 95.7%.
The 2, 6-diethyl-4-methyliodobenzene in this example is prepared from 2, 6-diethyl-4-methylaniline by diazotization and de-iodination in sequence.
In another embodiment of the present invention, the 2-methylphenyl malononitrile is prepared:
under the nitrogen atmosphere, 0.15mol of 2-methylphenyl malononitrile, 0.2mol of malononitrile, 5% mol of cuprous iodide, 10% mol of oxazoline, 0.64mol of cesium carbonate and DMF350ml are sequentially added into a reactor with a stirrer, a thermometer and a reflux condenser, then the mixture is heated to 70 ℃ for reaction for 21 hours, after the reaction is completed, 10% ammonium chloride aqueous solution is added for quenching, then ethyl acetate is used for extraction, sodium hydroxide and water are used for washing, and the yellow solid 2-methylphenyl malononitrile is obtained through drying and concentration, wherein the yield is 82% and the purity is 95.1%.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.

Claims (10)

1. A process for the preparation of aromatic malononitrile, the process comprising:
a step of reacting at least one aromatic iodine compound and malononitrile in a solvent in the presence of a coupling catalyst system comprising the following components, wherein said components comprise:
an effective amount of a cuprous halide complex formed from cuprous halide and a ligand;
an alkalinized compound.
2. The method of preparing aromatic malononitrile according to claim 1, wherein the aromatic iodine compound has the following structure:
Figure FDA0002332818500000011
wherein R is1、R2、R3Independently selected from any one of hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, acetamido ethyl, acetamido propyl, propargyl, vinyl, allyl, methoxy, ethoxy and combination thereof.
3. The method for producing an aromatic malononitrile according to claim 2, wherein the aromatic iodine compound is produced by diazotization, a deaminoiodo reaction.
4. The method according to claim 1, wherein the effective amount is 3 to 15 wt% of the cuprous halide complex based on the mass of the aromatic iodine compound.
5. The method for producing aromatic malononitrile according to claim 1, wherein the cuprous halide is selected from any one of cuprous chloride, cuprous bromide, cuprous iodide, and a combination thereof.
6. The method for producing an aromatic malononitrile according to claim 1, wherein the ligand is selected from any one of L-proline, bipyridine, triphenylphosphine, tributylphosphine, oxazoline, and a combination thereof.
7. The method for producing aromatic malononitrile according to claim 1, wherein the alkali compound is selected from any one of sodium hydroxide, sodium hydride, cesium carbonate, sodium tert-butoxide, sodium methoxide, and a combination thereof.
8. Process for the preparation of aromatic malononitrile according to claim 1, characterized in that the catalytic temperature of the coupling catalyst system is comprised between 50 and 100 ℃.
9. A coupling catalyst system, characterized in that the coupling catalyst system comprises the following components:
an effective amount of a cuprous halide complex formed from cuprous halide and a ligand;
an alkalinized compound.
10. The coupling catalyst system according to claim 9, wherein the cuprous halide is selected from any of cuprous chloride, cuprous bromide, cuprous iodide, and combinations thereof; the ligand is selected from any one of L-proline, bipyridyl, triphenylphosphine, tributylphosphine, oxazoline and a combination thereof.
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CN113929668A (en) * 2020-06-29 2022-01-14 江苏恒瑞医药股份有限公司 Preparation method of bicyclic substituted pyrazolone azo derivative
CN114181112A (en) * 2021-12-13 2022-03-15 浙江中山化工集团股份有限公司 Preparation method of 2, 6-diethyl-4-methylphenyl malononitrile

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