A method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on nitrogen-containing heteroarene carbon-hydrogen bond carboxylation reaction

Abstract

The application discloses a method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on nitrogen-containing heteroarene carbon-hydrogen bond carboxylation reaction and belongs to the technical field of organic synthesis, and specifically comprises the following steps: adding a reaction substrate, an organic catalyst, a base and an additive into a reaction container, then adding a solvent under a CO2 atmosphere, and stirring and reacting at room temperature or under heating in a light irradiation condition; and performing post-treatment on a reaction product, separating and purifying the reaction product, and obtaining nitrogen-containing heteroarene carboxylic acid compounds and derivatives thereof. The scheme has the characteristics of mild reaction condition, wide reaction substrate range, good yield and good regioselectivity, and cheap and easily-obtained raw materials, can efficiently realize nitrogen-containing heteroarene carbon-hydrogen bond carboxylation reaction, synthesize important nitrogen-containing heteroarene carboxylic acid compounds, and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on nitrogen-containing heteroarene carbon-hydrogen bond carboxylation. BACKGROUND

[0002] Aromatic heterocycles are widely present in nature and are widely used in medicine, pesticides, dyes and polymer materials as an important structural unit. Direct functionalization of aromatic heterocycle C-H bond is one of the most effective ways to quickly modify or construct complex molecules. At present, important progress has been made in the C-H bond functionalization of nitrogen-containing heteroarenes, but achieving high selectivity functionalization of nitrogen-containing heteroarenes is still a great challenge. On the other hand, nitrogen-containing heterocyclic carboxylic acid is an important aromatic carboxylic acid structure, which is widely present in natural products and drug molecules and is widely used in medicinal chemistry. For example, 4-carboxylic acid-2-phenyl quinoline compounds are important drug molecules. At present, the use of carbon dioxide in organic synthesis reactions to realize the chemical fixation of carbon dioxide is a research hotspot in recent years, and it is of great significance to use cheap and easily available recyclable carbon dioxide gas as a carbon one synthetic substrate to efficiently construct carboxylic acid compounds. Compared with other C-H bond functionalization of nitrogen-containing heteroarenes (including arylation, boronation, alkylation, etc.), direct C-H bond carboxylation of nitrogen-containing heteroarenes is less reported, and only two examples are early electrochemical carboxylation of quinoline compounds and ruthenium-catalyzed carboxylation of pyridine by directing group strategy. However, in general, this kind of method has the problems of poor selectivity and difficult removal of directing group or uses expensive gold catalyst. For nitrogen-containing aromatic carboxylic acid, it is of great significance to efficiently and quickly construct this kind of molecule because it is widely present in many important natural products and drug molecules. SUMMARY

[0003] In view of the deficiencies of the prior art, the purpose of the present application is to provide a method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on nitrogen-containing heteroarene carbon-hydrogen bond carboxylation, which can effectively solve the problems of using a sacrificial anode, equivalent metal reducing agent, noble metal catalyst, additional introduction of a directing group and harsh reaction conditions in the prior art for nitrogen-containing heteroarene carbon-hydrogen bond carboxylation, and can synthesize nitrogen-containing heteroarene carboxylic acid compounds under mild conditions using cheap thiophenol, thiol, organic amine or Hans ester as a catalyst, which has the characteristics of mild reaction conditions, wide range of reaction substrates, good yield and regioselectivity, and cheap and easily available raw materials.

[0004] In order to achieve the above purpose, the technical scheme adopted by the present application is to provide a method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on nitrogen-containing heteroarene carbon-hydrogen bond carboxylation, comprising the following steps:

[0005] In a CO2 atmosphere, the reaction substrate, catalyst, base and additive are mixed uniformly in a reaction container, then heated and stirred under light conditions at 0-100 DEG C for 0.1-80 h, followed by post-treatment and separation and purification to obtain a nitrogen-containing heteroarene carboxylic acid compound;

[0006] The structural general formula of the reaction substrate is shown in formula (I) or formula (II) or formula (III):

[0007]

[0008] wherein, R 1 , R 5 and R 11 are independently hydrogen atom, aryl, heteroaryl, amide, carboxyl or ester group; R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 , R 15 , R 16 are independently hydrogen atom, substituted phenyl, naphthyl, fluorenyl, heteroaryl, ester group, carboxyl, amide group, alkyl, alkenyl, alkynyl, cyano, boron group, silicon group, amine group, sulfide group, alkoxy group, acyloxy group or aryloxy group.

[0009] On the basis of the above technical solution, the application can also be improved as follows.

[0010] Further, the molar ratio of the reaction substrate, catalyst, base and additive is 1:0.001-1:0.5-10:0.01-2.

[0011] Further, the reaction substrate is a quinoline nitrogen heteroarene compound, a pyridine nitrogen heteroarene compound, a bipyridine nitrogen heteroarene compound, a phenanthroline nitrogen heteroarene compound or an acridine nitrogen heteroarene compound; wherein,

[0012] The quinoline nitrogen heteroarene compound is one of the following compounds:

[0013]

[0014] The pyridine, bipyridine, phenanthroline and acridine nitrogen heteroarene compound is one of the following compounds:

[0015]

[0016] Further, the catalyst is an organic small molecule catalyst.

[0017] Further, the organic small molecule catalyst is thiophenol, thiol, organic amine, Hans ester or silanol salt.

[0018] Further, the base is carbonate, bicarbonate, fluorinated salt, phosphate, hydrogen phosphate, carboxylate or organic base.

[0019] Further, the base is Na2CO3, K2CO3, CsF, KO t Bu, Cs2CO3, CsOAc, CsOPiv, KOMe, K3PO4, CF3CO2K, CF3CO2Cs, CsHCO3 or Me3SiOK.

[0020] Further, the additive is silane, organic amine or Hans ester.

[0021] Further, the additive is Ph2MeSiH, PhMe2SiH, MeEt2SiH, (TMS)3SiH, i Pr3SiH, Ph3SiH, Et3SiH, HBpin or polymethylhydrosiloxane.

[0022] Further, the solvent is DMSO, NMP, DMF, DMAc.

[0023] Further, the carbon dioxide pressure in the reaction container is 0.1-30 atm, the distance between the light source and the reaction container is 0.1-10 cm, the wavelength of the light is 300-600 nm, and the power of the light source is 1-100 W.

[0024] The beneficial effects of the present application are:

[0025] 1. The present application provides a method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on nitrogen-containing heteroarene carbon-hydrogen bond carboxylation reaction. Under the action of visible light and organic catalyst, quinoline nitrogen heteroarene compounds, pyridine nitrogen heteroarene compounds, bipyridine nitrogen heteroarene compounds, phenanthroline nitrogen heteroarene compounds and acridine nitrogen heteroarene compounds are used as substrates, carbon dioxide is used as a carboxylic acid source, and organic catalyst, base and additive are added at the same time to obtain nitrogen-containing heteroarene carboxylic acid compounds. The method has the characteristics of mild reaction conditions, wide reaction substrate range, good yield and good regioselectivity, and cheap raw materials are easy to obtain.

[0026] 2. The synthesis method provided by the present application has good reactivity for quinoline nitrogen heteroarene compounds, pyridine nitrogen heteroarene compounds, bipyridine nitrogen heteroarene compounds, phenanthroline nitrogen heteroarene compounds and acridine nitrogen heteroarene compounds, and has the characteristics of wide reaction substrate range, good yield and good regioselectivity.

[0027] 3、The application first realizes visible light promoted carboxylation of nitrogen-containing heteroarene C-H bond. The reaction efficiently realizes selective cleavage of nitrogen-containing heteroarene C-H bond and introduction of important carboxyl functional group under mild conditions, and important nitrogen-containing heteroarene carboxylic acid compounds are prepared, which have wide application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 The synthesis mechanism of the application is shown in the figure. DETAILED DESCRIPTION

[0029] The specific embodiment of the application will be described in detail below in combination with examples.

[0030] Example 1

[0031] A method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on carboxylation of nitrogen-containing heteroarene C-H bond, and the synthesis reaction formula is shown as formula (1-1).

[0032]

[0033] The synthesis method comprises the following steps:

[0034] A 10 ml Schlenk tube equipped with a stir bar was dried by heating under vacuum, then the substrate nitrogen-containing heteroarene compound (0.2 mmol, 1.0 equiv, if the substrate is solid) and the additive Ph3SiH (26 mg, 0.1 mmol, 0.5 equiv) were added. Then the tube was transferred into a glove box, then the base Cs2CO3 (130 mg, 0.4 mmol, 2.0 equiv) was added. After that, the tube was sealed with a corresponding stopper, removed from the glove box, and purged with CO2 three times using double-tube to make the CO2 pressure in the tube 20 atm. Then the substrate nitrogen-containing heteroarene compound (if the substrate is liquid), super dry DMSO (2 mL) and p-methoxythiophenol (5 mg, 0.04 mmol, 0.2 equiv) were injected into the tube using a syringe under CO2 atmosphere. The tube was immediately sealed after the addition was completed. The tube was fixed in an oil or water bath, the stirrer was set to 650 r / min, a 30 W blue LED lamp (wavelength about 450 nm) was used to irradiate at a distance of 1 cm, and a fan was used to dissipate heat, so that the reaction temperature was maintained at 50°C. After stirring for 16 hours, the tube was opened and 100 mg of Cs2CO3 was added to the reaction mixture, then 37 uL of iodomethane was added, the tube was sealed and placed on the heating stirrer for 2 hours, and the reaction temperature was maintained at 65°C. After the esterification was completed, 2 mL of ethyl acetate was added for dilution and 2 mL of water was added to quench the reaction. Then the reaction solution was extracted with 3 mL of ethyl acetate three times, the organic phases were combined and the residual solvent was completely removed using a rotary evaporator. Column chromatography was used for separation and purification. The purification conditions were as follows: using a mixture of petroleum ether: ethyl acetate = 100: 1 ~ 20: 1 (v:v) as the eluent, the target product was obtained. The specific reaction results are shown in Table 1.

[0035] Table 1. Yields of quinoline nitrogen-containing heteroarene compounds as substrates and their corresponding products

[0036]

[0037]

[0038] Note: The standard reaction conditions in Table 1 are the same as described above, and the yield is the isolated yield.

[0039] The above experimental results show that nitrogen-containing heteroarene compounds are converted to nitrogen-containing heterocyclic carboxylate compounds with high yield and good regioselectivity. Various functional groups such as tert-butyl, methoxy, sulfone, trifluoromethyl, fluorine atom, ester, amide, and substituted aromatic groups such as furan, thiophene, pyridine, quinoline and naphthalene can be compatible with the reaction system. Fluorenyl, naphthyl and dibenzofuran, thiophene, furan and other heterocycles can also be compatible with the reaction system.

[0040] Example 2

[0041] A method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on a nitrogen-containing heteroarene carbon-hydrogen bond carboxylation reaction, and a synthesis reaction formula is shown as formula (1-2).

[0042]

[0043] The synthesis method comprises the following steps:

[0044] After a 10 ml Schlenk reaction tube equipped with a stirrer was heated and dried under vacuum, the reaction substrate nitrogen-containing heteroarene compound (0.2 mmol, 1.0 equiv, if the substrate is a solid) and the additive Ph3SiH (26 mg, 0.1 mmol, 0.5 equiv) were added. Then the reaction tube was moved into the glove box, and then the base Cs2CO3 (130 mg, 0.4 mmol, 2.0 equiv) was added. Then the reaction tube was sealed with a corresponding stopcock, taken out of the glove box, and replaced with a CO2 atmosphere using double-tube pumping for 3 times, so that the CO2 pressure in the reaction tube was 30 times the atmospheric pressure. Then the reaction substrate nitrogen-containing heteroarene compound (if the substrate is a liquid), ultradry DMSO (2 mL), and p-methoxyphenyl mercaptan (5 mg, 0.04 mmol, 0.2 equiv) were sequentially injected into the reaction tube using a syringe under a CO2 atmosphere. Immediately after the addition was completed, the reaction tube was sealed. The reaction tube was fixed in an oil bath or a water bath, the stirring speed of the stirrer used for the reaction was adjusted to 650 r / min, a 30 W blue LED lamp (wavelength of about 450 nm) was used to irradiate at a distance of 0.5-1 cm, and a fan was used for cooling, so that the reaction temperature was maintained at 50°C. After stirring for 16 hours, the reaction tube was opened, 100 mg of Cs2CO3 was added to the reaction mixture, and then 37 uL of iodomethane was added. The reaction tube was then sealed and placed on a heating stirrer for 2 hours, and the reaction temperature was maintained at 65°C. After the esterification was completed, 2 mL of ethyl acetate was added for dilution, and 2 mL of water was added to quench the reaction. Then the reaction solution was extracted with 3 mL of ethyl acetate for 3 times, the organic phases were combined, and residual solvents were completely removed using a rotary evaporator. Column chromatography was used for separation and purification. The purification conditions were as follows: a mixed solvent of petroleum ether: ethyl acetate = 100:1-20:1 (v:v) was used for washing, and the target product was obtained. The specific reaction results are shown in Table 2.

[0045] Table 2. Yields of bipyridine nitrogen-containing heteroarene compounds as substrates and their corresponding products

[0046]

[0047] The above experimental data show that the substitution bipyridine nitrogen-containing heteroarene can also successfully undergo a carbon-hydrogen bond carboxylation reaction, and a bipyridine carboxylate product is obtained in a moderate yield.

[0048] Example 3

[0049] A method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on a nitrogen-containing heteroarene carbon-hydrogen bond carboxylation reaction, and a synthesis reaction formula is shown as formula (1-3).

[0050]

[0051] The synthesis method comprises the following steps:

[0052] After a 10 ml Schlenk reaction tube equipped with a stirrer is heated and dried under vacuum, the reaction substrate nitrogen-containing heteroarene compound (0.2 mmol, 1.0 equiv, if the substrate is a solid) and the additive Ph3SiH (26 mg, 0.1 mmol, 0.5 equiv) are added. Then the reaction tube is moved into a glove box, and then the base Cs2CO3 (130 mg, 0.4 mmol, 2.0 equiv) is added. Then the reaction tube is sealed with a corresponding stopcock, taken out of the glove box, and replaced with a CO2 atmosphere using double-tube pumping for 3 times, so that the CO2 pressure in the reaction tube is 10 times that of the atmosphere. Then the reaction substrate nitrogen-containing heteroarene compound (if the substrate is a liquid), ultradry DMSO (2 mL), and p-methoxyphenyl mercaptan (5 mg, 0.04 mmol, 0.2 equiv) are sequentially injected into the reaction tube using a syringe under a CO2 atmosphere. Immediately after the addition is completed, the reaction tube is sealed. The reaction tube is fixed in an oil bath or a water bath, the stirring speed of the stirrer used for the reaction is adjusted to 650 r / min, a 30 W blue LED lamp (wavelength of about 450 nm) is used to irradiate at a distance of 0.5-1 cm, and a fan is used for cooling, so that the reaction temperature is maintained at 50°C. After stirring for 16 hours, the reaction tube is opened, 100 mg of Cs2CO3 is added to the reaction mixture, and then 37 uL of iodomethane is added. The reaction tube is then sealed and placed on a heating stirrer for 2 hours, and the reaction temperature is maintained at 65°C. After the esterification is completed, 2 mL of ethyl acetate is added for dilution, and 2 mL of water is added to quench the reaction. Then the reaction solution is extracted with 3 mL of ethyl acetate for 3 times, the organic phases are combined, and residual solvents are completely removed using a rotary evaporator. Column chromatography is used for separation and purification. The purification conditions are as follows: using a mixed solvent of petroleum ether: ethyl acetate = 100:1-20:1 (v:v) for washing, to obtain the target product. The specific reaction results are shown in Table 3.

[0053] Table 3. Yields of pyridine compounds as substrates and their corresponding products

[0054]

[0055] Note: The standard reaction conditions in Table 3 are the same as above, and the yield is the isolated yield.

[0056] The above experimental results show that pyridine nitrogen-containing heteroarene substrates can also successfully undergo carbon-hydrogen bond carboxylation reactions, and the target products can be obtained in high yield.

[0057] Example 4

[0058] A method for synthesizing nitrogen-containing heteroarene carboxylic acid compounds based on nitrogen-containing heteroarene carbon-hydrogen bond carboxylation reactions, the synthesis reaction formula is shown in formula (1-4).

[0059]

[0060] The synthesis method comprises the following steps:

[0061] After a 10 ml Schlenk reaction tube equipped with a stirrer is dried under vacuum by heating, the reaction substrate nitrogen-containing heteroarene compound (0.2 mmol, 1.0 equiv, if the substrate is a solid) and the additive Ph3SiH (26 mg, 0.1 mmol, 0.5 equiv) are added. Then the reaction tube is moved into the glove box, and then the base Cs2CO3 (130 mg, 0.4 mmol, 2.0 equiv) is added. Then the reaction tube is sealed with a corresponding stopcock, taken out of the glove box, and replaced with a double-tube CO2 atmosphere, repeated 3 times, so that the CO2 pressure in the reaction tube is 20 times atmospheric pressure. Then the reaction substrate nitrogen-containing heteroarene compound (if the substrate is a liquid), ultradry DMSO (2 mL), and p-methoxyphenyl mercaptan (5 mg, 0.04 mmol, 0.2 equiv) are sequentially injected into the reaction tube under a CO2 atmosphere using a syringe. Immediately after the addition is complete, the reaction tube is sealed. The reaction tube is fixed in an oil bath or water bath, the stirrer speed for the reaction is adjusted to 650 r / min, a 30 W blue LED lamp (wavelength of about 450 nm) is used to irradiate at a distance of 0.5-1 cm, and a fan is used for cooling, so that the reaction temperature is maintained at 50°C. After stirring for 16 hours, the reaction tube is opened and 100 mg of Cs2CO3 is added to the reaction mixture, followed by the addition of 37 uL of iodomethane. The reaction tube is then sealed and placed on a heating stirrer for 2 hours at a reaction temperature of 65°C. After esterification, 2 mL of ethyl acetate is added for dilution and 2 mL of water is added to quench the reaction. Then the reaction solution is extracted with 3 mL of ethyl acetate 3 times, the organic phases are combined, and residual solvents are removed completely using a rotary evaporator. Column chromatography is used for separation and purification. The purification conditions are as follows: using a mixture of petroleum ether: ethyl acetate = 100:1-20:1 (v:v) as the eluent, the target product is obtained. The specific reaction results are shown in Table 4.

[0062] Table 4. Yields of naphthyridine, acridine, phenanthroline, and terpyridine arene compounds as substrates and their corresponding products

[0063]

[0064] Note: Standard reaction conditions in Table 4 are the same as above, and the yield is the isolated yield; a is the reaction temperature 80°C;

[0065] The above experimental results show that naphthyridine, acridine, phenanthroline and terpyridine nitrogen-containing heteroaromatic substrates can also successfully undergo carbon-hydrogen bond carboxylation reaction, and the target product is obtained in a high yield.

[0066] Experimental Example 1

[0067] In this experimental example 1, 2-phenylquinoline is used as the reaction substrate, and the influence on the yield of the reaction is investigated by changing the reaction conditions. The reaction conditions are as follows: substrate (0.2 mmol, 1 equiv), p-OMeC6H4SH (0.04 mmol, 20 mol%, 5.0 mg), Cs2CO3 (0.4 mmol, 2.0 equiv, 130 mg), Ph3SiH (0.1 mmol, 0.5 equiv, 26 mg), super dry solvent DMSO (2 ml), and the experimental results are shown in Table 5.

[0068] The reaction equation is shown as follows:

[0069]

[0070] Table 5. Product yield under different reaction conditions with 2-phenylquinoline as the reaction substrate

[0071] Serial number Reaction condition change case 2a yield 1 No change 81％(80％) 2 No light Not detected 3 none 12％ 4 <![CDATA[Replace CO2 with N2]]> Not detected 5 Without Cs2CO3 Not detected 6 Ph3SiH 25％ 8 [(p-OMeC6H4S)2in place of p-OMeC6H4SH] 63％ 9 DIPEA instead of Ph3SiH 45％ 10 Hans ester instead of Ph3SiH 65％ 11 [Ph3SiOH instead of Ph3SiH] 13％

[0072] Note: In Table 5, the NMR yield is with dibromomethane as the NMR hydrogen spectrum internal standard (the isolated yield is in the brackets).

[0073] As can be seen from the data in Table 5 above, the yield under the reaction conditions of the present application is as high as 80%. A series of control experiments show that light, CO2 and base play an important role in the reaction, and the target product cannot be obtained without any of them. The thiol catalyst and the additive play a significant role in promoting the reaction.

[0074] In addition, when the thiol catalyst (p-methoxythiophenol) is replaced by a thiol such as tert-butyl mercaptan, an organic amine such as diisopropylethylamine, a Hans ester or a silanol salt such as triphenylsilanol potassium catalyst (with the rest of the reaction conditions unchanged), the yield is basically unchanged; similarly, when the additive (Ph3SiH) is replaced by an organic amine such as diisopropylethylamine or a Hans ester (with the rest of the reaction conditions unchanged), the yield is also basically unchanged; no separate examples are listed for this.

[0075] On the basis of the existing experimental research results, the inventors propose a reaction mechanism, as shown in Figure 1The mechanism of the reaction is shown in the figure. First, the thiophenol is deprotonated to form thiophenolate anion under the action of base, and then the thiophenolate anion forms an electron transfer complex with the substrate. Then, under the action of visible light, the thiophenolate anion promotes the single electron transfer to the substrate to form thiophenyl radical and substrate radical anion. Subsequently, the substrate radical anion attacks CO2 to obtain a radical intermediate containing carboxylic acid, and then the sulfur radical captures the hydrogen of the radical intermediate to realize the aromatization process to obtain the target product and regenerate the thiophenol catalyst to realize the catalytic cycle. The additive may greatly promote the subsequent hydrogen capture aromatization process in the reaction.

[0076] The product prepared by the present application was characterized and analyzed by nuclear magnetic resonance and mass spectrometry. The results of nuclear magnetic and mass spectrometry characterization data are consistent with the obtained product. The specific characterization data are as follows:

[0077] 2-phenylquinoline-4-carboxylic acid methyl ester

[0078] 8.4,6.8,1.3Hz,1H),7.54(ddt,J=8.2,6.6,1.1Hz,2H),7.50–7.45(m,1H),4.06(s,3H).

[0079] 13 C NMR (101 MHz, Chloroform-d): δ 166.8, 156.7, 149.2, 138.7, 135.5, 130.3, 129.9, 129.7, 128.9, 127.8, 127.5, 125.4, 124.0, 120.3, 52.7.

[0080] 2-(4-methylphenyl)quinoline-4-carboxylic acid methyl ester

[0081] (ddd, J = 8.4, 6.8, 1.4 Hz, 1H), 7.60 (ddd, J = 8.3, 6.9, 1.3 Hz, 1H), 7.36 - 7.30 (m, 2H), 4.06 (s, 3H), 2.43 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.9, 156.7, 149.3, 139.9, 136.0, 135.5, 130.3, 129.9, 129.7, 127.6, 127.4, 125.4, 123.9, 120.2, 52.7, 21.4.

[0082] 2-(4-tert-butylphenyl)quinoline-4-carboxylic acid methyl ester

[0083] 1H), 7.60 (ddd, J = 8.4, 6.9, 1.3 Hz, 1H), 7.58 - 7.54 (m, 2H), 4.06 (s, 3H), 1.38 (s, 9H).

[0084] 13 C NMR (101 MHz, Chloroform-d) δ 167.2, 156.8, 153.1, 149.3, 136.1, 135.5, 130.3, 129.8, 127.6, 127.2, 125.9, 125.4, 123.9, 120.3, 52.7, 34.8, 31.3.

[0085] 2-(4-ethoxyphenyl)quinoline-4-carboxylic acid methyl ester

[0086] 8.4, 6.9, 1.3 Hz, 1H), 7.08 - 7.00 (m, 2H), 4.12 (q, J = 7.0 Hz, 2H), 4.06 (s, 3H), 1.46 (t, J = 7.0 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.9, 160.5, 156.3, 149.2, 135.4, 131.1, 130.1, 129.8, 128.8, 127.3, 125.3, 123.6, 119.9, 114.8, 63.6, 52.7, 14.8.

[0087] 2-(4-methyloxythiocarbonylphenyl)quinoline-4-carboxylic acid methyl ester

[0088] - 8.10 (m, 2H), 7.82 (ddd, J = 8.4, 6.8, 1.4 Hz, 1H), 7.69 (ddd, J = 8.4, 6.9, 1.3 Hz, 1H), 4.10 (s, 3H), 3.12 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.4, 154.3, 149.2, 143.8, 141.1, 136.1, 130.5, 130.4, 128.9, 128.3, 128.0, 125.5, 124.4, 120.0, 52.9, 44.6.

[0089] 2-(4-fluorophenyl)quinoline-4-carboxylic acid methyl ester

[0090] (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.25 - 7.19 (m, 2H), 4.08 (s, 3H).

[0091] 13 C NMR (101 MHz, Chloroform-d) δ 166.77, 164.05 (d, J = 249.9 Hz), 155.6, 149.2, 135.8, 134.9 (d, J = 3.0 Hz), 130.2, 130.1, 129.4 (d, J = 8.5 Hz), 127.9, 125.5, 123.9, 120.0, 115.9 (d, J = 21.5 Hz), 52.8. 19 F NMR (376 MHz, Chloroform-d) δ -1 1 1.69.

[0092] 2-(3-methoxyphenyl)quinoline-4-carboxylic acid methyl ester

[0093] 7.76 (ddd, J = 8.4, 6.9, 1.4 Hz, 1 H), 7.61 (ddd, J = 8.3, 6.8, 1.3 Hz, 1 H), 7.42 (t, J = 7.6 Hz, 1 H), 7.29 (ddt, J = 7.6, 1.8, 0.9 Hz, 1 H), 4.06 (s, 3 H), 2.48 (s, 3 H). 13 C NMR (101 MHz, Chloroform-d) δ 166.8, 156.9, 149.2, 138.7, 138.6, 135.5, 130.5, 130.3, 129.9, 128.8, 128.1, 127.7, 125.4, 124.6, 123.9, 120.5, 52.7, 21.6.

[0094] 2-(3-methoxyphenyl)quinoline-4-carboxylic acid methyl ester

[0095] 1 H), 7.78 - 7.71 (m, 2 H), 7.61 (ddd, J = 8.4, 6.9, 1.3 Hz, 1 H), 7.43 (t, J = 7.9 Hz, 1 H), 7.02 (ddd, J = 8.2, 2.7, 0.9 Hz, 1 H), 4.05 (s, 3 H), 3.92 (s, 3 H).

[0096] 13 C NMR (101 MHz, Chloroform-d) δ 166.8, 160.2, 156.4, 149.1, 140.2, 135.5, 130.3, 129.9, 129.9, 127.8, 125.4, 124.0, 120.4, 119.9, 115.7, 112.6, 55.4, 52.7.

[0097] 2-(3-Fluorophenyl)quinoline-4-carboxylic acid methyl ester

[0098] 8.4, 6.8, 1.4 Hz, 1 H), 7.64 (ddd, J = 8.4, 6.8, 1.4 Hz, 1 H), 7.49 (td, J = 7.6, 5.6 Hz, 1 H), 7.21 - 7.12 (m, 1 H), 4.07 (s, 3 H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 163.4 (d, J = 245.9 Hz), 155.1 (d, J = 2.7 Hz), 149.1, 141.0 (d, J = 7.5 Hz), 135.7, 130.4, 130.3, 130.1, 128.1, 125.4, 124.2, 122.9 (d, J = 2.9 Hz), 120.0, 116.6 (d, J = 21.4 Hz), 114.3 (d, J = 22.9 Hz), 52.8. 19 F NMR (376 MHz, Chloroform-d) δ -112.46.

[0099] 2-(3-Fluorophenyl)quinoline-4-carboxylic acid methyl ester

[0100] 8.4, 6.8, 1.4 Hz, 1 H), 7.64 (ddd, J = 8.4, 6.8, 1.4 Hz, 1 H), 7.49 (td, J = 7.6, 5.6 Hz, 1 H), 7.21 - 7.12 (m, 1 H), 4.07 (s, 3 H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 154.9, 149.2, 139.5, 136.0, 131.4 (q, J = 32.4 Hz), 130.6, 130.4, 130.2, 129.4, 128.3, 126.3 (q, J = 3.8 Hz), 125.9, 124.3 (q, J = 3.54), 124.2, 124.2 (q, J = 273.71 ), 119.8, 52.9. 19 F NMR (376 MHz, Chloroform-d) δ -62.54.

[0101] 2-(5-Benzo-1,3-dioxol)quinoline-4-carboxylic acid methyl ester

[0102] 6.8, 1.4 Hz, 1 H), 7.69 (dd, J = 8.2, 1.8 Hz, 1 H), 7.59 (ddd, J = 8.4, 6.9, 1.4 Hz, 1 H), 6.95 (d, J = 8.1 Hz, 1 H), 6.05 (s, 2 H), 4.06 (s, 3 H). 13 C NMR (101 MHz, Chloroform-d) δ 166.9, 156.0, 149.2, 149.2, 148.6, 135.5, 133.2, 130.1, 129.9, 127.6, 125.4, 123.8, 121.8, 120.0, 108.5, 107.7, 101.5, 52.7.

[0103] 2-(3,5-difluorophenyl)quinoline-4-carboxylic acid methyl ester

[0104] 8.4, 6.9, 1.4 Hz, 1 H), 6.91 (tt, J = 8.6, 2.4 Hz, 1 H), 4.08 (s, 3 H). 13 C NMR (101 MHz, Chloroform-d) δ 166.5, 163.50 (d, J = 248.4, 12.8 Hz), 153.9 (t, J = 3.2 Hz), 149.1, 142.0 (t, J = 9.1 Hz), 136.0, 130.4 (d, J = 14.6 Hz), 128.5, 125.5, 124.4, 119.7, 110.3 (d, J = 11.6 Hz), 110.3 (d, J = 26.4 Hz), 104.9 (t, J = 25.6 Hz), 52.86. 19 F NMR (376 MHz, Chloroform-d) δ -109.01.

[0105] 5,6-dihydrobenzo[c]acridine-7-carboxylic acid methyl ester

[0106] (ddd, J = 8.2, 6.9, 1.3 Hz, 1 H), 7.42 (td, J = 7.5, 1.6 Hz, 1 H), 7.38 (td, J = 7.4, 1.7 Hz, 1 H), 7.28 - 7.25 (m, 1 H), 4.08 (s, 3 H), 3.12 - 3.07 (m, 2 H), 3.00 (dd, J = 8.3, 5.2 Hz, 2 H).

[0107] 13C NMR (101 MHz, Chloroform-d) δ 168.3, 153.2, 147.3, 139.2, 136.7, 134.3, 130.2, 130.0, 129.3, 127.9, 127.5, 127.5, 127.2, 126.4, 124.4, 123.7, 52.7, 27.9, 26.6.

[0108] 2-(4-(2'-fluoro)biphenyl)-3-methyl-6-fluoroquinoline-4-carboxylic acid methyl ester

[0109] C NMR (101 MHz, Chloroform-d) δ 168.3, 153.2, 147.3, 139.2, 136.7, 134.3, 130.2, 130.0, 129.3, 127.9, 127.5, 127.5, 127.2, 126.4, 124.4, 123.7, 52.7, 27.9, 26.6.

[0110] 19 F NMR (376 MHz, Chloroform-d) δ -111.27, -117.76.

[0111] 2-(4-carbazolylphenyl)quinoline-4-carboxylic acid methyl ester

[0112] 1H), 7.51 (d, J = 8.2 Hz, 2H), 7.47 - 7.41 (m, 2H), 7.35 - 7.28 (m, 2H), 4.10 (s, 3H).

[0113] 13 C NMR (101 MHz, Chloroform-d) δ 168.3, 153.2, 147.3, 139.2, 136.7, 134.3, 130.2, 130.0, 129.3, 127.9, 127.5, 127.5, 127.2, 126.4, 124.4, 123.7, 52.7, 27.9, 26.6.

[0114] 2-phenyl-7-methylquinoline-4-carboxylic acid methyl ester

[0115] 4.05 (s, 3H), 2.57 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.9, 156.6, 149.5, 140.2, 138.9, 135.3, 130.1, 129.6, 129.3, 128.9, 127.4, 125.0, 122.0, 119.5, 52.6, 21.7.

[0116] 2-phenyl-5-methylquinoline-4-carboxylic acid methyl ester

[0117] 7.49 - 7.44 (m, 1H), 7.38 (dt, J = 7.0, 1.3 Hz, 1H), 4.04 (s, 3H), 2.61 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 170.6, 155.7, 149.5, 139.5, 138.5, 133.6, 129.7, 129.7, 128.9, 128.8, 127.4, 122.1, 117.7, 53.0, 20.9.

[0118] 2-phenyl-8-methylquinoline-4-carboxylic acid methyl ester

[0119] 2.91 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 167.1, 154.7, 148.1, 139.0, 138.1, 135.9, 130.0, 129.6, 128.8, 127.5, 127.3, 123.9, 123.2, 119.4, 52.7, 18.4.

[0120] 2-phenyl-6-fluoroquinoline-4-carboxylic acid methyl ester

[0121] MHz, Chloroform-d) δ 166.3, 161.4 (d, J = 248.8 Hz), 156.0 (d, J = 3.0 Hz), 146.5, 138.4, 134.6 (d, J = 6.0 Hz), 132.6 (d, J = 9.3 Hz), 129.8, 128.9, 127.3, 124.8 (d, J = 11.1 Hz), 121.2, 120.2 (d, J = 26.0 Hz), 109.5 (d, J = 25.1 Hz), 52.8. 19F NMR (376 MHz, Chloroform-d) δ -110.33.

[0122] 2-phenyl-6-trifluoromethylquinoline-4-carboxylic acid methyl ester

[0123] 2.0 Hz, 1H), 7.60 - 7.47 (m, 3H), 4.10 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.1, 158.8, 150.1, 138.1, 136.1, 131.4, 130.4, 129.3 (q, J = 32.6 Hz), 129.2, 127.6, 125.6 (q, J = 3.0 Hz), 124.1 (q, J = 272.5 Hz), 123.8 (q, J = 4.7 Hz), 123.1, 121.5, 53.0. 19 F NMR (376 MHz, Chloroform-d) δ -62.33.

[0124] 2-phenyl-6-trifluoromethylquinoline-4-carboxylic acid methyl ester

[0125] 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.2, 158.1, 148.3, 138.0, 135.4, 131.7 (q, J = 32.9 Hz), 130.3, 129.1, 127.9 (q, J = 4.3 Hz), 127.5, 127.0, 125.6, 123.8 (q, J = 273.2) 123.2 (q, J = 3.0 Hz), 122.1, 53.0. 19 F NMR (376 MHz, Chloroform-d) δ -62.93.

[0126] 2-phenyl-6-trifluoromethylquinoline-4-carboxylic acid methyl ester

[0127] 7.61 - 7.49 (m, 3H), 4.48 (q, J = 7.1 Hz, 2H), 4.09 (s, 3H), 1.47 (t, J = 7.1 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.4, 166.1, 157.6, 148.8, 138.3, 135.5, 132.6, 131.7, 130.1, 129.0, 127.5, 127.2, 126.5, 125.8, 122.0, 61.5, 52.9, 14.4.

[0128] 2-phenyl-7-diethylazanoylquinoline-4-carboxylic acid methyl ester

[0129] (m, 3H), 4.10 (s, 3H), 3.65 (q, J = 7.2 Hz, 2H), 3.36 (q, J = 7.2 Hz, 2H), 1.33 (t, J = 7.2 Hz, 3H), 1.16 (t, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 170.2, 166.5, 157.5, 148.7, 138.6, 138.4, 135.5, 130.0, 129.0, 127.6, 127.5, 126.2 126.0, 124.1, 121.0, 52.9, 43.4, 39.4, 14.4, 13.0.

[0130] 2-phenyl-6,7-difluoroquinoline-4-carboxylic acid methyl ester

[0131] 4.07 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.1, 157.2 (d, J = 3.0 Hz), 152.5 (dd, J = 256.0, 16.3 Hz), 150.9 (dd, J = 252.6, 15.2 Hz). 146.9 (d, J = 11.1 Hz), 138.1, 134.5 (dd, J = 5.7, 1.2 Hz), 130.0, 129.0, 127.3, 121.2 (dd, J = 8.9, 1.3 Hz), 120.5 (d, J = 2.3 Hz), 116.2 (dd, J = 16.0, 1.6 Hz), 111.9 (dd, J = 20.6, 1.5 Hz), 52.9. 19 F NMR (376 MHz, Chloroform-d) δ -131.00 (d, J = 21.6 Hz), -132.76 (d, J = 21.4 Hz).

[0132] 2-phenyl-6-methoxyquinoline-4-carboxylic acid methyl ester

[0133] 7.44 (m, 1H), 7.44 - 7.39 (m, 1H), 4.05 (s, 3H), 3.97 (s, 3H).

[0134] 13C NMR (101 MHz, Chloroform-d) δ 167.0, 159.1, 154.1, 145.7, 138.9, 133.3, 131.7, 129.3, 128.9, 127.2, 125.6, 122.8, 120.7, 103.2, 55.6, 52.6.

[0135] 2-phenyl-6,7-dimethoxyquinoline-4-carboxylic acid methyl ester

[0136] 4.04 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 167.1, 154.6, 152.6, 151.0, 146.9, 139.2, 132.7, 129.2, 128.9, 127.1, 120.4, 118.6, 108.7, 103.3, 56.1, 56.1, 52.6.

[0137] 2-(2-pyridyl)quinoline-4-carboxylic acid methyl ester

[0138] 1.4, 0.6 Hz, 1H), 7.87 (td, J = 7.7, 1.8 Hz, 1H), 7.77 (ddd, J = 8.4, 6.9, 1.5 Hz, 1H), 7.65 (ddd, J = 8.4, 6.8, 1.4 Hz, 1H), 7.37 (ddd, J = 7.5, 4.8, 1.2 Hz, 1H), 4.06 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 167.1, 154.6, 152.6, 151.0, 146.9, 139.2, 132.7, 129.2, 128.9, 127.1, 120.4, 118.6, 108.7, 103.3, 56.1, 56.1, 52.6.

[0139] 2-(2-quinolyl)quinoline-4-carboxylic acid methyl ester

[0140] 7.67 (ddd, J = 8.3, 6.8, 1.4 Hz, 1H), 7.58 (ddd, J = 8.1, 6.9, 1.2 Hz, 1H), 4.11 (s, 3H). 13C NMR (101 MHz, Chloroform-d) δ 167.0, 155.8, 155.4, 148.8, 147.9, 136.9, 135.7, 130.5, 130.0, 129.8, 129.7, 128.6, 128.5, 127.7, 127.2, 125.6, 125.2, 120.8, 119.1, 52.7.

[0141] 2-(2-thienyl)quinoline-4-carboxylic acid methyl ester

[0142] J = 8.4, 6.9, 1.4 Hz, 1H), 7.57 (ddd, J = 8.4, 6.9, 1.3 Hz, 1H), 7.49 (dd, J = 5.1, 1.1 Hz, 1H), 7.16 (dd, J = 5.0, 3.7 Hz, 1H), 4.06 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 151.8, 149.0, 144.5, 135.4, 130.0, 129.8, 129.1, 128.2, 127.5, 126.4, 125.4, 123.9, 119.1, 52.8.

[0143] 2-(2-furanyl)quinoline-4-carboxylic acid methyl ester

[0144] Hz, 1H), 7.59 (ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.27 (dd, J = 3.5, 0.8 Hz, 1H), 6.60 (dd, J = 3.4, 1.8 Hz, 1H), 4.06 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 166.7, 153.2, 149.2, 148.6, 144.6, 135.6, 130.2, 130.0, 127.8, 125.6, 124.0, 119.1, 112.5, 110.8, 52.9.

[0145] 2-(2-naphthalenyl)quinoline-4-carboxylic acid methyl ester

[0146] Hz, 1H), 7.99 (dd, J = 7.1, 3.6 Hz, 2H), 7.88 (dt, J = 7.1, 3.6 Hz, 1H), 7.77 (ddd, J = 8.4, 6.8, 1.4 Hz, 1H), 7.62 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H), 7.53 (dt, J = 6.2, 3.4 Hz, 2H), 4.08 (s, 3H).13 C NMR (101 MHz, Chloroform-d) δ 166.8, 156.4, 149.3, 136.0, 135.6, 134.0, 133.4, 130.3, 129.9, 128.9, 128.7, 127.8, 127.7, 127.2, 126.9, 126.4, 125.4, 124.7, 124.0, 120.4, 52.8.

[0147] 2-methyloxycarbonylquinoline-4-carboxylic acid methyl ester

[0148] (s, 1 H), 8.37 (ddd, J = 8.5, 1.4, 0.7 Hz, 1 H), 7.85 (ddd, J = 8.5, 6.9, 1.5 Hz, 1 H), 7.77 (ddd, J = 8.3, 6.8, 1.4 Hz, 1 H), 4.11 (s, 1 H), 4.07 (s, 1 H).

[0149] 13 C NMR (101 MHz, Chloroform-d) δ 166.8, 156.4, 149.3, 136.0, 135.6, 134.0, 133.4, 130.3, 129.9, 128.9, 128.7, 127.8, 127.7, 127.2, 126.9, 126.4, 125.4, 124.7, 124.0, 120.4, 52.8.

[0150] 2-methyloxycarbonylquinoline-4-carboxylic acid methyl ester

[0151] 7.70 (ddd, J = 8.3, 6.8, 1.4 Hz, 1 H), 4.04 (s, 3 H), 3.64 (q, J = 7.1 Hz, 2 H), 3.48 (q, J = 7.1 Hz, 2 H), 1.33 (t, J = 7.1 Hz, 3 H), 1.28 (t, J = 7.1 Hz, 3 H). 13 C NMR (101 MHz, Chloroform-d) δ 167.8, 166.2, 154.0, 147.5, 135.8, 130.3, 130.1, 129.0, 125.5, 124.9, 122.1, 52.7, 43.5, 40.6, 14.4, 12.8.

[0152] 8-methyloxycarbonylquinoline-4-carboxylic acid methyl ester

[0153] 4.2 Hz, 1 H), 4.08 (s, 3 H), 4.02 (s, 3 H). 13C NMR (101MHz, Chloroform-d) δ167.4,165.7,153.5,147.2,137.5,132.0,129.9,127.8,127.3,122.3,52.8,52.6.

[0154] 2-Phenylated-1,8-Naphthyl-4-carboxylic acid methyl ester

[0155] 4.08 (s, 3H). 13 C NMR (101MHz, Chloroform-d) δ165.8,159.9,156.7,154.2,137.8,136.5,135.3,130.7,129.1,128.0,123.0,121.3,119.5,53.1.

[0156] Acridine-9-carboxylic acid methyl ester

[0157] Hz, 2H), 7.82 (ddd, J=8.8, 6.6, 1.4Hz, 2H), 7.61 (ddd, J=8.8, 6.6, 1.2Hz, 2H), 4.21 (s, 3H). 13 C NMR (101MHz, Chloroform-d) δ167.9,148.3,137.3,130.6,129.6,127.3,125.2,122.4,53.1.

[0158] 2,6-Diphenylpyridine-4-carboxylic acid methyl ester

[0159] Chloroform-d)δ166.0,157.9,139.1,138.7,129.5,128.8,127.1,117.8,52.8.

[0160] 2,6-Diethyloxycarbonylpyridine-4-carboxylic acid methyl ester

[0161] 4.03(s,3H),1.48(t,J=7.1Hz,6H). 13 C NMR (101MHz, Chloroform-d) δ164.2,164.0,149.8,140.1,127.0,62.6,53.2,14.2.

[0162] 2,2'-Bipyridine-4,6-dicarboxylic acid dimethyl ester

[0163] 1H), 7.38 (ddd, J = 7.6, 4.8, 1.2 Hz, 1H), 4.06 (s, 3H), 4.02 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 165.1, 164.9, 157.6, 154.4, 149.3, 148.6, 139.8, 137.28, 124.7, 124.2, 123.7, 121.8, 53.0, 52.9.

[0164] 2,2'-Bipyridine-4,6,6'-tricarboxylic acid trimethyl ester

[0165] J = 7.8 Hz, 1H), 4.07 (s, 3H), 4.06 (s, 3H), 4.04 (s, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 165.6, 165.0, 164.9, 156.8, 154.8, 148.6, 147.8, 140.0, 138.2, 125.9, 125.1, 124.7, 124.1, 53.1, 53.0, 52.9.

[0166] 2,2':6',2"-Terpyridine-4'-carboxylic acid methyl ester

[0167] 8.64 (d, J = 8.0 Hz, 2H), 7.90 (td, J = 7.7, 1.8 Hz, 2H), 7.41 - 7.36 (m, 2H), 4.02 (s, 3H). 13 CNMR (101 MHz, Chloroform-d) δ 165.8, 156.4, 155.3, 149.2, 139.8, 137.2, 124.2, 121.4, 120.5, 52.7.

[0168] 2-Phenyl-1,10-phenanthrolin-4-carboxylic acid methyl ester

[0169] (m, 2H), 7.53 - 7.47 (m, 1H), 4.11 (s, 3H) 13 C NMR (101 MHz, Chloroform-d) δ 166.8, 157.2, 150.3, 146.7, 145.4, 138.6, 136.7, 136.0, 129.9, 129.0, 128.8, 128.0, 127.5, 125.0, 124.0, 123.5, 121.6, 53.0.

[0170] Although the specific embodiments of the present application have been described in detail, it should be understood that the present patent is not limited to the details of the foregoing embodiments. Various modifications and changes can be made to the described embodiments without departing from the scope of the present patent.

Claims

1. A method for synthesizing nitrogen-containing heteroaromatic carboxylic acid compounds based on the carboxylation reaction of nitrogen-containing heteroaromatic hydrocarbons, characterized in that, Includes the following steps: Under a CO2 atmosphere, the reaction substrate, catalyst, base, and additives are mixed thoroughly in a reaction vessel, and then, under light irradiation, the mixture is kept at a temperature of 0–100 °C. o The reaction was stirred at C for 0.1–80 h, followed by post-treatment and purification to obtain nitrogen-containing heteroaromatic carboxylic acid compounds. The molar ratio of the reaction substrate, catalyst, base, and additive was 1:0.001–1:0.5–10:0.01–2. The catalyst was thiophenol; the additive was silane or hensyl ester, wherein the silane was Ph₂MeSiH, PhMe₂SiH, MeEt₂SiH, (TMS)₃SiH, etc. i Pr3SiH, Ph3SiH, Et3SiH, HBpin, or polymethylhydrosiloxane; The general structural formula of the reaction substrate is shown in formula (I), formula (II), or formula (III): Among them, R 1 R 5 and R 11 Each group can be independently composed of a hydrogen atom, aryl, heteroaryl, amide, carboxyl, or ester group; R 2 R 3 R 4 R 6 R 7 R 8 R 9 R 10 R 12 R 13 R 14 R 15 R 16 Each can be a hydrogen atom, ester group, amide group, alkyl group, or alkoxy group, respectively.

2. The method for synthesizing nitrogen-containing heteroaromatic carboxylic acid compounds based on the C-H bond carboxylation reaction of nitrogen-containing heteroaromatic hydrocarbons according to claim 1, characterized in that: The base is a carbonate, bicarbonate, fluoride, alkoxy base, phosphate, hydrogen phosphate, carboxylate, or organic base.

3. The method for synthesizing nitrogen-containing heteroaromatic carboxylic acid compounds based on the C-H bond carboxylation reaction of nitrogen-containing heteroaromatic hydrocarbons according to claim 2, characterized in that: The alkali is Na2CO3, K2CO3, CsF, or KO. t Bu, Cs2CO3, CsOAc, CsOPiv, KOMe, K3PO4, CF3CO2K, CF3CO2Cs, CsHCO3 or Me3SiOK.

4. The method for synthesizing nitrogen-containing heteroaromatic carboxylic acid compounds based on the C-H bond carboxylation reaction of nitrogen-containing heteroaromatic hydrocarbons according to claim 1, characterized in that: The solvents are DMSO, NMP, DMF, and DMAc.

5. The method for synthesizing nitrogen-containing heteroaromatic carboxylic acid compounds based on the C-H bond carboxylation reaction of nitrogen-containing heteroaromatic hydrocarbons according to claim 1, characterized in that: The carbon dioxide pressure in the reaction vessel is 0.1 to 30 times the atmospheric pressure; the distance between the light source and the reaction vessel is 0.1 to 10 cm, the wavelength of the light is 300 to 600 nm, and the power of the light source is 1 to 100 W.

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