Application of Hollow Prism Bimetallic Oxide Catalyst in Cross-Dehydrogenative Coupling Reaction

Abstract

The present invention discloses the application of a hollow prism bimetallic oxide catalyst in cross-dehydrogenative coupling reactions. The catalyst is a bimetallic oxide CoFeO-Prism with a hollow prism morphology at the micron scale; the bimetallic oxide is a mixed oxide of Fe3O4 and Co3O4; a 2-phenyl-1,2,3,4-tetrahydroisoquinoline compound, the CoFeO-Prism, nitromethane, and a solvent are mixed and placed in a reaction vessel, and one of oxygen, nitrogen, and air is used as the reaction atmosphere to carry out cross-dehydrogenative coupling reactions. After the reaction, the catalyst is washed, the organic phase is collected by centrifugation, and finally 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds are prepared. Based on the fact that the hollow prism bimetallic oxide catalyst has a higher specific surface area and more exposed catalytic active sites, the present invention effectively improves the catalytic efficiency of the catalyst. The present invention proposes that this catalyst can efficiently catalyze cross-dehydrogenative coupling reactions under mild reaction conditions.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and specifically relates to the application of a hollow prism bimetallic oxide catalyst in a cross-dehydrogenation coupling reaction, and specifically relates to a reaction method for preparing 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline from 2-phenyl-1,2,3,4-tetrahydroisoquinoline using a hollow prism bimetallic oxide catalyst. Background Art

[0002] Developing more direct catalytic methods for the synthesis of chemical products is key to achieving chemical sustainability. Carbon-carbon bond formation is an important component of many chemical syntheses. Therefore, the study of the direct use of two different CH bonds to form CC bonds under oxidative conditions (cross-dehydrogenative coupling reaction) has attracted widespread attention. This strategy can avoid the pre-functionalization of the starting materials, thereby shortening the synthesis process and improving the overall efficiency. However, the search for efficient and green cross-dehydrogenative coupling reactions remains urgent.

[0003] At present, homogeneous catalysis and photocatalysis are both used in cross-dehydrogenation coupling reactions (ACS Catal. 12 (2022) 126-134; Tetrahedron. 73 (2017) 3118-3124; Chem. Commun. 51 (2015) 8280-8283; Chem. Commun. 51 (2015) 334-337; Org. Biomol. Chem. 8 (2010) 4077-4079). However, these catalytic systems have problems such as complicated catalyst preparation process, low catalyst recovery rate, harsh reaction conditions, and difficulty in industrialization. Summary of the invention

[0004] In view of the deficiencies and difficulties in the prior art, the present invention aims to provide an application of a hollow prism bimetallic oxide catalyst in a cross-dehydrogenation coupling reaction, and a reaction method for preparing 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds from 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds based on the catalysis of the hollow prism bimetallic oxide.

[0005] The present invention is achieved through the following technical solutions:

[0006] The invention discloses an application of a hollow prism bimetallic oxide catalyst in a cross-dehydrogenation coupling reaction. The catalyst is a bimetallic oxide CoFeO-Prism with a micrometer-scale hollow prism morphology. The bimetallic oxide is a mixed oxide of Fe3O4 and Co3O4. The catalyst catalyzes 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds to prepare 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds under mild reaction conditions.

[0007] Furthermore, the preparation method of the catalyst CoFeO-Prism includes:

[0008] Using polyvinylpyrrolidone and cobalt(II) acetate tetrahydrate as raw materials, after dissolving in ethanol, heating under reflux conditions for reaction, and then successively performing washing, centrifugation, and drying to obtain the Co-Prism precursor;

[0009] Dispersing the Co-Prism precursor in absolute ethanol and mixing it with K3[Fe(CN)6] dissolved in deionized water, stirring and mixing at room temperature for reaction, and then successively performing centrifugation, washing, and drying to obtain Co-Fe PBA(Prism);

[0010] Calcining Co-Fe PBA(Prism) at a low temperature of 200-300 °C (preferably 250 °C) for 1-2 h, stopping heating, opening the reactor, and cooling to room temperature to obtain CoFeO-Prism.

[0011] Furthermore, the 2-phenyl-1,2,3,4-tetrahydroisoquinoline compound has the structure shown in formula (1); the 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compound has the structure shown in formula (2):

[0012]

[0013] In the formula, R 1 is hydrogen, methyl, methoxy, cyano, trifluoromethyl or bromine; R 2 is hydrogen or an ether group

[0014] The reaction general formula is:

[0015]

[0016] The method is specifically as follows: Mix the 2-phenyl-1,2,3,4-tetrahydroisoquinoline compound, the CoFeO-Prism, nitromethane and a solvent, place them in a reaction vessel, use one of oxygen, nitrogen, and air as the reaction atmosphere, perform a cross-dehydrogenative coupling reaction, wash the catalyst after the reaction, collect the organic phase by centrifugation, and finally obtain the 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compound.

[0017] After the reaction, add an internal standard to the organic phase, and calculate the yield of the 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compound using NMR; the internal standard is 1,3,5-trimethoxybenzene; the molar ratio of the dosage of the internal standard to the 2-phenyl-1,2,3,4-tetrahydroisoquinoline compound is 0.5-1:1.

[0018] Further, the reaction temperature is 40 - 80 °C, the time is 24 - 30 h, and the pressure is 1 - 3 bar; the mass ratio of the catalyst dosage to the 2-phenyl-1,2,3,4-tetrahydroisoquinoline compound is 1:5 - 1:20.

[0019] Compared with the prior art, the hollow prism bimetallic oxide catalyst of the present invention has a higher specific surface area and more exposed catalytic active sites, effectively improving the catalytic efficiency of the catalyst. The present invention proposes that this catalyst can efficiently catalyze the cross-dehydrogenative coupling reaction under mild reaction conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a comparison diagram of the CoFeO-Prism XRD image with the Fe3O4 and CoFe2O4 PDF cards.

[0021] Figure 2 It is the SEM image of CoFeO-Prism

[0022] Figure 3 It is the TEM image of CoFeO-Prism.

[0023] Figure 4 It is the reaction formula and product structural formula for the expansion of the dehydrogenative cross-coupling reaction.

[0024] Figure 5 It is the data of the catalyst recycling catalytic reaction.

[0025] Figure 6 It is the SEM image of the catalyst after the recycling reaction. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention will be further described below with reference to the accompanying drawings.

[0027] Example 1 Preparation and Structure Analysis of the Hollow Prism Bimetallic Oxide Catalyst

[0028] 1. Preparation steps of the hollow prism bimetallic oxide catalyst:

[0029] The first step: Preparation of the Co-Prism precursor

[0030] (1) Weigh 1.0 g of polyvinylpyrrolidone (PVP, K30) and 0.64 g of cobalt acetate tetrahydrate, dissolve the two in 200 mL of ethanol at room temperature to form a transparent solution, and transfer it to a 500 mL round-bottom flask.

[0031] (2) Heat the solution in (1) to 85 °C under reflux conditions and react for 2 hours.

[0032] (3) Wash and centrifuge the solution at least 10 times to obtain the centrifuged product.

[0033] (4) Dry the centrifuged product in an oven at 60 °C overnight to obtain the Co-Prism precursor.

[0034] Step 2: Preparation of Co-Fe PBA (Prism)

[0035] (1) Weigh 0.02 g of the Co-Prism precursor (prepared in 2.3.1) and add it to 20 mL of absolute ethanol. Ultrasonically disperse it in ethanol to form Emulsion A.

[0036] (2) Weigh 0.02 g of K3[Fe(CN)6] and dissolve it in 20 mL of deionized water to obtain a transparent yellow solution as Solution B.

[0037] (3) Mix Emulsion A and Solution B together at room temperature and stir. React at room temperature for 1 hour.

[0038] (4) Centrifuge the reaction product, wash it several times with deionized water and absolute ethanol, and dry it in an oven at 60 °C overnight. After drying, Co-Fe PBA (Prism) is obtained.

[0039] Step 3: Preparation of CoFeO-Prism

[0040] (1) Weigh a certain amount of Co-Fe PBA (Prism) and add it to a crucible.

[0041] (2) Place the crucible in a muffle furnace and heat it to 250 °C, and maintain it for 1.5 h.

[0042] (3) Open the muffle furnace to cool down. After the furnace temperature drops, take out the crucible and let it cool naturally. After grinding, CoFeO-Prism is obtained.

[0043] 2. XRD Analysis

[0044] In order to determine the crystal structure characteristics and phase information of the synthesized material, XRD tests were carried out on the synthesized CoFeO-Prism material. Figure 1 The XRD image of CoFeO-Prism is compared with the Fe3O4 and CoFe2O4 PDF cards. It can be seen that the XRD image of CoFeO-Prism has four diffraction peaks at 2θ = 36.82°, 44.76°, 59.30° and 65.19°, corresponding to the characteristic diffraction peaks of the (311), (400), (511) and (440) crystal planes of the Fe3O4 structure in the Fe3O4 standard PDF card 26-1136.

[0045] The characteristic diffraction peaks of the (311), (400), (511), and (440) crystal planes of the Co3O4 structure in Standard PDF #42-1467 are basically consistent with those of PDF #26-1136. The characteristic peaks of iron-cobalt oxides basically overlap and are basically consistent with the overall XRD image of the sample. Moreover, compared with the image of cobalt-iron spinel in PDF #22-1086, the main characteristic peaks of the sample show certain shifts. In terms of the XRD image, the sample should be a mixed oxide of Fe3O4 and Co3O4.

[0046] 3. SEM Morphology and Structure Analysis

[0047] Figure 2 The SEM image of CoFeO-Prism shows that after calcination at 250 °C in an air atmosphere, the basic structure of PBAs remains intact, and the hollow prism morphology is successfully inherited to the oxide derivatives. The surface of the oxide derivatives becomes rough instead of smooth compared with the Prussian blue analogues, and the overall morphology of the material remains intact. This indicates that in this study, the prism morphology of Co-Prism is successfully inherited to the oxide derivatives through low-temperature calcination.

[0048] Comparing the SEM images of the two, it can be seen that the basic morphology of PBA can be relatively perfectly retained in the derivatives by calcination in an oxygen atmosphere with a stable temperature increase. The PBA derivatives can relatively well inherit the structure of the hollow prism of the precursor PBA, which also shows that in this study, various regularly shaped and uniformly sized PBA derivatives have been successfully prepared through a simple self-sacrificial template method and calcination.

[0049] 4. TEM Morphology and Structure Analysis

[0050] The TEM image of CoFeO-Prism is as Figure 3 shown. Through the TEM image, it can be clearly seen that CoFeO-Prism retains the hollow morphology of Co-Fe PBA (Prism), which indicates that in this study, the hollow morphology in PBAs is successfully inherited to the oxide derivatives through self-sacrificial template method calcination.

[0051] Judging from the electron microscope images, the hollow morphology appears at the PBA stage and is successfully inherited to the subsequent derivatives. The solid cube and its derivatives do not have a similar morphology. From the structural characterization, CoFeO is still a compound at the micron scale and shows a hollow morphology, and no obvious holes are seen on the outer surface of CoFeO-Prism.

[0052] Examples 2 to 20 are the preparation of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline by using the CoFeO-Prism catalyst prepared in Example 1 to catalyze 2-phenyl-1,2,3,4-tetrahydroisoquinoline. 2-Phenyl-1,2,3,4-tetrahydroisoquinoline, a bimetallic oxide catalyst (hereinafter briefly referred to as the catalyst), nitromethane and a solvent are mixed and placed in a reaction vessel. Using one of oxygen, nitrogen, and air as the reaction atmosphere, the reaction is carried out. After the reaction, the catalyst is washed with ethyl acetate, and the organic phase is collected by centrifugation. An appropriate amount of internal standard is added, and the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline is calculated by NMR.

[0053] The temperature of the above reaction is 40 - 80 °C, the time is 24 - 30 h, the pressure is 1 - 3 bar, the mass of the catalyst is 2 - 25 mg, the volume of the solvent is 1 - 4 mL, and the molar ratio of the dosage of the internal standard to 2-phenyl-1,2,3,4-tetrahydroisoquinoline is 0.5 - 1:1.

[0054] In a preferred embodiment of the present invention, the temperature of the above reaction is 60 °C, the time is 30 h, the reaction atmosphere is oxygen, the pressure is 1 bar, the mass of the catalyst is 5 mg, the molar ratio of nitromethane to 2-phenyl-1,2,3,4-tetrahydroisoquinoline is 10:1, and the volume of the solvent is 2 mL. In a preferred embodiment of the present invention, the internal standard used is 1,3,5-trimethoxybenzene.

[0055] Example 2:

[0056] 2-Phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), the catalyst (5 mg), ethanol (2 mL), and nitromethane (2 mmol) are successively added to a 10 mL reaction vial and mixed evenly. An oxygen balloon is fixed at the mouth of the reaction vial, the reaction pressure is 1 bar, and vigorous stirring (600 rpm) is carried out. The reaction is carried out at 60 °C for 30 h. After cooling to room temperature, the catalyst is washed with ethyl acetate (5 mL), centrifuged (6000 rpm, 5 mins), and the organic phase is collected. This is repeated three times, and the obtained organic phases are combined. 1,3,5-trimethoxybenzene (about 0.1 mmol) is added. After mixing evenly, a sample is taken, and the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline is calculated using NMR. The yield is 95%.

[0057] Examples 3 - 4: These two examples have the same experimental conditions except for the difference in reaction temperature.

[0058] Add 2-phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (5 mg), and nitromethane (2 mL) to a 10 mL reaction vial in sequence. Mix well. Fix an oxygen balloon at the mouth of the reaction vial. The reaction pressure is 1 bar. Stir vigorously (600 rpm). React at 100 °C and 80 °C for 30 h respectively. After cooling to room temperature, wash the catalyst with ethyl acetate (5 mL), centrifuge (6000 rpm, 5 mins), collect the organic phase, repeat three times, combine the obtained organic phases, add 1,3,5-trimethoxybenzene (about 0.1 mmol), sample after mixing evenly, and use NMR to calculate the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline. The yields are 67% and 97% respectively.

[0059] Examples 5 - 8: These 4 examples have the same experimental conditions except for the difference in the catalyst dosage.

[0060] Add 2-phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (2 mg) (10 mg) (15 mg) and (25 mg), ethanol (2 mL) and nitromethane (2 mmol) to a 10 mL reaction vial in sequence. Mix well. Fix an oxygen balloon at the mouth of the reaction vial. The reaction pressure is 1 bar. Stir vigorously (600 rpm). React at 60 °C for 30 h. After cooling to room temperature, wash the catalyst with ethyl acetate (5 mL), centrifuge (6000 rpm, 5 mins), collect the organic phase, repeat three times, combine the obtained organic phases, add 1,3,5-trimethoxybenzene (about 0.1 mmol), sample after mixing evenly, and use NMR to calculate the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline. The yields are 92%, 78%, 89% and 95% respectively.

[0061] Examples 9 - 11: These 3 examples have the same experimental conditions except for the difference in the solvent.

[0062] 2-Phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (5 mg), acetonitrile / water / tetrahydrofuran (2 mL), and nitromethane (2 mmol) were successively added to a 10 mL reaction vial, mixed well, an oxygen balloon was fixed at the mouth of the reaction vial, the reaction pressure was 1 bar, stirred vigorously (600 rpm), reacted at 60 °C for 30 h, cooled to room temperature, the catalyst was washed with ethyl acetate (5 mL), centrifuged (6000 rpm, 5 mins), the organic phase was collected, repeated three times, the obtained organic phases were combined, 1,3,5-trimethoxybenzene (about 0.1 mmol) was added, sampled after mixing well, and the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline was calculated using NMR. The yields were 49%, 82%, and 27% respectively.

[0063] Examples 12 - 13: These two examples had the same experimental conditions except for the difference in the volume of ethanol as the solvent.

[0064] 2-Phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (5 mg), ethanol (1 mL), (4 mL), and nitromethane (2 mmol) were successively added to a 10 mL reaction vial, mixed well, an oxygen balloon was fixed at the mouth of the reaction vial, the reaction pressure was 1 bar, stirred vigorously (600 rpm), reacted at 60 °C for 30 h, cooled to room temperature, the catalyst was washed with ethyl acetate (5 mL), centrifuged (6000 rpm, 5 mins), the organic phase was collected, repeated three times, the obtained organic phases were combined, 1,3,5-trimethoxybenzene (about 0.1 mmol) was added, sampled after mixing well, and the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline was calculated using NMR. The yields were 94% and 84% respectively.

[0065] Examples 14 - 15: These two examples had the same experimental conditions except for the difference in the reaction time.

[0066] To a 10 mL reaction vial, 2-phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (5 mg), ethanol (2 mL), and nitromethane (2 mmol) were added successively, mixed evenly. An oxygen balloon was fixed to the reaction vial mouth, the reaction pressure was 1 bar, and it was vigorously stirred (600 rpm). The reaction was carried out at 60 °C for 24 h and 48 h respectively. After cooling to room temperature, the catalyst was washed with ethyl acetate (5 mL), centrifuged (6000 rpm, 5 mins), the organic phase was collected, repeated three times, and the obtained organic phases were combined. 1,3,5-trimethoxybenzene (about 0.1 mmol) was added. After mixing evenly, a sample was taken and the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline was calculated using NMR. The yields were 90% and 83% respectively.

[0067] Example 16:

[0068] Preparation process of oxygenated ethanol: Take 6 mL of ethanol in a test tube, insert the needle below the liquid level, pass oxygen for 15 mins, and store it sealed.

[0069] To a 10 mL reaction vial, 2-phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (5 mg), the above-mentioned oxygenated ethanol (2 mL), and nitromethane (2 mmol) were added successively, mixed evenly. An oxygen balloon was fixed to the reaction vial mouth, the reaction pressure was 1 bar, and it was vigorously stirred (600 rpm). The reaction was carried out at 60 °C for 30 h. After cooling to room temperature, the catalyst was washed with ethyl acetate (5 mL), centrifuged (6000 rpm, 5 mins), the organic phase was collected, repeated three times, and the obtained organic phases were combined. 1,3,5-trimethoxybenzene (about 0.1 mmol) was added. After mixing evenly, a sample was taken and the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline was calculated using NMR. The yield was 95%.

[0070] Example 17:

[0071] To a 10 mL reaction vial, 2-phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (25 mg), ethanol (2 mL), and nitromethane (2 mmol) were added successively, mixed evenly. The air was connected, the reaction pressure was 1 bar, and it was vigorously stirred (600 rpm). The reaction was carried out at 60 °C for 30 h. After cooling to room temperature, the catalyst was washed with ethyl acetate (5 mL), centrifuged (6000 rpm, 5 mins), the organic phase was collected, repeated three times, and the obtained organic phases were combined. 1,3,5-trimethoxybenzene (about 0.1 mmol) was added. After mixing evenly, a sample was taken and the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline was calculated using NMR. The yield was 70%.

[0072] Example 18:

[0073] Preparation process of oxygenated ethanol in a drum: Take 6 mL of ethanol in a test tube, insert the needle below the liquid level, pass oxygen for 15 mins, and store it sealed.

[0074] Add 2-phenyl-1,2,3,4-tetrahydroisoquinoline (0.2 mmol), catalyst (5 mg), oxygenated ethanol in a drum (1 mL), and nitromethane (2 mmol) to a 10 mL pressure-resistant tube in sequence, mix evenly, pass 16 mL of oxygen into the pressure-resistant tube, the reaction pressure is 3 bar, stir vigorously (600 rpm), react at 60 °C for 30 h, wait until it cools to room temperature, wash the catalyst with ethyl acetate (5 mL), centrifuge (6000 rpm, 5 mins), collect the organic phase, repeat three times, combine the obtained organic phases, add 1,3,5-trimethoxybenzene (about 0.1 mmol), sample after mixing evenly, and use NMR to calculate the yield of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline, and the yield is 95%.

[0075] Expansion of the dehydrogenative cross-coupling reaction in Example 19

[0076] Under the same reaction conditions as in Example 2, the difference is that the raw materials are 2-phenyl-1,2,3,4-tetrahydroisoquinoline derivatives and nitromethane, and the solvent is anhydrous ethanol. Carry out the dehydrogenative cross-coupling reaction. The reaction general formula, products, and yields are as Figure 4 shown.

[0077] It can be seen that for the dehydrogenative cross-coupling reaction carried out based on the present invention, the substrate range is wide, which proves that the reaction has good adaptability and generally has a relatively high yield, and can be industrially produced.

[0078] Example 20 Catalyst recycling

[0079] After the reaction, adsorb the catalyst with a magnet for 10 mins, and all the catalyst can be adsorbed onto the magnet, which proves that the catalyst has magnetism and a high separation recovery rate. Keep the reaction conditions of Example 2 unchanged, and carry out repeated cyclic reactions with the separated and recovered catalyst. The data of 5 cyclic experiments are as Figure 5 shown.

[0080] In 5 cycles, for the dehydrogenative cross-coupling reaction, CoFeO-Prism catalyzes the preparation of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline from 2-phenyl-1,2,3,4-tetrahydroisoquinoline, and the product yield decreases from 91% to 80%, but the amplitude is not large, indicating that the prepared CoFeO has good stability and recyclability. The SEM image of the catalyst after cyclic reaction is as Figure 6 shown, proving that the catalyst morphology is stable.

[0081] The above only expresses the preferred embodiments of the present invention, and the description thereof is relatively specific and detailed. However, it should not be construed as a limitation on the scope of the patent for the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications, improvements and substitutions can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention shall be subject to the appended claims.

Claims

1. Application of a hollow prism bimetallic oxide catalyst in a cross-dehydrogenative coupling reaction, characterized in that: The catalyst is a bimetallic oxide CoFeO-Prism with a hollow prism morphology at the micron scale; the bimetallic oxide is a mixed oxide of Fe3O4 and Co3O4; the catalyst, under mild reaction conditions, uses one of oxygen and air as the reaction atmosphere to catalyze the preparation of 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds from 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds; The preparation method of the CoFeO-Prism includes: Using polyvinylpyrrolidone and cobalt acetate tetrahydrate as raw materials, dissolving them in ethanol, heating and reacting under reflux conditions, and then successively performing washing, centrifugation, and drying to obtain a Co-Prism precursor; Mixing the Co-Prism precursor dispersed in absolute ethanol with K3[Fe(CN)6] dissolved in deionized water, stirring and reacting at room temperature, and then successively performing centrifugation, washing, and drying to obtain Co-Fe PBA-Prism; Calcining Co-Fe PBA-Prism at a low temperature of 200-300 °C for 1-2 h, stopping heating, opening the reactor, and cooling to room temperature to obtain CoFeO-Prism; The 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds have the structure shown in formula (1); the 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds have the structure shown in formula (2): （1）； （2）； In the formula, R 1 is hydrogen, methyl, methoxy, cyano, trifluoromethyl or bromine; R 2 is hydrogen.

2. Use of the hollow prism bimetallic oxide catalyst according to claim 1 in the cross-dehydrogenative coupling reaction, characterized in that, The method for preparing 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds from 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds is specifically as follows: Mix the 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds, the CoFeO-Prism, nitromethane, and a solvent, place them in a reaction vessel, use one of oxygen and air as the reaction atmosphere, perform a cross-dehydrogenative coupling reaction, wash the catalyst after the reaction, collect the organic phase by centrifugation, and finally obtain 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds.

3. Use of the hollow prism bimetallic oxide catalyst according to claim 2 in the cross-dehydrogenative coupling reaction, characterized in that, The temperature of the reaction is 40-80 °C, the time is 24-30 h, and the pressure is 1-3 bar; the mass ratio of the catalyst dosage to the 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds is 1:5-1:20.

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