阅读说明：本技术 一种usy分子筛负载还原金属铜催化剂的制备方法及应用 (Preparation method and application of USY molecular sieve supported reduction metal copper catalyst ) 是由 焦林郁 白瑞 刘旭娟 贾楠 杨璐源 李卓 马晓迅 于 2021-09-28 设计创作，主要内容包括：本发明公开一种USY分子筛负载还原金属铜催化剂的制备方法及应用,将USY分子筛负载还原金属铜催化剂、芳基磺酰叠氮类化合物、芳基硼酸、添加剂和溶剂加入到容器中,搅拌均匀,在空气氛围下,在25～50℃下反应1～6h,过滤,将滤液减压浓缩,得到磺酰胺。本发明在室温条件下加入所制备的催化剂,在较短时间内芳基磺酰叠氮类化合物与芳基硼酸进行偶联反应,并且达到较高产率,对于合成的USY分子筛催化剂通过过滤、干燥等处理可进行循环实验,仍然具有较高的催化活性。(The invention discloses a preparation method and application of a USY molecular sieve loaded reduced metal copper catalyst. The prepared catalyst is added at room temperature, the coupling reaction of the aryl sulfonyl azide compound and the aryl boric acid is carried out in a short time, the high yield is achieved, the synthesized USY molecular sieve catalyst can be subjected to a circulating experiment through filtration, drying and other treatments, and still has high catalytic activity.)

1. A preparation method of a USY molecular sieve supported reduced metal copper catalyst is characterized by comprising the following steps:

(1) adding Cu (NO)₃)₂·3H₂Adding O into ionized water, stirring until the O is dissolved, adding a USY type molecular sieve, stirring until the O is viscous, shaking for 1.5-2.5 h, drying, and grinding to obtain blue powder;

(2) and drying the blue powder, and calcining the dried blue powder in a hydrogen atmosphere at the temperature of 250-300 ℃ for 2.5-4 h to obtain the USY molecular sieve supported reduction metal catalyst.

2. The method for preparing a USY molecular sieve supported reduced metal copper catalyst according to claim 1, wherein Cu (NO) is₃)₂·3H₂The ratio of the O, the ionic water and the USY type molecular sieve is 1.71-2.08 g: 5-9 mL: 4-6 g.

3. The preparation method of the USY molecular sieve supported reduced metal copper catalyst according to claim 1, wherein the USY molecular sieve has a silica-alumina ratio of 1: 1-3: 1; the drying temperature is 450-600 ℃, and the drying time is 4-6 h.

4. The application of the USY molecular sieve supported reduced metal copper catalyst in the synthesis of sulfonamide according to claim 1, which is characterized in that the USY molecular sieve supported reduced metal copper catalyst, the aryl sulfonyl azide compound, the aryl boric acid, the additive and the solvent are added into a container, uniformly stirred, reacted for 1-6 hours at 25-50 ℃ in the air atmosphere, filtered, and subjected to reduced pressure concentration to obtain the sulfonamide.

5. The application of the USY molecular sieve supported reduced metal copper catalyst in the synthesis of sulfonamide according to claim 4, wherein the aryl sulfonyl azide compound is p-toluenesulfonyl azide, benzenesulfonyl azide or 2-fluorobenzenesulfonyl azide.

6. The use of the USY molecular sieve supported reduced metal copper catalyst in the synthesis of sulfonamides as described in claim 4, wherein the arylboronic acid is phenylboronic acid, 4-chlorophenylboronic acid, 4-methoxyphenylboronic acid or 3-methoxyphenylboronic acid.

7. The use of the USY molecular sieve supported reduced metal copper catalyst in the synthesis of sulfonamides as described in claim 4, wherein the additive is sodium borohydride or sodium hydride; the solvent is methanol, ethanol, acetonitrile or toluene.

8. The use of the USY molecular sieve supported reduced metal copper catalyst in the synthesis of sulfonamides as claimed in claim 4, wherein the mass ratio of arylsulfonyl azide compound to arylboronic acid is 1: 1-1: 1.5.

9. the application of the USY molecular sieve supported reduced metal copper catalyst in the synthesis of sulfonamide according to claim 4, wherein the mass ratio of the aryl sulfonyl azide compound to the additive is 1: 0.1-1: 0.5.

10. the application of the USY molecular sieve supported reduced metal copper catalyst in the synthesis of sulfonamide according to claim 4, wherein the mass ratio of the aryl sulfonyl azide compound to the USY molecular sieve supported reduced metal copper catalyst is 1: 0.18 to 1: 0.25.

Technical Field

The invention relates to the field of heterogeneous catalysis and organic fine chemical engineering, in particular to a preparation method and application of a USY molecular sieve supported reduction metal copper catalyst.

Background

The N-aryl benzene sulfonyl compound has wide practical application, is an important synthetic raw material of a plurality of medicines particularly in the aspect of medicine, has high occupation ratio particularly in antibacterial medicines, for example, N-aryl sulfonyl substances in the antibacterial medicines are first artificial sulfonyl medicines, and in addition, the N-aryl benzene sulfonyl amine compound is also widely applied to the fields of inflammation diminishing, pain relieving, tumor resisting, virus resisting, parasite resisting, epilepsy resisting, diuresis and the like. Secondly, the compound is also listed as a preferred synthetic raw material in the aspects of pesticide and material synthesis and the like.

Substances containing N elements in the nature can play an important role, and not only frequently appear in various industrial materials, but also play an important role in basic proteins of organisms and medicine composition in medicine. In the pharmaceutical industry, nearly one fifth of the drug synthesis processes involve the building reaction of the C-N bond.

The Chan-Lam coupling reaction involving sulfonyl azide compounds provides a new nitrogen source for the construction of C-N bonds, and the reaction is mostly a homogeneous system in previous reports (Roy, s.et.al.chem.commun.2016,52,1170). In recent years, many groups have studied a method for synthesizing an N-arylbenzenesulfonamide compound in which a copper complex is used as a catalyst (Reddy, a.s.et.al.org.biomol.chem.2017,15,801), but the preparation method of such a Proline-complexed copper complex (MCM-41-L-Proline-CuCl) is generally complicated, complicated in steps, and long in time.

The molecular sieve as artificially synthesized zeolite has strong adsorbability and ion exchange capacity, wherein the Y-type molecular sieve has larger pore canal and better stability, and is often used as a carrier for preparing a catalyst (such as coke forest depression, flood drying and the like, a selective preparation method of copper-catalyzed alpha-nitronaphthalene, CN201910595417.X), so that the simple, economic and efficient preparation method of the catalyst is provided and has great significance for synthesizing N-aryl benzene sulfonamide substances.

Disclosure of Invention

The invention aims to provide a preparation method and application of a USY molecular sieve supported reduction metal copper catalyst.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a USY molecular sieve supported reduced metal copper catalyst comprises the following steps:

(1) adding Cu (NO)₃)₂·3H₂Adding O into ionized water, stirring until the O is dissolved, adding a USY type molecular sieve, stirring until the O is viscous, shaking for 1.5-2.5 h, drying, and grinding to obtain blue powder;

(2) and drying the blue powder, and calcining the dried blue powder in a hydrogen atmosphere at the temperature of 250-300 ℃ for 2.5-4 h to obtain the USY molecular sieve supported reduction metal catalyst.

Further, Cu (NO)₃)₂·3H₂The ratio of the O, the ionic water and the USY type molecular sieve is 1.71-2.08 g: 5-9 mL: 4-6 g.

Further, the silicon-aluminum ratio of the USY type molecular sieve is 1: 1-3: 1; the drying temperature is 450-600 ℃, and the drying time is 4-6 h.

The USY molecular sieve supported reduced metal copper catalyst is applied to synthesis of sulfonamide, the USY molecular sieve supported reduced metal copper catalyst, an aryl sulfonyl azide compound, aryl boric acid, an additive and a solvent are added into a container, the mixture is uniformly stirred, the mixture reacts for 1-6 hours at 25-50 ℃ in the air atmosphere, the filtering is carried out, and the filtrate is decompressed and concentrated to obtain the sulfonamide.

Further, the aryl sulfonyl azide compound is p-toluenesulfonyl azide, benzenesulfonyl azide or 2-fluorobenzenesulfonyl azide.

Further, the aryl boric acid is phenylboronic acid, 4-chlorobenzene boric acid, 4-methoxyphenylboronic acid or 3-methoxyphenylboronic acid.

Further, the additive is sodium borohydride or sodium hydride; the solvent is methanol, ethanol, acetonitrile or toluene.

Further, the mass ratio of the aryl sulfonyl azide compound to the aryl boric acid is 1: 1-1: 1.5.

further, the mass ratio of the aryl sulfonyl azide compound to the additive is 1: 0.1-1: 0.5.

further, the mass ratio of the aryl sulfonyl azide compound to the USY molecular sieve loaded reduction metal copper catalyst is 1: 0.18 to 1: 0.25.

compared with the prior art, the invention has the beneficial technical effects that:

during the preparation of the USY molecular sieve supported reduction metal copper catalyst, the USY molecular sieve and Cu (NO) are adopted₃)₂·3H₂The price of O is low, and the preparation process is simple; no toxic and harmful gas substances are generated in the preparation process; the USY molecular sieve has larger pore canals, and metal can be better attached to the molecular sieve. The USY molecular sieve loaded Cu catalyst plays a catalytic role in a reaction system, and mainly passes through H in the preparation process₂The catalyst is reduced, so that the valence state of Cu in the catalyst is reduced from divalent state to monovalent state, and the larger pore channel of the catalyst can provide a place for reaction, thereby improving the reaction yield.

According to the invention, USY molecular sieve loaded Cu is used as a catalyst, sulfonyl azide substances are used as a substrate, common aryl boric acid in a Chan-Lam reaction is used as a nucleophilic reagent, and the reaction is carried out under mild conditions to synthesize the sulfonamide compound. The valence state of Cu can be changed in the reaction process, but no oxidant is needed to be added in the reaction system, oxygen in the air is enough to oxidize the Cu, and the additive sodium borohydride provides an alkaline environment for the reaction and has reducibility. The catalytic reaction system is a multi-phase system, and the USY molecular sieve loaded Cu catalyst can be recovered by simple filtration after the reaction is finished; the USY molecular sieve loaded Cu catalyst can be recycled and can be reused; by X-ray diffraction (XRD), scanning electron microscope(SEM), Fourier transform Infrared Spectroscopy (FT-IR), X-ray photoelectron Spectroscopy (XPS), N₂A series of representations are carried out on the morphology, functional groups, composition, element valence states, content and the like of the USY molecular sieve loaded Cu catalyst by means of physical adsorption and the like, and the catalyst is proved to have good stability in the reaction system.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 shows N of USY molecular sieve supported reduced metal copper catalyst (Cu/USY) in example 1 of the present invention₂A physical adsorption profile wherein (a) is a freshly prepared Cu/USY catalyst; (b) is the Cu/USY catalyst recovered after the catalytic reaction.

FIG. 2 is an SEM image of a USY molecular sieve supported reduced metal copper catalyst (Cu/USY) in example 1 of the present invention, wherein (a) is a newly prepared Cu/USY catalyst; (b) is the Cu/USY catalyst recovered after the catalytic reaction.

FIG. 3 is an XRD pattern of a USY molecular sieve supported reduced metal copper catalyst (Cu/USY) in example 1 of the present invention, wherein (a) is the USY molecular sieve and (b) is the newly prepared Cu/USY catalyst; (c) is the Cu/USY catalyst recovered after the catalytic reaction.

FIG. 4 is a FT-IR spectrum of a USY molecular sieve supported reduced metal copper catalyst (Cu/USY) in example 1 of this invention, wherein (a) is the newly prepared Cu/USY catalyst; (b) is the Cu/USY catalyst recovered after the catalytic reaction.

Detailed Description

In order to further understand the present invention, the following examples are further illustrated, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.

The preparation method of the USY molecular sieve supported reduction metal catalyst comprises the following steps:

(1) weighing 1.71-2.08 g of Cu (NO)₃)₂·3H₂Adding 5-9 mL of ionized water into a beaker, stirring until the ionized water is dissolved, and then adding 4-6 g of USY type molecular sieve, wherein the ratio of silicon to aluminum is 1: 1-3: 1, preferably, silico-aluminiumThe ratio is 1.5: 1-2: 1, stirring until the mixture is viscous, shaking for 1.5-2.5 h, drying and grinding to obtain blue powder;

(2) drying the blue powder at the temperature of 450-600 ℃ for 4-6 h, calcining at the temperature of 250-300 ℃ in a hydrogen atmosphere for 2.5-4 h, washing, filtering and drying to obtain the USY molecular sieve supported reduction metal catalyst.

The invention uses p-toluenesulfonyl azide (TsN)₃) And the derivative thereof is taken as a substrate, a USY molecular sieve loaded reduction metal copper catalyst (Cu/USY) is taken as a catalyst, arylboronic acid (phenylboronic acid and the derivative thereof) is taken as a coupling reagent, methanol, ethanol, acetonitrile or toluene and the like are taken as solvents, and under the auxiliary action of an additive, a Chan-Lam reaction is carried out, so that the N-arylbenzenesulfonamide compound is prepared. The specific process is as follows:

adding a USY molecular sieve loaded reduction metal copper (Cu/USY) catalyst, aryl sulfonyl azide, aryl boric acid, an additive and methanol into a reaction tube, uniformly stirring, reacting for a certain time at a certain temperature, filtering the whole reaction system, washing with ethyl acetate, recovering the Cu/USY catalyst, decompressing and concentrating the filtrate, and separating and purifying the residue by column chromatography to obtain a target product.

TsN under the action of a USY molecular sieve supported reduced metal copper (Cu/USY) catalyst₃Or the derivative and the arylboronic acid are subjected to coupling reaction in the catalyst pore channel and on the surface of the catalyst pore channel, and after the reaction is finished, the supported catalyst can be recovered through simple filtration. The chemical reaction equation is as follows:

wherein the aryl sulfonyl azide compound is p-toluenesulfonyl azide (TsN)₃) The aryl boric acid is phenylboronic acid, 4-chlorobenzene boric acid, 4-methoxyphenylboronic acid or 3-methoxyphenylboronic acid.

The solvent is methanol, ethanol, acetonitrile or toluene.

The additive is sodium borohydride or sodium hydride.

The mass ratio of the aryl sulfonyl azide compound to the aryl boric acid is 1: 1-1: 1.5.

the mass ratio of the aryl sulfonyl azide compound to the additive is 1: 0.1-1: 0.5.

the mass ratio of the aryl sulfonyl azide compound to the catalyst is 1: 0.18 to 1: 0.25.

the N-arylbenzenesulfonamide compound is 4-methyl-N-phenylbenzenesulfonamide, 2-fluoro-N-phenylbenzenesulfonamide, N- (4-chlorophenyl) -4-methylbenzenesulfonamide, N- (4-methoxyphenyl) -4-methylbenzenesulfonamide or N- (4-methoxyphenyl) -4-methylbenzenesulfonamide.

The invention has the following advantages: (1) the synthesis method is simple and efficient, is simple and convenient to operate, has low cost of reaction raw materials, such as p-toluenesulfonyl azide, phenylboronic acid, copper nitrate, USY molecular sieve and the like, and is favorable for application of the method in actual production; (2) the method can realize higher conversion rate and higher separation yield of the target compound only by using lower catalyst dosage; (3) the method has mild reaction conditions, and can react at room temperature by using methanol and the like as solvents; (4) the method has wide applicability, can be suitable for various substrates of different types, and can efficiently prepare corresponding target compounds. (5) The catalytic synthesis reaction is a heterogeneous system, and the USY molecular sieve loaded Cu catalyst can be recovered by simple filtration after the reaction is finished; (6) the USY molecular sieve loaded Cu catalyst can be recycled and reused to TsN₃Taking phenylboronic acid as a raw material to prepare a compound 4-methyl-N-phenylbenzenesulfonamide as an example, after the reaction is finished, a Cu catalyst (Cu/USY) loaded on a USY molecular sieve is recovered through filtration and directly used for the next round of reaction and is recycled for five times, and the separation yields of target compounds are respectively 96%, 90%, 81%, 74% and 61%, so that the catalyst is proved to have good recycling performance, and still has good catalytic activity after five times; (7) by X-ray diffraction (XRD), Scanning Electron Microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), N₂Physical adsorption and other means for the appearance, functional group, composition, element valence state, content and the like of the USY molecular sieve loaded Cu catalystA series of characteristics are carried out, and the catalyst is proved to have good stability in the reaction system.

The following are specific examples.

The USY molecular sieve supported reduced metal catalysts employed in examples 1-10 were prepared by the following procedure:

to 1.8906g of Cu (NO)₃)₂·3H₂Dropwise adding 5mL of deionized water into O, stirring until the deionized water is dissolved, then adding 5g of USY type molecular sieve, stirring until the mixture is viscous, shaking for 2 hours, drying, and grinding to obtain blue powder;

the blue powder was dried at 550 ℃ for 4H and then at H₂Calcining for 3h at 280 ℃ in the atmosphere, washing, filtering and drying to obtain the USY molecular sieve supported reduction metal catalyst.

Example 1

Synthesis of 4-methyl-N-phenylbenzenesulfonamide: p-toluenesulfonylazide (0.25mmol, 1.0equiv), phenylboronic acid (1.5equiv), Cu/USY (32mg, 20 mol% [ Cu ] loading), and sodium borohydride (5mg, 0.125mmol, 0.5equiv) were added sequentially to a dry reaction tube equipped with a magnetic stir bar, finally methanol (1.0mL) was added dropwise with white smoke generation and heat evolution in the reaction tube as the solvent was added, the reaction mixture was stirred at 25 ℃, the reaction was monitored by Thin Layer Chromatography (TLC), and after 6h of the reaction, the solid material was washed with methanol, filtered, dried in an oven, and collected for the next catalytic reaction. The filtrate was diluted with ethyl acetate (10mL), and distilled under reduced pressure, and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as an eluent, to give the objective product with an isolated yield of 96%.

The physical properties and characterization data of the obtained compounds are as follows:

yellow oil:¹H NMR(400MHz,CDCl₃,298K):δ＝2.40(s,3H),7.11–7.16(m,3H),7.25–7.29(m,4H),7.42(br s,1H),7.75(d,J＝7.8Hz,2H)ppm。¹³C NMR(101MHz,CDCl₃,298K):δ＝21.6,121.4,125.2,127.3,129.3,129.7,136.0,136.7,143.9ppm。

as shown in the maps of (a) and (b) in FIG. 1, according to N₂The isothermal adsorption curve of physical adsorption and the related parameters of a pore structure, the isothermal adsorption line of the Cu/USY catalyst is an IV-type isothermal line, the catalyst contains rich pore channel structures, sufficient reaction sites are provided for reaction, the specific surface area and the pore volume of the recovered catalyst are reduced, but the degree is smaller, and the reason is that the reaction yield is reduced.

From the SEM spectra of (a) and (b) in fig. 2, it can be seen that, at a scale of 200nm, (a) is the synthesized heterogeneous catalyst Cu/USY, fine particles are attached to the surface of the USY after synthesis, most of which are Cu atoms, and since the pore size of the Y-type molecular sieve is larger, more Cu can be accommodated in the pore channel, and the difference between the surface morphology of the catalyst before reaction and the surface of the catalyst participating in the reaction is not large, which indicates that the performance of the catalyst is not seriously affected during the reaction.

As can be seen from the XRD patterns of (a) and (b) in fig. 3, the diffraction peak of the USY supporting Cu retains the main diffraction peak of the USY molecular sieve, indicating that the framework structure of the molecular sieve is not destroyed after the Cu component is supported on the USY molecular sieve, and the catalyst not participating in the reaction and the catalyst participating in the reaction include the characteristic diffraction peak of Cu in addition to the main diffraction peak of the USY molecular sieve. As the Cu loading amount in the catalyst is small, the characteristic peak is not obvious, and XRD results show that Cu is successfully loaded on a USY framework, so that the Cu/USY loaded catalyst is obtained.

As can be seen from the FT-IR spectra of (a) and (b) in FIG. 4, it is evident that the FT-IR spectrum is observed at 3300-3600 cm^-1There are many vibrational peaks due to stretching vibration of-OH in the molecular sieve framework and intramolecular hydrogen bonding, 1617cm^-1And 1402cm^-1The nearby vibration peak is 1188cm due to the shearing vibration of protons in lattice water molecules^-1And 980cm^-1The vibration peak existing nearby is caused by external SiO₄And AlO₄Two tetrahedrons have internal antisymmetric expansion and symmetric expansion, and are 577cm in length^-1The vibration peak existing nearby is the characteristic peak of the double six-membered ring of the Y molecular sieve. From the spectrum, the interaction between Cu atom and-OH can be knownTherefore, the stability of the heterogeneous catalyst is ensured, and the spectrum of the recovered catalyst is not greatly different from that of the catalyst which does not participate in the reaction.

Example 2

The USY molecular sieve supported reduced metal copper catalyst (Cu/USY) recovered in example 1 was used for the second time, and the catalytic reaction in example 1 was repeated to synthesize the target compound smoothly with a separation yield of 90%.

Example 3

The USY molecular sieve supported reduced metal copper catalyst (Cu/USY) recovered in example 1 was used for the third time, and the catalytic reaction in example 1 was repeated to synthesize the target compound smoothly with a separation yield of 81%.

Example 4

The USY molecular sieve supported reduced metal copper catalyst (Cu/USY) recovered in example 1 was used for the fourth time, and the catalytic reaction in example 1 was repeated to synthesize the target compound smoothly with a separation yield of 72%.

Example 5

The USY molecular sieve supported reduced metal copper catalyst (Cu/USY) recovered in example 1 was used for the fifth time, and the catalytic reaction in example 1 was repeated to synthesize the target compound smoothly with an isolated yield of 61%.

As can be seen from examples 1-5, at TsN₃And phenylboronic acid is taken as a raw material to prepare a compound 4-methyl-N-phenylbenzenesulfonamide, after the reaction is finished, the USY molecular sieve supported reduced metal copper catalyst (Cu/USY) is recovered through filtration and directly used for the next round of reaction and is recycled for five times, the separation yield of the target compound is respectively 96%, 90%, 81%, 72% and 61%, and the catalyst is proved to have good recycling performance and still have high catalytic activity after the five times.

Example 6

Synthesis of N-phenylbenzenesulfonamide: benzenesulfonyl azide (0.25mmol, 1.0equiv), phenylboronic acid (1.0equiv), Cu/USY (30mg, 20 mol% [ Cu ] loading), and sodium hydride (0.1equiv) were added sequentially to a dry reaction tube equipped with a magnetic stir bar, and finally ethanol (1.0mL) was added dropwise with white smoke generation and heat evolution in the reaction tube while adding the solvent, the reaction mixture was stirred at 50 ℃, the reaction was monitored by TLC, and after 1h of the reaction, the solid material was washed with methanol, filtered, dried in an oven, and collected for the next catalytic reaction. The filtrate was diluted with ethyl acetate (10mL), and distilled under reduced pressure, and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as an eluent, to obtain the objective product.

The physical properties and characterization data of the obtained compounds are as follows:

yellow oil:¹H NMR(400MHz,CDCl₃,298K):δ＝7.12–7.16(m,3H),7.21(br s,1H),7.26–7.30(m,2H),7.47(dd,J＝7.8Hz,J＝7.8Hz,2H),7.57(dd,J＝7.2Hz,J＝7.2Hz,1H),7.85(d,J＝7.8Hz,2H)ppm。¹³C NMR(101MHz,CDCl₃,298K):δ＝121.6,125.4,127.3,129.1,129.3,133.1,136.4,138.9ppm。

example 7

Synthesis of 2-fluoro-N-phenylbenzenesulfonamide: 2-fluorobenzenesulfonylazide (0.25mmol, 1.0equiv), phenylboronic acid (1.5equiv), Cu/USY (32mg, 20 mol% [ Cu ] load), and sodium borohydride (5mg, 0.125mmol, 0.5equiv) were added sequentially to a dry reaction tube equipped with a magnetic stir bar, and finally toluene (1.0mL) was added dropwise with white smoke generation and heat evolution in the reaction tube, the reaction mixture was stirred at 25 deg.C, the reaction was monitored by TLC, and after 6h of reaction, the solid material was washed with methanol and filtered, dried in an oven, and collected for the next catalytic reaction. The filtrate was diluted with ethyl acetate (10mL), and distilled under reduced pressure, and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as an eluent, to give the objective product with an isolated yield of 79%.

The physical properties and characterization data of the obtained compounds are as follows:

yellow oil:¹H NMR(400MHz,CDCl₃,298K):δ＝7.04(br s,1H),7.11–7.18(m,3H),7.21–7.30(m,4H),7.54–7.59(m,1H),7.87(dd,J＝7.2Hz,J＝7.2Hz,1H)ppm。¹³C NMR(101MHz,CDCl₃,298K):δ＝116.9(d,J＝20.5Hz),121.3,124.5(d,J＝3.7Hz),125.6,126.6(d,J＝13.2Hz),129.4,131.0,135.5(d,J＝9.6Hz),135.8,158.7(d,J＝252.9Hz)ppm。

example 8

Synthesis of N- (4-chlorophenyl) -4-methylbenzenesulfonamide: p-toluenesulfonylazide (0.25mmol, 1.0equiv), 4-chlorobenzeneboronic acid (1.5equiv), Cu/USY (35mg, 20 mol% [ Cu ] loading), and sodium borohydride (5mg, 0.125mmol, 0.5equiv) were added sequentially to a dry reaction tube equipped with a magnetic stir bar, and finally acetonitrile (1.0mL) was added dropwise with white smoke generation and heat evolution in the reaction tube, the reaction mixture was stirred at 25 ℃, the reaction was monitored by TLC, and after 6h of reaction, the solid material was washed with methanol and filtered, dried in an oven, and collected for the next catalytic reaction. The filtrate was diluted with ethyl acetate (10mL), and distilled under reduced pressure, and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as an eluent, to give the objective product with an isolated yield of 95%.

The physical properties and characterization data of the obtained compounds are as follows:

yellow oil:¹H NMR(400MHz,CDCl₃,298K):δ＝2.42(s,3H),7.09(d,_J＝8.6Hz,2H),7.22(d,J＝8.4Hz,2H),7.27(d,J＝8.2Hz,2H),7.56(br s,1H),7.73(d,J＝8.2Hz,2H)ppm。¹³C NMR(101MHz,CDCl₃,298K):_δ＝21.6,122.8,127.3,129.4,129.8,130.8,135.2,135.6,144.3ppm。

example 9

Synthesis of N- (4-methoxyphenyl) -4-methylbenzenesulfonamide: p-toluenesulfonylazide (0.25mmol, 1.0equiv), 4-methoxyphenylboronic acid (1.5equiv), Cu/USY (32mg, 20 mol% [ Cu ] loading), and sodium borohydride (5mg, 0.125mmol, 0.5equiv) were added sequentially to a dry reaction tube equipped with a magnetic stir bar, finally methanol (1.0mL) was added dropwise with white smoke generation and heat evolution in the reaction tube, the reaction mixture was stirred at 25 ℃, the reaction was monitored by TLC, and after 6h of reaction, the solid material was washed with methanol and filtered, dried in an oven, and collected for the next catalytic reaction. The filtrate was diluted with ethyl acetate (10mL), and distilled under reduced pressure, and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as an eluent, to give the objective product with an isolated yield of 94%.

The physical properties and characterization data of the obtained compounds are as follows:

yellow oil:¹H NMR(400MHz,CDCl₃,298K):δ＝2.40(s,3H),3.77(s,3H),6.78(d,J＝8.8Hz,2H),7.05(d,J＝8.8Hz,2H),7.20(br s,1H),7.22(d,J＝8.0Hz,2H),7.67(d,J＝8.4Hz,2H)ppm。¹³C NMR(101MHz,CDCl₃,298K):δ＝21.6,55.4,114.4,125.1,127.4,129.1,129.6,135.9,143.7,157.7ppm。

example 10

Synthesis of N- (3-methoxyphenyl) -4-methylbenzenesulfonamide: p-toluenesulfonylazide (0.25mmol, 1.0equiv), 3-methoxyphenylboronic acid (1.5equiv), Cu/USY (32mg, 20 mol% [ Cu ] loading), and sodium borohydride (5mg, 0.125mmol, 0.5equiv) were added sequentially to a dry reaction tube equipped with a magnetic stir bar, finally methanol (1.0mL) was added dropwise with white smoke generation and heat evolution in the reaction tube, the reaction mixture was stirred at 25 ℃, the reaction was monitored by TLC, and after 6h of reaction, the solid material was washed with methanol, filtered, dried in an oven, and collected for the next catalytic reaction. The filtrate was diluted with ethyl acetate (10mL), and distilled under reduced pressure, and purified by column chromatography using a mixture of petroleum ether and ethyl acetate as an eluent, to give the objective product with an isolated yield of 96%.

The physical properties and characterization data of the obtained compounds are as follows:

yellow oil:¹H NMR(400MHz,CDCl₃,298K):δ＝2.04(s,3H),3.76(s,3H),6.68(ddd,J＝8.4Hz,J＝8.4Hz,J＝1.8Hz,2H),6.74–6.76(m,1H),7.14(dd,J＝8.0Hz,J＝8.0Hz,1H),7.25(br s,1H),7.27–7.31(m,2H),7.76(d,J＝8.0Hz,2H)ppm。¹³C NMR(101MHz,CDCl₃,298K):δ＝21.6,55.3,106.7,110.8,113.2,127.3,129.7,130.0,136.0,137.9,144.0,160.3ppm。

examples 11-13 are examples of the preparation of USY molecular sieve supported reduced metal catalysts.

Example 11

The preparation method of the USY molecular sieve supported reduction metal catalyst comprises the following steps:

(1) 1.71g of Cu (NO) was weighed₃)₂·3H₂Adding 9mL of ionized water into a beaker, stirring until the ionized water is dissolved, and then adding 6g of USY type molecular sieve, wherein the silicon-aluminum ratio is 1.5: 1, stirring to be viscous, shaking for 2.5 hours, drying and grinding to obtain blue powder;

(2) and drying the blue powder at the temperature of 600 ℃ for 4h, calcining the blue powder at the temperature of 250 ℃ for 4h in a hydrogen atmosphere, washing, filtering and drying to obtain the USY molecular sieve supported reduction metal catalyst.

Example 12

(1) 2.08g Cu (NO) was weighed₃)₂·3H₂Adding 7mL of ionized water into a beaker, stirring until the ionized water is dissolved, and then adding 4g of USY type molecular sieve, wherein the silicon-aluminum ratio is 2: 1, stirring to be viscous, shaking for 1.5h, drying and grinding to obtain blue powder;

(2) and drying the blue powder at the temperature of 450 ℃ for 6h, calcining the blue powder at the temperature of 300 ℃ in a hydrogen atmosphere for 2.5h, washing, filtering and drying to obtain the USY molecular sieve supported reduction metal catalyst.

Example 13

(1) 1.9g of Cu (NO) was weighed₃)₂·3H₂Adding 5mL of ionized water into a beaker, stirring until the ionized water is dissolved, and then adding 5g of USY type molecular sieve, wherein the ratio of silicon to aluminum is 1: 1, stirring to be viscous, shaking for 2 hours, drying and grinding to obtain blue powder;

(2) and drying the blue powder at the temperature of 500 ℃ for 5h, calcining the blue powder at the temperature of 270 ℃ for 3h in a hydrogen atmosphere, washing, filtering and drying to obtain the USY molecular sieve supported reduction metal catalyst.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and these modifications and decorations shall also fall within the protection scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.