An iron complex with a triazacyclic nonane macrocyclic skeleton, its preparation method and application

Abstract

This invention discloses an iron complex with a triazacyclic nonane macrocyclic skeleton, its preparation method, and its applications, belonging to the field of coordination chemistry. The iron complex has a triazacyclic nonane macrocyclic skeleton with two acetate side groups and one pyridine-N derivative side group. The iron complex exhibits excellent catalytic activity in the aerobic oxidation of N-aryltetrahydroisoquinoline, while also possessing good stability. The solvents for the catalytic reaction are water and acetonitrile, resulting in low pollution. This invention features mild reaction conditions, simple synthesis operations, and straightforward post-processing, meeting the requirements of environmental friendliness and clean production.

Description

Technical Field

[0001] This invention belongs to the field of coordination chemistry technology, specifically relating to an iron complex with a triazacyclononane macrocyclic skeleton, its preparation method, and its application. Background Technology

[0002] Metal complex-catalyzed organic reactions have become a hot topic in coordination chemistry research in recent years due to their rapid and efficient nature. Iron complexes, in particular, have attracted widespread attention from chemists due to their high catalytic activity and good selectivity. Preparing ligands by reacting ferric ions with relevant ligands can improve the stability of iron ions and enhance their catalytic performance. Ligands can modify the electronic structure of the central iron atom through coordination field effects and steric hindrance effects, thereby regulating its reactivity. For example, CN106745656A discloses a method for enhancing the removal of organic pollutants from water using a homogeneous iron / persulfate system, by adding aminotriacetic acid and Fe... 2+ and Fe 3+ Coordination was performed, resulting in an oxidation efficiency of 80%-97% for 2,4-dichlorophenol. Although this method enhanced the ability of iron to activate persulfate, its oxidation rate for 2,4-dichlorophenol remained slow and needs further improvement. Other common ligands, such as oxalic acid, ethylenediaminetetraacetic acid, and citric acid, also failed to significantly improve the catalytic oxidation rate.

[0003] Currently, most synthetic routes for iron complexes utilize iron sources such as ferric chloride, ferric sulfate, and ferric perchlorate. However, using ferric salts like ferric chloride easily leads to the formation of excess inorganic salts, increasing the post-reaction processing steps. Therefore, it is essential to develop a simple method for preparing iron complexes with a triazacyclic nonane macrocyclic skeleton. Summary of the Invention

[0004] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0005] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0006] One object of the present invention is to provide an iron complex having a triazacyclononane macrocyclic skeleton.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: an iron complex having a triazacyclic nonane macrocyclic framework, the structural formula of which is shown in Formula I:

[0008] (Formula I);

[0009] R is selected from H, Cl or CH3.

[0010] Another object of the present invention is to provide a method for preparing iron complexes having a triazacyclononane macrocyclic skeleton as described above, comprising reacting the ligand PyNO2A-R shown in Formula II with Fe(OH)3 in water or methanol by stirring.

[0011] (Formula II);

[0012] In Equation II, R is the same as R in Equation I.

[0013] In a preferred embodiment of the method for preparing the iron complex with a triazacyclononane macrocyclic skeleton of the present invention, the molar ratio of the ligand PyNO2A-R to Fe(OH)3 is 1:1.2~2.0.

[0014] In a preferred embodiment of the method for preparing the iron complex with a triazacyclononane macrocyclic skeleton of the present invention, the reaction temperature is 20~40 °C.

[0015] As a preferred embodiment of the method for preparing the iron complex with a triazacyclononane macrocyclic skeleton of the present invention, the method for preparing the ligand PyNO2A-R includes: reacting 1,4,7-triazacyclononane trihydrochloride (Formula III) with N-succinimide tert-butyl carbonate to generate the compound shown in Formula IV; reacting the compound shown in Formula IV with a 2-chloromethylpyridine derivative (Formula V) to generate the compound shown in Formula VI; reacting the compound shown in Formula VI with hydrochloric acid to generate the compound shown in Formula VII; reacting the compound shown in Formula VII with tert-butyl bromoacetate to generate the compound shown in Formula VIII; and reacting the compound shown in Formula VIII with hydrochloric acid to generate the ligand PyNO2A-R (Formula II).

[0016] (Formula III); (Formula IV); (Form V); (Form VI); (Formula VII); (Form VIII).

[0017] Another object of the present invention is to provide a method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline, comprising reacting the above-mentioned iron complex having a triazacyclononane macrocyclic skeleton with N-aryltetrahydroisoquinoline and a base in a solvent in an oxygen atmosphere.

[0018] As a preferred embodiment of the method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline according to the present invention, the iron complex Fe-PyNO2A-R is 5~20% of the catalyst.

[0019] As a preferred embodiment of the method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline according to the present invention, the base is selected from DBN, DBU, Cs2CO3, etc., and the molar ratio of N-aryltetrahydroisoquinoline to base is 1:1.2~2.0.

[0020] In a preferred embodiment of the method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline according to the present invention, the solvent is water, acetonitrile, DMF, 1,4-dioxane, etc.

[0021] In a preferred embodiment of the method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline according to the present invention, the reaction temperature is 20~40 °C.

[0022] The optimal synthetic route for the aerobic oxidation of N-aryltetrahydroisoquinoline is as follows:

[0023] .

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] This invention designs a series of ligands with a triazacyclononane macrocyclic skeleton as the core and modified with pyridine-N derivative side chains. This structure forms iron complexes with iron. The iron complex Fe-PyNO2A-R has the potential to efficiently catalyze the aerobic oxidation of N-aryltetrahydroisoquinolines. The synthesis of the iron ligands is simple, requiring only one step, with mild reaction conditions. No additional reagents or complex reaction procedures are needed during the synthesis, and high-purity iron complexes can be obtained after purification. This method is suitable for the oxidation of N-aryltetrahydroisoquinolines, meeting the requirements of environmental friendliness and clean production. It provides a new approach for the chemical synthesis of N-aryltetrahydroisoquinoline oxidation products and has great development potential. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0027] Figure 1 A schematic diagram of the preparation process of ligand PyNO2A-R;

[0028] Figure 2ESI-MS spectrum of Fe-PyNO2A-H;

[0029] Figure 3 The ESI-MS spectrum of Fe-PyNO2A-CH3;

[0030] Figure 4 ESI-MS spectrum of Fe-PyNO2A-Cl;

[0031] Figure 5 The X-ray diffraction pattern of a single crystal of Fe-PyNO2A-H;

[0032] Figure 6 The oxidation product of N-aryltetrahydroisoquinoline 1 H NMR spectrum;

[0033] Figure 7 The oxidation product of N-aryltetrahydroisoquinoline 13 C NMR spectrum. Detailed Implementation

[0034] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0035] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0036] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0037] Unless otherwise specified, all raw materials used in the examples were commercially available. The preparation methods of ligand PyNO2A-R and freshly prepared Fe(OH)3 are as follows:

[0038] (1) Preparation of ligand PyNO2A-R: as follows Figure 1 The reaction formula shown in the middle includes five steps.

[0039] First, a (1.0 g, 4.2 mmol) was dissolved in 3 mL of saturated potassium hydroxide aqueous solution, followed by the addition of 30 mL of dichloromethane. The resulting mixture was stirred for 5 minutes. Under vigorous stirring at room temperature, 10 mL of a dichloromethane solution of Boc-OSu (1.72 g, 8.0 mmol) was added dropwise. After addition, the mixture was washed sequentially with 20 mL of 2 M sodium dihydrogen phosphate aqueous solution and 20 mL of brine. The DCM layer containing product b was then extracted using 5 M citric acid solution (3 × 5 mL). After separating and discarding the DCM layer, the aqueous phase was adjusted to pH 12 to promote the extraction of product b into the DCM (3 × 10 mL). The dichloromethane layer was separated, dried over sodium sulfate, and then evaporated to dryness to obtain substance b of sufficient purity for subsequent synthetic steps.

[0040] Dissolve b (0.66 g, 2.0 mmol) in 20 mL of acetonitrile. Add 1.2 equivalents of the 2-chloromethylpyridine derivative and 0.85 g (8.4 mmol) of triethylamine to the solution. Stir the solution overnight at room temperature. Then remove the solvent under reduced pressure, and redissolve the residue in 20 mL of ethyl acetate. Wash the solution successively with 2 M sodium dihydrogen phosphate aqueous solution (2 × 20 mL) and brine, dry to anhydrous sodium sulfate, and evaporate to dryness. The resulting crude product c is purified by column chromatography with dichloromethane containing 6% methanol as the mobile phase. The product is then dissolved in 5 mL of ethyl acetate. Add 1.0 mL of concentrated hydrochloric acid to the solution, and stir the mixture at room temperature for 3 hours. During this time, a white precipitate gradually forms. Collect the solid by centrifugation, wash with ethyl acetate (3 × 10 mL), and dry under vacuum to give a white solid compound d.

[0041] Compound d (0.6 g) was mixed with 1 mL of triethylamine in 20 mL of acetonitrile, followed by the addition of 200 μL of tert-butyl bromoacetate. The resulting solution was stirred at room temperature for 4 to 8 hours, with the reaction progress monitored by thin-layer chromatography. After the reaction was complete, the solvent was removed by rotary evaporation. The residue was redissolved in 20 mL of dichloromethane. This solution was washed successively with saturated aqueous sodium bicarbonate solution and brine, and then dried over sodium sulfate. The solution was then evaporated to dryness. The crude product was purified by column chromatography using dichloromethane containing 14% methanol as the mobile phase to give pure compound e. Compound e was dissolved in 5 mL of ethyl acetate. 1 mL of concentrated hydrochloric acid was added to this solution. The mixture was stirred at room temperature for 2 hours. During this time, a white precipitate formed, which was collected by filtration. The precipitate was washed with ethanol and dried under vacuum to give the PyNO2A-R ligand.

[0042] Different PyNO2A-R ligands can be obtained by adding different 2-chloromethylpyridine derivatives (2-chloromethylpyridine, 4-methyl-2-chloromethylpyridine, 4-chloro-2-chloromethylpyridine).

[0043] (2) Preparation of fresh Fe(OH)3: The specific steps are as follows: 2 g of sodium hydroxide is added to 10 mL of pure water to obtain a 16% sodium hydroxide solution for later use; 6 g of ferric nitrate nonahydrate is added to 12 mL of pure water to obtain a 33% ferric nitrate aqueous solution; the sodium hydroxide solution is slowly added to the ferric nitrate aqueous solution under rapid stirring until the pH reaches about 9, at which point the addition is stopped, resulting in an alkaline solution of ferric hydroxide. The precipitate is washed with pure water to remove the supernatant and remove impurity ions such as nitrate and sodium ions from the solution. Washing is repeated multiple times until the conductivity of the solution is below 2 mS·cm. -1 The washing process is stopped once the ions in the solution have been largely removed. After washing, 0.3 g of p-toluenesulfonic acid is added to adjust the pH of the solution to approximately 6. Ferric p-toluenesulfonate is then removed from the ferric hydroxide solution by washing. Finally, water is removed from the ferric hydroxide solution by freeze-drying to obtain solid activated ferric hydroxide.

[0044] Example 1

[0045] 0.505 g of ligand PyNO2A-H and 0.24 g of freshly prepared Fe(OH)3 were weighed into a 50 mL reaction flask equipped with a magnetic stir bar. 10 mL of deionized water was added to the flask, and the mixture was stirred until a suspension was formed. The mixture was stirred at 25 °C for 12 hours. Excess Fe(OH)3 was then removed by filtration, yielding a clear brown solution containing the iron complex. The solution was concentrated under reduced pressure to obtain a crude product of the iron complex. These iron complexes were then transferred to the methanol phase, and slow diffusion in anhydrous diethyl ether solution yielded purified Fe-PyNO2A-H as a brownish-yellow solid, with a yield of 90%.

[0046] The brownish-yellow crystals prepared in the above embodiments of suitable size were selected for X-ray single-crystal diffraction analysis. The analysis revealed that the complex structural unit cation center consisted of a Fe(III) ion and a triazacyclic nonane macrocyclic skeleton with two acetate side groups and a pyridine-N derivative side arm. Its structural formula is [C]. 16 H 22 [Fe], crystal system is orthorhombic, space group is Pbca, unit cell parameters α = 90°, β = 90°, γ = 90°; the iron ion has a six-coordinate geometry, with four nitrogen atoms and two oxygen atoms as the six coordinating atoms ( Figure 5 ).

[0047] ESI-MS spectrum. m / z = 390.0989, [M+H]+; calcd: 390.10.

[0048] Example 2

[0049] 0.526 g of ligand PyNO2A-CH3 and 0.24 g of freshly prepared Fe(OH)3 were weighed into a 50 mL reaction flask equipped with a magnetic stir bar. 10 mL of deionized water was added to the flask, and the mixture was stirred until a suspension was formed. The mixture was stirred at 25 °C for 12 hours. Excess Fe(OH)3 was then removed by filtration, yielding a clear brown solution containing the iron complex. The solution was concentrated under reduced pressure to obtain a crude product of the iron complex. These iron complexes were then transferred to the methanol phase, and slow diffusion in anhydrous diethyl ether solution yielded a purified brownish-yellow solid of Fe-PyNO2A-CH3, with a yield of 89%.

[0050] ESI-MS spectrum. m / z = 404.1124, [M+H] + ; calcd.: 404.11.

[0051] Example 3

[0052] 0.556 g of ligand PyNO2A-Cl and 0.24 g of freshly prepared Fe(OH)3 were weighed into a 50 mL reaction flask equipped with a magnetic stir bar. 10 mL of deionized water was added to the flask, and the mixture was stirred until a suspension was formed. The mixture was stirred at 25 °C for 12 hours. Excess Fe(OH)3 was then removed by filtration, yielding a clear brown solution containing the iron complex. The solution was concentrated under reduced pressure to obtain a crude product of the iron complex. These iron complexes were then transferred to the methanol phase, and slow diffusion in anhydrous diethyl ether solution yielded purified Fe-PyNO2A-Cl as a brownish-yellow solid, with a yield of 87%.

[0053] ESI-MS spectrum. m / z = 424.0495, [M+H] + calcd.: 424.05.

[0054] Example 4

[0055] N-aryltetrahydroisoquinoline (0.1 mmol, 23.9 mg) and Fe-PyNO2A-H catalyst (0.01 mmol, 3.9 mg) were added to a Schlenk tube fitted with a magnetic stir bar. DBN (0.15 mmol, 18 μL) was then injected using a microsyringe, followed by the addition of MeCN (2.0 mL) and H2O (2.0 mL). The reaction tube was purged with oxygen three times, and the reaction was maintained in an oxygen atmosphere using an oxygen balloon. The reaction was stirred at 30 °C for 8 h. After the reaction was complete, the product was extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then purified by column chromatography to obtain the oxidation product of N-aryltetrahydroisoquinoline, a pale yellow solid, with a yield of 83%. The 1H NMR spectrum of the oxidation product of N-aryltetrahydroisoquinoline is shown below. Figure 6 As shown; the carbon NMR spectrum of the oxidation product of N-aryltetrahydroisoquinoline is shown below. Figure 7 As shown.

[0056] 1 H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 7.6 Hz, 1H), 7.46 (t, J = 7.0Hz, 1H), 7.37 (t, J = 7.4 Hz, 1H), 7.26 (dd, J = 23.8, 8.1 Hz, 3H), 6.94 (d,J = 8.8 Hz, 2H), 3.94 (t, J = 6.5 Hz, 2H), 3.82 (s, 3H), 3.13 (t, J = 6.4 Hz,2H). 13 C NMR (101 MHz, CDCl3) δ 164.4, 157.8, 138.3, 136.1, 131.9, 129.8,128.7, 127.2, 127.0, 126.7, 114.3, 55.5, 49.7, 28.7.

[0057] Example 5

[0058] N-aryltetrahydroisoquinoline (0.1 mmol, 23.9 mg) and Fe-PyNO2A-CH3 catalyst (0.01 mmol, 4.0 mg) were added to a Schlenk tube fitted with a magnetic stir bar. DBN (0.15 mmol, 18 μL) was then injected using a microsyringe, followed by the addition of MeCN (2.0 mL) and H2O (2.0 mL). The reaction tube was purged three times with oxygen, and the reaction was maintained in an oxygen atmosphere using an oxygen balloon. The reaction was stirred at 30 °C for 8 h. After the reaction was complete, the product was extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then purified by column chromatography to obtain the N-aryltetrahydroisoquinoline oxidation product as a pale yellow solid, yield: 85%.

[0059] Example 6

[0060] N-aryltetrahydroisoquinoline (0.1 mmol, 23.9 mg) and Fe-PyNO2A-Cl catalyst (0.01 mmol, 4 mg) were added to a Schlenk tube fitted with a magnetic stir bar. DBN (0.15 mmol, 18 μL) was then injected using a microsyringe, followed by the addition of MeCN (2.0 mL) and H2O (2.0 mL). The reaction tube was purged with oxygen three times, and the reaction was maintained in an oxygen atmosphere using an oxygen balloon. The reaction was stirred at 30 °C for 8 h. After the reaction was complete, the product was extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then purified by column chromatography to obtain the N-aryltetrahydroisoquinoline oxidation product as a pale yellow solid, yield: 77%.

[0061] Example 7

[0062] Regarding the aerobic oxidation of N-aryltetrahydroisoquinoline catalyzed by iron complexes, this invention also optimized the reaction conditions, including the effects of different reaction solvents and base additives on the reaction yield. Details are shown in Table 1 below. The specific synthetic steps are the same as in Example 4, with only a single variable.

[0063] Table 1. Screening of conditions for the aerobic oxidation of N-aryltetrahydroisoquinoline catalyzed by iron complexes.

[0064]

[0065] The preparation of iron complexes in this invention uses solid-phase Fe(OH)3 as the iron source, avoiding the excessive inorganic salts formed by the usual use of iron salts such as ferric chloride; excess Fe(OH)3 can be removed by filtration, which has the advantages of simple synthesis operation, mild reaction conditions, simple post-processing, and high yield. This invention designs a series of ligands with a triazacyclononane macrocyclic skeleton as the core and modified by pyridine-N derivative side chains. This structure forms iron complexes with iron. Its main structural feature is the presence of two acetate side groups and one pyridine-N derivative side group. The three N atoms on the heterocyclic skeleton and the N atoms of the pyridine group and the two O atoms of the carboxyl group are coordinating atoms that form hexadectic coordination with iron. The triazacyclononane skeleton provides rigidity, which is a key element in enhancing the kinetic stability of the complex. Based on previous research on Fe complexes with a triazacyclononane skeleton... 2+ and Fe 3+ Through the study of the complex, this invention has discovered that a triazacyclononane macrocyclic ligand modified with two acetic acid groups can simultaneously stabilize both iron oxidation states. Furthermore, the integration of a pyridine-N donor into the structure to modulate the potential of the complex enables the iron complex Fe-PyNO2A-R to be used for the highly efficient catalytic aerobic oxidation of N-aryltetrahydroisoquinoline.

[0066] This invention discloses a method for preparing and using an iron complex catalyst with a triazacyclononane macrocyclic skeleton. The iron ligand synthesis is simple, requiring only one step, and is conducted under mild conditions. No other reagents or complex reaction procedures are needed during the synthesis, and high-purity iron complexes are obtained after purification. These iron complexes exhibit high catalytic activity and good catalytic effect as catalysts for the aerobic oxidation of N-aryltetrahydroisoquinoline compounds. The solvents for the catalytic reaction are water and acetonitrile, resulting in low pollution and mild reaction conditions. This method is suitable for the oxidation of N-aryltetrahydroisoquinoline compounds, meeting the requirements of environmental friendliness and clean production. It provides a new approach for the chemical synthesis of N-aryltetrahydroisoquinoline oxidation products and has great development potential.

[0067] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. An iron complex having a triazacyclic nonane macrocyclic skeleton, characterized in that: The structural formula of the iron complex is shown in Formula I: (Formula I); R is selected from H, Cl or CH3.

2. The method for preparing the iron complex having a triazacyclic nonane macrocyclic skeleton as described in claim 1, characterized in that: This includes reacting the ligand PyNO2A-R shown in Formula II with freshly prepared Fe(OH)3 in water or methanol with stirring. (Formula II); In Equation II, R is the same as R in Equation I.

3. The method for preparing iron complexes with a triazacyclic nonane macrocyclic skeleton as described in claim 2, characterized in that: The molar ratio of the ligand PyNO2A-R to freshly prepared Fe(OH)3 is 1:1.2~2.

0.

4. The method for preparing the iron complex having a triazacyclic nonane macrocyclic skeleton as described in claim 2, characterized in that: The reaction temperature is 20~40℃.

5. The method for preparing the iron complex having a triazacyclic nonane macrocyclic skeleton as described in claim 2, characterized in that: The preparation method of the ligand PyNO2A-R includes, The 1,4,7-triazacyclononane trihydrochloride shown in Formula III is reacted with N-succinimide tert-butyl carbonate to produce the compound shown in Formula IV; The compound shown in Formula IV reacts with the 2-chloromethylpyridine derivative shown in Formula V to produce the compound shown in Formula VI; The compound represented by formula VI reacts with hydrochloric acid to produce the compound represented by formula VII; The compound shown in Formula VII reacts with tert-butyl bromoacetate to produce the compound shown in Formula VIII; The compound shown in Formula VIII reacts with hydrochloric acid to produce the ligand PyNO2A-R shown in Formula II; (Formula III); (Formula IV); (Form V); (Form VI); (Formula VII); (Form VIII).

6. A method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline, characterized in that: This includes reacting the iron complex having a triazacyclononane macrocyclic skeleton as described in claim 1 with N-aryltetrahydroisoquinoline and a base in a solvent in an oxygen atmosphere; The N-aryltetrahydroisoquinoline structure is as follows: ； The structure of the oxidation product is as follows: 。 7. The method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline as described in claim 6, characterized in that: The iron complex Fe-PyNO2A-R has a catalytic content of 5-20%.

8. The method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline as described in claim 6 or 7, characterized in that: The base is selected from one or more of DBN, DBU, and Cs2CO3, wherein the molar ratio of N-aryltetrahydroisoquinoline to the base is 1:1.2~2.

0.

9. The method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline as described in claim 8, characterized in that: The solvent includes one or more of water, acetonitrile, DMF, and 1,4-dioxane.

10. The method for catalytic aerobic oxidation of N-aryltetrahydroisoquinoline as described in any one of claims 6, 7, and 9, characterized in that: The reaction temperature is 20~40℃.

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