A method for the light-promoted synthesis of urea compounds

Abstract

This application discloses a method for preparing urea compounds through photo-promoted synthesis. The method includes: reacting a mixture containing a catalyst, a co-catalyst, an amine compound, and a solvent under light in an atmosphere of oxygen and carbon monoxide to obtain the urea compound. In this method, the reagents are non-toxic and non-corrosive, the reaction atom utilization rate is high, and the reaction conditions are mild. By using light irradiation at room temperature and pressure to replace traditional heating and high-pressure conditions, production safety is improved and production costs are reduced.

Description

Technical Field

[0001] This application relates to a method for preparing a photo-promoted urea compound, belonging to the field of organic synthesis technology. Background Technology

[0002] Urea compounds are a very important type of organic chemical, widely found in various natural products and synthetic chemicals, such as pesticides, herbicides, and drug molecules.

[0003] The following are some of the reported methods for synthesizing urea: (1) Reaction of amines with phosgene to obtain the target product. However, phosgene is a highly toxic chemical, and the byproduct HCl can cause serious equipment corrosion and environmental problems. (2) Reaction of amines with triphosgene (CN104725280A). However, phosgene is used in the synthesis of triphosgene, and triphosgene itself will slowly decompose to generate phosgene and diphosgene. At the same time, this reaction will also produce HCl byproduct. (3) Reaction of amines with chloroformate (CN104513180A). This method has poor atom economy, and the byproducts are alcohols and HCl. (4) Reaction of amines with isocyanate (CN113444024A). The synthesis of isocyanate also requires the use of phosgene, and isocyanate itself is also toxic. (5) Reaction of amines with carbonate (CN105439908A). This reaction also has the problem of atom utilization, and carbonate needs to be pre-synthesized. (6) Reaction of amines with azides and carbon monoxide (Eur. J. Org. Chem. 2019, 2019, 7541.). Azides are hazardous chemicals and are difficult to synthesize. (7) Reaction of amines with haloalkanes under light (CN112920089A). This method produces toxic halogens. In view of this, the oxidative synthesis of urea using amines has received widespread attention. This method has high atom utilization and the only byproduct is water. For example, (8) reaction of amines with nitro compounds and carbon monoxide (CN1951914A), (9) reaction of amines with carbon monoxide and oxygen (CN1900055A). Both of these methods require high temperatures and pressures. Therefore, there is still a need to develop an environmentally friendly method with high atom utilization that can synthesize urea at room temperature and pressure. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention uses amines, carbon monoxide, and oxygen as raw materials, and under the conditions of a catalyst and light irradiation, can obtain the target urea product with high conversion rate and selectivity, avoiding problems such as low atom utilization, highly toxic reagents, environmental unfriendliness, and harsh reaction conditions.

[0005] According to one aspect of this application, a method for preparing a photo-promoted urea compound is provided, the method comprising:

[0006] Under an atmosphere of oxygen and carbon monoxide, a mixture containing a catalyst, a co-catalyst, an amine compound, and a solvent is reacted under light to yield urea compounds.

[0007] The amine compound is selected from at least one having the structure shown in Formula I-1, Formula I-2 and Formula I-3, wherein the structures shown in Formula I-2 and Formula I-3 are different amine compounds;

[0008] R-NH2 type I-1,

[0009] The urea compound is selected from one of the following formulas: II-1, II-2, II-3, II-4, II-5, and II-6.

[0010]

[0011] Wherein, R, R1, R2, R3, and R4 are independently selected from H, C1-C20 alkyl, C1-C20 substituted alkyl, C2-C20 alkenyl, C2-C20 substituted alkenyl, C2-C20 alkynyl, C2-C20 substituted alkynyl, C5-C20 heteroaryl, C5-C20 substituted heteroaryl, C6-C20 aromatic, and C6-C20 substituted aromatic.

[0012] The substituents in the C1-C20 substituted alkyl, C2-C20 substituted alkenyl, C2-C20 substituted alkynyl, C5-C20 substituted heteroaryl, and C6-C20 substituted aromatic groups are independently selected from at least one of halogen, hydroxyl, and alkoxy groups.

[0013] Optionally, R, R1, R2, R3, and R4 are independently selected from at least one of H, C1-C20 alkyl groups without heteroatoms or containing heteroatoms, C2-C20 alkenyl groups without heteroatoms or containing heteroatoms, C2-C20 alkynyl groups without heteroatoms or containing heteroatoms, C3-C20 cycloalkyl groups without heteroatoms or containing heteroatoms, C3-C20 heterocyclic groups, C5-C20 heteroaryl groups, and C6-C20 aromatic groups; wherein, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, heteroaryl, and aromatic groups may be further monosubstituted or polysubstituted with the same or different halogens, hydroxyl groups, or alkoxy groups.

[0014] Optionally, the amine compound is selected from at least one of morpholine, aniline, n-hexylamine, cyclohexylamine, benzylamine, α,α-dimethylbenzylamine, p-methoxybenzylamine, p-bromobenzylamine, o-chlorobenzylamine, p-methylaniline, p-methoxyaniline, phenethylamine, p-methylphenethylamine, p-methoxyphenethylamine, p-fluorophenethylamine, p-chlorophenethylamine, N-methylpiperazine, and diethylamine.

[0015] Optionally, the urea compound is selected from at least one of 4,4'-carbonyldimorpholine, 1,3-diphenylurea, 1,3-dihexylurea, 1,3-dicyclohexylurea, 1,3-dibenzylurea, N,N'-bis(α,α-dimethylbenzyl)urea, 1,3-bis(4-methoxybenzyl)urea, 1,3-bis(4-bromobenzyl)urea, 1,3-bis(2-chlorobenzyl)urea, 1,3-bis(4-methylphenyl)urea, 1,3-bis(4-methoxyphenyl)urea, 1,3-diphenylethylurea, 1,3-bis(4-methylphenylethyl)urea, 1,3-bis(4-methoxyphenylethyl)urea, benzalkonium chloride, and 1-diethylaminoformyl-4-methylpiperazine.

[0016] Optionally, the catalyst is selected from at least one of palladium acetate, palladium chloride, palladium acetylacetone, triphenylphosphine palladium, Pd2(dba)3, PdCl2(PPh3)2, Pd(dba)2 / dppb, Pd / C, Pd / SiO2, Pd / TiO2, and Pd / Al2O3.

[0017] Optionally, the co-catalyst is selected from at least one of KI, NaI, elemental iodine, tetraethylammonium iodide, and tetrabutylammonium iodide.

[0018] Optionally, the molar ratio of the catalyst to the amine compound is 1:1000 to 1:20, and the molar amount of the catalyst is calculated based on the molar amount of the Pd element.

[0019] Optionally, the molar ratio of the catalyst to the amine compound is independently selected from any value of 1:1000, 1:900, 1:800, 1:700, 1:600, 1:500, 1:400, 1:300, 1:200, 1:100, 1:90, 1:80, 1:70, 1:60, 1:50, 1:40, 1:30, 1:20 or a range between any two of the above.

[0020] Optionally, the molar ratio of the co-catalyst to the amine compound is 1:1000 to 1:5.

[0021] Optionally, the molar ratio of the co-catalyst to the amine compound is independently selected from any value of 1:1000, 1:900, 1:800, 1:700, 1:600, 1:500, 1:400, 1:300, 1:200, 1:100, 1:90, 1:80, 1:70, 1:60, 1:50, 1:40, 1:30, 1:20, 1:10, 1:5, or a range between any two of the above.

[0022] Optionally, when different amine compounds are selected,

[0023] The molar ratio of the compound shown in Formula I-1 to the compound shown in Formula I-2 is 1:1 to 1:10.

[0024] Optionally, the molar ratio of the compound shown in Formula I-1 to the compound shown in Formula I-3 is 1:1 to 1:10.

[0025] Optionally, the molar ratio of the compound shown in Formula I-2 to the compound shown in Formula I-3 is 1:1 to 1:10.

[0026] Optionally, the volume ratio of carbon monoxide to oxygen is 1:100 to 100:1.

[0027] Optionally, the volume ratio of carbon monoxide to oxygen is independently selected from any value among 1:100, 1:80, 1:60, 1:40, 1:20, 1:10, 1:1, 10:1, 20:1, 40:1, 60:1, 80:1, 100:1 or a range between any two of the above.

[0028] Optionally, the ratio of carbon monoxide to oxygen is 1:100 to 100:1, and air can be used instead of pure oxygen. The diluent gas includes, but is not limited to, nitrogen and argon.

[0029] Optionally, the solvent is selected from at least one of toluene, ethylbenzene, benzene, n-hexane, trifluorotoluene, dichloromethane, dichloroethane, cyclohexane, methanol, ethanol, diethyl ether, isopropanol, butanol, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, chloroform, and tetrachloromethane.

[0030] Optionally, the molar volume ratio of the amine compound to the solvent is 0.125–5 mol / L.

[0031] Optionally, the wavelength of the photoreaction is 200–600 nm.

[0032] Optionally, the light source for the photoluminescence reaction is selected from at least one of light-emitting diodes, xenon lamps, and mercury lamps.

[0033] Optionally, the temperature of the photoreaction is 5–55°C, and the photoreaction time is 8–72 h.

[0034] In this application, C1 to C20, C2 to C20, C5 to C20, etc., all refer to the number of carbon atoms contained in the group.

[0035] In this application, the terms "alkyl", "alkenyl", "alkynyl", etc., refer to groups formed by losing any one hydrogen atom from the molecules of alkane compounds, olefin compounds, and alkyne compounds.

[0036] In this application, the term "aromatic group" refers to a group formed by the loss of a hydrogen atom from an aromatic ring in an aromatic compound molecule; for example, p-tolyl formed by the loss of a hydrogen atom at the para-position of the methyl group on the benzene ring of toluene.

[0037] In this application, the term "halogen" refers to at least one of fluorine, chlorine, bromine, and iodine.

[0038] In this application, the term "heteroaryl" refers to a heterocyclic compound molecule that has a planar structure, in which the atoms in the ring form a closed conjugated system, the molecule is planar, and there are ring-shaped delocalized electron clouds on both sides of this plane. The number of p electrons in the conjugated system all conforms to Hückel's rule. It is a group formed by losing a hydrogen atom from the heteroaryl ring of the heteroaryl compound molecule.

[0039] In this application, "substituted alkyl", "substituted alkenyl", etc., refer to alkyl groups substituted by any group and alkenyl groups substituted by any group, respectively.

[0040] The beneficial effects that this application can produce include:

[0041] 1) The reagents used in the preparation method of urea compounds provided in this application are non-toxic and non-corrosive, have high atom utilization rate, and have mild reaction conditions. The method uses light irradiation to replace traditional heating and high pressure conditions at room temperature and pressure, which improves production safety and reduces production costs.

[0042] 2) The method for synthesizing substituted ureas provided in this application has excellent substrate applicability, and can synthesize not only symmetrical ureas, but also asymmetrical ureas. Attached Figure Description

[0043] Figure 1 This is the NMR characterization image of the urea compound prepared in Example 1 of this application.

[0044] Figure 2 This is the NMR characterization image of the urea compound prepared in Example 12 of this application.

[0045] Figure 3 This is the NMR characterization image of the urea compound prepared in Example 13 of this application.

[0046] Figure 4 This is the NMR characterization image of the urea compound prepared in Example 14 of this application.

[0047] Figure 5 This is the NMR characterization image of the urea compound prepared in Example 15 of this application.

[0048] Figure 6 This is the NMR characterization image of the urea compound prepared in Example 16 of this application.

[0049] Figure 7 This is the NMR characterization image of the urea compound prepared in Example 17 of this application.

[0050] Figure 8 This is the NMR characterization image of the urea compound prepared in Example 18 of this application.

[0051] Figure 9 This is the NMR characterization image of the urea compound prepared in Example 19 of this application. Detailed Implementation

[0052] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0053] Unless otherwise specified, the raw materials, reagents, instruments, and equipment used in the embodiments of this application can all be purchased from the market or prepared by existing methods.

[0054] Unless otherwise specified, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0055] The yield of the product in this application is obtained by dividing the actual product mass obtained by separation by the theoretical product mass.

[0056] In the embodiments of this application, under the action of light and catalyst, amine reacts with CO and O2 as shown in formula (1), and the only byproduct is water molecules.

[0057]

[0058] Example 1

[0059] 1 mmol of morpholine, 0.003 mmol of palladium acetate, and 0.05 mmol of potassium iodide were added to a 30 mL reaction tube, followed by 8 mL of acetonitrile. A balloon containing 20 mL of oxygen and 100 mL of carbon monoxide was attached, and the mixture was stirred and reacted for 10 h under blue LED illumination at 20 °C. After the reaction was completed, the target product 4,4'-carbonyldimorpholine was obtained by silica gel column chromatography with a yield of 76%. The specific experimental results are shown in Table 1.

[0060] like Figure 1 As shown, the spectrum of 4,4'-carbonyldimorpholine is resolved as follows: 1 H NMR (600MHz, CDCl3) δ3.70-3.65(m,8H),3.29-3.24(m,8H).

[0061] Example 2

[0062] By replacing acetonitrile with ethanol, and with other operations the same as in Example 1, the final yield of the target product was 88%. The specific experimental results are shown in Table 1.

[0063] Example 3

[0064] The acetonitrile was replaced with dioxane, and the other operations were the same as in Example 1. The final yield of the target product was 62%. The specific experimental results are shown in Table 1.

[0065] Example 4

[0066] By replacing acetonitrile with toluene, and with other operations the same as in Example 1, the final yield of the target product was 58%. The specific experimental results are shown in Table 1.

[0067] Table 1 Product yield under different solvents

[0068] Example solvent Product yield 1 Acetonitrile 76％ 2 ethanol 88％ 3 Dioxane 62％ 4 Toluene 58％

[0069] Example 5

[0070] Palladium acetate was replaced with palladium chloride, and other operations were the same as in Example 1. The final yield of the target product was 77%, and the specific experimental results are shown in Table 2.

[0071] Example 6

[0072] The palladium acetate was replaced with palladium acetylacetone, and the other operations were the same as in Example 1. The final yield of the target product was 67%. The specific experimental results are shown in Table 2.

[0073] Example 7

[0074] The palladium acetate was replaced with 0.3% Pd / TiO2 by mass, and the other operations were the same as in Example 1. The final yield of the target product was 70%. The specific experimental results are shown in Table 2.

[0075] Example 8

[0076] The palladium acetate was replaced with 0.3% Pd / Al2O3, and the other operations were the same as in Example 1. The final yield of the target product was 77%. The specific experimental results are shown in Table 2.

[0077] Table 2 Product yields under different Pd catalysts

[0078]

[0079]

[0080] Example 9

[0081] Replace potassium iodide with elemental iodine, and follow the same procedures as in Example 1. The final yield of the target product was 82%, and the specific experimental results are shown in Table 3.

[0082] Example 10

[0083] Potassium iodide was replaced with tetraethylammonium iodide, and other operations were the same as in Example 1. The final yield of the target product was 78%, and the specific experimental results are shown in Table 3.

[0084] Example 11

[0085] Replace potassium iodide with tetrabutylammonium iodide, and follow the same procedures as in Example 1. The final yield of the target product was 85%. The specific experimental results are shown in Table 3.

[0086] Table 3 Product yields under different iodine species

[0087] Example Iodine species Product yield 1 Potassium iodide 76％ 9 Elemental iodine 77％ 10 Tetraethylammonium iodide 67％ 11 Tetrabutylammonium iodide 70％

[0088] Example 12

[0089] Replacing morpholine with aniline, and following the same procedures as in Example 1, resulted in a final yield of 85% for the target 1,3-diphenylurea product. Figure 2 As shown, the spectrum of 1,3-diphenylurea is resolved as follows: 1 H NMR (600MHz, DMSO-d6) δ 8.67 (s, 2H), 7.45 (d, J = 7.9 Hz, 4H), 7.27 (t, J = 7.8 Hz, 4H), 6.97 (d, J = 7.3 Hz, 2H).

[0090] Example 13

[0091] Replacing morpholine with n-hexylamine, and performing the same procedures as in Example 1, resulted in a final yield of 78% for the target 1,3-dihexylurea product. Figure 3 As shown, the spectrum of 1,3-dihexylurea is resolved as follows: 1 H NMR (600MHz, CDCl3) δ4.28 (s, 2H), 3.14 (dd, J = 12.9, 7.1Hz, 4H), 1.52-1.44 (m, 4H), 1.34-1.26 (m, 12H), 0.88 (t, J = 6.9Hz, 6H).

[0092] Example 14

[0093] Replacing morpholine with cyclohexylamine, and performing the same procedures as in Example 1, resulted in a final yield of 58% for the target 1,3-dicyclohexylurea product. Figure 4 As shown, the spectrum of 1,3-dicyclohexylurea is resolved as follows: 1H NMR (600MHz, DMSO-d6) δ5.58(d,J=7.8Hz,2H),1.71(d,J=9.6Hz,4H),1.61(dd,J =9.4, 3.8Hz, 4H), 1.50 (d, J = 12.7Hz, 2H), 1.28-1.21 (m, 4H), 1.16-0.98 (m, 6H).

[0094] Example 15

[0095] After adding morpholine, 2 mmol of n-hexylamine was added, and the rest of the operation was the same as in Example 1. The final yield of the N-hexylmorpholine-4-carboxamide asymmetric urea product was 79%. Figure 5 As shown, the spectrum is analyzed as follows: 1 H NMR (600MHz, CDCl3) δ4.42 (s, 1H), 3.71-3.66 (m, 4H), 3.35-3.30 (m, 4H), 3.22 (dd, J = 13. 0, 7.2Hz, 2H), 1.49 (dd, J = 14.2, 7.2Hz, 2H), 1.30 (d, J = 9.0Hz, 6H), 0.88 (t, J = 6.7Hz, 3H).

[0096] Example 16

[0097] After adding morpholine, 2 mmol of cyclohexylamine was added, and the rest of the operation was the same as in Example 1. The final yield of the N-cyclohexylmorpholine-4-carboxamide asymmetric urea product was 49%. Figure 6 As shown, the spectrum is analyzed as follows: 1 H NMR (600MHz, CDCl3) δ4.27 (d, J = 6.2Hz, 1H), 3.71-3.56 (m, 5H), 3.34-3.28 (m, 4H), 1.9 4(d,J=9.0Hz,2H),1.72-1.55(m,3H),1.36(td,J=12.3,3.4Hz,2H),1.20-1.00(m,3H).

[0098] Example 17

[0099] After adding morpholine, 2 mmol of benzylamine was added, and the rest of the operation was the same as in Example 1. The final yield of the N-benzylmorpholine-4-formamide asymmetric urea product was 89%. Figure 7 As shown, the spectrum is analyzed as follows: 1 H NMR (600MHz, CDCl3) δ7.30 (ddd, J = 27.4, 13.8, 6.7Hz, 5H), 4.79 (s, 1H), 4.42 (d, J = 5.4Hz, 2H), 3.71-3.64 (m, 4H), 3.39-3.31 (m, 4H).

[0100] Example 18

[0101] Benzouron, a widely used herbicide, can be synthesized using this method. Morpholine is replaced with 1 mmol of o-chlorobenzylamine and 2 mmol of α,α-dimethylbenzylamine; other operations are the same as in Example 1. The final yield of the asymmetric urea product, benzuron, is 59%. Figure 8 As shown, the spectrum resolution is as follows: δH (600MHz, Chloroform-d) 7.45 (2H,d,J=8.0), 7.32 (2H,t,J=7.6), 7.24 (3H,dd,J 13.5,5.6), 7.14 (3H,s), 4.87 (1H,s), 4.52 (1H,s), 4.30 (2H,d,J 6.0), 1.62 (6H,s).

[0102] Example 19

[0103] 1-Diethylaminoformyl-4-methylpiperazine, currently the preferred antifilarial drug on the market, can be synthesized using this method. Morpholine is replaced with 1 mmol N-methylpiperazine and 2 mmol diethylamine; other operations are the same as in Example 1. The final asymmetric urea product, 1-diethylaminoformyl-4-methylpiperazine, has a yield of 48%. Figure 9 As shown, the spectrum is analyzed as follows: 1 HNMR (600MHz, CDCl3) δ3.29-3.17 (m, 8H), 2.44-2.35 (m, 4H), 2.30 (s, 3H), 1.12 (t, J = 7.1Hz, 6H).

[0104] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for the preparation of photo-promoted synthesis of urea-based compounds, characterized by, The preparation method includes: In an atmosphere of oxygen and carbon monoxide, a mixture containing a catalyst, a co-catalyst, an amine compound, and a solvent is subjected to photo-reaction at 5-55°C using a light source with a wavelength of 200-600 nm for 8-72 hours to obtain urea compounds. The amine compound is selected from at least one having the structure shown in Formula I-1, Formula I-2 and Formula I-3, wherein the structures shown in Formula I-2 and Formula I-3 are different amine compounds; Formula I-1, Formula I-2, Formula I-3; The urea compound is selected from one of the following formulas: II-1, II-2, II-3, II-4, II-5, and II-6. Formula II-1, Formula II-2 Formula II-3, Formula II-4, Formula II-5, Formula II-6, Wherein, R, R1, R2, R3, and R4 are independently selected from H, C1-C20 alkyl, C1-C20 substituted alkyl, C2-C20 alkenyl, C2-C20 substituted alkenyl, C2-C20 alkynyl, C2-C20 substituted alkynyl, C5-C20 heteroaryl, C5-C20 substituted heteroaryl, C6-C20 aromatic, and C6-C20 substituted aromatic. The substituents in the C1-C20 substituted alkyl, C2-C20 substituted alkenyl, C2-C20 substituted alkynyl, C5-C20 substituted heteroaryl, and C6-C20 substituted aromatic groups are independently selected from at least one of halogen, hydroxyl, and alkoxy groups. The catalyst includes at least one of palladium acetate, palladium chloride, palladium acetylacetone, triphenylphosphine palladium, Pd2(dba)3, PdCl2(PPh3)2, Pd(dba)2 / dppb, Pd / C, Pd / SiO2, Pd / TiO2, and Pd / Al2O3. The co-catalyst includes at least one of KI, NaI, elemental iodine, tetraethylammonium iodide, and tetrabutylammonium iodide.

2. A method for the preparation of photo-promoted synthesis of urea-based compounds, characterized by, The preparation method includes: In an atmosphere of oxygen and carbon monoxide, a mixture containing a catalyst, a co-catalyst, an amine compound, and a solvent is subjected to photo-reaction at 5-55°C using a light source with a wavelength of 200-600 nm for 8-72 hours to obtain urea compounds. The amine compound is selected from at least one of morpholine, aniline, n-hexylamine, cyclohexylamine, benzylamine, α,α-dimethylbenzylamine, p-methoxybenzylamine, p-bromobenzylamine, o-chlorobenzylamine, p-methylaniline, p-methoxyaniline, phenethylamine, p-methylphenethylamine, p-methoxyphenethylamine, p-fluorophenethylamine, p-chlorophenethylamine, N-methylpiperazine, and diethylamine; The urea compound is selected from at least one of 4,4'-carbonyldimorpholine, 1,3-diphenylurea, 1,3-dihexylurea, 1,3-dicyclohexylurea, 1,3-dibenzylurea, N,N'-bis(α,α-dimethylbenzyl)urea, 1,3-bis(4-methoxybenzyl)urea, 1,3-bis(4-bromobenzyl)urea, 1,3-bis(2-chlorobenzyl)urea, 1,3-bis(4-methylphenyl)urea, 1,3-bis(4-methoxyphenyl)urea, 1,3-diphenylethylurea, 1,3-bis(4-methylphenylethyl)urea, 1,3-bis(4-methoxyphenylethyl)urea, benzalkonium chloride, and 1-diethylaminoformyl-4-methylpiperazine; The catalyst includes at least one of palladium acetate, palladium chloride, palladium acetylacetone, triphenylphosphine palladium, Pd2(dba)3, PdCl2(PPh3)2, Pd(dba)2 / dppb, Pd / C, Pd / SiO2, Pd / TiO2, and Pd / Al2O3. The co-catalyst includes at least one of KI, NaI, elemental iodine, tetraethylammonium iodide, and tetrabutylammonium iodide.

3. The production method according to claim 1 or 2, characterized by, The molar ratio of the catalyst to the amine compound is 1:1000 to 1:20, and the molar amount of the catalyst is expressed as the molar amount of the Pd element.

4. The production method according to claim 1 or 2, characterized by, The molar ratio of the co-catalyst to the amine compound is 1:1000 to 1:

5.

5. The preparation method according to claim 1, characterized in that, When different amine compounds are selected, The molar ratio of the compound shown in Formula I-1 to the compound shown in Formula I-2 is 1:1 to 1:

10.

6. The method of claim 1, wherein, When different amine compounds are selected, The molar ratio of the compound shown in Formula I-1 to the compound shown in Formula I-3 is 1:1 to 1:

10.

7. The preparation method according to claim 1, characterized in that, When different amine compounds are selected, The molar ratio of the compound shown in Formula I-2 to the compound shown in Formula I-3 is 1:1 to 1:

10.

8. The production method according to claim 1 or 2, characterized by, The volume ratio of carbon monoxide to oxygen is 1:100 to 100:

1.

9. The production method according to claim 1 or 2, characterized by, The solvent is selected from at least one of toluene, ethylbenzene, benzene, n-hexane, trifluorotoluene, dichloromethane, dichloroethane, cyclohexane, methanol, ethanol, diethyl ether, isopropanol, butanol, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, trichloromethane, and tetrachloromethane.

10. The production method according to claim 1 or 2, characterized by, The molar volume ratio of the amine compound to the solvent is 0.125~5 mol / L.

11. The production method according to claim 1 or 2, characterized by, The light source for the photoluminescence reaction is selected from at least one of light-emitting diodes, xenon lamps, and mercury lamps.

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