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Method for continuously preparing dihydrobenzo [j] phenanthridine compound containing trifluoromethyl functional group by using micro-channel reaction device

A technology of trifluoromethyl function and microchannel reaction, which is applied in organic chemistry and other fields, can solve the problems of limited amplification potential and long reaction time, and achieve the effects of facilitating industrial amplification, shortening reaction time, and controlling reaction rate

Active Publication Date: 2020-08-04
NANJING UNIV OF TECH
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  • Abstract
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Problems solved by technology

However, these methods still suffer from long reaction times and limited scale-up potential, which will limit their further applications

Method used

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  • Method for continuously preparing dihydrobenzo [j] phenanthridine compound containing trifluoromethyl functional group by using micro-channel reaction device
  • Method for continuously preparing dihydrobenzo [j] phenanthridine compound containing trifluoromethyl functional group by using micro-channel reaction device
  • Method for continuously preparing dihydrobenzo [j] phenanthridine compound containing trifluoromethyl functional group by using micro-channel reaction device

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052]

[0053] Microchannel reaction device see figure 1 , weigh R 1 is phenyl, R 1 for hydrogen, R 3 0.2666 g (0.5 mmol, 1.0 equiv) of 1,7 enyne reactant (4-(tert-butyl) phenyl) sulfonyl), weak base 2,6-lutidine 0.107 g (1.0 mmol, 2.0 equiv) and dissolved in 1.25mL of dichloromethane to obtain a homogeneous solution A, weighed trifluoromethyl source Umemoto reagent (2b) 0.340g (1.0mmol, 2.0equiv), photocatalyst fac-Ir (ppy) 3 (pc -1) 0.0198g (3mol%) was dissolved in 1.25mL of dichloromethane to obtain a homogeneous solution B, which was loaded into syringes after complete dissolution. Homogeneous solution A and homogeneous solution B are simultaneously pumped into a reactor with a coil inner diameter of 0.5mm and mixed, the volume is 1mL, the flow rates of homogeneous solution A and homogeneous solution B are both 0.1mL / min, with blue The LED light source (50W, 455nm) was irradiated, and the reaction was carried out at 25° C., and the residence time was 10 minutes. A...

Embodiment 2

[0055]

[0056] The method is the same as in Example 1, except that the source of trifluoromethyl is changed to Yagupo'lskii-Umemoto reagent (2c) 0.404g (1.0mmol, 2.0equiv), and loaded into a syringe after being completely dissolved. Pump homogeneous solution A and homogeneous solution B into a reactor with a coil inner diameter of 0.5mm at the same time, with a volume of 1mL, and the flow rates of both homogeneous solution A and homogeneous solution B are 0.1mL / min. The light source (50W, 455nm) was irradiated, and the reaction was carried out at 25°C, and the residence time was 10min. After the reaction was finished, TLC detection was carried out, and the final product was obtained by column chromatography, 296.08 mg of white solid, with a yield of 98.5%. The characterization data are as follows: 1 H NMR (400MHz, Chloroform-d) δ8.17 (d, J = 8.6Hz, 2H), 7.62 (d, J = 8.6Hz, 2H), 7.55–7.37 (m, 4H), 7.35–7.10 (m, 7H), 6.87–6.72(m, 2H), 3.40(d, J=15.9Hz, 1H), 3.08(d, J=16.0H...

Embodiment 3

[0058] Method is the same as embodiment 2, and difference is that photocatalyst is changed into Ir(ppy) 2 (dtbppy)(PF 6 )( PC-2 ) 0.0138g (3mol%), which were loaded into syringes after being completely dissolved. Pump homogeneous solution A and homogeneous solution B into a reactor with a coil inner diameter of 0.5mm at the same time, with a volume of 1mL, and the flow rates of both homogeneous solution A and homogeneous solution B are 0.1mL / min. The light source (50W, 455nm) was irradiated, and the reaction was carried out at 25°C, and the residence time was 10min. After the reaction was completed, TLC detection was performed, and 289.17 mg of the final product was obtained as a white solid by column chromatography, with a yield of 96.2%. The characterization data are as follows: 1 H NMR (400MHz, Chloroform-d) δ8.17 (d, J = 8.6Hz, 2H), 7.62 (d, J = 8.6Hz, 2H), 7.55–7.37 (m, 4H), 7.35–7.10 (m, 7H), 6.87–6.72(m, 2H), 3.40(d, J=15.9Hz, 1H), 3.08(d, J=16.0Hz, 1H), 2.69–2.40(...

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Abstract

The invention discloses a method for continuously preparing a dihydrobenzo [j] phenanthridine compound containing a trifluoromethyl functional group by using a micro-channel reaction device, which comprises the following steps: (1) dissolving a 1,7-eneyne compound and alkali in a proper solvent to obtain a material I; (2) dissolving a trifluoromethyl reagent and a photocatalyst in a proper solventto obtain a material II; (3) respectively pumping the material I and the material II into a micro-channel reaction device, fully mixing, and carrying out a photocatalytic trifluoromethylation reaction to obtain a reaction solution; and (4) quenching the reaction liquid, adding a corresponding organic solvent for extraction, collecting an organic phase, drying, concentrating and recrystallizing toobtain a target product. The micro-channel reaction device is used for preparing the 1,7-eneyne trifluoromethylation product, the reaction conditions are milder, the reaction rate can be effectivelycontrolled, the reaction time is shortened, continuous production is achieved, side reactions are reduced, the maximum product yield can reach 99.3%, the amplification effect is basically avoided, andindustrial amplification is facilitated.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and specifically relates to a method for continuously preparing dihydrobenzo[j ] The method of phenanthridine compound Background technique [0002] Trifluoromethylated heterocycles, as valuable structures with special chemical and biological properties, have been an attractive topic in the fields of pharmaceuticals, agrochemistry and materials science. As such, it has received increasing attention over the past decade as a powerful strategy that has enabled unprecedented transformations leading to the development of novel and efficient approaches to construct CF-containing 3 of heterocycles. Compared with transitional trifluoromethylation of heterocycles, free radical-trifluoromethylation of various substrates is CF 3 One of the most promising strategies for the synthesis of substituted heterocycles, often exhibiting better economy and diversity. However, almost all of these class...

Claims

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Application Information

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IPC IPC(8): C07D221/18
CPCC07D221/18
Inventor 郭凯崔玉声孙蕲袁鑫邱江凯庄恺强覃龙洲段秀陈琳
Owner NANJING UNIV OF TECH
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