阅读说明：本技术 一种喹啉类化合物及其合成方法 (Quinoline compound and synthesis method thereof ) 是由 南江 陈璞 张佳雯 马养民 于 2019-10-29 设计创作，主要内容包括：本发明公开了一种喹啉类化合物的合成方法,向溶剂中加入重氮羰基类化合物和2-乙烯基苯胺类化合物,在惰性气体保护下进行反应后分离提纯即得到喹啉类化合物。本发明首次提出在无需金属催化剂的条件下,以重氮羰基类化合物和2-乙烯基苯胺类化合物为原料,经五加一环化反应合成喹啉类化合物,该方法操作简便。(The invention discloses a method for synthesizing quinoline compounds, which comprises the steps of adding diazocarbonyl compounds and 2-vinylaniline compounds into a solvent, reacting under the protection of inert gas, and then separating and purifying to obtain the quinoline compounds. The invention firstly proposes that a diazocarbonyl compound and a 2-vinylaniline compound are used as raw materials to synthesize the quinoline compound through an acanthopanax-cyclization reaction under the condition of not needing a metal catalyst, and the method is simple and convenient to operate.)

1. a quinoline compound, characterized in that the chemical formula of the quinoline compound is:

wherein R is¹Selected from hydrogen, alkyl, heterocycle, phenyl or substituted phenyl; r²Selected from alkyl, heterocycle, phenyl or substituted phenyl; r³The substituent in the substituted phenyl is alkyl, methoxy or halogen.

2. A method for synthesizing quinoline compounds is characterized in that diazocarbonyl compounds shown in formula 1 and 2-vinyl aniline compounds shown in formula 2 are added into a solvent, and after reaction under the protection of inert gas, separation and purification are carried out to obtain quinoline compounds shown in formula 3;

wherein R is¹Selected from hydrogen, alkyl, heterocycle,Phenyl or substituted phenyl; r²Selected from alkyl, heterocycle, phenyl or substituted phenyl; r³The substituent in the substituted phenyl is alkyl, methoxy or halogen.

3. The method for synthesizing the quinoline compound as claimed in claim 2, wherein the molar ratio of the diazocarbonyl compound to the 2-vinylaniline compound is 10.0:1.0-1.0: 2.0.

4. The method for synthesizing quinoline compounds as claimed in claim 3, wherein the diazocarbonyl compounds represented by formula 1 and the 2-vinylaniline compounds represented by formula 2 are added to the solvent, and the concentration of the 2-vinylaniline compounds in the solvent is 0.1-0.2 mol/l.

5. The method for synthesizing the quinoline compound according to claim 2, wherein the reaction specifically comprises: heating and stirring for 2-24 h at the temperature of 80-150 ℃.

6. The method for synthesizing the quinoline compound according to claim 2, wherein the solvent is one or a mixture of two of hexafluoroisopropanol and trifluoroacetic acid in any ratio.

Technical Field

The invention belongs to the field of organic synthesis, and particularly relates to a quinoline compound and a synthesis method thereof.

Background

Quinoline is one of the structures of important nitrogen-containing heterocyclic compounds, and organic molecules containing the skeleton have very wide application in the fields of pharmaceutical chemistry and materials, so that the search for a quinoline synthesis method with high efficiency and economy is always concerned. Diazo compounds are widely used as an important class of carbene precursors in the synthesis of various carbocycles and heterocycles, and the direct cyclization of carbon-hydrogen bonds by the participation of transition metals is a very efficient heterocycle synthesis strategy [ a) Tang G. -D., Pan C. -L.,. Li X.,. Org.Chem.Front.2016,3,87.b) Cheng Y.,. Bolm C.,. Angew.Chem., Int.Ed.2015.54, 12349.c) Shi L.,. Yu K.,. Wang B.,. Chem.Commun.2015,51,17277.d) Chen Chem X.,. BaiS., Deng Y., Jiang H.,. Zeng W.,. Org.Lett.2016,18,192. ]. Only one example of the current methods for synthesizing quinoline using diazo compounds as coupling fragments is reported [ e) Zhu, j.; hu, w.; sun, s.; yu, j. -t.; cheng, j.adv.synth.catal.2017,359,3725 ], but the method has severe reaction conditions, requires conversion by an expensive metal catalyst at high temperature (150 ℃), has high reaction cost and is not environment-friendly. Therefore, it is important to search for a green, economical, metal-free synthesis method using a diazo compound as a raw material.

Disclosure of Invention

The invention aims to provide a quinoline compound and a synthesis method thereof, aiming at overcoming the defects in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a quinoline compound having the formula:

wherein R is¹Selected from hydrogen, alkyl, heterocycle, phenyl or substituted phenyl; r²Selected from alkyl, heterocycle, phenyl or substituted phenyl; r³Selected from hydrogen, alkyl, methoxy, methylthio, ester, halogen, heterocycle or benzeneAnd the substituent in the substituted phenyl is alkyl, methoxy or halogen.

A method for synthesizing quinoline compounds comprises the steps of adding a diazocarbonyl compound shown as a formula 1 and a 2-vinyl aniline compound shown as a formula 2 into a solvent, reacting under the protection of inert gas, and then separating and purifying to obtain a quinoline compound shown as a formula 3;

wherein R is¹Selected from hydrogen, alkyl, heterocycle, phenyl or substituted phenyl; r²Selected from alkyl, heterocycle, phenyl or substituted phenyl; r³The substituent in the substituted phenyl is alkyl, methoxy or halogen.

Furthermore, the mol ratio of the diazocarbonyl compound to the 2-vinylaniline compound is 10.0:1.0-1.0: 2.0.

Further, diazocarbonyl compounds shown in formula 1 and 2-vinylaniline compounds shown in formula 2 are added into the solvent, and the concentration of the 2-vinylaniline compounds in the solvent is 0.1-0.2 mol/L.

Further, the reaction is specifically as follows: heating and stirring for 2-24 h at the temperature of 80-150 ℃.

Further, the solvent is one or a mixture of two of hexafluoroisopropanol and trifluoroacetic acid in any proportion.

Compared with the prior art, the invention has the following beneficial technical effects:

the invention firstly proposes that the diazocarbonyl compound and the 2-vinylaniline compound are used as raw materials to synthesize the quinoline compound through the eleutherococcus once cyclization reaction without a metal catalyst, the method has simple and convenient operation and short reaction time, and can efficiently obtain the target product; compared with a method for synthesizing quinoline by transition metal catalysis, the method has the advantages of low reaction temperature, no need of a metal catalyst and various additives, low reaction cost and environmental friendliness; in addition, the reaction of the invention has better universality to the substrate, the source of the substrate is wide, the target product is easy to separate under the optimized reaction condition, and the invention has potential application value in the fields of materials and medicines.

Drawings

FIG. 1 is a diagram of the product prepared in example 1¹H NMR spectrum;

FIG. 2 is a diagram of the product prepared in example 1¹³C NMR spectrum;

FIG. 3 is a photograph of the product prepared in example 2¹H NMR spectrum;

FIG. 4 is a photograph of the product prepared in example 2¹³C NMR spectrum;

FIG. 5 is a photograph of the product prepared in example 3¹H NMR spectrum;

FIG. 6 is a photograph of the product prepared in example 3¹³C NMR spectrum;

FIG. 7 is a photograph of the product prepared in example 4¹H NMR spectrum;

FIG. 8 is a photograph of the product prepared in example 4¹³C NMR spectrum;

FIG. 9 is a photograph of the product prepared in example 5¹H NMR spectrum;

FIG. 10 is a photograph of the product prepared in example 5¹³C NMR spectrum;

FIG. 11 is a photograph of the product prepared in example 6¹H NMR spectrum;

FIG. 12 is a photograph of the product prepared in example 6¹³C NMR spectrum;

FIG. 13 is a photograph of the product prepared in example 7¹H NMR spectrum;

FIG. 14 is a photograph of the product prepared in example 7¹³C NMR spectrum;

FIG. 15 is a photograph of the product prepared in example 8¹H NMR spectrum;

FIG. 16 is a photograph of the product prepared in example 8¹³C NMR spectrum;

FIG. 17 is a photograph of the product prepared in example 9¹H NMR spectrum;

FIG. 18 is a photograph of the product prepared in example 9¹³C NMR spectrum;

FIG. 19 is a photograph of the product prepared in example 10¹H NMR spectrum;

FIG. 20 is a photograph of the product prepared in example 10¹³C NMR spectrum;

FIG. 21 is a photograph of the product prepared in example 11¹H NMR spectrum;

FIG. 22 is a photograph of the product prepared in example 11¹³C NMR spectrum;

FIG. 23 is a photograph of the product prepared in example 12¹H NMR spectrum;

FIG. 24 is a photograph of the product prepared in example 12¹³C NMR spectrum;

FIG. 25 is a photograph of the product prepared in example 13¹H NMR spectrum;

FIG. 26 is a photograph of the product prepared in example 13¹³C NMR spectrum;

FIG. 27 is a photograph of the product prepared in example 14¹H NMR spectrum;

FIG. 28 is a photograph of the product prepared in example 14¹³C NMR spectrum;

FIG. 29 is a photograph of the product prepared in example 15¹H NMR spectrum;

FIG. 30 is a photograph of the product prepared in example 15¹³C NMR spectrum.

FIG. 31 is a photograph of the product prepared in example 16¹H NMR spectrum;

FIG. 32 is a photograph of the product prepared in example 16¹³C NMR spectrum.

FIG. 33 is a photograph of the product prepared in example 17¹H NMR spectrum;

FIG. 34 is a photograph of the product prepared in example 17¹³C NMR spectrum.

FIG. 35 is a photograph of the product prepared in example 18¹H NMR spectrum;

FIG. 36 shows the product prepared in example 18¹³C NMR spectrum.

FIG. 37 is a photograph of the product prepared in example 19¹H NMR spectrum;

FIG. 38 is a photograph of the product prepared in example 19¹³C NMR spectrum.

FIG. 39 is a photograph of the product prepared in example 20¹H NMR spectrum;

FIG. 40 is a photograph of the product prepared in example 20¹³C NMR spectrum.

FIG. 41 is a photograph of the product prepared in example 21¹H NMR spectrum;

FIG. 42 is a photograph of the product prepared in example 21¹³C NMR spectrum.

Detailed Description

Embodiments of the invention are described in further detail below:

a method for synthesizing quinoline compounds comprises the steps of adding a diazocarbonyl compound shown as a formula 1 and a 2-vinyl aniline compound shown as a formula 2 into a solvent, wherein the molar ratio of the diazocarbonyl compound to the 2-vinyl aniline compound is 10.0:1.0-1.0:2.0, adding the diazocarbonyl compound and the 2-vinyl aniline compound into the solvent, then, heating and stirring the 2-vinyl aniline compound in the solvent for 2h-24h at the temperature of 80-150 ℃ under the protection of inert gas, and then, separating and purifying to obtain the quinoline compounds shown as a formula 3.

Wherein R is¹Selected from hydrogen, alkyl, heterocycle, phenyl or substituted phenyl; r²Selected from alkyl, heterocycle, phenyl or substituted phenyl; r³The substituent in the substituted phenyl is alkyl, methoxy or halogen.

The solvent is one or a mixture of two of hexafluoroisopropanol and trifluoroacetic acid in any proportion.

The present invention is described in further detail below with reference to examples: