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A kind of preparation method of p-amino substituted phenol compound

A phenolic compound, p-amino technology, applied in the direction of organic chemistry, can solve few problems, and achieve the effect of short reaction time, good regioselectivity, simple and mild reaction conditions

Active Publication Date: 2022-05-03
WUHAN INNERSE PHARMA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Therefore, the para-amination reaction of phenols has attracted the attention of many chemists, but there are still few methods that can realize the para-amination of phenols.

Method used

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  • A kind of preparation method of p-amino substituted phenol compound
  • A kind of preparation method of p-amino substituted phenol compound
  • A kind of preparation method of p-amino substituted phenol compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Preparation of Diethyl 1-(4-Hydroxy-3-methylphenyl)hydrazine-1,2-dicarboxylate

[0023]

[0024] Add catalyst 3mol% Ag sequentially 2 O, 0.2mmol o-cresol, 0.4mmol diethyl azodicarboxylate, 2mL water and a No. 5 magnet. The reactor was placed in an ice bath to react for 0.5 hours. The reaction solution was poured into a separatory funnel, 15 mL of water was added, extracted 3 times with 10 mL of ethyl acetate, the resulting organic phases were combined, spin-dried by a rotary evaporator, and the crude product was separated and purified by column chromatography to obtain 1-(4-hydroxyl -32.1 mg of diethyl 3-methylphenyl)hydrazine-1,2-dicarboxylate, as a white solid, with a yield of 57%.

[0025] Its structure was confirmed by H NMR and C NMR 1 H NMR (400MHz, CDCl 3 ): δ7.19(s,1H),7.12(s,1H),7.02(d,J=7.80Hz,1H),6.62(d,J=8.56Hz,1H),6.21(s,1H),4.25 –4.16(m,4H),2.17(s,3H),1.28–1.22(m,6H); 13 C NMR (100MHz, CDCl 3 ): δ156.6, 155.9, 153.5, 134.0, 128.3, 124.8, 115.1, 6...

Embodiment 2

[0027] Preparation of Diethyl 1-(4-Hydroxy-3-methoxyphenyl)hydrazine-1,2-dicarboxylate

[0028]

[0029] Add catalyst 3mol% Ag sequentially 2 O, 0.2mmol 2-fluorophenol, 0.4mmol diethyl azodicarboxylate, 2mL water and a No. 5 magnet. The reactor was placed in an ice bath to react for 0.5 hours. The reaction solution was poured into a separatory funnel, 15 mL of water was added, extracted 3 times with 10 mL of ethyl acetate, the resulting organic phases were combined, spin-dried by a rotary evaporator, and the crude product was separated and purified by column chromatography to obtain 1-(4-hydroxyl -44.7 mg of diethyl 3-methoxyphenyl)hydrazine-1,2-dicarboxylate, a white solid, with a yield of 75%.

[0030] Its structure was confirmed by H NMR and C NMR 1 H NMR (400MHz, CDCl 3 ):δ7.24(s,1H),7.01(s,1H),6.88–6.84(m,1H),6.83(d,J=8.44Hz,1H),5.83(s,1H),4.24–4.18( m,4H),3.84(s,3H),1.28–1.22(m,6H); 13 C NMR (100MHz, CDCl 3 ): δ156.5, 155.5, 146.3, 144.8, 134.3, 114.1, 63.0, 62...

Embodiment 3

[0032] Preparation of Diethyl 1-(3-fluoro-4-hydroxyphenyl)hydrazine-1,2-dicarboxylate

[0033]

[0034] Add catalyst 3mol% Ag sequentially 2 O, 0.2mmol 2-fluorophenol, 0.4mmol diethyl azodicarboxylate, 2mL water and a No. 5 magnet. The reactor was placed in an ice bath to react for 0.5 hours. The reaction solution was poured into a separatory funnel, 15 mL of water was added, extracted 3 times with 10 mL of ethyl acetate, the resulting organic phases were combined, spin-dried by a rotary evaporator, and the crude product was separated and purified by column chromatography to obtain 1-(3-fluoro -45.2 mg of diethyl 4-hydroxyphenyl)hydrazine-1,2-dicarboxylate, a white solid, with a yield of 79%.

[0035] Its structure was confirmed by H NMR and C NMR 1 H NMR (400MHz, CDCl 3 ):δ7.24(s,1H),7.17(d,J=11.64Hz,1H),7.03(d,J=8.88Hz,1H),6.89–6.83(m,1H),6.31(s,1H) ,4.26–4.19(m,4H),1.29–1.24(m,6H); 13 C NMR (100MHz, CDCl 3 ): δ156.6, 155.3, 150.4 (d, J = 238.12Hz), 142.8, 134.3, 1...

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Abstract

The present invention relates to a kind of preparation method of p-amino substituted phenolic compounds, comprising the following steps: adding catalyst Ag into the reactor sequentially 2 O, reactant one, reactant two, water, the reactor is placed in an ice bath to react for 0.5-10 hours. The reaction solution was extracted with an organic solvent, and the organic phase was distilled under reduced pressure to obtain a crude product, which was separated and purified by column chromatography to obtain p-amino-substituted phenol compounds. The reaction conditions of the present invention are cheap and easy to obtain raw materials, are carried out in a green solvent water phase, the reaction time is short, the reaction conditions are simple and mild, the regioselectivity is good, and the product has important application value in organic synthesis.

Description

technical field [0001] The invention relates to a method for preparing p-amino-substituted phenolic compounds through transition metal-catalyzed para-position carbon-hydrogen bond amination of phenolic compounds. Background technique [0002] The phenolic moiety is ubiquitous in natural products, dyes, pharmaceuticals, and materials, and is a cheap and readily available starting material for building molecules of other compounds in the chemical sciences. Therefore, the selective functionalization of phenolic compounds is of great interest. However, the conversion of phenolic C–H bonds to other C–X bonds with high chemoselectivity and high regioselectivity is challenging: first, free phenolic hydroxyl groups are acidic and nucleophilic, usually leading to O–H substitutions in preference to C–H substitutions; secondly, , in the electrophilic reaction, since the ortho and para positions on the aromatic ring are both nucleophilic, the regioselectivity of the reaction is reduced...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C281/02
CPCC07C281/02
Inventor 李栋赵瑞楠张谦
Owner WUHAN INNERSE PHARMA
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