CN112778184B - A kind of arylation method of tertiary amine α position - Google Patents

Abstract

The invention discloses a method for arylation at the α position of a tertiary amine. The method uses a tertiary amine and a benzonitrile derivative as raw materials for the first time, uses an inorganic base, and stirs for a certain period of time in an organic solvent under visible light irradiation, and then the reaction solution After post-treatment, the α-arylation derivatives of tertiary amines are obtained. The raw materials used in the invention are simple and easy to obtain, the reaction conditions are green and mild, the operation is simple, the oxidant and metal catalyst are not used, the reaction system does not need nitrogen protection and anhydrous treatment, and has good industrial application value.

Description

A kind of arylation method of tertiary amine α position

technical field

The invention relates to the technical field of medicine, in particular to a method for arylation at the α-position of a tertiary amine.

Background technique

Tertiary amine compounds are a class of important compounds with diverse biological and physiological activities, which are widely found in natural and non-natural products such as nimesulide and flutamide. Functionalized aryl tertiary amines, especially those modified with fragile groups (C–I, C–Br, C=C, C≡C, C=O, C=N or/and C=N, etc.) Important organic raw materials have important applications in the fields of medicine, pesticides, dyes, and materials, and their green, efficient, and atom-economical synthesis has always been one of the focuses of organic synthesis research.

In recent years, chemists have carried out a lot of modification work on the α-position C-H of tertiary amines, and the obtained tertiary amine derivatives can be used to synthesize various pharmaceutical intermediates. This work not only enriches the types of tertiary amine derivatives, but also expands the application of tertiary amines in medicine. The synthesis of tertiary amine derivatives is of great significance. However, at present, the modification of the α-position C-H bond of tertiary amines is mostly metal catalysis and other methods, most of which use expensive metal catalysts for coupling reactions and usually require high temperature reactions. Therefore, it is necessary to develop some simple green methods for structurally diverse modification of tertiary amines.

SUMMARY OF THE INVENTION

The object of the present invention is to overcome the deficiencies of the above-mentioned prior art, provide a kind of arylation method of tertiary amine α position, the raw material used is simple and easy to obtain, the reaction condition is green, mild, the operation is simple, does not use oxidant and metal catalyst, the reaction system It does not need nitrogen protection and anhydrous treatment, and has good industrial application value.

In order to achieve the above object, the present invention adopts the following technical solutions:

A method for arylation at the α position of a tertiary amine, comprising the following steps: in an organic solvent, mixing a tertiary amine, a benzonitrile derivative and a base, stirring and reacting under visible light irradiation, and then post-processing the reaction solution to obtain a tertiary amine Amine α-arylation derivatives; the structural formula of the tertiary amine α-arylation derivatives is:

one of the

Among them, 1≤n≤3 and n is an integer;

R ₁ is H, methyl or halogen atom, the substitution position is ortho position, meta position, para position, including mono-substitution and multi-substitution, and the substitution position of R ₁ is preferably o-position mono-substitution or multi-substitution, meta-position mono-substitution or multi-substitution Substitution, para-substitution;

R ₂ includes, but is not limited to, cyano, methoxycarbonyl, and the R ₂ group is ortho-, meta- or para-substituted;

R ₃ is C _m H _2m+1 , R ₄ is C _m H _2m , 1≤m≤5 and m is an integer.

The organic solvent is one of N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, acetonitrile, and N-methylpyrrolidone.

Described tertiary amine is selected from a kind of in following structural formula:

The material ratio of the tertiary amine, the benzonitrile derivative and the base is 2-4:1:2-4, preferably 2:1:2.

The benzonitrile derivatives include, but are not limited to, 1,2-cyanobenzene, 1,3-dicyanobenzene, 1,4-dicyanobenzene, methyl 4-cyanobenzoate.

The base is an inorganic base, including one of sodium carbonate, sodium acetate, potassium phosphate, potassium acetate, potassium carbonate, cesium carbonate and cesium acetate.

The visible light is blue light generated by LEDs.

The stirring reaction time is 15-40 h, and the reaction temperature is room temperature.

The post-processing method is as follows: after the reaction is completed, the generated product is subjected to extraction, rotary evaporation, column chromatography, rotary evaporation and suction to dry to obtain the α-arylation derivative of the tertiary amine.

The structural formula of the α-arylation derivative of the tertiary amine is one of the structural formulas shown in formula (A) to formula (L):

The beneficial effects of the present invention are:

(1) The reaction conditions are mild: the raw materials are mixed and stirred at room temperature and under blue light irradiation to generate the product.

(2) The reaction conditions are green, and the operation is simple: the reaction does not require a metal catalyst, an oxidant, and the reaction system does not require water removal and oxygen-free operations.

(3) Tertiary amine and benzonitrile derivatives are simple and easy to obtain, and it is easy to obtain tertiary amine derivatives with various structures and high purity by changing the raw materials.

Detailed ways

Below in conjunction with specific embodiment, the present invention is further described:

Example 1

Investigate the influence and effect of different bases on the reaction: add magneton, 1-phenylpyrrolidine (0.75mmol), terephthalonitrile (0.5mmol), different bases (0.75mmol), N,N into a 20mL reaction tube in turn. - Dimethylacetamide (5 mL), reacted at room temperature and under blue light irradiation for 16 hours. The reaction solution was extracted with ethyl acetate, and rotary-evaporated. Using 1,3,5-trimethoxybenzene as the internal standard, the yield was calculated by H NMR spectrum, as shown in Table 1.

Table 1

serial number base yield Example 1-1 K₃PO₄ 64% Example 1-2 KOAc 56% Examples 1-3 K₂CO₃ 66% Examples 1-4 Cs₂CO₃ 81%

Analysis: The comparison shows that under the same conditions, the product obtained by Cs ₂ CO ₃ catalysis has the highest yield and is cheap.

The products of Examples 1-4 were identified by ¹ H-NMR and ¹³ C-NMR, and the ¹ H-NMR and ¹³ C-NMR data were as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.61 (d, J=8.4 Hz, 2H), 7.38 (d, J=8.0 Hz, 2H), 7.21-7.16 (m, 2H), 6.71 (dd, J=7.2 ,7.6Hz,1H),6.48(d,J=7.6Hz,2H),4.78(dd,J=8.8,2.4Hz,1H),3.80-3.75(m,1H),3.49-3.43(m,1H) ,2.51-2.43(m,1H),2.8-2.01(m,2H),1.97-1.92(m,1H).

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 150.5, 146.7, 132.5 (×2), 129.2 (×2), 126.8 (×2), 119.0, 116.5, 112.4 (×2), 110.6, 62.8, 49.2, 35.9, 23.1.

The product structure is:

Example 2

Investigate the influence and effect of different solvents on the reaction: add magneton, 1-phenylpyrrolidine (1.5mmol), terephthalonitrile (0.5mmol), Cs ₂ CO ₃ , and different solvents (5 mL) to a 20 mL reaction tube in turn. , at room temperature and under blue light irradiation for 16 hours. The reaction solution was extracted with ethyl acetate, and rotary-evaporated. Using 1,3,5-trimethoxybenzene as the internal standard, the yield was calculated by H NMR spectrum, as shown in Table 2.

Table 2

serial number Organic solvents Cs₂CO₃ dosage yield Example 2-1 DMA 1.1mmol 87% Example 2-2 DMSO 1mmol 36% Example 2-3 DMF 1mmol 78% Example 2-4 NMP 1mmol 77% Example 2-5 CH₂Cl₂ 1mmol 0%

Analysis: The comparison shows that under the same conditions, the product obtained by using DMA as the solvent has the highest yield and is cheap.

Example 3

Investigate the influence and effect of different reactant ratios on the reaction: in a 20mL reaction tube, add magneton, 1-phenylpyrrolidine (x mmol), terephthalonitrile (0.5mmol), Cs ₂ CO ₃ (y mmol) in turn , different solvents (5 mL), and reacted for 16 hours at room temperature and under blue light irradiation. The reaction solution was extracted with ethyl acetate, rotary evaporated, separated by column chromatography, the solvent was removed by rotary evaporation, and the target product was obtained after vacuum oil pump drying. The yield of each product was obtained by weighing and calculation, as shown in Table 3.

table 3

Analysis: The comparison shows that, under the same other conditions, when the ratio of tertiary amine: terephthalonitrile: Cs ₂ CO ₃ is 2:1:2, the product yield is high and cheap.

Example 4

Into a 20 mL reaction tube were sequentially added magneton, 1-(3,5-dimethylphenyl)pyrrolidine (1 mmol), terephthalonitrile (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N- Dimethylacetamide (5 mL) was reacted at room temperature under blue light irradiation for 15 hours. The reaction solution was extracted with ethyl acetate, rotary-evaporated, separated by column chromatography, and the solvent was removed by rotary evaporation. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR, and the data of ¹ H-NMR and ¹³ C-NMR are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.70 (d, J=7.6 Hz, 1H), 7.47 (ddd, J=8.0, 8.0, 1.2 Hz, 1H), 7.35-7.30 (m, 2H), 6.37 (s ,1H),6.09(s,2H),5.04(dd,J=8.8,2.0Hz,1H),3.79-3.74(m,1H),3.47-3.41(m,1H),2.57-2.51(m,1H) ), 2.21(s, 6H), 2.05-1.97(m, 3H).

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 149.3, 146.7, 138.7, 133.6, 133.0, 127.2, 126.9, 118.8, 117.8, 110.5 (×2), 110.0, 61.5, 49.5, 35.3, 23.2, 21.7.

The product structure is:

Example 5

Into a 20 mL reaction tube were sequentially added magneton, 1-(3-bromophenyl)pyrrolidine (1 mmol), terephthalonitrile (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N-dimethylethyl acetate The amide (5 mL) was reacted at room temperature under blue light irradiation for 40 hours. The reaction solution was extracted with ethyl acetate, rotary-evaporated, separated by column chromatography, and then rotary-evaporated to remove the solvent, and the target product was obtained after being dried by a vacuum oil pump, and the yield was 50%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR, and the data of ¹ H-NMR and ¹³ C-NMR are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.59 (d, J=8.4 Hz, 2H), 7.31 (d, J=8.4 Hz, 2H), 6.96 (dd, J=8.0, 8.0 Hz, 1H), 6.78 ( dd,J＝7.6,0.8Hz,1H),6.62(dd,J＝2.0,2.0Hz,1H),6.30(dd,J＝8.0,2.0Hz,1H),4.74(dd,J＝8.8,2.0Hz ,1H),3.72-3.67(m,1H),3.42-3.38(m,1H),2.48-2.40(m,1H),2.06-1.89(m,3H).

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 149.6, 147.9, 132.6 (×2), 130.4, 126.7 (×2), 123.3, 119.3, 118.9, 115.1, 111.2, 110.8, 62.7, 49.3, 35.9, 23.0.

The product structure is:

Example 6

Into a 20 mL reaction tube were sequentially added magnetron, 1-(3-chlorophenyl)pyrrolidine (1 mmol), terephthalonitrile (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N-dimethylethyl acetate The amide (5 mL) was reacted at room temperature under blue light irradiation for 40 hours. The reaction solution was extracted with ethyl acetate, rotary evaporated, separated by column chromatography, then rotary evaporated to remove the solvent, and the target product was obtained after drying by vacuum oil pump with a yield of 54%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR. , ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.59 (d, J=8.4 Hz, 2H), 7.31 (d, J=8.0 Hz, 2H), 7.03 (dd, J=8.0, 8.0 Hz, 1H), 6.64 ( dd,J＝7.2,1.2Hz,1H),6.45(dd,J＝2.4,2.0Hz,1H),6.27(dd,J＝8.0,2.0Hz,1H),4.74(dd,J＝8.8,2.4Hz ,1H),3.73-3.68(m,1H),3.45-3.38(m,1H),2.50-2.41(m,1H),2.05-2.02(m,2H),1.95-1.89(m,1H).

¹³ C NMR (100MHz, CDCl ₃ ) δppm 149.7, 147.7, 135.0, 132.6 (×2), 130.1, 126.7 (×2), 118.9, 116.4, 112.3, 110.8, 62.7, 49.3, 35.8, 23.0.

The product structure is:

Example 7

Into a 20 mL reaction tube were sequentially added magneton, 1-(3,5-dimethylphenyl)pyrrolidine (1 mmol), phthalonitrile (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N- Dimethylacetamide (5 mL) was reacted at room temperature under blue light irradiation for 40 hours. The reaction solution was extracted with ethyl acetate, rotary-evaporated, separated by column chromatography, and then rotary-evaporated to remove the solvent. The target product was obtained after drying by a vacuum oil pump. The yield was 51%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR. , ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.70 (d, J=7.6 Hz, 1H), 7.47 (ddd, J=8.0, 8.0, 1.2 Hz, 1H), 7.35-7.30 (m, 2H), 6.37 (s ,1H),6.09(s,2H),5.04(dd,J=8.8,2.0Hz,1H),3.79-3.74(m,1H),3.47-3.41(m,1H),2.57-2.51(m,1H) ), 2.21(s, 6H), 2.05-1.97(m, 3H).

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 149.3, 146.7, 138.7, 133.6, 133.0, 127.2, 126.9, 118.8, 117.8, 110.5 (×2), 110.0, 61.5, 49.5, 35.3, 23.2, 21.7.

The product structure is:

Example 8

Into a 20mL reaction tube were sequentially added Magnon, 1-phenylpyrrolidine (1mmol), isophthalonitrile (0.5mmol), Cs ₂ CO ₃ (1mmol), and N,N-dimethylacetamide (5mL), React at room temperature and under blue light irradiation for 40 hours. The reaction solution was extracted with ethyl acetate, rotary evaporated, separated by column chromatography, and then the solvent was removed by rotary evaporation. The target product was obtained after drying with a vacuum oil pump. The yield was 48%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR. , ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400MHz, CDCl ₃ ) δppm 7.56-7.50 (m, 3H), 7.44 (d, J=7.6Hz, 1H), 7.21-7.17 (m, 2H), 6.72 (dd, J=7.6, 7.2Hz ,1H),6.49(d,J＝7.6Hz,2H),4.76(dd,J＝8.4,2.0Hz,1H),3.80-3.75(m,1H),3.48-3.42(m,1H),2.50- 2.41(m,1H),2.07-2.00(m,2H),1.95-1.91(m,1H).

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 146.7, 146.5, 130.6 (×2), 129.7, 129.4, 129.2 (×2), 119.1, 116.6, 112.6 (×2), 112.5, 62.5, 49.3, 36.0, 23.1.

The product structure is:

Example 9

Into a 20 mL reaction tube were sequentially added magneton, 1-phenylazepane (1 mmol), terephthalonitrile (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N-dimethylacetamide ( 5mL), reacted for 15 hours at room temperature and under blue light irradiation. The reaction solution was extracted with ethyl acetate, rotary-evaporated, separated by column chromatography, and the solvent was removed by rotary evaporation. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR, and the data of ¹ H-NMR and ¹³ C-NMR are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.63 (d, J=8.4 Hz, 2H), 7.36 (d, J=8.4 Hz, 2H), 7.20 (dd, J=7.2, 7.2, 0.8 Hz, 2H) ,6.70(dd,J＝7.2,7.2Hz,1H),6.61(d,J＝8.0Hz,2H),4.68(dd,J＝12.0,6.0Hz,1H),3.91(dd,J＝17.6,4.0 Hz,1H),3.56-3.49(m,1H),2.52-2.45(m,1H),2.03-1.73(m,5H),1.58-1.48(m,1H),1.46-1.30(m,1H)

¹³ C NMR (100 MHz, CDCl ₃ ) δ 150.2, 148.5, 132.7 (×2), 129.3 (×2), 126.7 (×2), 119.0, 116.1, 111.4 (×2), 110.5, 63.0, 45.3, 38.2, 29.6 , 28.3, 26.6.

The product structure is:

Example 10

Into a 20 mL reaction tube were sequentially added magneton, 1-(naphthalen-2-yl)pyrrolidine (1 mmol), terephthalonitrile (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N-dimethylethyl acetate The amide (5 mL) was reacted at room temperature under blue light irradiation for 15 hours. The reaction solution was extracted with ethyl acetate, rotary-evaporated, separated by column chromatography, the solvent was removed by rotary evaporation, and the target product was obtained after drying with a vacuum oil pump in a yield of 55%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR, ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.67-7.56 (m, 5H), 7.37 (d, J=8.0 Hz, 2H), 7.37-7.33 (m, 1H), 7.21-7.17 (m, 1H), 6.82 (dd,J=9.2,2.8Hz,1H),6.70(d,J=2.4Hz,1H),4.90(dd,J=8.8,2.0Hz,1H),3.88-3.83(m,1H),3.59- 3.53(m,1H),2.55-2.45(m,1H),2.10-1.94(m,3H).

¹³ C NMR (100MHz, CDCl ₃ ) δppm 150.4, 144.5, 134.9, 132.5 (×2), 128.9, 127.6, 126.8 (×2), 126.6, 126.4, 126.0, 121.9, 119.0, 115.9, 110.7, 106.0, 62.8, 49.4, 36.0, 23.2.

The product structure is:

Example 11

Into a 20mL reaction tube were sequentially added magnon, 4-phenylmorpholine (1mmol), terephthalonitrile (0.5mmol), Cs ₂ CO ₃ (1mmol), N,N-dimethylacetamide (5mL), React at room temperature and under blue light irradiation for 15 hours. The reaction solution was extracted with ethyl acetate, rotary-evaporated, separated by column chromatography, the solvent was removed by rotary evaporation, and the target product was obtained after drying by a vacuum oil pump with a yield of 30%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR. ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.49 (d, J=8.4 Hz, 2H), 7.43 (d, J=8.4 Hz, 2H), 7.16 (dd, J=8.8, 8.8 Hz, 2H), 6.89 ( d, J=7.6Hz, 2H), 6.88 (dd, J=7.6, 7.6Hz, 1H), 4.44-4.41 (m, 1H), 3.98-3.94 (m, 3H), 3.65-3.60 (m, 1H) ,3.42(dt,J＝12.4,3.6Hz,1H),3.15-3.09(m,1H).

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 150.4, 144.9, 132.2 (×2), 129.0 (×2), 128.6 (×2), 122.4, 121.1 (×2), 118.7, 111.1, 72.6, 67.6, 61.4, 52.6.

The product structure is:

Example 12

Into a 20 mL reaction tube were sequentially added magneton, N,N-dimethylaniline (1 mmol), terephthalonitrile (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N-dimethylacetamide (5 mL) ) for 15 hours at room temperature and under blue light irradiation. The reaction solution was extracted with ethyl acetate, rotary evaporated, separated by column chromatography, the solvent was removed by rotary evaporation, and the target product was obtained after drying with a vacuum oil pump in a yield of 43%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR. ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.64 (d, J=8.0 Hz, 2H), 7.39 (d, J=7.6 Hz, 2H), 7.28 (dd, J=8.0, 8.0 Hz, 2H), 6.80 (dd,J=7.2,7.2Hz,1H),6.75(d,J=8.4Hz,2H),4.62(s,2H),3.09(s,3H).

¹³ C NMR (100 MHz, CDCl ₃ ) δ 149.2, 145.0, 132.5 (×2), 129.4 (×2), 127.4 (×2), 118.9, 117.3, 112.5 (×2), 110.8, 56.7, 38.9.

The product structure is:

Example 13

Into a 20mL reaction tube were sequentially added magneton, 1-phenylpyrrolidine (1mmol), phthalonitrile (0.5mmol), Cs ₂ CO ₃ (1mmol), and N,N-dimethylacetamide (5mL), React at room temperature and under blue light irradiation for 40 hours. The reaction solution was extracted with ethyl acetate, rotary evaporated, separated by column chromatography, the solvent was removed by rotary evaporation, and the target product was obtained after drying by a vacuum oil pump with a yield of 48%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR, ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.70 (dd, J=7.6, 0.8 Hz, 1H), 7.47 (ddd, J=7.6, 7.6, 1.6 Hz, 1H), 7.34-7.29 (m, 2H), 7.18 -7.14(m,2H),6.68(dd,J=7.6,7.6Hz,1H),6.44(d,J=8.0Hz,2H),5.05(dd,J=10.0,2.0Hz,1H),3.81- 3.76(m,1H),3.49-3.43(m,1H),2.63-2.53(m,1H),2.09-1.98(m,3H)

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 149.0, 146.5, 133.6, 133.0, 129.1 (×2), 127.3, 126.8, 117.7, 116.6, 112.5 (×2), 110.1, 61.5, 49.4, 35.3, 23.3.

The product structure is:

Example 14

Into a 20 mL reaction tube were added magneton, 1-phenylpyrrolidine (1 mmol), methyl p-cyanobenzoate (0.5 mmol), Cs ₂ CO ₃ (1 mmol), N,N-dimethylacetamide ( 5mL), reacted for 15 hours at room temperature and under blue light irradiation. The reaction solution was extracted with ethyl acetate, rotary evaporated, separated by column chromatography, the solvent was removed by rotary evaporation, and the target product was obtained after drying by vacuum oil pump with a yield of 11%. The structure of the product was confirmed by ¹ H-NMR and ¹³ C-NMR. ¹ H-NMR and ¹³ C-NMR data are as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δppm 7.97 (d, J=8.0 Hz, 2H), 7.31 (d, J=8.0 Hz, 2H), 7.17-7.12 (m, 2H), 6.66 (t, J=8.0 Hz, 1H), 6.47(d, J=8.0Hz, 2H), 4.75(dd, J=8.4, 2.4Hz, 1H), 3.90(s, 3H), 3.76-3.71(m, 1H), 3.43(q , J＝8.0Hz, 1H), 2.45-2.38(m, 1H), 2.05-1.96(m, 2H), 1.95-1.92(m, 1H)

¹³ C NMR (100 MHz, CDCl ₃ ) δppm 167.0, 150.2, 146.9, 129.9 (×2), 129.1 (×2), 128.7, 126.0 (×2), 116.2, 112.4 (×2), 62.9, 52.0, 49.2, 35.9, 23.2.

The product structure is:

The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection of the present invention. within the range.

Claims (4)

1. the arylation method of a tertiary amine α position, it is characterized in that: comprise the following steps: in organic solvent, after tertiary amine, benzonitrile derivative, alkali are mixed, stirring reaction under visible light irradiation, then reaction solution After post-treatment, the α-arylation derivatives of tertiary amines are obtained; Described tertiary amine is selected from a kind of in following structural formula:

The organic solvent is one of N,N-dimethylacetamide, N,N-dimethylformamide and N-methylpyrrolidone; the benzonitrile derivative is 1,2-dicyano One of benzene, 1,3-dicyanobenzene and 1,4-dicyanobenzene; the base is one of potassium phosphate, potassium acetate, potassium carbonate, and cesium carbonate; the visible light is made of LED The blue light generated; the tertiary amine α-arylation derivative is one of the following structural formulas:

2. the arylation method of a kind of tertiary amine α position as claimed in claim 1, it is characterized in that: the ratio of the amount of substance of described tertiary amine, benzonitrile derivative, alkali is 2～4:1:2 ~4. 3. The arylation method of a tertiary amine α-position as claimed in claim 1, characterized in that: the stirring reaction time is 15-40 h, and the reaction temperature is room temperature. 4. the arylation method of a kind of tertiary amine α position as claimed in claim 1, it is characterized in that: described post-processing method is: after reaction finishes, the product generated is through extraction, rotary evaporation, column chromatography, rotary Evaporate and drain to obtain α-arylation derivatives of tertiary amines.