CN108675942B - Preparation method of aromatic nitrile compound - Google Patents

Preparation method of aromatic nitrile compound Download PDF

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CN108675942B
CN108675942B CN201810632166.3A CN201810632166A CN108675942B CN 108675942 B CN108675942 B CN 108675942B CN 201810632166 A CN201810632166 A CN 201810632166A CN 108675942 B CN108675942 B CN 108675942B
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CN108675942A (en
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张国富
王桂莲
郑卫华
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HANGZHOU TORRY BIOTECHNOLOGY Co.,Ltd.
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Hangzhou Shengman Biotechnology Co ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
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Abstract

The invention discloses a preparation method of aromatic nitrile compounds, which comprises the following steps: taking a toluene derivative shown as a formula (I) as a raw material, taking nano ferrovanadium as a catalyst, taking hydrogen peroxide as a cocatalyst, adding a ligand and an ammonia source, reacting for 6-24 hours at the temperature of 80-180 ℃ in an oxygen atmosphere under the working pressure of 0.1-1.5 MPa to obtain a reaction mixed solution, and carrying out post-treatment to obtain a target product, namely an aromatic nitrile compound shown as a formula (II); the method realizes the conversion of the methyl aromatic hydrocarbon to the aromatic nitrile compound under mild conditions, has high reaction yield and industrial application prospect, uses oxygen as a clean oxidant, reduces the generation of toxic and harmful byproducts in the reaction process of the traditional inorganic salt oxidant, and is an environment-friendly strategy.

Description

Preparation method of aromatic nitrile compound
(I) technical field
The invention relates to a novel method for preparing an aromatic nitrile compound by catalyzing methyl aromatic hydrocarbon to be subjected to direct ammoxidation through nano ferrovanadium.
(II) background of the invention
Cyano, a group widely used in organic synthesis, can be relatively easily converted by functional groups to prepare the corresponding amines, amides, carboxylic acids, aldehydes, ketones and heterocyclic compounds. In addition, aromatic nitriles have also proven to have important applications in natural products, materials, pharmaceutical syntheses, agrochemicals and dyes. As shown in formula 1, drugs such as Febuxostat (Febuxostat), Letrozole (Letrozole) and Citalopram (Citalopram) all contain a cyano group in their molecule.
Figure 1
At present, aromatic nitriles are industrially produced by using methyl aromatic hydrocarbon as a raw material through an ammoxidation method [ adv. Synth. Catal.,2004,346(12):1407], using oxygen as an oxidant and vanadium, nickel and other transition metals as catalysts at a temperature of 300 ℃ and 800 ℃ and a pressure of 0.5-1.5 MPa. The method has the obvious defects of higher temperature and pressure, which increases the difficulty of industrial application and higher preparation cost. In recent years, the liquid phase ammoxidation of aromatic hydrocarbon to prepare aromatic nitrile has attracted considerable attention because of its relatively mild reaction conditions, relatively high selectivity and yield. In 2009, Jiao et al [ angelw.chem. int.ed.,2009,48(38):7094] methyl groups substituted with electron rich groups in the para position were converted to the corresponding arylnitriles using copper sulfate as catalyst, sodium azide as nitrogen source, iodobenzene diacetate (PIDA) as oxidant. In 2011, Randolph k. belter [ j. fluorine chem.,2011,132(5):318] uses nitrogen trifluoride in industrial tail gas to prepare aromatic nitrile by selective ammoxidation reaction with methyl aromatic hydrocarbon at 400 ℃, and benzonitrile is obtained in 46% yield when toluene is used as a substrate. In 2013, Wang et al [ Angew. chem. int. Ed.,2013,52(40):10573] reacted at 70 ℃ using palladium acetate as catalyst and tert-butyl nitrite (TBN) as nitrogen source and oxidant to prepare arylnitrile, and when the substrate was toluene, the yield was 50%. In 2014, conversion of methyl aromatic hydrocarbon to arylnitrile can be realized by carrying out bromination, aminolysis, oxidation and other steps on Togo topic group [ Eur.J. org.chem., 2014(19):4115], wherein ammonia water can be used as a nitrogen source, and iodine is used as an oxidant. In 2015, Cheng et al [ chem. Commun.,2015,51(24):5085] developed a process for converting aromatic hydrocarbons to arylnitriles using ammonium fluoride as the ammonia source, iodine as the catalyst, and t-butanol peroxide as the oxidant. When DMSO is used as a solvent, the reaction temperature is 70 ℃, and the reaction time is 48 hours, the highest yield of the product can reach 83%. In 2016, Kang et al [ J.Am.chem.Soc.,2016,47(34):3294] developed a process for the preparation of arylnitriles using aluminum chloride and N-hydroxyphthalimide (NHPI) as catalysts and tert-butyl nitrite as an oxidant. In the same year, Xiao et al [ nat. Commun.,2017,8:15240] immobilized manganese oxide in the internal channels of zeolite and used it as catalyst (MnOx @ S-1) to convert the methyl group on the aromatic ring into cyano group. The method takes oxygen as an oxidant and urea as a nitrogen source, and when toluene is taken as a substrate, the reaction is carried out for 4 hours at 160 ℃, and the yield of the benzonitrile can reach 88.6%.
In view of the above, most of the ammoxidation systems reported above use iodine, tert-butyl nitrite, etc. as stoichiometric oxidants, and their reduction oxidation by-products are still discharged to the environment as waste, which increases the environmental burden.
Disclosure of the invention
In order to solve the problems in the prior art, the invention aims to provide a novel method for preparing aromatic nitrile compounds by ammoxidation of methyl aromatic hydrocarbon with high efficiency and high selectivity under the catalysis of transition metal and mild conditions.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing aromatic nitrile compounds is characterized in that: the method comprises the following steps:
taking a toluene derivative shown as a formula (I) as a raw material, taking nano ferrovanadium as a catalyst, taking hydrogen peroxide as a cocatalyst, adding a ligand and an ammonia source, reacting in an organic solvent at a temperature of 80-180 ℃ in an oxygen atmosphere under a working pressure of 0.1-1.5 MPa for 6-24 hours to obtain a reaction mixed solution, and carrying out post-treatment to obtain a target product, namely an aromatic nitrile compound shown as a formula (II); the ligand is pyridine, 2' -bipyridine or 1, 10-phenanthroline; the ammonia source is ammonia gas, ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium chloride, ammonium formate, ammonium acetate or 28% ammonia water by mass fraction; the quantity ratio of the toluene derivative shown in the formula (I), hydrogen peroxide, ligand and ammonia source is 1: 0.05-0.2: 0.05-0.2: 1-8; the addition amount of the catalyst is 0.01-0.2 g/g based on the mass of the toluene derivative shown in the formula (I);
Figure BDA0001700418490000031
in formula (I) or formula (II):
r is hydrogen, methyl, methoxy, cyano, fluorine, chlorine, bromine, iodine or phenyl.
Further, the method of claim 1, wherein: the organic solvent is acetic acid, acetonitrile, N-dimethylformamide or N, N-dimethylacetamide.
Still further, the amount of the organic solvent added is 1 to 3ml/mmol based on the amount of the toluene derivative represented by the formula (I).
Further, the ratio of the amounts of the toluene derivative represented by the formula (I), hydrogen peroxide, ligand, and ammonia source is preferably 1: 0.1-0.2: 0.1-0.2: 1 to 6.
Furthermore, the adding amount of the catalyst is 0.1-0.2 g/g based on the mass of the toluene derivative shown in the formula (I).
Further, the reaction temperature is preferably 100-150 ℃, and the working pressure is preferably 0.5-1.5 MPa.
Further, the post-treatment method of the reaction mixed liquid comprises the following steps: and after the reaction is finished, extracting the obtained reaction mixed liquid by using ethyl acetate, combining organic phases, washing the organic phases for 1-3 times by using saturated saline solution, drying, and distilling under reduced pressure to remove the solvent to obtain the target product.
The catalyst nano ferrovanadium is prepared by the following method:
(1) heating industrial vanadium pentoxide flaky crystals and iron nitrate heptahydrate in a high-temperature box-type resistance furnace to 800 ℃ for melting, preserving heat for 10-30 min, taking out, putting into distilled water for water quenching, electrically stirring to form sol, and aging the sol to obtain ferrovanadium gel; the mass ratio of the vanadium pentoxide flaky crystal to the ferric nitrate heptahydrate is 1: 1; the adding amount of the distilled water is 25-40 mL/g based on the total mass of the vanadium pentoxide and the ferric nitrate;
(2) fully mixing diatomite, sulfur powder and potassium sulfate, grinding for 30min, adding ferrovanadium gel, rolling for 30min, pressing into strips of 3-5 cm by using an automatic catalyst extrusion molding machine, drying at room temperature for 12-18 h, then keeping the constant temperature of 70-80 ℃ in a constant-temperature drying oven for 12-15 h, finally calcining at 550-600 ℃ for not less than 5h, and keeping the oxidizing atmosphere to obtain the ferrovanadium catalyst; the mass ratio of the diatomite, the sulfur powder, the potassium sulfate and the ferrovanadium gel is 100: 8: 17: 10.
the self-made ferrovanadium catalyst can be used for researching the morphology of the catalyst and the microstructure of the nano ferrovanadium catalyst by a Transmission Electron Microscope (TEM) and a Scanning Electron Microscope (SEM) respectively, and an intelligent particle strength tester is used for testing the mechanical strength of the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) realizes the conversion of methyl aromatic hydrocarbon to aromatic nitrile compound under mild condition, has high reaction yield and has industrial application prospect.
(2) The oxygen is used as a clean oxidant, so that the generation of toxic and harmful byproducts to the environment in the reaction process of the traditional inorganic salt oxidant is reduced, and the method is an environment-friendly strategy.
(3) Ammonia water or ammonia gas is used as a nitrogen source, the utilization rate of nitrogen atoms is high, and the atom economy is good.
(IV) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
preparing a nano ferrovanadium catalyst: 15g of industrial V are taken2O5Crystal, 15gFe (NO)3)3·6H2And putting the O crystal into a crucible, heating and melting the O crystal in a high-temperature box type resistance furnace at 800 ℃, keeping the temperature for 10min, taking out the O crystal, and adding the O crystal into 500mL of distilled water for water quenching. Forming sol after electric stirring, and converting the sol into gel after aging. Fully mixing 150g of diatomite, 12g of sulfur powder and 25g of potassium sulfate, grinding for 30min, adding 20g of gel, grinding for 30min again, pressing the sol into strips of 5cm by using an automatic catalyst extrusion molding machine, drying for 15h at room temperature,then keeping the temperature of the mixture in a constant-temperature drying oven at 80 ℃ for 12 hours, and then roasting the mixture at 550 ℃ for 5 hours in an oxygen atmosphere to obtain 200g of the nano ferrovanadium catalyst. Catalyst analysis and characterization: particle size analysis was performed using a laser particle sizer, and the V in the colloid was studied using a Transmission Electron Microscope (TEM) and a Scanning Electron Microscope (SEM), respectively2O5、Fe(NO3)3·6H2The morphology of the O particles and the microstructure of the nano ferrovanadium catalyst, and the mechanical strength of the catalyst is tested by an intelligent particle strength tester. The appearance of the particles in the colloid observed by a transmission electron microscope has two shapes of needle and sphere, and the sizes of the particles are in the nanometer level. The vanadium iron particles in the catalyst can be observed by a Scanning Electron Microscope (SEM) to be about 50-150 nm.
Example 1: preparation of benzonitrile
Figure BDA0001700418490000051
Preparation of benzonitrile: in a 500mL autoclave, 18g of toluene, 0.18g of nano ferrovanadium, 1mL (0.05 equivalent) of hydrogen peroxide, 3.12g (0.1 equivalent) of 2, 2' -bipyridine, 50mL (8 equivalents) of 28% ammonia water, and 100mL of N, N-dimethylformamide were added to the system, and the system was replaced with an oxygen atmosphere at a pressure of 1atm, and stirred at 80 ℃ for reaction for 6 hours. After the reaction is finished, adding 200mL of water into the reaction system, mixing, adding 200mL of ethyl acetate, extracting the water layer twice with ethyl acetate (200mL x 2), combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, and removing the solvent by reduced pressure distillation to obtain 15g of the aromatic nitrile compound product, namely benzonitrile with the yield of 75%.
1H NMR:(400MHz,Chloroform-d)δ＝7.62(d,J＝7.2Hz,2H),7.57(d, J＝8.2Hz,2H),7.48(t,J＝6.2Hz,1H).
Example 2: preparation of p-methylbenzonitrile
Figure BDA0001700418490000061
Preparation of p-methylbenzonitrile: in a 500mL autoclave, 21g of p-xylene, 2.1g of nano ferrovanadium, 2mL (0.1 equivalent) of hydrogen peroxide, 3.12g (0.1 equivalent) of 2, 2' -bipyridine, 50mL (8 equivalents) of 28% ammonia water, and 200mL of N, N-dimethylformamide were added to the system, and the system was replaced with an oxygen atmosphere at a pressure of 5atm and reacted at 80 ℃ for 6 hours. After the reaction is finished, adding 200mL of water into the reaction system, mixing, adding 200mL of ethyl acetate, extracting the water layer twice with ethyl acetate (200mL x 2), combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, and removing the solvent by reduced pressure distillation to obtain 20g of the aromatic nitrile compound product, namely the p-methylbenzonitrile, with the yield of 87%.
1H NMR:(400MHz,Chloroform-d)δ＝7.53(d,J＝8.2Hz,2H),7.27(d, J＝8.2Hz,2H),2.42(s,3H).
Example 3: preparation of m-methoxybenzonitrile
Figure BDA0001700418490000071
Preparation of m-methoxybenzonitrile: in a 500mL autoclave, 24g of m-methyl anisole, 0.48g of nano ferrovanadium, 2mL (0.1 equivalent) of hydrogen peroxide and 1.56g (0.05 equivalent) of 2, 2' -bipyridine are added into the system, the system is vacuumized, 300mL of N, N-dimethylformamide is added, ammonia gas is introduced to 0.2MPa, then oxygen gas is introduced to 0.4MPa, and the reaction is carried out for 6h at 80 ℃. After the reaction is finished, adding 200mL of water into the reaction system, mixing, adding 200mL of ethyl acetate, extracting the water layer twice with ethyl acetate (200mL x 2), combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, and removing the solvent by reduced pressure distillation to obtain 25g of the aromatic nitrile compound product, namely the m-methoxybenzonitrile, with the yield of 93%.
1H NMR:(400MHz,Chloroform-d)δ＝7.57-7.53(m,2H),7.03-6.98(m, 2H),3.93(s,3H).
Example 4: preparation of m-bromobenzonitrile
Figure BDA0001700418490000072
Preparation of m-bromobenzonitrile: in a 500mL autoclave, 34g of m-bromotoluene, 6.8g of nano ferrovanadium, 2mL (0.1 equivalent) of hydrogen peroxide, 1.58g (0.1 equivalent) of pyridine, 19.2g (1 equivalent) of ammonium carbonate, and 200mL of acetic acid were added to the system, and the system was replaced with an oxygen atmosphere at 15atm and reacted at 100 ℃ for 10 hours. After the reaction was completed, hydrogen peroxide was removed by saturated sodium persulfate, and acetic acid was distilled off under reduced pressure. And adding 100mL of water into the rest reaction solution, mixing, adding 200mL of ethyl acetate for extraction, extracting the water layer twice with ethyl acetate (200mL by 2), combining organic phases, washing the organic phases once with saturated saline, drying the organic phases with anhydrous sodium sulfate, and removing the solvent by distillation under reduced pressure to obtain 29g of the aromatic nitrile compound, namely the m-bromobenzonitrile, with the yield of 80%.
1H NMR:(400MHz,Chloroform-d)δ＝7.79(t,J＝1.6Hz,1H), 7.76-7.74(m,1H),7.62-7.60(m,1H),7.37(t,J＝8.0Hz,1H).
Example 5: preparation of p-iodobenzonitrile
Figure BDA0001700418490000081
Preparation of p-iodobenzonitrile: in a 500mL autoclave, 44g of p-iodotoluene, 4.4g of nano ferrovanadium, 2mL (0.1 equivalent) of hydrogen peroxide, 1.58g (0.1 equivalent) of pyridine, 31.6g (2 equivalents) of ammonium hydrogencarbonate and 200mL of acetic acid were added to the system, and the system was replaced with an oxygen atmosphere at 15atm and reacted at 120 ℃ for 10 hours. After the reaction was completed, hydrogen peroxide was removed by saturated sodium persulfate, and acetic acid was distilled off under reduced pressure. Adding 200mL of water into the remaining reaction solution, mixing, adding 200mL of ethyl acetate, extracting the water layer twice with ethyl acetate (200mL 2), combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, and distilling under reduced pressure to remove the solvent to obtain 42g of the aromatic nitrile compound product, namely, p-iodobenzonitrile, with the yield of 92%.
1H NMR:(400MHz,Chloroform-d)δ＝7.85(d,J＝8.4Hz,2H),7.37(d, J＝8.4Hz,2H).
Example 6: preparation of p-chlorobenzonitrile
Figure BDA0001700418490000091
Preparation of p-chlorobenzonitrile: in a 500mL autoclave, 25g of p-chlorotoluene, 2.5g of nano ferrovanadium, 4mL (0.2 equivalent) of hydrogen peroxide, 3.16g (0.2 equivalent) of pyridine, 26.4g (1 equivalent) of ammonium sulfate, and 200mL of acetonitrile were charged into the system, and the system was replaced with an oxygen atmosphere at 15atm and reacted at 150 ℃ for 24 hours. After completion of the reaction, hydrogen peroxide was removed by saturated sodium persulfate, and acetonitrile was removed by distillation under reduced pressure. Adding 200mL of water into the remaining reaction solution, mixing, adding 200mL of ethyl acetate, extracting the water layer twice with ethyl acetate (200mL x 2), combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, and distilling under reduced pressure to remove the solvent to obtain 22g of the aromatic nitrile compound product p-chlorobenzonitrile with the yield of 82%.
1H NMR:(400MHz,Chloroform-d)δ＝7.61(d,J＝8.6Hz,2H),7.47(d, J＝8.6Hz,2H).
Example 7: preparation of p-fluorobenzonitrile
Figure BDA0001700418490000092
Preparation of p-fluorobenzonitrile: in a 500mL high-pressure autoclave, 22g of p-fluorotoluene, 4.4g of nano ferrovanadium, 5mL (0.2 equivalent) of hydrogen peroxide, 7.2g (0.2 equivalent) of 1, 10-phenanthroline, 21.2g (2 equivalent) of ammonium chloride and 200mL of acetonitrile are added into the system, the system is replaced by an oxygen atmosphere, the pressure is 15atm, and the reaction is carried out for 24 hours at 180 ℃. After completion of the reaction, hydrogen peroxide was removed by saturated sodium persulfate, and acetonitrile was removed by distillation under reduced pressure. And adding 200mL of water into the rest reaction solution, mixing, adding 200mL of ethyl acetate for extraction, extracting the water layer twice with ethyl acetate (200mL by 2), combining organic phases, washing the organic phases once with saturated saline, drying the organic phases with anhydrous sodium sulfate, and removing the solvent by reduced pressure distillation to obtain 19g of the aromatic nitrile compound, namely the p-fluorobenzonitrile, with the yield of 78%.
1H NMR:(400MHz,Chloroform-d)δ＝7.71-7.67(m,2H),7.21-7.16(m, 2H).
Example 8: preparation of 4-cyanobiphenyl
Figure BDA0001700418490000101
Preparation of 4-cyanobiphenyl: in a 500mL autoclave, 34g of 4-methylbiphenyl, 6.8g of nano ferrovanadium, 2mL (0.1 equivalent) of hydrogen peroxide, 1.8g (0.05 equivalent) of 1, 10-phenanthroline, 25.2g (2 equivalent) of ammonium formate and 100mL of N, N-dimethylacetamide are added into the system, and the system is replaced into an oxygen atmosphere at a pressure of 5atm and reacted at 80 ℃ for 6 hours. After the reaction is finished, adding 200mL of water into the reaction system, mixing, adding 200mL of ethyl acetate, extracting the water layer twice with ethyl acetate (200mL x 2), combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, and removing the solvent by reduced pressure distillation to obtain 31g of the aromatic nitrile compound product 4-cyanobiphenyl with the yield of 88%.
1H NMR:(400MHz,Chloroform-d)δ＝7.72-7.66(m,4H),7.59-7.57(m, 2H),7.49-7.25(m,3H).
Example 9: preparation of terephthalonitrile
Figure BDA0001700418490000111
Preparation of terephthalonitrile: in a 500mL high-pressure autoclave, adding 23g of p-tolunitrile, 4.6g of nano ferrovanadium, 4mL (0.2 equivalent) of hydrogen peroxide, 3.6g (0.1 equivalent) of 1, 10-phenanthroline, 30.8g (2 equivalent) of ammonium acetate and 300mL of N, N-dimethylacetamide into the system, replacing the system with oxygen atmosphere, reacting at the pressure of 15atm and at the temperature of 180 ℃ for 24 hours. After the reaction is finished, adding 200mL of water into the reaction system, mixing, adding 200mL of ethyl acetate, extracting the water layer twice with ethyl acetate (200mL by 2), combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, and removing the solvent by reduced pressure distillation to obtain 17g of the aromatic nitrile compound product terephthalonitrile with the yield of 66%.
1H NMR:(400MHz,Chloroform-d)δ＝7.81(s,4H)。

Claims (7)

1. A method for preparing aromatic nitrile compounds is characterized in that: the method comprises the following steps:
taking a toluene derivative shown as a formula (I) as a raw material, taking nano ferrovanadium as a catalyst, taking hydrogen peroxide as a cocatalyst, adding a ligand and an ammonia source, reacting in an organic solvent at a temperature of 80-180 ℃ in an oxygen atmosphere under a working pressure of 0.1-1.5 MPa for 6-24 hours to obtain a reaction mixed solution, and carrying out post-treatment to obtain a target product, namely an aromatic nitrile compound shown as a formula (II); the ligand is pyridine, 2' -bipyridine or 1, 10-phenanthroline; the ammonia source is ammonia gas, ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium chloride, ammonium formate, ammonium acetate or 28% ammonia water by mass fraction; the quantity ratio of the toluene derivative shown in the formula (I), hydrogen peroxide, ligand and ammonia source is 1: 0.05-0.2: 0.05-0.2: 1-8; the addition amount of the catalyst is 0.01-0.2 g/g based on the mass of the toluene derivative shown in the formula (I);
Figure FDA0002760757560000011
in formula (I) or formula (II):
r is hydrogen, methyl, methoxy, cyano, fluorine, chlorine, bromine, iodine or phenyl;
the nano ferrovanadium is prepared by the following method:
(1) heating industrial vanadium pentoxide flaky crystals and iron nitrate heptahydrate in a high-temperature box-type resistance furnace to 800 ℃ for melting, preserving heat for 10-30 min, taking out, putting into distilled water for water quenching, electrically stirring to form sol, and aging the sol to obtain ferrovanadium gel; the mass ratio of the vanadium pentoxide flaky crystal to the ferric nitrate heptahydrate is 1: 1; the adding amount of the distilled water is 25-40 mL/g based on the total mass of the vanadium pentoxide and the ferric nitrate;
(2) fully mixing diatomite, sulfur powder and potassium sulfate, grinding for 30min, adding ferrovanadium gel, rolling for 30min, pressing into strips of 3-5 cm by using an automatic catalyst extrusion molding machine, drying at room temperature for 12-18 h, then keeping the constant temperature of 70-80 ℃ in a constant-temperature drying oven for 12-15 h, finally calcining at 550-600 ℃ for not less than 5h, and keeping the oxidizing atmosphere to obtain the nano ferrovanadium; the mass ratio of the diatomite, the sulfur powder, the potassium sulfate and the ferrovanadium gel is 100: 8: 17: 10.
2. the method of claim 1, wherein: the organic solvent is acetic acid, acetonitrile, N-dimethylformamide or N, N-dimethylacetamide.
3. The method of claim 1, wherein: the addition amount of the organic solvent is 1-3 ml/mmol based on the amount of the toluene derivative shown in the formula (I).
4. The method of claim 1, wherein: the quantity ratio of the toluene derivative shown in the formula (I), hydrogen peroxide, ligand and ammonia source is 1: 0.1-0.2: 0.1-0.2: 1 to 6.
5. The method of claim 1, wherein: the addition amount of the catalyst is 0.1-0.2 g/g based on the mass of the toluene derivative shown in the formula (I).
6. The method of claim 1, wherein: the reaction temperature is 100-150 ℃, and the working pressure is 0.5-1.5 MPa.
7. The method of claim 1, wherein: the post-treatment method of the reaction mixed liquid comprises the following steps: and after the reaction is finished, extracting the obtained reaction mixed liquid by using ethyl acetate, combining organic phases, washing the organic phases for 1-3 times by using saturated saline solution, drying, and distilling under reduced pressure to remove the solvent to obtain the target product.
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CN110841702B (en) * 2019-11-12 2022-06-17 常州大学 Preparation method of catalyst for synthesizing aromatic nitrile and synthesis method of aromatic nitrile
CN114426502B (en) * 2020-10-13 2024-02-09 中国石油化工股份有限公司 Process for the preparation of nitriles
CN112939811B (en) * 2021-01-27 2022-05-17 三峡大学 Preparation method of aromatic nitrile compound
CN115215764B (en) * 2022-07-11 2023-12-08 浙大宁波理工学院 Preparation method of deuterated aromatic nitrile compound
CN115322116B (en) * 2022-07-27 2023-05-23 浙江工业大学 Preparation process of nitrile compound

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