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A kind of method for the selective synthesis of halogenated aromatic amines by copper catalysis

A halogenated arylamine and selective technology, which is applied in the field of copper-catalyzed selective synthesis of halogenated arylamines, to achieve the effects of high product yield, wide substrate applicability, and high selectivity

Active Publication Date: 2022-01-14
ZHEJIANG UNIV OF TECH
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Problems solved by technology

However, the halogenation reaction of 1-naphthylamine derivatives and aniline derivatives is rarely reported

Method used

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  • A kind of method for the selective synthesis of halogenated aromatic amines by copper catalysis
  • A kind of method for the selective synthesis of halogenated aromatic amines by copper catalysis
  • A kind of method for the selective synthesis of halogenated aromatic amines by copper catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Add N-(naphthyl)pyridine amide (49.62mg, 0.2mmol), chlorosuccinimide (77.99mg, 0.6mmol), copper chloride (5.31mg, 20mol%), iodine acetate in a 25mL single-necked bottle Benzene (128.79 mg, 2.0 eq), N,N-dimethylformamide (4 mL). Stir at 60 °C for 3.0 h under air atmosphere. Then the mixture was cooled to room temperature, filtered after cooling and concentrated under reduced pressure. After purification by silica gel column chromatography (developing solvent: petroleum ether: ethyl acetate = 80:1), 39.19 mg of the target product was obtained as a white solid, with a yield of 62%.

[0029] 1 H NMR (400MHz, CDCl 3 )δ9.96(s,1H),8.71(d,J=4.4Hz,1H),8.33(d,J=7.6Hz,1H),8.28(d,J=8.7Hz,1H),7.95(t, J=7.8Hz, 2H), 7.70(s, 1H), 7.62(dd, J=13.8, 6.7Hz, 2H), 7.56(dd, J=7.3, 4.9Hz, 1H). 13 C NMR (101MHz, CDCl 3 )δ163.37,149.23,148.49,137.83,132.09,131.87,130.18,129.42,128.94,128.23,127.58,127.02,126.93,125.10,124.28,123.00.HRMS(ESI+):Calculated for 16 h 10 Cl 2 N 2 OH:[M+H] +...

Embodiment 2

[0032] Add N-(naphthyl)pyridine amide (49.62mg, 0.2mmol), bromosuccinimide (83.49mg, 0.48mmol), copper bromide (8.83mg, 20mol%), iodine acetate in a 25mL single-necked bottle Benzene (128.79 g, 2.0 eq), N,N-dimethylformamide (4 mL). Stir at 60 °C for 3.0 h under air atmosphere. Then the mixture was cooled to room temperature, filtered after cooling and concentrated under reduced pressure. After purification by silica gel column chromatography (developing solvent: petroleum ether: ethyl acetate = 80:1), 61.40 mg of the target product was obtained as a white solid, with a yield of 76%.

[0033] 1 H NMR (400MHz, CDCl 3 )δ9.94(s,1H),8.71(d,J=4.7Hz,1H),8.33(d,J=7.8Hz,1H),8.24(d,J=8.4Hz,1H),8.05(d, J=1.6Hz, 1H), 7.95(dd, J=7.6, 5.8Hz, 2H), 7.63(t, J=7.6Hz, 1H), 7.60–7.52(m, 2H). 13 C NMR (101MHz, CDCl 3 )δ163.24, 149.21, 148.50, 137.82, 132.83, 132.10, 132.01, 131.78, 128.22, 128.00, 127.87, 127.04, 124.57, 122.99, 122.77, 119.51.HRMS(ESI+): Calculated for 16 h 10 Br 2 N 2...

Embodiment 3

[0036]Add 3-methyl-N-(naphthyl)pyridineamide (52.42mg, 0.2mmol), chlorosuccinimide (77.99mg, 0.6mmol), copper chloride (5.31mg, 20mol %), iodobenzene acetate (128.79 mg, 2.0 eq), N,N-dimethylformamide (4 ml). Stir at 60 °C for 3.0 h under air atmosphere. Then the mixture was cooled to room temperature, filtered after cooling and concentrated under reduced pressure. After purification by silica gel column chromatography (developing solvent: petroleum ether: ethyl acetate = 80:1), 49.50 mg of the target product was obtained as a white solid, with a yield of 75%.

[0037] 1 H NMR (400MHz, CDCl 3 )δ10.03(s,1H),8.23(d,J=8.3Hz,1H),8.13(d,J=7.0Hz,1H),8.05(s,1H),7.95(d,J=8.2Hz, 1H), 7.82(t, J=7.1Hz, 1H), 7.60(dt, J=14.8, 7.1Hz, 2H), 7.40(d, J=7.3Hz, 1H), 2.68(s, 3H). 13 C NMR (101MHz, CDCl 3 )δ164.70, 146.23, 145.79, 141.28, 136.59, 131.97, 131.68, 130.06, 129.83, 128.83, 128.12, 127.42, 126.84, 126.45, 124.97, 124.34, 20.82. 17 h 12 Cl 2 N 2 OH:[M+H] + 331.0399,Found: 331....

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Abstract

A copper-catalyzed method for selectively synthesizing halogenated arylamine compounds, the method comprising: reacting a reaction substrate and a halogenation reagent (III) in an organic solvent under the action of a catalyst and an oxidizing agent at 0-80°C 0.5~6h, after the reaction is finished, the reaction solution is post-treated to obtain the product halogenated arylamine compounds; the present invention realizes the direct synthesis of halogenated arylamine compounds for the first time, avoiding the expensive metal catalysts and halogenated reagents in traditional methods. High toxicity, many by-products and other problems; at the same time, the product can remove the pyridine guiding group through simple hydrolysis, and can also be further functionalized to synthesize aromatic heterocyclic compounds; the invention is easy to operate, with mild reaction conditions and high selectivity. The product yield is high, and the substrate has wide applicability. It is an efficient organic synthesis method; substrate: halogenation reagent: product:

Description

technical field [0001] The invention relates to a new method for selectively synthesizing halogenated arylamine compounds with copper catalysis, belonging to the field of organic synthesis. Background technique [0002] As a class of important organic small molecules, halogenated aromatic amines have a wide range of biological activities, and are often used in the synthesis of drugs and their intermediates, functional materials, etc., and can also be used as raw materials for the further transformation of compounds containing aromatic rings . Typical drugs include vascular endothelial growth factor receptor (VEGFR) antagonist or oral tyrosine kinase inhibitor vandetanib, epidermal growth factor receptor (EGFR) antagonist gefitinib, vanilla Acid receptor (TRPV-1) antagonist, vanilloid receptor type I (VR1) activity inhibitor. Such compounds have been widely used in the fields of medicine and pesticides such as antineoplastic drugs, anti-inflammatory drugs, local anesthetics...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/81C07D241/24
CPCC07D213/81C07D241/24
Inventor 谢媛媛程科王凯侯加浩魏婷婷
Owner ZHEJIANG UNIV OF TECH
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