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A method for synthesizing 8-(nitromethyl) quinolines

A technology of methyl quinoline and nitromethyl, applied in the field of organic compound synthesis, can solve the problems of difficult nitration reaction, low product yield and purity, affecting reaction and the like, and achieves good selectivity and substrate adaptability. Good, simple reaction steps

Active Publication Date: 2017-07-28
ZHEJIANG UNIV OF TECH
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AI Technical Summary

Problems solved by technology

In the current industrial synthesis method of nitro compounds, nitric acid and sulfuric acid mixed acid nitration method is mainly used. For aromatic compounds containing substituents, the nitration products are usually a mixture of multiple isomers, and in most cases the products are difficult to separate. In addition, because this method has oxidative properties due to concentrated nitric acid, 8-methylquinoline will be oxidized to cause ring opening, which leads to low yield and purity of the product
Simultaneously, nitric acid and sulfuric acid are easy to form salts with quinoline compounds in the reaction process, which affects the reaction and causes waste of raw materials. In addition, excessive strong acids such as nitric acid and sulfuric acid are needed in the process, which emits a large amount of heat, which is easy to cause production danger and produce a large amount of heat. waste gas and waste acid, causing serious environmental problems
The most important thing is that the mixed acid nitration method is easy to nitrate the aromatic ring, and it is difficult to nitrate the methyl group of the raw material 8-methylquinoline

Method used

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  • A method for synthesizing 8-(nitromethyl) quinolines
  • A method for synthesizing 8-(nitromethyl) quinolines
  • A method for synthesizing 8-(nitromethyl) quinolines

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] (1) 0.5 mmol (71.5 mg) of 8-methylquinoline, 0.05 mmol (11.2 mg) of palladium diacetate, 0.75 mmol (100.1 mg) of N-chlorosuccinimide, and 0.75 mmol (115.4 mg) of silver nitrite mg) and 5ml of acetonitrile were sequentially added into a sealed pressure vessel with a volume of 25ml. The mixture was heated in an oil bath at 90°C for 48 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 Eluate, eluate was evaporated to obtain 8-(nitromethyl)quinoline (93% yield).

[0033]

[0034] White solid; m.p.64-65°C; IR(KBr):ν=1518(NO 2 )cm -1 ; 1 H NMR (CDCl 3 ,500MHz):δ8.98(dd,J 1 =4.5,J 2 =2.0Hz,1H),8.20(dd,J 1 =8.5,J 2 =2.0Hz,1H),7.89(dd,J 1 =8.5Hz,J 2 =1.0Hz, 1H), 7.81(d, J=7.0Hz, 1H), 7.57(t, J=8.5Hz, 1H), 7.48(dd, J 1 =8.0Hz,J 2 =4.5Hz, ...

Embodiment 2

[0036] 0.5 mmol of 5,8-dimethylquinoline, 0.05 mmol of palladium dichloride, 1 mmol of N-chlorosuccinimide, 1 mmol of silver nitrite and 4 ml of acetonitrile were sequentially added into a 25 ml sealed pressure vessel. The mixture was heated and reacted in an oil bath at 100° C. for 48 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 Eluate, eluate was evaporated to give 5-methyl-8-(nitromethyl)quinoline (43% yield).

[0037]

[0038] White solid, m.p.82-84℃; IR(neat):ν=1515(NO 2 )cm -1 ; 1 H NMR (CDCl 3 ,500MHz):δ8.98(dd,J 1 =4.5Hz,J 2=1.5Hz,1H),8.38(dd,J 1 =8.5Hz,J 2 =2.0Hz,1H),7.70(d,J=9.0Hz,1H),7.50(dd,J 1 =8.5Hz,J 2 =4.0Hz, 1H), 7.40(d, J=7.0Hz, 1H), 6.17(s, 2H), 2.72(s, 3H); 13 C NMR (CDCl 3 ,125MHz): δ149.8,146.3,136.8,132.9,130...

Embodiment 3

[0040] 0.5 mmol of 6,8-dimethylquinoline, 0.05 mmol of palladium trifluoroacetate, 0.75 mmol of N-chlorosuccinimide, 0.75 mmol of silver nitrite and 5 ml of acetonitrile were sequentially added into a 25 ml sealed pressure vessel. The mixture was heated and reacted in an 80° C. oil bath for 30 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 Eluate, eluate was evaporated to give 6-methyl 8-(nitromethyl)quinoline (53% yield).

[0041]

[0042] White solid; m.p.62-64°C; IR(KBr):ν=1517(NO 2 )cm -1 ; 1 H NMR (CDCl 3 ,500MHz): δ8.90(d,J=2.5Hz,1H),8.11(dd,J 1 =8.0Hz,J 2 =1.5Hz,1H),7.64(s,2H),7.44(dd,J 1 =8.0Hz,J 2 =4.0Hz, 1H), 6.18(s, 2H), 2.56(s, 3H); 13 C NMR (CDCl 3 ,125MHz): δ149.5,144.8,136.1,135.6,132.2,130.2,128.4,128.2,71.2,21.6;

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Abstract

The invention provides a method for synthesizing 8-(nitro methyl) quinoline compounds. 8-methylquinoline compounds are taken as a raw material and are added into an organic solvent together with a catalyst and a nitration reagent, the mixture is sealed and heated to 80-130 DEG C for a reaction, the reaction is traced with TLC (thin-layer chromatography) until the reaction ends, a reaction liquid is subjected to aftertreatment, and the 8-(nitro methyl) quinoline compounds shown in the formula II are obtained. The nitration method has the advantage of specifity of the nitration position, nitration is only performed on methyl, no nitration products are generated on a benzene ring, the reaction process is safe and environment-friendly, the substrate adaptability is good, and methyl nitration of all substituent groups can be realized; 8-methylquinoline is directly taken as a raw material, the reaction steps are simple, and the method is a new way for synthesizing 8-(nitro methyl) quinoline compounds containing substituent groups.

Description

technical field [0001] The invention relates to a method for synthesizing organic compounds, in particular to a method for preparing 8-(nitromethyl)quinoline compounds. Background technique [0002] 8-Methylquinoline 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 8-methylquinoline methyl segment can make this type of compound have potential physiological activity, and thus can obtain 8-aminomethylquinoline derivatives that are also physiologically active as drug intermediates . The 8-methylquinolines containing different substituents have expanded the types of such compounds through the above-mentioned process of introducing nitro groups, and can also make such compounds more widely used. In the current industrial synthesis method of nitro compounds, nitric acid and sulfuric acid mixed acid ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D215/12C07D215/18
CPCC07D215/12C07D215/18
Inventor 刘运奎张巍
Owner ZHEJIANG UNIV OF TECH
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