阅读说明：本技术 一种含氮杂环硫醇一价铜化合物在羰基化合物光催化反应中的应用 (Application of nitrogen heterocyclic mercaptan cuprous compound in carbonyl compound photocatalytic reaction ) 是由 张梦娟 马伟 沈悦 于 2021-03-24 设计创作，主要内容包括：本发明公开了一种含氮杂环硫醇一价铜化合物在羰基化合物光催化反应中的应用,涉及光催化剂应用技术领域,具体为：采用含氮杂环硫醇一价铜化合物作为光催化剂对羰基化合物进行光催化还原反应制备醇化合物。本发明以含氮杂环硫醇一价铜化合物作为羰基化合物光催化还原反应的光催化剂,成功催化可见光诱导羰基化合物的还原为醇化合物,该催化剂价格低廉,催化效果好,能够降低生产成本。(The invention discloses an application of a nitrogen heterocyclic mercaptan monovalent copper compound in a carbonyl compound photocatalytic reaction, which relates to the technical field of application of photocatalysts and specifically comprises the following steps: the alcohol compound is prepared by carrying out photocatalytic reduction reaction on a carbonyl compound by using a nitrogen heterocyclic mercaptan cuprous compound as a photocatalyst. The invention takes the nitrogen heterocyclic mercaptan cuprous compound as the photocatalyst of the carbonyl compound photocatalytic reduction reaction to successfully catalyze the reduction of the visible light induced carbonyl compound into the alcohol compound, and the catalyst has low price, good catalysis effect and can reduce the production cost.)

1. The application of the nitrogen heterocyclic mercaptan cuprous compound in the carbonyl compound photocatalytic reaction is characterized in that the nitrogen heterocyclic mercaptan cuprous compound is used as a photocatalyst to carry out the photocatalytic reduction reaction on the carbonyl compound to prepare the alcohol compound.

2. The use according to claim 1, wherein the azacyclic thiol monovalent copper compound has the general chemical formula:

wherein the content of the first and second substances,is composed of OrOne kind of (1).

3. Use according to claim 2, characterised in that saidIs composed of。

4. The application of claim 1, wherein the reaction system of the photocatalytic reduction reaction further comprises an electron donor, and the electron donor is diethyl 1, 4-dihydro-2, 6-dimethyl-3, 5-pyridinedicarboxylate, triethylamine, N-diisopropylethylamine, or triethanolamine.

5. The use of claim 1, wherein the reaction system of the photocatalytic reduction reaction further comprises an inorganic base, isopropanol and acetonitrile.

6. The use according to claim 5, wherein the molar ratio of the carbonyl compound, the inorganic base and the nitrogen-containing heterocyclic thiol monovalent copper compound in the photocatalytic reduction reaction is 1: 0.1-0.3: 0.015 to 0.02.

7. Use according to claim 1, wherein the carbonyl compound is an aldehyde or a ketone.

8. Use according to claim 1, wherein the light of the photocatalytic reaction is visible light.

9. The use according to claim 1, wherein the photocatalytic reaction is carried out under an atmosphere of an inert gas, the inert gas being one of nitrogen, helium, neon and argon.

10. Use according to claim 1, wherein the alcohol compound is a primary alcohol, a secondary alcohol or pinacol.

Technical Field

The invention relates to the technical field of application of photocatalysts, in particular to application of a nitrogenous heterocyclic mercaptan cuprous compound in a carbonyl compound photocatalytic reaction.

Background

Visible light-induced redox reactions have been the primary means of organic transformation for the last decade. The visible light catalysis has the advantages of mild condition, wide source, strong reaction adaptability, small pollution and the like, and is increasingly favored by people. At present, the main photocatalyst is a rare noble metal (ruthenium or iridium) complex and an organic dye, and the complex and the organic dye are in Single Electron Transfer (SET) interaction with substrate molecules under the irradiation of visible light, and the construction of reducing unsaturated bonds and C-X bonds (X = C, N, O … …) in a green, energy-saving and efficient manner by utilizing free radicals or free radical ion intermediates formed in the reaction process. Although the organic dye can better realize photocatalytic organic conversion, the organic dye has low light stability and is difficult to separate and recycle from a reaction system; rare noble metal (ruthenium or iridium) complexes are used as the photocatalyst, and the use cost of the catalyst is increased due to the price of the noble metals, so that the photocatalyst is difficult to popularize and apply on a large scale.

The literature now reports that mono-or heteroleptic copper (I) compounds modified by diamine/bisphosphine chelating ligands are used as photoredox catalysts, which mostly effect organic transformations by oxidative quenching processes (OQC). Copper (I) photocatalyst (CuPC) with more negative reduction potential CuPC-/CuPC (E [ Cu (dap))₂]⁺/[Cu(dap)₂]It is rarely reported that dap =2,9-bis (4-anisyl) -1,10-phenanthroline) undergoes a reductive quenching process (RQC). The transfer of light-induced electrons from a photocatalyst to a suitable substrate molecule plays a significant role in photosynthesis, however, there have been few reports on the photoreduction of carbonyl compounds. Carbonyl compounds have more negative reduction potential than commonly used photosensitizers, and therefore, it is difficult for most visible photocatalysts to achieve photoreduction of carbonyl compounds. In 1983, Pac et al first reported [ Ru (bpy)3]Cl2 can photocatalytically catalyze the reduction of aromatic carbonyl compounds with the aid of 1-benzyl-1, 4-dihydronicotinamide (BNAH), and only bis (2-pyridyl) methanone can be reduced to the corresponding alcohol. Rueping topic group successfully realizes the generation frequency of aldehyde or ketone by photocatalytic reduction self-coupling by using cyclometalated Ir (III) complex(iii) a product of the pinacols. In addition, Poly (p-phenylene) can realize the reduction of aromatic aldehyde; however, these catalytic systems either require a noble metal photocatalyst or have a limited substrate range and are difficult to popularize.

Disclosure of Invention

In order to solve the problems, the invention provides an application of a nitrogen-containing heterocyclic thiol cuprous compound in a carbonyl compound photocatalytic reaction, wherein the nitrogen-containing heterocyclic thiol cuprous compound is used as a photocatalyst to carry out a photocatalytic reduction reaction on the carbonyl compound to prepare an alcohol compound.

Further, the chemical general formula of the azacyclic thiol monovalent copper compound is as follows:

furthermore, the reaction system of the photocatalytic reduction reaction also comprises an electron donor, wherein the electron donor is 1, 4-dihydro-2, 6-dimethyl-3, 5-pyridinedicarboxylic acid diethyl ester, triethylamine, N-diisopropylethylamine or triethanolamine.

Furthermore, the reaction system of the photocatalytic reduction reaction also comprises an inorganic base, isopropanol and acetonitrile.

Further, the molar ratio of the carbonyl compound, the inorganic base and the nitrogen-containing heterocyclic thiol monovalent copper compound in the photocatalytic reduction reaction is 1: 0.1-0.3: 0.015 to 0.02.

Still further, the carbonyl compound is an aldehyde or a ketone.

Further, the light of the photocatalytic reaction is visible light.

Further, the photocatalytic reaction is carried out in an inert gas atmosphere, and the inert gas is one of nitrogen, helium, neon and argon.

Further, the alcohol compound is a primary alcohol, a secondary alcohol or pinacol.

The invention has the beneficial effects that:

the invention takes the nitrogen heterocyclic mercaptan cuprous compound as the photocatalyst of the carbonyl compound photocatalytic reduction reaction to successfully catalyze the reduction of the visible light induced carbonyl compound into the alcohol compound, and the catalyst has low price, good catalysis effect and can reduce the production cost.

The catalytic process is as follows: under the irradiation of visible light, an electron donor such as diethyl 1, 4-dihydro-2, 6-dimethyl-3, 5-pyridinedicarboxylate (Hantzsch Ester, abbreviated as HEH) assists Cu (I) in the nitrogenous heterocyclic thiol monovalent copper compound to undergo reduction quenching, Cu (0) with more negative reduction potential is generated, and then single electron transfer is carried out between the electron donor and a carbonyl compound.

The photocatalytic system has good functional group tolerance, and a series of primary alcohol, secondary alcohol and pinacol are synthesized mildly and efficiently; in addition, the system takes environment-friendly and economic isopropanol as an electronic sacrificial agent and a hydrogen source, thereby avoiding using amine compounds as sacrificial coreductants and reducing the pollution to the environment.

In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

An application of nitrogen heterocyclic mercaptan cuprous compound in carbonyl compound photocatalytic reaction, wherein the nitrogen heterocyclic mercaptan cuprous compound is used as a photocatalyst to carry out photocatalytic reduction reaction on the carbonyl compound to prepare an alcohol compound.

Wherein the chemical general formula of the azacyclo-mercaptan monovalent copper compound is as follows:

in one embodiment, the reaction system of the photocatalytic reduction reaction further includes an electron donor, where the electron donor is diethyl 1, 4-dihydro-2, 6-dimethyl-3, 5-pyridinedicarboxylate, triethylamine, N-diisopropylethylamine, or triethanolamine.

In one embodiment, the reaction system of the photocatalytic reduction reaction further comprises an inorganic base, isopropanol and acetonitrile. The inorganic salt can be inorganic metal hydroxide, and isopropanol is used as an electronic sacrificial agent and a hydrogen source, so that environmental pollution caused by using an amine compound as a sacrificial agent is avoided.

In one embodiment, the molar ratio of the carbonyl compound, the inorganic base and the nitrogen-containing heterocyclic thiol monovalent copper compound in the photocatalytic reduction reaction is 1: 0.1-0.3: 0.015 to 0.02.

In one embodiment, the carbonyl compound is an aldehyde or ketone, illustratively acetophenone, methylacetophenone, 4-fluoroacetophenone, 2-acetylthiophene, or acetophenone with other substituents.

In one embodiment, the light for the photocatalytic reaction is visible light, such as blue light.

In one embodiment, the photocatalytic reaction is performed in an inert gas atmosphere, and the inert gas is one of nitrogen, helium, neon and argon.

In one embodiment, the alcohol compound is a primary alcohol, a secondary alcohol, or pinacol.

Example 1: nitrogen heterocyclic mercaptan cuprous compound catalyzed acetophenone hydrogen transfer reaction

0.2mmoL acetophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg nitrogen heterocyclic mercaptan cuprous compound are added into a drying reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile with the volume ratio of 3:1 is added for stirring and reaction. During the reaction with N₂Replacing for 3 times, adopting blue LEDs as catalytic reaction light source, reacting for 24h, and adding 5Extracting with 3X 5mL of ethyl acetate in mL of water, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, concentrating the filtrate by rotary evaporation, and separating by silica gel chromatography to obtain the target product, wherein the yield of the target product is 98%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(600MHz,DMSO-d₆)δ7.28 (d,J=7.5Hz,2H),7.23(t,J=7.6Hz,2H),7.13(t,J=7.3Hz,1H),5.08(d,J=4.0Hz,1H),4.65(s,1H),1.26(d,J=6.5Hz,3H).¹³CNMR(151MHz,DMSO-d₆)δ185.1,165.7,164.2,163.0,105.9,63.7。

EXAMPLE 2 catalysis of the Hydrogen transfer reaction of p-methylacetophenone by Nitrogen-containing heterocyclic thiol monovalent copper Compounds

1mmoL of p-methylacetophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic mercaptan cuprous compound are added into a drying reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile in a volume ratio of 3:1 is added and stirred for reaction. Helium is used for replacing 3 times in the reaction process, blue LEDs are used as a catalytic reaction light source, stirring is carried out for 36 hours of reaction, 5mL of water is added after the reaction is finished, 3X 5mL of ethyl acetate is used for extraction, organic phases are combined, anhydrous magnesium sulfate is used for drying and filtering, the filtrate is subjected to rotary evaporation and concentration, and a target product is obtained through silica gel chromatographic column chromatography separation, wherein the yield of the target product is 99%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(400MHz,CDCl₃)δ12.18(d,J =7.6Hz,2H),12.09(d,J=7.7Hz,2H),9.73(d,J= 6.4Hz,1H),7.71(d,J=23.7 Hz,1H),7.30(s,3H),6.39(d,J=6.5Hz,3H).¹³CNMR(151MHz,CDCl₃)δ163.0, 161.4,141.6,127.1,115.4–115.2,69.8,25.4。

EXAMPLE 3 catalysis of the Hydrogen transfer reaction of 4-fluoroacetophenone by Nitrogen-containing heterocyclic thiol monovalent copper Compounds

1mmoL 4-fluoroacetophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic thiol cuprous compound are added into a dry reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile in a volume ratio of 3:1 is added and stirred for reaction. Replacing 3 times with neon in the reaction process, adopting blue LEDs as a catalytic reaction light source, stirring for reaction for 30h, adding 5mL of water after the reaction is finished, extracting with 3X 5mL of ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, filtering, performing rotary evaporation concentration on the filtrate, and performing silica gel chromatographic column separation to obtain the target product, wherein the yield of the target product is 97%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(400MHz,CDCl₃)δ7.64–7.54 (m,2H),7.29(d,J=8.6Hz,1H),5.12(q,J=5.5Hz,1H),2.56–2.43(m,1H),1.72(d,J=6.3Hz,3H).¹³C NMR(151MHz, CDCl₃)δ143.0,136.9,129.0,125.4, 69.9,25.1–21.1。

example 4: hydrogen transfer reaction of 4-chloroacetophenone catalyzed by nitrogenous heterocyclic mercaptan cuprous compound

1mmoL 4-chloroacetophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic thiol cuprous compound are added into a dry reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile in a volume ratio of 3:1 is added for stirring and reaction. Using N in the course of the reaction₂The replacement is carried out for 3 times, blue LEDs are used as a catalytic reaction light source, and the reaction is carried out for 30 hours under stirring. After the reaction is finished, 5mL of water is added, then 3X 5mL of ethyl acetate is used for extraction, organic phases are combined, anhydrous magnesium sulfate is used for drying, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, silica gel chromatographic column chromatography separation is carried out, and the target product yield is 92%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(400MHz,DMSO-d₆)δ7.35(s, 4H),5.24(d,J=4.0Hz,1H),4.75–4.68(m, 1H),1.30(d,J=6.4Hz,3H).¹³C NMR(151MHz,DMSO-d₆)δ184.0,168.8,165.6,164.8,105.2,63.5。

EXAMPLE 5 catalysis of the Hydrogen transfer reaction of o-methylacetophenone by Nitrogen-containing heterocyclic thiol monovalent copper Compounds

1mmoL of o-methylacetophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic mercaptan cuprous compound are added into a drying reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile in a volume ratio of 3:1 is added and stirred for reaction. Using N in the reaction₂The replacement is carried out for 3 times, blue LEDs are used as a catalytic reaction light source, and the reaction is carried out for 36 hours under stirring. After the reaction is finished, 5mL of water is added, extraction is carried out by using 3X 5mL of ethyl acetate, organic phases are combined, drying is carried out by using anhydrous magnesium sulfate, filtration is carried out, filtrate is concentrated by rotary evaporation, and silica gel chromatographic column chromatography separation is carried out to obtain the target product, wherein the yield of the target product is 98%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR (400MHz,CDCl₃)δ7.47(d,J= 7.6Hz,1H),7.22–7.09(m,3H),5.06(d,J= 6.4 Hz,1H),2.31(s,4H),1.42(d, J= 6.4 Hz,3H).13CNMR(151MHz,CDCl₃)δ143.9,134.2,130.3,127.1,126.3, 124.5,66.7,23.9,18.9。

EXAMPLE 6 catalysis of the Hydrogen transfer reaction of m-methylacetophenone by Nitrogen-containing heterocyclic thiol monovalent copper Compounds

1mmoL of m-methylacetophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic mercaptan cuprous compound are added into a dry reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile in a volume ratio of 3:1 is added and stirred for reaction. Using N in the course of the reaction₂The replacement is carried out for 3 times, blue LEDs are used as a catalytic reaction light source, and the reaction is carried out for 36 hours under stirring. After the reaction is finished, 5mL of water is added, and then 3 templates are usedExtracting with 5mL of ethyl acetate, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, concentrating the filtrate by rotary evaporation, and separating by silica gel chromatography to obtain the target product, wherein the yield of the target product is 97%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(600MHz, CDCl₃)δ8.07(d,J=7.9Hz,1H),7.88(d,J=7.3Hz,1H),7.77(d,J=8.2Hz,1H), 7.65(d,J=7.1Hz,1H),7.47(dd,J=22.1,14.5Hz,3H),5.59(d,J=6.5Hz,1H), 2.48(s,1H),1.63(d,J=6.5Hz,3H).¹³C NMR(151MHz,CDCl₃)δ145.9,138.2, 128.5,128.3,126.2,122.5,70.5,25.2,21.6。

example 7A nitrogenous heterocyclic thiol cuprous compound catalyzes the hydrogen transfer reaction of 2, 4, 6-trimethylacetophenone.

1mmoL 1-propiophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic thiol cuprous compound are added into a drying reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile in a volume ratio of 3:1 is added for stirring and reaction. Using N in the course of the reaction₂The replacement is carried out for 3 times, blue LEDs are used as a catalytic reaction light source, and the reaction is carried out for 24 hours under stirring. After the reaction is finished, 5mL of water is added, then 3X 5mL of ethyl acetate is used for extraction, organic phases are combined, anhydrous magnesium sulfate is used for drying, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, silica gel chromatographic column chromatography separation is carried out, and the target product yield is 93%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(400MHz,DMSO-d₆)δ 7.35–7.19(m,5H), 5.12(s,1H),4.44(s,1H),1.61(s,2H),0.83(t,J=7.1 Hz,3H).¹³C NMR(151MHz,DMSO-d₆)δ146.6,128.3,126.9,126.3,74.1,32.5, 10.5。

example 8: hydrogen transfer reaction of 2-acetonaphthone catalyzed by nitrogen heterocyclic mercaptan cuprous compound

1mmoL 2-acetonaphthone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg nitrogen heterocyclic mercaptan cuprous compound are added into a drying reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile with the volume ratio of 3:1 is added for stirring and reaction. Using N in the course of the reaction₂The replacement is carried out for 3 times, blue LEDs are used as a catalytic reaction light source, and the reaction is carried out for 36 hours under stirring. After the reaction is finished, 5mL of water is added, then 3X 5mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous magnesium sulfate and filtered, the filtrate is concentrated by rotary evaporation, and then silica gel chromatographic column chromatography is carried out to obtain the target product, wherein the yield of the target product is 91%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(600MHz, CDCl₃)δ7.82(d,J= 8.4Hz,3H),7.79(s,1H),7.50–7.47(m,2H),5.04(q,J=6.5Hz,1H),2.07(d, J=16.9Hz,1H),1.57(d,J=6.5Hz,3H).¹³C NMR(151 MHz, CDCl3)δ143.3,133.4,133.0,128.4,128.0,127.8,126.2,125.9,123.9,70.6,25.2。

EXAMPLE 9 catalysis of benzophenone by Nitrogen-containing heterocyclic thiol monovalent copper Compounds

1mmoL benzophenone, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic mercaptan monovalent copper compound are added into a drying reflux reaction tube with a magnetic stirring bar, and then 5mL of anhydrous isopropanol and acetonitrile mixed solution with the volume ratio of 3:1 is added for stirring and reaction. Using N in the course of the reaction₂And (3) replacing for 3 times, adopting blue LEDs as a catalytic reaction light source, stirring for reacting for 24 hours, adding 5mL of water after the reaction is finished, extracting with 3X 5mL of ethyl acetate, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, performing rotary evaporation concentration on the filtrate, and performing silica gel chromatographic column separation to obtain the target product, wherein the yield of the target product is 95%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(400MHz,CDCl₃)δ7.37–7.25 (m,10H),5.80(s,1H),2.26(s,1H).¹³C NMR(151MHz,CDCl₃)δ143.9,128.6, 127.7,126.7,76.4。

EXAMPLE 10 catalysis of the Hydrogen transfer reaction of 2-acetylthiophene by Nitrogen-containing heterocyclic thiol monovalent copper Compounds

1mmoL 2-acetylthiophene, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic mercaptan cuprous compound are added into a drying reflux reaction tube with a magnetic stirring bar, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile with the volume ratio of 3:1 is added for stirring and reaction. Using N in the course of the reaction₂And (3) replacing for 3 times, adopting blue LEDs as a catalytic reaction light source, stirring for reacting for 36 hours, adding 5mL of water after the reaction is finished, extracting with 3X 5mL of ethyl acetate, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, performing rotary evaporation concentration on the filtrate, and performing silica gel chromatographic column separation to obtain the target product, wherein the yield of the target product is 83%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product:¹H NMR(600MHz,DMSO-d₆)δ7.34(dd, J=5.0,1.0Hz,1H),6.96–6.94(m,1H),6.93–6.92(m,1H),5.52(d,J=4.8Hz, 1H),4.97–4.94(m,1H),1.43(d,J=6.4Hz,3H).¹³C NMR(151MHz,DMSO-d₆)δ152.3,126.9,124.2,122.7,64.9,26.4。

example 11 nitrogen-containing heterocyclic thiol monovalent copper compounds catalyze the hydrogen transfer reaction of benzaldehyde.

1mmoL benzaldehyde, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic mercaptan monovalent copper compound are added into a drying reflux reaction tube with a magnetic stirring bar, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile with the volume ratio of 3:1 is added for stirring and reaction. Using N in the course of the reaction₂And (3) replacing for 3 times, adopting blue LEDs as a catalytic reaction light source, stirring for reacting for 36 hours, adding 5mL of water after the reaction is finished, extracting with 3X 5mL of ethyl acetate, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, performing rotary evaporation concentration on the filtrate, and performing silica gel chromatographic column separation to obtain the target product, wherein the yield of the target product is 83%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product: 1H NMR (600 MHz, CDCl)₃) δ7.39–7.29 (m, 5H), 4.59 (s, 2H), 3.40 (s, 1H).¹³C NMR (151 MHz, CDCl₃) δ141.0, 128.5, 127.5, 127.0, 64.9。

Example 12 nitrogen-containing heterocyclic thiol monovalent copper compounds catalyze the hydrogen transfer reaction of 4-trifluoromethylbenzaldehyde.

1mmoL 4-trifluoromethylbenzaldehyde, 0.1mmoLNaOH, 0.3mmoLHEH and 4mg of nitrogen heterocyclic mercaptan cuprous compound are added into a dry reflux reaction tube with a magnetic stirrer, and then 5mL of a mixed solution of anhydrous isopropanol and acetonitrile in a volume ratio of 3:1 is added for stirring and reaction. Using N in the course of the reaction₂And (3) replacing for 3 times, adopting blue LEDs as a catalytic reaction light source, stirring for reacting for 36 hours, adding 5mL of water after the reaction is finished, extracting with 3X 5mL of ethyl acetate, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, performing rotary evaporation and concentration on the filtrate, and performing silica gel chromatographic column separation to obtain the target product, wherein the yield of the target product is 90%.

Nuclear magnetic spectrum analysis data of the obtained catalytic product: 1H NMR (600 MHz, CDCl)₃)δ7.57(d, J= 8.1 Hz,2H), 7.40(d,J = 8.0Hz,2H), 4.67 (s,2H), 2.81 (s,1H). 13C NMR(151 MHz, CDCl₃)δ144.6,129.8, 126.8,125.4,123.2,64.2。

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.