A method for preparing 9-aryl-10-sulfonylphenanthrene compounds under electrocatalysis

Abstract

The present invention discloses a method for preparing a 9-aryl-10-sulfonylphenanthrene compound under electrocatalysis, which belongs to the field of organic synthesis technology. The method comprises the following steps: adding a substituted diaryl internal alkyne, a substituted benzenesulfonyl hydrazide, and tetrabutylammonium tetrafluoroborate to a reactor. After the reaction is completed by electrocatalytic promotion in a solvent, a rotary evaporator is used to concentrate the crude product, and the crude product is separated by silica gel column chromatography to obtain a target product. The present invention provides a method for synthesizing a 9-aryl-10-sulfonylphenanthrene compound under electrocatalysis, which has the characteristics of scientific rationality, mild conditions, simple operation, and no need for external oxidants and additives. The reaction equation is as follows:

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a 9-aryl-10-sulfonylphenanthrene compound under electrocatalysis. Background Art

[0002] 9-Aryl-10-sulfonylphenanthrene compounds belong to both diarylphenanthrene and phenanthrene compounds and have a wide range of applications. Their fused-ring compounds possess photophysical properties and can be widely used in luminescent materials: (a) China Pat., CN, 114464738A, 2022; (b) China Pat., CN, 108218664A, 2018.

[0003] In view of the application value of 9-aryl-10-sulfonylphenanthrene compounds, it is of great significance to develop a new method for the practical and effective synthesis of 9-aryl-10-sulfonylphenanthrene compounds.

[0004] Methods for synthesizing 9-aryl-10-sulfonylphenanthrene compounds include:

[0005] In 2016, Jiang Bo's group reported an efficient copper-catalyzed method for synthesizing 9-aryl-10-sulfonylphenanthrene compounds via alkynylsulfonylation of diaryl alkynes with alkynes (Org. Chem. Front., 2016, 3, 1452).

[0006] The above method for preparing 9-aryl-10-sulfonylphenanthrene compounds has obvious disadvantages and shortcomings: 1) the use of metal catalysts and oxidants; 2) high reaction temperature; 3) long reaction time; 4) the need for molecular sieves to remove water. Summary of the Invention

[0007] In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a method for preparing 9-aryl-10-sulfonylphenanthrene compounds under electrocatalysis.

[0008] Electrocatalytic synthesis reactions have many significant advantages: they can avoid the use of toxic or difficult-to-handle catalysts, do not require oxidants, electrons are green reaction reagents, reaction products are highly pure and easy to separate, and are almost pollution-free to the environment; in electrocatalytic reactions, the reaction rate can be controlled by changing the electrode voltage or current to avoid the occurrence of side reactions, thereby improving the selectivity and yield of the target product.

[0009] A method for preparing a 9-aryl-10-sulfonylphenanthrene compound under electrocatalysis, wherein the 9-aryl-10-sulfonylphenanthrene compound has a structure shown in Formula I:

[0010]

[0011] In Formula I, R 1is selected from chlorine atoms and R 3 When selected from methyl, R 2 The substituent group is selected from hydrogen, chlorine, methyl, tert-butyl, phenyl; or R 1 is a hydrogen atom and R 3 When selected from methyl, R 2 The substituent group is selected from hydrogen, chlorine, methyl, ethyl, methoxy; or R 1 is selected from chlorine atoms and R 2 When selected from hydrogen, R 3 The substituent group is selected from chlorine atoms, iodine atoms, and tert-butyl groups. It is characterized in that substituted diaryl alkyne, substituted benzenesulfonyl hydrazide, and tetrabutylammonium tetrafluoroborate are added to the reactor in a molar ratio of 1:3:1.2. The solvent is 3mL of hexafluoroisopropanol and 2mL of dichloroethane, and the system concentration is 0.02mol / L. Under the action of electricity, stirring at 60°C, after the reaction is completed, a rotary evaporator is used to concentrate to obtain a crude product, and the crude product is separated by silica gel column chromatography to obtain the target product. The chemical reaction process is shown in Formula II:

[0012]

[0013] The beneficial effects of the present invention are as follows: the method for synthesizing multi-substituted 9-aryl-10-sulfonylphenanthrene compounds under electrocatalysis provided by the present invention is scientific and reasonable, provides a new approach for synthesizing 9-aryl-10-sulfonylphenanthrene derivatives, and obtains 9-aryl-10-sulfonylphenanthrene compounds with various substituents by the method. The method has the following characteristics: mild conditions, simple operation, no need for external oxidants and additives, safe, green, and low-cost, and the functional groups have wide universality. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 NMR spectrum of compound 3aa prepared in Example 1;

[0015] Figure 2 NMR spectrum of compound 3ea prepared in Example 5;

[0016] Figure 3 This is the NMR spectrum of compound 3fa prepared in Example 6. DETAILED DESCRIPTION

[0017] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments:

[0018] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are all commercially available unless otherwise specified.

[0019] Example 1

[0020] Preparation of 9-aryl-10-sulfonylphenanthrene compound 3aa

[0021]

[0022] A 10 mL three-necked flask was charged with diaryl alkyne 1a (0.1 mmol, 28.9 mg), p-toluenesulfonylhydrazide 2a (0.3 mmol, 55.9 mg), and tetrabutylammonium tetrafluoroborate (0.12 mmol, 39.2 mg). The system was sealed with a rubber stopper. A platinum electrode (1 cm x 1 cm x 0.1 cm) was used as the cathode, and a graphite felt electrode (1 cm x 1 cm x 0.5 cm) was used as the anode. The system was then purged with nitrogen, and hexafluoroisopropanol / dichloroethane (3 mL:2 mL) was added. The reaction was continued at 60°C and 4 mA for 5 hours. After completion of the reaction, the solvent was removed using a rotary evaporator to obtain the crude product. The crude product was separated by column chromatography (200-300 mesh silica gel) (petroleum ether / ethyl acetate = 10 / 1), and the solvent was removed using a rotary evaporator to obtain the target product, 9-(4-chloro)phenyl-10-p-toluenesulfonylphenanthrene derivative 3aa, in 87% yield.

[0023] Spectral analysis data 3aa:

[0024] 1 H NMR (500MHz, CDCl3): δ9.03(d,J=8.6Hz,1H),8.72(t,J=8.0Hz,2H),7.74(t,J=7.6Hz,1H),7.68(t,J=7.6Hz,1H),7.60(t,J=7.7Hz,1H),7.56( d,J=8.1Hz,2H),7.48(t,J=7.7Hz,1H),7.40(d,J=8.1Hz,2H),7.35(d,J=8.3Hz,1H),7.21(d,J=8.1Hz,2H),7.14(d,J=8.1Hz,2H),2.33(s,3H). 13 C NMR (125MHz, CDCl3): δ143.01,141.71,140.23,135.74,133.27,132.67,131.77,130.92,130.89,130.47,129.17,12 8.98,128.84,127.40,127.09,127.02,126.86,126.65,126.31,125.94,122.46,122.06,21.03.HRMS(ESI-TOF,[M+Na + ]):For C 27 H 19 ClNaO2S,465.0692,found 465.0687.

[0025] Example 2

[0026] 1a in Example 1 was replaced by 1b. Other conditions were the same as those in Example 1. The experimental results are shown in Table 1.

[0027]

[0028] Spectral analysis data 3ba:

[0029] 1 H NMR (500MHz, CDCl3): δ9.05 (d, J=8.6Hz, 1H), 8.67 (dd, J=11.5, 8.6Hz, 2H), 7.69 (dd, J=8.9, 2.5Hz, 2H), 7.63 (t, J=7.8 Hz,1H),7.54(d,J=8.1Hz,2H),7.41(d,J=8.4Hz,2H),7.30(d,J=2.2Hz,1H),7.17(dd,J=17.3,8.3Hz,4H),2.35(s,3H). 13 C NMR (125MHz, CDCl3): δ143.69,140.92,140.43,135.34,134.65,134.16,133.62,132.56,131.39,130.56,130.51,13 0.08,129.51,128.19,128.14,127.96,127.78,127.29,126.74,126.47,124.25,122.88,21.55.HRMS(ESI-TOF,[M+Na + ]):For C 27 H 18 Cl2NaO2S,499.0302,found 499.0305.

[0030] Example 3

[0031] 1a in Example 1 was replaced by 1c. Other conditions were the same as those in Example 1. The experimental results are shown in Table 1.

[0032]

[0033] Spectral analysis data 3ca:

[0034] 1H NMR (500MHz, CDCl3): δ9.02–8.96(d,1H),8.69(d,J=8.3Hz,1H),8.61(d,J=8.5Hz,1H),7.65(ddd,J=8.3,6.9,1. 2Hz,1H),7.60–7.52(m,4H),7.41(d,J=8.3Hz,2H),7.14(d,J=8.0Hz,2H),7.11(s,1H),2.39(s,3H),2.33(s,3H). 13 C NMR (125MHz, CDCl3): δ142.90,141.50,140.31,136.86,135.77,133.17,132.55,130.94,130.91,130.48,129.67,128.9 3,128.22,127.37,126.97,126.59,126.55,125.92,125.87,122.22,122.00,21.20,21.02.HRMS(ESI-TOF,[M+H+]):For C 28 H 22 ClO2S,457.1029,found 457.1021.

[0035] Example 4

[0036] 1a in Example 1 is replaced by 1d. Other conditions are the same as those in Example 1. The experimental results are shown in Table 1.

[0037]

[0038] Spectral analysis data 3da:

[0039] 1 H NMR (500MHz, CDCl3): δ9.00(d,J=8.5,2.9Hz,1H),8.72–8.62(dd,2H),7.82(dd,J=8.7,2.3Hz,1H),7.65(t,J=7.7Hz,1H),7.59–7.51(m,3H),7 .44–7.39(m,2H),7.33(d,J=2.2Hz,1H),7.23(dd,J=8.5,2.5Hz,2H),7.12(dd,J=8.6,2.5Hz,2H),2.32(s,J=2.5Hz,3H),1.23(s,J=2.6Hz,9H). 13C NMR (125MHz, CDCl3): δ150.29,143.39,142.44,140.83,136.42,133.66,132.92,131.43,131.16,130.86,130.14,129.42,127. 98,127.77,127.47,127.10,127.08,126.57,126.40,125.11,122.79,122.37,34.95,31.05,21.52.HRMS(ESI-TOF,[M+H+]):For C 31 H 28 ClO2S,499.1499,found 499.1497.

[0040] Example 5

[0041] 1e is used to replace 1a in Example 1. Other conditions are the same as those in Example 1. The experimental results are shown in Table 1.

[0042]

[0043] Spectral analysis data 3ea:

[0044] 1 H NMR (500MHz, CDCl3): δ9.04(d,J=8.6Hz,1H),8.77(dd,J=16.9,8.5Hz,2H),8.00(dd,J=8.6,2.0Hz,1H),7.70(t,J=7.6Hz,1H),7.61(t ,J=7.8Hz,1H),7.58–7.54(m,3H),7.50–7.39(m,6H),7.37(d,J=7.0Hz,1H),7.26(d,J=6.3Hz,2H),7.15(d,J=8.0Hz,2H),2.34(s,3H). 13 C NMR (125MHz, CDCl3): δ143.49,142.25,140.67,140.00,136.00,133.87,133.63,131.72,131.44,131.27,130.77,129.45,129.0 5,128.86,127.97,127.84,127.67,127.48,127.21,127.17,126.78,126.42,123.19,122.96,21.53,-0.00.HRMS(ESI-TOF,[M+Na + ]):For C 33 H 23ClNaO2S,541.1005,found 541.1005.

[0045] Example 6

[0046] 1f is used to replace 1a in Example 1. Other conditions are the same as those in Example 1. The experimental results are shown in Table 1.

[0047]

[0048] Spectral analysis data 3fa:

[0049] 1 H NMR (500MHz, CDCl3): δ9.03(d,J=8.5Hz,1H),8.74(t,J=8.9Hz,2H),7.74(t,J=7.6Hz,1H),7.68(t,J=7.6Hz,1H),7.59( dd,J=16.0,8.1Hz,3H),7.51–7.40(m,4H),7.37(d,J=8.4Hz,1H),7.32–7.27(m,2H),7.12(d,J=8.1Hz,2H),2.33(s,3H). 13 C NMR (125MHz, CDCl3): δ143.63,143.18,140.84,137.72,132.73,132.21,131.72,130.85,130.06,129.65,129.47 ,129.37,127.54,127.37,127.33,127.17,127.14,126.89,126.45,122.88,122.38,21.49.HRMS(ESI-TOF,[M+Na + ]):For C 27 H 20 NaO2S,431.1082,found431.1081.

[0050] Example 7

[0051] 1g was used to replace 1a in Example 1. Other conditions were the same as those in Example 1. The experimental results are shown in Table 1.

[0052]

[0053] Spectral analysis data 3ga:

[0054] 1H NMR (500MHz, CDCl3): δ9.06(dd,J=8.6,1.3Hz,1H),8.71–8.61(m,2H),7.72–7.65(m,2H),7.62(ddd,J=8.5,7.0,1.4Hz,1H) ,7.55(dd,J=8.5,2.0Hz,2H),7.48–7.40(m,3H),7.32(d,J=2.2Hz,1H),7.28–7.21(m,2H),7.17–7.07(m,2H),2.33(s,3H). 13 C NMR (125MHz, CDCl3): δ143.38,142.41,140.58,136.87,134.23,133.42,132.97,130.53,130.42,130.07,129.90,129.4 3,128.55,127.94,127.78,127.73,127.65,127.30,126.86,126.51,124.10,122.83,21.51,-0.00.HRMS(ESI-TOF,[M+Na + ]):For C 27 H 19 ClNaO2S,465.0692, found 465.0690.

[0055] Example 8

[0056] 1a in Example 1 was replaced by 1h. Other conditions were the same as those in Example 1. The experimental results are shown in Table 1.

[0057]

[0058] Spectral analysis data 3ha:

[0059] 1 H NMR (500MHz, CDCl3): δ8.99(dd,J=8.6,1.2Hz,1H),8.69(dd,J=8.5,1.3Hz,1H),8.61(d,J=8.5Hz,1H),7.68–7.62(m,1H),7.56(dd ,J=8.5,2.2Hz,4H),7.46–7.41(m,2H),7.30–7.26(m,2H),7.13(d,J=5.1Hz,2H),7.11(d,J=1.8Hz,1H),2.37(s,3H),2.32(s,3H). 13C NMR (125MHz, CDCl3): δ143.48,143.11,140.96,137.77,137.12,132.65,131.82,131.27,130.90,130.14,130.09,12 9.37,129.08,127.52,127.25,127.10,126.94,126.53,126.42,122.68,122.36,21.71,21.50.HRMS(ESI-TOF,[M+Na + ]):For C 28 H 22 NaO2S,445.1238,found 445.1238.

[0060] Example 9

[0061] 1a in Example 1 is replaced by 1i. Other conditions are the same as those in Example 1. The experimental results are shown in Table 1.

[0062]

[0063] Spectral analysis data 3ia:

[0064] 1 H NMR (500MHz, CDCl3): δ9.01(d,J=8.7Hz,1H),8.66(dd,J=31.9,8.5Hz,2H),7.63(d,J=8.3Hz,1H),7.56(dd,J=8.5,2.3Hz,4H),7.49–7 .39(m,3H),7.29(dd,J=5.8,2.3Hz,2H),7.15(s,1H),7.10(d,J=8.2Hz,2H),2.65(q,J=7.6Hz,2H),2.31(s,3H),1.15(t,J=7.6Hz,3H). 13 C NMR (125MHz, CDCl3): δ143.57,143.30,143.08,140.94,137.78,132.58,131.84,130.88,130.34,130.10,130.07,129.33,1 27.92,127.50,127.47,127.22,127.07,126.91,126.55,126.40,122.69,122.44,28.83,21.47,15.31.HRMS(ESI-TOF,[M+Na + ]):For C 29 H 24NaO2S,459.1395,found459.1389.

[0065] Example 10

[0066] 1a in Example 1 is replaced by 1j. Other conditions are the same as those in Example 1. The experimental results are shown in Table 1.

[0067]

[0068] Spectral analysis data 3ja:

[0069] 1 H NMR (500MHz, CDCl3): δ8.96(d,J=8.0Hz,1H),7.61–7.56(m,2H),7.47(d,J=7.5Hz,1H),7.42–7.27(m,5H),7.28–7.21(m,1H),7 .20–7.14(m,2H),7.10(d,J=8.0Hz,2H),6.72(dd,J=8.2,2.3Hz,1H),5.34(d,J=2.4Hz,1H),3.26(s,J=1.4Hz,3H),2.33(s,3H). 13 C NMR (125MHz, CDCl3): δ158.69,144.09,142.55,142.24,141.84,139.87,136.70,135.35,134.76,134.08,131.01,130.81,1 30.28,129.11,129.08,129.06,128.83,126.50,119.97,118.45,116.82,111.94,54.85,21.55,-0.00.HRMS(ESI-TOF,[M+Na + ]):ForC 27 H 19 ClNaO3S,481.0641, found 481.0632.

[0070] Example 11

[0071] 2a in Example 1 was replaced by 2b, and other conditions were the same as in Example 1. The experimental results are shown in Table 1.

[0072]

[0073] Spectral analysis data 3ab:

[0074] 1H NMR (500MHz, CDCl3): δ9.01(d,J=8.5Hz,1H),8.75(dd,J=11.5,8.4Hz,2H),7.77(t,J=7.6Hz,1H),7.72(t,J=7.7Hz,1H),7.64(t,J=7.7Hz,1 H),7.58(d,J=8.2Hz,2H),7.51(t,J=7.7Hz,1H),7.42(d,J=7.9Hz,2H),7.37(d,J=8.5Hz,1H),7.32(d,J=8.2Hz,2H),7.20(d,J=7.9Hz,2H). 13 C NMR (125MHz, CDCl3): δ142.50,142.10,139.11,135.82,134.05,132.66,132.33,131.54,131.19,130.97,129.90 ,129.30,129.11,127.98,127.83,127.76,127.65,127.47,126.85,126.60,123.08,122.60.HRMS(ESI-TOF,[M+H + ]):For C 26 H 16 Cl2O2S,4463.0326, found 463.0322.

[0075] Example 12

[0076] 2a in Example 1 was replaced by 2c. Other conditions were the same as those in Example 1. The experimental results are shown in Table 1.

[0077]

[0078] Spectral analysis data 3ac:

[0079] 1 H NMR (500MHz, CDCl3): δ9.01(d,J=8.6Hz,1H),8.75(dd,J=11.9,8.4Hz,2H),7.77(t,J=7.6Hz,1H),7.70(t,J=7.3Hz,3 H),7.65(t,J=8.0Hz,1H),7.51(t,J=7.6Hz,1H),7.41(d,J=7.9Hz,2H),7.35(d,J=7.9Hz,3H),7.19(d,J=8.0Hz,2H). 13C NMR (125MHz, CDCl3): δ143.30,142.46,138.05,135.78,134.06,132.62,132.32,131.55,131.17,130.96,129.91 ,129.30,128.00,127.78,127.74,127.68,127.48,126.86,126.59,123.10,122.62,100.08.HRMS(ESI-TOF,[M+H + ]):For C 26 H 16 ClIO2S,554.9682,found554.9673.

[0080] Example 13

[0081] 2a in Example 1 is replaced by 2d. Other conditions are the same as those in Example 1. The experimental results are shown in Table 1.

[0082]

[0083] Spectral analysis data 3ad:

[0084] 1 H NMR (500MHz, CDCl3): δ9.14 (d, J=8.5Hz, 1H), 8.72 (dd, J=13.5, 8.3Hz, 2H), 7.71 (dt, J=15.8, 7.7Hz, 2H), 7.64 (t, J= 7.7Hz,1H),7.55(d,J=8.2Hz,2H),7.46(t,J=7.7Hz,1H),7.33(d,J=7.7Hz,5H),7.16(d,J=7.9Hz,2H),1.27(s,9H). 13 C NMR (125MHz, CDCl3): δ156.04,141.33,140.18,135.60,133.34,133.30,131.82,131.29,130.88,130.57,129.23,128.8 0,127.47,127.22,127.13,126.93,126.86,126.52,125.92,125.47,122.56,122.19,34.72,30.68.HRMS(ESI-TOF,[M+Na + ]):For C 30 H 25 ClNaO2S,507.1161,found 507.1154.

[0085] Table 1

[0086]

[0087]

Claims

1. A method for preparing a 9-aryl-10-sulfonylphenanthrene compound under electrocatalysis, wherein the 9-aryl-10-sulfonylphenanthrene compound has the structure shown in Formula I: In Formula I, R 1 is selected from chlorine atoms and R 3 When selected from methyl, R 2 The substituent group is selected from hydrogen, chlorine, methyl, tert-butyl, phenyl; or R 1 is a hydrogen atom and R 3 When selected from methyl, R 2 The substituent group is selected from hydrogen, chlorine, methyl, ethyl, methoxy; or R 1 is selected from chlorine atoms and R 2 When selected from hydrogen, R 3 The substituent group is selected from a chlorine atom, an iodine atom, and a tert-butyl group; the method is characterized in that a substituted diaryl internal alkyne, a substituted benzenesulfonyl hydrazide, and tetrabutylammonium tetrafluoroborate are added to a reactor at a molar ratio of 1:3:1.2; the solvent is 3 mL of hexafluoroisopropanol and 2 mL of dichloroethane, and the system concentration is 0.02 mol / L; after the reaction is completed under the action of electricity, a rotary evaporator is used to concentrate to obtain a crude product, which is then separated by silica gel column chromatography to obtain the target product. The chemical reaction process is shown in Formula II:

2. The method for preparing the 9-aryl-10-sulfonylphenanthrene compound according to item 1, characterized in that: A platinum electrode was used as the cathode and a graphite felt (GF) electrode was used as the anode. The reaction was promoted by electrocatalysis at a constant current of 4 mA, a reaction temperature of 60°C, N2 conditions, and a reaction time of 5 h.

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