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Ortho-halogenated arylamine compound and synthesis method thereof

A halogenated aryl amine and a synthetic method technology, applied in the field of organic chemical synthesis, can solve problems such as bad by-products, difficult to separate, high reagents, etc., and achieve the effects of good tolerance, excellent yield, and easy preparation

Active Publication Date: 2021-08-03
SHANDONG GUIKE NEW MATERIAL CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007]While these methods are effective, they have some limitations: (1) usually require the use of highly toxic or hazardous reagents; (2) usually only some activated aromatic The ring can react; (3) It will produce some undesirable by-products, such as polyhalogenated products or the presence of multiple regioisomers that make it difficult to separate
However, these strategies are often hampered by specific catalysts and narrow substrate scope

Method used

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  • Ortho-halogenated arylamine compound and synthesis method thereof
  • Ortho-halogenated arylamine compound and synthesis method thereof
  • Ortho-halogenated arylamine compound and synthesis method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0081] Embodiment 1, N-(2-chloro-4-(1H-indol-1-yl)phenyl)benzamide

[0082]

[0083] In a 25mL Schlenk tube, add N-(4-(1H-indol-1-yl)phenyl)-N-hydroxybenzamide (0.2mmol, 66mg) and sodium carbonate (0.1mmol), and purify with nitrogen After three times, tetrahydrofuran (1 mL) was added in a nitrogen atmosphere, and after cooling to 0 °C, thionyl chloride (0.24 mmol) was added dropwise while stirring at 0 °C. After the addition was completed, the reaction process was tracked by TLC. After the reaction was completed, the reaction mixture was removed by rotary evaporation to remove the solvent, and the crude product was subjected to column chromatography (eluent: petroleum ether: ethyl acetate = 5:1) to obtain pure white powder N-(2-chloro-4-( 1H-indol-1-yl)phenyl)benzamide, the yield was 66%.

[0084] 1 H NMR (500MHz, CDCl 3 ):δ8.63(d,J=8.8Hz,1H),8.39(s,1H),7.90-7.81(m,2H),7.60(d,J=7.8Hz,1H),7.55-7.47(m, 2H), 7.45(t, J=7.6Hz, 3H), 7.39(dd, J=8.8, 2.4Hz, 1H), 7.20(t, J=3.8Hz...

Embodiment 2

[0086] Embodiment 2, 2-chloro-N-methyl-4-nitroaniline

[0087]

[0088] In a 25mL Schlenk tube, add N-methyl-N-(4-nitrophenyl)hydroxylamine (0.2mmol, 34mg) and sodium carbonate (0.1mmol), after three times of nitrogen pumping, add tetrahydrofuran under nitrogen atmosphere (1mL), after cooling to 0°C, thionyl chloride (0.24mmol) was added dropwise while stirring at 0°C, after the dropwise addition was completed, the reaction process was tracked by TLC, and after the reaction was completed, the reaction mixture was evaporated by rotary evaporation The solvent was removed, and the crude product was subjected to column chromatography (eluent: petroleum ether: ethyl acetate = 5:1) to obtain pure product 2-chloro-N-methyl-4-nitroaniline in the form of colorless oil with a yield of 65 %.

[0089] 1 H NMR (500MHz, CDCl 3):δ8.19(d,J=2.5Hz,1H),8.09(dd,J=9.1,2.5Hz,1H),6.60(d,J=9.1Hz,1H),5.16(s,1H),3.02 (d, J=5.0Hz, 3H).

[0090] 13 C NMR (126MHz, CDCl 3 ): δ149.8, 137.4, 125.3,...

Embodiment 3

[0091] Example 3, N-(2-chloro-6-methoxy-5-(triisopropylsilyl)ethynyl)pyridin-3-yl)benzamide

[0092]

[0093] In a 25 mL Schlenk tube, add N-hydroxy-N-(6-methoxy-5-(triisopropylsilyl)ethynyl)pyridin-3-yl)benzamide (0.2 mmol, 85 mg) and Sodium carbonate (0.1mmol), nitrogen pumped and ventilated three times, tetrahydrofuran (1mL) was added in nitrogen atmosphere, after cooling to 0°C, thionyl chloride (0.24mmol) was added dropwise while stirring at 0°C, and After the completion, the reaction process was tracked by TLC. After the reaction was completed, the reaction mixture was removed from the solvent by rotary evaporation, and the crude product was subjected to column chromatography (eluent: petroleum ether:ethyl acetate=5:1) to obtain pure white powder. Product N-(2-chloro-6-methoxy-5-(triisopropylsilyl)ethynyl)pyridin-3-yl)benzamide, the yield was 95%.

[0094] 1 H NMR (500MHz, CDCl 3 ): δ8.81(s,1H),8.10(s,1H),7.90(d,J=7.6Hz,2H),7.59(t,J=7.3Hz,1H),7.52(t,J=7.6Hz ,2H), ...

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Abstract

The present invention relates to an ortho-halogenated arylamine compound and a synthesis method thereof. The ortho-halogenated arylamine compound has a structure represented by a formula (III), and in the formula (III), X is Cl or Br, Ar is one of substituted naphthyl, phenyl and heteroaryl, and R is one of a benzoyl group, an acetyl group, a pivaloyl group, an ester group, a t-butyloxycarbonyl group, a carbobenzoxy group and a methyl group. According to the invention, cheap and easily available thionyl dihalide reacts with the aryl hydroxylamine compound, efficient synthesis of o-haloarylamine is realized under mild conditions, the universality is good, and various functional groups can well tolerate.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and relates to an ortho-halogen (ortho-chlorine, ortho-bromine) aromatic amine compound and a synthesis method thereof. Background technique [0002] Aryl halides are very valuable compounds in modern organic chemistry, and they are widely used in transition metal-catalyzed cross-coupling reactions as building blocks for different carbon-carbon, carbon-nitrogen, carbon-oxygen, and carbon-sulfur bonds. key substrate. In addition, aryl halides are also widely used in transition metal-free catalyzed transformations, such as nucleophilic aromatic substitution reactions, highly active organometallic reagents (such as aryl lithium, aryl magnesium reagents) and the preparation of benzyne intermediates, etc. . Furthermore, aryl halides are key components of many natural products, pharmaceuticals, and functional materials. Among these aryl halide compounds, halogenated arylamines are...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C211/59C07C211/52C07C209/54C07D209/08C07D209/86C07F7/08C07H9/04C07H1/00C07D493/14C07C229/60C07C227/04C07J41/00C07J1/00C07C213/02C07C217/80C07C217/84C07D213/74
CPCC07C211/59C07C211/52C07C209/54C07D209/08C07D209/86C07F7/0812C07F7/083C07H9/04C07H1/00C07D493/14C07C229/60C07C227/04C07J41/0055C07J1/0011C07C213/02C07C217/80C07C217/84C07D213/74C07B2200/07C07C2601/14C07C2602/42
Inventor 渠源孔凡振李朋涛齐士林孔岩张琳琳
Owner SHANDONG GUIKE NEW MATERIAL CO LTD
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