A simple and efficient method for synthesizing triaromatic amine compounds

Abstract

The invention discloses a simple and efficient synthesis method of triaromatic amine compounds, comprising the steps of: adding 8-quinolyl substituted benzamide compounds, benzohydroxamic acid compounds, nickel catalysts, bis-diphenylphosphine ligands, potassium adamantanecarboxylate, and silver phosphate to an organic solvent N, N-dimethylformamide, heating to 130 DEG C under nitrogen conditions to react, reacting for 15h, and after the reaction is complete, post-processing (extraction and column chromatography separation) obtains the corresponding triaromatic amine compounds. In the present invention, directly using simple, easy to prepare, stable benzohydroxamic acid as aminating reagent, one-pot preparation of triaromatic amine compounds can be achieved via nickel-catalyzed inert carbon-hydrogen bond amination reaction. The conversion operation is simple, reactive, atom economy is good, substrates are widely used, and functional group compatibility is good, providing a kind of efficient synthetic route for the preparation of triaromatic amine compounds.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of triaromatic amines. Background Art

[0002] Aromatic amines are an important class of nitrogen-containing compounds. The introduction of nitrogen atoms can significantly improve the physical, chemical and biological properties of molecules. According to statistics, as of 2019, about 50% of the top 200 drugs sold worldwide contain aromatic amine skeletons; in addition, triaromatic amine skeletons are also an important class of optoelectronic material primitives, which can be used in the preparation of organic light-emitting diodes, sensitized solar cells, and photochromic materials. Based on the wide range of uses of aromatic amine compounds in important fields related to people's livelihood such as biomedicine and chemical materials, exploring efficient synthesis methods of triaromatic amine compounds occupies an important research position in the field of synthesis. Among them, the classic transition metal-catalyzed coupling reaction can achieve efficient preparation of aromatic amine compounds. However, in the above transformation, a pre-functionalized highly active halogenated aromatic hydrocarbon is required as a substrate, which reduces the step economy of the reaction and is accompanied by the generation of a large amount of metal halides.

[0003] On the other hand, the cross-dehydrogenation reaction of inert carbon-hydrogen bonds with aniline catalyzed by transition metals provides a more step-economical synthetic strategy for the preparation of aromatic amines. However, the strong coordination and nucleophilicity of aniline often lead to the deactivation of transition metal catalysts, and aniline often needs to be greatly excessive in the above transformation. In view of this, chemists have further developed carbon-hydrogen amination reactions using azide, nitrogen oxides and periodinimine reagents as amination reagents. However, the above reagents are difficult to prepare, difficult to store, and have poor atom economy. Therefore, it is particularly important to develop simple and easy-to-prepare amination reagents to achieve the efficient construction of triaromatic amine compounds. Summary of the invention

[0004] The present invention provides a synthesis method for efficiently preparing triaromatic amine compounds in one pot by directly reacting an 8-quinolyl substituted benzamide compound with a benzohydroxamic acid substrate through a double carbon-hydrogen bond amination reaction. The synthesis method has a wide range of substrate applications, good functional group compatibility, good chemical selectivity, and exhibits superior step economy and atom economy.

[0005] A simple, green and efficient synthesis method of triaromatic amine compounds comprises the following steps: adding an 8-quinolyl substituted benzamide compound, a benzohydroxamic acid compound, a nickel catalyst, a bis(diphenylphosphine) ligand, potassium adamantanecarboxylate and silver phosphate to an organic solvent, heating to 130° C. under nitrogen conditions for reaction, reacting for 15 hours, and after the reaction is complete, post-processing (extraction and column chromatography separation) to obtain the corresponding triaromatic amine compounds;

[0006] The structure of the 8-quinolyl substituted benzamide compound is shown in formula (II):

[0007]

[0008] The structure of the benzohydroxamic acid compound is shown in formula (III):

[0009]

[0010] The structure of the triaromatic amine compound is shown in formula (I):

[0011]

[0012] In formulas (I) to (III), R 1 One or more selected from H, C1-C5 alkyl, C1-C5 alkoxy, halogen, trifluoromethyl (when there are more than one, it means that there are multiple positions on the benzene ring with substitution);

[0013] R 2 One or more selected from H, C1-C5 alkyl, C1-C5 alkoxy, phenyl, halogen, trifluoromethyl, naphthyl (when there are more than one, it means that there are multiple positions on the benzene ring with substitution).

[0014] In the present invention, the simple, easy-to-prepare and stable benzohydroxamic acid is directly used as an amination reagent, and the triaromatic amine compounds can be prepared in one step through the amination reaction of the nickel-catalyzed doubly inert carbon-hydrogen bond.

[0015] Preferably, the R 1 is selected from one or more of H, methyl, methoxy, F, Cl, Br, I, and trifluoromethyl; R 2 One or more selected from H, methyl, tert-butyl, methoxy, phenyl, F, Cl, Br, I, trifluoromethyl, and naphthyl.

[0016] Preferably, the nickel catalyst is nickel (II) acetate tetrahydrate.

[0017] Preferably, the ligand is bis(diphenylphosphinothane) (dppm).

[0018] Preferably, the base is potassium adamantanecarboxylate.

[0019] Preferably, the additive is silver phosphate.

[0020] Preferably, the molar ratio of the benzohydroxamic acid compound, the 8-quinolyl substituted benzamide compound, the nickel catalyst, the ligand, the base and the additive is 1:2.5-3.5:0.1-0.4:0.1-0.4:3.0-4.0:1.5-2.5.

[0021] Preferably, the organic solvent is N,N-dimethylacetamide.

[0022] Preferably, the reaction temperature is 130° C. and the reaction time is 15 hours.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] (1) The present invention is the first to use a simple, easy-to-prepare, and stable benzohydroxamic acid substrate as an amination reagent to achieve a one-pot method for preparing triaromatic amine compounds.

[0025] (2) The synthetic method of the present invention is easy to operate, has high reaction activity, and has a wide substrate adaptability and good functional group compatibility.

[0026] (3) The present invention has excellent atom economy, step economy and chemical selectivity, and can selectively prepare triaromatic amine compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The hydrogen and carbon spectra of the compound obtained in Example 1;

[0028] Figure 2 The hydrogen and carbon spectra of the compound obtained in Example 2;

[0029] Figure 3 The hydrogen and carbon spectra of the compound obtained in Example 3;

[0030] Figure 4 The hydrogen and carbon spectra of the compound obtained in Example 4;

[0031] Figure 5 The hydrogen and carbon spectra of the compound obtained in Example 5;

[0032] Figure 6 The hydrogen and carbon spectra of the compound obtained in Example 6;

[0033] Figure 7 The hydrogen and carbon spectra of the compound obtained in Example 7;

[0034] Figure 8 The hydrogen and carbon spectra of the compound obtained in Example 8;

[0035] Fig. 9 The hydrogen and carbon spectra of the compound obtained in Example 9;

[0036] Fig.10 The hydrogen and carbon spectra of the compound obtained in Example 10;

[0037] Fig.11The hydrogen and carbon spectra of the compound obtained in Example 11;

[0038] Fig.12 The hydrogen and carbon spectra of the compound obtained in Example 12;

[0039] Fig.13 The hydrogen and carbon spectra of the compound obtained in Example 13;

[0040] Fig.14 The hydrogen and carbon spectra of the compound obtained in Example 14;

[0041] Fig.15 The hydrogen and carbon spectra of the compound obtained in Example 15;

[0042] Fig.16 The hydrogen and carbon spectra of the compound obtained in Example 16;

[0043] The hydrogen spectrum was tested on a 500MHz nuclear magnetic resonance instrument. The carbon spectrum was tested on a 125MHz nuclear magnetic resonance instrument. The test conditions were all room temperature with tetramethylsilane as the internal standard and the samples were dissolved in deuterated chloroform. DETAILED DESCRIPTION

[0044] The present invention is further described below in conjunction with specific embodiments, and the following specific embodiments are all optimal implementation modes of the present invention.

[0045] Examples 1 to 18

[0046] According to the raw material ratio in Table 1, 8-quinolyl substituted benzamide compound (II, 0.3mmol), benzohydroxamic acid substrate (III, 0.1mmol), nickel catalyst (0.04mmol), bis(diphenylphosphine) (0.04mmol), silver phosphate (0.2mmol), potassium adamantanecarboxylate (0.4mmol) and organic solvent N,N-dimethylacetamide (1mL) were added to a 25mL sealed tube, mixed and stirred evenly, and reacted in an oil bath (130°C) under a nitrogen atmosphere for 15h. After the reaction was completed according to the reaction conditions in Table 2, it was cooled, 20mL of 1M NaOH solution was added, the organic phase was extracted and collected, dried with sodium sulfate, mixed with silica gel, and purified by column chromatography to obtain the corresponding triaromatic amine compound (I). The reaction process is shown in the following formula:

[0047]

[0048] Table 1 Raw material ratios of Examples 1 to 18

[0049]

[0050]

[0051] Table 2 Reaction conditions and reaction results of Examples 1 to 18

[0052]

[0053]

[0054] In Table 1 and Table 2, T is the reaction temperature, t is the reaction time, dimethyl is dimethyl, and naphthyl is naphthyl.

[0055] The structural confirmation data of some compounds prepared in Examples 1 to 18 are as follows:

[0056]

[0057] 6,6'-(phenylazanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-1): White solid (43.0 mg, 70%); mp: 213-214°C. Column chromatography on silica gel (Eluent: petroleum ether / ethyl acetate, 5 / 1). 1 H NMR (500MHz, CDCl3) δ9.95(s,2H),8.71(s,2H),8.53(d,J=6.5Hz,2H),8.10(d,J=8.0Hz,2H),7.44(d,J=6.5Hz,4H),7.39-7.36(m ,2H),7.03-6.98(m,4H),6.91(d,J=8.0Hz,2H),6.76(t,J=8.0Hz,2H),6.69(t,J=6.5Hz,1H),6.50(d,J=7.0Hz,2H),2.21(s,6H). 13 C NMR (125MHz, CDCl3) δ166.8,148.6,148.0,144.4,138.5,136.6,136.1,134.6,134.6,129.5,1 28.7,127.7,127.1,126.1,125.7,123.4,121.9,121.4,116.7,19.6.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 40 H 32 N5O2614.2551; Found 614.2562.

[0058]

[0059] 2,2'-(phenylazanediyl)bis(N-(quinolin-8-yl)benzamide)(I-2):Whitesolid(28.1mg,48%);mp:239-240℃.Column chromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ10.56(s,2H),8.61(s,2H),8.38(d,J=7.0Hz,2H),8.08(d,J=8.0Hz,2H),7.65(d,J=7.0Hz,2H),7.42-7.36(m,8H),7.28(d,J=7.0Hz,2H),7.06(t,J=7.0Hz,2H),6.85(d,J=7.5Hz,2H),6.76(t,J=7.5Hz,2H),6.58(t,J=7.0Hz,1H). 13 C NMR(125MHz,CDCl3)δ166.2,147.9,147.6,145.3,138.6,136.1,134.5,132.5,131.2,130.0,128.6,128.0,127.7,127.2,124.2,123.0,122.6,121.4,121.4,116.6.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 38 H 28 N5O2 586.2238;Found 586.2234.

[0060]

[0061] 2,2'-(phenylazanediyl)bis(4-methyl-N-(quinolin-8-yl)benzamide)(I-3):White solid(27.5mg,45%);mp:172-173℃.Column chromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1H NMR(500MHz,CDCl3)δ10.44(s,2H),8.60(s,2H),8.43(d,J=7.0Hz,2H),8.09(d,J=8.0Hz,2H),7.50(d,J=7.5Hz,2H),7.42-7.37(m,6H),7.05(s,2H),6.94(d,J=8.0Hz,2H),6.87(t,J=7.5Hz,2H),6.79(d,J=7.5Hz,2H),6.67(t,J=7.0Hz,1H),1.99(s,6H). 13 C NMR(125MHz,CDCl3)δ166.4,147.8,147.8,145.1,141.5,138.5,136.0,134.6,130.1,129.9,128.6,127.7,127.2,125.0,122.8,122.3,122.2,121.4,121.2,116.4,21.1.HRMS(ESI-TOF)m / z:[M+H] + Calcd forC 40 H 32 N5O2 614.2551;Found 614.2556.

[0062]

[0063] 2,2'-(phenylazanediyl)bis(4-(tert-butyl)-N-(quinolin-8-yl)benzamide)(I-4):White solid(37.6 mg,54%);mp:252-253℃.Column chromatography on silicagel(Eluent:petroleumether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ10.50(s,2H),8.57(s,2H),8.45(d,J=7.0Hz,2H),8.07(d,J=8.0Hz,2H),7.54(d,J=8.0Hz,2H),7.41-7.33(m,6H),7.23(s,2H),7.08(d,J=7.5Hz,2H),7.00(d,J=8.0Hz,2H),6.95(t,J=7.0Hz,2H),6.75(t,J=7.0Hz,1H),0.93(s,18H). 13C NMR(125MHz,CDCl3)δ166.4,154.4,148.0,147.9,145.0,138.5,136.0,134.6,129.9,129.5,128.6,127.8,127.3,124.8,123.1,122.4,121.4,121.3,121.1,116.5,34.6,30.7..HRMS(ESI-TOF)m / z:[M+H] + Calcdfor C 46 H 44 N5O2698.3490;Found 698.3493.

[0064]

[0065] 2,2'-(phenylazanediyl)bis(4-fluoro-N-(quinolin-8-yl)benzamide)(I-5):White solid(24.3mg,39%);mp:231-232℃.Column chromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ10.44(s,2H),8.59(s,2H),8.31(d,J=7.5Hz,2H),8.04(d,J=8.5Hz,2H),7.53(t,J=7.0Hz,2H),7.37(d,J=8.0Hz,2H),7.34-7.31(m,4H),6.91(d,J=10.5Hz,2H),6.86-6.80(m,4H),6.66(t,J=7.5Hz,3H). 13 C NMR(125MHz,CDCl3)δ165.2,164.2(C-F,J C-F =250.0Hz),148.0,146.8,146.8,146.6,138.6,136.2,134.2,131.74(C-F,J C-F =10.0Hz),129.0,128.6,127.8,127.2,124.0,121.6(C-F,J C-F =15.0Hz),116.7,114.4(C-F,J C-F =23.8Hz),111.6,111.4.HRMS(ESI-TOF)m / z:[M+H] +Calcd for C 38 H 26 F2N5O2 784.0917;Found 784.0911.

[0066]

[0067] 2,2'-(phenylazanediyl)bis(4-bromo-N-(quinolin-8-yl)benzamide)(I-6):White solid(55.2mg,66%);mp:230-231℃.Column chromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ10.42(s,2H),8.70(s,2H),8.43(d,J=7.0Hz,2H),8.12(d,J=8.0Hz,2H),7.52(s,2H),7.49-7.39(m,6H),7.29-7.24(m,4H),7.00(s,4H),6.83(s,1H). 13 C NMR(125MHz,CDCl3)δ165.3,148.2,146.6,145.4,138.4,136.5,136.2,134.0,133.4,132.0,131.1,129.1,127.9,127.4,123.9,121.8,1217,121.6,116.6,96.8..HRMS(ESI-TOF)m / z:[M+H] + Calcd for Calcd forC38H26I2N5O2838.0170;Found 838.0176.

[0068]

[0069] 2,2'-(phenylazanediyl)bis(N-(quinolin-8-yl)-4-(trifluoromethyl)benzamide)(I-7):White solid(33.3 mg,46%);mp:251-252℃.Column chromatographyon silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1H NMR(500MHz,CDCl3)δ10.47(s,2H),8.68(d,J=3.5Hz,2H),8.39(d,J=7.5Hz,2H),8.14(d,J=8.5Hz,2H),7.58(d,J=8.0Hz,2H),7.49(d,J=8.0Hz,2H),7.43-7.40(m,4H),7.35(s,2H),7.18-7.13(m,4H),7.09(d,J=8.0Hz,2H),6.98(t,J=6.5Hz,1H). 13 C NMR(125MHz,CDCl3)δ165.0,148.2,146.6,145.0138.4,136.2,135.2,133.7,132.9(C-F,J C-F =32.5Hz),130.4,129.5,127.8,127.2,124.6(C-F,J C-F =5.0Hz),124.5,124.4,123.0(C-F,J C-F =272.5Hz),122.1,121.9,120.7(C-F,J C-F =3.8Hz),116.8..HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 40 H 26 F6N5O2722.1958;Found 722.1983.

[0070]

[0071] 6,6'-(phenylazanediyl)bis(2,3-dimethyl-N-(quinolin-8-yl)benzamide)(I-8):White solid(18.6mg,29%);mp:214-215℃.Column chromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1H NMR(500MHz,CDCl3)δ9.90(s,2H),8.72(d,J=3.0Hz,2H),8.61(d,J=6.0Hz,2H),8.12(d,J=8.0Hz,2H),7.47(d,J=6.5Hz,4H),7.40-7.38(m,2H),7.06-6.97(m,4H),6.82(d,J=8.0Hz,2H),6.71(t,J=6.5Hz,1H),6.51(d,J=8.0Hz,2H),2.02(s,6H),1.57(s,6H). 13 C NMR(125MHz,CDCl3)δ167.4,149.2,147.9,141.9,138.4,136.0,135.2,134.8,134.2,132.8,130.9,128.6,127.7,127.2,126.2,122.4,121.3,121.2,121.0,116.6,19.2,16.4.HRMS(ESI-TOF)m / z:[M+H] + Calcdfor C 42 H 36 N5O2 642.2864;Found 642.2879.

[0072]

[0073] 6,6'-(phenylazanediyl)bis(4-bromo-2-methyl-N-(quinolin-8-yl)benzamide)(I-9):White

[0074] solid(47.7 mg,62%);mp:218-219℃.Columnchromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ10.00(s,2H),8.76(d,J=4.0Hz,2H),8.55(t,J=4.0Hz,2H),8.14(d,J=8.0Hz,2H),7.50(d,J=4.0Hz,4H),7.42-7.40(m,2H),7.14-7.08(m,4H),6.94(s,2H),6.88(t,J=7.0Hz,1H),6.62(s,2H),2.15(s,6H). 13C NMR(125MHz,CDCl3)δ165.6,148.1,147.6,145.0,138.4,138.3,136.2,134.0,133.4,129.1,128.8,128.7,127.8,127.5,124.1,123.3,123.2,121.8,121.5,116.8,19.4.HRMS(ESI-TOF)m / z:[M+H] + Calcd forC 40 H 30 Br2N5O2 770.0761;Found 770.0734.6,6'-(p-tolylazanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-10):White solid(28.8mg,46%);mp:216-217℃.Columnchromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ9.90(s,2H),8.71(s,2H),8.52(d,J=6.0Hz,2H),8.09(d,J=8.0Hz,2H),7.43(d,J=6.0Hz,4H),7.39-7.36(m,2H),6.91(d,J=7.0Hz,4H),6.79(t,J=8.0Hz,2H),6.73(d,J=8.0Hz,2H),6.52(d,J=7.5Hz,2H),2.21(s,6H),1.91(s,3H). 13 C NMR(125MHz,CDCl3)δ166.9,147.9,146.1,144.9,138.5,136.5,136.0,134.6,134.4,131.7,129.4,129.3,127.7,127.1,125.8,125.4,124.0,121.3,121.3,116.6,20.4,19.6.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 41 H 34 N5O2 628.2707;Found 628.2723.

[0075]

[0076] 6,6'-((4-bromophenyl)azanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-11):White solid(36.1mg,54%);mp:196-197℃.Column chromatographyon silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ9.85(s,2H),8.70(s,2H),8.49(d,J=7.0Hz,2H),8.08(d,J=8.0Hz,2H),7.41(d,J=8.0Hz,4H),7.39-7.35(m,2H),7.01(d,J=8.0Hz,2H),6.89-6.84(m,6H),6.58(d,J=7.5Hz,2H),2.23(s,6H),0.92(s,9H). 13 C NMR(125MHz,CDCl3)δ166.8,147.98,145.6,145.0,144.6,138.5,136.5,136.0,134.5,134.4,129.6,127.7,127.7,127.1,126.0,125.5,125.4,123.1,121.3,116.6,33.8,31.0,19.6.HRMS(ESI-TOF)m / z:[M+H] + Calcd forC 44 H 40 N5O2 670.3177;Found 670.3190.

[0077]

[0078] 6,6'-((4-bromophenyl)azanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-12):White solid(41.3mg,60%);mp:205-206℃.Column chromatographyon silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1H NMR(500MHz,CDCl3)δ9.87(s,2H),8.63(s,2H),8.52(s,2H),8.01(d,J=8.0Hz,2H),7.38(d,J=4.0Hz,4H),7.31-7.07(m,9H),7.03-6.99(m,4H),6.90-6.78(m,2H),6.56(d,J=7.0Hz,2H),2.22(s,6H). 13 C NMR(125MHz,CDCl3)δ166.7,147.9,144.4,140.7,138.4,136.7,136.0,134.8,134.6,134.4,129.6,128.4,127.7,127.3,127.1,126.5,126.4,126.3,126.0 123.3,121.4,121.4,116.53,19.64.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 46 H 36 N5O2 690.2864;Found 690.2880.

[0079]

[0080] 6,6'-((4-(trifluoromethyl)phenyl)azanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-13):White solid(23.8mg,35%)mp:200-201℃.Columnchromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ9.80(s,2H),8.65(d,J=3.5Hz,2H),8.52(d,J=7.0Hz,2H),8.10(d,J=8.5Hz,2H),7.46-7.41(m,4H),7.39-7.36(m,2H),7.09(d,J=8.0Hz,2H),7.05(d,J=8.0Hz,2H),6.93(d,J=8.0Hz,2H),6.88(t,J=8.0Hz,2H),6.65(d,J=7.0Hz,2H),2.27(s,6H). 13C NMR(125MHz,CDCl3)δ166.4,151.2,147.9,143.4,138.2,136.8,136.1,135.2,134.3,129.8,127.7,127.0(C-F,J C-F =18.8Hz),126.6,125.8(C-F,J C-F =3.8Hz),124.2(C-F,J C-F =270Hz),122.5,122.2,121.6,121.4,121.2,116.4,19.6.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 41 H 31 F3N5O2 682.2424;Found 682.2417.

[0081]

[0082] 6,6'-(m-tolylazanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-14):White solid(39.5 mg,63%);mp:223-224℃.Column chromatography on silicagel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ9.90(s,2H),8.70(s,2H),8.53(d,J=3.5Hz,2H),8.09(d,J=8.0Hz,2H),7.43(d,J=6.0Hz,4H),7.38-7.36(m,2H),6.93(d,J=8.0Hz,2H),6.83-6.78(m,5H),6.54(d,J=7.5Hz,2H),6.42(s,1H),2.22(s,6H),1.95(s,3H). 13 C NMR(125MHz,CDCl3)δ166.8,148.5,147.9,144.7,138.5,138.4,136.6,136.0,134.6,134.6,129.4,128.5,127.7,127.1,126.1,125.6,124.4,122.9,121.4,121.3,121.0,116.6,21.2,19.6.HRMS(ESI-TOF)m / z:[M+H]+ Calcd forC 41 H 34 N5O2 628.2707;Found 628.2726.

[0083]

[0084] 6,6'-([1,1'-biphenyl]-3-ylazanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-15):White solid(35.1mg,51%);mp:148-149℃.Column chromatographyon silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ9.92(s,2H),8.53(d,J=6.0Hz,4H),8.07(d,J=8.0Hz,2H),7.40(d,J=9.5Hz,4H),7.34(s,2H),7.21(s,3H),7.16(s,1H),7.05-6.98(m,6H),6.86(t,J=7.5Hz,2H),6.79(s,1H),6.60(s,2H),2.25(s,6H). 13 C NMR(125MHz,CDCl3)δ166.7,148.8,148.0,144.6,141.6,140.9,138.4,136.7,136.0,134.6,134.5,129.6,129.0,128.3,127.6,127.2,127.0,126.9,126.2,126.0,122.4,122.0,121.4,121.3,120.7,116.5,19.7.HRMS(ESI-TOF)m / z:[M+H] + Calcd forC 46 H 36 N5O2 690.2864;Found 690.2882.

[0085]

[0086] 6,6'-((3,5-dimethylphenyl)azanediyl)bis(4-fluoro-2-methyl-N-(quinolin-8-yl)benzamide)(I-16):White solid(37.9 mg,56%)mp:281-282℃.Columnchromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ9.91(s,2H),8.74(d,J=2.5Hz,2H),8.55(d,J=3.5Hz,2H),8.12(d,J=8.5Hz,2H),7.46(d,J=5.5Hz,4H),7.41-7.39(m,2H),6.64(s,2H),6.58(d,J=10.0Hz,2H),6.27(d,J=10.0Hz,3H),2.19(s,6H),1.94(s,6H). 13 C NMR(125MHz,CDCl3)δ166.0,162.7(C-F,J C-F =246.2Hz),148.0,147.3,146.3,146.2,138.8(C-F,J C-F =10.0Hz),138.6,138.4,136.2,134.3,130.6,127.7,127.2,125.3,122.7,121.5(C-F,J C-F =11.2Hz),116.4,112.8,112.6(C-F,J C-F =15.0 Hz),21.0,19.8..HRMS(ESI-TOF)m / z:[M+H] + CalcdforC 42 H 34 F2N5O2 678.2675;Found 678.2680.

[0087]

[0088] 6,6'-((3,5-dimethylphenyl)azanediyl)bis(4-bromo-2-methyl-N-(quinolin-8-yl)benzamide)(I-17):White solid(39.1mg,50%);mp:288-289℃.Columnchromatography on silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1 H NMR(500MHz,CDCl3)δ9.92(s,2H),8.76(d,J=3.0Hz,2H),8.55(d,J=8.5Hz,2H),8.13(d,J=8.0Hz,2H),7.49(d,J=6.5Hz,4H),7.42-7.39(m,2H),6.96(s,2H),6.67(s,4H),6.39(s,1H),2.16(s,6H),2.02(s,6H). 13 C NMR(125MHz,CDCl3)δ165.6,148.0,147.4,145.4,138.7,138.3,138.3,136.2,134.1,133.3,128.7,128.5,127.7,127.5,125.5,123.2,122.6,121.6,121.5,116.7,21.1,19.4..HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 42 H 34 Br2N5O2798.1074;Found798.1065.

[0089]

[0090] 6,6'-(naphthalen-2-ylazanediyl)bis(2-methyl-N-(quinolin-8-yl)benzamide)(I-18):Whitesolid(26.5mg,40%);mp:245-246℃.Column chromatographyon silica gel(Eluent:petroleum ether / ethyl acetate,5 / 1). 1H NMR(500MHz,CDCl3)δ9.89(s,2H),8.57(s,1H),8.47(d,J=7.0Hz,2H),8.04(d,J=8.5Hz,2H),7.45-7.33(m,9H),7.30(d,J=3.5Hz,2H),7.23-7.18(m,2H),7.10(t,J=7.5Hz,1H),6.97(d,J=7.5Hz,2H),6.80(t,J=8.0Hz,2H),6.57(d,J=7.5Hz,2H),2.24(s,6H). 13 C NMR(125MHz,CDCl3)δ166.7,147.8,146.2,144.4,138.3,136.6,135.9,134.8,134.4,134.2,129.6,129.6,128.4,127.6,127.1,127.0,126.8,126.3,126.2,126.0,125.7,123.8,123.7,121.3,119.8,116.5,19.6.HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 44 H 34 N5O2 664.2707;Found664.2703。

Claims

1. A method for synthesizing triaromatic amine compounds, characterized in that: The method comprises the following steps: adding an 8-quinolyl substituted benzamide compound, a benzohydroxamic acid compound, a nickel catalyst, a ligand, a base and an additive into an organic solvent, controlling the temperature at 120 to 140° C. under an inert gas condition to react for 10 to 20 hours, and after the reaction is complete, post-treating to obtain the triaromatic amine compound; The structure of the 8-quinolyl substituted benzamide compound is shown in formula (II): The structure of the benzohydroxamic acid compound is shown in formula (III): The structure of the triaromatic amine compound is shown in formula (I): In formulas (I) to (III), R 1 One or more selected from H, C1-C5 alkyl, C1-C5 alkoxy, halogen, trifluoromethyl; R 2 One or more selected from H, C1-C5 alkyl, C1-C5 alkoxy, phenyl, halogen, trifluoromethyl, naphthyl; The nickel catalyst is nickel acetate (II) tetrahydrate; The ligand is bis(diphenylphosphinothioic acid) (dppm); The base is potassium adamantanecarboxylate; The additive is silver phosphate.

2. The method for synthesizing triaromatic amine compounds according to claim 1, characterized in that: The R 1 is selected from one or more of H, methyl, methoxy, F, Cl, Br, I, and trifluoromethyl; R 2 One or more selected from H, methyl, tert-butyl, methoxy, phenyl, F, Cl, Br, I, trifluoromethyl, and naphthyl.

3. The method for synthesizing triaromatic amine compounds according to claim 1, characterized in that: The organic solvent is N,N-dimethylacetamide.

4. The method for synthesizing triaromatic amine compounds according to claim 1, characterized in that: The reaction temperature was 130° C., under nitrogen reaction conditions, and the reaction time was 15 hours.

5. The method for synthesizing triaromatic amine compounds according to claim 1, characterized in that: The molar ratio of the benzohydroxamic acid compound, the 8-quinolyl substituted benzamide compound, the nickel catalyst, the ligand, the base and the additive is 1:2.5-3.5:0.1-0.4:0.1-0.4:3.0-4.0:1.5-2.

5.

6. The method for synthesizing triaromatic amine compounds according to claim 1, characterized in that: The triaromatic amine is one of the following compounds:

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