CN113862704A - Preparation method of 9-aryl xanthene compound - Google Patents

Preparation method of 9-aryl xanthene compound Download PDF

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CN113862704A
CN113862704A CN202111351789.1A CN202111351789A CN113862704A CN 113862704 A CN113862704 A CN 113862704A CN 202111351789 A CN202111351789 A CN 202111351789A CN 113862704 A CN113862704 A CN 113862704A
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宋仁杰
危斌
欧阳旋慧
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Nanchang Hangkong University
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Abstract

The invention discloses a novel preparation method of 9-aryl xanthene compounds, wherein the xanthene compounds are subjected to C (sp) reaction with aromatic hydrocarbon through a free radical process3) The preparation method of the 9-aryl xanthene compound has the advantages of no need of using traditional transition metal catalyst, oxidant, high temperature and other harsh reaction conditions, mild reaction condition, wide substrate adaptation range, good atom economy and convenienceThe advantages of quick reaction operation.

Description

Preparation method of 9-aryl xanthene compound
Technical Field
The application belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a 9-aryl xanthene compound.
Background
Xanthene compounds are important building blocks in organic synthesis, and are also backbone structures in many important molecules such as drugs, catalysts, and fluorescent dyes. Based on the wide application of xanthene compounds, a method for synthesizing functionalized xanthene compounds is particularly important.
The traditional method for synthesizing xanthene compounds is oftenThe arylation based on benzyl position is usually carried out successfully with palladium or nickel catalysis using halogenated aromatic hydrocarbons as precursors. For example, the Walsh's topic group reports C (sp) for diarylmethanes and halogenated aromatic precursors3) -H arylation reaction, synthesizing triarylmethane compound under the catalysis of palladium or nickel
Figure BDA0003355173770000011
While other methods for synthesizing 9-aryl xanthenes involve harsh reaction conditions, such as Klussmann's report that xanthene compounds are coupled with electron-rich aromatic hydrocarbons under the catalysis of Brensted acid, and 9-aryl xanthene compounds are prepared through a hydroxyperoxide intermediate in an oxygen atmosphere
Figure BDA0003355173770000012
However, the method can be carried out only in a high-pressure oxygen environment, and the experimental production safety is poor. Subsequently, Zhang's and Loh's developed C (sp) respectively3)-C(sp2) Method for constructing 9-aryl xanthene compound by bond C-H activation cross-coupling reaction
Figure BDA0003355173770000021
However, the method requires a specific expensive catalytic system, high reaction temperature and long reaction time, and has harsh reaction conditions, high cost and low efficiency.
Therefore, based on the defects of the synthesis method of the 9-aryl xanthene compound reported in the prior art, the method for preparing the 9-aryl xanthene compound, which is green and feasible, high in atom economy, low in reaction cost, high in target product yield and wide in substrate adaptability, is provided, and is particularly urgent. The organic electrochemical synthesis can utilize anodic oxidation or cathodic reduction, plays a role of a chemical oxidant or a chemical reducing agent, and has the advantages of environmental protection and high atom utilization rate. At the same time, C (sp)3) H functionalization has become a revolutionary tool for the construction of C-C bonds in the synthesis of organic molecules. The inventors have conducted intensive and systematic studies in the field of organic electrochemical synthesis (see CN108863982A, CN109761963A, etc.). In the present inventionAn efficient and mild electrochemical synthesis strategy is provided, and xanthene compounds are subjected to C (sp) reaction with aromatic hydrocarbon through a free radical process3) And a series of 9-aryl xanthene compounds are conveniently prepared and obtained through the-H arylation reaction, so that the harsh conditions of using an oxidant, a noble metal catalyst, high temperature and the like in the traditional synthetic method in the prior art are overcome.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel method for preparing 9-aryl xanthene compounds, wherein the xanthene compounds are subjected to C (sp) reaction with aromatic hydrocarbon through a free radical process3) And (2) performing H-arylation reaction to prepare a series of 9-aryl xanthene compounds, which has the remarkable advantages over the prior art that the harsh reaction conditions such as traditional transition metal catalysts, oxidants, high temperature and the like are not needed, and the method has the advantages of mild reaction conditions, wide substrate adaptation range, good atom economy and convenient reaction operation.
The invention provides a preparation method of a 9-aryl xanthene compound, which comprises the following steps:
adding xanthene compounds shown in formula II, compounds shown in formula III or formula IV, N-hydroxyphthalimide, methanesulfonic acid, quaternary ammonium salt electrolyte and solvent acetonitrile into a reactor provided with an anode and a cathode, then leading constant current to electrolyze and stir for reaction, and obtaining target products shown in formula I-1 'or I-2' after the reaction is completed and post-processing, wherein the reaction formula is as follows:
Figure BDA0003355173770000031
in the above reaction formula, m, n, b is an integer of 1, 2, 3 or 4, and a is an integer of 1, 2, 3, 4 or 5;
R1、R2represents a substituent on the attached phenyl ring, each R1、R2Identical or different, independently of one another, from H, halogen, C1-20Alkyl radical, C1-20Alkoxy radical, C6-20Aryl, -CN, -NO2、C1-20An acyl group; and/or two adjacent R1Or R2The radicals being linked to each other and to the two R1Or R2The carbon atoms of the benzene rings of the groups together being optionally N, O, S, NRa，SiRaRbA five to seven membered ring structure of heteroatoms/heterostructural units;
x and Y are selected from O, S and NRa，SiRaRbAny one of the above;
each R is3Independently of one another, from hydrogen, halogen, -OH, C1-20Alkyl radical, C1-20Alkoxy, -NR5R6(ii) a Provided that at least one R3Is selected from C1-20Alkoxy or-NR5R6；
R5、R6Independently of one another, from C1-20Alkyl, substituted C1-20Alkyl, and/or R5、R6Are connected to each other and to the connection R5、R6With or without N, O, S, NRa，SiRaRbA five to seven membered ring structure of heteroatoms/heterostructural units; and wherein said substituted C1-20In the alkyl group, the substituents are selected from halogen, -OH, C1-6Alkoxy radical, C6-12An aryl group;
Ra，Rbselected from hydrogen, C1-20An alkyl group;
R4represents a substituent on the attached benzene ring, each R4Independently of one another, selected from H, halogen, C1-20Alkyl radical, C1-20Alkoxy radical, C6-20Aryl, -CN, -NO2、C1-20An acyl group.
Preferably, m, n, b is an integer of 1, 2, 3 or 4, a is an integer of 1, 2, 3, 4 or 5;
R1、R2represents a substituent on the attached phenyl ring, each R1、R2Identical or different from each other, independently of one another, selected from H, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, tert-butoxy, methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, tert-butoxy, methyl, isobutyl, tert-butoxy, and tert-butoxy,Phenyl, naphthyl, -CN, -NO2An acetyl group; and/or two adjacent R1Or R2The radicals being linked to each other and to the two R1Or R2The carbon atoms of the benzene rings of the groups jointly form a benzene ring structure;
x and Y are selected from any one of O and S;
each R3 is independently selected from hydrogen, fluoro, chloro, bromo, iodo, -OH, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, tert-butoxy, -NR5R6(ii) a Provided that at least one R3Selected from methoxy, ethoxy, tert-butoxy or-NR5R6；
R5、R6Independently of one another, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, substituted C1-6Alkyl, and/or R5、R6Are connected to each other and to the connection R5、R6The N atoms of the N-substituted heterocyclic ring form a pyrrolidine, piperidine, morpholine and piperazine ring structure; and wherein said substituted C1-6In the alkyl, the substituent is selected from-OH, methoxy, ethoxy or phenyl;
Ra，Rbis selected from C1-20An alkyl group;
R4represents a substituent on the attached benzene ring, each R4Independently of one another, from H, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, tert-butoxy, phenyl, naphthyl, -CN, -NO2And an acetyl group.
Most preferably, the compound of formula II has the following structure:
Figure BDA0003355173770000051
the compound of formula III has the following structure:
Figure BDA0003355173770000052
the compound of formula IV has the following structure:
Figure BDA0003355173770000053
according to the preparation method of the invention, the anode material is a graphite rod, and the cathode material is a platinum plate; and/or the anode material is a platinum plate, and the cathode material is a graphite rod; and/or the anode and cathode materials are both graphite rods. Preferably, the anode material is a graphite rod and the cathode material is a platinum plate.
The preparation method according to the present invention, wherein the quaternary ammonium salt electrolyte is selected fromnBu4NBF4、nBu4NPF6、nBu4NI、nBu4NCl、nBu4Any one or a mixture of more of NBr; preferably, the quaternary ammonium salt electrolyte isnBu4NBF4。
According to the preparation method, the xanthene compound shown in the formula II, the compound shown in the formula III or the formula IV, the N-hydroxyphthalimide and the methanesulfonic acid are fed in a molar ratio of 1: 1-3: 0.2-1.0: 1-5; preferably, the feeding molar ratio of the xanthene compound shown in the formula II, the compound shown in the formula III or the formula IV, the N-hydroxyphthalimide and the methanesulfonic acid is 1: 2: 0.5: 2.5.
According to the preparation method, the concentration of the quaternary ammonium salt electrolyte in the reaction liquid is 0.01-0.1 mol/L, and preferably 0.05 mol/L.
According to the preparation method, the constant current is 5-20 mA, and preferably 10 mA.
According to the preparation method, the reaction temperature is room temperature, the reaction time is 1-5 h, and preferably 3.5 h.
According to the preparation method of the invention, the post-treatment operation is as follows: concentrating the reaction solution in vacuum, separating the residue by silica gel column chromatography, and eluting with n-hexane/ethyl acetate mixed solvent to obtain the target product shown in formula I-1 'or 1-2'.
The invention has the beneficial effects that:
the invention reports a novel method for preparing 9-aryl xanthene compounds under organic electrosynthesis condition for the first time, wherein the xanthene compounds are subjected to C (sp) reaction with aromatic hydrocarbon through a free radical process3) And (2) performing an arylation reaction to prepare a series of 9-arylxanthene compounds, wherein N-hydroxyphthalimide and methanesulfonic acid are used as auxiliary agents to remarkably promote the reaction and improve the yield.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
Examples 1-18 optimization of reaction conditions
Xanthene shown in formula II-1 and N, N-dimethylaniline shown in formula III-1 are used as template substrates, the influence of different organic electronic synthesis conditions on the optimization result of the reaction process is discussed, representative examples 1-18 are selected, and the results are shown in Table 1, and the reaction formula is as follows:
Figure BDA0003355173770000071
wherein a typical experimental procedure for example 1 is as follows:
to a cathode (1.0X 1.0 cm) equipped with a graphite rod anode and a platinum plate cathode2) In a 10mL septum-free three-necked flask, xanthene (0.2mmol) represented by the formula II-1, N-dimethylaniline (0.4mmol, 2 equivalents) represented by the formula III-1, N-hydroxyphthalimide (NHPI, 0.1mmol, 0.5 equivalents), methanesulfonic acid (0.5mmol, 2.5 equivalents), and,nBu4NBF4(0.05M), and MeCN (8mL), followed byElectrolyzing by constant current of 10mA in air atmosphere and stirring for 3.5h, monitoring completion of reaction by TLC and/or GC-MS, concentrating the reaction solution in vacuum, separating the residue by silica gel column chromatography, and eluting with N-hexane/ethyl acetate to obtain 9- (4-N, N-dimethylaminophenyl) xanthene shown in formula I-1' -a with yield of 41mg and 68%. A white solid;1H NMR(500MHz，CDCl3)δ：7.19-7.15(m，2H)，7.11-7.09(m，2H)，7.07-7.04(m，4H)，6.97-6.94(m，2H)，6.65-6.61(m，2H)，5.15(s，1H)，2.88(s，6H)；13C NMR(125MHz，CDCl3)δ：151.0，149.2，134.7，129.7，129.0，127.5，125.1，123.1，116.3，112.7，43.3，40.6；HRMS m/z(ESI)calcd for C21H20NO([M+H]+)302.1539，found 302.1538.。
table 1:
Figure BDA0003355173770000072
Figure BDA0003355173770000081
each english abbreviation in table 1 has the following meaning:
TBAI: tetrabutylammonium iodide; NHIP: n-hydroxyphthalimide; msOH: methanesulfonic acid; AcOH: acetic acid; TfOH: trifluoromethanesulfonic acid; HFIP: hexafluoroisopropanol.
As can be seen from Table 1, the selection of the electrode material has an influence on the reaction, but the reaction proceeds smoothly in both cases where the graphite rod anode and the platinum plate cathode (1.0X 1.0 cm)2) The best results (examples 1-3), the reaction was not possible without the application of constant current (example 4), the increase and/or decrease in the magnitude of the constant current resulted in a decrease in the yield (examples 5-6), other electrolytes, such as TBAI andnBu4NPF6the reaction effect is not as good as that ofnBu4NBF4(examples 7 to 8). The yield decreased to 51% when the electrolyte concentration was increased to 0.1M (example 9). N is a radical ofHIP as a promoter, acting as an indirect oxidation in the reaction of the present invention, reduced the yield to 34% without the addition of NHIP (example 10), but when other oxidizing agents such as TEMPO were used instead of NHIP, a significant reduction in yield was caused (example 11). MsOH as another promoter of the reaction, the yield decreased significantly to 17% without the addition of MsOH (example 14), while interestingly, similarly characterized species such as AcOH and TfOH did not exhibit a promoting effect on the reaction (examples 12-13), and the decrease in the amount of MsOH used resulted in a greater decrease in the yield of the desired product (examples 15-16). In addition, the inventors have found that other reaction solvents are not as effective as acetonitrile, and that the target product is produced only in trace amounts as detected by GC-MS when dichloroethane is used as the reaction solvent (examples 17 to 18).
Based on the optimal reaction conditions, the inventor further aims at the electrochemical free radical C (sp)3) The universality of the-H arylation reactions was investigated by carrying out the reaction under the reaction conditions of example 1 to prepare a series of 9-arylxanthene compounds of the desired structure by replacing the reaction substrate (formula II, formula III or formula IV) for the different substituents/building blocks. The reaction formula, product structure and yield are as follows:
Figure BDA0003355173770000091
Figure BDA0003355173770000101
structural characterization of the product:
compound I-1' -b: 46mg, 70%; a yellow solid;1H NMR(500MHz，CDCl3)δ：7.19-7.16(m，2H)，7.11-7.09(m，4H)，7.01-6.94(m，4H)，6.57-6.54(m，2H)，5.13(s，1H)，3.30-3.26(m，4H)，1.11(t，J＝7.0Hz，6H)；13C NMR(125MHz，CDCl3)δ：151.1，146.5，133.4，129.7，129.1，127.5，125.3，123.1，116.3，111.7，44.2，43.3，12.6；HRMS m/z(ESI)calcd for C23H24NO([M+H]+)330.1852，found 330.1854.。
compound I-1' -c: 521ng, 73%; a yellow solid;1H NMR(500MHz，CDCl3)δ：7.18-7.14(m，2H)，7.10-7.18(m，4H)，7.00-6.93(m，4H)，6.53-6.48(m，2H)，5.11(s，1H)，3.15(t，J＝7.5Hz，4H)，1.58-1.51(m，4H)，0.87(t，J＝7.5Hz，6H)；13C NMR(125MHz，CDCl3)δ：151.1，146.9，133.2，129.7，129.0，127.4，125.4，123.1，116.3，111.6，52.9，43.3，20.4，11.4；HRMS m/z(ESI)calcd for C25H28NO([M+H]+)358.2165，found 358.2164.。
compound I-1' -d: 44mg, 49%; a yellow solid;1H NMR(500MHz，CDCl3)δ：7.31-7.28(m，4H)，7.23-7.15(m，8H)，7.11-7.07(m，2.8Hz，4H)，6.99-6.93(m，4H)，6.62-6.59(m，2H)，5.11(s，1H)，4.58(s，4H)；13C NMR(125MHz，CDCl3)δ：151.2，147.9，138.7，134.8，129.7，128.9，128.6，127.5，126.8，126.6，125.2，123.1，116.4，112.5，54.3，43.5；HRMS m/z(ESI)calcd for C33H28NO([M+H]+)454.2165，found 454.2166.。
compound I-1' -e: 49mg, 71%; a yellow solid;1H NMR(500MHz，CDCl3)δ：7.19-7.16(m，2H)，7.11-7.07(m，4H)，7.03-6.99(m，2H)，6.98-6.95(m，2H)，6.67-6.62(m，2H)，5.13(s，1H)，3.71(t，J＝5.5Hz，2H)，3.38(t，J＝6.0Hz，2H)，3.35-3.31(m，2H)，1.09(t，J＝7.0Hz，3H)；13C NMR(125MHz，CDCl3)δ：151.1，147.0，134.9，129.7，129.1，127.6，125.1，123.1，116.4，113.0，60.1，52.5，45.6，43.3，11.9；HRMS m/z(ESI)calcd for C23H24NO2([M+H]+)346.1802，found 346.1803.。
compound I-1' -f: 29mg, 45%; a white solid;1H NMR(500MHz，CDCl3)δ：7.19-7.14(m，2H)，7.12-7.01(m，6H)，6.97-6.94(m，2H)，6.50-6.45(m，2H)，5.14(s，1H)，3.23(t，J＝5.0Hz，4H)，1.99-1.92(m，4H)；13C NMR(125MHz，CDCl3)δ：151.0，146.6，133.5，129.8，129.2，127.4，125.3，123.0，116.3，111.6，47.5，43.3，25.5；HRMS m/z(ESI)calcd for C23H22NO([M+H]+)328.1696，found 328.1692.。
compound I-1' -g: 32mg, 46%; a white solid;1H NMR(500MHz，CDCl3)δ：7.20-7.16(m，2H)，7.11-7.09(m，2H)，7.07-7.03(m，4H)，6.97-6.94(m，2H)，6.84-6.81(m，2H)，5.16(s，1H)，3.09(t，J＝5.0Hz，4H)，1.69-1.64(m，4H)，1.56-1.51(m，2H)；13C NMR(125MHz，CDCl3)δ：151.0，150.8，137.0，129.7，129.0，127.6，124.9，123.1，116.5，116.4，50.5，43.4，25.9，24.2；HRMS m/z(ESI)calcd for C24H24NO([M+H]+)342.1852，found 342.1848.。
compound I-1' -h: 39mg, 57%; a white solid;1H NMR(500MHz，CDCl3)δ：7.19-7.16(m，2H)，7.12-7.06(m，4H)，7.05-7.03(m，2H)，6.97-6.94(m，2H)，6.82-6.77(m，2H)，5.17(s，1H)，3.82-3.78(m，4H)，3.11-3.06(m，4H)；13C NMR(125MHz，CDCl3)δ：151.0，149.8，138.0，129.7，129.1，127.7，124.8，123.1，116.4，115.7，66.9，49.2，43.4；HRMS m/z(ESI)calcd for C23H22NO2([M+H]+)344.1645，found 344.1642.。
compound I-1' -I: 18mg, 31%; a white solid;1H NMR(500MHz，CDCl3)δ：7.46-7.41(m，1H)，7.38-7.36(m，1H)，7.34-7.32(m，2H)，7.30-7.25(m，2H)，7.21-7.13(m，4H)，7.08-7.05(m，2H)，6.27(s，1H)，5.50(s，1H)；13C NMR(125MHz，CDCl3)δ：159.8，155.1，151.4，129.6，128.6，128.3，123.7，123.2，122.6，120.7，120.6，116.8，111.2，103.5，38.5；HRMS m/z(ESI)calcd for C21H15O2([M+H]+)299.1067，found 299.1066.。
compound I-1' -j: the total amount of the components was 44mg,70 percent; a white solid;1H NMR(500MHz，CDCl3)δ：7.18-7.13(m，2H)，7.09-7.04(m，2H)，7.02-7.00(m，1H)，6.94-6.87(m，4H)，6.57-6.49(m，2H)，5.42(s，1H)，2.91(s，6H)，2.15(s，3H)；13C NMR(125MHz，CDCl3)δ：150.9，149.3，136.6，131.9，131.8，129.3，127.5，124.9，123.0，116.1，114.9，110.6，40.5，20.5；HRMS m/z(ESI)calcd for C22H22NO([M+H]+)316.1696，found 316.1696.。
compound I-1' -k: 26mg, 41%; a white solid;1H NMR(500MHz，CDCl3)δ：7.21-7.16(m，2H)，7.12-7.07(m，4H)，6.98-6.94(m，2H)，6.92(d，J＝8.5Hz，1H)，6.29-6.26(m，1H)，6.14(d，J＝2.5Hz，1H)，5.48(s，1H)，4.73(s，1H)，2.89(s，6H)；13C NMR(125MHz，CDCl3)δ：153.6，151.3，150.9，131.7，129.3，127.8，124.3，123.2，116.3，105.7，100.5，40.5，38.0；HRMS m/z(ESI)calcd for C21H20NO2([M+H]+)318.1489，found 318.1490.。
compound I-1' -1: 43mg, 65%; a white solid;1H NMR(500MHz，CDCl3)δ：7.15-7.12(m，2H)，7.12-7.11(m，1H)，7.10-7.09(m，1H)，7.07-7.05(m，2H)，6.94-6.71(m，2H)，6.77(d，J＝8.5Hz，1H)，6.25(d，J＝2.5Hz，1H)，6.20-6.18(m，1H)，5.66(s，1H)，3.82(s，3H)，2.89(s，6H)；13C NMR(125MHz，CDCl3)δ：157.2，151.5，150.5，130.6，129.5，127.2，125.5，123.9，122.9，116.0，105.3，96.2，55.5，40.6，36.3；HRMS m/z(ESI)calcd for C22H22NO2([M+H]+)332.1645，found 332.1643.。
compound I-1' -m: 23mg, 36%; a white solid;1H NMR(500MHz，CDCl3)δ：7.18-7.15(m，2H)，7.10-7.07(m，4H)，6.95-6.92(m，2H)，6.83(d，J＝8.5Hz，1H)，6.46(d，J＝2.5Hz，1H)，6.36-6.34(m，1H)，5.70(s，1H)，3.82(s，3H)，3.74(s，3H)；13C NMR(125MHz，CDCl3)δ：159.3，157.2，151.4，130.7，129.4，128.0，127.4，125.1，123.0，116.2，104.8，98.7，55.6，55.3，36.4；HRMS m/z(ESI)calcd for C21H19O3([M+H]+)319.1329，found 319.1331.。
compound I-1' -n: 17mg, 23%; a white solid;1H NMR(500MHz，CDCl3)δ：7.10-7.07(m，2H)，7.05-6.89(m，4H)，6.87-6.83(m，2H)，5.88(s，3H)，3.92(s，3H)，3.29(s，3H)，2.93(s，6H)；13C NMR(125MHz，CDCl3)δ：151.5，150.9，128.7，126.6，125.3，122.2，115.3，113.1，55.8，40.6，31.6；HRMS m/z(ESI)calcd for C23H24NO3([M+H]+)362.1751，found 362.1756.。
compound I-1' -o: 45mg, 64%; a white solid;1H NMR(500MHz，CDCl3)δ：7.09(t，J＝8.0Hz，2H)，6.99(d，J＝8.5Hz，2H)，6.93(d，J＝8.0Hz，2H)，6.84(t，J＝7.5Hz，2H)，6.09(s，2H)，5.92(s，1H)，3.74(m，9H)；13C NMR(125MHz，CDCl3)δ：160.1，151.5，128.6，126.8，124.7，122.2，116.5，115.3，55.8，55.1，31.7；HRMS m/z (ESI)calcd for C22H21O4([M+H]+)349.1434，found 349.1431。
compound I-1' -p: 41mg, 62%; a white solid;1H NMR(500MHz，CDCl3)δ：7.10(t，J＝7.5Hz，2H)，7.00(d，J＝8.5Hz，2H)，6.93(d，J＝8.0Hz，2H)，6.85(t，J＝7.5Hz，2H)，6.34(s，2H)，5.98(s，1H)，3.90(s，3H)，3.30(s，3H)，2.30(s，3H)；13C NMR(125MHz，CDCl3)δ：151.5，138.3，128.6，126.8，124.6，122.3，120.9，115.4，55.9，31.8，22.0；HRMS m/z(ESI)calcd for C22H21O3([M+H]+)333.1485，found 333.1484.。
compound I-1' -q: 23mg, 34%; a white solid;1H NMR(500MHz，CDCl3)δ：7.17-7.14(m，2H)，7.06-7.04(m，2H)，6.99-6.97(m，2H)，6.93-6.89(m，2H)，6.21(d，J＝15.0Hz，2H)，5.82(s，1H)，3.75(s，6H)；13C NMR(125MHz，CDCl3)δ：160.1，159.9，151.3，128.8，127.4，123.3，122.6，115.9，55.9，55.5，31.7；HRMS m/z (ESI)calcd for C21H18FO3([M+H]+)337.1234，found 337.1230.。
compound I-1' -bb: 46mg, 60%; a yellow solid;1H NMR(500MHz，CDCl3)δ：8.00(d，J＝8.5Hz，1H)，7.79-7.74(m，2H)，7.44-7.41(m，1H)，7.39-7.37(m，2H)，7.35-7.32(m，1H)，7.19-7.14(m，2H)，7.09(d，J＝8.5Hz，2H)，7.05-7.02(m，1H)，6.46(d，J＝8.5Hz，2H)，5.70(s，1H)，3.22-3.18(m，4H)，1.03(t，J＝7.0Hz，6H)；13C NMR(125MHz，CDCl3)δ：150.4，149.4，146.4，133.5，131.9，130.8，129.3，128.6，128.5，128.1，127.3，126.6，126.0，124.0，123.6，123.3，118.0，116.7，116.5，111.9，44.2，40.9，12.6；HRMS m/z(ESI)calcd for C27H26NO([M+H]+)380.2009，found 380.2010.。
compound I-1' -cb: 40mg, 53%; a yellow solid; 1H NMR (500MHz, CDCl)3)δ：8.00(d，J＝8.5Hz，1H)，7.79-7.74(m，2H)，7.44-7.41(m，1H)，7.39-7.32(m，3H)，7.19-7.14(m，2H)，7.09(d，J＝8.0Hz，2H)，7.04(t，J＝6.5Hz，1H)，6.46(d，J＝8.5Hz，2H)，5.70(s，1H)，3.22-3.17(m，4H)，1.03(t，J＝7.0Hz，6H)；13C NMR(125MHz，CDCl3)δ：150.4，149.4，146.4，133.5，131.9，130.8，129.3，128.6，128.5，128.1，127.3，126.6，126.0，124.0，123.6，123.3，118.0，116.7，116.5，111.9，44.2，40.9，12.6；HRMS m/z(ESI)calcd for C27H26NO([M+H]+)380.2009，found 380.2007.。
Compound I-1' -db: 40mg, 51%; a yellow oily liquid;1H NMR(500MHz，CDCl3)δ：7.73(d，J＝2.5Hz，1H)，7.65(d，J＝9.0Hz，1H)，7.36(d，J＝8.5Hz，1H)，7.29(d，J＝8.5Hz，1H)，7.20(d，J＝8.0Hz，1H)，7.17-7.12(m，2H)，7.03-6.99(m，4H)，6.54(d，J＝8.5Hz，2H)，5.24(s，1H)，4.01(s，3H)，3.28-3.23(m，4H)，1.08(t，J＝7.0Hz，6H)；13C NMR(125MHz，CDCl3)δ：157.9，150.8，146.5，144.8，133.8，129.9，129.2，129.1，128.6，127.4，125.2，125.1，124.8，123.3，122.3，119.4，118.5，116.5，111.7，100.2，55.4，44.2，43.6，12.6；HRMS m/z(ESI)calcd for C28H28NO([M+H]+)394.2165，found 349.2167.。
compound I-1' -eb: 28mg, 41%; a yellow oily liquid; 1H NMR (500MHz, CDCl)3)δ：7.15(t，J＝8.0Hz，1H)，7.07(d，J＝7.5Hz，2H)，7.00-6.92(m，5H)，6.89(s，1H)，6.55(d，J＝8.5Hz，2H)，5.06(s，1H)，3.29-3.25(m，4H)，2.21(s，3H)，1.10(t，J＝7.5Hz，6H)；13C NMR(125MHz，CDCl3)δ：151.2，149.1，146.5，133.7，132.3，129.9，129.7，129.0，128.2，127.4，125.4，124.9，122.9，116.3，116.0，111.7，44.2，43.5，20.7，12.6；HRMS m/z(ESI)calcd for C24H26NO([M+H]+)344.2009，found 344.2011.。
Compound I-1' -fb: 43mg, 60%; a yellow oily liquid;1H NMR(500MHz，CDCl3)δ：7.16(t，J＝8.0Hz，1H)，7.08(t，J＝7.0Hz，2H)，7.03(d，J＝9.0Hz，1H)，6.99(d，J＝8.0Hz，2H)，6.94(t，J＝7.5Hz，1H)，6.74-6.72(m，1H)，6.61(d，J＝3.0Hz，1H)，6.55(d，J＝8.0Hz，2H)，5.08(s，1H)，3.69(s，3H)，3.29-3.25(m，4H)，1.10(t，J＝7.0Hz，6H)；13C NMR(125MHz，CDCl3)δ：155.2，151.4，146.5，145.4，133.2，129.7，129.0，127.4，126.1，124.9，122.8，117.0，116.2，114.0，113.4，111.8，55.6，44.2，43.8，12.6；HRMS m/z(ESI)calcd for C24H26NO2([M+H]+)360.1958，found 360.1959.。
compound I-1' -gb: 25mg, 37%; a yellow oily liquid;1H NMR(500MHz，CDCl3)δ：7.19-7.15(m，1H)，7.09-7.02(m，3H)，6.99-6.95(m，3H)，6.88-6.84(m，1H)，6.79-6.76(m，1H)，6.58-6.54(m，2H)，5.07(s，1H)，3.31-.326(m，4H)，1.11(t，J＝7.0Hz，6H)；13C NMR(125MHz，CDCl3)δ：159.4，157.4，151.1，147.2，146.7，132.5，129.7，129.2，129.2，127.6，126.8(d，J＝7.25Hz，2C)，124.3，123.2，117.4(d，J＝8.13Hz，2C)，116.3，115.6，115.5，115.3，114.5，114.3，111.8，111.8，44.2，43.6，12.6，12.5；19F NMR(471MHz，CDCl3)δ：-120.5(s)；HRMS m/z(ESI)calcd for C23H23FNO([M+H]+)348.1758，found 348.1755.。
compound I-1' -ha: 31mg, 46%; a white solid;1H NMR(500MHz，CDCl3)δ：7.21-7.16(m，1H)，7.14-7.08(m，2H)，7.05-7.02(m，5H)，6.99-6.95(m，1H)，6.65(d，J＝8.5Hz，2H)，5.10(s，1H)，2.91(s，6H)；13C NMR(125MHz，CDCl3)δ：150.7，149.6，149.4，133.8，129.7，129.3，129.0，127.7，127.7，127.6，126.8，124.4，123.4，117.8，116.3，112.7，43.3，40.5；HRMS m/z(ESI)calcd for C21H19ClNO([M+H]+)336.1150，found 336.1148.。
compound I-1' ia: 29mg, 46%; a yellow oily liquid;1H NMR(500MHz，CDCl3)δ：7.42(d，J＝7.0Hz，2H)，7.38(d，J＝7.5Hz，2H)，7.24-7.19(m，4H)，6.88(d，J＝8.0Hz，2H)，6.57(d，J＝9.0Hz，2H)，5.22(s，1H)，2.85(s，6H)；13C NMR(125MHz，CDCl3)δ：149.2，138.0，133.0，129.4，128.6，127.0，126.5，126.4，112.4，52.2，40.5；HRMS m/z(ESI)calcd for C21H20NS([M+H]+)318.1311，found 318.1313.。
the embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.

Claims (10)

1. A preparation method of a 9-aryl xanthene compound is characterized by comprising the following steps:
adding xanthene compounds shown in formula II, compounds shown in formula III or formula IV, N-hydroxyphthalimide, methanesulfonic acid, quaternary ammonium salt electrolyte and solvent acetonitrile into a reactor provided with an anode and a cathode, then leading constant current to electrolyze and stir for reaction, and obtaining target products shown in formula I-1 'or I-2' after the reaction is completed and post-processing, wherein the reaction formula is as follows:
Figure FDA0003355173760000011
in the above reaction formula, m, n, b is an integer of 1, 2, 3 or 4, and a is an integer of 1, 2, 3, 4 or 5;
R1、R2represents a substituent on the attached phenyl ring, each R1、R2Identical or different, independently of one another, from H, halogen, C1-20Alkyl radical, C1-20Alkoxy radical, C6-20Aryl, -CN, -NO2、C1-20An acyl group; and/or two adjacent R1Or R2The radicals being linked to each other and to the two R1Or R2The carbon atoms of the benzene rings of the groups together being optionally N, O, S, NRa，SiRaRbA five to seven membered ring structure of heteroatoms/heterostructural units;
x and Y are selected from O, S and NRa，SiRaRbAny one of the above;
each R is3Independently of one another, from hydrogen, halogen, -OH, C1-20Alkyl radical, C1-20Alkoxy, -NR5R6(ii) a Provided that at least one R3Is selected from C1-20Alkoxy or-NR5R6；
R5、R6Independently of one another, from C1-20Alkyl, substituted C1-20Alkyl, and/or R5、R6Are connected to each other and to the connection R5、R6With or without N, O, S, NRa，SiRaRbA five to seven membered ring structure of heteroatoms/heterostructural units; and wherein said substituted C1-20In the alkyl group, the substituents are selected from halogen, -OH, C1-6Alkoxy radical, C6-12An aryl group;
Ra，Rbselected from hydrogen, C1-20An alkyl group;
R4represents a substituent on the attached benzene ring, each R4Independently of one another, selected from H, halogen, C1-20Alkyl radical, C1-20Alkoxy radical, C6-20Aryl, -CN, -NO2、C1-20An acyl group.
2. The method according to claim 1, wherein m, n, b is an integer of 1, 2, 3 or 4, a is an integer of 1, 2, 3, 4 or 5;
R1、R2represents a substituent on the attached phenyl ring, each R1、R2Identical or different, independently of one another, from the group consisting of H, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, tert-butoxy, phenyl, naphthyl, -CN, -NO2An acetyl group; and/or two adjacent R1Or R2The radicals being linked to each other and to the two R1Or R2The carbon atoms of the benzene rings of the groups jointly form a benzene ring structure;
x and Y are selected from any one of O and S;
each R is3Independently of one another, from hydrogen, fluorine, chlorine, bromine, iodine, -OH, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, tert-butoxy, -NR5R6(ii) a Provided that at least one R3Selected from methoxy, ethoxy, tert-butoxy or-NR5R6；
R5、R6Independently of one another, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, substitutedC of (A)1-6Alkyl, and/or R5、R6Are connected to each other and to the connection R5、R6The N atoms of the N-substituted heterocyclic ring form a pyrrolidine, piperidine, morpholine and piperazine ring structure; and wherein said substituted C1-6In the alkyl, the substituent is selected from-OH, methoxy, ethoxy or phenyl;
Ra，Rbis selected from C1-20An alkyl group;
R4represents a substituent on the attached benzene ring, each R4Independently of one another, from H, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, tert-butoxy, phenyl, naphthyl, -CN, -NO2And an acetyl group.
3. The process of claim 1 or 2, wherein the compound of formula II has the structure:
Figure FDA0003355173760000031
the compound of formula III has the following structure:
Figure FDA0003355173760000032
the compound of formula IV has the following structure:
Figure FDA0003355173760000033
4. the production method according to claim 1 or 2, wherein the anode material is a graphite rod, and the cathode material is a platinum plate; and/or the anode material is a platinum plate, and the cathode material is a graphite rod; and/or the anode and cathode materials are graphite rods; preferably, the anode material is a graphite rod and the cathode material is a platinum plate.
5. The method according to claim 1 or 2, wherein the quaternary ammonium salt electrolyte is selected from the group consisting ofnBu4NBF4、nBu4NPF6、nBu4NI、nBu4NCl、nBu4Any one or a mixture of more of NBr; preferably, the quaternary ammonium salt electrolyte isnBu4NBF4。
6. The method according to claim 1 or 2, wherein the xanthene compound represented by formula II, the compound represented by formula III or formula IV, the N-hydroxyphthalimide and the methanesulfonic acid are fed in a molar ratio of 1: 1 to 3: 0.2 to 1.0: 1 to 5; preferably, the feeding molar ratio of the xanthene compound shown in the formula II, the compound shown in the formula III or the formula IV, the N-hydroxyphthalimide and the methanesulfonic acid is 1: 2: 0.5: 2.5.
7. The method according to claim 1 or 2, wherein the concentration of the quaternary ammonium salt electrolyte in the reaction solution is 0.01 to 0.1mol/L, preferably 0.05 mol/L.
8. The method according to claim 1 or 2, wherein the constant current is 5 to 20mA, preferably 10 mA.
9. The preparation method according to claim 1 or 2, wherein the reaction temperature is room temperature, and the reaction time is 1-5 h, preferably 3.5 h.
10. The method according to claim 1 or 2, characterized in that the post-treatment operation is as follows: concentrating the reaction solution in vacuum, separating the residue by silica gel column chromatography, and eluting with n-hexane/ethyl acetate mixed solvent to obtain the target product shown in formula I-1 'or 1-2'.
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