A direct electrochemical synthesis method for triarylamine compounds

Abstract

The present invention relates to a direct electrochemical synthesis method of triarylamine compounds, wherein the method comprises the following steps: using phenothiazine compounds (II) and 2-aryl indolizine compounds (III) as reaction raw materials, adopting a three-electrode system, using a graphite electrode or a Pt electrode as a cathode and an anode, using a 0.1 mol / L silver nitrate acetonitrile solution as a reference electrode, stirring in an organic solvent containing a supporting electrolyte at 15 to 45° C. and 0.1 to 0.3 V to carry out an electrolytic reaction, and obtaining a triarylamine compound having a structure as shown in formula (I) through separation treatment after the reaction is completed. The beneficial effects of the present invention are mainly reflected in the following aspects: (1) the present invention uses clean electric energy as an oxidant, thereby reducing environmental costs; (2) the universality of the reaction substrate is good; and (3) the product yield is high.

Description

(I) Technical field

[0001] The invention relates to a direct electrochemical synthesis method of triarylamine compounds. (II) Background technology

[0002] Triarylamine compounds have good hole transport capabilities and are widely used in organic light-emitting diodes, sensitized solar cells, photochromic materials and other fields. Phenothiazine compounds, as a special class of diarylamine compounds, have mature production technology, low prices, and a wide range of uses. In addition, 2-arylindolizine compounds have good optoelectronic properties like phenothiazine compounds. Therefore, the synthesis of triarylamine compounds using these two as raw materials has good development prospects in the field of optoelectronic materials.

[0003] Traditionally, triarylamine compounds are synthesized by using diarylamine and aromatic hydrocarbons as raw materials and constructing CN bonds. However, these synthesis methods inevitably require the use of chemical oxidants, transition metal catalysts or photosensitizers, and will encounter problems such as isomer mixing. At the same time, they are not in line with the characteristics of sustainable development and green chemistry.

[0004] In recent years, electrochemistry, as an environmentally friendly and efficient synthesis method, has provided new possibilities for green organic synthesis. In the electrochemical reaction process, electricity acts as a redox agent and catalyst, without the need for external oxidants and catalysts, which not only improves the atomic utilization rate, but also facilitates the separation and purification of products. (III) Summary of the invention

[0005] The purpose of the present invention is to provide a direct electrochemical synthesis method of triarylamine compounds.

[0006] The technical solution adopted by the present invention is:

[0007] A direct electrochemical synthesis method for triarylamine compounds, the method comprising: using a phenothiazine compound with a structural formula as shown in formula (II) and a 2-aryl indolizine compound with a structural formula as shown in formula (III) as reaction raw materials, using a three-electrode system, using a graphite electrode or a Pt electrode as a cathode and an anode (the cathode and the anode materials may be the same or different), using a 0.1 mol / L silver nitrate acetonitrile solution as a reference electrode, stirring in an organic solvent containing a supporting electrolyte at 15 to 45° C. and 0.1 to 0.3 V for electrolysis reaction, and after the reaction is completed, separating and treating to obtain a triarylamine compound with a structural formula as shown in formula (I); the supporting electrolyte is LiClO4, n Bu4NBF4, nBu4NPF6 or NaClO4, preferably LiClO4, the organic solvent is N,N-dimethylformamide, acetonitrile or ethyl acetate, preferably N,N-dimethylformamide;

[0008]

[0009] In formulas (I) to (III),

[0010] R1 is H, C1-C4 alkyl, halogen, C1-C2 alkoxy, nitro, cyano, trifluoromethyl or acetyl;

[0011] R2 is phenyl, substituted phenyl, naphthyl or substituted naphthyl, and the substituents of the substituted phenyl and substituted naphthyl (the substituents may be one or more) are independently selected from one of the following: halogen, nitro, C1-C4 alkyl or C1-C4 alkoxy;

[0012] R3 is H, C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine or fluorine.

[0013] Preferably, R1 is H, Cl, methoxy, methylthio, trifluoromethyl, cyano or acetyl, R2 is phenyl, halogenated phenyl, C1-C4 alkyl substituted phenyl, C1-C4 alkoxy substituted phenyl or naphthyl, and R3 is H, methyl or bromine.

[0014] The molar ratio of the phenothiazine compound to the indolizine compound is 100:80-150, preferably 100:110-130.

[0015] The reaction involved in the present invention is as follows:

[0016]

[0017] The reaction mechanism is shown above: indolizine loses an electron at the anode to form an indolizine cation free radical, phenothiazine loses an electron and a hydrogen ion at the anode to form a phenothiazine free radical, and the indolizine cation free radical and the phenothiazine free radical are coupled and then lose a hydrogen ion to obtain a product. The chemical synthesis reaction can also be synthesized by a constant current method, but the product yield is low, mainly because the raw materials will polymerize on the electrode surface under constant current conditions. The present invention adopts a three-electrode system, which significantly improves the product yield.

[0018] The three-electrode system is designed to eliminate the large error in electrode potential caused by polarization current. It introduces a reference electrode to stabilize the working electrode on the basis of the conventional two-electrode system (working electrode and counter electrode).

[0019] The supporting electrolyte is an electrolyte that increases the conductivity of the solution in the chemical battery and does not participate in the electrochemical reaction. Preferably, the concentration of the supporting electrolyte in the organic solvent is 0.05 to 0.15 mol / L.

[0020] The recommended amount of organic solvent is 150 to 400 times the mass of the reaction substrate phenothiazine compound.

[0021] Specifically, the separation method is as follows: after the reaction is completed, the solvent is evaporated under reduced pressure, and then thin layer chromatography is performed, a mixed solution of petroleum ether / ethyl acetate in a volume ratio of 20:1 is used as a developing solvent, a thin layer containing the target compound is collected, eluted with dichloromethane, filtered, and the solvent is evaporated from the filtrate to obtain the triarylamine compound.

[0022] Preferably, the method is as follows: using a phenothiazine compound with a structural formula as shown in formula (II) and a 2-aryl indolizine compound with a structural formula as shown in formula (III) as raw materials, using a three-electrode system, the cathode and the anode are both Pt electrodes, and a 0.1 mol / L silver nitrate acetonitrile solution is used as a reference electrode. In an N,N-dimethylformamide solution containing 0.05-0.15 mol / L LiClO4, the electrolysis reaction is stirred at 15-45°C and 0.1-0.3V for 3.5-7.0 hours, and then the solvent is evaporated under reduced pressure, and then thin layer chromatography is performed, using a mixed solution of petroleum ether / ethyl acetate in a volume ratio of 20:1 as a developing solvent, collecting a thin layer containing the target compound, eluting with dichloromethane, filtering, and evaporating the filtrate to remove the solvent to obtain the triarylamine compound.

[0023] The beneficial effects of the present invention are mainly reflected in: (1) the present invention uses clean electric energy as an oxidant, thereby reducing environmental costs; (2) the universality of the reaction substrate is good; and (3) the product yield is high. (IV) Description of the drawings

[0024] Figure 1 is the H NMR spectrum of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1));

[0025] Figure 2 This is the carbon NMR spectrum of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1)). (V) Specific implementation methods

[0026] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0027] The structural formulas of the triarylamine compounds prepared in the examples are shown in formulas (I-1) to (I-26):

[0028]

[0029]

[0030] Example 1: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0031] The reaction adopts a three-electrode system, with both the cathode and the anode being Pt electrodes, and a 0.1 mol / L silver nitrate acetonitrile solution as a reference electrode. Add 0.1 mol / L LiClO4 in N,N-dimethylformamide solution (15 mL), phenothiazine (0.20 mmol), and 2-phenylindoleazine (0.24 mmol) into a 30 ml beaker. Electrolysis was performed at 25°C and 0.2 V at constant potential, and the reaction was completed after 3.5 h. The solvent was evaporated under reduced pressure, and then thin layer chromatography was performed, using a mixed solution of petroleum ether / ethyl acetate in a volume ratio of 20:1 as the developing solvent, and the thin layer containing the target compound was collected, eluted with dichloromethane, filtered, and the filtrate was evaporated to remove the solvent to obtain the product 10-(2-phenylindoleazine-3-yl)-10H-phenothiazine (see Figure 1 for the H NMR spectrum and see Figure 1 for the C NMR spectrum). Figure 2 ), with a yield of 85%.

[0032] 1 H NMR (400MHz, CDCl3) δ7.87-7.83(m,3H),7.51-7.49(m,1H), 7.38-7.35(m,2H),7.26-7.25(m,1H),7.10-7.08(m,2H),6.95(s,1H), 6.86-6.79(m,5H),6.55-6.51(m,1H),6.13-6.11(m,2H). 13 C NMR(101MHz, CDCl3)δ141.6,134.0,131.0,128.9,127.7,127.2,127.1,127.0,125.6,123.6, 121.6,121.2,119.3,118.8,116.5,115.9,111.3,96.9.HRMS(ESI)calculated for C 26 H 19 N2S + [M+H] + :391.1263; found:391.1263.

[0033] Example 2: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0034] The reaction steps were the same as those in Example 1, except that the voltage was changed to 0.1 V, the reaction time was 7.0 h, and the yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 82%.

[0035] Example 3: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0036] The reaction steps were the same as those in Example 1, except that the voltage was changed to 0.3 V, the reaction time was 2.0 h, and the yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 79%.

[0037] Example 4: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0038] The reaction steps were the same as in Example 1, except that the temperature was changed to 15° C. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 72%.

[0039] Example 5: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0040] The steps were the same as those in Example 1, except that the temperature was changed to 35°C. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 85%.

[0041] Example 6: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0042] The reaction steps were the same as those in Example 1, except that the amount of 2-phenylindolizine was changed to 0.20 mmol. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 79%.

[0043] Example 7: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0044] The reaction steps were the same as those in Example 1, except that the amount of 2-phenylindolizine was changed to 0.30 mmol. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 85%.

[0045] Example 8: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0046] The reaction steps were the same as those in Example 1, except that the solvent was changed to acetonitrile. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 55%.

[0047] Example 9: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0048] The reaction steps are the same as in Example 1, except that the supporting electrolyte is changed to n The yield of Bu4NBF4,10-(2-phenylindolizin-3-yl)-10H-phenothiazine was 63%.

[0049] Example 10: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0050] The reaction steps are the same as in Example 1, except that the supporting electrolyte is changed to n The yield of Bu4NPF6,10-(2-phenylindolizin-3-yl)-10H-phenothiazine was 67%.

[0051] Example 11: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0052] The reaction steps were the same as those in Example 1, except that the supporting electrolyte was changed to NaClO4. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 75%.

[0053] Example 12: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0054] The reaction steps were the same as those in Example 1, except that the anode was changed to a graphite electrode. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 80%.

[0055] Example 13: Preparation of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-1))

[0056] The reaction steps were the same as those in Example 1, except that the cathode and the anode were both replaced with graphite electrodes. The yield of 10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 75%.

[0057] Example 14: Preparation of 2-chloro-10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-2))

[0058] The reaction steps were the same as those in Example 1, except that phenothiazine was replaced by 2-chlorophenothiazine. The yield of 2-chloro-10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 79%.

[0059] 1H NMR (500MHz, CDCl3) δ7.82-7.78(m,3H),7.51(d,J=8.9Hz, 1H),7.39-7.36(m,2H),7.27-7.24(m,1H),7.07(m,1H),6.97(d,J=8.2Hz, 1H),6.93(s,1H),6.88–6.79(m,4H),6.57-6.55(m,1H),6.08-6.07(m,2H). 13 C NMR (125MHz, CDCl3) δ142.9,141.1,133.7,133.5,131.2,129.0,127.9, 127.6,127.3,127.2,127.0,125.7,124.0,123.6,121.3,120.8,119.7,119.5, 119.0,116.1,115.96,115.6,111.6,97.2.HRMS(ESI)m / zcalculated for C 26 H 18 ClN2S + [M+H] + 425.0874, found 425.0870.

[0060] Example 15: Preparation of 2-trifluoromethyl-10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-3))

[0061] The reaction steps were the same as those in Example 1, except that phenothiazine was replaced by 2-trifluoromethylphenothiazine. The yield of 2-trifluoromethyl-10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 72%.

[0062] 1 H NMR (500MHz, CDCl3) δ7.83-7.81(m,1H),7.76-7.72(m,2H), 7.51(d,J=9.0Hz,1H),7.35(t,J=7.7Hz,2H),7.27-7.22(m,1H),7.12(d,J =8.0Hz,1H),7.07-7.06(m,2H),6.93(s,1H),6.90-6.81(m,3H),6.59-6.54 (m,1H),6.27(d,J=0.8Hz,1H),6.09-6.07(m,1H). 13 C NMR(125MHz, CDCl3)δ142.3,141.2,133.8,131.3,130.0(q,J C-F=32.8Hz),129.0,128.2, 127.34,127.26,127.2,127.1,126.1,124.2,123.7(q,J C-F =273.4Hz),121.3,120.24,120.23(q,J C-F =3.8Hz),119.5,119.0,116.2,115.3,112.4(q,J C-F = 3.8Hz),111.6,97.4. 19 F NMR(377MHz,CDCl3)δ-63.13(s).HRMS(ESI) m / z calculated forC 27 H 18 F3N2S + [M+H] + 459.1137, found 459.1135.

[0063] Example 16: Preparation of 2-acetyl-10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-4))

[0064] The reaction steps were the same as those in Example 1, except that phenothiazine was replaced by 2-acetylphenothiazine. The yield of 2-acetyl-10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 72%.

[0065] 1 H NMR (600MHz, CDCl3) δ7.89(d,J=7.0Hz,1H),7.80(d,J=7.7Hz,2H),7.53(d,J=9.0Hz,1H),7.44-7.42(m,1H),7.37(t,J=7.7Hz,2H), 7.28-7.25(m,1H),7.15-7.06(m,2H),6.96(s,1H),6.92-6.81(m,3H),6.67(d, J=1.3Hz,1H),6.57(t,J=6.7Hz,1H),6.15(d,J=8.0Hz,1H),2.14(s,3H). 13C NMR (151MHz, CDCl3) δ196.8,141.6,141.3,136.5,134.0,131.2, 129.0,128.23,128.21,127.3,127.2,127.0,126.8,126.1,124.0,123.4,121.3, 120.3,119.5,118.9,116.2,115.54,115.52,111.5,97.3,26.3.HRMS(ESI)m / zcalculated for C 28 H 21 N2OS + [M+H] + 433.1369, found 433.1367.

[0066] Example 17: Preparation of 2-cyano-10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-5))

[0067] The reaction steps were the same as those in Example 1, except that phenothiazine was replaced by 2-cyanophenothiazine. The yield of 2-cyano-10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 41%.

[0068] 1 H NMR(600MHz, CDCl3)δ7.76-7.72(m,3H),7.52(d,J=8.9Hz, 1H),7.36-7.34(m,2H),7.26-7.24(m,1H)7.05-7.01(m,3H),6.91(s,1H), 6.88-6.81(m,3H),6.58-6.56(m,1H),6.15(s,1H),6.04(d,J=7.9Hz, 1H). 13 C NMR (151MHz, CDCl3) δ142.4,140.5,133.5,131.5,129.0,128.5, 128.3,127.4,127.3,127.1,127.0,125.7,124.4,121.0,119.7,119.4,119.2, 118.6,118.0,116.2,114.8,111.9,111.0,97.5.HRMS(ESI)m / z calculated for C 27 H 17 N3S + [M+Na] + 438.1035, found 438.1036.

[0069] Example 18: Preparation of 2-methylthio-10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-6))

[0070] The reaction steps were the same as those in Example 1, except that phenothiazine was replaced by 2-methylthiophenothiazine. The yield of 2-methylthio-10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 86%.

[0071] 1 H NMR (500MHz, CDCl3) δ7.85(d,J=7.1Hz,1H),7.81-7.77(m,2H),7.47(d,J=8.9Hz,1H),7.34(t,J=7.7Hz,2H),7.25-7.21(m,1H), 7.10-7.08(m,1H),6.97(d,J=8.5Hz,1H),6.91(s,1H),6.87-6.84(m,1H), 6.82-6.77(m,2H),6.55-6.50(m,1H),6.43-6.41(m,1H),6.13-6.11(m,1H), 5.78(d,J=2.5Hz,1H),3.43(s,3H). 13 C NMR (125MHz, CDCl3) δ159.8, 143.0,141.5,134.0,131.0,129.0,127.6,127.4,127.2,127.1,127.0,125.8, 123.6,121.9,121.6,119.3,118.8,116.3,116.1,112.0,111.3,108.5,103.3,97.0,55.2.HRMS(ESI)calculated for C 27 H 21 N2S2 + [M+H] + :437.1141; found: 437.1124.

[0072] Example 19: Preparation of 2-methoxy-10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-7))

[0073] The reaction steps were the same as those in Example 1, except that phenothiazine was replaced by 2-methoxyphenothiazine. The yield of 2-methoxy-10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 88%.

[0074] 1H NMR (500MHz, CDCl3) δ7.89-7.86(m,1H),7.79-7.78(m,2H), 7.48(d,J=9.0Hz,1H),7.35(t,J=7.7Hz,2H),7.25-7.22(m,1H),7.10-7.08 (m,1H),6.97(d,J=8.1Hz,1H),6.92(s,1H),6.89-6.77(m,3H),6.76-6.74 m,1H),6.55-6.52(m,1H),6.16-6.14(m,1H),6.06(d,J=1.9Hz,1H),2.00 (s,3H). 13 C NMR (125MHz, CDCl3) δ142.1,141.6,138.0,134.0,131.0, 129.0,127.7,127.2,127.0,126.0,123.7,122.0,121.6,121.5,119.3,118.8,118.0,116.2,116.0,114.2,111.37,96.9,15.7.HRMS(ESI)calculated for C 27 H 20 KN2S + [M+K] + :459.0928; found:459.0931.

[0075] Example 20: Preparation of 1-chloro-10-(2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-8))

[0076] The reaction steps were the same as those in Example 1, except that phenothiazine was replaced by 1-chlorophenothiazine. The yield of 1-chloro-10-(2-phenylindolizine-3-yl)-10H-phenothiazine was 55%.

[0077] 1 H NMR (400MHz, CDCl3) δ7.85 (d, J = 7.0Hz, 1H), 7.83-7.77 (m, 2H), 7.49 (d, J = 9.0Hz, 1H), 7.37 (t, J = 7.7Hz, 2H), 7.27-7.23 (m, 1H), 7.09-7.08(m,1H),6.95-6.75(m,5H),6.67(t,J=8.1Hz,1H),6.57-6.53(m,1H),6.04-6.01(m,1H),5.94-5.92(m,1H). 13CNMR(101MHz, CDCl3)δ 142.5,140.7,133.7,131.1,130.9,129.0,128.1,127.6,127.3,127.2,127.1, 125.7,123.8,121.4,121.1,119.9,119.4,118.9,115.9,115.8,113.9,111.5, 96.99.HRMS(ESI)m / z calculated for C 26 H 18 ClN2S + [M+H] + 425.0874, found425.0874.

[0078] Example 21: Preparation of 10-(2-(p-Tolyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-9))

[0079] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(p-tolyl)indolizine. The yield of 10-(2-(p-tolyl)indolizine-3-yl)-10H-phenothiazine was 87%.

[0080] 1 H NMR (500MHz, CDCl3) δ7.86 (d, J = 7.2 Hz, 1H), 7.73 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 9.0 Hz, 1H), 7.17 (d, J = 8.1 Hz, 2H), 7.09-7.07 (M, 2H), 6.92(s,1H),6.86-6.85(M,2H),6.82-6.77(m,3H),6.53-6.50(m,1H), 6.13-6.11(m,2H),2.33(s,3H). 13 C NMR (125MHz, CDCl3) δ141.7,136.9, 131.0,129.7,129.3,127.7,127.0,126.9,125.7,123.5,121.6,121.2,119.2, 118.7,116.2,116.0,111.1,96.7,21.3.HRMS(ESI)m / z calculated forC 27 H 21 N2S + [M+H] + 405.1420, found 405.1415.

[0081] Example 22: Preparation of 10-(2-(4-methoxyphenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-10))

[0082] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(4-methoxyphenyl)indolizine. The yield of 10-(2-(4-methoxyphenyl)indolizine-3-yl)-10H-phenothiazine was 91%.

[0083] 1 H NMR (500MHz, CDCl3) δ7.85-7.82(m,1H),7.77-7.72(m,2H), 7.46(d,J=9.0Hz,1H),7.08-7.06(m,2H),6.91-6.88(m,2H),6.86-6.82(m, 3H),6.81-6.77(m,3H),6.52-6.50(m,1H),6.11-6.10(m,2H),3.78(s,3H). 13 C NMR (125MHz, CDCl3) δ158.9,141.7,131.0,128.3,127.7,127.0,126.5, 125.5,123.6,121.6,121.2,119.1,118.7,115.94,115.86,114.4,111.0,96.4, 55.3.HRMS(ESI)m / z calculated for C 27 H 21 N2OS + [M+H] + 421.1369, found 421.1366.

[0084] Example 23: Preparation of 10-(2-(4-bromophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-11))

[0085] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(4-bromophenyl)indolizine. The yield of 10-(2-(4-bromophenyl)indolizine-3-yl)-10H-phenothiazine was 75%.

[0086] 1 H NMR (500MHz, CDCl3) δ7.83-7.81(m,1H),7.69-7.64(m,2H), 7.50-7.44(m,3H),7.08-7.06(m,2H),6.87-6.83(m,3H),6.82-6.78(m,3H), 6.55-6.52(m,1H),6.05-6.03m,2H).13 C NMR (125MHz, CDCl3) δ141.5, 132.9,132.1,131.1,128.7,127.8,127.1,124.4,123.7,121.7,121.2,121.1, 119.4,119.0,116.6,115.7,111.6,96.7.HRMS(ESI)m / zcalculated for C 26 H 18 BrN2S + [M+H] + 469.0369, found 469.0369.

[0087] Example 24: Preparation of 10-(2-(4-fluorophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-12))

[0088] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(4-fluorophenyl)indolizine, the developing solvent was petroleum ether, and the yield of 10-(2-(4-fluorophenyl)indolizine-3-yl)-10H-phenothiazine was 73%.

[0089] 1 H NMR (400MHz, CDCl3) δ7.85-7.78m, 3H), 7.50 (d, J = 9.0Hz, 1H), 7.13-7.01 (m, 4H), 6.91-6.77 (m, 6H), 6.56 -6.52m, 1H), 6.09 (d, J = 8.0Hz, 2H). 13 C NMR(101MHz,CDCl3)δ162.09(d,J C-F =246.4Hz),141.6,131.1, 130.1(d,J C-F =3.1Hz),128.8(d,J C-F =7.9Hz),127.7,127.1,124.6,123.7, 121.6,121.1,119.3,118.9,116.2,115.9,115.7(d,J C-F =3.1Hz),111.4,96.7. 19 F NMR(377MHz,CDCl3)δ-115.22(s).HRMS(ESI)m / z calculated for C 26 H 18 FN2S + [M+H] + 409.1169, found 409.1169.

[0090] Example 25: Preparation of 10-(2-(4-chlorophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-13))

[0091] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(4-chlorophenyl)indolizine. The yield of 10-(2-(4-chlorophenyl)indolizine-3-yl)-10H-phenothiazine was 83%.

[0092] 1 H NMR (500MHz, CDCl3) δ7.84-7.82(m,1H),7.77-7.71(m,2H),7.49 (d,J=9.0Hz,1H),7.34-7.29(m,2H),7.09-7.07(m,2H),6.89-6.78(m,6H), 6.56-6.51(m,1H),6.07-6.05(m,2H). 13 C NMR (125MHz, CDCl3) δ141.5, 132.9,132.4,131.1,129.1,128.4,127.7,127.1,124.4,123.7,121.6,121.2, 119.4,119.01,116.5,115.7,111.5,96.7.HRMS(ESI)m / z calculated for C 26 H 18 ClN2S + [M+H] + 425.0874, found 425.0870.

[0093] Example 26: Preparation of 10-(2-(2-fluorophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-14))

[0094] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(2-fluorophenyl)indolizine. The yield of 10-(2-(2-fluorophenyl)indolizine-3-yl)-10H-phenothiazine was 70%.

[0095] 1 H NMR (400MHz, CDCl3) δ7.77(d,J=7.0Hz,1H),7.74-7.70m,1H), 7.55(d,J=9.0Hz,1H),7.25-7.04(m,6H),6.88-6.80(m,4H),6.58-6.52(m, 1H),6.04-6.02(m,2H). 13CNMR (101MHz,CDCl3)δ160.3(d,J C-F =249.3 Hz),141.7,130.7(d,J C-F =1.4Hz),130.0(d,J C-F =3.5Hz),128.7(d,J C-F = 8.5Hz),127.7,127.0,124.5(d,J C-F =3.5Hz),123.5,121.8(d,J C-F =12.4Hz), 121.5,120.7,119.7(d,J C-F =8.0Hz),118.6,117.1,116.3,116.0,115.5,111.5, 100.0(d,J C-F =9.5Hz). 19 F NMR(377MHz,CDCl3)δ-114.43(s).HRMS (ESI)m / z calculated for C 26 H 18 FN2S + [M+H] + 409.1169, found 409.1169.

[0096] Example 27: Preparation of 10-(2-(2-chlorophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-15))

[0097] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(2-chlorophenyl)indolizine. The yield of 10-(2-(2-chlorophenyl)indolizine-3-yl)-10H-phenothiazine was 77%.

[0098] 1 H NMR (400MHz, DMSO) δ7.57-7.54(m,2H),7.39-7.37(m,1H), 7.20-7.07(m,3H),6.95-6.89(m,2H),6.84-6.70(m,6H),6.59-6.53(m,1H), 5.73-5.66(m,2H). 13C NMR (101MHz, DMSO) δ141.3,132.6,132.5, 131.05,130.1,130.0,129.2,127.8,127.1,126.9,123.7,122.5,121.5,119.7, 119.0,18.9,116.8,114.6,111.9,100.3.HRMS(ESI)m / zcalculated for C 26 H 18 ClN2S + [M+H] + 425.0874, found 425.0870.

[0099] Example 28: Preparation of 10-(2-(3-methoxyphenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-16))

[0100] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(3-methoxyphenyl)indolizine. The yield of 10-(2-(3-methoxyphenyl)indolizine-3-yl)-10H-phenothiazine was 88%.

[0101] 1 H NMR (500MHz, CDCl3) δ7.82-7.80(m,1H),7.50(d,J=8.9Hz, 1H),7.43-7.36(m,2H),7.28-7.24(m,1H),7.06-7.05(m,2H),6.92(s,1H), 6.87-6.76(m,6H),6.54-6.51(m,1H),6.06-6.04(m,2H),3.69(s,3H). 13 C NMR (125MHz, CDCl3) δ156.0,141.6,135.2,131.0,129.8,127.7,126.9, 125.3,123.6,121.6,120.8,119.7,119.4,118.8,116.4,115.8,113.7,111.9, 111.3,97.1,55.1.HRMS(ESI)m / z calculated for C 27 H 21 N2OS + (M+H) + 421.1369, found 421.1365.

[0102] Example 29: Preparation of 10-(2-(3-chlorophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-17))

[0103] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(3-chlorophenyl)indolizine. The yield of 10-(2-(3-chlorophenyl)indolizine-3-yl)-10H-phenothiazine was 82%.

[0104] 1 H NMR (500MHz, CDCl3) δ7.81-7.80(m,2H),7.67-7.66(m,1H), 7.50(d,J=9.0Hz,1H),7.25–7.18(m,2H),7.08-7.07(m,2H),6.88(s,1H), 6.87-6.78(m,5H),6.56-6.52(m,1H),6.04-6.02(m,2H). 13 C NMR (125MHz, CDCl3) δ141.6,135.8,134.7,131.1,130.2,127.7,127.4,127.1,125.2,124.0, 123.7,121.7,121.3,119.5,119.1,116.9,115.7,115.2,111.6,97.0.HRMS (ESI)m / z calculated for C 26 H 18 ClN2S + [M+H] + 425.0874, found 425.0877.

[0105] Example 30: Preparation of 10-(2-(3-bromophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-18))

[0106] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(3-bromophenyl)indolizine. The yield of 10-(2-(3-bromophenyl)indolizine-3-yl)-10H-phenothiazine was 77%.

[0107] 1 H NMR (500MHz, CDCl3) δ7.97(t,J=1.8Hz,1H),7.79(d,J=7.0 Hz,1H),7.73-7.68(m,1H),7.52-7.45(m,1H),7.35-7.33(m,1H),7.17(t,J= 7.9Hz,1H),7.09-7.07(m,2H),6.88-6.78(m,6H),6.56-6.53(m,1H), 6.03-6.01(m,2H). 13C NMR (125MHz, CDCl3) δ141.6,136.1,131.1,130.5, 130.3,123.0,127.7,127.1,125.6,123.8,123.7,123.0,121.7,121.3,119.6, 119.1,116.9,115.7,111.6,96.9.HRMS(ESI)m / z calculated forC 26 H 18 BrN2S + [M+H] + 469.0369, found 469.0370.

[0108] Example 31: Preparation of 10-(2-(3,4-dimethoxyphenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-19))

[0109] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(3,4-dimethoxyphenyl)indolizine. The yield of 10-(2-(3,4-dimethoxyphenyl)indolizine-3-yl)-10H-phenothiazine was 84%.

[0110] 1 H NMR (500MHz, CDCl3) δ7.81-7.75(m,1H),7.48(d,J=8.9Hz, 1H),7.40-7.33(m,2H),7.04(dd,J=7.4,1.7Hz,2H),6.90-6.77(m,7H), 6.51(td,J=7.0,1.0Hz,1H),6.04-6.02m,2H),3.86(s,3H),3.71(s,3H). 13 C NMR (125MHz, CDCl3) δ149.0,148.2,141.5,131.1,127.8,126.9,126.8, 125.1,123.6,121.5,120.6,119.5,119.2,118.7,115.8,115.7,111.5,111.1, 110.4,96.6,55.9,55.6.HRMS(ESI)m / z calculated for C 28 H 23 N2O2S + [M+H] + 451.1475, found 451.1473.

[0111] Example 32: Preparation of 10-(2-(3,4-dichlorophenyl)indolizine-3-yl)-10H-phenothiazine (Formula (I-20))

[0112] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(3,4-dichlorophenyl)indolizine. The yield of 10-(2-(3,4-dichlorophenyl)indolizine-3-yl)-10H-phenothiazine was 79%.

[0113] 1 H NMR (400MHz, CDCl3) δ7.90(d,J=2.1Hz,1H),7.78(d,J=7.0Hz,1H),7.62-7.60(m,1H),7.53-7.47(m,1H),7.37(d,J=8.4Hz,1H), 7.10-7.07(m,2H),6.91-6.78(m,6H),6.58-6.54(m,1H),6.01-6.98(m,2H). 13 C NMR (101MHz, CDCl3) δ141.5,134.1,132.8,131.2,130.9,129.1,127.8, 127.2,126.3,123.9,122.9,121.7,121.3,119.6,119.3,117.0,115.5,115.1, 111.8,96.8.HRMS(ESI)m / z calculated for C 26 H 17 Cl2N2S + (M+H) + 459.0484, found 459.0482.

[0114] Example 33: Preparation of 10-(8-methyl-2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-21))

[0115] The reaction steps were the same as those in Example 1, except that 2-phenylindoleazine was replaced by 8-methyl-2-phenylindoleazine. The yield of 10-(8-methyl-2-phenylindoleazine-3-yl)-10H-phenothiazine was 86%.

[0116] 1H NMR (500MHz, CDCl3) δ7.84-7.82(m,2H),7.74(d,J=6.9Hz, 1H),7.35(t,J=7.7Hz,2H),7.24(d,J=7.4Hz,1H),7.07-7.05(m,2H),6.90 (s,1H),6.85-6.77(m,4H),6.63(d,J=6.5Hz,1H),6.48(t,J=6.8Hz,1H), 6.10-6.08(m,2H),2.53(s,3H). 13 C NMR (125MHz, CDCl3) δ141.8,134.1, 131.9,128.9,128.4,127.7,127.2,127.0,126.9,125.1,123.5,121.1,119.7, 118.1,116.9,115.9,111.5,95.4,17.9.HRMS(ESI)m / z calculated for C 27 H 21 N2S + [M+H] + 405.1420, found 405.1418.

[0117] Example 34: Preparation of 10-(7-methyl-2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-22))

[0118] The reaction steps were the same as those in Example 1, except that 2-phenylindoleazine was replaced by 7-methyl-2-phenylindoleazine. The yield of 10-(7-methyl-2-phenylindoleazine-3-yl)-10H-phenothiazine was 90%.

[0119] 1 H NMR (400MHz, CDCl3) δ7.85-7.80(m,2H),7.76(d,J=7.1Hz, 1H),7.40-7.33(m,2H),7.28-7.21(m,2H),7.11-7.06(m,2H),6.89-6.78(m, 5H),6.40-6.38(m,1H),6.13-6.10(m,2H),2.34(s,3H). 13C NMR(101MHz, CDCl3)δ141.8,134.1,131.4,129.0,128.9,127.7,127.1,127.0,126.9,125.3, 123.5,121.2,121.1,117.4,115.9,115.7,114.0,95.2,21.2.HRMS(ESI)m / z calculated for C 27 H 21 N2S + (M+H) + 405.1420, found 405.1418.

[0120] Example 35: Preparation of 10-(6-methyl-2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-23))

[0121] The reaction steps were the same as those in Example 1, except that 2-phenylindoleazine was replaced by 6-methyl-2-phenylindoleazine. The yield of 10-(6-methyl-2-phenylindoleazine-3-yl)-10H-phenothiazine was 85%.

[0122] 1 H NMR (500MHz, CDCl3) δ7.81-7.79(m,2H),7.63(s,1H),7.41(d,J=9.0Hz,1H),7.34(t,J=7.7Hz,2H),7.23-7.20(m,1H),7.08-7.06(m,2H), 6.86-6.80(m,5H),6.67(d,J=8.8Hz,1H),6.11-6.09(m,2H),2.19(d,J=0.6Hz,3H). 13 C NMR (125MHz, CDCl3) δ141.7,134.1,130.0,129.5,128.9, 127.7,127.1,126.9,125.1,123.5,122.2,121.1,120.9,119.0,118.9,116.2, 115.9,115.3,18.8.HRMS(ESI)m / z calculated for C 27 H 21 N2S + [M+H] + 405.1420, found 405.1415.

[0123] Example 36: Preparation of 10-(7-bromo-2-phenylindolizine-3-yl)-10H-phenothiazine (Formula (I-24))

[0124] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 7-bromo-2-phenylindolizine. The yield of 10-(7-bromo-2-phenylindolizine-3-yl)-10H-phenothiazine was 68%.

[0125] 1 H NMR (400MHz, CDCl3) δ7.78 (d, J=1.2Hz, 1H), 7.62-7.54 (m, 3H), 7.36 (t, J=7.4Hz, 2H), 7.33-7.28 (m, 1H), 7.02-6.98 (m, 2H), 6.86-6.77 (m,5H),6.67-6.64(m,1H),5.96-5.94(m,2H). 13 C NMR (101MHz, CDCl3) δ141.5,131.5,129.6,129.4,128.6,128.0,127.7,127.1,126.2,123.8,122.6, 120.7,120.4,117.9,115.9,115.2,113.4,85.6.HRMS(ESI)m / z calculated for C 26 H 18 BrN2S + [M+H] + 469.0369, found 469.0364.

[0126] Example 37: Preparation of 10-(2-(4-chlorophenyl)-7-methylindolizine-3-yl)-10H-phenothiazine (Formula (I-25))

[0127] The reaction steps were the same as those in Example 1, except that 2-phenylindolizine was replaced by 2-(4-chlorophenyl)-7-methylindolizine. The yield of 10-(2-(4-chlorophenyl)-7-methylindolizine-3-yl)-10H-phenothiazine was 75%.

[0128] 1 H NMR (400MHz, CDCl3) δ7.78-7.70(m,3H),7.36-7.29(m,3H), 7.10-7.08(m,2H),6.89-6.80(m,4H),6.74(s,1H),6.41-6.39(m,1H), 6.08-6.05(m,2H),2.34(s,3H). 13C NMR (101MHz, CDCl3) δ141.7,132.7, 132.6,131.5,129.5,129.0,128.3,127.7,127.0,124.1,123.6,121.2,121.1, 117.48,115.9,115.7,114.2,95.1,21.2.HRMS(ESI)m / z calculated for C 27 H 20 ClN2S + [M+H] + 439.1030, found 439.1032.

[0129] Example 38: Preparation of 10-(2-(naphthalene-2-yl)indolizine-3-yl)-10H-phenothiazine (Formula (I-26))

[0130] The reaction steps are the same as those in Example 1, except that 2-phenylindolizine is replaced by 2-(naphthalene-2-yl)indolizine. The yield of 10-(2-(naphthalene-2-yl)indolizine-3-yl)-10H-phenothiazine (Formula 26) is 73%.

[0131] 1 H NMR (500MHz, CDCl3) δ8.41 (d, J=1.0Hz, 1H), 7.99-7.97 (m, 1H), 7.89-7.76 (m, 4H), 7.54 (d, J=9.0Hz, 1H), 7.48-7.40 (m, 2H), 7.13-7.11 (m,2H),7.08(s,1H),6.89-6.78(m,5H),6.57-6.54(m,1H),6.17-6.15(m,2H). 13 C NMR (125MHz, CDCl3) δ141.8,133.7,132.6,131.3,131.2,128.5, 128.4,127.8,127.6,127.0,126.1,126.0,125.9,125.5,125.2,123.7,121.6, 121.3,119.4,118.8,117.0,115.9,111.4,97.1.HRMS(ESI)m / zcalculated for C 30 H 21 N2S + [M+H] + 441.1420, found 441.1416.

Claims

1. A direct electrochemical synthesis method of triarylamine compounds, the method comprising: A phenothiazine compound with a structural formula as shown in formula (II) and a 2-aryl indolizine compound with a structural formula as shown in formula (III) are used as raw materials, a three-electrode system is adopted, a graphite electrode or a Pt electrode is used as a cathode and an anode, a 0.1 mol / L silver nitrate acetonitrile solution is used as a reference electrode, and electrolysis is carried out under stirring at 15 to 45° C. and 0.1 to 0.3 V in an organic solvent containing a supporting electrolyte. After the reaction is completed, a triarylamine compound with a structural formula as shown in formula (I) is obtained by separation treatment; the supporting electrolyte is LiClO4, n Bu4NBF4, n Bu4NPF6 or NaClO4, the organic solvent is N,N-dimethylformamide, acetonitrile or ethyl acetate; In formulas (I) to (III), R1 is H, C1-C4 alkyl, halogen, C1-C2 alkoxy, nitro, cyano, trifluoromethyl or acetyl; R2 is phenyl, substituted phenyl, naphthyl or substituted naphthyl, and the substituents of the substituted phenyl and substituted naphthyl are independently selected from one of the following: halogen, nitro, C1-C4 alkyl or C1-C4 alkoxy; R3 is H, C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine or fluorine.

2. The method according to claim 1, characterized in that: R1 is H, Cl, methoxy, methylthio, trifluoromethyl, cyano or acetyl, R2 is phenyl, halogenated phenyl, alkyl substituted phenyl, alkoxy substituted phenyl or naphthyl, and R3 is H, methyl or bromine.

3. The method according to claim 1 or 2, characterized in that: The molar ratio of the phenothiazine compound to the indolizine compound is 100:80-150.

4. The method according to claim 1 or 2, characterized in that: The molar concentration of the supporting electrolyte in the organic solvent is 0.05-0.15 mol / L.

5. The method according to claim 1 or 2, characterized in that: After the reaction is completed, the solvent is evaporated under reduced pressure, and then thin layer chromatography is performed, using a mixed solution of petroleum ether / ethyl acetate in a volume ratio of 20:1 as a developing solvent, collecting the thin layer containing the target compound, eluting with dichloromethane, filtering, and evaporating the filtrate to remove the solvent to obtain the triarylamine compound.

6. The method according to claim 1 or 2, characterized in that The method is as follows: using a phenothiazine compound with a structural formula as shown in formula (II) and a 2-aryl indolizine compound with a structural formula as shown in formula (III) as raw materials, using a three-electrode system, the cathode and the anode are both Pt electrodes, using a 0.1 mol / L silver nitrate acetonitrile solution as a reference electrode, in an N,N-dimethylformamide solution containing 0.05-0.15 mol / L LiClO4, stirring the electrolytic reaction at 15-45°C and 0.1-0.3V for 3.5-7.0 hours, then evaporating the solvent under reduced pressure, and then performing thin layer chromatography separation, using a mixed solution of petroleum ether / ethyl acetate in a volume ratio of 20:1 as a developing solvent, collecting a thin layer containing the target compound, eluting with dichloromethane, filtering, and evaporating the filtrate to remove the solvent, so as to obtain the triarylamine compound.

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