CN114716357A - Alkyl substituted chalcogenide and preparation method thereof - Google Patents

Alkyl substituted chalcogenide and preparation method thereof Download PDF

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CN114716357A
CN114716357A CN202210554964.5A CN202210554964A CN114716357A CN 114716357 A CN114716357 A CN 114716357A CN 202210554964 A CN202210554964 A CN 202210554964A CN 114716357 A CN114716357 A CN 114716357A
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alkyl
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chalcogenide
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杨道山
崔文文
郭国菊
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
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    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
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    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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Abstract

The invention relates to the technical field of organic synthesis and medicinal chemistry, in particular to an alkyl substituted chalcogenide and a preparation method and application thereof, and particularly relates to a synthesis method and application of a photoinduced sulfonium salt ring-opening compound. Substituted sulfonium salt and diether derivative are used as substrates, and under the action of a photocatalyst and alkali, near blue light irradiation is adopted, so that alkyl substituted chalcogenide is synthesized by a one-pot method. The preparation method provided by the invention is simple and convenient to operate, efficient in reaction, safe and environment-friendly, and suitable for industrial and large-scale production and application.

Description

Alkyl substituted chalcogenide and preparation method thereof
Technical Field
The invention relates to the technical field of medicinal chemistry, in particular to an alkyl substituted chalcogenide and a preparation method and application thereof.
Background
Alkyl-substituted chalcogenides such as alkyl sulfides, alkyl selenides and alkyl tellurides are important organic compounds with pharmaceutical activity, are not only widely applied to anti-tumor and anti-cancer, but also have important application values in the research of enzyme regulators, antioxidants and cell growth inhibitors. In addition, the alkyl sulfide and the alkyl selenide are also applied to agricultural chemicals, can be used as herbicides, insect repellents and bactericides, and have a larger research space. At present, the research on the application development of alkyl sulfide and alkyl selenide and the research on a novel efficient synthesis method arouse great attention and become one of the research hotspots in recent years.
The traditional methods for synthesizing alkyl-substituted chalcogenides and alkylselenides are nucleophilic substitution reactions of selenols or thiols with alkyl halides, and michael addition reactions of thiols and selenols with olefins. However, these reactions have several disadvantages, including harsh conditions, instability of the reagents used, and strong alkaline or acidic reaction conditions. Therefore, developing more efficient, economical and practical synthetic methods to construct alkyl-substituted chalcogenides is a challenging but very attractive task. In the past few years, visible light-promoted photoredox catalysis has become a versatile tool for organic synthesis and opens a green and sustainable route to the construction of challenging structural frameworks and chemical bonds. Sulfonium salts are common sulfur-containing reagents and are widely used in organic chemistry because of their high stability, ease of preparation, high chemical reactivity, and wide structural diversity. Recently, the literature reports that sulfonium salts can generate aryl and alkyl carbon radicals under metal-free or photocatalytic conditions for further selective construction of carbon-carbon bonds. However, to our knowledge, methods for the synthesis of alkyl sulfides, alkyl selenides, alkyl tellurides based on the visible light-induced sulfonium salt ring opening strategy have not been developed to date. Therefore, it is necessary to develop a more practical, fast and efficient method for synthesizing alkyl sulfides, alkyl selenides and alkyl tellurides.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a synthesis method and application of light-induced alkyl substituted sulfide, alkyl selenide and alkyl telluride, which do not need harsh reaction conditions, can synthesize various alkyl sulfides, alkyl selenide and alkyl telluride and derivatives thereof in one step, and have higher universality on various functional groups.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an alkyl-substituted chalcogenide, in particular alkyl sulfides, alkyl selenides, and alkyl arsenides, having the structure shown in formula I,
Figure BDA0003651985610000021
wherein:
R1one selected from hydrogen and methyl;
R2one selected from aryl or straight-chain alkyl;
R3one selected from alkyl and aryl;
y is selected from S, Se or Te.
Y is selected from S, Se or Te.
Further, alkyl-substituted chalcogenides of formula I are preferred as are compounds represented by:
Figure BDA0003651985610000031
Figure BDA0003651985610000041
Figure BDA0003651985610000051
secondly, the invention provides a preparation method of the alkyl substituted chalcogenide shown in the formula I, which specifically comprises the following steps:
the alkyl substituted chalcogenide can be obtained by using substituted sulfonium salt shown in a formula II and diether derivative (disulfide, diselenide or ditelluride) shown in a formula III as substrates and irradiating the substrates by using near blue light under the action of a photocatalyst and alkali in a one-pot method.
Specifically, the sulfonium salt shown in the formula II and the diether derivative shown in the formula III are shown as follows:
Figure BDA0003651985610000052
in the formula
R1One selected from hydrogen and methyl;
R2one selected from aryl or straight-chain alkyl;
R3one selected from alkyl and aryl;
x is selected from PF6、BF4One of I or II;
y is selected from S, Se or Te.
Further, a method of preparing an alkyl-substituted chalcogenide of formula I, comprising the steps of:
adding substituted sulfonium salt and diether derivative into a reaction tube; adding a photocatalyst and alkali into a solvent to form a mixed solution; under the condition of inert gas, adding the mixed solution into a reaction tube, irradiating the reaction solution by adopting near blue light, stirring for reaction, finishing the reaction, and carrying out post-treatment to obtain the alkyl substituted chalcogenide.
Further, the inert gas is nitrogen or argon.
Further, the wavelength range of the near blue light is 420nm-470 nm.
Further, the light source of near blue light is preferably a blue LED lamp.
Further, the molar ratio of the diether derivative to the sulfonium salt is 0.5-1.0: 1.
further, the molar ratio of the photocatalyst to the sulfonium salt is 0.1-0.4: 1.
further, the photocatalyst is selected from copper complexes, organic dye compounds or iridium complexes.
Further, the photocatalyst may be selected from 4CzIPN, fac- [ Ir (ppy)3]、Cu(CH3CN)4PF6Methylene blue, eosin B, rhodamine 6G, cuprous chloride, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene, 4, 7-diphenyl-1, 10-phenanthroline, eosin Y, CuCl, terpyridine, binaphthyl diphenyl phosphine, 1, 10-phenanthroline, Cu (CH)3CN)4BF4Or acridine red.
Further, the molar ratio of the alkali to the sulfonium salt is 1.0-3.0: 1.
further, the stirring reaction is carried out under the standard atmospheric pressure, and the reaction time is 12-24 h.
Further, the base is a nitrogen-containing organic base, preferably triethylamine, N-diisopropylethylamine or pyridine.
Further, the solvent is one of an organic solvent or water; wherein the organic solvent is selected from dimethyl sulfoxide DMSO, acetonitrile, dichlorosilane DCE, tetrahydrofuran THF, N-methylpyrrolidone NMP or toluene.
Further, the post-processing step comprises: after the reaction is finished, adding a proper amount of deionized water into the reaction solution, taking ethyl acetate as an extractant to perform liquid phase separation extraction, extracting a crude product from the reaction solution, combining the extracting solutions, and removing the solvent through a rotary evaporator; purifying the residue with chromatographic column to obtain alkyl substituted chalcogenide.
The invention further provides an application of the alkyl chalcogenide shown in the formula I, wherein the application specifically comprises the following steps:
for the preparation of enzyme modulators, antioxidants or cytostatics;
or used for preparing antitumor or anticancer biological medicine lead compounds;
or for the preparation of herbicides, insect repellents and fungicides in agrochemicals.
The invention provides a method for synthesizing alkyl substituted chalcogenide with high efficiency through light induction, and methodology research is carried out on the method. By studying the possible mechanism of this transition (process shown in FIG. 1), initially, the ground state photocatalyst PC is photo-activated to its excited state PC*(ii) a Next, in sulfonium salt 1 and PC*A single electron transfer process is carried out between the two to generate alkyl free radical 1' and PC +; the alkyl free radical 1 'reacts with the disulfides 2 to generate a target product 3, and the free radical 2' undergoes a homologous coupling reaction to obtain 2. At this stage, the photocatalyst radical cation PC+·The base state photocatalyst PC is generated again by the reduction of the organic base, and the photocatalysis circulation is completed.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides an alkyl substituted chalcogenide shown in formula I, in particular to an alkyl sulfide, an alkyl selenide and an alkyl telluride, and the compound is expected to be applied to anti-tumor and anti-cancer and has important application value in the research of enzyme regulators, antioxidants and cell growth inhibitors.
(2) The invention provides a novel high-efficiency synthesis method, which does not need harsh reaction conditions, only needs one-step illumination reaction and is suitable for synthesizing various alkyl substituted chalcogenides, alkyl selenides and alkyl tellurides, the photoinduction synthesis method has higher universality on various functional groups on an aromatic ring, and the number and the types of substituents of sulfonium salts and disulfide or diselenide or ditelluride are not specially limited.
(3) The synthesis method has simple preparation process and required devices, takes near blue light as energy, takes a copper complex, an organic dye compound or an iridium complex as a photocatalyst, does not need complex pretreatment of a light source, and has the characteristics of low toxicity and mild reaction conditions.
Drawings
FIG. 1 is a reaction scheme of a synthetic method
Detailed Description
The present application is described in further detail below by way of examples to enable those skilled in the art to practice the present application. It is to be understood that other embodiments may be utilized and that changes may be made without departing from the spirit or scope of the present application. To avoid detail not necessary to enable those skilled in the art to practice the application, the description may omit certain information known to those skilled in the art. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims. The following examples are presented to facilitate a better understanding of the present application and are not intended to limit the scope of the present application.
In the preparation method of the present invention, the order of addition of various materials and the specific reaction steps can be adjusted by those skilled in the art, and the method is not only suitable for small-scale preparation in a laboratory, but also suitable for industrial large-scale production in a chemical plant. In industrial mass production, the specific reaction parameters can be determined by the person skilled in the art by routine adjustment.
Unless otherwise specified, reagents, materials and the like used in the following examples are commercially available or synthesized from commercially available raw materials.
Example 1:
Figure BDA0003651985610000081
the sulfonium salt substituted in the above reaction scheme (0.2mmol), diphenyldiselenide (0.1mmol), 4CzIPN (0.02mmol) was added to a 25mL Schlenk tube filled with nitrogen and equipped with a magnetic stirrer at room temperature; dissolving N, N-diisopropylethylamine (0.4mmol) in DCM, adding the above mixed solution to a reaction tube in a nitrogen atmosphere using a syringe, and placing the reaction tube at a distance of 3cm from a 10-watt 455nm wavelength blue LED lamp, irradiating with blue light and stirring for 24 hours; after the reaction is finished, removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (100:1v/v)) to give 60.0mg of the objective product in a yield of 90%. The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.47–7.40(m,2H),7.20(t,J＝6.5Hz,5H),7.05(d,J＝7.8Hz,2H),2.87–2.81(m,4H),2.28(s,3H),1.81–1.76(m,2H),1.72–1.65(m,2H).
13C NMR(CDCl3,125MHz,ppm)δ136.2,132.7,130.4,130.2,129.8,129.1,126.9,34.0,29.3,29.2,27.4,21.1.
the high resolution mass spectra data are: HRMS calcd for C17H21SSe+[M+H]+:337.0524；found 337.0520.
Example 2:
Figure BDA0003651985610000091
the sulfonium salt (0.35mmol), diphenyldiselenide (0.11mmol), Cs substituted in the above reaction formula were reacted at room temperature2CO3(0.45mmol), acridine red (0.023mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer, the organic solvent DMSO was added to the reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed at a distance of 3cm from a 10 Watt 450nm wavelength blue LED lamp, irradiated with blue light and stirred for 20 hours, after the reaction was completed, 2mL of saturated saline was added to the reaction solution and stirred uniformly; 3mL of ethyl acetate was used as an extractant each time, and a crude product was extracted from the reaction solution by a liquid phase separation extraction operation,combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (90:1 v/v)). The desired product was obtained in 63.0mg, 89% yield.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.51–7.44(m,2H),7.33(d,J＝8.7Hz,2H),7.25(q,J＝5.6Hz,3H),6.84(d,J＝8.6Hz,2H),3.80(s,3H),2.89(t,J＝7.3Hz,2H),2.81(t,J＝7.2Hz,2H),1.85–1.78(m,2H),1.73–1.66(m,2H).
13C NMR(CDCl3,125MHz,ppm)δ159.0,133.4,132.7,130.4,129.1,126.9,126.5,114.7,55.4,35.4,29.4,29.1,27.4.
the high resolution mass spectra data are: HRMS calcd for C17H21OSSe+[M+H]+:353.0473；found353.0471.
Example 3:
Figure BDA0003651985610000101
the sulfonium salt (0.4mmol) substituted in the above reaction formula, 3-chloro-4-methyldiphenyldiselenide (0.2mmol), methylene blue (0.04mmol), K, were reacted at room temperature2CO3(0.5mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer; adding an organic solvent DMF into a reaction tube in a nitrogen environment by using an injector, placing the reaction tube at a position 3cm away from a 10-watt 420nm blue LED lamp, and irradiating and stirring the reaction tube by blue light for 15 hours; after the reaction is finished, adding 2mL of saturated saline solution into the reaction solution, uniformly stirring, taking 3mL of ethyl acetate as an extracting agent each time, extracting a crude product from the reaction solution through liquid phase separation and extraction operation, combining extract solutions, and removing a solvent through a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (60:1 v/v)). The desired product was obtained in 74.0mg with a yield of 87%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.46(s,1H),7.30(d,J＝8.3Hz,2H),7.26(d,J＝8.6Hz,3H),7.10(d,J＝7.8Hz,1H),2.87(dd,J＝10.2,4.1Hz,4H),2.34(s,3H),1.83–1.79(m 2H),1.77–1.72(m,2H),1.30(s,9H).
13C NMR(CDCl3,125MHz,ppm)δ159.0,134.9,134.8,133.4,133.0,131.4,131.2,128.4,126.5,114.7,55.4,35.4,29.4,29.0,27.8,19.8.
the high resolution mass spectra data are: HRMS calcd for C21H28ClSSe+[M+H]+:427.0760；found427.0756.
Example 4:
Figure BDA0003651985610000111
the sulfonium salt substituted in the above reaction scheme (0.45mmol), 3-fluorodiphenyldiselenide (0.22mmol) was added to a 25mL Schlenk tube filled with argon and equipped with a magnetic stirrer at room temperature; methylene blue (0.03mmol) and Et3Dissolving N (0.5mmol) in CH3CN, the mixed solution is added into a reaction tube in a nitrogen environment by using a syringe, the reaction tube is placed at a distance of 3cm from a 10 watt 445nm wavelength blue LED lamp, blue light irradiation is carried out, stirring is carried out for 11 hours, after the reaction is finished, a solvent is removed by a rotary evaporator, and a residue is purified by a silica gel column (the specification of the silica gel is 200 meshes-300 meshes, and the eluent is petroleum ether/ethyl acetate (40:1v/v)), so that 62.5mg of a target product is obtained, and the yield is 83%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.25–7.18(m,6H),7.15(d,J＝8.5Hz,1H),6.93–6.89(m,1H),2.92–2.86(m,4H),1.86–1.80(m,2H),1.76–1.70(m,2H).13C NMR(CDCl3,125MHz,ppm)δ163.8,135.0,130.8,129.2,127.8,119.1,118.9,113.9,113.8,33.5,29.1,29.0,27.3.
the high resolution mass spectra data are: HRMS calcd for C16H17ClFSSe+[M+H]+:374.9883；found374.9878.
Example 5:
Figure BDA0003651985610000121
the sulfonium salt substituted in the above reaction scheme (0.2mmol), 3-chloro-4-methyldiphenyldiselenide (0.11mmol), eosin B (0.05mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer, at room temperature; piperidine (0.4mmol) was dissolved in DCE, the above mixed solution was added to a reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed 3cm from a 10 watt 470nm wavelength blue LED lamp, irradiated with blue light and stirred for 13 hours; after the reaction is finished, removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (8:1v/v)) to give 76.3mg of the objective product in a yield of 90%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.78(d,J＝7.8Hz,1H),7.75–7.70(m,3H),7.57–7.29(m,5H),7.28–7.11(m,2H),3.00(t,J＝6.8Hz,2H),2.87(t,J＝6.8Hz,2H),1.88–1.73(m,4H).
13C NMR(CDCl3,125MHz,ppm)δ134.9,134.8,134.1,133.9,133.0,131.8,131.4,131.3,128.5,128.3,127.8,127.5,127.1,126.9,126.6,125.7,33.1,29.2,29.1,27.8,19.8.
the high resolution mass spectral data are: HRMS calcd for C21H22ClSSe+[M+H]+:421.0290；found421.0294.
Example 6:
Figure BDA0003651985610000131
the substituted sulfonium salt (0.15mmol) in the above reaction scheme, diselenide (0.1mmol) in the above reaction scheme, 4CzIPN (0.03mmol), K at room temperature3PO4(0.3mmol) was added to a 25mL Schlenk tubeThe tube was filled with argon and equipped with a magnetic stirrer; adding an organic solvent 1, 4-dioxane into a reaction tube in a nitrogen environment by using an injector, placing the reaction tube at a position 3cm away from a 10-watt 420-nm blue LED lamp, and irradiating and stirring the mixture for 12 hours by using blue light; after the reaction is finished, removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (20:1v/v)) to give 54.8mg of the objective product in 71% yield.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.34(d,J＝8.7Hz,2H),7.30(t,J＝7.4Hz,2H),7.21(dd,J＝11.5,7.1Hz,3H),6.84(d,J＝8.7Hz,2H),3.79(s,3H),3.03–2.90(m,2H),2.83–2.78(m,4H),2.53(t,J＝7.3Hz,2H),1.80–1.74(m,2H),1.69–1.63m,2H).
13C NMR(CDCl3,125MHz,ppm)δ158.9,141.4,133.3,128.6,128.5,126.6,126.5,114.7,55.5,37.4,35.4,29.5,29.5,24.9,23.6.
the high resolution mass spectra data are: HRMS calcd for C19H25OSSe+[M+H]+:381.0786；found381.0785.
Example 7:
Figure BDA0003651985610000141
the sulfonium salt (0.5mmol) substituted in the above reaction formula, diphenyldiselenide (0.3mmol), t-BuOK (0.95mmol), rhodamine B (0.05mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer, at room temperature; adding an organic solvent DMSO into a reaction tube in a nitrogen environment by using a syringe, placing the reaction tube at a position 3cm away from a 10 watt 445nm blue LED lamp, irradiating by blue light and stirring for 14 hours; after the reaction is finished, adding 2mL of saturated salt solution into the reaction solution, and uniformly stirring; extracting the crude product from the reaction solution by liquid phase separation and extraction operation with 3mL of ethyl acetate as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (25:1v/v)) to obtain 55.6mg of the objective product in 78% yield.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.52(d,J＝7.1Hz,2H),7.29(dd,J＝11.6,5.9Hz,5H),7.13(d,J＝7.8Hz,2H),2.94–2.88(m,4H),2.36(s,3H),1.78–1.70(m,2H),1.69–1.63(m,2H),1.60–1.56(m,2H).
13C NMR(CDCl3,125MHz,ppm)δ136.1,132.9,132.6,130.5,130.1,129.7,129.1,126.8,34.3,29.78,28.9,28.8,27.7,21.1.
the high resolution mass spectra data are: HRMS calcd for C18H23SSe+[M+H]+:351.0680；found351.0685.
Example 8:
Figure BDA0003651985610000151
the sulfonium salt (0.2mmol) substituted in the above reaction formula, 4-chlorodiphenyldiselenide (0.12mmol), K, was reacted at room temperature2CO3(0.7mmol)，fac-[Ir(ppy)3](0.04mmol) was put into a 25mL Schlenk's tube filled with argon and equipped with a magnetic stirrer, the organic solvent NMP was added to the reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed 3cm from a 10W 460nm wavelength blue LED lamp, irradiated with blue light and stirred for 18 hours, after the reaction was completed, 2mL of saturated saline was added to the reaction solution and stirred uniformly. Extracting the crude product from the reaction solution by liquid phase separation and extraction operation with 3mL of ethyl acetate as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (15:1v/v)) to obtain 56.1mg of the objective product in a yield of 73%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.45–7.39(m,2H),7.29–7.25(m,2H),7.22(d,J＝8.2Hz,2H),7.10(d,J＝7.7Hz,2H),3.28–3.03(m,1H),2.87(t,J＝7.2Hz,2H),2.33(d,J＝4.3Hz,3H),1.90–1.75(m,2H),1.71–1.55(m,2H),1.23(d,J＝6.7Hz,3H).
13C NMR(CDCl3,125MHz,ppm)δ137.3,134.1,133.1,133.1,131.1,129.7,129.3,128.6,43.4,36.6,28.1,27.5,21.3,21.2.
the high resolution mass spectra data are: HRMS calcd for C18H22ClSSe+[M+H]+:385.0290；found385.0291.
Example 9:
Figure BDA0003651985610000161
the substituted sulfonium salt (0.3mmol), 3-bromodiphenyl diselenide (0.16mmol), rhodamine 6G (0.06mmol) in the above reaction scheme was added to a 25mL Schlenk tube filled with nitrogen and equipped with a magnetic stirrer at room temperature, Et3N (0.7mmol) was dissolved in THF, the above mixed solution was added to a reaction tube in a nitrogen atmosphere using a syringe, the reaction tube was placed at a distance of 3cm from a 10-watt 455nm blue LED lamp, irradiated with blue light and stirred for 10 hours, and after the reaction was completed, 2mL of saturated saline was added to the reaction solution and stirred uniformly. Extracting the crude product from the reaction solution by liquid phase separation and extraction operation with 3mL of ethyl acetate as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (20:1v/v)) to give 62.2mg of the objective product in a yield of 72%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.62(s,1H),7.47–7.33(m,2H),7.27(dd,J＝22.9,8.2Hz,2H),7.12(t,J＝7.3Hz,3H),3.33–3.07(m,1H),2.94–2.86(m,2H),2.34(s,3H),1.92–1.77(m,2H),1.72–1.58(m,2H),1.25(d,J＝6.7Hz,3H).
13C NMR(CDCl3,125MHz,ppm)δ137.3,134.7,133.2,132.7,131.0,130.8,130.4,129.8,129.7,122.9,53.6,43.4,36.6,27.9,27.4,21.3.
the high resolution mass spectral data are: HRMS calcd for C18H22BrSSe+[M+H]+:428.9785；found428.9783.
Example 10:
Figure BDA0003651985610000162
at room temperature, sulfonium salt (0.5mmol) substituted in the above reaction formula, 4-chlorodiphenyldiselenide (0.3mmol), cuprous chloride (0.05mmol), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (0.07mmol), 4, 7-diphenyl-1, 10-phenanthroline (0.07mmol) were added to a 25mL Schlenk tube filled with nitrogen and equipped with a magnetic stirrer; dissolving N, N-diisopropylethylamine in toluene, adding the mixed solution into a reaction tube in a nitrogen environment by using an injector, placing the reaction tube at a position 3cm away from a 10 watt 450nm blue LED lamp, and irradiating and stirring the mixture for 16 hours by using blue light; after the reaction is finished, adding 2mL of saturated salt water into the reaction solution, uniformly stirring, taking 3mL of ethyl acetate as an extracting agent each time, extracting a crude product from the reaction solution through liquid phase separation extraction operation, combining extraction solutions, and removing a solvent through a rotary evaporator; the residue was purified by a silica gel column (specification of silica gel: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (80:1v/v)) to give 42.7mg of the objective product in a yield of 63%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.41(d,J＝8.2Hz,2H),7.22(d,J＝8.2Hz,2H),2.90(t,J＝7.2Hz,2H),2.49(dd,J＝14.3,7.1Hz,4H),1.82–1.75(m,2H),1.72–1.66(m,2H),1.57–1.53(m,2H),1.43–1.36(m,2H),0.91(t,J＝7.3Hz,3H).
13C NMR(CDCl3,125MHz,ppm)δ134.1,133.1,129.3,128.6,31.9,31.9,31.6,29.7,29.3,27.9,22.2,13.9.
the high resolution mass spectra data are: HRMS calcd for C14H22ClSSe+[M+H]+:337.0290；found337.0289.
Example 11:
Figure BDA0003651985610000171
the sulfonium salt (0.4mmol), 2-methyldiphenyldiselenide (0.21mmol), K substituted in the above reaction scheme was reacted at room temperature3PO4(0.75mmol), rhodamine 6G (0.04mmol), was added to a 25mL Schlenk tube, which was filled with argon and equipped with a magnetic stirrer; adding an organic solvent DMF into a reaction tube in a nitrogen environment by using an injector, placing the reaction tube at a position 3cm away from a 10-watt 425 nm-wavelength blue LED lamp, irradiating blue light and stirring for 14 hours; after the reaction, 2mL of saturated saline was added to the reaction mixture, and the mixture was stirred well. Extracting the crude product from the reaction solution by liquid phase separation and extraction operation with 3mL of ethyl acetate as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (80:1v/v)) to give 60.6mg of the objective product in 81% yield.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.39(d,J＝7.9Hz,2H),7.07(d,J＝7.8Hz,2H),2.87(t,J＝7.2Hz,2H),2.52–2.46(m,4H),2.32(s,3H),1.82–1.74(m,2H),1.69(t,J＝7.0Hz,2H),1.60–1.53(m,2H),1.29(d,J＝19.3Hz,10H),0.88(t,J＝6.8Hz,3H).
13C NMR(CDCl3,125MHz,ppm)δ136.9,133.2,129.9,126.4,32.2,31.9,31.6,29.8,29.7,29.4,29.3,29.3,29.1,27.9,22.8,21.2,14.2.
the high resolution mass spectra data are: HRMS calcd for C19H33SSe+[M+H]+:373.1463；found373.1464.
Example 12:
Figure BDA0003651985610000181
at room temperature, taking out the above reaction formulaSulfonium salt (0.3mmol), dibutyl diselenide (0.2mmol), Na2CO3(0.6mmol), eosin Y (0.06mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer; adding an organic solvent THF into a reaction tube in a nitrogen environment by using an injector, placing the reaction tube at a position 3cm away from a 10-watt 455nm blue LED lamp, irradiating by blue light and stirring for 12 hours; after the reaction, 2mL of saturated saline was added to the reaction mixture, and the mixture was stirred well. Extracting the crude product from the reaction solution by liquid phase separation and extraction operation with 3mL of ethyl acetate as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (specification of silica gel: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (90:1v/v)) to give the objective product 39.8mg, yield 62%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.27(d,J＝8.3Hz,2H),7.11(d,J＝7.9Hz,2H),2.91(t,J＝7.1Hz,2H),2.56(t,J＝7.4Hz,4H),2.34(s,3H),1.89–1.78(m,2H),1.76–1.70(m,2H),1.68–1.58(m,2H),1.48–1.30(m,2H),0.93(t,J＝7.3Hz,3H).13C NMR(CDCl3,125MHz,ppm)δ136.2,132.8,130.2,129.8,34.1,32.9,29.7,29.5,23.9,23.3,23.2,21.1,13.8.
the high resolution mass spectra data are: HRMS calcd for C15H25SSe+[M+H]+:317.0837；found317.0838.
Example 13:
Figure BDA0003651985610000191
the sulfonium salt substituted in the above reaction scheme (0.55mmol), diheptyldiselenoether (0.3mmol), 4CzIPN (0.015mmol) was added to a 25mL Schlenk tube filled with argon and equipped with a magnetic stirrer at room temperature. Triethylamine (0.8mmol) was dissolved in DCM, and the above mixed solution was added to a reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed 3cm from a 10 watt 440nm wavelength blue LED lamp, irradiated with blue light and stirred for 14 hours. After the reaction is finished, removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (80:1 v/v)). 51.3mg of the expected product are obtained with a yield of 71%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.27(d,J＝8.2Hz,2H),7.11(d,J＝7.9Hz,2H),2.91(t,J＝7.1Hz,2H),2.55(t,J＝7.5Hz,4H),2.34(s,3H),1.83–1.78(m,2H),1.76–1.70(m,2H),1.68–1.62(m,2H),1.39–1.34(m,2H),1.33–1.27(m,6H),0.90(t,J＝6.7Hz,3H).
13C NMR(CDCl3,125MHz,ppm)δ136.2,132.8,130.2,129.8,34.1,31.9,30.8,30.1,29.7,29.5,28.9,24.2,23.3,22.8,21.1,14.2.
the high resolution mass spectra data are: HRMS calcd for C18H31SSe+[M+H]+:359.1306；found359.1303.
Example 14:
Figure BDA0003651985610000201
the sulfonium salt substituted in the above reaction scheme (0.2mmol), 4-cyanodisulfide (0.12mmol), methylene blue (0.03mmol) was added to a 25mL Schlenk tube filled with argon and equipped with a magnetic stirrer at room temperature. N, N-diisopropylethylamine (0.43mmol) was dissolved in THF, the above mixed solution was added to a reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed at a distance of 3cm from a 10-watt 460nm wavelength blue LED lamp, irradiated with blue light and stirred for 15 hours. After the reaction, 2mL of saturated saline was added to the reaction mixture, and the mixture was stirred well. Extracting the crude product from the reaction solution by liquid phase separation and extraction with ethyl acetate 3mL each time as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (20:1 v/v)). The desired product was obtained in 31.9mg, 49% yield.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.54(d,J＝8.2Hz,2H),7.30(d,J＝8.7Hz,2H),7.27(d,J＝7.9Hz,2H),7.13(d,J＝7.8Hz,2H),3.00(t,J＝7.0Hz,2H),2.93(t,J＝6.8Hz,2H),2.35(s,3H),1.90–1.75(m,4H).
13C NMR(CDCl3,125MHz,ppm)δ144.9,136.5,132.4,130.4,129.9,126.9,124.1,119.0,108.2,34.0,31.6,28.3,27.5,21.2.
the high resolution mass spectra data are: HRMS calcd for C18H20NS2 +[M+H]+:314.1032；found314.1034.
Example 15:
Figure BDA0003651985610000211
the sulfonium salt (0.3mmol) substituted in the above reaction formula, 4-phenyldisulfide (0.2mmol), CuCl (0.03mmol), terpyridine (0.045mmol), binaphthyldiphenylphosphine (0.045mmol), Cs were reacted at room temperature2CO3(0.5mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer; adding an organic solvent DMSO (dimethyl sulfoxide) into a reaction tube in a nitrogen environment by using an injector, placing the reaction tube at a position 3cm away from a 10-watt 420nm blue LED lamp, and irradiating and stirring the reaction tube by blue light for 15 hours; after the reaction, 2mL of saturated saline was added to the reaction mixture, and the mixture was stirred well. Extracting the crude product from the reaction solution by liquid phase separation and extraction with ethyl acetate 3mL each time as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (70:1v/v)) to give the objective product 48.1mg, yield 63%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.59(d,J＝7.6Hz,2H),7.53(d,J＝8.1Hz,2H),7.45(t,J＝7.6Hz,2H),7.42–7.33(m,3H),6.97(s,2H),6.82(s,1H),2.98(t,J＝6.2Hz,2H),2.94(t,J＝6.3Hz,2H),2.30(s,6H),1.87–1.78(m,4H).
13C NMR(CDCl3,125MHz,ppm)δ140.6,138.9,138.6,136.1,135.8,129.5,128.9,127.9,127.6,127.4,126.9,126.9,33.3,33.2,28.3,28.2,21.4.
the high resolution mass spectra data are: HRMS calcd for C24H27S2 +[M+H]+379.1549; found 379.1548 example 16:
Figure BDA0003651985610000221
the substituted sulfonium salt of the above reaction scheme (0.45mmol), 4CzIPN (0.03mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer, at room temperature. 3-chlorodiphenyldisulfide (0.3mmol), N, N-diisopropylethylamine (0.9mmol) was dissolved in NMP, and the above mixed solution was added to a reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed at a distance of 3cm from a 10 watt 430nm wavelength blue LED lamp, irradiated with blue light and stirred for 16 hours. After the reaction, 2mL of saturated saline was added to the reaction mixture, and the mixture was stirred well. Extracting the crude product from the reaction solution by liquid phase separation and extraction operation with 3mL of ethyl acetate as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (70:1 v/v)). 49.7mg of the expected product are obtained with a yield of 72%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.31–7.27(m,2H),7.26–7.20(m,1H),7.19–7.14(m,2H),7.11(d,J＝7.8Hz,2H),3.24–3.01(m,1H),2.93–2.85(m,2H),2.34(s,3H),1.86–1.75(m,2H),1.72–1.61(m,2H),1.26(t,J＝5.9Hz,3H).
13C NMR(CDCl3,125MHz,ppm)δ139.1,137.3,134.8,133.2,131.0,129.9,129.7,128.3,126.8,125.9,53.6,43.5,35.6,33.3,26.4,21.3.
the high resolution mass spectra data are: HRMS calcd for C18H22ClS2 +[M+H]+:337.0846；found337.0846.
Example 17:
Figure BDA0003651985610000231
the sulfur salt (0.2mmol) substituted in the above reaction scheme, diphenyl disulfide (0.15mmol), Cu (CH) at room temperature3CN)4PF6(0.02mmol), 1, 10-phenanthroline (0.03mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer; pyridine (0.5mmol) was dissolved in DCE, the above mixed solution was added to a reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed at a distance of 3cm from a 10 watt 455nm wavelength blue LED lamp, irradiated with blue light and stirred for 13 hours; after the reaction is finished, removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (80:1v/v)) to give 24.7mg of the objective product in a yield of 56%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.33(d,J＝7.6Hz,2H),7.30–7.26(m,2H),7.17(t,J＝7.2Hz,1H),2.94(t,J＝6.2Hz,2H),2.50(t,J＝6.2Hz,2H),2.09(s,3H),1.77–1.59(m,4H).
13C NMR(CDCl3,125MHz,ppm)δ136.7,129.3,129.0,126.0,33.8,33.4,28.3,28.2,15.6.
the high resolution mass spectra data are: HRMS calcd for C11H17S2 +[M+H]+:213.0766；found 213.0765.
Example 18:
Figure BDA0003651985610000241
the sulfur salt (0.6mmol) substituted in the above reaction scheme, 4-phenyldisulfide (0.4mmol), Cu (CH) was reacted at room temperature3CN)4BF4(0.08mmol), 1, 10-phenanthroline (0.03mmol), binaphthyl diphenyl phosphine (0.03mmol), Na2CO3(1.0mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped with a magnetic stirrer; adding an organic solvent DMSO (dimethyl sulfoxide) into a reaction tube in a nitrogen environment by using a syringe, placing the reaction tube at a position 3cm away from a blue LED lamp with the wavelength of 10W 436nm, irradiating by blue light and stirring for 18 hours; after the reaction, 2mL of saturated saline was added to the reaction mixture, and the mixture was stirred well. Extracting the crude product from the reaction solution by liquid phase separation and extraction operation with 3mL of ethyl acetate as an extractant, combining the extracts, and removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (specification of silica gel: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (60:1v/v)) to give 58.7mg of the objective product in a yield of 75%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.58(d,J＝7.5Hz,2H),7.52(d,J＝8.2Hz,2H),7.44(t,J＝7.6Hz,2H),7.40(d,J＝8.3Hz,2H),7.34(t,J＝7.3Hz,1H),2.98(t,J＝6.9Hz,2H),2.55–2.49(m,4H),1.82–1.73(m,4H),1.57(t,J＝7.4Hz,2H),1.38–1.25(m,10H),0.89(t,J＝6.8Hz,3H).
13C NMR(CDCl3,125MHz,ppm)δ140.6,138.9,135.9,129.4,128.9,127.7,127.4,126.9,33.4,32.3,31.9,31.7,29.8,29.4,29.3,29.1,28.8,28.4,22.8,14.2.
the high resolution mass spectra data are: HRMS calcd for C24H35S2 +[M+H]+:387.2175；found 387.2170.
Example 19:
Figure BDA0003651985610000251
at room temperature, a sulfur salt (0.3mmol) substituted in the above reaction formula, diphenyl ditelluride (0.2mmol), acridine red (0.06mmol), Cs2CO3(0.6mmol) was added to a 25mL Schlenk tube, which was filled with nitrogen and equipped withA magnetic stirrer; an organic solvent toluene was added to the reaction tube in a nitrogen atmosphere using a syringe, and the reaction tube was placed 3cm from a 10 watt 440nm wavelength blue LED lamp, irradiated with blue light and stirred for 12 hours. After the reaction is finished, removing the solvent by a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (60:1v/v)) to obtain 53.7mg of the objective product in 66% yield.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.48(d,J＝6.7Hz,2H),7.25(d,J＝8.8Hz,3H),6.93(s,2H),6.80(s,1H),2.92(d,J＝7.3Hz,2H),2.88(d,J＝7.2Hz,2H),2.28(s,6H),1.88–1.80(m,2H),1.78–1.73(m,2H).
13C NMR(CDCl3,125MHz,ppm)δ138.6,136.1,132.8,130.4,129.2,127.9,126.9,33.2,29.3,29.3,27.4,21.4.
the high resolution mass spectral data are: HRMS calcd for C18H23STe+[M+H]+:401.0577；found 401.0582.
Example 20:
Figure BDA0003651985610000252
the sulfur salt substituted in the above reaction scheme (0.45mmol), diphenyl ditelluroether (0.3mmol), eosin B (0.09mmol) was added to a 25mL Schlenk tube filled with nitrogen and equipped with a magnetic stirrer at room temperature; dissolving triethylamine (0.6mmol) in an organic solvent NMP, adding the above mixed solution into a reaction tube in a nitrogen atmosphere by using a syringe, placing the reaction tube at a distance of 3cm from a 10-watt 460nm blue LED lamp, irradiating with blue light and stirring for 16 hours; after the reaction is finished, adding 2mL of saturated saline solution into the reaction solution, uniformly stirring, taking 3mL of ethyl acetate as an extracting agent each time, extracting a crude product from the reaction solution through liquid phase separation and extraction operation, and removing the solvent through a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (90:1v/v)) to give 51.7mg of the objective product in a yield of 64%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.76–7.46(m,2H),7.37–7.30(m,2H),7.30–7.19(m,3H),6.85(d,J＝8.5Hz,2H),3.82(s,3H),2.89(dd,J＝16.2,8.9Hz,2H),2.82(t,J＝7.2Hz,2H),1.96–1.78(m,2H),1.73–1.66(m,2H).
13C NMR(CDCl3,125MHz,ppm)δ159.0,138.6,133.4,132.7,130.4,129.2,126.9,114.7,55.5,35.5,29.5,29.2,27.4.
the high resolution mass spectra data are: HRMS calcd for C17H21OSTe+[M+H]+:403.0370；found403.0373.
Example 21:
Figure BDA0003651985610000261
the sulfur salt substituted in the above reaction scheme (0.6mmol), diphenyl ditelluroether (0.31mmol), 4CzIPN (0.09mmol) was added to a 25mL Schlenk tube filled with nitrogen and equipped with a magnetic stirrer at room temperature; dissolving N, N-diisopropylethylamine (1.2mmol) in an organic solvent DMSO, adding the above mixed solution to a reaction tube in a nitrogen atmosphere using a syringe, and placing the reaction tube at a distance of 3cm from a 10W 460nm blue LED lamp, irradiating with blue light and stirring for 20 hours; after the reaction is finished, adding 2mL of saturated saline solution into the reaction solution, uniformly stirring, taking 3mL of ethyl acetate as an extracting agent each time, extracting a crude product from the reaction solution through liquid phase separation and extraction operation, and removing the solvent through a rotary evaporator; the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh; eluent: petroleum ether/ethyl acetate (85:1v/v)) to give 52.7mg of the objective product in a yield of 63%.
The nuclear magnetic spectrum data of the obtained product are as follows:
1H NMR(CDCl3,500MHz,ppm)δ7.50(d,J＝6.3Hz,2H),7.35(d,J＝8.6Hz,2H),7.30–7.22(m,3H),6.86(d,J＝8.6Hz,2H),3.81(s,3H),2.90(t,J＝7.4Hz,2H),2.81(t,J＝7.1Hz,2H),1.75–1.67(m,2H),1.63–1.58(m,2H),1.57–1.50(m,2H).13C NMR(CDCl3,125MHz,ppm)δ158.9,133.2,132.6,130.5,129.1,126.8,126.7,114.6,55.4,35.8,29.8,28.9,27.8.
the high resolution mass spectra data are: HRMS calcd for C18H23OSTe+[M+H]+:417.0526；found417.0526.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes and modifications made according to the spirit of the present disclosure should be covered within the scope of the present disclosure.

Claims (10)

1. An alkyl-substituted chalcogenide having the structure of formula I,
Figure FDA0003651985600000011
wherein:
R1one selected from hydrogen and methyl;
R2one selected from aryl or straight-chain alkyl;
R3one selected from alkyl and aryl;
y is selected from S, Se or Te.
2. The alkyl-substituted chalcogenide of claim 1, wherein the alkyl-substituted chalcogenide is represented by formula I, wherein:
R1one selected from hydrogen and methyl;
R2one selected from aryl or straight-chain alkyl;
R3one selected from alkyl and aryl;
y is selected from S, Se or Te.
3. A method for preparing an alkyl-substituted chalcogenide represented by formula I, comprising the following steps:
using substituted sulfonium salt shown in a formula II and diether derivative shown in a formula III as substrates, and irradiating the substrates by using near blue light under the action of a photocatalyst and alkali to obtain alkyl substituted chalcogenide by a one-pot method;
the sulfonium salt shown in the formula II and the diether derivative shown in the formula III are shown as follows:
Figure FDA0003651985600000021
in the formula
R1One selected from hydrogen and methyl;
R2one selected from aryl or straight-chain alkyl;
R3one selected from alkyl and aryl;
x is selected from PF6 -、BF4 -Or I-One of (1);
y is selected from S, Se or Te.
4. The method of claim 3, comprising the steps of:
adding substituted sulfonium salt and diether derivative into a reaction tube; adding a photocatalyst and alkali into a solvent to form a mixed solution; under the condition of inert gas, adding the mixed solution into a reaction tube, irradiating the reaction solution by adopting near blue light, stirring for reaction, and carrying out post-treatment after the reaction is finished to obtain the alkyl substituted chalcogenide.
5. The production method according to claim 3 or 4, wherein the wavelength of the near-blue light is in a range of 420nm to 470 nm.
6. The method according to claim 3 or 4, wherein the molar ratio of the photocatalyst to the sulfonium salt is 0.1 to 0.4: 1.
7. the method according to claim 3 or 4, wherein the molar ratio of the diether derivative to the sulfonium salt is 0.5 to 1.0: 1.
8. the method according to claim 3, wherein the photocatalyst is selected from the group consisting of copper complexes, organic dyes, iridium complexes, etc.; the base is a nitrogen-containing organic base.
9. The method of claim 3, wherein the solvent is one of an organic solvent or water; wherein the organic solvent is selected from dimethyl sulfoxide DMSO, acetonitrile, dichloroalkyl DCM, tetrahydrofuran THF, N-methylpyrrolidone NMP or toluene.
10. The application of the alkyl substituted chalcogen compound shown as the formula I is characterized by specifically comprising the steps of preparing an enzyme regulator, an antioxidant or a cell growth inhibitor; or used for preparing lead compounds for screening anti-tumor or anti-cancer biological medicines; or for the preparation of herbicides, insect repellents and fungicides in agrochemicals.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0866049A2 (en) * 1997-03-17 1998-09-23 The University of Wales Swansea Chlorination of aromatic compounds and catalysts therefor
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Publication number Priority date Publication date Assignee Title
EP0866049A2 (en) * 1997-03-17 1998-09-23 The University of Wales Swansea Chlorination of aromatic compounds and catalysts therefor
CN1347811A (en) * 2000-10-05 2002-05-08 王子制纸株式会社 Ink jet recording paper

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ALAIN KRIEF等: "《Synthesis of hexylselenol and hexyl selenides from hexylthiol involving hexylthiolanium salts》", 《SYNLETT》, no. 16, pages 2601 - 2604 *
HIROYUKI HIGUCHI等: "《Flash pyrolysis of selenides. Syntheses of bibenzyls, olefins, and related compounds》", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》, vol. 55, no. 1, pages 182 - 187 *
MATHEW A等: "《Unexpected Leaving Ability of (Phenyltelluro)formates in the Presence of Internal Nucleophiles: Complications during Alkyl and Oxyacyl Radical Generation in the Preparation of Sulfur- and Selenium-Containing Heterocycles》", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 63, no. 9, pages 3032 - 3036 *

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