CN115368243B - Gradient oxygen doped MoS 2 Application in catalyzing C-N coupling reaction - Google Patents

Gradient oxygen doped MoS 2 Application in catalyzing C-N coupling reaction Download PDF

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CN115368243B
CN115368243B CN202211039770.8A CN202211039770A CN115368243B CN 115368243 B CN115368243 B CN 115368243B CN 202211039770 A CN202211039770 A CN 202211039770A CN 115368243 B CN115368243 B CN 115368243B
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杨福
董雪雪
刘阳
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Jiangsu University of Science and Technology
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Abstract

The application discloses a gradient oxygen doped MoS 2 The method is applied to catalyzing C-N coupling reaction, wherein the C-N coupling reaction is a process of preparing N-aromatic amine by taking a nitro compound as a reaction substrate and carrying out heterogeneous catalysis in the presence of a boric acid compound and a reducing agent. The advantages are as follows: (1) Under the condition of thermal driving or room temperature light radiation, the nitrogen (hetero) aromatic amine can be synthesized by respectively carrying out heterogeneous catalysis on the C-N coupling reaction; (2) The method has a substrate expansion effect of high-efficiency synthesis of a wide target product in a series of substituent nitrobenzene compound reduction coupling reactions; (2) Oxygen doped MoS 2 Compared with the initial 2H phase MoS 2 The reaction activity is obviously improved; (3) Oxygen modification and original MoS 2 Further improvement of catalytic activity after the reaction and oxygen modified MoS can be obtained 2 Compared with the initial MoS 2 Has higher yield of N-aromatic amine; (4) In the C-N coupling reaction, the light radiation reaction and the thermocatalysis can be carried out in one reactor, and the method is simple and convenient to operate and wide in universality.

Description

Gradient oxygen doped MoS 2 Application in catalyzing C-N coupling reaction
Technical Field
The application belongs to the technical field of heterogeneous organic catalysis, and relates to a method for enhancing the photocatalytic and thermocatalytic synthesis efficiency of N-aromatic amine, in particular to gradient oxygen doped MoS 2 In the catalysis of C-N couplingUse in reactions.
Background
N-arylamine compounds are important intermediates in the fields of petrochemical industry, rubber industry, fine chemical synthesis, drug development, dye preparation and the like. The organic conversion of simple starting materials into complex N-arylamine compounds by catalytic techniques has attracted considerable attention from researchers over the last decades. At present, complex metal organic complexes, phosphine-rich complexes, noble metals and the like are mostly used as catalysts for N-arylamine synthesis reactions, for example: pd/AlO (OH) reported by Sundaram et al (Catal Lett.,2017,147,2619-2629) catalyzes the coupling of bromobenzene with p-toluidine at 120 ℃. One organic Ni catalyzed and photo-promoted aryl halide reported by Xue et al (Angew. Chem. Int. Ed.,2021,60,5230-5234) was coupled with C-N of nitroaromatics under ultraviolet light at 70 ℃. Chinese patent CN108373416a discloses a method for synthesizing diarylamine by light/nickel synergistic catalysis, which comprises the following steps: under the nitrogen atmosphere, adding bromoarene and aromatic amine into an organic solvent, then sequentially adding nickel salt, BODIPY organic photosensitizer, organic alkali and additive, raising the temperature of the reaction solution to 50-80 ℃, reacting for 12-40 h under the irradiation of visible light, and separating to obtain the diaryl amine.
Compared with a homogeneous catalyst, the heterogeneous catalyst has the characteristics of easy separation, high stability, long cycle life, environmental friendliness, economy, high efficiency and the like, and is a research trend of catalyzing organic conversion. In recent years, transition metal heterogeneous catalysis has been demonstrated to successfully build N-aryl amines by C-N coupling reactions, providing a greener approach to N-aryl amine synthesis. For example, alpha-MoO reported by Yang et al (Green chemistry,2022,24,4012-4025) 3 Heterogeneous catalytic synthesis of nanosheets in C-N coupling reactions reveals that under thermal or optical drive, the coordinated oxygen atom on the molybdenum site can be abstracted by triphenylphosphine moiety, then bonded to nitro compounds, and further coupled to boric acid compounds to N-arylamine compounds. Although heterogeneous catalysts have great advantages in terms of separation and recovery of the catalyst, there are fewer cases of highly efficient heterogeneous active catalysts in reductive coupling reactions for nitroaromatics, and in addition, current reports existIn the research work, the reactivity and selectivity of heterogeneous catalysts in reaction substrates with specific substituents are still relatively low, and the popularization of industrial application is still limited. Therefore, aiming at the reaction of synthesizing the nitrogen aromatic amine by reducing C-N coupling of nitroaromatic hydrocarbon, the heterogeneous industrial prospect catalyst with excellent catalytic activity is developed, so that the efficient formation of C-N bonds is of great significance.
Disclosure of Invention
The technical problems to be solved are as follows: in order to overcome the reaction inertia or activity deficiency of active atoms in the two-dimensional heterogeneous catalytic material surface, a heterogeneous catalyst which can simultaneously perform thermocatalysis and photocatalysis C-N reduction coupling reaction and obviously enhance the reaction activity is obtained; the application enables MoS to be realized through programmed temperature control 2 The nano-sheet carries out gradient oxygen doping in the crystal lattice to lead to the deformation of the crystal lattice stress and in-plane Mo position to form MoO 3 MoS (MoS) 2 The intergrowth phase interface of the oxygen dopant and the intergrowth is correspondingly used to catalyze the C-N reduction coupling reaction.
The technical scheme is as follows: gradient oxygen doped MoS 2 Use in catalyzing C-N coupling reactions.
Preferably, the C-N coupling reaction is a process of preparing N-aromatic amine by using a nitro compound as a substrate and in the presence of a boric acid compound and a reducing agent through catalysis.
Further, the specific steps of the C-N coupling reaction are as follows:
s1, mixing nitro compound with the mass ratio of 1:0.05-0.7:1-4:4-10 with gradient oxygen doped MoS 2 Adding boric acid compound and reducing agent into a reactor with a vacuum valve, and adding an organic solvent which is 5-12 times of the total mass of the raw materials into the reactor;
s2, connecting the reactor to a gas exchange device through a double-joint pipe, and adopting inert gas to exchange air in the reactor to obtain reaction mother liquor; wherein the inert gas is nitrogen, helium, neon or argon.
S3, photo-catalytic reaction or thermo-catalytic reaction
Photocatalytic reaction: placing the reactor of S2 under a light source with the wavelength of 200-800 nm, wherein the light source surrounds the reactor in a surrounding manner, the illumination distance is 5-50cm, and continuously stirring for 6-24 h by using mechanical stirring to obtain N-arylamine;
and (3) performing thermocatalytic reaction: and (3) placing the reactor of the S2 in an oil bath, wherein the temperature of the oil bath is 40-120 ℃, and continuously stirring for 6-24 hours to obtain the N-aromatic amine.
The yield of the N-aromatic amine prepared by the method can be calculated by an internal standard-NMR quantitative or column chromatography method, wherein the internal standard is selected from any one of 4-fluorotoluene, 1,3, 5-trimethoxybenzene and tetraethoxysilane, and the addition amount of the internal standard is 0.3-1.5 times of that of the nitro compound.
Preferably, the nitro compound is methyl 4-nitrobenzoate, 2-methoxy-5 nitropyridine, 4-fluoronitrobenzene, 3-bromonitrobenzene, 4-chloronitrobenzene, 4-methylnitrobenzene, 4-methoxynitrobenzene, methyl 4-nitrobenzenesulfonate, 4-ethylnitrobenzene, 2-chloro-5-nitropyridine or 4-nitrobenzotrifluoride.
Preferably, the boric acid compound is phenylboric acid, 4-methoxyphenylboric acid, 4-fluorophenylboric acid, isopropylboric acid, 6-fluoropyridine-3-boric acid, 4-methylthiophenylboric acid, or cyclopropylboric acid.
Preferably, the reducing agent is at least one of triphenylphosphine, hydrazine hydrate, sodium borohydride and phenylsilane.
Preferably, the organic solvent is at least one of dichloromethane, ethanol, dimethyl sulfoxide, toluene, cyclopentyl methyl ether, tetrahydrofuran, acetonitrile and N-N dimethylformamide.
Preferably, the light source is a fluorescent lamp, an incandescent lamp, a xenon lamp or an LED lamp.
Preferably, the gradient oxygen is doped with MoS 2 The preparation method comprises the following steps:
(1) Preparing an aqueous solution or an ethanol solution containing molybdenum salt and a sulfur source, wherein the concentration of the molybdenum salt is 0.03-0.15M, and the mass ratio of the molybdenum salt to the sulfur source is 1:0.2-3.5;
(2) Placing the solution in the step (1) into a reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the reaction temperature is 160-230 ℃ and the reaction time is 12-48 h, centrifuging and drying the product after the reaction is finished to obtain MoS 2 A nanoplatelet precursor;
(3) Heat-treating the precursor in the step (2) in an oxygen-containing atmosphere, wherein the heat-treatment temperature is 300-500 ℃ and the time is 0.5-5 h, so as to obtain the oxygen-doped MoS with different gradients 2 。
Preferably, the molybdenum salt is phosphomolybdic acid, ammonium molybdate, ammonium dimolybdate, ammonium heptamolybdate or ammonium molybdate tetrahydrate; the sulfur source is thiourea, thioacetamide, cysteine, glutathione or sodium sulfide.
The principle of the symbiotic phase catalytic C-N coupling reaction is as follows: the application adopts a gradient oxygen injection method to regulate and control two-dimensional MoS 2 The electronic structure and coordination environment of Mo position in the nano sheet obviously reconstruct MoS 2 Activity of Mo center on two-dimensional inert basal plane. Under the condition of thermal driving or optical driving, the reducing agent can partially abstract the coordination atom on the Mo position, then form a bond with the nitro compound, and couple with the boric acid compound to generate the N-aromatic amine.
The beneficial effects are that: (1) The material can be used for synthesizing nitrogen (hetero) aromatic amine by heterogeneous catalysis of C-N coupling reaction under the conditions of thermal driving or room temperature light radiation; (2) The material has a substrate expansion effect of high-efficiency synthesis of a wide target product in a series of substituent nitrobenzene compound reduction coupling reactions; (2) Oxygen doped MoS 2 Compared with the initial 2H phase MoS 2 The method has the advantages that the reaction activity is obviously improved, and the improvement of the yield of the N-aromatic amine after oxygen doping is particularly realized; (3) Oxygen modification and original MoS 2 Further improvement of catalytic activity after the reaction and oxygen modified MoS can be obtained 2 Compared with the initial MoS 2 Has higher yield of N-aromatic amine; (4) In the C-N coupling reaction, the light radiation reaction and the thermocatalysis can be carried out in one reactor, and the method is simple and convenient to operate and wide in universality.
Drawings
FIG. 1 is a gradient oxygen doped MoS obtained by the preparation of example 1 2 Wherein (a), (b) are MoS 2 (c) and (d) are MoS 2-x O x -1H, (e) and (f) are MoS 2-x O x -2H, (g), (H) is MoS 2-x O x -Transmission Electron Microscopy (TEM) of 3H;
FIG. 2 is a real worldGradient oxygen doped MoS prepared in example 1 2 Is a XRD pattern of (C).
Detailed Description
The following examples further illustrate the application but are not to be construed as limiting the application. Modifications and substitutions to the method, steps or conditions of the application without departing from the spirit and nature of the application are intended to be within the scope of the application.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
Example 1 preparation of intergrowth phase
The method comprises the following specific steps:
(1) Preparing 30mL of ammonium molybdate tetrahydrate aqueous solution with the concentration of 0.3M, and adding a certain amount of thiourea, wherein the mass ratio of the ammonium molybdate tetrahydrate to the thiourea is 1:2; stirring for 30min until the solute is completely dissolved.
(2)MoS 2 Preparing a nanosheet precursor, namely placing the reactant in the step 1 into a reaction kettle with 50mL polytetrafluoroethylene lining, performing hydrothermal reaction at 220 ℃ for 18h, repeatedly cleaning and centrifugally separating a reaction product by deionized water and ethanol after the reaction is finished, placing the precursor product into a vacuum drying oven at 60 ℃ for 12h, and drying to obtain MoS 2 A nanoplatelet precursor.
(3)MoS 2-x O x Preparation of nanosheets MoS is prepared 2 The nanosheet precursors are placed in an air atmosphere tube furnace, the temperature is raised to 300 ℃ at 1 ℃/min, and the temperature is kept for 1h/2h/3h respectively, and the obtained samples are respectively marked as MoS 2-x O x -1H，MoS 2-x O x -2H，MoS 2-x O x -3H。
Fig. 1 (a-h) TEM images show direct and clear evidence of fine morphology changes during molybdenum sulfide "gradient oxygen injection". It can be observed that MoS 2 The sample has a typical flower-like structure composed of nano sheets, and the appearance of the sample has a certain change trend along with the extension of the treatment time. Wherein MoS 2-x O x -1H and initial MoS 2 Compared with the appearance of only approximately uniform morphology, the oxygen is probably only injected into MoS 2 Surface withoutThere are serious structural injuries caused. Prolonged heat treatment breaks the typical MoS 2 The appearance of the nanoflower is that some blocky nanoflakes appear, which accords with MoO 3 The characteristics of the nanoplatelets further reveal the formation of intergrowth. FIG. 2 Wide-angle XRD technique for MoS 2 And MoS 2-x O x The series of crystalline phases were characterized. MoS (MoS) 2-x O x Diffraction peak distribution of-1H with MoS 2 Similarly, describe MoS 2-x O x No molybdenum oxide crystals were present in 1H. At this time, it is presumed that the oxygen atom only slightly enters MoS 2 Does not cause the formation of a new phase structure. Calculation of MoS using the Shelle formula 2-x O x -1H and MoS 2 The average grain sizes of (2) are 4.02nm and 4.12nm, respectively, suggesting a weak change in morphology and size structure, which is also confirmed by the TEM results of FIG. 1. MoS is carried out 2-x O x -2H and MoS 2-x O x Comparing XRD spectra of-3H with corresponding standard cards, it was found that both catalysts had two types of crystalline phases, moS respectively 2 (JCPDS No. 47-1320) and alpha-MoO 3 (JCPDS No. 37-1492), which is MoS 2 MoS formed by excessive injection of oxygen 2 And alpha-MoO 3 provides typical evidence.
EXAMPLE 2 analysis of the Performance of gradient oxygen doped MoS2 obtained in example 1
1. Catalytic performance
8 parts of 40.5mg of 3-bromonitrobenzene, 42mg of 4-fluorobenzeneboronic acid and 157mg of triphenylphosphine are respectively weighed and respectively placed in eight 10ml reaction tubes with vacuum valves, the reaction tubes are marked as reactions 1 to 8 in sequence, and 24mg of MoS is added into the reaction tubes 1 and 2 2 24mg MoS was added to the reaction 3, 4 tubes 2-x O x -1H, 24mg MoS was added to the reaction 5, 6 tubes 2-x O x -2H, 24mg MoS was added to the reaction 7, 8 tubes 2-x O x And adding methylene dichloride solution into the eight reaction tubes according to 8 times of the total mass, and then uniformly mixing by ultrasonic. The reaction tube was then connected to a double row of tubes filled with nitrogen, the air in the reaction tube was evacuated and filled with 1bar nitrogen by a continuous operation of vacuum-aeration with nitrogen.
Photocatalytic reaction: and placing the reaction tube under an LED lamp with the wavelength of 365nm, and continuously stirring for 24 hours at the illumination distance of 5-50cm to obtain the N-aromatic amine. And (3) performing thermocatalytic reaction: the reaction tube was placed in an oil bath at 100℃and continuously stirred for 24 hours to give N-arylamine. The results are shown in Table 1, wherein "%" is expressed as a percentage of the actual yield of the product to the theoretical yield:
TABLE 1 gradient oxygen doped MoS 2 Photocatalytic and thermocatalytic performance results
2. Cycle test
Weighing 2 parts of 40.5mg of 3-bromonitrobenzene, 42mg of 4-fluorobenzeneboronic acid and 157mg of triphenylphosphine respectively, placing the materials into eight 10ml reaction tubes with vacuum valves, respectively marking the materials as reaction 1 and reaction 2, and adding 24mg of MoS into the reaction 1 tube 2 24mg MoS was added to the reaction 2 tube 2-x O x -3H, and adding toluene solution to both reaction tubes at 8 times of the total mass, and then mixing uniformly by ultrasound. The reaction tube was then connected to a double row of tubes filled with nitrogen, the air in the reaction tube was evacuated and filled with 1bar nitrogen by a continuous operation of vacuum-aeration with nitrogen. Then the reaction tube 1 and the reaction tube 2 are placed in an oil bath pot with the temperature of 100 ℃ and continuously stirred for 24 hours to obtain the N-aromatic amine. After the reaction was completed, the collected solution was subjected to nuclear magnetic resonance spectroscopy, and the reaction yield was calculated. The catalyst is then separated from the reaction mother liquor by centrifugation, washed and dried for the next reaction cycle. The specific results are shown in Table 2, wherein "%" is expressed as a percentage of the actual yield of the product to the theoretical yield:
TABLE 2 gradient oxygen doped MoS 2 Results of cyclic test
As shown in Table 2, moS 2-x O x The catalytic efficiency of the 3H after four reactions is still91% can be achieved, which indicates that the prepared catalyst has better stability. In addition, after the second reaction, the catalytic efficiency increased from 77% to 95%, which was comparable to MoS during the reaction 2-x O x Partial S atoms of 3H are related to the substitution of active oxygen after removal by the reducing agent. To better understand the mechanism of activity enhancement of the catalyst during the reaction cycle, for MoS 2 The cyclic reaction was carried out and it was found that in the second reaction cycle, moS 2 The activity enhancement of (a) was increased from the initial 18% yield to 45%. However, it should be noted that the MoS resulting from the reaction reconstruction 2 The enhancement of activity was not sustainable, indicating that only part of S present during the reaction could be replaced by oxygen.
3. Applicability(s)
Similar to the above experiment, only the types of nitro compound and boric acid compound were changed, and the remaining conditions were kept the same, and the expansion of the substrate range as shown in table 3 was performed to further explain the applicability of the synthetic catalyst.
TABLE 3 gradient oxygen doped MoS 2 Suitability test results

Claims (5)

1. Gradient oxygen doped MoS 2 The application in catalyzing the C-N coupling reaction is characterized in that the C-N coupling reaction is a process of preparing N-aromatic amine by catalyzing with a nitro compound serving as a substrate in the presence of a boric acid compound and a reducing agent;
the nitro compound is 4-nitrobenzoic acid methyl ester, 2-methoxy-5-nitropyridine, 4-fluoronitrobenzene, 3-bromonitrobenzene, 4-chloronitrobenzene, 4-methylnitrobenzene, 4-methoxynitrobenzene, 4-nitrobenzenesulfonic acid methyl ester, 4-ethylnitrobenzene, 2-chloro-5-nitropyridine or 4-nitrobenzotrifluoride;
the boric acid compound is phenylboric acid, 4-methoxyphenylboric acid, 4-fluorophenylboric acid, isopropylboric acid, 6-fluoropyridine-3-boric acid, 4-methylthiophenylboric acid or cyclopropylboric acid;
the reducing agent is triphenylphosphine;
gradient oxygen doped MoS 2 The preparation method comprises the following steps:
(1) Preparing an aqueous solution or an ethanol solution containing molybdenum salt and a sulfur source, wherein the concentration of the molybdenum salt is 0.03-0.15M, and the mass ratio of the molybdenum salt to the sulfur source is 1:0.2-3.5;
(2) Placing the solution in the step (1) into a reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the reaction temperature is 160-230 ℃ and the reaction time is 12-48 hours, centrifuging and drying the product after the reaction is finished to obtain MoS 2 A nanoplatelet precursor;
(3) Performing heat treatment on the precursor in the step (2) in an oxygen-containing atmosphere, wherein the heat treatment temperature is 300-500 ℃ and the time is 0.5-5 h, so as to obtain the oxygen doped MoS with different gradients 2 。
2. The use according to claim 1, characterized in that the specific steps of the C-N coupling reaction are:
s1, doping a nitro compound with a mass ratio of 1:0.05-0.7:1-4:4-10 with gradient oxygen to form MoS 2 Adding boric acid compound and reducing agent into a reactor with a vacuum valve, and adding an organic solvent which is 5-12 times of the total mass of the raw materials into the reactor;
s2, connecting the reactor to a gas exchange device through a double-joint pipe, and adopting inert gas to exchange air in the reactor to obtain reaction mother liquor;
s3, photo-catalytic reaction or thermo-catalytic reaction
Photocatalytic reaction: placing the reactor of the S2 under a light source with the light wavelength of 200-800 nm, surrounding the reactor by the light source in a surrounding manner, and continuously stirring for 6-24 hours by using mechanical stirring to obtain N-arylamine, wherein the illumination distance is 5-50 cm;
and (3) performing thermocatalytic reaction: and (3) placing the reactor of the S2 in an oil bath, wherein the temperature of the oil bath is 40-120 ℃, and continuously stirring for 6-24 hours to obtain the N-aromatic amine.
3. The use according to claim 2, wherein the organic solvent is at least one of dichloromethane, ethanol, toluene, cyclopentyl methyl ether, acetonitrile, N-N dimethylformamide.
4. Use according to claim 2, wherein the light source is a fluorescent lamp, an incandescent lamp, a xenon lamp or an LED lamp.
5. Use according to claim 1, characterized in that the molybdenum salt is phosphomolybdic acid, ammonium molybdate, ammonium dimolybdate, ammonium heptamolybdate or ammonium molybdate tetrahydrate; the sulfur source is thiourea, thioacetamide, cysteine, glutathione or sodium sulfide.
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Gradient oxygen-injecting MoS2 nanosheets catalyst boosting reductive C-N coupling of nitroarenes: Mechanistic insight into activity reconstruction;Xuexue Dong et al;Applied Surface Science;第624卷;第1-12页 *
Reductive C􀀀 N Coupling of Nitroarenes: Heterogenization of MoO3 Catalyst by Confinement in Silica;Fu Yang et al;ChemSusChem;第14卷;第3413-3421页 *
利用介孔分子筛中高度分散的Cu⁃Co 氧化物的 高效协同作用提高VOCs 的催化消除效率;杨福 等;无机化学学报;第37卷(第7期);第1322-1336页 *

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