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A kind of ortho-sulfonylated arylamine compound and synthetic method thereof

A technology of sulfonylated aromatic amine and synthesis method, applied in the field of organic chemical synthesis, can solve the problems of incomplete conversion of sulfoxide, long reaction time, excessive oxidant, etc., and achieves high synthesis difficulty, good reaction repeatability, and common substrate. good effect

Active Publication Date: 2022-07-29
SHANDONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Although these methods are effective, they have some limitations: (1) usually require excess oxidant, high reaction temperature and long reaction time; (2) produce some undesirable by-products, such as incomplete conversion of sulfoxide leading to Difficult to separate from sulfone
[0015] However, these strategies are often hampered by specific catalysts and narrow substrate scope

Method used

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  • A kind of ortho-sulfonylated arylamine compound and synthetic method thereof
  • A kind of ortho-sulfonylated arylamine compound and synthetic method thereof
  • A kind of ortho-sulfonylated arylamine compound and synthetic method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] Example 1, 2-((trifluoromethyl)sulfonyl)aniline

[0079]

[0080] Under nitrogen atmosphere, N-phenylhydroxylamine (0.2 mmol, 1.0 eq.) was dissolved in an ultra-dry solution of dichloromethane (2 mL) and cooled to 0 °C. Then triethylamine (0.3 mmol, 1.5 eq.) was added slowly, and trifluoromethylsulfinyl chloride (0.24 mmol, 1.2 eq.) was added dropwise with stirring. The reaction mixture was stirred at 0°C for 10 minutes. After the reaction was completed, the reaction mixture was diluted with DCM and the solvent was removed by rotary evaporation. The crude product was subjected to column chromatography (eluent: petroleum ether:ethyl acetate=10:1) After purification, pure 2-((trifluoromethyl)sulfonyl)aniline was obtained as a colorless oil with a yield of 87%.

[0081] 1 H NMR (500MHz, CDCl 3 ): δ7.67(d, J=8.2Hz, 1H), 7.51-7.40(m, 1H), 6.93-6.59(m, 2H), 5.38(s, 2H).

[0082] 13 C NMR (126MHz, CDCl 3 ):δ150.0,138.2,132.6,120.5(q,J C-F = 326.6Hz), 118.0, 117.8, 10...

Embodiment 2

[0084] Example 2, 4-chloro-2-((trifluoromethyl)sulfonyl)aniline

[0085]

[0086] Under nitrogen atmosphere, N-(4-chlorophenyl)hydroxylamine phenylhydroxylamine (0.2 mmol, 1.0 eq.) was dissolved in an ultra-dry solution of dichloromethane (2 mL) and cooled to 0 °C. Then triethylamine (0.3 mmol, 1.5 eq.) was added slowly, and trifluoromethylsulfinyl chloride (0.24 mmol, 1.2 eq.) was added dropwise with stirring. The reaction mixture was stirred at 0°C for 10 minutes. After the reaction was completed, the reaction mixture was diluted with DCM and the solvent was removed by rotary evaporation. The crude product was subjected to column chromatography (eluent: petroleum ether:ethyl acetate=10:1) After purification, pure yellow solid 4-chloro-2-((trifluoromethyl)sulfonyl)aniline was obtained with a yield of 92%.

[0087] 1 H NMR (500MHz, CDCl 3 ): δ7.65 (d, J=2.3Hz, 1H), 7.40 (dd, J=8.9, 2.4Hz, 1H), 6.72 (d, J=8.9Hz, 1H), 5.39 (s, 2H).

[0088] 13 C NMR (126MHz, CDCl 3 ): δ...

Embodiment 3

[0090] Example 3, 4-(2-methyl-1,3-dioxolan-2-yl)-2-((trifluoromethyl)sulfonyl)aniline

[0091]

[0092]Under nitrogen atmosphere, N-(4-(2-methyl-1,3-dioxolan-2-yl)phenyl)hydroxylamine (0.2 mmol, 1.0 eq.) was dissolved in ultra-dry dichloromethane ( 2 mL) solution and cooled to 0 °C. Then triethylamine (0.3 mmol, 1.5 eq.) was added slowly, and trifluoromethylsulfinyl chloride (0.24 mmol, 1.2 eq.) was added dropwise with stirring. The reaction mixture was stirred at 0°C for 10 minutes. After the reaction was completed, the reaction mixture was diluted with DCM and the solvent was removed by rotary evaporation. The crude product was subjected to column chromatography (eluent: petroleum ether:ethyl acetate=10:1) Purification to obtain pure 4-(2-methyl-1,3-dioxolan-2-yl)-2-((trifluoromethyl)sulfonyl)aniline as a white solid with a yield of 97%.

[0093] 1 H NMR (500MHz, CDCl 3 ): δ7.78(s, 1H), 7.55(dd, J=8.6, 1.6Hz, 1H), 6.74(d, J=8.6Hz, 1H), 5.40(s, 2H), 4.02(t, J= 6.9Hz, ...

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Abstract

The present invention relates to an ortho-sulfonylated arylamine compound and a synthesis method thereof. The compound has the structure represented by formula (III). Under mild conditions without transition metals and oxidants, the synthesis of aryl sulfones with high efficiency and high regioselectivity was achieved through the tandem rearrangement reaction of aryl hydroxylamine compounds and sulfinyl chloride. In the present invention, the arylhydroxylamine is used as the substrate, and the sulfonyl group is introduced into the aromatic ring through the [2,3]-rearrangement reaction, thereby synthesizing the aryl sulfone compound. The method does not need to use metal catalysts and complex oxidants, does not require high temperature conditions, and is mild and efficient.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and relates to an ortho-sulfonylated aromatic amine compound and a synthesis method thereof. Background technique [0002] Sulfones are very valuable compounds in modern organic chemistry and are an important class of organosulfur compounds. They are widely used and can be used to synthesize polymers, be used as solvents and synthesize important chemical products. Sulfones have a variety of biological activities and are of great significance in the pharmaceutical and pesticide industries, especially aryl sulfones, which have a variety of pharmacological properties and are used for their unique antitumor, antischizophrenia, anti-inflammatory and anti-HIV activities Treat various diseases. [0003] Aryl sulfone compounds have a wide range of important applications in medicine, pesticides, industrial materials and other fields, but the introduction of the main functional group su...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C317/36C07D317/28C07D213/73C07D307/91C07C315/00C07B45/00
CPCC07C317/36C07D317/28C07D213/73C07D307/91C07B45/00
Inventor 高洪银刘越杜远博
Owner SHANDONG UNIV
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