CN107628996B - Synthesis method of polysubstituted quinoline - Google Patents

Synthesis method of polysubstituted quinoline Download PDF

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CN107628996B
CN107628996B CN201711088854.XA CN201711088854A CN107628996B CN 107628996 B CN107628996 B CN 107628996B CN 201711088854 A CN201711088854 A CN 201711088854A CN 107628996 B CN107628996 B CN 107628996B
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quinoline
acetophenone
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polysubstituted quinoline
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郭灿城
湛西
刘玉峰
郭欣
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Yuanjiang Hualong Catalyst Technology Co ltd
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Abstract

The invention discloses a method for synthesizing polysubstituted quinoline, which comprises the following steps of reacting acetophenone, aniline compounds and dimethyl sulfoxide in an oxygen-containing atmosphere in one pot in the presence of a ferric salt and/or ferrous salt catalyst to obtain polysubstituted quinoline; the method enriches the variety of quinoline derivatives, provides more intermediates for drug synthesis, has wide raw material source, simple steps, mild reaction conditions and high yield, and is beneficial to industrial production.

Description

Synthesis method of polysubstituted quinoline
Technical Field
The invention relates to a method for synthesizing a quinoline derivative, in particular to a method for generating polysubstituted quinoline by one-step reaction of acetophenone, aniline compounds and dimethyl sulfoxide through air oxidation under the catalysis of ferric salt and/or ferrous salt, belonging to the field of synthesis of pharmaceutical intermediates.
Background
As an important N-heterocyclic fine chemical raw material, the quinoline compound has wide application in the aspects of medicines, pesticides, spices, foods, dyes, synthetic feed additives, auxin and the like. The quinoline compound is widely existed in nature, but the separation and purification from nature not only has various operation steps, complicated separation devices, large energy consumption, higher process cost and serious environmental pollution, such as: quinoline was first extracted from wash oil of coal tar or naphthalene oil. Washing the naphthalene oil fraction and the wash oil fraction with dilute sulfuric acid to obtain quinoline sulfate base solution, steaming to remove impurities such as neutral oil, and decomposing with alkali or ammonia. The separated crude quinoline and the homologue thereof are rectified by a high-yield distillation tower after being dehydrated, and the distillation section with the boiling range of 237.5-239.5 ℃ is cut to obtain the crude quinoline containing 83% of quinoline and 15% of isoquinoline.
At present, the synthesis method of quinoline compounds becomes a hotspot of research of researchers, the most representative method for industrially synthesizing quinoline in early stage is a Skraup synthesis method, aromatic amine, concentrated sulfuric acid and glycerol are heated together with a mild oxidant, the glycerol is dehydrated into acrolein under the action of the concentrated sulfuric acid at high temperature, then condensed with aniline into dihydroquinoline, and finally oxidized to obtain quinoline, the reaction has the defects that the reaction is carried out in a concentrated sulfuric acid environment and under the high temperature condition, the reaction condition is harsh, and the yield is not high.
For example, Chinese patent Nos. CN 102134219A and CN 102070521A both disclose a method for preparing quinoline derivatives, specifically disclose that substituted aniline reacts with α unsaturated aldehyde, ketone or ester compounds in the presence of rare earth catalysts to obtain the target product (reaction formula 1 below), or aniline derivatives react with α, β -unsaturated aldehyde and ketone in acidic ionic liquid under the catalysis of iodine or iodide to obtain quinoline derivatives (reaction formula 2 below), which has the disadvantages of expensive ketene compounds and expensive rare earth metals in acidic ionic liquid, and high production cost, for example, Chinese patent No. CN103554020A discloses a method for synthesizing quinoline derivatives, specifically, imine and alkyne are used as substrates in organic solvents to react under iron catalysis to obtain quinoline compounds (reaction formula 3 below), which has the disadvantages of poor stability, and requires a sealed reaction of imine substrates under the conditions, and a method for preparing quinoline derivatives under the conditions of corrosion of triflic acid, which is not favorable for preparing quinoline derivatives under the conditions of trifluoro methanesulfonic acid, and requires the industrial corrosion of a novel method for preparing quinoline derivatives under the conditions of trifluoro methanesulfonic acid, and the disadvantages of the prior art (CN 106380463).
Reaction formula 1:
Figure BDA0001460711950000021
reaction formula 2:
Figure BDA0001460711950000022
reaction formula 3:
Figure BDA0001460711950000023
reaction formula 4:
Figure BDA0001460711950000024
disclosure of Invention
Aiming at the defects of the existing method for synthesizing the quinoline derivative, the invention aims to provide a method for generating the quinoline derivative by oxidizing acetophenone, aniline compounds and dimethyl sulfoxide in one step through oxygen under the catalysis of ferric salt and/or ferrous salt.
In order to achieve the technical purpose, the invention provides a method for preparing polysubstituted quinoline derivatives, in an oxygen-containing atmosphere, acetophenone, an aniline compound shown in formula 1 and dimethyl sulfoxide are subjected to one-pot reaction in the presence of a ferric salt and/or ferrous salt catalyst to obtain a quinoline derivative shown in formula 2;
Figure BDA0001460711950000031
wherein the content of the first and second substances,
R1and R2Independently selected from hydrogen, alkyl, alkoxy, alkylthio, alkoxyacyl, halogen, cyano, aryl or arylheterocyclyl.
In a preferred embodiment, the aniline compound is aniline, 4-isopropylaniline, 3-methylaniline, 3, 4-dimethylaniline, 2-phenylaniline, 4-chloroaniline, 3-chloroaniline or 3-bromoaniline.
In a preferable scheme, the concentration of the acetophenone in the dimethyl sulfoxide is 0.05-0.5 mol/L; more preferably 0.1 to 0.3 mol/L; most preferably 0.15 to 0.25 mol/L.
In a preferable scheme, the molar weight of the ferric salt and/or ferrous salt catalyst is 5-30% of that of the aryl ethanone compound; more preferably 8 to 20%.
In a more preferred embodiment, the iron salt comprises a haloiron salt; ferric chloride is more preferred.
In a more preferred embodiment, the ferrous salt comprises a halogen ferrous salt, and is more preferably ferrous chloride.
In a preferable scheme, the molar weight of the aniline compound is 2-5 times of that of acetophenone; more preferably 2.3 to 3.5 times.
In a preferred embodiment, the reaction conditions are as follows: the reaction temperature is 90-140 ℃, and the reaction time is 18-30 h. More preferably, the reaction conditions are as follows: the reaction temperature is 100-130 ℃, and the reaction time is 20-28 h; the most preferable reaction time is 22-26 h at 115-125 ℃.
Preferably, the oxygen-containing atmosphere is air, oxygen, or other oxygen-containing atmosphere.
In the technical scheme of the invention, ferric salt and ferrous salt are used as catalysts, and oxygen-containing gas is used as an oxidant. The pyridine ring contained in the quinoline derivative is formed by cyclizing one molecule of aniline compound, one molecule of acetophenone and one molecule of dimethyl sulfoxide, wherein an acetyl group of one molecule of acetophenone compound, an amino group of one molecule of aniline compound and a methyl group of one molecule of dimethyl sulfoxide are subjected to a series of complex chemical reactions such as oxidative dehydrogenation, condensation cyclization and the like under the catalysis of a ferric salt and ferrous salt catalyst, so that the quinoline derivative is obtained.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) according to the technical scheme, the acetophenone, the aniline compound and the dimethyl sulfoxide are subjected to oxidative cyclization to obtain the quinoline compound for the first time, and a brand new thought is provided for synthesizing the pharmaceutical intermediate of the quinoline compound.
2) The technical scheme of the invention adopts the conventional acetophenone, aniline compounds and dimethyl sulfoxide as raw materials, and the raw materials have wide sources and have the advantage of low cost compared with keto-alkene compounds.
3) The technical scheme of the invention has simple steps and mild reaction conditions, can realize the synthesis of the quinoline compound by a one-pot method, has high reaction yield and is beneficial to large-scale production.
4) The quinoline compound synthesized by the technical scheme of the invention contains aryl and other groups which are easy to modify again, and has obvious advantages when being used as a quinoline drug synthesis intermediate.
5) The catalyst of the invention is common ferric salt and ferrous salt, and has wide source and low cost.
Drawings
FIG. 1 is a 1H NMR spectrum of the quinoline derivative in example 1;
FIG. 2 is a 13C NMR spectrum of the quinoline derivative in example 1;
FIG. 3 is a 1H NMR spectrum of the quinoline derivative in example 3;
FIG. 4 is a 13C NMR spectrum of the quinoline derivative in example 3;
FIG. 5 is a 1H NMR spectrum of the quinoline derivative in example 4;
FIG. 6 is a 13C NMR spectrum of the quinoline derivative in example 4;
FIG. 7 is a 1H NMR spectrum of the quinoline derivative in example 6;
FIG. 8 is a 13C NMR spectrum of the quinoline derivative in example 6.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The substrate starting materials, solvents and the like mentioned in the following examples were all commercial products (analytical reagents) on the market and were not further purified.
The product is separated by chromatography, column silica gel (300-400 mesh).
1H NMR (400MHz), 13C NMR (100MHz), in CDCl3As solvent, TMS was used as internal standard.
Multiplicity is defined as follows: s (singlet); d (doublet); t (triplet); q (quartet) and m (multiplet). Coupling constant J (Hertz).
Condition optimization experiment: the optimal reaction conditions were found by the following control experimental groups: the reaction is exemplified by using acetophenone, aniline and dimethyl sulfoxide as reaction raw materials, and using excessive dimethyl sulfoxide as a reaction solvent, and the specific reaction is as follows:
the catalyst, acetophenone and aniline were dissolved in DMSO in a 25mL Schlenk tube and stirred in the presence of an oxidant at a temperature for 24 hours. After the reaction is finished, cooling the obtained solution to room temperature; the solution was diluted with ethyl acetate (10mL), washed with water (5mL), extracted with ethyl acetate (3X 5mL), and extracted with anhydrous Na2SO4Dried and concentrated in vacuo. The crude product was purified by flash column chromatography on silica gel to give the desired product.
Figure BDA0001460711950000051
Figure BDA0001460711950000052
Figure BDA0001460711950000061
Reaction conditions of control experiment groups 1-8 are acetophenone (0.5mmol), DMSO (2.5mL), aniline (1.5mmol), catalyst (10 mol%), oxygen (1 atm)/oxidant (1.0mmol), reaction temperature is 120 ℃, and reaction time is 24 h.
The reaction temperature of the control experiment group 9 was 100 deg.C, and other conditions were the same as those of the experiment group 1.
The reaction temperature of the control experiment group 10 was 130 deg.C, and other conditions were the same as those of the experiment group 1.
FeCl of control experiment group 113·6H2O (5 mol%), other conditions were the same as in Experimental group 1.
FeCl of control experiment group 123·6H2O (20 mol%), other conditions were the same as in Experimental group 1.
It can be seen from comparison experiment groups 1-4 in the table that the reaction can be smoothly carried out under the catalysis of ferric salt and ferrous salt, and the catalytic reaction effect of cobalt salt and nickel salt is lower than that of corresponding ferric salt, ferrous salt and the like although cobalt salt and nickel salt have certain catalytic activity. Experiments show that the iron salt has the best catalytic effect in all the catalysts, and the yield of the quinoline derivative is correspondingly higher.
As can be seen from comparison of experimental groups 2 and 5-8 in the table, except that oxygen can enable the reaction to be carried out smoothly, higher yield is obtained, other conventional oxidants such as hydrogen peroxide and K2S2O8And peroxide TBHP and the like are difficult to synthesize quinoline derivatives, and only low yield or target products cannot be obtained.
As can be seen from comparison of experimental groups 2 and 9-10 in the table, the yield is correspondingly reduced when the reaction temperature is too high or too low, and the optimal reaction effect can be achieved at about 120 ℃.
In summary, the optimal reaction conditions can be obtained by comparing the experimental groups 1-12: acetophenone (0.5mmol), aniline (1.5mmol), DMSO (2.5mL), FeCl3.6H2O (10 mol%), oxygen (1atm), reaction temperature 120 ℃ and reaction time 24 h.
The following examples 1 to 9 and comparative examples 1 and 2 were reacted under the optimized reaction conditions as described above:
example 1
Aniline compound:
Figure BDA0001460711950000071
acetophenone:
Figure BDA0001460711950000072
quinoline derivatives:
Figure BDA0001460711950000073
yield: 65 percent.
1H NMR(400MHz,CDCl3)δ8.23(d,J＝8.6Hz,1H),8.17(d,J＝8.5Hz,1H),8.13(d,J＝8.1Hz,2H),7.85(d,J＝3.6Hz,1H),7.83(d,J＝3.0Hz,1H),7.74(t,J＝7.7Hz,1H),7.57-7.48(m,3H).13C NMR(100MHz,CDCl3)δ156.0,148.2,138.0,137.1,135.6,129.9,129.7,129.0,128.9,127.5,127.2,126.6,118.6.
Example 2
Aniline compound:
Figure BDA0001460711950000074
acetophenone:
Figure BDA0001460711950000075
quinoline derivatives:
Figure BDA0001460711950000076
yield: 59 percent.
1H NMR(400MHz,CDCl3)δ8.19-8.04(m,4H),7.81(d,J＝8.6Hz,1H),7.56-7.49(m,4H),7.44(t,J＝7.2Hz,1H),2.53(s,3H).13C NMR(100MHz,CDCl3)δ156.5,146.8,139.8,136.2,136.2,132.0,129.4,129.2,128.8,127.5,127.2,126.4,119.0,21.6.
Example 3
Aniline compound:
Figure BDA0001460711950000081
acetophenone:
Figure BDA0001460711950000082
quinoline derivatives:
Figure BDA0001460711950000083
yield: 60 percent.
1H NMR(400MHz,CDCl3)δ8.20-8.07(m,4H),7.83(d,J＝8.5Hz,1H),7.65-7.58(m,2H),7.51(t,J＝7.5Hz,2H),7.44(t,J＝7.1Hz,1H),1.36(d,J＝6.9Hz,6H).13C NMR(100MHz,CDCl3)δ156.7,147.0,139.9,136.5,129.6,129.5,129.1,128.8,127.5,127.2,123.6,122.8,119.0,34.1,23.9.
Example 4
Aniline compound:
Figure BDA0001460711950000084
acetophenone:
Figure BDA0001460711950000085
quinoline derivatives:
Figure BDA0001460711950000086
yield: 52 percent.
1H NMR(400MHz,CDCl3)δ8.27(d,J＝7.6Hz,2H),8.20(d,J＝8.5Hz,1H),7.91(d,J＝8.5Hz,1H),7.67(d,J＝8.1Hz,1H),7.60-7.51(m,3H),7.49–7.40(m,2H),2.92(s,3H).13CNMR(100MHz,CDCl3)δ155.6,147.0,139.7,137.6,137.2,129.9,129.3,128.8,127.6,127.1,126.1,125.4,118.3,17.9.
Example 5
Aniline compound:
Figure BDA0001460711950000087
acetophenone:
Figure BDA0001460711950000091
quinoline derivatives:
Figure BDA0001460711950000092
yield: 58 percent.
1H NMR(400MHz,CDCl3)δ8.31(d,J＝8.7Hz,1H),8.15(d,J＝7.6Hz,2H),7.88-7.76(m,2H),7.51(t,J＝7.4Hz,2H),7.45(t,J＝7.1Hz,1H),7.19(s,1H),2.65(s,3H),2.52(s,3H).13C NMR(100MHz,CDCl3)δ156.8,148.8,139.7,139.6,134.0,133.1,129.2,128.9,128.8,127.5,126.9,124.6,117.8,21.9,18.5.
Example 6
Aniline compound:
Figure BDA0001460711950000093
acetophenone:
Figure BDA0001460711950000094
quinoline derivatives:
Figure BDA0001460711950000095
yield: 45 percent.
1H NMR(400MHz,CDCl3)δ8.25(d,J＝8.6Hz,1H),8.16(d,J＝7.8Hz,2H),7.95(d,J＝8.6Hz,1H),7.86(d,J＝7.8Hz,2H),7.83-7.76(m,2H),7.60-7.40(m,7H).13C NMR(100MHz,CDCl3)δ156.0,145.6,140.8,139.5,139.4,137.1,131.2,130.4,129.3,128.8,127.7,127.4,127.2,126.2,118.1.
Example 7
Aniline compound:
Figure BDA0001460711950000096
acetophenone:
Figure BDA0001460711950000101
quinoline derivatives:
Figure BDA0001460711950000102
yield: and 64 percent.
1H NMR(400MHz,CDCl3)δ8.14(d,J＝7.6Hz,2H),8.10(d,J＝8.8Hz,2H),7.87(d,J＝8.7Hz,1H),7.78(s,1H),7.64(d,J＝8.9Hz,1H),7.49(dt,J＝14.0,7.6Hz,3H).13C NMR(100MHz,CDCl3)δ157.6,146.6,139.2,135.9,132.0,131.3,130.6,129.6,128.9,127.7,127.6,126.2,119.8.
Example 8
Aniline compound:
Figure BDA0001460711950000103
acetophenone:
Figure BDA0001460711950000104
quinoline derivatives:
Figure BDA0001460711950000105
yield: 62 percent.
1H NMR(400MHz,CDCl3)δ8.20-8.11(m,4H),7.85(d,J＝8.6Hz,1H),7.73(d,J＝8.6Hz,1H),7.54-7.45(m,4H).13C NMR(100MHz,CDCl3)δ158.2,148.6,139.1,136.6,135.5,131.0,129.7,128.9,128.7,127.6,127.3,125.5,119.1.
Example 9
Aniline compound:
Figure BDA0001460711950000106
acetophenone:
Figure BDA0001460711950000107
quinoline derivatives:
Figure BDA0001460711950000108
yield: 58 percent.
1H NMR(400MHz,CDCl3)δ8.37(s,1H),8.16(t,J＝8.5Hz,3H),7.88(d,J＝8.5Hz,1H),7.68(d,J＝8.6Hz,1H),7.60(d,J＝8.6Hz,1H),7.55-7.48(m,3H).13C NMR(100MHz,CDCl3)δ158.2,148.9,139.1,136.7,132.0,129.8,129.7,128.9,128.7,127.6,125.8,123.8,119.3.
Comparative example 1
Aniline compound:
Figure BDA0001460711950000111
acetophenone:
Figure BDA0001460711950000112
quinoline derivatives:
Figure BDA0001460711950000113
yield: none.
Comparative example 2
Amine compounds:
Figure BDA0001460711950000114
acetophenone:
Figure BDA0001460711950000115
quinoline derivatives:
Figure BDA0001460711950000116
yield: none.

Claims (9)

1. A method for synthesizing polysubstituted quinoline is characterized in that: in an oxygen-containing atmosphere, acetophenone, aniline compounds and dimethyl sulfoxide react in one pot in the presence of a ferric salt and/or ferrous salt catalyst to obtain polysubstituted quinoline;
Figure FDA0002172668410000011
wherein the content of the first and second substances,
the aniline compound is
Figure FDA0002172668410000012
Figure FDA0002172668410000013
The polysubstituted quinoline is
Figure FDA0002172668410000014
Figure FDA0002172668410000015
2. The method for synthesizing polysubstituted quinoline according to claim 1, wherein: the concentration of the acetophenone in the dimethyl sulfoxide is 0.05-0.5 mol/L.
3. The method for synthesizing polysubstituted quinoline according to claim 2, wherein: the concentration of the acetophenone in the dimethyl sulfoxide is 0.1-0.3 mol/L.
4. The method for synthesizing polysubstituted quinoline according to claim 1, wherein: the molar weight of the ferric salt and/or ferrous salt catalyst is 5-30% of that of the aryl ethanone compound.
5. The method for synthesizing polysubstituted quinoline according to claim 4, wherein: the iron salt comprises a haloiron salt; the ferrous salts include halogen ferrous salts.
6. The method for synthesizing polysubstituted quinoline according to claim 5, wherein: the iron salt comprises ferric chloride; the ferrous salt includes ferrous chloride.
7. The method for synthesizing polysubstituted quinoline according to claim 1, wherein: the molar weight of the aniline compound is 2-5 times of that of the acetophenone.
8. The method for synthesizing polysubstituted quinoline according to claim 1,3, 5 or 6, wherein: the reaction conditions are as follows: the reaction temperature is 90-140 ℃, and the reaction time is 18-30 h.
9. The method for synthesizing polysubstituted quinoline according to claim 8, wherein: the reaction conditions are as follows: the reaction temperature is 115-125 ℃, and the reaction time is 22-26 h.
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