CN109336811B - Preparation method of quinoline-4-formate compound - Google Patents
Preparation method of quinoline-4-formate compound Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/50—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 4
- C07D215/52—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 4 with aryl radicals attached in position 2
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
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- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention discloses a preparation method of quinoline-4-formate compounds, which comprises the steps of dissolving aniline compounds shown in a formula (II), aldehyde compounds shown in a formula (III) and pyruvate compounds shown in a formula (IV) in an organic solvent, carrying out multi-component reaction under the action of a large steric hindrance borane catalyst, and preparing quinoline-4-formate compounds shown in a formula (I) by a one-pot method;
in the formula (I), formula (II), formula (III) and formula (IV), R1Is C1-C4 alkyl, phenyl, fluorine, chlorine, trifluoromethyl or methoxy; r2Is aryl, heteroaryl, C1-C4 alkyl or C3-C7 cycloalkyl; r3Is methyl or ethyl. The method adopts the non-metal catalyst, avoids the use of the metal catalyst from the source and can avoid the heavy metal pollution in medical chemicals; the catalyst has wide substrate applicability, and has better catalytic yield for arylamine compounds, aromatic or aliphatic aldehydes and different pyruvate compounds containing different functional groups.
Description
Technical Field
The invention belongs to the technical field of pharmaceutical and chemical intermediate synthesis, and particularly relates to a preparation method of a quinoline-4-formate compound.
Background
Quinoline-4-formic ether is a very important organic synthesis intermediate, and is mainly applied to the fields of organic synthesis, medicine and the like. For example, it is a key raw material for synthesizing Quinoline-4-carboxamide (Design, Synthesis, and biologica evaluation of 4-Quinoline Carboxylic Acids as Inhibitors of dihydrootetrahydrogenase.J.Med.chem., 2018,61, 5162-. The most representative of them is the novel multi-stage antimalarial drug DDD107498(A novel-stage antimalarial agent that inhibit protein synthesis. Nature,2015,522,315-320.) which has entered the clinical stage. Because of the key application of quinoline-4-formate in the pharmaceutical chemical field, the synthesis method thereof also becomes a research hotspot. However, there are few reports on the synthesis thereof.
In 2010, Wang topic team (Yb (OTf)3:an efficient catalyst forthe synthesis of3-arylbenzo[f]quinoline-1, 2-dicarboxylic acid derivatives via imine-Diels-alder reaction tetrahedron lett, 2010,51, 5721-ketone 5723) prepared from aldehyde derivatives, 2-naphthylamine and derivatives of diacetylene diester by reacting ytterbium triflate (Yb (OTf)3) Under the catalysis, the quinoline-4-formate derivative is synthesized by multi-component reaction. The reaction system is innovative in that the catalyst is low in dosage, the aromatic aldehyde has good reaction activity and applicability, the product yield is 76-92%, the aliphatic aldehyde is not applicable, and the chemical reaction formula is as follows:
in 2015, the Zhou topic group (Synthesis of Quinoliness by Visible-Light induced radial Reaction of Vinyl Azides and α -Carbonyl benzylidene bromides. adv. Synth. Catal.2015,357, 2479-2484) reported that Visible Light promoted metallic iridium (Ir) catalyzes the preparation of quinoline-4-carboxylates from α -Carbonyl benzylidene bromides and Vinyl Azides. The method can realize smooth reaction at room temperature, the product yield is 40-77%, and the chemical reaction formula is as follows:
2017 Gao topic group (Triple zircone @)
acid/CuO synergistic catalysis system for tandem Mannich addition/C-C formation cyclization RSCAdv, 2017,7,28616-28625.) reports that zirconocene dichloride, copper oxide and benzoic acid jointly catalyze multicomponent reactions of aromatic amines, aldehydes and pyruvate compounds, and a one-pot method is used for preparing quinoline-4-formate compounds with the yield of 90-95%, and the chemical reaction formula is as follows:
the above methods can produce quinoline-4-carboxylic acid esters with high efficiency, but all use metal catalysts. With the continuous attention paid to the problem of heavy metal residue in the drugs, the development of a method for preparing quinoline-4-formate compounds by non-metal catalysis is urgent.
Disclosure of Invention
In view of the above technical problems in the prior art, the present invention aims to provide a preparation method of quinoline-4-carboxylic acid ester compounds.
The preparation method of the quinoline-4-formate compound is characterized by comprising the following preparation steps: the preparation method comprises the following steps of (1) dissolving aniline compounds shown in a formula (II), aldehyde compounds shown in a formula (III) and pyruvate ester compounds shown in a formula (IV) in an organic solvent, and carrying out multi-component reaction under the action of a large steric hindrance borane catalyst to obtain quinoline-4-formate compounds shown in a formula (I) by a one-pot method;
in the formula (I), the formula (II), the formula (III) and the formula (IV), R1Is C1-C4 alkyl, phenyl, fluorine, chlorine, trifluoromethyl, methoxy or substituted phenyl, wherein the substituent of the substituted phenyl is chlorine, trifluoromethyl or methoxy; r2Is aryl, heteroaryl or C1-C4 alkyl or C3-C7 cycloalkyl; r3Is methyl or ethyl. R1Preferably methyl, methoxy or phenyl, R2Preferably substituted phenyl, the substituent of which is chlorine, trifluoromethyl or methoxy, R3Preferably methyl.
The reaction formula for preparing the quinoline-4-formate compound is as follows:
the preparation method of the quinoline-4-formate compound is characterized in that the reaction temperature is 0-100 ℃, and preferably 30-60 ℃; the reaction time is 1 to 15 hours, preferably 2 to 12 hours.
The preparation method of the quinoline-4-formate compound is characterized in that the large steric hindrance borane catalyst is triphenylborane, tri (2, 6-dichlorophenyl) borane or tri (pentafluorophenyl) borane, preferably tri (pentafluorophenyl) borane.
The preparation method of the quinoline-4-formate compound is characterized in that the molar ratio of the aniline compound shown in the formula (II), the aldehyde compound shown in the formula (III), the pyruvate compound shown in the formula (IV) and the high steric hindrance borane catalyst is 1-4: 1: 0.001-0.1, preferably 2-4: 1: 0.001-0.05.
The preparation method of the quinoline-4-formate compound is characterized in that the organic solvent is toluene, chlorobenzene, acetonitrile, tetrahydrofuran, chloroform or n-hexane, preferably chloroform.
The preparation method of the quinoline-4-formate compound is characterized in that in the formula (I) and the formula (III), R2Is substituted phenyl, and the substituent of the substituted phenyl is chlorine, trifluoromethyl or methoxy.
Compared with the prior art, the invention has the following advantages:
1) the method adopts the non-metal catalyst, avoids the use of the metal catalyst from the source and can avoid the heavy metal pollution in medical chemicals;
2) the dosage of the non-metal catalyst can be reduced to 0.1 mol%, and the catalyst is resistant to moisture and air and has potential industrial prospect;
3) the reaction atom economy is high, the reaction time is short, the conditions are mild, and the green chemical concept is met;
4) the substrate has wide applicability, has better catalytic yield (up to 95 percent) for arylamine compounds, aromatic or aliphatic aldehydes and different pyruvate compounds containing different functional groups, and has better application value and potential social and economic benefits.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1: preparation of methyl 2- (4-chlorophenyl) quinoline-4-carboxylate (Ia)
A solution of aniline (2.7g,30mmol), 4-chlorobenzaldehyde (5.1g,30mmol), methyl pyruvate (1.0g,10mmol) and tris (pentafluorophenyl) borane (5mg,0.01mmol) in chloroform (chloroform volume 20mL) was stirred at 60 ℃ for 6 hours. After the reaction, the reaction mixture was distilled under reduced pressure to remove the chloroform solvent, and the resulting concentrate was separated by silica gel column chromatography (eluent was a mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 5: 1) to give the desired methyl 2- (4-chlorophenyl) quinoline-4-carboxylate (Ia) as a white solid (2.7g, melting point: 86.2-88.4 ℃, and the yield is calculated by methyl pyruvate: 92 percent.
Ia structural formula is:
1HNMR(400MHz,Chloroform-d)8.76(d,J＝8.4Hz,1H),8.37(s,1H),8.21(t,J＝12.6Hz,1H),8.18(d,J＝8.4Hz,2H),7.79(t,J＝7.8Hz,1H),7.71–7.62(m,1H),7.53(d,J＝8.4Hz,2H),4.10(s,3H).13CNMR(100MHz,Chloroform-d)166.7,155.3,149.2,137.1,136.0,135.7,130.3,130.1,129.1(2C),128.7(2C),128.0,125.5,124.0,119.9,52.8.MS(ESI):m/e＝298.1[M+H]+.HRMS:calcdforC17H12ClNO2[M+H]+:298.0557.Found:298.0551。
example 2: preparation of methyl 2- (4-chlorophenyl) -6-fluoroquinoline-4-carboxylate (Ib)
A solution of 4-fluoroaniline (2.3g,20mmol), 4-chlorobenzaldehyde (2.8g,20mmol), methyl pyruvate (1.0g,10mmol) and tris (pentafluorophenyl) borane (25mg,0.05mmol) in n-hexane (n-hexane volume 20mL) was stirred at 30 ℃ for 4 hours. After the reaction is finished, the reaction solution is decompressed and distilled to remove the normal hexane solvent, and the obtained concentrate is separated by silica gel column chromatography (eluent is a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 5: 1) to obtain the required 2- (4-chlorphenyl) -4-fluoroquinoline-4-methyl formate (Ib), 2.6g of white solid, melting point: 112.3-113.9 ℃, and the yield is calculated by methyl pyruvate: 81 percent. Ib is represented by the structural formula:
1H NMR(400MHz,Chloroform-d)8.53(d,J＝10.8Hz,1H),8.47(s,1H),8.28–8.20(m,1H),8.17(d,J＝8.0Hz,2H),7.59(d,J＝8.4Hz,1H),7.54(d,J＝8.0Hz,2H).13C NMR(100MHz,Chloroform-d)166.3,162.8,160.4,154.7,146.5,136.8,136.1,134.9(d,J＝5.9Hz),132.7(d,J＝9.3Hz),129.2(2C),128.6,125.0(d,J＝11.3Hz),120.8,120.5(d,J＝26.0Hz),109.6(d,J＝25.1Hz),52.9.MS(ESI):m/e＝316.0[M+H]+.HRMS:calcd forC17H11ClFNO2[M+H]+:316.0426.Found:316.0428。
example 3: preparation of methyl 2- (4-chlorophenyl) -6-methoxyquinoline-4-carboxylate (Ic)
A toluene solution of 4-methoxyaniline (2.4g,20mmol), 4-chlorobenzaldehyde (2.8g,20mmol), methyl pyruvate (1.0g,10mmol) and triphenylborane (121mg,0.5mmol) (toluene volume 20mL) was stirred at 60 ℃ for 6 hours. After the reaction, the reaction solution was distilled under reduced pressure to remove the toluene solvent, and the resulting concentrate was separated by silica gel column chromatography (eluent was a mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 5: 1) to give the desired methyl 2- (4-chlorophenyl) -4-methoxyquinoline-4-carboxylate (Ic) as a white solid (2.4g, melting point: 119.2-121.6 ℃, and the yield is calculated by methyl pyruvate: 75 percent. Ic is of the formula:
1H NMR(400MHz,Chloroform-d)8.37(s,1H),8.21(s,1H),8.11(t,J＝10.4Hz,3H),7.50(d,J＝8.0Hz,2H),7.43(d,J＝9.2Hz,1H),4.65–4.49(m,2H),3.99(s,3H),1.53(t,J＝6.8Hz,3H).13C NMR(100MHz,Chloroform-d)166.4,159.1,152.7,145.6,137.3,135.4,133.9,131.6,129.0(2C),128.4,125.6,123.0,120.2,103.3,61.8,55.6,14.4.MS(ESI):m/e＝328.1[M+H]+.HRMS:calcd for C18H14ClNO3[M+H]+:328.0662.Found:328.0661。
example 4: preparation of methyl 2- (4- (trifluoromethyl) phenyl) benzoquinoline-4-carboxylate (Id)
A solution of 1-naphthylamine (4.3g,30mmol), 4-chlorobenzaldehyde (4.2g,30mmol), methyl pyruvate (1.0g,10mmol) and tris (2, 6-dichlorophenyl) borane (90mg,0.3mmol) in tetrahydrofuran (20 mL volume of tetrahydrofuran) was stirred at 40 ℃ for 10 hours. After the reaction is finished, the reaction solution is decompressed and distilled to remove the tetrahydrofuran solvent, and the obtained concentrate is separated by silica gel column chromatography (eluent is a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 5: 1) to obtain the required 2- (4-trifluoromethylphenyl) -4-methoxyquinoline-4-methyl formate (Id), 3.1g of white solid, melting point: 148.6-149.9 ℃, yield calculated as methyl pyruvate: 95 percent. Id is of the formula:
1H NMR(400MHz,Chloroform-d)9.46–9.39(m,1H),8.61(d,J＝9.2Hz,1H),8.42(d,J＝9.2Hz,3H),7.90(t,J＝8.8Hz,2H),7.85–7.72(m,4H),4.11(s,3H).13C NMR(100MHz,Chloroform-d)166.8,152.9,147.4,142.0,135.6,133.4,131.4,129.6,128.8,127.7(2C),127.5(2C),127.3(2C),125.87–125.67(m),125.0,123.0,122.1(2C),119.5,52.8.MS(ESI):m/e＝382.1[M+H]+.HRMS:calcd for C22H14F3NO2[M+H]+:383.0977.Found:383.0979。
example 5: preparation of methyl 2- (2-methoxyphenyl) benzoquinoline-4-carboxylate (Ie)
A chloroform solution (chloroform volume 20mL) of 1-naphthylamine (4.2g,30mmol), 2-methoxybenzaldehyde (3.9g,30mmol), methyl pyruvate (1.0g,10mmol) and triphenylborane (48mg,0.2mmol) was stirred at 60 ℃ for 8 hours. After the reaction, the reaction solution was distilled under reduced pressure to remove the chloroform solvent, and the resulting concentrate was separated by silica gel column chromatography (eluent was a mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 5: 1) to give the desired methyl 2- (2-methoxyphenyl) benzoquinoline-4-carboxylate (Ie) as a white solid (2.7g, melting point: 134.0-135.8 ℃, yield calculated as methyl pyruvate: 80 percent. Ie has the structural formula:
1H NMR(400MHz,Chloroform-d)9.51(dd,J＝7.8,1.6Hz,1H),8.75–8.62(m,2H),8.25(dt,J＝7.8,1.6Hz,1H),7.98–7.89(m,2H),7.76(pd,J＝7.2,1.6Hz,2H),7.55–7.45(m,1H),7.25(q,J＝7.8Hz,1H),7.10(d,J＝8.3Hz,1H),4.11(s,3H),3.96(s,3H).13C NMR(100MHz,Chloroform-d)167.5,157.6,154.4,147.3,134.4,133.3,132.0,132.7,130.7,128.9,128.8,128.4,127.6,127.1,125.2,124.5,122.4,122.2,121.3,111.6,55.8,52.7.MS(ESI):m/e＝344.1[M+H]+.HRMS:calcd for C22H17NO3[M+H]+:344.1208.Found:344.1210。
example 6: preparation of methyl 6-methoxy-2- (3-pyridyl) quinoline-4-carboxylate (If)
A solution of 4-methoxyaniline (4.8g,40mmol), 3-pyridinecarboxaldehyde (4.0g,40mmol), methyl pyruvate (1.0g,10mmol) and tris (pentafluorophenyl) borane (255mg,0.5mmol) in chlorobenzene (chlorobenzene volume 20mL) was stirred at 0 ℃ for 12 h. After the reaction is finished, the chlorobenzene solvent is removed by reduced pressure distillation of the reaction liquid, and the obtained concentrate is separated by silica gel column chromatography (eluent is a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 5: 1) to obtain the required 6-methoxy-2- (3-pyridyl) quinoline-4-methyl formate (If), 2.7g of white solid, melting point: 121.3-122.5 ℃, and the yield is calculated by methyl pyruvate: 90 percent. If structural formula is:
1H NMR(400MHz,Chloroform-d)9.12(s,1H),8.78(d,J＝4.4Hz,1H),8.65(d,J＝8.0Hz,1H),8.31(d,J＝2.4Hz,1H),8.15(d,J＝9.2Hz,1H),7.91(t,J＝7.6Hz,1H),7.46(dd,J＝9.2,2.4Hz,1H),7.44–7.37(m,1H),4.08(s,3H),4.02(s,3H).13C NMR(100MHz,Chloroform-d)167.0,159.6,155.7,153.0,149.1,145.3,137.1,133.3,131.8,126.8,124.0,122.9,121.4,120.8,103.31,55.7,52.5.MS(ESI):m/e＝295.1[M+H]+.HRMS:calcdfor C17H14N2O3[M+H]+:295.1004.Found:295.1008。
example 7: preparation of methyl 2-cyclohexyl-6-methoxyquinoline-4-carboxylate (Ig)
A toluene solution of 4-methoxyaniline (3.6g,30mmol), cyclohexylformaldehyde (3.3g,30mmol), methyl pyruvate (1.0g,10mmol) and tris (2, 6-dichlorophenyl) borane (15mg,0.05mmol) (toluene volume 20mL) was stirred at 50 ℃ for 8 hours. After the reaction is finished, the reaction solution is decompressed and distilled to remove the toluene solvent, and the obtained concentrate is separated by silica gel column chromatography (eluent is a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 5: 1) to obtain the required 2-cyclohexyl-6-methoxyquinoline-4-methyl formate (Ig), 2.9g of white solid, melting point: 122.3-124.1 ℃, yield calculated as methyl pyruvate: 95 percent. The Ig structural formula is:
1H NMR(400MHz,Chloroform-d)8.18(d,J＝2.8Hz,1H),8.00(d,J＝9.2Hz,1H),7.87(s,1H),7.39(dd,J＝9.2,2.8Hz,1H),4.04(s,3H),3.97(s,3H),3.00–2.85(m,1H),2.09–2.01(m,2H),1.95–1.88(m,2H),1.81(d,J＝12.4Hz,1H),1.65(dd,J＝12.4,3.2Hz,2H),1.49(dt,J＝12.8,2.8Hz,2H),1.36(d,J＝4.8Hz,1H).13C NMR(100MHz,Chloroform-d)167.1,163.5,158.5,145.1,133.0,130.9(2C),125.2,122.3,121.5,103.3,55.5,52.5,47.1,32.8,29.7,26.5,26.0.MS(ESI):m/e＝300.1[M+H]+.HRMS:calcd for C18H21NO3[M+H]+:300.1521.Found:300.1524。
example 8: preparation of ethyl 2- (4-chlorophenyl) -6-methoxyquinoline-4-carboxylate (Ih)
A solution of 4-methoxyaniline (2.4g,20mmol), 4-chlorobenzaldehyde (2.8g,20mmol), ethyl pyruvate (1.2g,10mmol) and tris (pentafluorophenyl) borane (5mg,0.1mmol) in acetonitrile (acetonitrile volume 20mL) was stirred at 50 ℃ for 3 h. After the reaction is finished, the reaction solution is decompressed and distilled to remove the acetonitrile solvent, and the obtained concentrate is separated by silica gel column chromatography (eluent is a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 5: 1) to obtain the required methyl 2- (4-chlorphenyl) -4-methoxyquinoline-4-carboxylate (Ih), 3.1g of white solid, melting point: 128.1-129.3 ℃, and the yield is calculated by ethyl pyruvate: 91 percent. The structural formula of Ih is:
1H NMR(400MHz,Chloroform-d)8.37(s,1H),8.21(s,1H),8.11(t,J＝10.4Hz,3H),7.50(d,J＝8.0Hz,2H),7.43(d,J＝9.2Hz,1H),4.64–4.49(m,2H),3.99(s,3H),1.53(t,J＝6.8Hz,3H).13C NMR(100MHz,Chloroform-d)166.4,159.1,152.7,145.6,137.3,135.4,133.9,131.6,129.0(2C),128.4(2C),125.6,123.0,120.2,103.3,61.8,55.6,14.4.MS(ESI):m/e＝342.1[M+H]+.HRMS:calcd for C19H16ClNO3[M+H]+:342.0819.Found:342.0817。
examples 9 to 17:
an aniline derivative represented by the formula (II) (20mmol), a benzaldehyde derivative represented by the formula (III) (20mmol), methyl pyruvate represented by the formula (IV) (10mmol) and tris (pentafluorophenyl) borane (5mg,0.01mmol) were dissolved in 20mL of chloroform, and the reaction was stirred at 50 ℃ for 2 to 8 hours. After the reaction is finished, the reaction solution is decompressed and distilled to remove the chloroform solvent, and the obtained concentrate is separated by silica gel column chromatography (eluent is a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 5: 1) to obtain the target compound (Ii-Iq), wherein the reaction formula is as follows:
in the formulae (II) and (III), the substituent R1And R2The yield was calculated from methyl pyruvate, and the yield of the objective compound (Ii-Iq) was as shown in Table 1;
TABLE 1
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (5)
1. A preparation method of quinoline-4-formate compounds shown in formula (I) is characterized in that aniline compounds shown in formula (II), aldehyde compounds shown in formula (III) and pyruvate compounds shown in formula (IV) are dissolved in an organic solvent, multi-component reaction is carried out for 1-15 hours at 0-100 ℃ under the action of a large steric hindrance borane catalyst, and quinoline-4-formate compounds shown in formula (I) are prepared by a one-pot method;
in the formulae (I), (II), (III) and (IV), R1Is fluorine, methoxy, phenyl or substituted phenyl, and the substituent of the substituted phenyl is chlorine, trifluoromethyl or methoxy; r2Is aryl, heteroaryl, C1-C4 alkyl or C3-C7 cycloalkyl; r3Is methyl or ethyl;
the high steric hindrance borane catalyst is any one of triphenylborane, tri (2, 6-dichlorophenyl) borane or tri (pentafluorophenyl) borane;
the organic solvent is toluene, chlorobenzene, acetonitrile, tetrahydrofuran, chloroform or normal hexane;
the molar ratio of the aniline compound shown in the formula (II), the aldehyde compound shown in the formula (III), the pyruvate compound shown in the formula (IV) and the high-steric-hindrance borane catalyst is 1-4: 1: 0.001-0.1.
2. The method for preparing quinoline-4-carboxylic acid ester compounds according to claim 1, wherein the reaction temperature is 30 to 60 ℃; the reaction time is 2-12 h.
3. The method for preparing quinoline-4-carboxylic acid ester compound as claimed in claim 1, wherein the sterically hindered borane catalyst is tris (pentafluorophenyl) borane.
4. The method for preparing quinoline-4-formate compounds according to claim 1, wherein the molar ratio of the aniline compound represented by formula (II), the aldehyde compound represented by formula (III), the pyruvate compound represented by formula (IV) and the bulky-hindrance borane catalyst is 2-4: 1: 0.001-0.05.
5. The method for producing a quinoline-4-carboxylic acid ester compound according to claim 1, wherein the organic solvent is chloroform.
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