CN114349656A

CN114349656A - Preparation method of hydrazide compound

Info

Publication number: CN114349656A
Application number: CN202210053887.5A
Authority: CN
Inventors: 郑绿茵; 卓小丫; 郭维
Original assignee: Gannan Normal University
Current assignee: Gannan Normal University
Priority date: 2022-01-18
Filing date: 2022-01-18
Publication date: 2022-04-15
Anticipated expiration: 2042-01-18
Also published as: CN114349656B

Abstract

The invention provides a preparation method of a hydrazide compound, belonging to the technical field of medicinal chemistry. The method comprises the steps of mixing a 1, 1-disubstituted hydrazine compound, an aldehyde compound, an iridium composite photocatalyst, trichlorobromomethane and a polar organic solvent, and then carrying out cross coupling reaction under the illumination condition to obtain the hydrazide compound. The preparation method has the advantages of mild conditions (room temperature can be used for reaction), easy control of atom and step economy (one-step construction of a carbon-nitrogen bond (or a carbon-bromine bond), high yield), strong regioselectivity (construction of the carbon-bromine bond is the 4 th position on a benzene ring), good functional group tolerance (tolerance of substrates substituted by different substituents such as ester groups, hydroxyl groups, trifluoromethyl or cyano groups and generation of corresponding products in the reaction process) and the like, and the prepared hydrazide compound has high purity which is 98.5-99.9%, and has great market popularization value.

Description

Preparation method of hydrazide compound

Technical Field

The invention relates to the technical field of medicinal chemistry, in particular to a preparation method of a hydrazide compound.

Background

The hydrazide and the derivatives thereof have wide application, and the hydrazide skeleton is one of important organic synthesis intermediates and has important functions in medicines and agrochemicals. The compound containing hydrazide skeleton has strong physiological activity, such as antibacterial, antidepressant, antituberculosis and antiinflammatory etc. In addition, hydrazides have some role in pesticides, for example, butyryl hydrazine is a plant growth regulator. The construction of hydrazide backbones has attracted considerable attention in recent years due to their good biological activity and synthetic applications.

At present, methods for synthesizing hydrazide compounds mainly include: (a) ester and hydrazine are catalyzed by an N-heterocyclic carbene reagent to synthesize hydrazide or the hydrazine reacts with amide, carboxylic acid, trichloromethyl ketone and acyl chloride to generate hydrazide, such as:

(b) under the catalysis of 2-chloro-1-methylpyridine iodide or p-toluenesulfonyl chloride, hydroxyl benzamide and amine generate hydrazide, or under the catalysis of iridium or iron, hydroxyl benzamide and amine generate hydrazide from the reaction between dioxazalone and amine, such as:

(c) preparation of hydrazides or oxidation of hydrazones from alpha-azo hydroxides in the presence of acids such as:

however, the above method has many disadvantages, such as: pre-functionalization of the substrate, resulting in low atom economy or waste gas generation.

Disclosure of Invention

The invention aims to provide a preparation method of a hydrazide compound, which has the advantages of mild and easily controlled conditions, high atom and step economy, strong regioselectivity and good functional group tolerance.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of a hydrazide compound, which comprises the following steps:

mixing a 1, 1-disubstituted hydrazine compound, an aldehyde compound, an iridium composite photocatalyst, trichlorobromomethane and a polar organic solvent, and carrying out cross coupling reaction under the condition of illumination to obtain a hydrazide compound; the temperature of the cross coupling reaction is 20-30 ℃;

the 1, 1-disubstituted hydrazine compound has a structure shown in a formula I:

formula I; in the formula I, R¹And R²Independently phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, halogen-substituted phenyl or quinoline;

the aldehyde compound has a structural formula of R³C ═ O, and R³Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, nitrile substituted phenyl, trifluoromethyl substituted phenyl, ester substituted phenyl, hydroxyl substituted phenyl, aliphatic hydrocarbon group, heterocyclic group, olefin group or benzo heterocyclic group.

Preferably, the molar ratio of the 1, 1-disubstituted hydrazine compound to the aldehyde compound is (1.5-3): 1.

Preferably, the molar ratio of the aldehyde compound to the iridium composite photocatalyst is 1 (0.01-0.003).

Preferably, in the mixing process of the 1, 1-disubstituted hydrazine compound, the aldehyde compound, the iridium composite photocatalyst, the trichlorobromomethane and the polar organic solvent, tetrabutylammonium bromide is added; the molar ratio of the aldehyde compound to the tetrabutylammonium bromide is 1 (0.35-0.5).

Preferably, the molar ratio of the aldehyde compound to trichlorobromomethane is 1 (1-3).

Preferably, the polar organic solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, toluene, ethyl acetate, 1, 2-dichloroethane, acetonitrile, tetrahydrofuran and dichloromethane.

Preferably, the ratio of the volume of the polar organic solvent to the amount of the aldehyde compound is 1L (0.1 to 0.2) mol.

Preferably, the wavelength of the light source of the illumination is 200-1000 nm.

Preferably, the time of the cross-coupling reaction is 6-24 h.

The invention provides a preparation method of a hydrazide compound, which comprises the steps of mixing a 1, 1-disubstituted hydrazine compound, an aldehyde compound, an iridium composite photocatalyst, trichlorobromomethane and a polar organic solvent, and then carrying out cross coupling reaction under the illumination condition to obtain the hydrazide compound. The preparation method has the advantages of mild conditions (higher temperature and harsh conditions are not needed, the reaction can be carried out at room temperature), easy control of atom and step economy (carbon-nitrogen bond (or carbon-bromine bond) is constructed in one step, the yield is high), the regioselectivity is strong (the carbon-bromine bond is constructed as the 4 th position on a benzene ring), the tolerance of functional groups is good (substrates substituted by different substituents such as ester group, hydroxyl, trifluoromethyl or cyano can be tolerated in the reaction process, and corresponding products are generated), and the like, and the prepared hydrazide compound has higher purity which is 98.5-99.9%, and has higher market popularization value.

The preparation method provided by the invention provides the required energy for the cross dehydrogenation coupling reaction by utilizing illumination, and has the advantages of simple method, easily obtained raw materials and low cost.

Detailed Description

the 1, 1-disubstituted hydrazine compound has a structure shown in a formula I:

In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.

In the invention, the 1, 1-disubstituted hydrazine compound has a structure shown in a formula I:

in the present invention, when said R is¹When it is methyl, R²Is benzeneAlkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, quinoline hydrazine; the alkyl-substituted phenyl is preferably C1-C10 alkyl-substituted phenyl, and is further preferably p-methylphenyl, m-methylphenyl or o-methylphenyl; the halogen-substituted phenyl is preferably F-substituted phenyl, Cl-substituted phenyl or Br-substituted phenyl, and is further preferably p-chlorophenyl, p-bromophenyl, m-bromophenyl, o-chlorophenyl or o-fluorophenyl; the alkoxy-substituted phenyl is preferably o-methoxyphenyl; when said R is²When it is phenyl, said R¹The alkyl group is more preferably an ethyl group, a propyl group, an isopropyl group, or a butyl group. When R is₁And R₂In the case of quinoline, quinoline hydrazine is more preferable.

In the present invention, the 1, 1-disubstituted hydrazine compound is preferably 1-methyl-1-phenylhydrazine, 1-methyl-1-o-tolylhydrazine, 1-methyl-1-o-methoxyphenylhydrazine, 1-methyl-1-o-fluorophenylhydrazine, 1-methyl-1-m-tolylhydrazine, 1-methyl-1-m-bromophenylhydrazine, 1-butyl-1-phenylhydrazine, 1-propyl-1-phenylhydrazine, 1-isopropyl-1-phenylhydrazine, 1-ethyl-1-m-methylphenylhydrazine, 3, 4-dihydroisoquinoline-2 (1H) -amine, 1-methyl-1-p-methylphenylhydrazine or 1-methyl-1-p-chlorophenylhydrazine.

In the invention, the aldehyde compound has a structural formula of R³C ═ O, and R³Is phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, halogen substituted phenyl, nitrile substituted phenyl, trifluoromethyl substituted phenyl, ester substituted phenyl, hydroxyl substituted phenyl, aliphatic hydrocarbon group, heterocyclic group, olefin group or benzo heterocyclic group. In the present invention, the alkyl-substituted phenyl group is preferably a C1 to C10 alkyl-substituted phenyl group, and more preferably a p-methylphenyl group, a m-methylphenyl group or an o-methylphenyl group; the alkoxy-substituted phenyl group is preferably a methoxy-substituted phenyl group, and is more preferably a p-methoxyphenyl group or a m-methoxyphenyl group; the halogen-substituted phenyl group is preferably a fluorine-substituted phenyl group, a chlorine-substituted phenyl group or a bromine-substituted phenyl group, and is more preferably a p-fluorophenyl group, a p-chlorophenyl group, a p-bromophenyl group, a m-chlorophenyl group, a m-bromophenyl group, a m-fluorophenyl group, an o-chlorophenyl group or an o-bromophenyl group; the R is³Is an aliphatic hydrocarbon, such asOne step is preferably heptyl, isoamyl, 3-methylbut-1-enyl, cyclohexyl or adamantyl; the R is³The heterocyclic group is more preferably a p-pyrazolylphenyl group, a thienyl group, a benzothienyl group or a pyrazolyl group.

In the present invention, the aldehyde compound is preferably benzaldehyde, p-tolualdehyde, p-methoxybenzaldehyde, p-hydroxybenzaldehyde, p-fluorobenzaldehyde, p-trifluoromethylbenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, p-esterbenzaldehyde, p-cyanobenzaldehyde, m-methylbenzaldehyde, m-methoxybenzaldehyde, m-hydroxybenzaldehyde, m-chlorobenzaldehyde, o-methylbenzaldehyde, o-hydroxybenzaldehyde, o-bromobenzaldehyde, p-fluorom-methylbenzaldehyde, p-fluoroo-chlorobenzaldehyde, p-hydroxym-methoxybenzaldehyde, thiophenecarbaldehyde, pyrazolecarbaldehyde, p-pyrazolecarbaldehyde, benzothiophenecarbaldehyde, isovaleraldehyde, heptaldehyde, cyclohexanecarbaldehyde, 3-methylbut-2-enal or adamantanecarbaldehyde.

In the invention, the molar ratio of the 1, 1-disubstituted hydrazine compound to the aldehyde compound is preferably (1.5-3): 1, and more preferably 3: 1.

In the present invention, the iridium composite photocatalyst is preferably Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆(ii) a The mol ratio of the aldehyde compound to the iridium composite photocatalyst is preferably 1 (0.01-0.003).

In the invention, tetrabutylammonium bromide is added in the mixing process of the 1, 1-disubstituted hydrazine compound, the aldehyde compound, the iridium composite photocatalyst, trichlorobromomethane and the polar organic solvent; the mol ratio of the aldehyde compound to the tetrabutylammonium bromide is preferably 1 (0.35-0.5); the molar ratio of the aldehyde compound to trichlorobromomethane is preferably 1 (1-3), and more preferably 1: 1.5. The invention uses trichlorobromomethane as oxidant and bromine source, and uses tetrabutyl ammonium bromide as alkali.

In the present invention, the polar organic solvent preferably includes one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, toluene, ethyl acetate, 1, 2-dichloroethane, acetonitrile, tetrahydrofuran and dichloromethane; when the polar organic solvents are more than two of the above, the proportion of the polar organic solvents of different types is not particularly limited, and the polar organic solvents can be mixed at any proportion.

In the present invention, the ratio of the volume of the polar organic solvent to the amount of the aldehyde compound is preferably 1L (0.1 to 0.2) mol.

The process of mixing the 1, 1-disubstituted hydrazine compound, the aldehyde compound, the iridium complex photocatalyst, tetrabutylammonium bromide, trichlorobromomethane and the polar organic solvent is not particularly limited and can be carried out according to the process known in the field.

In the invention, the wavelength of the light source for illumination is preferably 200-1000 nm, and more preferably 465-800 nm; the temperature of the cross coupling reaction is 20-30 ℃; the time is preferably 6-24 h, and more preferably 8-20 h; the cross-coupling reaction is preferably carried out under stirring conditions; the light source of the present invention is not particularly limited, and a light source having the above wavelength may be provided. The stirring rate is not particularly limited in the present invention, and the reaction can be carried out smoothly according to the procedures known in the art.

The invention preferably regulates the reaction product through the type of the solvent, namely controls the substitution of bromine on the bromine source trichlorobromomethane on the hydrazide compound through different solvents; specifically, when the solvent is acetonitrile, the bromohydrazide compound is obtained through one-step reaction, and the yield of the bromohydrazide compound can be improved by adding tetrabutylammonium bromide; when the solvent is N, N-dimethylformamide, tetrabutylammonium bromide is not added, and the bromine-free hydrazide compound is obtained by one-step reaction, wherein the specific reaction formulas are as follows:

after the cross-coupling reaction is completed, the product system is preferably purified, the purification mode is preferably chromatographic separation, and the eluent used for the chromatographic separation is preferably a mixed solvent of petroleum ether and ethyl acetate; the volume ratio of the petroleum ether to the ethyl acetate in the mixed solvent is preferably 1-30: 1, more preferably 5-20: 1, more preferably 5: 1. the present invention has no special limitation on the specific process of the column chromatography, and the method is well known to those skilled in the art. According to the invention, petroleum ether and ethyl acetate are used as eluent to purify the mixed solution after the cross dehydrogenation coupling reaction, so that the hydrazide compound with higher purity can be obtained.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the following examples, the mole percentages of the iridium composite photocatalyst and tetrabutylammonium bromide are relative to the mole percentage of the aldehyde compound;

example 1

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 85%, and the purity is 99.9%.

The structure of the product obtained was characterized, and the structural characterization data were as follows:

¹HNMR(400MHz,DMSO-d₆,ppm)δ10.74(s,1H),7.90-7.92(m,2H),7.57-7.62(m,1H),7.51(t,J＝8.0Hz,2H),7.35(d,J＝8.0Hz,2H),6.77(d,J＝8.0Hz,2H),3.20(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.4,149.2,132.6,131.9,131.4,128.5,127.4,114.3,109.4,40.2；MS(EI,70eV)：m/z304,199,185,155,105.HRMS(ESI)calcdC₁₄H₁₄BrN₂O[M+H]⁺m/z305.0284,foundm/z305.0280.

according to the data, the obtained product is a target product, and the structure of the target product is shown as the formula (1):

example 2

To the reaction tube were added 0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-tolualdehyde, 1 mol% Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 79%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.65(s,1H),7.80(d,J＝8.0Hz,2H),7.30-7.35(m,4H),6.75(d,J＝8.0Hz,2H),3.18(s,3H),2.37(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.3,149.3,141.9,131.4,129.8,129.0,127.4,114.3,109.3,40.2,21.0.MS(EI,70eV)m/z 318,199,185,155,119.HRMS(ESI)calcd C₁₅H₁₆BrN₂O[M+H]⁺m/z 319.0441,found m/z319.0457.

according to the data, the obtained product is a target product, and the structure of the target product is shown as the formula (2):

example 3

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-methoxybenzaldehyde and 1 mol% of Ir [ dF (CF) were put into a reaction tube₃)ppy]₂(dtbpy)PF₆35mol percent of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile, stirring and reacting for 12h under the irradiation of a 465nm light source, and reacting byAnd (4) performing chromatography, separation and purification, wherein the volume ratio of the petroleum ether to the ethyl acetate in the eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 71%, and the purity is 99.9%.

The structure of the resulting product was characterized and the structural characterization data is as follows:

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.60(s,1H),7.88(d,J＝8.0Hz,2H),7.34(d,J＝8.0Hz,2H),7.04(d,J＝8.0Hz,2H),6.75(d,J＝8.0Hz,2H),3.82(s,3H),3.18(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.9,162.1,149.4,131.4,129.3,124.8,114.3,113.7,109.2,55.4,40.2.MS(EI,70eV)m/z 334,199,185,155,135,107.HRMS(ESI)calcd C₁₅H₁₆BrN₂O₂[M+H]⁺m/z 335.0390,foundm/z 335.0406.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as the formula (3):

example 4

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-hydroxybenzaldehyde and 1 mol% of Ir [ dF (CF) were added to the reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 3:1, so that the purified target product is obtained, the yield is 65%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.49(s,1H),10.12(s,1H),7.77(d,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,2H),6.84(d,J＝8.0Hz,2H),6.73(d,J＝8.0Hz,2H),3.17(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.1,160.7,149.4,131.4,129.4,123.2,115.0,114.2,109.1,40.2.HRMS(ESI)calcd C₁₄H₁₄BrN₂O₂[M+H]⁺m/z 321.0233,found m/z 321.0224.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as the formula (4):

example 5

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-fluorobenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 80%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.76(s,1H),7.98(dd,J＝8.0,4.0Hz,2H),7.33-7.37(m,4H),6.77(d,J＝8.0Hz,2H),3.19(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.5,164.5,163.0,149.2,131.4,130.2,130.1,129.1,129.1,115.6,115.4,114.4,109.5,40.2.MS(EI,70eV)m/z 322,199,183,155,123,105.HRMS(ESI)calcd C₁₄H₁₃BrFN₂O[M+H]⁺m/z 323.0190,found m/z 323.0204.

according to the data, the obtained product is a target product, and the structure of the target product is shown as the formula (5):

example 6

To the reaction tube were added 0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-trifluoromethylbenzaldehyde, and 1 mol% of Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 85%, and the purity is 99.9%.

¹HNMR(400MHz,DMSO-d₆,ppm)δ10.95(s,1H),8.10(d,J＝8.0Hz,2H),7.90(d,J＝8.0Hz,2H),7.36(d,J＝12.0Hz,2H),6.80(d,J＝8.0Hz,2H),3.21(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.4,149.0,136.5,131.9,131.6,131.5,130.1,128.4,125.6,125.5,125.5,125.5,125.2,122.5,114.5,109.7,40.1.MS(EI,70eV)m/z 372,199,185,172,145,120；HRMS(ESI)calcd C₁₅H₁₃BrF₃N₂O[M+H]⁺m/z 373.0158,found m/z 373.0152.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as the formula (6):

example 7

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-chlorobenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 63%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.82(s,1H),7.93(d,J＝12.0Hz,2H),7.59(d,J＝8.0Hz,2H),7.35(d,J＝8.0Hz,2H),6.77(d,J＝8.0Hz,2H),3.19(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.5,149.1,136.7,131.4,131.4,129.3,128.6,114.4,109.5,40.1.MS(EI,70eV)m/z 340,199,183,155,139.HRMS(ESI)calcd C₁₄H₁₃BrClN₂O[M+H]⁺m/z 338.9894,found m/z338.9887.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (7):

example 8

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-bromobenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 65%, and the purity is 99.9%.

¹HNMR(400MHz,DMSO-d₆,ppm)δ10.81(s,1H),7.84(d,J＝8.0Hz,2H),7.73(d,J＝8.0Hz,2H),7.35(d,J＝12.0Hz,2H),6.77(d,J＝8.0Hz,2H),3.18(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.6,149.1,131.8,131.6,131.4,129.5,125.7,114.4,109.5,40.1.MS(EI,70eV)m/z 384,199,183,155,104.HRMS(ESI)calcd C₁₄H₁₃Br₂N₂O[M+H]⁺m/z 382.9389,found m/z382.9381.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (8):

example 9

To the reaction tube were added 0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-esterbenzaldehyde, 1 mol% Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 3:1, so that the purified target product is obtained, the yield is 65%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.91(s,1H),8.05(q,J＝8.0Hz,4H),7.36(d,J＝12.0Hz,2H),6.79(d,J＝8.0Hz,2H),3.89(s,3H),3.20(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.6,164.7,149.0,136.8,132.3,131.4,129.3,127.8,114.4,109.6,52.4,40.1.MS(EI,70eV)m/z 362,333,281,199,185,163,135.HRMS(ESI)calcd C₁₆H₁₆BrN₂O₃[M+H]⁺m/z 363.0339,found m/z 363.0334.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (9):

example 10

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-cyanobenzaldehyde and 1 mol% of Ir [ dF (CF) were charged in a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 61%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.96(s,1H),8.02(q,J＝8.0Hz,4H),7.35(d,J＝8.0Hz,2H),6.79(d,J＝8.0Hz,2H),3.19(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.2,149.0,136.7,132.6,131.5,128.3,118.2,114.5,114.2,109.7,40.1.MS(EI,70eV)m/z 329,199,185,157,130.HRMS(ESI)calcd C₁₅H₁₃BrN₃O⁺[M+H]⁺m/z 330.0237,found m/z 330.0245.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (10):

example 11

To the reaction tube were added 0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of m-tolualdehyde, 1 mol% Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 72%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.67(s,1H),7.73(s,1H),7.68-7.71(m,1H),7.39-7.40(m,2H),7.35(d,J＝8.0Hz,2H),6.76(d,J＝8.0Hz,2H),3.18(s,3H),2.37(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.6,149.2,137.8,132.7,132.4,131.4,128.4,127.9,124.5,114.3,109.3,40.2,20.9；MS(EI,70eV)m/z 318,201,183,155,119.HRMS(ESI)calcd C₁₅H₁₆BrN₂O[M+H]⁺m/z 319.0441,found m/z 319.0455.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (11):

example 12

To the reaction tube were added 0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of m-methoxybenzaldehyde, and 1 mol% Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 73%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.73(s,1H),7.49(d,J＝8.0Hz,1H),7.40-7.46(m,2H),7.35(d,J＝8.0Hz,2H),7.16(dd,J＝8.0Hz,4.0Hz,1H),6.77(d,J＝8.0Hz,2H),3.82(s,3H),3.19(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.2,159.3,149.2,134.0,131.4,129.7,119.6,117.8,114.3,112.5,109.4,55.3,40.2.MS(EI,70eV)m/z 334,199,185,152,135,107.HRMS(ESI)calcd C₁₅H₁₆BrN₂O₂[M+H]⁺m/z 335.0390,found m/z 335.0406.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as a formula (12):

example 13

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of m-hydroxybenzaldehyde, 1 mol% Ir [ dF (CF) were charged into a reaction tube₃)ppy]₂(dtbpy)PF₆35mol percent of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile, stirring and reacting for 12 hours under the irradiation of a 465nm light source, and separating pure ammonium bromide through chromatographic separation after the reaction is finishedAnd (3) carrying out column chromatography on the eluent, wherein the volume ratio of the petroleum ether to the ethyl acetate is 5:1, so as to obtain the purified target product, wherein the yield is 74%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.62(s,1H),9.76(s,1H),7.35(d,J＝12.0Hz,2H),7.27-7.32(m,3H),6.97(dd,J＝8.0Hz,4.0Hz,1H),6.75(d,J＝8.0Hz,2H),3.17(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.6,157.5,149.3,134.1,131.4,129.6,118.8,117.8,114.3,114.3,109.4,40.2.HRMS(ESI)calcd C₁₄H₁₄BrN₂O₂[M+H]⁺m/z 321.0233,found m/z 321.0228.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (13):

example 14

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of m-fluorobenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 84%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.84(s,1H),7.77(d,J＝8.0Hz,1H),7.70(dd,12.0Hz,4.0Hz,1H),7.57(td,J＝8.0Hz,4.0Hz,1H),7.45(t,J＝8.0Hz,1H),7.35(d,J＝8.0Hz,2H),6.79(d,J＝12.0Hz,2H),3.20(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.2,164.2,163.2,160.7,149.1,135.0,134.9,131.4,130.8,130.7,123.6,123.6,118.9,118.7,114.4,114.4,114.1,109.6,40.1.MS(EI,70eV)m/z 322,199,183,155,123,105.HRMS(ESI)calcd C₁₄H₁₃BrFN₂O[M+H]⁺m/z 323.0190,found m/z 323.0205.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (14):

example 15

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of m-chlorobenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 80%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.85(s,1H),7.95(s,1H),7.86(dd,J＝8.0Hz,4.0Hz,1H),7.68(dd,J＝8.0Hz,4.0Hz,1H),7.56(t,J＝8.0Hz,1H),7.36(d,J＝8.0Hz,2H),6.79(d,J＝8.0Hz,2H),3.19(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.2,149.1,134.7,133.4,131.7,131.4,130.6,127.2,126.2,114.5,109.6,40.1.MS(EI,70eV)m/z 340,199,185,155,139.

HRMS(ESI)calcd C₁₄H₁₃BrClN₂O[M+H]⁺m/z 338.9894,found m/z338.9911.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (15):

example 16

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of o-methylbenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 72%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.42(s,1H),7.48(d,J＝8.0Hz,1H),7.37-7.41(m,3H),7.30(d,J＝8.0Hz,2H),6.82(d,J＝8.0Hz,2H),3.20(s,3H),2.38(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ168.1,149.2,135.8,134.6,131.5,130.6,130.0,127.3,125.7,114.4,109.5,40.2,19.3.MS(EI,70eV)m/z 320,199,185,155,136,119.HRMS(ESI)calcd C₁₅H₁₆BrN₂O[M+H]⁺m/z 319.0441,found m/z 319.0454.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (16):

example 17

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of o-hydroxybenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 77%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ11.76(s,1H),10.77(s,1H),7.86(d,J＝8.0Hz,1H),7.44(t,J＝8.0Hz,1H),7.36(d,J＝8.0Hz,2H),7.00-6.89(m,2H),6.79(d,J＝8.0Hz,2H),3.20(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ167.9,159.1,148.9,134.0,131.5,128.2,119.0,117.3,115.2,114.4,109.6,40.1.HRMS(ESI)calcd C₁₄H₁₄BrN₂O₂[M+H]⁺m/z 321.0233,found m/z321.0247.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (17):

example 18

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of o-bromobenzaldehyde and 1 mol% of Ir [ dF (CF) were added to the reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 73%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.57(s,1H),7.71(d,J＝8.0Hz,1H),7.57(d,J＝8.0Hz,1H),7.50(t,J＝8.0Hz,1H),7.43(t,J＝8.0Hz,1H),7.38(d,J＝12.0Hz,2H),6.88(d,J＝8.0Hz,2H),3.21(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ166.3,148.9,136.9,132.8,131.5,131.4,129.1,127.7,119.2,114.6,109.7,40.0.MS(EI,70eV)m/z 384,199,185,155,105.HRMS(ESI)calcd C₁₄H₁₃Br₂N₂O[M+H]⁺m/z 382.9389,found m/z 382.9385.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (18):

example 19

To the reaction tube were added 0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-fluorom-tolualdehyde, 1 mol% Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 76%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.70(s,1H),7.86(d,J＝8.0Hz,1H),7.76-7.80(m,1H),7.34(d,J＝8.0Hz,2H),7.27(t,J＝8.0Hz,1H),6.76(d,J＝8.0Hz,2H),3.18(s,3H),2.29(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.6,164.0,161.5,149.2,131.4,131.2,131.2,128.8,128.8,127.4,127.3,124.7,124.5,115.2,115.0,114.4,109.4,40.2,14.1,14.1.MS(EI,70eV)m/z 336,199,183,155,137,109；HRMS(ESI)calcd C₁₅H₁₅BrFN₂O[M+H]⁺m/z 337.0346,found m/z 337.0343.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (19):

example 20

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-fluoro-o-chlorobenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆35mol percent of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile under the irradiation of a light source of 465nm,stirring and reacting for 12h, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the chromatography is 5:1, so that the purified target product is obtained, the yield is 71%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.60(s,1H),7.69(t,J＝8.0Hz,1H),7.58(dd,J＝8.0Hz,4.0Hz,1H),7.38(d,J＝12.0Hz,2H),7.34(dd,J＝8.0Hz,4.0Hz,1H),6.86(d,J＝8.0Hz,2H),3.19(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.7,163.7,161.2,148.8,131.8,131.7,131.4,131.4,131.0,130.9,117.3,117.1,114.7,114.6,114.5,109.8,40.1.MS(EI,70eV)m/z358,199,185,157,129.

HRMS(ESI)calcd C₁₄H₁₂BrClFN₂O[M+H]⁺m/z 356.9800,found m/z356.9815.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (20):

example 21

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-hydroxym-methoxybenzaldehyde and 1 mol% of Ir [ dF (CF) were put in a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 57%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.52(s,1H),9.71(s,1H),7.47(d,J＝4.0Hz,1H),7.41(dd,J＝8.0Hz,4.0Hz,1H),7.34(d,J＝8.0Hz,2H),6.85(d,J＝8.0Hz,1H),6.74(d,J＝8.0Hz,2H),3.82(s,3H),3.17(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.0,150.1,149.4,147.3,131.4,123.4,121.0,115.0,114.3,111.3,109.2,55.7,40.2.HRMS(ESI)calcd C₁₅H₁₆BrN₂O₃[M+H]⁺m/z 351.0339,found m/z 351.0355.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as a formula (21):

example 22

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of thiophenecarboxaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 58%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.59(s,1H),8.25(d,J＝4.0Hz,1H),7.65(dd,J＝8.0Hz,4.0Hz,1H),7.55(d,J＝4.0Hz,1H),7.35(d,J＝12.0Hz,2H),6.76(d,J＝12.0Hz,2H),3.18(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ161.2,149.2,135.4,131.4,129.7,127.2,126.6,114.3,109.4,40.2.MS(EI,70eV)m/z 312,199,185,155,111.HRMS(ESI)calcd C₁₂H₁₂BrN₂OS[M+H]⁺m/z 310.9848,found m/z 310.9844.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as a formula (22):

example 23

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of pyrazolecarboxaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 53%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.33(s,1H),8.20(s,1H),7.91(s,1H),7.33(d,J＝8.0Hz,2H),6.73(d,J＝12.0Hz,2H),3.87(s,3H),3.16(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ161.1,149.4,138.5,132.4,131.4,116.0,114.3,109.3,40.4,38.8.HRMS(ESI)calcd C₁₂H₁₄BrN₄O[M+H]⁺m/z309.0346,found m/z 309.0342.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (23):

example 24

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-pyrazole benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 68%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.80(s,1H),8.63(d,J＝4.0Hz,1H),8.01(q,J＝8.0Hz,4H),7.81(d,J＝4.0Hz,1H),7.36(d,J＝8.0Hz,2H),6.79(d,J＝8.0Hz,2H),6.60(d,J＝4.0,1.7Hz,1H),3.21(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.7,149.2,142.0,141.8,131.4,129.9,129.0,128.2,117.9,114.4,109.5,108.5,40.2.HRMS(ESI)calcd C₁₇H₁₆BrN₄O[M+H]⁺m/z 371.0502,found m/z 371.0522.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (24):

example 25

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of benzothiophenecarboxaldehyde and 1 mol% of Ir [ dF (CF) were added to the reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 48%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.72(s,1H),8.54(s,1H),8.39-8.41(m,1H),8.06-8.09(m,1H),7.43-7.47(m,2H),7.36(d,J＝12.0Hz,2H),6.83(d,J＝8.0Hz,2H),3.24(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ162.3,149.3,139.4,137.1,131.8,131.4,128.5,125.1,125.0,124.2,122.8,114.4,109.5,40.3；MS(EI,70eV)m/z 362,281,207,185,161.HRMS(ESI)calcd C₁₆H₁₄BrN₂OS[M+H]⁺m/z 361.0005,found m/z 361.0005.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (25):

example 26

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of isovaleraldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 39%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.00(s,1H),7.32(d,J＝8.0Hz,2H),6.68(d,J＝12.0Hz,2H),3.06(s,3H),2.01(s,3H),0.92(d,J＝8.0Hz,6H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ170.6,149.1,131.3,114.2,109.2,42.4,40.1,25.4,22.3.MS(EI,70eV)m/z 286,200,185,155,105.HRMS(ESI)calcd C₁₂H₁₈BrN₂O[M+H]⁺m/z 285.0597,found m/z 285.0609.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (26):

example 27

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of heptanal, and 1 mol% Ir [ dF (CF) were put in a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, the purified target product is obtained, and the yield is 36%The purity was 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ9.98(s,1H),7.31(d,J＝12.0Hz,2H),6.67(d,J＝12.0Hz,2H),3.05(s,3H),2.12(t,J＝8.0Hz,2H),1.23-1.30(m,8H),0.87(t,J＝8.0Hz,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ171.3,149.2,131.3,114.2,109.2,40.2,33.2,30.9,28.3,24.9,22.0,13.9.MS(EI,70eV)m/z 314,200,185,155,105.HRMS(ESI)calcd C₁₄H₂₂BrN₂O[M+H]⁺m/z 313.0910,found m/z 313.0907.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (27):

example 28

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of cyclohexanecarboxaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 39%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ9.94(s,1H),7.31(d,J＝12.0Hz,2H),6.66(d,J＝8.0Hz,2H),3.04(s,3H),2.12-2.20(m,1H),1.71-1.77(m,4H),1.14-1.40(m,6H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ174.1,149.2,131.3,114.1,109.1,42.0,40.2,28.9,25.4,25.1.MS(EI,70eV)m/z 310,200,185,155,105.HRMS(ESI)calcd C₁₄H₂₀BrN₂O[M+H]⁺m/z 311.0754,found m/z 311.0751.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as the formula (28):

example 29

To the reaction tube were added 0.3mmol of 1-methyl-1-o-tolylhydrazine, 0.1mmol of benzaldehyde, and 1 mol% of Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 86%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.32(s,1H),7.81(d,J＝8.0Hz,2H),7.54(t,J＝8.0Hz,1H),7.46(t,J＝8.0Hz,2H),7.29-7.34(m,2H),7.12(d,J＝8.0Hz,1H),3.05(s,3H),2.21(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.1,147.9,132.7,132.5,132.5,131.0,128.1,127.9,126.8,119.3,113.9,41.2,18.0.MS(EI,70eV)m/z 318,215,199,171,117,105.HRMS(ESI)calcd C₁₅H₁₆BrN₂O⁺[M+H]⁺m/z 319.0441,found m/z 319.0433.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as a formula (29):

example 30

0.3mmol of 1-methyl-1-o-methoxyphenylhydrazine, 0.1mmol of benzaldehyde, and 1 mol% of Ir [ dF (CF) were put into a reaction tube₃)ppy]₂(dtbpy)PF₆35 mol% tetrabutylammonium bromide, 0.15mmol of trichlorobromineAnd (2) stirring methane and 1mL acetonitrile under the irradiation of a 465nm light source for reaction for 12 hours, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in column chromatography eluent is 5:1, so that the purified target product is obtained, the yield is 70%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.37(s,1H),7.83(dd,J＝8.0Hz,4.0Hz,2H),7.54(t,J＝8.0Hz,1H),7.47(t,J＝8.0Hz,2H),7.09(s,1H),7.04(d,J＝8.0Hz,1H),6.95(d,J＝12.0Hz,1H),3.79(s,3H),3.14(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.8,151.1,139.2,133.3,131.4,128.3,127.3,122.9,118.9,115.2,113.5,56.0,42.1.MS(EI,70eV)m/z 318,215,199,171,117,105.HRMS(ESI)calcd C₁₅H₁₆BrN₂O₂ ⁺[M+H]⁺m/z 335.0390,found m/z 335.0385.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (30):

example 31

0.3mmol of 1-methyl-1-o-fluorophenylhydrazine, 0.1mmol of benzaldehyde, and 1 mol% of Ir [ dF (CF) were put into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 70%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.74(s,1H),7.84(dd,J＝8.0Hz,4.0Hz,2H),7.57(t,J＝8.0Hz,1H),7.48(t,J＝8.0Hz,2H),7.39(dd,J＝8.0Hz,4.0Hz,1H),7.27(dd,J＝8.0Hz,4.0Hz,1H),7.01(t,8.0Hz,1H),3.20(d,J＝4.0Hz,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.1,153.4,150.9,137.9,137.8,132.7,131.8,128.5,127.3,127.3,127.2,119.4,119.2,119.2,111.3,111.2,41.9,41.8.MS(EI,70eV)m/z 324,217,203,190,105.HRMS(ESI)calcd C₁₄H₁₃BrFN₂O[M+H]⁺m/z 323.0190,found m/z 323.0186.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as a formula (31):

example 32

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of 3-methylbut-2-enal, and 1 mol% Ir [ dF (CF) were added to the reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 35%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)9.92(s,1H),7.32(d,J＝8.0Hz,2H),6.66(d,J＝12.0Hz,2H),5.69(s,1H),3.08(s,3H),2.08(s,3H),1.83(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.1,151.9,149.2,131.3,116.1,114.1,109.0,40.2,27.0,19.5.MS(EI,70eV)m/z 310,200,185,155,105.HRMS(ESI)calcd C₁₂H₁₆BrN₂O⁺[M+H]⁺m/z 283.0441,found m/z 283.0434.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (32):

example 33

To the reaction tube were added 0.3mmol of 1-methyl-1-m-tolylhydrazine, 0.1mmol of benzaldehyde, and 1 mol% of Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 63%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.71(s,1H),7.90(dd,J＝8.0Hz,4.0Hz,2H),7.59(t,J＝8.0Hz,1H),7.51(t,J＝8.0Hz,2H),7.34(d,J＝8.0Hz,1H),6.80(d,J＝4.0Hz,1H),6.59(dd,J＝8.0Hz,4.0Hz,1H),3.19(s,3H),2.28(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.5,149.5,137.2,132.7,132.1,131.9,128.5,127.4,114.7,112.1,112.0,40.2,22.8.MS(EI,70eV)m/z 318,213,187,169,105.HRMS(ESI)calcd C₁₅H₁₆BrN₂O[M+H]⁺m/z319.0441,found m/z 319.0436.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (33):

example 34

Is added into a reaction tube0.3mmol of 1-methyl-1-m-bromophenylhydrazine, 0.1mmol of benzaldehyde, 1 mol% of Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 73%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.83(s,1H),7.91(d,J＝8.0Hz,2H),7.60(t,J＝8.0Hz,1H),7.52(t,J＝8.0Hz,3H),7.11(s,1H),6.77(dd,J＝8.0Hz,4.0Hz,1H),3.21(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.4,150.3,133.5,132.4,132.0,128.6,127.4,124.2,116.4,113.5,110.9,40.1.MS(EI,70eV)m/z 384,279,263,235,155,105.HRMS(ESI)calcd C₁₄H₁₃Br₂N₂O[M+H]⁺m/z 382.9389,found m/z 382.9384.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (34):

example 35

0.3mmol of 1-butyl-1-phenylhydrazine, 0.1mmol of benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 74%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.54(s,1H),7.91(d,J＝8.0Hz,2H),7.60(t,J＝8.0Hz,1H),7.52(t,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,2H),6.76(d,J＝12.0Hz,2H),3.49(t,J＝8.0Hz,2H),1.54-1.62(m,2H),1.34-1.44(m,2H),0.90(t,J＝8.0Hz,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.6,148.6,132.7,131.8,131.4,128.5,127.4,114.2,108.9,51.0,28.8,19.6,13.9.MS(EI,70eV)m/z 346,303,227,199,157,105.HRMS(ESI)calcd C₁₇H₂₀BrN₂O[M+H]⁺m/z 347.0754,found m/z 347.0750.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (35):

example 36

0.3mmol of 1-propyl-1-phenylhydrazine, 0.1mmol of benzaldehyde, and 1 mol% of Ir [ dF (CF) were put into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting 35 mol% of tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile for 12 hours under the irradiation of a 465nm light source, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 74%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.55(s,1H),7.92(d,J＝4.0Hz,2H),7.60(t,J＝8.0Hz,4.0Hz,1H),7.51(t,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,2H),6.77(d,J＝8.0Hz,2H),3.46(t,J＝8.0Hz,2H),1.59-1.64(m,2H),0.95(t,J＝8.0Hz,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.6,148.7,132.7,131.9,131.4,128.5,127.4,114.2,109.0,53.0,20.0,11.3.MS(EI,70eV)m/z 332,303,227,211,185,155,132,105.HRMS(ESI)calcd C₁₆H₁₈BrN₂O[M+H]⁺m/z 333.0597,found m/z 333.0613.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (36):

example 37

0.3mmol of 1-isopropyl-1-phenylhydrazine, 0.1mmol of benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆Stirring and reacting for 12 hours under the irradiation of a 465nm light source, 35 mol% tetrabutylammonium bromide, 0.15mmol trichlorobromomethane and 1mL acetonitrile, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, obtaining the purified target product with the yield of 65 percent and the purity of 99.9 percent.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.10(s,1H),7.93(d,J＝8.0Hz,2H),7.60(t,J＝8.0Hz,1H),7.52(t,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,2H),6.74(d,J＝8.0Hz,2H),4.21-4.27(m,1H),1.15(d,J＝4.0Hz,6H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ166.9,147.3,132.9,131.8,131.5,128.5,127.6,114.5,108.6,49.8.MS(EI,70eV)m/z 334,275,229,213,199,185,155,105.HRMS(ESI)calcd C₁₆H₁₈BrN₂O⁺[M+H]⁺m/z 333.0597,found m/z333.0590.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as a formula (37):

example 38

0.3mmol of 1-ethyl-1-m-methylphenylhydrazine, 0.1mmol of benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆35 mol% tetrabutylammonium bromide, 0.15mmol of trichlorobromomethane and 1mL of acetonitrile at 465nmStirring and reacting for 12h under source irradiation, separating and purifying by chromatography after the reaction is finished, wherein the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 61%, and the purity is 99.9%.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.50(s,1H),7.92(d,J＝8.0Hz,2H),7.60(t,J＝8.0Hz,1H),7.51(t,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,1H),6.81(d,J＝4.0Hz,1H),6.60(dd,J＝8.0Hz,4.0Hz,1H),3.55(q,J＝8.0Hz,2H),2.27(s,3H),1.16(t,J＝8.0Hz,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.8,148.6,137.2,132.8,132.2,131.8,128.5,127.4,114.7,112.1,111.9,45.4,22.8,11.9；MS(EI,70eV)m/z 346,303,227,199,157,105.HRMS(ESI)calcd C₁₆H₁₈BrN₂O[M+H]⁺m/z 333.0597,found m/z 333.0594.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (38):

example 39

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of adamantanecarboxaldehyde and 1 mol% of Ir [ dF (CF) were put in a reaction tube₃)ppy]₂(dtbpy)PF₆0.15mmol of trichlorobromomethane and 1mLN, N-dimethylformamide are stirred and reacted for 6 hours under the irradiation of a light source with the wavelength of 465nm, after the reaction is finished, the reaction product is separated and purified by chromatography, and the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 51 percent, and the purity is 99.9 percent.

¹H NMR(400MHz,DMSO-d₆,ppm)δ9.68(s,1H),7.17(t,J＝8.0Hz,2H),6.69-6.72(m,3H),3.04(s,3H),1.98-2.00(m,3H),1.86(d,J＝4.0Hz,6H),1.68-1.69(m,6H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ175.6,150.1,128.7,117.7,111.9,40.0,39.4,38.4,36.1,27.6.MS(EI,70eV)m/z 284,180,135,121,105,93.HRMS(ESI)calcd C₁₈H₂₅N₂O⁺[M+H]⁺m/z 285.1961,found m/z 285.1959.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (39):

example 40

Into the reaction tube were added 0.3mmol of 3, 4-dihydroisoquinoline-2 (1H) -amine, 0.1mmol of benzaldehyde, 1 mol% of Ir [ dF (CF)₃)ppy]₂(dtbpy)PF₆0.15mmol of trichlorobromomethane and 1mLN, N-dimethylformamide are stirred and reacted for 6 hours under the irradiation of a light source of 465nm, after the reaction is finished, the reaction product is separated and purified by chromatography, and the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 35 percent, and the purity is 99.9 percent.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.52(s,1H),7.91(dd,J＝8.0Hz,4.0Hz,2H),7.59(t,J＝8.0Hz,1H),7.51(t,J＝8.0Hz,2H),6.95-6.99(m,2H),6.61-6.66(m,2H),3.50(s,2H),2.75(t,J＝8.0Hz,2H),2.00-2.06(m,2H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.9,146.4,133.5,132.2,129.2,129.0,127.8,127.2,122.5,118.4,112.1,50.9,27.2,22.4；MS(EI,70eV)m/z252,207,147,105,77.HRMS(ESI)calcd C₁₆H₁₆NO⁺[M+H]⁺m/z 253.1335,found m/z 253.1335.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (40):

EXAMPLE 41

0.3mmol of 1-methyl-1-p-methylphenylhydrazine, 0.1mmol of benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆0.15mmol of trichlorobromomethane and 1mLN, N-dimethylformamide are stirred and reacted for 6 hours under the irradiation of a light source of 465nm, after the reaction is finished, the reaction product is separated and purified by chromatography, and the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 45 percent, and the purity is 99.9 percent.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.58(s,1H),7.91(d,J＝8.0Hz,2H),7.58(t,J＝8.0Hz,1H),7.50(t,J＝8.0Hz,2H),7.02(d,J＝8.0Hz,2H),6.74(d,J＝8.0Hz,2H),3.18(s,3H),2.20(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.4,147.9,133.0,131.7,129.3,128.4,127.3,126.8,112.5,40.3,20.0.MS(EI,70eV)m/z 240,135,119,105,91,77.HRMS(ESI)calcd C₁₅H₁₇N₂O⁺[M+H]⁺m/z 241.1335,found m/z 241.1335.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as a formula (41):

example 42

0.3mmol of 1-methyl-1-p-chlorophenylhydrazine, 0.1mmol of benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆0.15mmol of trichlorobromomethane and 1mLN, N-dimethylformamide, under the irradiation of a 465nm light source, stirring and reacting for 6h, after the reaction is finished, separating and purifying by chromatography, wherein the volume ratio of petroleum ether to ethyl acetate in the eluent of the column chromatography is 5:1, obtaining the purified target product with the yield of 40 percent and the purity of 99.9 percent.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.71(s,1H),7.90(dd,J＝8.0Hz,4.0Hz,2H),7.59(t,J＝8.0Hz,1H),7.51(t,J＝8.0Hz,2H),7.23(d,J＝8.0Hz,2H),6.82(d,J＝8.0Hz,2H),3.20(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.5,148.8,132.7,131.8,128.5,128.5,127.3,121.8,113.8,40.2.MS(EI,70eV)m/z 260,224,155,139,105,77.HRMS(ESI)calcd C₁₄H₁₄ClN₂O⁺[M+H]⁺m/z 261.0789,found m/z 261.0789.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (42):

example 43

0.3mmol of 1-methyl-1-o-chlorophenylhydrazine, 0.1mmol of benzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆0.15mmol of trichlorobromomethane and 1mLN, N-dimethylformamide are stirred and reacted for 6 hours under the irradiation of a light source of 465nm, after the reaction is finished, the reaction product is separated and purified by chromatography, and the volume ratio of petroleum ether to ethyl acetate in eluent of the column chromatography is 5:1, so that the purified target product is obtained, the yield is 46 percent, and the purity is 99.9 percent.

¹HNMR(400MHz,DMSO-d₆,ppm)δ10.52(s,1H),7.83(d,J＝8.0Hz,2H),7.53(d,J＝8.0Hz,1H),7.46(t,J＝8.0Hz,2H),7.26-7.36(m,3H),7.00(t,J＝8.0Hz,1H),3.17(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ164.7,147.1,133.2,131.5,130.5,128.4,127.4,127.4,125.0,123.5,120.0,41.7.MS(EI,70eV)m/z260,224,155,139,105,77.HRMS(ESI)calcdC₁₄H₁₄ClN₂O⁺[M+H]⁺m/z261.0789,foundm/z261.0788.

according to the analysis of the data, the obtained product is a target product, and the structure of the target product is shown as a formula (43):

example 44

0.3mmol of 1-methyl-1-phenylhydrazine, 0.1mmol of p-fluorobenzaldehyde and 1 mol% of Ir [ dF (CF) are added into a reaction tube₃)ppy]₂(dtbpy)PF₆0.15mmol of trichlorobromomethane and 1mLN, N-dimethylformamide, under the irradiation of a 465nm light source, stirring and reacting for 6h, after the reaction is finished, separating and purifying by chromatography, wherein the volume ratio of petroleum ether to ethyl acetate in the eluent of the column chromatography is 5:1, obtaining the purified target product with the yield of 55 percent and the purity of 99.9 percent.

¹H NMR(400MHz,DMSO-d₆,ppm)δ10.67(s,1H),7.98(dd,J＝8.0Hz,4.0Hz,2H),7.35(t,J＝8.0Hz,2H),7.21(t,J＝8.0Hz,2H),6.82(d,J＝8.0Hz,2H),6.76(t,J＝8.0Hz,1H),3.20(s,3H).¹³C{¹H}NMR(100MHz,DMSO-d₆,ppm)δ165.4,164.5,162.9,149.9,130.1,130.0,129.4,129.4,128.9,118.3,115.6,115.4,112.3,40.1；MS(EI,70eV)m/z 244,214,123,121,105,77.HRMS(ESI)calcd C₁₄H₁₄FN₂O⁺[M+H]⁺m/z 245.1085,found m/z 245.1080.

according to the data analysis, the obtained product is a target product, and the structure of the target product is shown as the formula (44):

the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of hydrazide compounds is characterized by comprising the following steps:

the 1, 1-disubstituted hydrazine compound has a structure shown in a formula I:

2. The preparation method according to claim 1, wherein the molar ratio of the 1, 1-disubstituted hydrazine compound to the aldehyde compound is (1.5-3): 1.

3. The preparation method according to claim 1, wherein the molar ratio of the aldehyde compound to the iridium composite photocatalyst is 1 (0.01 to 0.003).

4. The preparation method according to claim 1, wherein the mixing process of the 1, 1-disubstituted hydrazine compound, the aldehyde compound, the iridium complex photocatalyst, the trichlorobromomethane and the polar organic solvent further comprises adding tetrabutylammonium bromide; the molar ratio of the aldehyde compound to the tetrabutylammonium bromide is 1 (0.35-0.5).

5. The method according to claim 1, wherein the molar ratio of the aldehyde compound to trichlorobromomethane is 1 (1-3).

6. The method according to claim 1, wherein the polar organic solvent comprises one or more selected from the group consisting of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, toluene, ethyl acetate, 1, 2-dichloroethane, acetonitrile, tetrahydrofuran and dichloromethane.

7. The method according to claim 1 or 6, wherein the ratio of the volume of the polar organic solvent to the amount of the aldehyde compound is 1L (0.1 to 0.2) mol.

8. The method according to claim 1, wherein the light source wavelength of the light is 200 to 1000 nm.

9. The preparation method according to claim 1 or 8, wherein the time of the cross-coupling reaction is 6-24 h.