Preparation method of p-amino substituted phenol compound

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

Active Publication Date: 2020-08-07
WUHAN INNERSE PHARMA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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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  • Preparation method of p-amino substituted phenol compound
  • Preparation method of p-amino substituted phenol compound
  • 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 invention relates to a preparation method of a p-amino substituted phenol compound. The preparation method comprises the following steps: sequentially adding a catalyst Ag2O, a reactant I, a reactant II and water into a reactor, and putting the reactor into an ice bath to react for 0.5-10 hours; and extracting the reaction solution with an organic solvent, carrying out reduced pressure distillation on the organic phase to obtain a crude product, and carrying out column chromatography separation and purification to obtain the p-amino substituted phenol compound. Reaction conditions and rawmaterials are cheap and easy to obtain and 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 Applications(China)
IPC IPC(8): C07C281/02
CPCC07C281/02
Inventor 李栋赵瑞楠张谦
Owner WUHAN INNERSE PHARMA
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