CN113322479A - Synthesis method of 9-aryl-9H-oxygen/thioxanthone compound - Google Patents

Synthesis method of 9-aryl-9H-oxygen/thioxanthone compound Download PDF

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CN113322479A
CN113322479A CN202110634463.3A CN202110634463A CN113322479A CN 113322479 A CN113322479 A CN 113322479A CN 202110634463 A CN202110634463 A CN 202110634463A CN 113322479 A CN113322479 A CN 113322479A
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高慧
王培龙
李洪基
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Huaibei Normal University
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Abstract

The invention discloses a synthesis method of a 9-aryl-9H-oxygen/thioxanthone compound, belonging to the technical field of organic chemistry. Oxygen/thioxanthene 1 and arene 2 are used as raw materials to carry out C-H/C-H coupling under electrochemical anodic oxidation, and the rapid synthesis of 9-aryl-9H-oxygen/thioxanthene compounds 3 is realized. The invention has high atom/step economy for direct coupling of C-H/C-H by adopting electrochemistry, realizes the reaction without a catalyst and an oxidant, is green and environment-friendly, and provides a new way for synthesizing 9-aryl-9H-oxygen/thioxanthene series products with rapidness, high efficiency, economy and greenness.

Description

Synthesis method of 9-aryl-9H-oxygen/thioxanthone compound
Technical Field
The invention relates to a synthesis method of 9-aryl-9H-oxygen/thioxanthene, belonging to the technical field of organic chemistry.
Background
Xanthene and thioxanthene derivatives, especially 9-aryl-9H-xanthene and 9-aryl-9H-thioxanthene and the like, are backbone structures of many natural products and drug molecules. Over the past several years, a great deal of research has been conducted on the synthesis of 9-aryl-9H-oxo/thioxanthenes, the most classical of which is starting from diarylmethanol derivatives, which however require the use of metal catalysts or complex organic molecular catalysts. In 2020, it was reported that triarylmethanol derivatives were used as starting materials in NaHSO4/SiO2The synthesis of 9-aryl-9H-xanthene and 9-aryl-9H-thiaanthracene is realized under catalysis, but the reaction raw materials are not commercialized and are difficult to synthesize. Another synthetic strategy is to use a benzyne precursor to react with an aldehyde or ketone, however atom economy is poor.
In 2012, C-H/C-H coupling of xanthene and aromatic hydrocarbon was reported, and the reaction uses trifluoromethanesulfonic acid catalyst, however, the reaction conditions are harsh, high pressure oxygen (10bar) and low boiling point solvent dichloromethane 100 ℃ are required, and the yield is only 27% in the case of 9- (4-methoxyphenyl) -9H-xanthene. In 2016, a palladium/copper co-catalyzed xanthene to arene reaction was reported using 5 mol% Pd (OAc)2And 10 mol% Cu (OTf)2As a catalyst, the use of noble metals increases the production cost and the difficulty of product purification. Meanwhile, the reaction conditions are harsh, aromatic hydrocarbon is used as a solvent, and the reaction temperature is as high as 130-145 ℃. In 2018, the reaction is also realized in the presence of 20 mol% of p-toluenesulfonic acid monohydrate by using a graphene oxide material as a catalyst, and the reaction temperature is 100 ℃. However, the catalyst used in the reaction has complex preparation process and high price, which limits the industrial production.
The method directly uses cheap and easily-obtained xanthene or thioxanthene and arene to carry out C-H/C-H coupling, does not need to prepare a functionalized substrate, has high atom economy and step economy, and is a method for quickly and efficiently preparing 9-aryl-9H-xanthene and 9-aryl-9H-thioxanthene. However, there is no relevant literature report, so it is still necessary to explore methods for constructing 9-aryl-9H-xanthene, 9-aryl-9H-thioxanthene and the like under the conditions of no catalyst, no oxidant and mild conditions.
Disclosure of Invention
In order to overcome the defect of C-H/C-H coupling reaction between xanthene or thioxanthene and arene, the invention adopts a carbon rod as an anode, so that the xanthene or thioxanthene is directly oxidized at the anode, the No. 9 carbon of the xanthene or thioxanthene is firstly oxidized into free radicals and then oxidized into carbonium ions, and then electrophilic substitution reaction is carried out with arene, and 9-aryl-9H-xanthene and 9-aryl-9H-thioxanthene are obtained. The method provides a new way for synthesizing 9-aryl-9H-oxygen/thioxanthene series products, which is rapid, efficient, economic and green.
The invention relates to a synthesis method of 9-aryl-9H-oxygen/thioxanthene, which comprises the following operations: taking oxygen/thiaanthracene 1 and arene 2 as raw materials, and reacting under an electrochemical condition to obtain 9-aryl-9H-xanthene 3.
The reaction equation is as follows:
Figure RE-GDA0003147014310000021
wherein R is1And R2Each independently selected from C1-C4 alkyl, C1-C4 alkoxy, hydrogen, halogen, hydroxy; ar is selected from phenyl, thienyl or benzofuranyl; r is one or more of C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, hydrogen, halogen and hydroxyl.
Further, in the above technical scheme, the reaction is carried out in the presence of an acid additive.
Further, in the above technical solution, the acid additive is selected from acetic acid, propionic acid, trifluoroacetic acid, pivalic acid, methanesulfonic acid or p-toluenesulfonic acid monohydrate.
Further, in the above technical means, the electrode material is selected from the group consisting of C (+)/C (-), Pt (+)/Pt (-), C (+)/Pt (-), or Pt (+)/C (-); the current intensity is 2-8 mA.
Further, in the technical scheme, the molar ratio of the oxygen/thiaanthracene 1 to the aromatic hydrocarbon 2 is 1: 10-30; preferably in a molar ratio of 1: 20.
Further, in the above technical solution, the reaction is carried out in the presence of an electrolyte selected from n-Bu4NPF6、n-Bu4NBF4、n-Bu4ClO4、n-Bu4NOAc、 n-Bu4NHSO4、n-Bu4NI or n-Bu4NBr。
Further, in the above technical scheme, the reaction is carried out in a solvent, and the organic solvent is selected from acetonitrile, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide, methanol, ethanol, acetic acid, water or hexafluoroisopropanol.
Further, in the above technical scheme, the reaction temperature is selected from 50 ℃ to 80 ℃.
Further, in the above technical means, the reaction is carried out in an air or inert gas atmosphere, preferably an air atmosphere.
To further explore the reaction principles, the following comparative experiments were performed and the reaction results were as follows:
1) cyclic voltammetry experiments found that xanthene had an oxidation potential of about 1.9V, while anisole had an oxidation potential of about 2.5V, and methanesulfonic acid was not oxidized by the electrode. It follows that xanthene is more easily oxidized, so the first step of the reaction is that xanthene is oxidized.
2) TEMPO and BHT experiments showed that free radicals were generated during the reaction, and the results are as follows:
(a)
Figure RE-GDA0003147014310000041
(b)
Figure RE-GDA0003147014310000042
from the above results, it is assumed that the reaction mechanism is as shown in the following formula, taking the reaction of 1a and 2a to form 3a as an example:
Figure RE-GDA0003147014310000043
the No. 9 carbon of the xanthene is changed into carbon free radical under the electrode oxidation, then the xanthene is continuously oxidized into carbonium ion by the anode, and the carbonium ion continuously carries out electrophilic substitution reaction with anisole to obtain 9- (4-methoxyphenyl) -9H-xanthene. H of methanesulfonic acid at the cathode+To obtain electrons, which are reduced to hydrogen.
The invention has the beneficial effects that:
the electrochemical anode is adopted to oxidize xanthene or thioxanthene and arene to carry out C-H/C-H coupling, thereby realizing the rapid synthesis of 9-aryl-9H-xanthene, 9-aryl-9H-thioxanthene and the like. The electric energy is clean energy, the direct coupling of C-H/C-H has high atom economy and step economy, and the reaction is realized without a catalyst and an oxidant, so that the method is green and environment-friendly. Meanwhile, the reaction condition is mild, and high temperature and high pressure are not needed.
Detailed Description
Example 1
Optimization of reaction conditions
Xanthene (1a,32.2mg,0.5mmol), electrolyte (0.4 mol%), anisole (2a,1.0814g,10mmol), additive (2eq,1mmol), organic solvent (5mL) were added to a 10mL diaphragm-free electrolytic cell in that order. The bottle mouth is plugged with a rubber plug inserted with an electrode, an empty balloon is inserted, a constant potential rectifier is connected with the electrode, the current intensity is set, the current is introduced, and the reaction is carried out for 12 hours at the temperature of 80 ℃. After completion of the reaction, distilled water (30mL) was added and extracted with an organic solvent. The organic layers were combined, dried over anhydrous sodium sulfate, and distilled under reduced pressure using a rotary evaporator to give a crude product, which was purified by a silica gel column (petroleum ether/ethyl acetate: 30:1) to give product 3 a. The optimized reaction results are as follows:
Figure RE-GDA0003147014310000051
Figure RE-GDA0003147014310000071
in the process of screening reaction conditions, the influences of additives (reference numbers 1-6), the molar ratio of 1a to 2a (reference number 7), different electrode materials (reference numbers 8-10), different electrolytes (reference numbers 11-16), different solvents (reference numbers 17-24), different current intensities (reference numbers 25-26), reaction temperature (reference number 27), whether nitrogen protection is available (reference number 28) and the like are examined. Finally, C (+)/Pt (-) is determined as the optimal electrode material, MsOH is determined as the optimal additive, n-BuN4BF4For the best electrolyte, DCE is the best solvent.
Example 2:
xanthene (1a,91.1mg,0.5mmol), n-Bu4NBF4(131.7mg,0.4mol%), anisole (2a,1.0814g,10mmol), methanesulfonic acid (2eq,96.1mg, 1mmol), 1, 2-dichloroethane (5mL) were added in succession to a 10mL diaphragm-free electrolytic cell. The bottle mouth was plugged with a rubber stopper with an inserted electrode (carbon rod as anode, 1 cm. times.1 cm platinum electrode as cathode), an empty balloon was inserted, a potentiostat was connected to the electrode, the current intensity was set at 5mA, and the reaction was carried out at 80 ℃ for 12 hours with the passage of current. After completion of the reaction, distilled water (30mL) was added and extracted with ethyl acetate (3X 30 mL). The combined organic layers were dried over anhydrous sodium sulfate and distilled under reduced pressure using a rotary evaporator to give the crude product which was purified by silica gel column purification (petroleum ether/ethyl acetate 30:1) to give 116.5mg of product 3a as a pale yellow solid in 81% yield.
9-(4-methoxyphenyl)-9H-xanthene(3a):Pale yellow solid.；116.5mg, 81％yield；1H NMR(600MHz,CDCl3)δ7.22-7.19(m,2H),7.14-7.11 (m,4H),7.06(d,J＝7.2Hz,2H),6.98(td,J＝7.7,1.1Hz,2H),6.83-6.81 (m,2H),5.22(s,1H),3.76(s,3H).13C NMR(151MHz,CDCl3)δ158.5, 151.2,139.0,129.8,129.5,127.9,124.9,123.3,116.6,114.3,55.4,43.7. HRMS(ESI)calcd.for C20H17O2 +([M+H]+):289.1223,found:289.1220.
Example 3:
according to the reaction conditions of example 2, only the structure of the substrate 1 or the substrate 2 was changed to obtain the following reaction product results:
9-(3,4-dimethoxyphenyl)-9H-xanthene(3b):Pale yellow solid；113.6 mg,71％yield；1H NMR(600MHz,CDCl3)δ7.22-7.28(m,2H),7.13 (dd,J＝8.2,1.1Hz,2H),7.06(d,J＝7.0Hz,2H),6.98(td,J＝7.5,1.2 Hz,2H),6.79(d,J＝1.0Hz,2H),6.66(s,1H),5.20(s,1H),3.84(s,3H), 3.76(s,3H).13C NMR(151MHz,CDCl3)δ151.2,149.4,148.0,139.1, 129.8,128.0,124.7,123.3,120.8,116.6,111.7,111.2,56.0,44.1.HRMS (ESI)calcd.for C21H18NaO3 +([M+Na]+):341.1148,found:341.1147.
2-methyl-4-(9H-xanthen-9-yl)phenol(3c):Pale yellow solid；74.7mg, 52％yield；1H NMR(600MHz,CDCl3)δ7.18(t,J＝7.5Hz,2H),7.11 (d,J＝8.1Hz,2H),7.04(d,J＝7.5Hz,2H),6.96(t,J＝7.4Hz,2H), 6.91(s,1H),6.88(dd,J＝8.1,1.5Hz,1H),6.64(d,J＝8.1Hz,1H),5.14 (s,1H),4.63(s,1H),2.15(s,3H).13C NMR(151MHz,CDCl3)δ152.6, 151.1,139.1,131.1,129.8,127.9,127.2,124.9,124.2,123.3,116.6, 115.2,43.7,16.0.HRMS(ESI)calcd.for C20H17O2 +([M+H]+):289.1223, found:289.1218.
9-(benzofuran-2-yl)-9H-xanthene(3d):Prepared following general procedure using MeCN as a solvent instead of DCE；Yellow solid； 125.1mg,84％yield；1H NMR(600MHz,CDCl3)δ7.42(d,J＝7.4Hz, 1H),7.37(d,J＝8.0Hz,1H),7.32(d,J＝7.6Hz,2H),7.28-7.25(m,2H), 7.20-7.13(m,4H),7.06(td,J＝7.5,1.1Hz,2H),6.26(s,1H),5.49(s, 1H).13C NMR(151 MHz,CDCl3)δ160.0,155.2,151.6,129.7,128.8, 128.5,123.9,123.4,122.8,120.9,120.8,116.9,111.4,103.7,38.6. HRMS(EI)calcd.for C21H14O2 +(M+):298.0988,found:298.0984.
9-(5-iodothiophen-2-yl)-9H-xanthene(3e):Brown Solid；122.4 mg,63％ yield；1H NMR(600 MHz,CDCl3)δ7.26-7.20(m,4H),7.12(d,J＝8.1 Hz,2H),7.05(t,J＝7.5 Hz,2H),6.98(d,J＝3.7 Hz,1H),6.45(d,J＝ 3.7 Hz,1H),5.49(s,1H).13C NMR(151 MHz,CDCl3)δ156.2,151.1, 136.5,129.5,128.7,126.4,123.6,123.3,117.0,72.8,39.9.HRMS(EI) calcd.for C17H11IOS+(M+):389.9570,found:389.9575.
9-(4-methoxyphenyl)-2-methyl-9H-xanthene(3f):Yellow solid；80.8 mg,53％yield；1H NMR(600 MHz,CDCl3)δ7.19-7.16(m,1H),7.12- 7.08(m,3H),7.04-6.94(m,4H),6.83-6.79(m,3H),5.15(s,1H),3.75(s, 3H),2.22(s,3H).13C NMR(151 MHz,CDCl3)δ158.4,151.3,149.1, 139.2,132.6,130.0,129.8,129.5,128.6,127.8,124.9,124.4,123.1, 116.6,116.4,114.2,55.4,43.8,20.9.HRMS(ESI)calcd.for C21H19O2 + ([M+H]+):303.1380,found:303.1380.
2-chloro-9-(4-methoxyphenyl)-9H-xanthene(3g):Pale yellow solid； 132.0 mg,82％yield；1H NMR(600 MHz,CDCl3)δ7.21-7.19(m,1H), 7.14(dd,J＝8.7,2.5 Hz,1H),7.09(t,J＝8.1 Hz,3H),7.05(d,J＝8.7 Hz, 1H),7.02-6.97(m,3H),6.82(d,J＝8.6 Hz,2H),5.15(s,1H),3.77(s, 3H).13C NMR(151 MHz,CDCl3)δ158.6,150.8,149.7,138.2,129.8, 129.6,129.4,128.1,128.0,128.0,126.5,124.1,123.6,118.1,116.6,114.4, 55.4,43.6.HRMS(EI)calcd.for C20H15ClO2 +(M+):322.0755,found: 322.0752.
9-(benzofuran-2-yl)-2-chloro-9H-xanthene(3h):White solid；87.5 mg, 53％yield；1H NMR(600 MHz,CDCl3)δ7.45(d,J＝7.6 Hz,1H),7.38 (d,J＝8.2 Hz,1H),7.30-7.26(m,3H),7.23-7.19(m,2H),7.15(dd,J＝ 15.3,7.9 Hz,2H),7.09-7.05(m,2H),6.31(s,1H),5.44(s,1H).13C NMR (151 MHz,CDCl3)δ159.1,155.3,151.3,150.2,129.7,129.3,129.0, 128.9,128.3,128.1,124.2,123.7,122.9,122.3,121.0,120.0,118.4, 117.0,111.4,104.0,38.5.HRMS(EI)calcd.for C21H13ClO2 +(M+): 332.0599,found:332.0595.
2-methoxy-9-(4-methoxyphenyl)-9H-xanthene(3i):Pale yellow solid； 65.8 mg,41％yield；1H NMR(600 MHz,CDCl3)δ7.20-7.17(m,1H), 7.12-7.02(m,5H),6.95(td,J＝7.6,1.1 Hz,1H),6.81-6.79(m,2H),6.76 (dd,J＝8.9,3.0 Hz,1H),6.55(d,J＝2.9 Hz,1H),5.16(s,1H),3.75(s, 3H),3.69(s,3H).13C NMR(151 MHz,CDCl3)δ158.4,155.4,151.4, 145.4,138.7,129.7,129.5,127.9,125.6,124.4,123.1,117.3,116.6,114.2, 114.1,113.8,55.7,55.4,44.1.HRMS(ESI)calcd.for C21H19O3 +([M+H]+): 319.1329,found:319.1327.
4-methoxy-9-(4-methoxyphenyl)-9H-xanthene(3j):Pale yellow solid； 88.7 mg,56％yield；1H NMR(600 MHz,CDCl3)δ7.25(dd,J＝8.1,1.0 Hz,1H),7.25(d,J＝1.0 Hz,1H),7.21-7.18(m,1H),7.12-7.10(m,2H), 7.05-7.04(m,1H),6.98(td,J＝7.6,1.2 Hz,1H),6.91(t,J＝7.9 Hz,1H), 6.81-6.78(m,3H),6.66(d,J＝7.5 Hz,1H),5.20(s,1H),3.96(s,3H), 3.74(s,3H).13C NMR(151 MHz,CDCl3)δ158.4,150.9,148.1,140.8, 139.0,129.7,129.4,127.9,125.7,124.6,123.5,122.9,121.4,117.0, 114.2,110.0,56.3,55.3,43.7.HRMS(ESI)calcd.for C21H19O3 +([M+H]+): 319.1329,found:319.1330.
9-(4-methoxyphenyl)-9H-xanthen-2-ol(3k):Brown solid；48.2 mg,32％ yield；1H NMR(600 MHz,CDCl3)δ7.19-7.17(m,1H),7.11-7.07(m, 3H),7.01-6.99(m,2H),6.96-6.93(m,1H),6.82-6.79(m,2H),6.67(dd,J ＝8.7,2.9 Hz,1H),6.47(d,J＝2.9 Hz,1H),5.12(s,1H),4.61(brs,1H), 3.75(s,3H).13C NMR(151 MHz,CDCl3)δ158.5,151.3,151.2,145.4, 138.6,129.8,129.6,127.9,125.8,124.2,123.1,117.5,116.5,115.6, 115.2,114.3,55.4,43.9.HRMS(EI)calcd.for C20H16O3 +(M+):304.1094, found:304.1086.
12-(4-methoxyphenyl)-12H-benzo[a]xanthene(3l):Pale yellow solid； 67.7 mg,40％yield；1H NMR(600 MHz,CDCl3)δ7.94(d,J＝8.4 Hz, 1H),7.79(t,J＝8.6 Hz,2H),7.44-7.39(m,2H),7.36-7.34(m,2H), 7.22-7.16(m,4H),7.04(td,J＝7.6,1.5 Hz,1H),6.73-6.70(m,2H),5.77 (s,1H),3.67(s,3H).13C NMR(151 MHz,CDCl3)δ158.2,150.3,149.5, 139.0,131.8,131.0,129.4,129.1,128.7,128.4,127.7,126.8,125.4, 124.2,123.8,123.3,118.1,116.8,116.2,114.3,55.3,41.2.HRMS(ESI) calcd.for C24H19O3 +([M+H]+):339.1380,found:339.1386.
12-(4-methoxyphenyl)-10-methyl-12H-benzo[a]xanthene(3m):Pale yellow solid；63.8mg,36％yield；1H NMR(600MHz,CDCl3)δ7.92(d, J＝8.5Hz,1H),7.76(dd,J＝13.3,8.5Hz,2H),7.42-7.37(m,2H),7.32 (t,J＝7.4Hz,1H),7.19(d,J＝8.6Hz,2H),7.12(s,1H),7.05(d,J＝8.2 Hz,1H),6.97(d,J＝8.0Hz,1H),6.70(d,J＝8.6Hz,2H),5.70(s,1H), 3.64(s,3H),2.27(s,3H).13C NMR(151MHz,CDCl3)δ158.2,149.6, 148.2,139.1,133.1,131.8,130.9,129.6,129.0,128.7,128.4,126.8, 124.9,124.1,123.2,118.2,116.5,116.2,114.3,55.2,41.3,21.0.HRMS (EI)calcd.for C25H20O2 +(M+):352.1458,found:352.1458.
example 4:
mixing thioxanthene (1b,99.1mg,0.5mmol) and n-Bu4NBF4(131.7mg,0.4 mol%), anisole (2a,1.0814g,10mmol), methanesulfonic acid (2eq,96.1mg, 1mmol), and 1, 2-dichloroethane (5mL) were charged in this order to a 10mL diaphragm-free electrolytic cell. The bottle mouth was plugged with a rubber stopper with an inserted electrode (carbon rod as anode, 1 cm. times.1 cm platinum electrode as cathode), an empty balloon was inserted, a potentiostat was connected to the electrode, the current intensity was set at 5mA, and the reaction was carried out at 80 ℃ for 12 hours with the passage of current. After completion of the reaction, distilled water (30mL) was added and extracted with ethyl acetate (3X 30 mL). The combined organic layers were dried over anhydrous sodium sulfate and distilled under reduced pressure using a rotary evaporator to give the crude product which was purified on a silica gel column (50: 1 petroleum ether/ethyl acetate) to give 98.3mg of the product 3ba as a pale yellow solid in 65% yield.
9-(4-methoxyphenyl)-9H-thioxanthene(3ba):Pale yellow solid；98.3 mg,65％yield；1H NMR(600MHz,CDCl3)δ7.43(d,J＝7.5Hz,2H), 7.39(d,J＝7.3Hz,2H),7.27-7.21(m,4H),6.92(d,J＝8.7Hz,2H),6.73 (d,J＝8.7Hz,2H),5.27(s,1H),3.71(s,3H).13C NMR(151MHz, CDCl3)δ158.3,137.8,133.3,133.0,129.6,129.0,127.3,126.9,126.7, 113.7,55.3,52.4.
Example 5:
according to the reaction conditions of example 4, only the structure of the substrate 2 was changed to obtain the following reaction product results:
9-(3,4-dimethoxyphenyl)-9H-thioxanthene(3bb):White solid；125.8 mg,75％yield；1H NMR(600MHz,CDCl3)δ7.44(dd,J＝7.5,1.5Hz, 2H),7.39(dd,J＝7.4,1.5Hz,2H),7.27-7.22(m,4H),6.70(d,J＝8.3Hz, 1H),6.62(d,J＝2.0Hz,1H),6.54-6.52(m,1H),5.24(s,1H),3.79(s, 3H),3.69(s,3H).13C NMR(151MHz,CDCl3)δ148.8,147.8,137.7, 133.7,133.2,129.6,127.3,127.0,126.7,120.1,111.6,110.8,55.9,55.8, 52.7.HRMS(ESI)calcd.for C21H18NaO2S+([M+Na]+):357.0920,found: 357.0921.
9-(2,4-dimethoxyphenyl)-9H-thioxanthene(3bc):Pale yellow oil；83.5 mg,50％yield；1H NMR(600MHz,CDCl3)δ7.41-7.38(m,2H),7.37- 7.33(m,2H),7.17-7.13(m,4H),6.96(d,J＝8.5Hz,1H),6.46(d,J＝2.5 Hz,1H),6.33(dd,J＝8.5,2.5Hz,1H),5.64(s,1H),3.85(s,3H),3.73(s, 3H).13C NMR(151MHz,CDCl3)δ159.8,157.6,137.7,133.1,130.3, 129.7,126.8,126.6,126.5,122.3,104.1,98.9,55.4,55.4,45.8.HRMS (EI)calcd.for C21H18O2S+(M+):334.1022,found:334.1019.
9-(2,5-dimethoxyphenyl)-9H-thioxanthene(3bd):Pale yellow oil；68.4 mg,41％yield；1H NMR(600 MHz,CDCl3)δ7.41-7.36(m,4H),7.18- 7.14(m,4H),6.80(d,J＝8.9 Hz,1H),6.74(d,J＝3.0 Hz,1H),6.68(dd, J＝8.8,3.0 Hz,1H),5.75(s,1H),3.84(s,3H),3.62(s,3H).13C NMR (151 MHz,CDCl3)δ153.5,150.8,137.2,132.9,131.5,129.8,126.8, 126.8,126.5,116.2,112.1,111.8,56.1,55.6,46.0.HRMS(ESI)calcd.for C21H19O2S+([M+H]+):335.1100,found:335.1103.
9-(2,4,6-trimethoxyphenyl)-9H-thioxanthene(3be):White solid；76.2 mg,42％yield；1H NMR(600 MHz,CDCl3)δ7.38(d,J＝7.7 Hz,2H), 7.11(t,J＝7.4 Hz,2H),7.04(t,J＝7.5 Hz,2H),6.87(d,J＝7.8 Hz,2H), 6.29(s,2H),5.53(s,1H),3.90(s,3H),3.65(s,6H).13C NMR(151 MHz, CDCl3)δ161.0,159.8,138.0,132.7,127.4,126.0,125.9,125.9,108.3, 91.3,55.7,55.5,41.2.HRMS(EI)calcd.for C22H20O3S+(M+):364.1128, found:364.1133.
9-(4-(methylthio)phenyl)-9H-thioxanthene(3bf):Yellow solid；78.1 mg, 49％yield；1H NMR(600 MHz,CDCl3)δ7.44(d,J＝7.4 Hz,2H),7.39 (d,J＝7.2 Hz,2H),7.29-7.25(m,2H),7.25-7.22(m,2H),7.08(d,J＝8.4 Hz,2H),6.93(d,J＝8.3 Hz,2H),5.28(s,1H),2.39(s,3H).13C NMR (151 MHz,CDCl3)δ138.0,137.3,136.6,133.3,129.6,128.5,127.4, 127.1,126.8,126.7,52.7,16.0.HRMS(EI)calcd.for C20H16S2 +(M+): 320.0688,found:320.0685.
2-methyl-4-(9H-thioxanthen-9-yl)phenol(3bg):Yellow solid；94.3 mg, 62％yield；1H NMR(600 MHz,CDCl3)δ7.43(dd,J＝7.5,1.0 Hz,2H), 7.39-7.37(m,2H),7.27-7.21(m,4H),6.79(d,J＝1.6Hz,1H),6.69(dd, J＝8.3,2.0Hz,1H),6.58(d,J＝8.3Hz,1H),5.22(s,1H),4.52(s,1H), 2.12(s,3H).13C NMR(151MHz,CDCl3)δ152.6,137.8,133.2,133.2, 130.7,129.6,127.3,126.9,126.7,126.6,123.6,114.7,52.5,16.1.HRMS (EI)calcd.for C20H16OS+(M+):304.0916,found:304.0916.
2,6-dimethyl-4-(9H-thioxanthen-9-yl)phenol(3bh):Yellow solid；86.9 mg,55％yield；1H NMR(600MHz,CDCl3)δ7.43(d,J＝7.7Hz,2H), 7.37(d,J＝7.3Hz,2H),7.26-7.20(m,4H),6.63(s,2H),5.19(s,1H), 4.44(s,1H),2.11(s,6H).13C NMR(151MHz,CDCl3)δ151.0,137.9, 133.1,132.7,129.6,128.2,127.3,126.8,126.7,122.8,52.5,16.2.HRMS (EI)calcd.for C21H18OS+(M+):318.1073,found:318.1069.
the foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.

Claims (9)

1. A method for synthesizing 9-aryl-9H-oxygen/thiaanthracene is characterized by comprising the following operations: taking oxygen/thiaanthracene 1 and arene 2 as raw materials, reacting under electrochemical conditions to obtain 9-aryl-9H-xanthene 3, wherein the reaction equation is as follows:
Figure FDA0003102792440000011
wherein R is1And R2Each independently selected from C1-C4 alkyl, C1-C4 alkoxy, hydrogen, halogen, hydroxy; ar is selected from phenyl, thienyl or benzofuranyl; r is one or more of C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, hydrogen, halogen and hydroxyl.
2. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to claim 1, characterized in that: the reaction is carried out in the presence of an acid additive.
3. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to claim 2, characterized in that: the acid additive is selected from acetic acid, propionic acid, trifluoroacetic acid, pivalic acid, methanesulfonic acid or p-toluenesulfonic acid monohydrate.
4. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to claim 1, characterized in that: the electrode material is selected from C (+)/C (-), Pt (+)/Pt (-), C (+)/Pt (-), or Pt (+)/C (-); the current intensity is 2-8 mA.
5. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to claim 1, characterized in that: the molar ratio of the oxygen/thiaanthracene 1 to the aromatic hydrocarbon 2 is 1: 10-30.
6. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to claim 1, characterized in that: the reaction is carried out in the presence of an electrolyte selected from n-Bu4NPF6、n-Bu4NBF4、n-Bu4ClO4、n-Bu4NOAc、n-Bu4NHSO4、n-Bu4NI or n-Bu4NBr。
7. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to claim 1, characterized in that: the reaction is carried out in a solvent selected from acetonitrile, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide, methanol, ethanol, acetic acid, water or hexafluoroisopropanol.
8. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to claim 1, characterized in that: the reaction temperature is selected from 50 ℃ to 80 ℃.
9. The method of synthesizing 9-aryl-9H-oxo/thioxanthene according to any one of claims 1 to 8, characterized in that: the reaction is carried out under air or an inert gas atmosphere.
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