CN107629090B - N,N-coordinated rhodium complexes, synthetic methods and applications - Google Patents

Abstract

The invention belongs to the technical field of organometallic compound synthesis, and particularly relates to N, N-coordination rhodium metal complexes, a synthesis method and application thereof₂The invention has simple synthesis method, the complex can be used as a catalyst for catalyzing reductive amination reaction of series acetophenone and aniline derivatives, and the product yield is good and is more than 90%.

Description

N,N-coordinated rhodium complexes, synthetic methods and applications

technical field

The invention belongs to the technical field of organometallic compound synthesis, in particular to an N,N-coordinated rhodium complex, a synthesis method and applications thereof.

Background technique

In nature, amine groups widely exist in various natural products, such as antibiotics, proteins, alkaloids, etc. At the same time, as important raw materials and intermediates of chemicals, amine compounds have an important position. Among them, the reaction of ketones (aldehydes) with amines (ammonia) to form amine compounds in the presence of reducing agents is a widely used research method. Coordinate unsaturated transition metal complexes have unique structures and excellent catalytic activity. As catalysts, metal complexes greatly promote the development of high selectivity for reductive amination reactions. Therefore, it is of great significance to design ligands and explore the synthesis methods and applications of such complexes.

SUMMARY OF THE INVENTION

The purpose of the present invention is to prepare a kind of N, N-coordinated rhodium metal complex, and to study the application of the rhodium complex as a catalyst to catalyze the reductive amination reaction of a series of derivatives of acetophenone and aniline. Compared with the cationic metal rhodium catalysts reported in the past, the neutral rhodium compound in the present invention has better solubility in organic solvents, and the catalytic efficiency is more excellent; in addition, the use of hydrogen as a cleaning agent as a hydrogen source avoids the use of A large amount of waste residue produced by metal hydrides such as borohydride as a hydrogen source.

The technical solutions of the present invention are specifically introduced as follows.

The technical solutions of the present invention are specifically introduced as follows.

The present invention provides a kind of N, N-coordination rhodium metal complex, has the structure shown in formula I:

The present invention also provides a kind of above-mentioned N, the synthetic method of N-coordination rhodium metal complex, and concrete steps are as follows:

1) First use methyl 1H-pyrrole-2-carboxylate as raw material, hydrolyze under alkaline conditions to generate 1H-pyrrole-2-carboxylic acid; then dissolve 1H-pyrrole-2-carboxylic acid in SOCl ₂ for reflux reaction 1H-pyrrole-2-acid chloride is generated; finally, under alkaline conditions, 1H-pyrrole-2-acid chloride and pyrazole are reacted to generate ligand L, whose structure is shown in formula II:

2) The ligand L and Rh(COD) ₂ Cl are reacted under alkaline conditions to generate N,N-coordinated rhodium metal complexes.

In the present invention, in step 2), the molar ratio of ligand L and Rh(COD) ₂ Cl is 0.95:1 to 1.05:1.

In the present invention, in step 2), the alkali used in the alkaline condition is NaH.

The present invention further provides the application of the above-mentioned N,N-coordinated rhodium metal complex in the reductive amine reaction of the derivatives of acetophenone and aniline.

In the present invention, the structures of the derivatives of acetophenone and aniline are respectively shown in formula III and formula IV:

Wherein: R ₁ and R ₂ are monosubstituted; R ₁ and R ₂ are independently selected from hydrogen, linear or branched C ₁ -C ₁₀ alkyl, linear or branched C ₁ -C ₁₀ alkoxy, halogen , CN or any one of dimethylamino groups.

In the present invention, R ₁ is selected from any one of hydrogen, linear or branched C ₁ -C ₄ groups, linear or branched C ₁ -C ₁₀ alkoxy, halogen, CN or dimethylamino; R ₂ is selected from any one of hydrogen, linear or branched C ₁ -C ₄ group, linear or branched C ₁ -C ₁₀ alkoxy or halogen.

In the present invention, the concrete steps of the application method are as follows:

Acetophenone derivatives, aniline derivatives, N,N-coordinated rhodium metal complexes and MeOH are subjected to reductive amination reaction under the action of H ₂ under heating and pressure to obtain amine compounds.

Compared with the prior art, the present invention has the beneficial effects that the synthesis method is simple and has excellent selectivity; The yield is good, above 90%.

Description of drawings

Figure 1 shows the single crystal structure of complex 1.

Detailed ways

The present invention is further described below through examples, but the present invention is not limited to the following examples.

Example 1: Synthesis of Ligand L

At room temperature, KOH aqueous solution (2.24 g, 40 mmol) was added to the MeOH solution of methyl 1H-pyrrole-2-carboxylate (1.25 g, 10 mmol), followed by stirring for 7 h. After the reaction, 0.5M HCl was added to the solution pH=8, after extraction, filtration, and vacuum concentration, 1H-pyrrole-2-carboxylic acid was obtained. 1H-pyrrole-2-carboxylic acid was dissolved in SOCl ₂ (20 mL), refluxed for 2 h, and the solvent was removed in vacuo to obtain 1H-pyrrole-2-acid chloride. Pyrazole (0.68 g, 10 mmol), 1H-pyrrole-2-acid chloride, _Et3N (1.5 g) was stirred in Et2O for ₂ h at 0 °C. The resulting mixture was concentrated and purified by silica gel column chromatography (n-hexane:ethyl acetate 6:1) to obtain Ligand L as a pale yellow solid (1.35 g, total yield 85%).

Elemental analysis: _C8H7N3O : C 59.62, H _4.38 , N _26.07 ; found: C 59.38, H 4.35, N 26.22.

Example 2: Synthesis of complex 1

Ligand L (48.0 mg, 0.3 mmol), Rh(COD) ₂ Cl (121 mg, 0.3 mmol), NaH (8.6 mg, 0.36 mmol) were stirred in CH ₂ Cl ₂ for 2 h to obtain the crude product. After rotary evaporation and recrystallization, analytically pure rhodium complex 1 (81.43 mg, 73% yield) was obtained.

Elemental analysis: C ₁₆ H ₁₈ N ₃ ORh: C 51.76, H 4.89, N11.32; found: C 51.68, H 4.85, N11.27.

Example 3: General procedure for reductive amination

A series of acetophenone (0.5 mmol), aniline (0.5 mmol) derivatives, complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis.

Example 4: Catalytic acetophenone, reaction 1 of reductive amination of aniline

Adopt the complex 1 that embodiment 2 prepares to catalyze acetophenone, the reductive amination of aniline:

Acetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Example 5: Catalysis 4-methylacetophenone, reaction 2 of reductive amination of aniline

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-methylacetophenone, the reaction of aniline reductive amination:

The substrate 4-methylacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 95% yield.

Example 6: Catalysis 2-methylacetophenone, reaction 3 of reductive amination of aniline

Adopt the complex 1 that embodiment 2 prepares to catalyze 2-methylacetophenone, the reaction of aniline reductive amination:

The substrate 2-methylacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 91% yield.

Example 7: Catalysis of 4-methoxyacetophenone, reaction 4 of reductive amination of aniline

Adopt the complex 1 of embodiment 2 to catalyze 4-methoxyacetophenone, the reaction of aniline reductive amination:

The substrate 4-methoxyacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 8: Catalysis of 4-cyanoacetophenone, reaction 5 of reductive amination of aniline

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-cyanoacetophenone, the reaction of aniline reductive amination:

The substrate 4-cyanoacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Example 9: Catalysis 4-chloroacetophenone, reaction 6 of aniline reductive amination

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-chloroacetophenone, the reaction of aniline reductive amination:

The substrate 4-chloroacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 93% yield.

Example 10: Catalysis of 4-fluoroacetophenone, the reaction of reductive amination of aniline 7

Adopt the complex 1 of embodiment 2 to catalyze 4-fluoroacetophenone, the reaction of aniline reductive amination:

The substrate 4-fluoroacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Example 11: Catalysis of 4-dimethylaminoacetophenone, reaction 8 of the reductive amination of aniline

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-dimethylaminoacetophenone, the reaction of aniline reductive amination:

The substrate 4-dimethylaminoacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 12: Catalysis of 4-isopropylacetophenone, the reaction of reductive amination of aniline 9

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-isopropylacetophenone, the reaction of aniline reductive amination:

The substrate 4-isopropylacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Example 13: Catalysis of 4-tert-butylacetophenone, reaction of aniline reductive amination 10

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-tert-butylacetophenone, the reaction of aniline reductive amination:

The substrate 4-tert-butylacetophenone (0.5 mmol), aniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 91% yield.

Example 14: Catalytic reaction of acetophenone, 4-methoxyaniline reductive amination 11

Adopt the complex 1 that embodiment 2 prepares to catalyze acetophenone, the reductive amination of 4-methoxyaniline:

Acetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 15: Catalytic reaction of 4-methylacetophenone, 4-methoxyaniline reductive amination 12

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-methylacetophenone, the reaction of 4-methoxyaniline reductive amination:

The substrates 4-methylacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Example 16: Catalytic reaction of 2-methylacetophenone, 4-methoxyaniline reductive amination 13

Adopt the complex 1 prepared by embodiment 2 to catalyze 2-methylacetophenone, the reaction of 4-methoxyaniline reductive amination:

The substrates 2-methylacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 92% yield.

Example 17: Catalytic reaction of 4-methoxyacetophenone, 4-methoxyaniline reductive amination 14

Adopt the complex 1 of embodiment 2 to catalyze 4-methoxyacetophenone, the reaction of 4-methoxyaniline reductive amination:

The substrates 4-methoxyacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Example 18: Catalytic reaction of 4-cyanoacetophenone, 4-methoxyaniline reductive amination 15

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-cyanoacetophenone, the reaction of reductive amination of 4-methoxyaniline:

The substrates 4-cyanoacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 19: Catalytic reaction of 4-chloroacetophenone, 4-methoxyaniline reductive amination 16

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-chloroacetophenone, the reaction of 4-methoxyaniline reductive amination:

The substrates 4-chloroacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 95% yield.

Example 20: Catalytic reaction of 4-fluoroacetophenone, 4-methoxyaniline reductive amination 17

The complex 1 prepared in Example 2 is used to catalyze 4-fluoroacetophenone, the reaction of the reductive amination of 4-methoxyaniline:

The substrates 4-fluoroacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 91% yield.

Example 21: Catalytic reaction of 4-dimethylaminoacetophenone, 4-methoxyaniline reductive amination 18

Using complex 1 prepared in Example 2 to catalyze the reductive amination of 4-dimethylaminoacetophenone, 4-methoxyaniline: the substrate 4-dimethylaminoacetophenone (0.5mmol), 4-methylaminoacetophenone Oxyaniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 96% yield.

Example 22: Catalytic reaction of 4-isopropylacetophenone, 4-methoxyaniline reductive amination 19

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-isopropylacetophenone, the reaction of 4-methoxyaniline reductive amination:

The substrates 4-isopropylacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 92% yield.

Example 23: Catalytic reaction of 4-tert-butylacetophenone, 4-methoxyaniline reductive amination 20

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-tert-butylacetophenone, the reaction of 4-methoxyaniline reductive amination:

The substrates 4-tert-butylacetophenone (0.5 mmol), 4-methoxyaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 24: Catalytic acetophenone, 4-chloroaniline reductive amination reaction 21

Adopt the complex 1 that embodiment 2 prepares to catalyze acetophenone, the reductive amination of 4-chloroaniline:

Acetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 25: Catalytic reaction of 4-methylacetophenone, 4-chloroaniline reductive amination 22

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-methylacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 4-methylacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 91% yield.

Example 26: Catalytic reaction of 2-methylacetophenone, 4-chloroaniline reductive amination 23

Adopt the complex 1 that embodiment 2 prepares to catalyze 2-methylacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 2-methylacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 95% yield.

Example 27: Catalytic reaction of 4-methoxyacetophenone, 4-chloroaniline reductive amination 24

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-methoxyacetophenone, the reaction of reductive amination of 4-chloroaniline:

The substrates 4-methoxyacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 92% yield.

Example 28: Catalytic Reductive Amination of 4-Cyanoacetophenone, 4-Chloroaniline 25

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-cyanoacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 4-cyanoacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol %) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Example 29: Catalytic reaction of 4-chloroacetophenone, 4-chloroaniline reductive amination 26

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-chloroacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 4-chloroacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 93% yield.

Example 30: Catalytic Reductive Amination of 4-Fluoroacetophenone, 4-Chloroaniline 27

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-fluoroacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 4-fluoroacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 31: Catalysis of 4-Dimethylaminoacetophenone, Reductive Amination of 4-Chloroaniline 28

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-dimethylaminoacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 4-dimethylaminoacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 91% yield.

Example 32: Catalytic reaction of 4-isopropylacetophenone, 4-chloroaniline reductive amination 29

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-isopropylacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 4-isopropylacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 94% yield.

Example 33: Catalytic reaction of 4-tert-butylacetophenone, 4-chloroaniline reductive amination 30

Adopt the complex 1 that embodiment 2 prepares to catalyze 4-tert-butylacetophenone, the reaction of 4-chloroaniline reductive amination:

The substrates 4-tert-butylacetophenone (0.5 mmol), 4-chloroaniline (0.5 mmol), complex 1 (5 mol%) and MeOH (2 mL) were added to a 10 ml flask. The flask was transferred to the autoclave, disconnected from the H source after _three cycles of pressurization/evacuation, and the autoclave was heated to the desired temperature for the reaction. After stirring for 12 h, the autoclave was cooled and the pressure was slowly released. The resulting mixture was added to the internal standard (n-tridecane) to obtain a drop for GC analysis in 90% yield.

Claims (3)

1. The application of N, N-coordination rhodium metal complexes in reductive amination reaction of acetophenone and aniline derivatives, wherein the N, N-coordination rhodium metal complexes have a structure shown in formula I:

   

   wherein:

   the structures of the derivatives of acetophenone and aniline are respectively shown in formula III and formula IV:

   

   wherein: r₁，R₂Is monosubstituted; r₁、R₂Independently selected from hydrogen, straight or branched chain C₁～C₁₀Alkyl, straight or branched C₁～C₁₀ of alkoxy, halogen, CN or dimethylamino.
2. 2.Use according to claim 1, wherein R is₁Selected from hydrogen, straight or branched C₁～C₄Radical, straight-chain or branched C₁～C₁₀ of alkoxy, halogen, CN or dimethylamino₂Selected from hydrogen, straight or branched C₁～C₄Radical, straight-chain or branched C₁～C₁₀ of alkoxy or halogen.
3. 3. The application of claim 1, wherein the application method comprises the following specific steps:

   reacting acetophenone derivatives, aniline derivatives, N, N-coordinated rhodium metal complexes and MeOH in the presence of H₂Under the action of the reaction, heating and pressurizing to perform reductive amination reaction to obtain the amine compound.

Images