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Bivalent manganese catalyzed arylamine ortho-enylation reaction method

A technology of divalent manganese catalysis and divalent manganese, which is applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of large amount of Lewis acid, increased production cost, large amount of catalyst, etc., and achieves good results. Catalytic effect, improved yield, low environmental pollution effect

Active Publication Date: 2021-03-12
杨锦飞
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  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, the method of synthesizing ortho-alkenyl arylamines from arylamines and terminal alkynes is mainly obtained through the catalytic synthesis of Lewis acids. The amount of Lewis acids used in this method Larger, higher economic cost, and because the Lewis acid is easy to coordinate with the nitrogen atom of the arylamine, resulting in a lower yield
[0005] In summary, the o-alkenyl arylamine compounds have high application value in the pharmaceutical industry and chemical industry, but the amount of catalyst used in the existing synthesis methods Larger, high economic cost, and low product yield, leading to further increase in production costs, making large-scale production face many difficulties

Method used

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  • Bivalent manganese catalyzed arylamine ortho-enylation reaction method
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  • Bivalent manganese catalyzed arylamine ortho-enylation reaction method

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Synthesis of N-benzyl-2-(1-phenylvinyl)aniline:

[0037]

[0038] In the reaction flask, add 0.20 mmol of 1a and 0.04 mmol of MnCl in sequence 2 , 0.4mmol of 2a and 2.0mL of toluene, stirred at 120°C for 24 hours, cooled to room temperature, added 5mL of ethyl acetate to dilute, washed with 5mL of saturated brine, dried the organic phase with anhydrous magnesium sulfate, and spin-dried the column Chromatography, the eluent was ethyl acetate: n-hexane = 1:100, the product 3a was obtained as 46 mg of white solid, and the yield was 80%. 1 H NMR (400MHz, CDCl 3 ):δ7.39–7.10(m,10H),7.05–6.99(m,2H),6.73(t,J=7.4Hz,1H),6.61(d,J=8.0Hz,1H),5.79(d, J=1.2Hz, 1H), 5.37(d, J=1.2Hz, 1H), 4.21(s, 2H), 4.06 (s, 1H); 13 C NMR (100MHz, CDCl 3 ): δ147.3, 145.2, 139.9, 139.4, 130.7, 129.1, 128.7, 128.6, 128.2, 127.4, 127.1, 127.1, 126.8, 117.0, 116.6, 110.8, 48.0.

Embodiment 2

[0040] Synthesis of N-benzyl-2-(1-(2-chlorophenyl)vinyl)aniline:

[0041]

[0042] In the reaction flask, add 0.20 mmol of 1a and 0.04 mmol of MnCl in sequence 2 , 0.4mmol of 2b and 2.0mL of toluene, stirred at 120°C for 24 hours, cooled to room temperature, added 5mL of ethyl acetate to dilute, washed with 5mL of saturated brine, dried the organic phase with anhydrous magnesium sulfate, and spin-dried the column Chromatography, the eluent was ethyl acetate: n-hexane = 1:100, the product 3b was obtained as a white solid 55mg, and the yield was 86%. 1 H NMR (400MHz, CDCl 3 ):δ7.38–7.11(m,10H),7.00(dd,J=7.6,1.6Hz,1H),6.68–6.66(m,2H),5.73(d,J=1.6Hz,1H),5.60( d,J=1.6Hz,1H),4.56(s,1H),4.29–4.28(m,2H); 13 C NMR (100MHz, CDCl 3 ): δ145.1, 140.9, 139.3, 132.6, 130.8, 130.1, 129.7, 128.8, 128.7, 128.5, 127.2, 127.0, 126.7, 121.0, 116.7, 110.9, 48.2; HRMS(ESI) m / z Calcd for C 2 1H 18 ClN[M+H] + 319.1128, Found 319.1131.

Embodiment 3

[0044] Synthesis of N-benzyl-2-(1-(4-chlorophenyl)vinyl)aniline:

[0045]

[0046] In the reaction flask, add 0.20mmol of 1a and 0.04mmol of MnBr successively. 2 , 0.4mmol of 2c and 2.0mL of toluene, stirred at 120°C for 24 hours, cooled to room temperature, added 5mL of ethyl acetate to dilute, washed with 5mL of saturated brine, dried the organic phase with anhydrous magnesium sulfate, and spin-dried the column layer Analysis, the eluent was ethyl acetate:n-hexane=1:100, the product 3c was obtained as 58 mg of white solid, and the yield was 90%. 1 H NMR (400MHz, CDCl 3 ):δ7.29–7.19(m,8H), 7.10(dd,J=7.2,1.6Hz,1H),7.07–7.03(m,2H),6.74(td,J=7.2,0.8Hz, 1H), 6.63(d, J=8.0Hz, 1H), 5.78(d, J=1.2Hz, 1H), 5.39(d, J=1.2Hz, 1H), 4.23(s, 2H), 3.99(s, 1H); 13 C NMR (100MHz, CDCl 3 ): δ146.0, 145.1, 139.2, 138.2, 134.0, 130.5, 129.2, 128.7, 128.5, 128.0, 127.1, 127.1, 126.7, 117.0, 116.9, 110.8, 48.0.

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Abstract

The invention discloses a bivalent manganese catalyzed arylamine ortho-enylation reaction method, which comprises the following steps of: sequentially adding a weighed arylamine compound (1), substituted acetylene (2) and a metal catalyst MmXn into a reaction bottle, adding a corresponding solvent, performing stirring for 1h-48h in air under the reaction condition of 60-120DEG C, conducting cooling to room temperature, adding ethyl acetate for dilution, performing washing with saturated edible salt water, drying an organic phase with anhydrous magnesium sulfate, and carrying out column chromatography separation to obtain a target product (3). The method has the advantages that: arylamine and substituted acetylene are used as raw materials, the target product is obtained under the catalysisof divalent manganese, and compared with a traditional lewis acid catalytic synthesis strategy, the economic cost is greatly reduced, operation is convenient, product selectivity is good, safety andreliability are achieved, substrate universality is wider, the yield is high, and the method is suitable for industrial production.

Description

technical field [0001] The invention relates to the technical field of pharmaceutical and chemical applications, in particular to a divalent manganese-catalyzed ortho-olefination reaction method of arylamines. Background technique [0002] Ortho-alkenyl arylamine is a very important intermediate for the synthesis of drug molecules, such as carbamazepine, opiramol, and indopan all contain an ortho-alkenyl arylamine skeleton, as shown below. In addition, o-alkenyl arylamines also widely exist in various heterocycles, such as indole, quinoline, and octinoline, which are key building blocks of many biologically important compounds. Therefore, it is of great significance to develop an economical and efficient method for the ortho-alkenylation of aromatic amines. In the traditional Lewis acid-catalyzed strategy, the ortho olefination reaction is difficult to achieve because the Lewis acid easily coordinates with the nitrogen atom in the arylamine, resulting in the deactivation of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/68C07C211/48C07C211/52C07C213/08C07C217/84
CPCC07C209/68C07C213/08C07C211/48C07C211/52C07C217/84Y02P20/584
Inventor 杨锦飞
Owner 杨锦飞
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