Preparation method of N′,N′-diaryl hydrazide compounds

Abstract

The present invention belongs to the technical field of organic synthesis, and specifically relates to a preparation method of N',N'-diarylhydrazide compounds. The present invention provides a preparation method of N',N'-diarylhydrazide compounds, which comprises the following steps: mixing an arylhydrazine compound, an aldehyde compound, a catalyst, a base and a polar organic solvent, and carrying out a coupling addition reaction to obtain the N',N'-diarylhydrazide compound. The preparation method of the present invention has the advantages of mild conditions, easy control, high reaction efficiency, step economy, cheap and easily available raw materials, no use of oxidants, good functional group tolerance, etc., and the prepared N',N'-diarylhydrazide compounds have a high purity, with a purity of 98.5-99.9%, and have great market promotion value. Compared with multi-step synthesis reactions, the target product can be obtained by a one-step reaction in the present invention, and the reaction yield reaches 88%, having the advantages of high reaction efficiency and step economy.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing N′,N′-diaryl acylhydrazine compounds. Background Art

[0002] Derivatives of diaryl acylhydrazine are a class of important compounds with a wide range of applications. In pharmaceuticals, diaryl acylhydrazine is one of the most important skeletons. In addition, many aryl acylhydrazine scaffold drugs contain diaryl acylhydrazine derivatives and have a wide range of biological activities. For example, PGI2 (an anticoagulant drug) receptor agonists and neurokinin receptor antagonists. Due to their good biological activities and synthetic applications, the construction of the diaryl acylhydrazine skeleton has attracted great attention in recent years.

[0003] Currently, the methods for synthesizing diaryl acylhydrazine derivatives mainly include:

[0004] (a) Ji-Quan Zhang et al. (A, Ji Quan Zhang, et al. "Copper(ii)-catalyzed coupling reaction: an efficient and regioselective approach to N′,N′-diarylacylhydrazines 1." (2015).) reported that 1-benzoyl-2-phenylhydrazine generates N′,N′-diaryl acylhydrazine under the catalysis of copper acetate, such as:

[0005]

[0006] (b) Wei-juan Wang et al. (Wang, Wei-juan, Zhang, Ting, Duan, Li-jun, KO t -Bu promoted homocoupling and decomposition of N′-aryl acylhydrazines: synthesis of unsymmetric N′,N′-diaryl acylhydrazines[J]. Tetrahedron, 2015, 71(48):9073-9080. DOI:10.1016 / j.tet.2015.10.023.) reported that 1-benzoyl-2-phenylhydrazine generates N′,N′-diaryl acylhydrazine under the oxidation of potassium tert-butoxide and oxygen, such as:

[0007]

[0008] (c) Xiaodong Xiong et al. (Xiong Xiaodong, Jiang Yongwen, Ma Dawei. Assembly of N,N-disubstituted hydrazines and 1-aryl-1H-indazoles via copper-catalyzed coupling reactions. [J]. Cheminform, 2012, 43(38): 2552-2555. DOI: 10.1002 / chin.201238053.) found that 1-benzoyl-2-phenylhydrazine and aryl iodide reagents can generate N′,N′-diarylhydrazides under the catalysis of cuprous iodide, such as:

[0009]

[0010] However, the above method still has the defects of complex process, the need to use oxidants, and limited substrate scope. Summary of the Invention

[0011] The purpose of the present invention is to provide a method for preparing N′,N′-diarylhydrazide compounds. The method provided by the present invention has the advantages of simple process, mild conditions, no use of oxidants, and good functional group tolerance.

[0012] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0013] The present invention provides a method for preparing N′,N′-diarylhydrazide compounds, comprising the following steps:

[0014] Mix an arylhydrazine compound, an aldehyde compound, a catalyst, a base, and a polar organic solvent, and carry out a coupling addition reaction to obtain the N′,N′-diarylhydrazide compound;

[0015] The arylhydrazine compound has the structure shown in Formula I:

[0016]

[0017] R1 is an aryl group;

[0018] The aldehyde compound has the structure shown in Formula II:

[0019]

[0020] R2 is an aryl group or an alkyl group;

[0021] The N′,N′-diarylhydrazide compound has the structure shown in Formula III:

[0022]

[0023] Preferably, the arylhydrazine compounds include phenylhydrazine, 2-methylphenylhydrazine, 4-cyanophenylhydrazine, 2-fluorophenylhydrazine, 3-chlorophenylhydrazine, 4-bromophenylhydrazine, 4-trifluoromethylphenylhydrazine, 3,4-dimethylphenylhydrazine or 3,5-dichlorophenylhydrazine;

[0024] The aldehyde compounds include benzaldehyde, 2-methylbenzaldehyde, 2-methoxybenzaldehyde, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, terephthalaldehyde, 1-naphthaldehyde, 3-methyl-4-methoxybenzaldehyde, 4-pyridinecarboxaldehyde, 1-methyl-1H-pyrazole-4-carboxaldehyde, 4-pyrazol-1-ylbenzaldehyde, 3-thiophenecarboxaldehyde, furfural, ferrocenecarboxaldehyde, butyraldehyde, cyclopropanecarboxaldehyde, cyclohexanecarboxaldehyde, adamantanecarboxaldehyde, citronellal, piperonyl propionaldehyde, hydroxycitronellal or decanal.

[0025] Preferably, the catalyst includes a copper-containing compound;

[0026] The copper-containing compound includes one or more of copper acetate, copper chloride, copper bromide, copper trifluoromethanesulfonate, cuprous chloride and cuprous bromide.

[0027] Preferably, the base includes an inorganic base and / or an organic base;

[0028] The inorganic base includes one or more of potassium carbonate, potassium hydroxide and dipotassium hydrogen phosphate; the organic base includes 1,8-diazabicyclo[5.4.0]undec-7-ene and / or triethylamine.

[0029] Preferably, the polar organic solvent includes acetonitrile, tetrahydrofuran, dichloromethane and / or ethanol.

[0030] Preferably, the molar ratio of the arylhydrazine compound to the aldehyde compound is 1:1 to 2;

[0031] The molar ratio of the arylhydrazine compound to the catalyst is 1:0.1 to 0.5;

[0032] The molar ratio of the arylhydrazine compound to the base is 1:1 to 2;

[0033] The dosage ratio of the polar organic solvent to the arylhydrazine compound is 1 L:0.1 to 0.2 mol.

[0034] Preferably, the temperature of the coupling addition reaction is 0 °C and the time is 6 to 24 h.

[0035] The present invention provides a method for preparing N′,N′-diarylhydrazide compounds, comprising the following steps: mixing an arylhydrazine compound, an aldehyde compound, a catalyst, a base, and a polar organic solvent, and performing a coupling addition reaction to obtain the N′,N′-diarylhydrazide compound. The preparation method of the present invention has the advantages of mild conditions, easy control, high reaction efficiency, economical steps, cheap and easily available raw materials, no use of oxidants, good functional group tolerance, etc. Moreover, the prepared N′,N′-diarylhydrazide compound has a high purity, with a purity of 98.5-99.9%, and has great market promotion value. Compared with multi-step synthesis reactions, the target product can be obtained in one step in the present invention, and the reaction yield reaches 88%, having the advantages of high reaction efficiency and economical steps. Detailed Embodiments

[0036] The present invention provides a method for preparing N′,N′-diarylhydrazide compounds, comprising the following steps:

[0037] Mixing an arylhydrazine compound, an aldehyde compound, a catalyst, a base, and a polar organic solvent, and performing a coupling addition reaction to obtain the N′,N′-diarylhydrazide compound;

[0038] The arylhydrazine compound has the structure shown in Formula I:

[0039]

[0040] R1 is an aryl group;

[0041] The aldehyde compound has the structure shown in Formula II:

[0042]

[0043] R2 is an aryl group or an alkyl group;

[0044] The N′,N′-diarylhydrazide compound has the structure shown in Formula III:

[0045]

[0046] In the present invention, unless otherwise specified, all preparation raw materials are commercially available products well-known to those skilled in the art.

[0047] In the present invention, the arylhydrazine compound preferably includes phenylhydrazine, 2-methylphenylhydrazine, 4-cyanophenylhydrazine, 2-fluorophenylhydrazine, 3-chlorophenylhydrazine, 4-bromophenylhydrazine, 4-trifluoromethylphenylhydrazine, 3,4-dimethylphenylhydrazine, or 3,5-dichlorophenylhydrazine.

[0048] In the present invention, the aldehyde compounds preferably include benzaldehyde, 2-methylbenzaldehyde, 2-methoxybenzaldehyde, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, terephthalaldehyde, 1-naphthaldehyde, 3-methyl-4-methoxybenzaldehyde, 4-pyridinecarboxaldehyde, 1-methyl-1H-pyrazole-4-carboxaldehyde, 4-pyrazol-1-ylbenzaldehyde, 3-thiophenecarboxaldehyde, furan-2-carboxaldehyde, ferrocenecarboxaldehyde, butyraldehyde, cyclopropanecarboxaldehyde, cyclohexanecarboxaldehyde, adamantanecarboxaldehyde, citronellal, piperonyl propionaldehyde, hydroxycitronellal or decanal.

[0049] In the present invention, the catalyst preferably includes a copper-containing compound; the copper-containing compound preferably includes one or more of copper acetate, copper chloride, copper bromide, copper trifluoromethanesulfonate, cuprous chloride and cuprous bromide.

[0050] In the present invention, the base preferably includes an inorganic base and / or an organic base; the inorganic base preferably includes one or more of potassium carbonate, potassium hydroxide and dipotassium hydrogen phosphate; the organic base preferably includes 1,8-diazabicyclo[5.4.0]undec-7-ene and / or triethylamine. The present invention utilizes the base to provide a basic environment.

[0051] In the present invention, the polar organic solvent preferably includes acetonitrile, tetrahydrofuran, dichloromethane or ethanol.

[0052] In the present invention, the molar ratio of the arylhydrazine compound to the aldehyde compound is preferably 1:1 to 2. In the present invention, the molar ratio of the arylhydrazine compound to the catalyst is 1:0.1 to 0.5, more preferably 1:0.2 to 0.3. In the present invention, the molar ratio of the arylhydrazine compound to the base is preferably 1:1 to 2. In the present invention, the dosage ratio of the polar organic solvent to the arylhydrazine compound is preferably 1 L:0.1 to 0.2 mol.

[0053] The present invention has no special limitation on the mixing process, and the materials can be mixed evenly according to the process well-known in the art.

[0054] In the present invention, the temperature of the coupling addition reaction is preferably 0 °C, the time is preferably 6 to 24 h, more preferably 12 to 15 h; the coupling addition reaction is preferably carried out under stirring conditions. The present invention has no special limitation on the stirring rate, and the reaction can be ensured to proceed smoothly according to the process well-known in the art.

[0055] After the conjugate addition reaction, the present invention preferably includes purifying the resulting product system. The preferred purification method is column chromatography, and the eluent used in the column chromatography is preferably a mixed solvent of petroleum ether and ethyl acetate; the volume ratio of petroleum ether to ethyl acetate in the mixed solvent is preferably 1-20:1, and more preferably 10-15:1. The present invention does not have any special limitations on the specific process of the column chromatography, and a method well-known to those skilled in the art can be used. By using petroleum ether and ethyl acetate as the eluent for purification, the present invention can obtain a target compound with a relatively high purity.

[0056] In the present invention, the N′,N′-diarylhydrazide compounds preferably include:

[0057]

[0058]

[0059]

[0060] In the present invention, the purity of the N′,N′-diarylhydrazide compounds is preferably 98.5-99.9%.

[0061] To further illustrate the present invention, the following examples are used to describe in detail a preparation method of an N′,N′-diarylhydrazide compound provided by the present invention, but they should not be construed as limiting the protection scope of the present invention.

[0062] Example 1

[0063] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0064]

[0065] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1, and the purified target product is obtained. The yield is 75% and the purity is 99.9%;

[0066] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0067] 11H NMR (400 MHz, DMSO-d6, ppm) δ 11.24 (s, 1H), 7.97 - 7.95 (d, J = 8.0 Hz, 2H), 7.63 - 7.59 (t, J = 16.0 Hz, 1H), 7.55 - 7.51 (t, J = 16.0 Hz, 2H), 7.33 - 7.29 (t, J = 16.0 Hz, 4H), 7.19 - 7.17 (d, J = 8.0 Hz, 4H), 7.01 - 6.98 (t, J = 12.0 Hz, 2H);

[0068] 13 C{ 1 13C{1H} NMR (100 MHz, DMSO-d6, ppm) δ 166.29, 146.21, 132.93, 132.49, 129.59, 129.54, 129.08, 127.93, 122.59;

[0069] MS (EI, 70 eV) m / z 288, 183, 167, 105, 77.

[0070] Example 2

[0071] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0072]

[0073] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of 2-methylbenzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 88% and a purity of 99.9%;

[0074] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0075] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 10.96 (s, 1H), 7.53 - 7.51 (d, J = 8.0 Hz, 1H), 7.43 - 7.40 (t, J = 12.0 Hz, 1H), 7.37 - 7.31 (q, J = 24.0 Hz, 6H), 7.24 - 7.22 (d, J = 8.0 Hz, 4H), 7.05 - 7.01 (t, J = 16.0 Hz, 2H), 2.38 (s, 3H);

[0076] 13 C{1 1H NMR (100 MHz, DMSO-d6, ppm) δ 168.88, 146.28, 136.36, 135.01, 131.18, 130.53, 129.57, 127.68, 126.19, 122.67, 119.24, 19.82;

[0077] MS (EI, 70 eV) m / z 302, 183, 169, 119, 77.

[0078] Example 3

[0079] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0080]

[0081] 0.2 mmol of phenylhydrazine, 0.3 mmol of 2-methoxybenzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile were added to a reaction tube, and the mixture was stirred at 0 °C for 12 h. After the reaction was completed, it was separated and purified by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent was 10:1, and the purified target product was obtained with a yield of 65% and a purity of 99.9%;

[0082] The structure of the obtained product was characterized, and the structure characterization data are as follows:

[0083] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 10.72 (s, 1H), 7.62 - 7.60 (d, J = 8.0 Hz, 1H), 7.54 - 7.50 (t, J = 16.0 Hz, 1H), 7.34 - 7.31 (t, J = 12.0 Hz, 4H), 7.24 - 7.22 (d, J = 8.0 Hz, 4H), 7.19 - 7.17 (d, J = 8.0 Hz, 1H), 7.08 - 7.04 (t, J = 16.0 Hz, 1H), 7.02 - 6.98 (t, J = 16.0 Hz, 2H), 3.93 (s, 3H);

[0084] 13 13C{ 1 1H}NMR (100 MHz, DMSO-d6, ppm) δ 166.13, 157.38, 146.15, 132.81, 130.30, 129.43, 123.32, 122.41, 120.98, 119.14, 112.42, 56.33;

[0085] MS (EI, 70 eV) m / z 318, 183, 167, 135, 77。

[0086] Example 4

[0087] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0088]

[0089] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of 4-fluorobenzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 75% and a purity of 99.9%;

[0090] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0091] 1 H NMR (400 MHz, DMSO-d6, ppm) δ 11.26 (s, 1H), 8.04 - 8.01 (t, J = 12.0 Hz, 2H), 7.40 - 7.35 (t, J = 20.0 Hz, 2H), 7.33 - 7.29 (t, J = 16.0 Hz, 4H), 7.17 - 7.15 (d, J = 8.0 Hz, 4H), 7.01 - 6.98 (d, J = 12.0 Hz, 2H);

[0092] 13 C{ 1 H}NMR (100 MHz, DMSO-d6, ppm) δ 165.26, 146.16, 130.73, 130.64, 129.56, 122.64, 119.16, 116.21, 115.99;

[0093] MS (EI, 70 eV) m / z 306, 183, 167, 123, 77。

[0094] Example 5

[0095] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0096]

[0097] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of 4-chlorobenzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube. Stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 66% and a purity of 99.9%;

[0098] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0099] 1 H NMR(400 MHz, DMSO-d6, ppm) δ 11.30(s, 1H), 7.98 - 7.96(d, J = 8.0 Hz, 2H), 7.63 - 7.60(d, J = 12.0 Hz, 2H), 7.33 - 7.29(t, J = 16.0 Hz, 4H), 7.17 - 7.15(d, J = 8.0 Hz, 4H), 7.02 - 6.98(t, J = 16.0 Hz, 2H);

[0100] 13 C{ 1 H}NMR(100 MHz, DMSO-d6, ppm) δ 165.32, 146.12, 137.35, 131.67, 129.88, 129.57, 129.20, 122.70, 119.19;

[0101] MS(EI, 70 eV) m / z 322, 183, 169, 139, 77.

[0102] Example 6

[0103] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0104]

[0105] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of terephthalaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube. Stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 51% and a purity of 99.9%;

[0106] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0107] 11H NMR (400 MHz, DMSO-d6, ppm) δ 11.42 (s, 1H), 10.12 (s, 1H), 8.14 - 8.12 (d, J = 8.0 Hz, 2H), 8.07 - 8.05 (d, J = 8.0 Hz, 2H), 7.34 - 7.30 (t, J = 16.0 Hz, 4H), 7.18 - 7.17 (d, J = 4.0 Hz, 4H), 7.03 - 6.99 (t, J = 16.0 Hz, 2H);

[0108] 13 C{ 1 13C{1H} NMR (100 MHz, DMSO-d6, ppm) δ 193.37, 165.43, 146.06, 138.78, 137.85, 130.08, 129.61, 128.72, 122.78, 119.25;

[0109] MS (EI, 70 eV) m / z 316, 183, 169, 133, 77.

[0110] Example 7

[0111] The N′,N′-diarylhydrazide compound obtained in this example has the structure shown below:

[0112]

[0113] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of 1-naphthaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 72% and a purity of 99.9%;

[0114] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0115] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.24 (s, 1H), 8.18 (s, 1H), 8.12 - 8.10 (d, J = 8.0 Hz, 1H), 8.04 - 8.02 (t, J = 8.0 Hz, 1H), 7.83 (s, 1H), 7.65 - 7.59 (q, J = 24.0 Hz, 3H), 7.40 - 7.36 (t, J = 16.0 Hz, 4H), 7.31 (s, 4H), 7.07 - 7.04 (t, J = 12.0 Hz, 2H);

[0116] 13C{ 1 H} NMR (100 MHz, DMSO-d6, ppm) δ 168.40, 146.29, 133.71, 132.40, 131.17, 130.46, 129.66, 128.92, 127.64, 126.96, 126.23, 125.48, 125.30, 122.79, 119.27;

[0117] MS (EI, 70 eV) m / z 338, 183, 155, 127, 77.

[0118] Example 8

[0119] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0120]

[0121] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of 3-methyl-4-methoxybenzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 67% and a purity of 99.9%;

[0122] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0123] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.05 (s, 1H), 7.87 - 7.85 (d, J = 8.0 Hz, 1H), 7.81 (s, 1H), 7.32 - 7.28 (t, J = 16.0 Hz, 4H), 7.19 - 7.17 (d, J = 8.0 Hz, 4H), 7.06 - 7.04 (d, J = 8.0 Hz, 1H), 7.00 - 6.96 (t, J = 16.0 Hz, 2H), 3.86 (s, 3H), 2.21 (s, 3H);

[0124] 13 C{ 1 H} NMR (100 MHz, DMSO-d6, ppm) δ 165.95, 160.76, 146.37, 130.22, 129.47, 127.58, 126.15, 124.55, 122.44, 119.12, 110.40, 56.03, 16.51;

[0125] MS (EI, 70 eV) m / z 332, 183, 169, 149, 77。

[0126] Example 9

[0127] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0128]

[0129] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of 4-pyridinecarboxaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 70% and a purity of 99.9%;

[0130] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0131] 1 H NMR (400 MHz, DMSO-d6, ppm) δ 11.53 (s, 1H), 8.81 - 8.79 (d, J = 8.0 Hz, 2H), 7.87 - 7.85 (d, J = 8.0 Hz, 2H), 7.34 - 7.30 (t, J = 16.0 Hz, 4H), 7.18 - 7.16 (d, J = 8.0 Hz, 4H), 7.03 - 7.00 (t, J = 12.0 Hz, 2H);

[0132] 13 C{ 1 H}NMR (100 MHz, DMSO-d6, ppm) δ 164.89, 150.97, 145.91, 139.93, 129.64, 122.89, 121.84, 119.25;

[0133] MS (EI, 70 eV) m / z 289, 183, 167, 139, 77。

[0134] Example 10

[0135] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0136]

[0137] 0.2 mmol of phenylhydrazine, 0.3 mmol of 1-methyl-1H-pyrazole-4-carbaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile were added to a reaction tube. The reaction was stirred at 0 °C for 12 h. After the reaction was completed, it was separated and purified by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent was 10:1, and the purified target product was obtained with a yield of 70% and a purity of 99.9%;

[0138] The structure of the obtained product was characterized, and the structure characterization data was as follows:

[0139] 1 H NMR (400 MHz, DMSO-d6, ppm) δ 10.84 (s, 1H), 8.25 (s, 1H), 7.97 (s, 1H), 7.31 - 7.27 (t, J = 16.0 Hz, 4H), 7.14 - 7.12 (d, J = 8.0 Hz, 4H), 7.00 - 6.96 (t, J = 16.0 Hz, 2H), 3.88 (s, 3H);

[0140] 13 C{ 1 H}NMR (100 MHz, DMSO-d6, ppm) δ 161.88, 146.33, 139.03, 132.97, 129.51, 122.52, 119.04, 116.21, 39.31;

[0141] MS (EI, 70 eV) m / z 292, 183, 167, 109, 77.

[0142] Example 11

[0143] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0144]

[0145] 0.2 mmol of phenylhydrazine, 0.3 mmol of 4-pyrazol-1-ylbenzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile were added to a reaction tube. The reaction was stirred at 0 °C for 12 h. After the reaction was completed, it was separated and purified by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent was 10:1, and the purified target product was obtained with a yield of 65% and a purity of 99.9%;

[0146] The structure of the obtained product was characterized, and the structure characterization data was as follows:

[0147] 11H NMR (400 MHz, DMSO-d6, ppm) δ 11.28 (s, 1H), 8.64 (s, 1H), 8.10 - 8.08 (d, J = 8.0 Hz, 2H), 8.03 - 8.01 (d, J = 8.0 Hz, 2H), 7.82 (s, 1H), 7.34 - 7.30 (t, J = 16.0 Hz, 4H), 7.19 - 7.17 (d, J = 8.0 Hz, 2H), 6.61 (s, 1H);

[0148] 13 C{ 1 13C{1H} NMR (100 MHz, DMSO-d6, ppm) δ 165.47, 146.21, 142.61, 142.25, 130.14, 129.57, 128.66, 122.64, 119.19, 118.40, 109.02;

[0149] MS (EI, 70 eV) m / z 354, 183, 171, 143, 77.

[0150] Example 12

[0151] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0152]

[0153] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of 3-thiophenecarboxaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 68% and a purity of 99.9%;

[0154] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0155] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.10 (s, 1H), 8.31 (s, 1H), 7.69 - 7.67 (q, J = 8.0 Hz, 1H), 7.60 - 7.59 (d, J = 4.0 Hz, 1H), 7.32 - 7.28 (t, J = 16.0 Hz, 4H), 7.16 - 7.14 (d, J = 8.0 Hz, 4H), 7.01 - 6.97 (t, J = 16.0 Hz, 2H);

[0156] 13 C{ 11H NMR (100 MHz, DMSO-d6, ppm) δ 162.02, 146.22, 135.62, 130.42, 129.54, 127.81, 127.19, 122.61, 119.13;

[0157] MS (EI, 70 eV) m / z 294, 183, 169, 111, 77.

[0158] Example 13

[0159] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0160]

[0161] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of furfural, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 75% and a purity of 99.9%;

[0162] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0163] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.16 (s, 1H), 7.93 (s, 1H), 7.32 - 7.28 (t, J = 16.0 Hz, 5H), 7.14 - 7.12 (d, J = 8.0 Hz, 4H), 7.01 - 6.98 (t, J = 12.0 Hz, 2H), 6.70 - 6.69 (q, J = 4.0 Hz, 1H);

[0164] 13 13C{ 1 1H}NMR (100 MHz, DMSO-d6, ppm) δ 157.75, 146.49, 146.20, 139.01, 129.54, 122.71, 119.24, 115.36, 112.44;

[0165] MS (EI, 70 eV) m / z 278, 183, 169, 95, 77.

[0166] Example 14

[0167] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0168]

[0169] 0.2 mmol of phenylhydrazine, 0.3 mmol of ferrocene formaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile were added to a reaction tube. The reaction was stirred at 0 °C for 12 h. After the reaction was completed, it was separated and purified by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent was 10:1, and the purified target product was obtained with a yield of 50% and a purity of 99.9%;

[0170] The structure of the obtained product was characterized, and the structure characterization data was as follows:

[0171] 1 H NMR (400 MHz, DMSO-d6, ppm) δ 10.57 (s, 1H), 7.34 - 7.30 (t, J = 16.0 Hz, 4H), 7.20 - 7.18 (d, J = 8.0 Hz, 4H), 7.02 - 6.98 (t, J = 16.0 Hz, 2H), 4.93 (s, 2H), 4.46 (s, 2H), 4.20 (s, 5H);

[0172] 13 C{ 1 H}NMR (100 MHz, DMSO-d6, ppm) δ 169.37, 146.43, 129.85, 122.49, 119.16, 74.54, 70.99, 69.71, 68.84;

[0173] MS (EI, 70 eV) m / z 396, 213, 185, 129, 77.

[0174] Example 15

[0175] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0176]

[0177] 0.2 mmol of phenylhydrazine, 0.3 mmol of butyraldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile were added to a reaction tube. The reaction was stirred at 0 °C for 12 h. After the reaction was completed, it was separated and purified by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent was 10:1, and the purified target product was obtained with a yield of 79% and a purity of 99.9%;

[0178] The structure of the obtained product was characterized, and the structure characterization data was as follows:

[0179] 11H NMR (400 MHz, DMSO-d6, ppm) δ 10.48 (s, 1H), 7.30 - 7.26 (t, J = 16.0 Hz, 4H), 7.08 - 7.06 (d, J = 8.0 Hz, 4H), 6.99 - 6.95 (t, J = 16.0 Hz, 2H), 2.21 - 2.17 (t, J = 16.0 Hz, 2H), 1.64 - 1.55 (q, J = 36.0 Hz, 2H), 0.92 - 0.88 (t, J = 16.0 Hz, 3H);

[0180] 13 C{ 1 13C{1H} NMR (100 MHz, DMSO-d6, ppm) δ 172.04, 146.30, 129.45, 122.46, 119.07, 35.60, 18.90, 14.11;

[0181] MS (EI, 70 eV) m / z 254, 184, 168, 115, 77.

[0182] Example 16

[0183] The N′,N′-diaryl hydrazide compound obtained in this example has the following structure:

[0184]

[0185] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of cyclopropylcarboxaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 62% and a purity of 99.9%.;

[0186] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0187] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 10.74 (s, 1H), 7.32 - 7.28 (t, J = 16.0 Hz, 4H), 7.10 - 7.08 (d, J = 8.0 Hz, 4H), 7.00 - 6.97 (t, J = 12.0 Hz, 2H), 1.73 - 1.67 (q, J = 24.0 Hz, 1H), 0.8 - 0.78 (d, J = 8.0 Hz, 4H);

[0188] 13 C{ 11H NMR (100 MHz, DMSO-d6, ppm) δ 172.90, 146.37, 129.49, 122.52, 119.13, 12.37, 7.05;

[0189] MS (EI, 70 eV) m / z 252, 184, 168, 115, 77.

[0190] Example 17

[0191] The N′,N′-diaryl hydrazide compound obtained in this example has the following structure:

[0192]

[0193] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of cyclohexyl formaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 65% and a purity of 99.9%;

[0194] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0195] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 10.45 (s, 1H), 7.30 - 7.26 (t, J = 16.0 Hz, 4H), 7.09 - 7.07 (d, J = 8.0 Hz, 4H), 6.98 - 6.94 (t, J = 16.0 Hz, 2H), 2.31 - 2.24 (q, J = 28.0 Hz, 1H), 1.81 - 1.73 (t, J = 32.0 Hz, 4H), 1.66 - 1.63 (d, J = 12.0 Hz, 1H), 1.45 - 1.36 (q, J = 36.0 Hz, 2H), 1.32 - 1.16 (q, J = 64.0 Hz, 3H);

[0196] 13 13C{ 1 1H} NMR (100 MHz, DMSO-d6, ppm) δ 174.85, 146.28, 129.42, 122.35, 118.91, 42.47, 29.35, 25.83, 25.61;

[0197] MS (EI, 70 eV) m / z 294, 184, 168, 115, 77.

[0198] Example 18

[0199] The N′,N′-diarylhydrazide compounds obtained in this example have the following structure:

[0200]

[0201] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of adamantanecarbaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 48% and a purity of 99.9%;

[0202] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0203] 1 H NMR(400 MHz, DMSO-d6, ppm) δ 10.31(s, 1H), 7.29 - 7.25(t, J = 16.0 Hz, 4H), 7.09 - 7.07(d, J = 8.0 Hz, 4H), 6.96 - 6.93(t, J = 12.0 Hz, 2H), 2.01(s, 3H), 1.91(s, 6H), 1.70(s, 6H);

[0204] 13 C{ 1 H}NMR(100 MHz, DMSO-d6, ppm) δ 176.23, 146.25, 129.34, 122.11, 118.73, 38.83, 36.52, 28.04;

[0205] MS(EI, 70 eV) m / z 346, 183, 167, 135, 77.

[0206] Example 19

[0207] The N′,N′-diarylhydrazide compounds obtained in this example have the following structure:

[0208]

[0209] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of citronellal, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 64% and a purity of 99.9%;

[0210] The structure of the obtained product was characterized, and the structure characterization data are as follows:

[0211] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 10.50 (s, 1H), 7.30 - 7.26 (t, J = 16.0 Hz, 4H), 7.10 - 7.07 (d, J = 12.0 Hz, 4H), 6.99 - 6.96 (t, J = 12.0 Hz, 2H), 5.10 - 5.06 (t, J = 16.0 Hz, 1H), 2.24 - 2.19 (q, J = 20.0 Hz, 1H), 2.07 - 1.92 (q, J = 60.0 Hz, 4H), 1.66 (s, 3H), 1.58 (s, 3H), 1.38 - 1.30 (q, J = 32.0 Hz, 1H), 1.22 - 1.14 (q, J = 32.0 Hz, 1H), 0.91 - 0.90 (d, J = 4.0 Hz, 3H);

[0212] 13 13C{ 1 1H} NMR (100 MHz, DMSO-d6, ppm) δ 171.57, 146.33, 131.14, 129.40, 124.84, 122.48, 119.13, 41.11, 36.82, 30.21, 25.98, 25.34, 19.92, 17.98;

[0213] MS (EI, 70 eV) m / z 336, 184, 168, 115, 77.

[0214] Example 20

[0215] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0216]

[0217] 0.2 mmol of phenylhydrazine, 0.3 mmol of piperonyl propionaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile were added to a reaction tube, and the mixture was stirred at 0 °C for 12 h. After the reaction was completed, it was separated and purified by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent was 10:1, and the purified target product was obtained with a yield of 70% and a purity of 99.9%;

[0218] The structure of the obtained product was characterized, and the structure characterization data are as follows:

[0219] 11H NMR (400 MHz, DMSO-d6, ppm) δ 10.43 (s, 1H), 7.21 - 7.15 (q, J = 24.0 Hz, 5H), 6.99 - 6.92 (q, J = 28.0 Hz, 4H), 6.86 - 6.84 (d, J = 8.0 Hz, 2H), 6.81 (s, 1H), 6.69 - 6.67 (d, J = 8.0 Hz, 1H), 6.02 (s, 1H), 5.99 (s, 1H), 2.79 - 2.70 (q, J = 36.0 Hz, 2H), 2.63 - 2.60 (q, J = 12.0 Hz, 1H), 1.12 - 1.11 (d, J = 4.0 Hz, 3H);

[0220] 13 13C{ 1 1H} NMR (100 MHz, DMSO-d6, ppm) δ 174.48, 147.59, 146.06, 146.00, 133.95, 129.29, 122.54, 109.90, 108.45, 101.18, 39.46, 18.23;

[0221] MS (EI, 70 eV) m / z 374, 184, 168, 135, 77.

[0222] Example 21

[0223] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0224]

[0225] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of lagotis aldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 73% and a purity of 99.9%;

[0226] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0227] 11H NMR (400 MHz, DMSO-d6, ppm) δ 10.43 (s, 1H), 7.19 - 7.12 (q, J = 28.0 Hz, 9H), 6.99 - 6.93 (q, J = 24.0 Hz, 5H), 2.94 - 2.89 (q, J = 20.0 Hz, 1H), 2.86 - 2.81 (q, J = 20.0 Hz, 1H), 2.75 - 2.70 (q, J = 20.0 Hz, 1H), 2.64 - 2.59 (q, J = 20.0 Hz, 1H), 1.24 - 1.22 (q, J = 8.0 Hz, 6H), 1.13 - 1.11 (d, J = 8.0 Hz, 3H);

[0228] 13 C{ 1 13C{1H} NMR (100 MHz, DMSO-d6, ppm) δ 174.60, 146.54, 146.01, 137.48, 129.38, 129.29, 126.54, 122.24, 118.76, 39.27, 33.53, 24.48, 24.41, 18.41;

[0229] MS (EI, 70 eV) m / z 372, 184, 168, 133, 77.

[0230] Example 22

[0231] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0232]

[0233] Add 0.2 mmol of phenylhydrazine, 0.3 mmol of decanal, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 73% and a purity of 99.9%;

[0234] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0235] 11H NMR (400 MHz, DMSO-d6, ppm) δ 10.47 (s, 1H), 7.30 - 7.26 (t, J = 16.0 Hz, 4H), 7.08 - 7.06 (d, J = 8.0 Hz, 4H), 6.99 - 6.96 (t, J = 12.0 Hz, 2H), 2.22 - 2.18 (t, J = 16.0 Hz, 2H), 1.58 - 1.55 (t, J = 12.0 Hz, 2H), 1.26 (s, 12H), 0.89 - 0.86 (t, J = 12.0 Hz, 3H);

[0236] 13 C{ 1 13C{1H} NMR (100 MHz, DMSO-d6, ppm) δ 172.15, 146.29, 129.42, 122.47, 119.06, 33.58, 31.75, 29.38, 29.13, 29.09, 29.04, 25.40, 22.57, 14.42;

[0237] MS (EI, 70 eV) m / z 338, 184, 168, 115, 77.

[0238] Example 23

[0239] The N′,N′-diaryl hydrazide compound obtained in this example has the structure shown below:

[0240]

[0241] Add 0.2 mmol of 2-methylphenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 20:1 to obtain the purified target product with a yield of 55% and a purity of 99.9%;

[0242] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0243] 11H NMR (400 MHz, DMSO-d6, ppm) δ 10.97 (s, 1H), 7.89 - 7.87 (d, J = 8.0 Hz, 2H), 7.58 - 7.55 (t, J = 12.0 Hz, 1H), 7.50 - 7.47 (t, J = 12.0 Hz, 2H), 7.19 - 7.18 (d, J = 4.0 Hz, 2H), 7.16 - 7.12 (t, J = 16.0 Hz, 2H), 7.04 - 6.99 (q, J = 20.0 Hz, 4H), 2.07 (s, 6H);

[0244] 13 13C{ 1 1H} NMR (100 MHz, DMSO-d6, ppm) δ 165.02, 146.59, 133.41, 132.08, 132.02, 131.59, 128.93, 127.80, 126.83, 124.31, 122.10, 18.65;

[0245] MS (EI, 70 eV) m / z 316, 194, 180, 105, 77.

[0246] Example 24

[0247] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0248]

[0249] Add 0.2 mmol of 4-cyanophenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 1:1 to obtain the purified target product with a yield of 32% and a purity of 99.9%;

[0250] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0251] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.68 (s, 1H), 7.99 - 7.97 (d, J = 8.0 Hz, 2H), 7.80 - 7.78 (d, J = 8.0 Hz, 4H), 7.67 - 7.63 (t, J = 16.0 Hz, 1H), 7.58 - 7.54 (t, J = 16.0 Hz, 2H), 7.40 - 7.38 (d, J = 8.0 Hz, 4H);

[0252] 13 C{ 1 H} NMR (100 MHz, DMSO-d6, ppm) δ 166.32, 148.44, 134.19, 133.02, 132.00, 129.22, 128.09, 119.61, 119.46, 105.16;

[0253] MS (EI, 70 eV) m / z 338, 219, 191, 105, 77.

[0254] Example 25

[0255] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0256]

[0257] Add 0.2 mmol of 2-fluorophenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 20:1 to obtain the purified target product with a yield of 60% and a purity of 99.9%;

[0258] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0259] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.42 (s, 1H), 7.94 - 7.93 (d, J = 4.0 Hz, 2H), 7.63 - 7.59 (t, J = 16.0 Hz, 1H), 7.55 - 7.51 (t, J = 16.0 Hz, 2H), 7.23 - 7.13 (q, J = 40.0 Hz, 6H), 7.11 - 7.08 (t, J = 12.0 Hz, 2H);

[0260] 13 C{ 1 H} NMR (100 MHz, DMSO-d6, ppm) δ 166.16, 155.48, 153.03, 134.57, 134.49, 132.75, 132.53, 129.06, 127.96, 125.10, 125.06, 124.75, 124.67, 122.26, 116.71, 116.51;

[0261] MS (EI, 70 eV) m / z 324, 219, 205, 105, 77.

[0262] Example 26

[0263] The N′,N′-diarylhydrazide compound obtained in this example has the structure shown below:

[0264]

[0265] Add 0.2 mmol of 3-chlorophenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 20:1 to obtain the purified target product with a yield of 50% and a purity of 99.9%;

[0266] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0267] 1 H NMR(400MHz,DMSO-d6,ppm)δ11.38(s,1H),7.96 - 7.95(d,J = 4.0Hz,2H),7.66 - 7.62(t,J = 16.0Hz,1H),7.57 - 7.53(t,J = 20.0Hz,2H),7.38 - 7.34(t,J = 16.0Hz,2H),7.16 - 7.14(t,J = 8.0Hz,4H),7.11 - 7.09(d,J = 8.0Hz,2H);

[0268] 13 C{ 1 H}NMR(100MHz,DMSO-d6,ppm)δ166.32,147.09,134.12,132.82,132.35,131.39,129.20,128.00,123.03,118.89,118.15;

[0269] MS(EI,70eV)m / z 356,251,201,105,77。

[0270] Example 27

[0271] The N′,N′-diarylhydrazide compound obtained in this example has the structure shown below:

[0272]

[0273] Add 0.2 mmol of 4-bromophenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 20:1 to obtain the purified target product with a yield of 46% and a purity of 99.9%;

[0274] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0275] 1 H NMR(400 MHz, DMSO-d6, ppm) δ 11.33(s, 1H), 7.94 - 7.92(d, J = 8.0 Hz, 2H), 7.64 - 7.61(t, J = 12.0 Hz, 1H), 7.56 - 7.52(t, J = 16.0 Hz, 2H), 7.49 - 7.47(d, J = 8.0 Hz, 4H), 7.13 - 7.11(d, J = 8.0 Hz, 4H);

[0276] 13 C{ 1 H}NMR(100 MHz, DMSO-d6, ppm) δ 166.23, 145.13, 132.71, 132.42, 129.13, 127.96, 121.31, 114.43;

[0277] MS(EI, 70 eV) m / z 446, 341, 327, 105, 77.

[0278] Example 28

[0279] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0280]

[0281] Add 0.2 mmol of 4-trifluoromethylphenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 20:1 to obtain the purified target product with a yield of 45% and a purity of 99.9%;

[0282] Characterize the structure of the obtained product. The structure characterization data are as follows:

[0283] 11H NMR (400 MHz, DMSO-d6, ppm) δ 11.58 (s, 1H), 7.98 - 7.96 (d, J = 8.0 Hz, 2H), 7.70 - 7.68 (d, J = 8.0 Hz, 4H), 7.65 - 7.63 (d, J = 8.0 Hz, 1H), 7.58 - 7.54 (t, J = 16.0 Hz, 2H), 7.41 - 7.39 (d, J = 8.0 Hz, 4H);

[0284] 13 13C{ 1 1H} NMR (100 MHz, DMSO-d6, ppm) δ 166.30, 148.43, 132.91, 132.21, 129.20, 128.04, 127.10, 127.06, 126.21, 123.51, 123.44, 123.12, 119.33;

[0285] MS (EI, 70 eV) m / z 424, 319, 235, 105, 77.

[0286] Example 29

[0287] The N′,N′-diarylhydrazide compound obtained in this example has the following structure:

[0288]

[0289] Add 0.2 mmol of 3,4-dimethylphenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 20:1 to obtain the purified target product with a yield of 60% and a purity of 99.9%;

[0290] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0291] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.03 (s, 1H), 7.94 - 7.92 (d, J = 8.0 Hz, 2H), 7.61 - 7.58 (t, J = 12.0 Hz, 1H), 7.54 - 7.50 (t, J = 16.0 Hz, 2H), 7.04 - 7.02 (d, J = 8.0 Hz, 2H), 6.91 (s, 2H), 6.86 - 6.84 (d, J = 8.0 Hz, 2H), 2.15 (s, 12H);

[0292] 13 C{ 1 H} NMR (100 MHz, DMSO-d6, ppm) δ 166.12, 144.63, 137.01, 133.19, 132.31, 130.34, 130.09, 129.02, 127.89, 120.49, 116.81, 20.19, 19.10;

[0293] MS (EI, 70 eV) m / z 344, 239, 225, 105, 77.

[0294] Example 30

[0295] The N′,N′-diaryl hydrazide compound obtained in this example has the following structure:

[0296]

[0297] Add 0.2 mmol of 3,5-dichlorophenylhydrazine, 0.3 mmol of benzaldehyde, 0.08 mmol of copper trifluoromethanesulfonate as a catalyst, 0.3 mmol of dipotassium hydrogen phosphate and 2 mL of acetonitrile into a reaction tube, stir and react at 0 °C for 12 h. After the reaction is completed, separate and purify by column chromatography. The volume ratio of petroleum ether to ethyl acetate in the column chromatography eluent is 10:1 to obtain the purified target product with a yield of 43% and a purity of 99.9%;

[0298] Characterize the structure of the obtained product, and the structure characterization data are as follows:

[0299] 1 1H NMR (400 MHz, DMSO-d6, ppm) δ 11.47 (s, 1H), 7.96 - 7.94 (d, J = 8.0 Hz, 2H), 7.67 - 7.63 (t, J = 16.0 Hz, 1H), 7.57 - 7.54 (t, J = 12.0 Hz, 2H), 7.28 - 7.27 (d, J = 4.0 Hz, 2H), 7.18 - 7.17 (d, J = 4.0 Hz, 4H);

[0300] 13 C{ 1 H} NMR (100 MHz, DMSO-d6, ppm) δ 166.36, 147.47, 135.21, 133.05, 131.92, 129.24, 128.10, 123.21, 118.27;

[0301] MS (EI, 70 eV) m / z 426, 307, 269, 105, 77.

[0302] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, rather than all embodiments. Other embodiments can be obtained based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A N',N' - Preparation method of diaryl hydrazide compounds, characterized in that comprising the following steps: Mix an arylhydrazine compound, an aldehyde compound, a catalyst, a base, and a polar organic solvent, and carry out a coupling addition reaction to obtain the N',N' -diarylhydrazide compound; The catalyst is copper trifluoromethanesulfonate; The arylhydrazine compound has the structure shown in Formula I: Formula Ⅰ; The arylhydrazine compound is phenylhydrazine, 2-methylphenylhydrazine, 4-cyanophenylhydrazine, 2-fluorophenylhydrazine, 3-chlorophenylhydrazine, 4-bromophenylhydrazine, 4-trifluoromethylphenylhydrazine, 3,4-dimethylphenylhydrazine or 3,5-dichlorophenylhydrazine; The aldehyde compound has the structure shown in Formula II: Formula II; The aldehyde compound is benzaldehyde, 2-methylbenzaldehyde, 2-methoxybenzaldehyde, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, terephthalaldehyde, 1-naphthaldehyde, 3-methyl-4-methoxybenzaldehyde, 4-pyridinecarboxaldehyde, 1-methyl-1H-pyrazole-4-carboxaldehyde, 4-pyrazol-1-ylbenzaldehyde, 3-thiophenecarboxaldehyde, furfural, ferrocenecarboxaldehyde, butyraldehyde, cyclopropanecarboxaldehyde, cyclohexanecarboxaldehyde, adamantanecarboxaldehyde, citronellal, piperonylacetaldehyde, hydroxycitronellal or decanal; The described N',N' -The diarylhydrazide compounds have the structure shown in Formula III: Formula III.

2. The preparation method according to claim 1, characterized in that The base is an inorganic base and / or an organic base; The inorganic base is one or more of potassium carbonate, potassium hydroxide and dipotassium hydrogen phosphate; the organic base is 1,8-diazabicyclo[5.4.0]undec-7-ene and / or triethylamine.

3. The preparation method according to claim 1, wherein, The polar organic solvent is acetonitrile, tetrahydrofuran, dichloromethane or ethanol.

4. The preparation method according to claim 1, characterized in that, The molar ratio of the arylhydrazine compound to the aldehyde compound is 1:1 to 2; The molar ratio of the arylhydrazine compound to the catalyst is 1:0.1 to 0.5; The molar ratio of the arylhydrazine compound to the base is 1:1 to 2; The dosage ratio of the polar organic solvent to the arylhydrazine compound is 1 L:0.1 to 0.2 mol.

5. The preparation method according to claim 1, wherein The temperature of the coupling addition reaction is 0 °C and the time is 6 to 24 h.

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