阅读说明：本技术 一种制备3-芳基喹啉的方法 (Method for preparing 3-arylquinoline ) 是由 郭灿城 杨统林 郭欣 于 2021-08-27 设计创作，主要内容包括：本发明公开了一种制备3-芳基喹啉的方法,该方法是在含氧气氛下,邻胺基芳基甲醇和芳基甲醛,在含碱的DMSO溶液体系中进行一锅反应,即得3-芳基喹啉化合物；该方法制得的3-芳基喹啉化合物结构中,2位碳原子由DMSO提供,3位碳原子及3位上的芳基由芳基甲醛提供,喹啉化合物结构中的所有其它原子都由原料邻胺基芳基甲醇提供。该合成3-芳基喹啉的方法,原料来源广泛易得,绿色环保,价格低廉,操作简单,有利于工业化生产。(The invention discloses a method for preparing 3-aryl quinoline, which comprises the following steps of carrying out one-pot reaction on o-amino aryl methanol and aryl formaldehyde in a DMSO solution system containing alkali in an oxygen-containing atmosphere to obtain a 3-aryl quinoline compound; in the structure of the 3-aryl quinoline compound prepared by the method, a 2-position carbon atom is provided by DMSO, a 3-position carbon atom and an aryl group on the 3 position are provided by aryl formaldehyde, and all other atoms in the structure of the quinoline compound are provided by raw material o-amino aryl methanol. The method for synthesizing the 3-arylquinoline has the advantages of wide and easily-obtained raw material source, environmental protection, low price and simple operation, and is beneficial to industrial production.)

1. A method of preparing a 3-arylquinoline, comprising: performing one-pot reaction on o-amino aryl methanol and aryl formaldehyde in a DMSO solution system containing alkali to synthesize a 3-aryl quinoline compound; in 6 atoms of a pyridine ring of the 3-arylquinoline compound prepared by the method, the raw material o-amino arylcarbinol provides a nitrogen atom and 3 carbon atoms connected with the nitrogen atom, DMSO provides another carbon atom at the 2-position connected with the nitrogen atom, and arylformaldehyde provides the carbon atom at the 3-position and an aryl group at the 3-position;

the o-amino aryl carbinol has the structure of formula 1:

the aryl formaldehyde has the structure of formula 2:

Ar-CHO

formula 2

The 3-arylquinoline has the structure of formula 3:

wherein the content of the first and second substances,

r in the formula 1 can be hydrogen, methyl, methoxy, fluorine, chlorine and bromine, and can be positioned at ortho-position, para-position or meta-position of amino;

ar in the formula 2 can be hydrogen, benzene, substituted benzene, thiophene, furan, naphthalene, pyridine and quinoline;

when Ar is substituted benzene, the selection range of the substituent on the benzene ring is wide, and the substituent can be alkyl, substituted alkyl, halogen, alkoxy, amino and aryl; preferred alkyl groups are methyl, ethyl, tert-butyl, preferred substituted alkyl groups are trifluoromethyl, preferred halogen is fluorine, chlorine, bromine, preferred alkoxy is methoxy, preferred amino is dimethylamino, preferred aryl is phenyl; the number of the substituents on the benzene ring may be 1-2, and they may be located at different positions of the benzene ring;

when Ar is thiophene, furan, naphthalene, pyridine or quinoline, the Ar can be connected to the 3-carbon atom of the quinoline through any position on the ring.

2. A process according to claim 1 for the preparation of 3-arylquinolines, characterized in that:

the alkali comprises at least one of sodium benzoate, potassium benzoate, sodium acetate, potassium ethoxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, strontium carbonate, sodium hydroxide and potassium hydroxide. The preferred base is potassium hydroxide.

3. A process according to claim 1 for the preparation of 3-arylquinolines, characterized in that:

DMSO is both a solvent and a reaction raw material.

4. A process according to claim 1 for the preparation of 3-arylquinolines, characterized in that: the reaction conditions are as follows: reacting for 20-50 min at 80-140 ℃ in air or oxygen atmosphere.

Technical Field

The invention relates to a method for synthesizing 3-aryl quinoline, in particular to a method for synthesizing 3-aryl quinoline by taking o-amino aryl methanol and aryl formaldehyde as raw materials and reacting in a DMSO solution system containing alkali, belonging to the field of organic synthesis.

Background

Quinoline is a chemical structure with important physiological activity and wide synthetic applications. Quinoline rings exist at different positions, and can be connected with different substituents, and the physiological activity and the synthetic application of the quinoline compound formed by connecting different substituents at different positions are different. 3-arylquinoline compounds are present in many natural products, and this structure is also present in some drug molecules. Simple 3-arylquinolines can be obtained from 3-arylanilines by Skraup reaction with glycerol, while complex 3-arylquinolines require special synthesis methods. The literature (S.B.Wakade, D.K.Tiwari, P.S.K.P.Ganesh, M.Phanindrudu, P.R.Likhar, D.K.Tiwari, org.Lett.2017,19, 4948-one 4951) reports the synthesis of 3-aroyl-substituted quinolines by reacting arylmethyl ketones, benzisoxazoles and DMSO in the presence of potassium peroxodisulfate:

the method for synthesizing the 3-aroyl substituted quinoline needs a benzisoxazole raw material which is difficult to obtain, and only can obtain the 3-aroyl quinoline;

the document (P.Zhang, Y.Yang, Z.Chen, Z.xu, X.xu, Z.Zhou, X.Yu, W.Yi, adv. Synth.Catl.2019, 361,3002-3007) reports a method for synthesizing 3-aryl substituted quinoline by catalyzing aniline, aryl terminal alkyne and DMSO by using trivalent cobalt complexes:

the synthesis method can obtain a wide range of 3-aryl substituted quinoline, but requires the use of an aryl terminal alkyne which is a difficult raw material and an unstable 3-valent cobalt complex which is difficult to obtain.

Disclosure of Invention

Aiming at the defects of raw materials and catalysts which are difficult to obtain in the existing 3-aryl quinoline synthesis method, the invention aims to provide a method for obtaining a 3-aryl quinoline compound from easily obtained raw materials of o-amino aryl methanol and aryl formaldehyde in an oxygen-containing atmosphere.

In order to realize the technical purpose, the invention provides a method for obtaining a 3-arylquinoline compound by carrying out one-pot reaction on o-amino arylcarbinol and arylformaldehyde in a DMSO solution system containing alkali in an oxygen-containing atmosphere;

the o-amino aryl carbinol has the structure of formula 1:

the aryl formaldehyde has the structure of formula 2:

ArCHO

formula 2

The 3-arylquinoline has the structure of formula 3:

wherein the content of the first and second substances,

r in the formula 1 can be hydrogen, methyl, methoxy, fluorine, chlorine and bromine, and can be positioned at ortho-position, para-position or meta-position of amino;

ar in the formula 2 can be hydrogen, benzene, substituted benzene, thiophene, furan, naphthalene, pyridine and quinoline;

when Ar is substituted benzene, the selection range of the substituent on the benzene ring is wide, and the substituent can be alkyl, substituted alkyl, halogen, alkoxy, amino and aryl; preferred alkyl groups are methyl, ethyl, tert-butyl, preferred substituted alkyl groups are trifluoromethyl, preferred halogen is fluorine, chlorine, bromine, preferred alkoxy is methoxy, preferred amino is dimethylamino, preferred aryl is phenyl; the number of the substituents on the benzene ring may be 1-2, and they may be located at different positions of the benzene ring;

when Ar is thiophene, furan, naphthalene, pyridine or quinoline, the Ar can be connected to the 3-carbon atom of the quinoline through any position on the ring.

The synthesis reaction of the present invention requires the presence of an organic base and an inorganic base. The sodium benzoate-potassium carbonate-sodium hydroxide composite material specifically comprises at least one of sodium benzoate, potassium benzoate, sodium acetate, potassium ethoxide, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, strontium carbonate, sodium hydroxide and potassium hydroxide. The preferred base is potassium hydroxide.

In the invention, DMSO is used as a solvent and a reaction raw material.

The oxygen-containing atmosphere in the present invention may be air or a pure oxygen atmosphere, and is preferably a pure oxygen atmosphere.

The DMSO solution system mainly contains dimethyl sulfoxide which is a benign reaction solvent and one of carbon sources in the synthesis process of 3-arylquinoline, and other solvents cannot be replaced. The reaction system can contain organic solvents such as dimethyl sulfoxide, toluene and the like, but the reaction effect is obviously inferior to that of the single DMSO solvent.

In the synthesis process of the 3-aryl quinoline, o-amino aryl methanol and aryl formaldehyde react according to an equal molar ratio, and DMSO is used as a solvent and a reaction substrate, so that a large amount of excess is needed.

The reaction conditions are as follows: reacting for 20-50 minutes at 80-140 ℃ in air or oxygen atmosphere. In a more preferred embodiment, the reaction conditions are as follows: the reaction was carried out at 120 ℃ for 30 minutes under an air or oxygen atmosphere.

In the preferred scheme, after the reaction is finished, a product is separated and purified by adopting a column chromatography; the eluent adopted by the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is (20-40): 1.

The reaction equation of the method for synthesizing the 3-substituted quinoline provided by the invention is as follows:

in 6 atoms of a pyridine ring of the 3-arylquinoline compound prepared by the method, the raw material o-amino arylcarbinol provides a nitrogen atom and 3 carbon atoms connected with the nitrogen atom, DMSO provides another carbon atom at the 2-position connected with the nitrogen atom, and aryl formaldehyde provides the carbon atom at the 3-position and aryl at the 3-position. The principle of the above reaction can be illustrated by the procedure of carrying out a one-pot reaction of ortho-aminobenzyl alcohol and benzaldehyde in a DMSO solution system to obtain 3-phenylquinoline:

firstly, oxidizing raw material o-aminobenzyl alcohol into o-aminobenzaldehyde A and an isomer B thereof, reacting the raw material benzaldehyde with DMSO to generate methylsulfinyl substituted styrene C, and further oxidizing the methylsulfinyl substituted styrene C into methylsulfonyl substituted styrene D by air; then, the isomer B of o-aminobenzaldehyde and methylsulfonyl substituted styrene D undergo [4+2] cycloaddition reaction to form a cycloaddition product E, the cycloaddition product E is dehydrated under the action of alkali to form a cyclized intermediate F, and finally, under the heating condition, one molecule of methanesulfonic acid is removed from the cyclized intermediate F to obtain the 3-phenylquinoline product. Both reactive intermediates A, C, D and F were captured for their presence by GC-MS.

Experiments show that if aliphatic aldehyde is used for replacing aromatic aldehyde, a corresponding target product cannot be obtained; if ketone is used to replace aldehyde, the corresponding target product can not be obtained; the target product obtained if dimethyl sulfoxide is replaced by substituted sulfoxide is not the desired target product.

Compared with the existing synthesis method and technology, the invention has the following advantages and effects:

1) the invention realizes the direct cyclization synthesis of 3-aryl quinoline from o-amino aryl methanol and aryl formaldehyde in DMSO for the first time;

2) the invention uses easily obtained raw materials, does not need to use difficultly obtained or expensive raw materials, has wide raw material source and low cost;

3) the invention adopts common organic base or inorganic base, avoids using expensive metal complex as catalyst, and meets the requirements of environmental protection, economy, saving and the like;

4) the reaction process of the invention is carried out in oxygen-containing atmosphere and at lower temperature, and the reaction condition is mild;

5) the yield of the 3-aryl quinoline compound synthesized by the method is high;

6) the synthesis process of the invention adopts a one-pot reaction, and has the advantages of few reaction steps and simple operation.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters not specifically mentioned.

All reactions were performed in Schlenk tubes unless otherwise noted.

All reaction starting solvents were obtained from commercial sources and used without further purification.

The product is separated by a silica gel chromatographic column and silica gel (the granularity is 300-400 meshes).

1H NMR (400MHz) and 13C NMR (100MHz) measurements were carried out using a Bruker ADVANCE III spectrometer with CDCl₃As solvent, TMS as internal standard, chemical shifts in parts per million (ppm) and reference shifts of 0.0ppm tetramethylsilane. The following abbreviations (or combinations thereof) are used to explain the multiplicity: s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, br is broad. Coupling constant J is in Hertz (Hz). Chemical shifts are expressed in ppm, with the center line for the triplet state referenced to deuterated chloroform at 77.0ppm or the center line for the heptad state referenced to deuterated DMSO at 39.52 ppm.

1. Carrying out the process

Adding 0.5 mmol of 2-aminobenzyl alcohol, 0.5 mmol of benzaldehyde, 2 mmol of potassium hydroxide and 2 ml of DMSO solvent into a reaction tube, heating at 120 ℃ under the atmosphere of oxygen, magnetically stirring, reacting for 0.5 hour, cooling to room temperature, concentrating, and performing column chromatography separation and purification to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate.

2. Effects of the implementation

The reaction equation is as follows:

the reaction is carried out according to the implementation process to obtain the implementation effect that:

3. hydrogen and carbon spectra data for partially performed products

3-Phenylquinoline(1)

A yellow oily liquid.¹H NMR(400MHz,CDCl3)δ9.20(d,J＝1.7Hz,1H),8.32(s, 1H),8.22–8.10(m,1H),7.89(d,J＝8.1Hz,1H),7.73(t,J＝7.8Hz,3H),7.56(dt,J ＝21.5,7.6Hz,3H),7.45(t,J＝7.2Hz,1H)；13C NMR(101MHz,CDCl3)δ149.83, 147.22,137.83,133.85,133.30,129.42,129.16,129.15,128.11,128.02,127.98, 127.41,127.02.

3-(p-tolyl)quinoline(2)

Light brown solid.¹H NMR(400MHz,CDCl3)δ9.18(s,1H),8.27(s,1H),8.14(d,J＝ 8.4Hz,1H),7.87(d,J＝8.1Hz,1H),7.71(t,J＝7.6Hz,1H),7.62(d,J＝7.0Hz,2H), 7.57(t,J＝7.5Hz,1H),7.33(d,J＝7.5Hz,2H),2.44(s,3H)；¹³C NMR(101MHz, CDCl3)δ149.90,147.13,138.04,134.91,133.75,132.82,129.87,129.19,129.13, 128.07,127.91,127.21,126.92,21.16.

3-(4-(tert-butyl)phenyl)quinoline(3)

A yellow liquid.¹H NMR(400MHz,CDCl3)δ9.20(s,1H),8.30(s,1H),8.13(t,J＝9.3 Hz,1H),7.88(d,J＝8.1Hz,1H),7.70(dd,J＝20.3,7.6Hz,3H),7.62–7.52(m,3H), 1.40(s,9H)；¹³C NMR(101MHz,CDCl3)δ151.31,149.92,147.15,134.91,133.70, 132.92,129.22,129.16,128.10,127.94,127.07,126.93,126.15,34.65,31.31.

3-(4-Ethylphenyl)quinoline(4)

Brown solid.¹H NMR(400MHz,CDCl3)δ9.19(s,1H),8.30(s,1H),8.15(d,J＝8.4 Hz,1H),7.88(d,J＝8.1Hz,1H),7.72(t,J＝7.6Hz,1H),7.65(d,J＝7.5Hz,2H), 7.58(t,J＝7.5Hz,1H),7.37(d,J＝7.6Hz,2H),2.74(q,J＝7.5Hz,2H),1.31(t,J＝ 7.8Hz,3H)；¹³C NMR(101MHz,DMSO)δ149.89,147.08,144.45,135.15,133.83, 132.96,129.25,129.11,128.72,127.94,127.34,126.97,28.58,15.55.

3-(4-Fluorophenyl)quinoline(5)

A yellow liquid.¹H NMR(400MHz,CDCl3)δ9.13(s,1H),8.23(s,1H),8.14(d,J＝8.4 Hz,1H),7.85(d,J＝8.1Hz,1H),7.71(t,J＝7.6Hz,1H),7.68–7.61(m,2H),7.57(t, J＝7.5Hz,1H),7.20(t,J＝8.6Hz,2H)；¹³C NMR(101MHz,CDCl3)δ162.87(d,J ＝248.0Hz),149.58,147.22,133.93(d,J＝3.3Hz),133.01,132.82,129.41,129.17, 129.01(d,J＝8.2Hz),127.88,127.06,116.11(d,J＝21.6Hz).

3-(4-Chlorophenyl)quinoline(6)

A yellow liquid.¹H NMR(400MHz,CDCl3)δ9.13(s,1H),8.26(s,1H),8.14(d,J＝8.4 Hz,1H),7.87(d,J＝8.1Hz,1H),7.73(t,J＝7.6Hz,1H),7.66–7.54(m,3H),7.49 (d,J＝7.8Hz,2H)；¹³C NMR(101MHz,CDCl3)δ149.40,147.36,136.28,134.38, 133.18,132.61,129.61,129.35,129.20,128.60,127.95,127.87,127.16.

3-(4-Methoxyphenyl)quinoline(7)

Light yellow liquid.¹H NMR(400MHz,CDCl3)δ9.16(s,1H),8.25(s,1H),8.13(d,J＝ 8.4Hz,1H),7.86(d,J＝8.1Hz,1H),7.74–7.62(m,3H),7.56(t,J＝7.5Hz,1H), 7.06(d,J＝8.7Hz,2H),3.88(s,3H)；¹³C NMR(101MHz,CDCl3)δ159.79,149.76, 146.91,133.47,132.41,130.23,129.07,128.48,128.11,127.84,126.93,114.66, 55.39.

N,N-dimethyl-4-(quinolin-3-yl)aniline(8)

Light yellow solid.¹H NMR(400MHz,CDCl3)δ8.15(dd,J＝15.2,8.7Hz,4H),7.83(d, J＝8.6Hz,1H),7.77(d,J＝8.0Hz,1H),7.68(t,J＝7.5Hz,1H),7.46(t,J＝7.4Hz, 1H),6.84(d,J＝8.3Hz,2H),3.05(s,6H)；¹³C NMR(101MHz,CDCl3)δ157.21, 151.45,136.52,129.49,129.02,128.58,127.35,126.63,125.43,118.31,112.23, 40.32.

3-Biphenyl-4-ylquinoline(9)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.25(s,1H),8.36(s,1H),8.17(d,J＝8.4 Hz,1H),7.91(d,J＝8.1Hz,1H),7.77(dt,J＝13.6,7.9Hz,5H),7.67(d,J＝7.5Hz, 2H),7.60(t,J＝7.5Hz,1H),7.49(t,J＝7.3Hz,2H),7.40(t,J＝7.3Hz,1H)；¹³C NMR(101MHz,CDCl3)δ149.71,147.25,141.02,140.35,136.65,133.36,133.14, 129.46,129.16,128.89,128.00,127.89,127.74,127.61,127.07.

3-(4-(Trifluoromethyl)phenyl)quinoline(10)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.14(s,1H),8.27(s,1H),8.14(d,J＝8.4 Hz,1H),7.86(d,J＝8.0Hz,1H),7.81–7.69(m,5H),7.57(t,J＝7.4Hz,1H)；¹³C NMR(101MHz,CDCl3)δ149.28,147.62,141.30,133.67,132.25,129.88,129.22, 128.02,127.69,127.60,127.23,126.01(q,J＝3.7Hz,1C),125.41,122.71.

3-(o-Tolyl)quinoline(11)

Brown oily liquid.¹H NMR(400MHz,CDCl3)δ8.94(s,1H),8.18(d,J＝8.4Hz, 1H),8.11(s,1H),7.86(d,J＝8.1Hz,1H),7.75(t,J＝7.6Hz,1H),7.60(t,J＝7.4Hz, 1H),7.34(d,J＝8.6Hz,4H),2.34(s,3H)；¹³C NMR(101MHz,CDCl3)δ151.33, 146.84,138.05,135.83,135.46,134.84,130.63,130.17,129.44,129.16,128.20, 127.85,127.76,126.94,126.17,20.44.

3-(2-fluorophenyl)quinoline(12)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.10(s,1H),8.27(s,1H),8.14(d,J＝8.5 Hz,1H),7.82(d,J＝8.1Hz,1H),7.71(t,J＝7.6Hz,1H),7.59–7.47(m,2H),7.41–7.32(m,1H),7.25(t,J＝7.5Hz,1H),7.22–7.15(m,1H)；¹³C NMR(101MHz, CDCl3)δ159.88(d,J＝248.6Hz),150.59(d,J＝3.4Hz),147.13,135.40(d,J＝3.3 Hz),130.59(d,J＝3.2Hz),129.82(d,J＝8.3Hz),129.56,129.08,128.65,127.91, 127.61,126.82,125.54(d,J＝13.6Hz),124.63(d,J＝3.7Hz),116.20(d,J＝22.4 Hz).

3-(m-Tolyl)quinoline(13)

Brown oily liquid.¹H NMR(400MHz,CDCl3)δ9.19(s,1H),8.29(s,1H),8.15(d,J ＝8.4Hz,1H),7.87(d,J＝8.1Hz,1H),7.72(t,J＝7.6Hz,1H),7.57(t,J＝7.5Hz, 1H),7.52(d,J＝7.9Hz,2H),7.41(t,J＝7.5Hz,1H),7.25(d,J＝7.1Hz,1H),2.47(s, 3H)；¹³C NMR(101MHz,CDCl3)δ149.95,147.27,138.81,137.81,133.93,133.11, 129.24,129.17,129.03,128.82,128.10,128.01,127.93,126.90,124.49,21.50.

3-(3-chlorophenyl)quinoline(14)

Brown solid.¹H NMR(400MHz,CDCl3)δ9.13(s,1H),8.27(s,1H),8.15(d,J＝8.4 Hz,1H),7.87(d,J＝8.1Hz,1H),7.74(t,J＝7.6Hz,1H),7.69(s,1H),7.59(t,J＝7.4 Hz,2H),7.48–7.38(m,2H)；¹³C NMR(101MHz,CDCl3)δ149.39,147.51,139.66, 135.09,133.48,132.43,130.38,129.74,129.21,128.11,128.02,127.81,127.46, 127.19,125.52.

3-(3-Methoxyphenyl)quinoline(15)

A yellow oily liquid.¹H NMR(400MHz,CDCl3)δ9.17(d,J＝1.9Hz,1H),8.25(s, 1H),8.15(d,J＝8.4Hz,1H),7.84(d,J＝8.1Hz,1H),7.70(t,J＝7.6Hz,1H),7.55(t, J＝7.5Hz,1H),7.41(t,J＝7.9Hz,1H),7.30–7.18(m,2H),6.96(dd,J＝8.2,1.5Hz, 1H),3.87(s,3H)；¹³C NMR(101MHz,CDCl3)δ160.08,149.69,147.20,139.12, 133.54,133.18,130.08,129.30,129.00,127.88,127.84,126.88,119.70,113.26, 113.10,55.23.

3-(3-(Trifluoromethyl)phenyl)quinoline(16)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.17(s,1H),8.33(s,1H),8.17(d,J＝8.5 Hz,1H),7.95(s,1H),7.90(t,J＝7.0Hz,2H),7.76(t,J＝7.6Hz,1H),7.65(m,3H)；¹³C NMR(101MHz,CDCl3)δ149.32,147.59,138.75,133.73,132.43,131.84, 131.51,130.68,129.92,129.69,129.26,128.06,127.82,127.33,124.78(q,J＝3.7 Hz),124.19(q,J＝3.9Hz).

3-(3,4-dimethylphenyl)quinoline(17)

Brown oily liquid.¹H NMR(400MHz,CDCl3)δ9.18(s,1H),8.28(s,1H),8.11(dd,J ＝20.9,7.5Hz,1H),7.87(d,J＝8.1Hz,1H),7.71(t,J＝7.6Hz,1H),7.57(t,J＝7.5 Hz,1H),7.52–7.44(m,2H),7.29(d,J＝7.7Hz,1H),2.38(s,3H),2.35(s,3H)；¹³C NMR(101MHz,CDCl3)δ149.95,147.11,137.44,136.73,135.35,133.87,132.77, 130.43,129.12,128.55,128.09,127.90,126.87,124.73,19.94,19.49.

3-(3,4-Dimethoxyphenyl)quinoline(18)

Yellow solid.¹H NMR(400MHz,CDCl3)δ8.17(d,J＝8.4Hz,2H),7.89(s,1H), 7.82(dd,J＝16.7,8.3Hz,2H),7.75–7.63(m,2H),7.50(t,J＝7.4Hz,1H),6.99(d, J＝8.3Hz,1H),4.05(s,3H),3.97(d,J＝14.6Hz,3H)；¹³C NMR(101MHz,CDCl3) δ156.78,150.43,149.41,148.13,136.64,132.46,129.60,129.42,127.39,126.95, 125.98,120.25,118.58,111.08,110.51,56.02,55.98.

3-(Thiophen-2-yl)quinoline(19)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.20(s,1H),8.26(s,1H),8.10(d,J＝8.4 Hz,1H),7.83(d,J＝8.1Hz,1H),7.69(t,J＝7.6Hz,1H),7.55(t,J＝7.5Hz,1H), 7.49(d,J＝2.6Hz,1H),7.39(d,J＝4.9Hz,1H),7.16(t,J＝3.7Hz,1H)；¹³C NMR (101MHz,CDCl3)δ148.59,147.26,140.71,131.34,129.28,128.38,127.91,127.78, 127.56,127.21,126.08,124.40.

3-(Thiophene-3-yl)quinoline(20)

Brown solid.¹H NMR(400MHz,CDCl3)δ9.21(s,1H),8.28(s,1H),8.12(d,J＝8.3 Hz,1H),7.85(d,J＝8.1Hz,1H),7.69(dd,J＝15.5,7.8Hz,2H),7.60–7.47(m,3H)；¹³C NMR(101MHz,CDCl3)δ149.43,147.15,138.87,132.04,129.21,128.76, 128.08,127.85,127.07,126.09,121.65.

3-(4-Pyridinyl)quinoline(21)

Brown solid.¹H NMR(400MHz,CDCl3)δ8.79(d,J＝4.5Hz,2H),8.31(d,J＝8.5 Hz,1H),8.20(d,J＝8.5Hz,1H),8.11(d,J＝4.7Hz,2H),7.92(d,J＝8.5Hz,1H), 7.88(d,J＝8.1Hz,1H),7.78(t,J＝7.8Hz,1H),7.60(t,J＝7.4Hz,1H)；¹³C NMR (101MHz,CDCl3)δ154.18,149.92,148.30,147.17,137.33,130.17,130.03,127.88, 127.54,127.32,121.78,118.41.

3-(Furan-2-yl)quinoline(22)

A white solid.¹H NMR(400MHz,CDCl3)δ9.22(s,1H),8.36(s,1H),8.09(d,J＝8.5 Hz,1H),7.84(d,J＝8.1Hz,1H),7.68(t,J＝7.6Hz,1H),7.63–7.49(m,2H),6.87 (s,1H),6.56(s,1H)；¹³C NMR(101MHz,CDCl3)δ151.37,147.08,147.05,143.13, 129.25,129.15,127.95,127.88,127.18,124.07,111.97,106.71.

3-(Naphthalen-2-yl)quinoline(23)

Light yellow solid.¹H NMR(400MHz,CDCl3)δ9.32(s,1H),8.36(d,J＝14.2Hz,1H), 8.19(d,J＝8.4Hz,1H),8.14(s,1H),8.00–7.86(m,4H),7.81(d,J＝8.5Hz,1H), 7.73(t,J＝7.6Hz,1H),7.62–7.49(m,3H)；¹³C NMR(101MHz,CDCl3)δ149.94, 147.23,134.99,133.60,133.55,133.35,132.78,129.35,129.14,128.89,128.19, 127.97,127.94,127.64,126.96,126.56,126.40,126.32,125.09.

3-(benzo[d][1,3]dioxol-5-yl)quinoline(24)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.11(s,1H),8.21(s,1H),8.13(d,J＝8.4 Hz,1H),7.85(d,J＝8.1Hz,1H),7.70(t,J＝7.6Hz,1H),7.56(t,J＝7.5Hz,1H), 7.18(s,2H),6.96(d,J＝8.4Hz,1H),6.04(s,2H)；¹³C NMR(101MHz,CDCl3)δ 149.72,148.53,147.82,147.05,133.58,132.67,132.00,129.21,129.13,128.01, 127.85,127.00,121.16,108.97,107.72,101.38.

3,8'-biquinoline(25)

Brown solid.¹H NMR(400MHz,CDCl3)δ8.96(s,1H),8.70–8.53(m,2H),8.41– 8.18(m,4H),8.02(d,J＝8.5Hz,1H),7.86(d,J＝8.0Hz,1H),7.76(t,J＝7.6Hz, 1H),7.56(t,J＝7.3Hz,1H),7.50–7.39(m,1H)；¹³C NMR(101MHz,CDCl3)δ 156.24,150.98,148.34,137.65,137.01,136.90,129.94,129.89,129.75,128.76, 127.51,127.28,126.88,126.61,121.57,118.97.

Quinoline(26)

A colorless liquid.¹H NMR(400MHz,CDCl3)δ8.90(s,1H),8.11(t,J＝7.0Hz,2H),7.79 (d,J＝8.1Hz,1H),7.70(t,J＝7.6Hz,1H),7.52(t,J＝7.4Hz,1H),7.40–7.33(m, 1H)；¹³C NMR(101MHz,CDCl3)δ150.33,148.23,135.93,129.39,129.35,128.20, 127.69,126.44,120.97.

6-Methyl-3-Phenylquinoline(27)

A yellow liquid.¹H NMR(400MHz,CDCl3)δ9.12(d,J＝2.0Hz,1H),8.21(d,J＝1.7 Hz,1H),8.04(d,J＝8.6Hz,1H),7.74–7.67(m,2H),7.63(s,1H),7.58–7.49(m, 3H),7.47–7.40(m,1H),2.56(s,3H)；¹³C NMR(101MHz,CDCl3)δ148.92, 145.86,137.99,136.87,133.78,132.62,131.70,129.10,128.78,128.03,127.98, 127.35,126.76,21.60.

6-Fluoro-3-phenylquinoline(28)

A yellow liquid.¹H NMR(400MHz,CDCl3)δ9.14(s,1H),8.24(s,1H),8.14(dd,J＝ 9.9,5.2Hz,1H),7.70(d,J＝7.6Hz,2H),7.58–7.44(m,5H)；¹³C NMR(101MHz, CDCl3)δ162.02,159.55,149.28,149.25,144.40,137.49,134.59,132.54,132.49, 131.76,131.67,129.21,128.80,128.70,128.35,127.99,127.58,127.45,119.72, 119.46,110.96,110.75.

6-Chloro-3-phenylquinoline(29)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.16(s,1H),8.19(s,1H),8.07(d,J＝9.0 Hz,1H),7.85(s,1H),7.69(d,J＝7.5Hz,2H),7.64(d,J＝9.0Hz,1H),7.53(t,J＝ 7.3Hz,2H),7.45(t,J＝7.3Hz,1H)；¹³C NMR(101MHz,CDCl3)δ150.13,145.61, 137.34,134.69,132.73,132.16,130.80,130.25,129.23,128.65,128.39,127.41, 126.54.

6-Bromo-3-phenylquinoline(30)

Yellow solid.¹H NMR(400MHz,CDCl3)δ9.18(d,J＝1.3Hz,1H),8.20(s,1H), 8.07–7.97(m,2H),7.78(dd,J＝8.9,1.1Hz,1H),7.69(d,J＝8.0Hz,2H),7.54(t,J ＝7.5Hz,2H),7.47(d,J＝7.8Hz,1H)；¹³C NMR(101MHz,CDCl3)δ150.17, 145.71,137.28,134.68,132.83,132.13,130.85,129.92,129.25,129.16,128.43, 127.41,120.96.

6-Methoxy-3-phenylquinoline(31)

A yellow liquid.¹H NMR(400MHz,CDCl3)δ9.03(s,1H),8.22(s,1H),8.06(d,J＝9.1 Hz,1H),7.70(d,J＝7.4Hz,2H),7.52(t,J＝7.4Hz,2H),7.44(t,J＝7.3Hz,1H), 7.38(d,J＝9.1Hz,1H),7.14(s,1H),3.96(s,3H)；¹³C NMR(101MHz,CDCl3)δ 158.24,147.01,143.03,137.86,134.18,132.43,130.27,129.14,128.12,127.39, 122.41,105.33,55.57.

7-Methyl-3-phenylquinoline(32)

A yellow liquid.¹H NMR(400MHz,CDCl3)δ9.15(s,1H),8.27(s,1H),7.94(s,1H), 7.78(d,J＝8.2Hz,1H),7.71(d,J＝7.6Hz,2H),7.52(t,J＝7.3Hz,2H),7.43(t,J＝ 6.9Hz,2H),2.60(s,3H)；¹³C NMR(101MHz,CDCl3)δ149.61,147.32,139.93, 137.96,133.19,133.10,129.37,129.14,128.01,127.97,127.63,127.33,126.10, 21.93。