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Method for synthesizing (nitroalkynyl)benzene compounds

A technology for nitroalkynyl and compound, applied in the field of preparation of benzene compounds, can solve the problems of difficult nitration reaction, low product yield and purity, difficult to obtain target product and the like, and achieves good selectivity, simple reaction steps, Good substrate adaptability

Active Publication Date: 2017-03-08
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In the current industrial synthesis method of nitro compounds, nitric acid and sulfuric acid mixed acid nitration method is mainly used. For aromatic alkynyl compounds containing substituents, the nitration products are usually a mixture of various isomers in which nitro groups are introduced into the aromatic ring. , it is difficult to obtain the target product. In addition, this method has oxidative properties due to concentrated nitric acid, and phenylacetylene will be oxidized, which leads to low yield and purity of the product.
At the same time, nitric acid and sulfuric acid release a large amount of heat during the reaction process, which is likely to cause production hazards, generate a large amount of waste gas and waste acid, and cause serious environmental problems.
The most important thing is that the mixed acid nitration method is easy to nitrate on the aromatic ring, and it is difficult to nitrate on the alkyne group of the raw material phenylacetylene

Method used

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  • Method for synthesizing (nitroalkynyl)benzene compounds
  • Method for synthesizing (nitroalkynyl)benzene compounds
  • Method for synthesizing (nitroalkynyl)benzene compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] (1) Add 0.5mmol (89mg) of 2-phenylphenylacetylene, 1mmol (133mg) of N-chlorosuccinimide, 1mmol (154mg) of silver nitrite and 5ml of acetonitrile into a sealed pressure vessel with a volume of 25ml. The mixture was reacted at 25°C for 8 hours. After the TLC detection reaction finished, the reaction solution was diluted with dichloromethane, filtered to obtain the clear liquid, separated by column chromatography (eluent ratio: sherwood oil to ethyl acetate volume ratio 10:1), and collected the product containing Eluent, the eluent was distilled off to obtain 2-(nitroalkynyl)-1,1'biphenyl (78% yield).

[0033]

[0034] yellow solid; 1 H NMR (CDCl 3 ,500MHz):δ7.79(d,J=1.0Hz,1H),7.66(t,J=1.5Hz,1H),7.57(m,2H),7.47(m,5H),

Embodiment 2

[0036] Add 0.5mmol (65mg) of 2,6-dimethylphenylacetylene, 0.5mmol (67mg) of N-chlorosuccinimide, 0.5mmol (77mg) of silver nitrite and 5ml of acetonitrile into a 25ml sealed pressure vessel in sequence middle. The mixture was reacted at 25°C for 8 hours. After the TLC detection reaction finished, the reaction solution was diluted with dichloromethane, filtered to obtain the clear liquid, separated by column chromatography (eluent ratio: sherwood oil to ethyl acetate volume ratio 10:1), and collected the product containing Eluent, eluent was distilled off to obtain 2,6-dimethyl-(nitroalkynyl)benzene (56% yield).

[0037]

[0038] white solid, 1 H NMR (CDCl 3 ,500MHz):δ7.35(t,J=7.5Hz,1H),7.13(d,J=7.5Hz,2H),6.17(s,6H).

Embodiment 3

[0040] Add 0.5mmol (80mg) of 3,5-dimethoxyphenylacetylene, 1mmol (133mg) of N-chlorosuccinimide, 1mmol (154mg) of silver nitrite and 4ml of acetonitrile into a sealed pressure vessel with a volume of 25ml. . The mixture was reacted at 40°C for 8 hours. After the TLC detection reaction finished, the reaction solution was diluted with dichloromethane, filtered to obtain the clear liquid, separated by column chromatography (eluent ratio: sherwood oil to ethyl acetate volume ratio 10:1), and collected the product containing Eluent, eluent was distilled off to obtain 1,3-dimethoxy-5-(nitroalkynylbenzene) (66% yield).

[0041]

[0042] white solid; 1 H NMR (CDCl 3 ,500MHz): δ6.76(d,J=2.5Hz,2H),6.66(d,J=2.0Hz,1H),3.81(s,6H)

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Abstract

The invention provides a method for synthesizing (nitroalkynyl)benzene compounds shown in formula II, comprising: adding phenylacetylene compounds shown in formula I as materials, along with a nitrifying agent, into an organic solvent, hermetically reacting at 20-50 DEG C, performing TLC (thin layer chromatography) tracing until the reaction is over, and post-treating the reacted liquid to obtain (nitroalkynyl)benzene compounds shown in the formula II. The nitrifying method of the invention has the advantage of good nitrifying site specificity, nitrifying is carried out only on alkynyl, no nitrification products are produced on benzene rings, the reaction process is good in safety, environment-friendly and good in substrate adaptability, and it is possible to provide alkynyl nitrifying for various substituents.

Description

technical field [0001] The invention relates to a method for synthesizing organic compounds, in particular to a method for preparing (nitroalkynyl) benzene compounds. Background technique [0002] Phenylacetylene compounds are an important class of chemical raw materials, mainly used as intermediates in medicine and organic synthesis, and are widely used in the pharmaceutical and chemical industries. The introduction of a nitro group on the phenylethynyl moiety can make this type of compound have potential physiological activity. The phenylacetylenes containing different substituents expand the types of such compounds through the above-mentioned process of introducing nitro groups, and can also make such compounds more widely used. [0003] In the current industrial synthesis method of nitro compounds, nitric acid and sulfuric acid mixed acid nitration method is mainly used. For aromatic alkynyl compounds containing substituents, the nitration products are usually a mixture...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/02C07C201/08C07C205/04C07C205/32C07C205/06C07C205/09C07C253/30C07C255/50
Inventor 刘运奎张巍张剑
Owner ZHEJIANG UNIV OF TECH
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