CN109810030B - Preparation method of visible light-promoted asymmetric sulfoxide compound - Google Patents
Preparation method of visible light-promoted asymmetric sulfoxide compound Download PDFInfo
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Abstract
The invention belongs to the field of organic synthetic chemistry, and particularly relates to a preparation method of an asymmetric sulfoxide compound, in particular to a method for synthesizing the asymmetric sulfoxide compound based on visible light catalysis. Adding the compound shown in the general formula I and the compound shown in the general formula II into a reactor, adding a mixture of an organic solvent and water as a reaction solvent, communicating the reactor with air, and reacting for 16-40 hours at room temperature under the irradiation of a visible light lamp. After the TLC thin-layer chromatography plate detection reaction is finished, adding purified water, then extracting, combining extract liquor, drying the extract liquor, and concentrating and purifying the extract liquor to obtain a compound shown as a general formula III, namely the asymmetric sulfoxide compound; avoids the pollution of metal reagents and saves the reaction cost.
Description
Technical Field
The invention belongs to the field of organic synthetic chemistry, and particularly relates to a preparation method of an asymmetric sulfoxide compound, in particular to a method for synthesizing the asymmetric sulfoxide compound based on visible light catalysis.
Background
Asymmetric sulfoxides are valuable organic structural backbones that are not only abundant in natural products and pharmacologically active molecules, but also can be used to construct a variety of important chemicals and therapeutics, such as antiulcer, antifungal, and antiatherosclerotic drugs (j.nat. prod.,2008,71, 2036; j.nat. prod.,2002,65, 935; j.nat. prod.,2010,73, 1306). Representative marketed drugs containing a sulfoxide backbone structure such as esomeprazole (a. aktiebolag, US5877192A,1998) which is a drug used for the treatment of the gastrointestinal tract and modafinil (l.l. lafon, US4927855A,1990) which is a drug clinically used for the treatment of hypersomnia and anorexia. Due to the diversity of their structures and remarkable biological functions, the synthesis of sulfoxides has attracted a wide range of attention from organic synthesis chemists and pharmacologists.
The traditional sulfoxide synthesis method mainly relies on thioether oxidation reaction, which generally adopts stoichiometric high-valence iodine or peroxide as an oxidant and utilizes the catalytic action of various transition metals such as iron, vanadium, copper, titanium, cobalt, magnesium, silver, zinc and the like to promote thioether oxidation (reaction formula 1). Obviously, these methods involve the use of some toxic metal reagents and hazardous oxidizing agents, which result in the generation of large amounts of waste and environmental pollution. Another problem faced by conventional synthesis methods is that most sulfoxides are over-oxidized to sulfones.
Reaction scheme 1
Due to the advantages of cleanliness, cheapness, and reproducibility, visible light has been considered as an ideal energy source for promoting organic synthetic transformations. In recent years, especially after 2008, visible light has become a mild and powerful synthetic tool for building a variety of important organic compounds. In the field of visible light catalysis, the oxidation of thioethers by photocatalysts using oxygen or air as oxidant has developed into a method for the efficient synthesis of sulfoxides (Green chem.,2013,15, 357; chem.sci.,2015,6, 5000; chem.commun.,2018,54, 7127; j.org.chem.,2017,82, 9054; adv.synth.catal.,2018,360,386). However, these reactions require the preparation of thioether compounds in advance by complicated procedures.
Recently, several reports have been made on the synthesis of sulfoxides directly using commercial thiophenols or thiols. For example, visible light-promoted oxidative sulfoxidation of olefins with thiophenols constructs β -carbonyl sulfoxides and sulfones (equation 2) (Green chem.,2014,16, 3986; chem. Commun.,2017,53, 10463; Green chem.,2017,19, 3520). In 2018, Lee reports that a visible light promoted silver nitrate catalysis method is used for constructing diaryl sulfoxides and diaryl sulfones, and the method utilizes aryl diazonium salts and aryl thiophenols as raw materials, 3 equivalents of potassium persulfate as an oxidizing agent, and 3 equivalents of pyridine as an additive (reaction formula 3) (org. lett.2018,20,764). However, this type of photocatalytic reaction also has some drawbacks, such as narrow substrate range (limited to olefins or to arylthiophenols), use of metal catalysts and equivalent amounts of inorganic oxidants, which limit their widespread use in organic synthesis.
Reaction formula 3
Disclosure of Invention
The invention aims to provide a method for preparing an asymmetric sulfoxide compound based on photoinduced catalysis. The method overcomes the defects of the prior art, adopts aryl azo methyl sulfone with wide substrate range and aromatic thiophenol or aliphatic mercaptan as raw materials, takes air as an oxidant, does not use a photocatalyst, and efficiently synthesizes the asymmetric sulfoxide compound under the illumination of room temperature.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a method for preparing an asymmetric sulfoxide compound by photoinduction, which comprises the following steps: adding the compound shown in the general formula I and the compound shown in the general formula II into a reactor, adding a mixture of an organic solvent and water as a reaction solvent, communicating the reactor with air, and reacting for 16-40 hours at room temperature under the irradiation of a visible light lamp. After the TLC thin-layer chromatography plate detection reaction is finished, adding purified water, then extracting, combining extract liquor, drying the extract liquor, concentrating and purifying the extract liquor to obtain a compound shown as a general formula III, namely the asymmetric sulfoxide compound, wherein the reaction formula is as follows:
wherein R is1Is optionally substituted ester, cyano, alkoxy, aryl, heteroaryl, fluoro, chloro, bromo, or 1-4 carbon alkyl;
R2is optionally substituted aryl, heteroaryl, cycloalkyl, alkyl or allyl;
further, in the above reaction, the molar ratio of the compound represented by the general formula I to the compound represented by the general formula II was 3: 1.
Further, the organic solvent is acetonitrile, ethyl acetate, N-dimethylformamide, dichloromethane, 1, 4-dioxane, toluene, benzene, chloroform, 1, 2-dichloroethane, tetrahydrofuran, 1, 2-dimethoxyethane or dimethyl sulfoxide, preferably an acetonitrile/water mixed solvent, and the acetonitrile/water mixing ratio is preferably 1: 1.
Further, the light source illuminated by the visible light lamp is a blue LED lamp with power of 3w-60w, a white LED lamp with power of 3w-60w or a green LED lamp with power of 3w-60w, preferably a blue LED lamp with power of 3 w.
Further, the room temperature is 20-30 ℃, preferably 25 ℃.
The reaction provided by the invention is carried out in air.
Further, the concrete treatment after the extract liquid is combined is as follows: drying the extract liquid by anhydrous sodium sulfate, carrying out vacuum decompression concentration treatment on the extract liquid by 0.06-0.10Mpa to obtain a crude product without containing an organic solvent, and then carrying out column chromatography treatment on the crude product by a silica gel column to obtain the asymmetric sulfoxide compound, wherein the column chromatography separation and purification treatment is washing by a mixed eluent of petroleum ether and ethyl acetate according to the volume ratio of 5: 1.
In the method provided by the invention, no photocatalyst is required to be added in the reaction process.
Has the advantages that:
1. the method adopts the next step of visible light catalysis to synthesize the sulfoxide compound, has mild reaction conditions, clean energy and no need of strong oxidant, and improves the safety of the reaction;
2. the reaction of the invention does not need a photocatalyst, thereby avoiding the pollution caused by using a metal reagent and saving the reaction cost;
3. the reaction adopts a mixed solvent of an organic solvent and water, and is environment-friendly.
Detailed Description
The invention is further illustrated by the following specific examples, it being understood that the preparation of the examples is illustrative only and is not intended to be limiting; on the premise of the conception of the invention, simple modification of the preparation method of the invention belongs to the protection scope of the invention.
It should also be noted that various preferred features of the method of the present invention mentioned above and various specific features in the embodiments specifically described below may be combined, and all combinations of these features, all numerical ranges bounded by upper and lower numerical values specifically disclosed herein, and the like, fall within the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
The materials and reagents used in the following examples are commercially available or synthesized from commercially available starting materials, unless otherwise specified.
Specific examples of the present invention will be described in detail below with reference to the technical solutions, but the process conditions are not limited to these examples.
Example 1:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction at 25 ℃ for 16h under the irradiation of a 3W blue LED lamp. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 36.7mg of yellow oily solid, and the yield is 79%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
example 2:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under illumination by a 3W blue LED lamp at a reaction temperature of 30 ℃ for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 36.0mg of yellow oily solid, and the yield is 78%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
example 3:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under illumination by a 3W blue LED lamp at a reaction temperature of 20 ℃ for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 36.0mg of yellow oily solid, and the yield is 78%.
Obtained byThe product profile data were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
example 4:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction for 16h under the irradiation of a 3W green LED lamp at a reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 19.5mg of yellow oily solid, and the yield is 42%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
example 5:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), tetrahydrofuran 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction at 25 ℃ for 16h under the irradiation of a 3W white LED lamp. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extracts are combined, after the extracts are dried by anhydrous sodium sulfate, the extracts are concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 22.7mg of yellow oily solid, and the yield is 49%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
example 6:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), tetrahydrofuran 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction at 25 ℃ for 16h under the irradiation of a 3W blue LED lamp. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 17.2mg of yellow oily solid, and the yield is 37%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
example 7:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), ethanol 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction for 16h under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 17.6mg of yellow oily solid, and the yield is 38%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
example 8:
in a 15mL reaction tube, p-methoxybenzyl azomethylsulfone 1a (0.6mmol), p-methylthiophenol 2b (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction at 25 ℃ for 16h under the irradiation of a 3W blue LED lamp. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 40.4mg of yellow oily solid, and the yield is 82%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.55(d,J＝8.9 Hz,2H),7.49(d,J＝8.2 Hz,2H),7.25(d,J＝8.7 Hz,2H),6.95(d,J＝8.9 Hz,2H),3.81(s,3H),2.37(s,3H)；13C NMR(CDCl3,125 MHz,ppm):161.9,142.7,141.3,137.0,129.9,127.1,124.8,114.8,55.5,21.4；MS(EI)；[M+H]+:247.1.
example 9:
in a 15mL reaction tube, p-methoxybenzene azomethylsulfonyl 1a (0.6mmol), o-methylphenol 2c (0.2mmol), acetonitrile 1mL and water 1mL are sequentially added, uniformly mixed, and then stirred and reacted for 16h under the irradiation of a 3W blue LED lamp at the reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 39.4mg of yellow oily solid, and the yield is 80%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):8.03-8.01(m,1H),7.52(d,J＝8.9 Hz,2H),7.44(t,J＝7.6 Hz,1H),7.38-7.35(m,1H),7.15(d,J＝7.5 Hz,1H),6.93(d,J＝8.9 Hz,2H),3.81(s,3H),2.26(s,3H)；13C NMR(CDCl3,125 MHz,ppm):162.0,142.8,135.5,135.3,130.9,130.8,128.5,127.0,124.2,114.8,55.5,18.5；MS(EI)；[M+H]+:247.2.
example 11:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfonylmethylsulfone 1a (0.6mmol), o-methoxyphenylthiophenol 2d (0.2mmol), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is yellow oily solid 43.0mg, and the yield is 82%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.94-7.92(m,1H),7.61(d,J＝8.8 Hz,2H),7.42-7.38(m,1H),7.16(t,J＝7.5 Hz,1H),6.91(d,J＝8.8 Hz,2H),6.84(d,J＝8.2 Hz,1H),3.80(s,3H),3.77(s,3H)；13C NMR(CDCl3,125 MHz,ppm):116.7,115.5,136.6,133.3,132.0,127.5,124.5,121.5,114.4,111.0,55.7,55.4；HRMS calc.forC14H15O3S(M+H)+,263.0742；found,263.0745.
experimental example 12:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), p-methoxyphenylthiophenol 2e (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 42.5mg of yellow oily solid, and the yield is 81%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.53(d,J＝8.8 Hz,4H),6.95(d,J＝8.8 Hz,4H),3.82(s,6H)；13C NMR(CDCl3,125 MHz,ppm):161.8,137.0,126.9,114.7,55.5；HRMS calc.for C14H15O3S(M+H)+,263.0742；found,263.0746.
experimental example 13:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfonylmethylsulfone 1a (0.6mmol), 3, 4-dimethoxythiophenol 2f (0.2mmol), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 hours. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 38.6mg of yellow oily solid, and the yield is 66%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.54(d,J＝8.8 Hz,2H),7.16–7.14(m,2H),6.96(d,J＝8.8 Hz,2H),6.91(d,J＝8.8 Hz,1H),3.89(s,3H),3.88(s,3H),3.82(s,3H).；13C NMR(CDCl3,125 MHz,ppm):161.9,151.3,149.9,137.1,137.0,126.9,118.5,114.7,111.0,107.0,56.1,56.1,55.5；HRMS calc.for C15H17O4S(M+H)+,293.0848；found,293.0849.
experimental example 14:
in a 15mL reaction tube, p-methoxybenzyl azomethylsulfone 1a (0.6mmol), 4-hydroxyphenylthiophenol 2g (0.2mmol), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 40.2mg of yellow oily solid, and the yield is 81%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.49(d,J＝8.8 Hz,2H),7.38(d,J＝8.6 Hz,2H),6.95(d,J＝8.8 Hz,2H),6.88(d,J＝8.7 Hz,2H),3.81(s,3H).13CNMR(CDCl3,125 MHz,ppm):162.0,160.3,135.2,133.9,127.7,127.1,116.7,114.9,55.5；HRMS calc.for C13H13O3S(M+H)+,249.0585；found,249.0589.
experimental example 16:
in a 15mL reaction tube, p-methoxybenzyl azomethylsulfone 1a (0.6mmol), p-fluorobenzothiophenol 2h (0.2mmol), acetonitrile 1mL and water 1mL are sequentially added, uniformly mixed, and then stirred and reacted for 16h under the irradiation of a 3W blue LED lamp at the reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 38.5mg of yellow oily solid, and the yield is 77%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62–7.58(m,2H),7.55(d,J＝8.9 Hz,2H),7.15(t,J＝8.6 Hz,2H),6.97(d,J＝8.8 Hz,2H),3.82(s,3H).13C NMR(CDCl3,125 MHz,ppm):164.2(d,JCF＝250.0 Hz),162.2,141.3(d,JCF＝2.9 Hz),136.4,127.2,127.0(d,JCF＝8.9 Hz),116.5(d,JCF＝22.4 Hz),114.9,55.5；MS(EI)；[M+H]+:251.1.
experimental example 17:
in a 15mL reaction tube, p-methoxybenzyl azomethylsulfone 1a (0.6mmol), p-chlorothiophenol 2i (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction for 16h under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 36.2mg of yellow oily solid, and the yield is 68%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.58–7.52(m,4H),7.43(d,J＝8.6 Hz,2H),6.97(d,J＝8.8 Hz,2H),3.83(s,3H)；13C NMR(CDCl3,125 MHz,ppm):162.3,144.3,137.0,136.2,129.5,127.3,126.0,115.0,55.6；MS(EI)；[M+H]+:267.2.
experimental example 18:
in a 15mL reaction tube, p-methoxybenzyl azomethylsulfone 1a (0.6mmol), p-bromothiophenol 2j (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 36.0mg of yellow oily solid, and the yield is 58%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.59(d,J＝8.6 Hz,2H),7.55(d,J＝8.9 Hz,2H),7.47(d,J＝8.6 Hz,2H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H).；13CNMR(CDCl3,125 MHz,ppm):162.3,145.0,136.2,132.4,127.3,126.1,125.2,115.0,55.6；HRMS calc.for C13H12BrO2S(M+H)+,310.9741；found,310.9743.
experimental example 19:
in a 15mL reaction tube, p-methoxybenzyl azomethylsulfone 1a (0.6mmol), 2-mercapto-5-methyl-1, 3, 4-thiadiazole 2k (0.2mmol), acetonitrile 1mL and water 1mL are sequentially added, uniformly mixed, and then stirred and reacted for 40h under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, 23.4mg of yellow oily solid and the yield of 46%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.74(d,J＝8.8 Hz,2H),7.04(d,J＝8.8 Hz,2H),3.85(s,3H),2.79(s,3H)；13C NMR(CDCl3,125 MHz,ppm):162.9,133.7,126.9,126.5,115.3,114.7,55.6,16.1；HRMS calc.for C10H11N2O2S2(M+H)+,255.0262；found,255.0265.
experimental example 21:
in a 15mL reaction tube, p-methoxybenzyl azomethylsulfone 1a (0.6mmol,128.4mg), 2-mercaptobenzothiazole 2l (0.2mmol,30.8mg), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 40 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extracts are combined, after the extracts are dried by anhydrous sodium sulfate, the extracts are concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 27.2mg of yellow oily solid, and the yield is 47%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):8.02(d,J＝7.9 Hz,1H),7.93(d,J＝8.1 Hz,1H),7.81(d,J＝8.9 Hz,2H),7.53–7.48(m,1H),7.46–7.41(m,1H),7.01(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125 MHz,ppm):178.7,162.9,153.8,135.9,134.0,127.1,126.8,126.3,124.2,122.3,115.2,55.6；HRMS calc.for C14H12NO2S2(M+H)+,290.0309；found,290.0308.
experimental example 22:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol,128.4mg), 2-phenethyl mercaptan 2m (0.2mmol,27.6mg), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 38.0mg of yellow oily solid, and the yield is 73%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.58(d,J＝8.8 Hz,2H),7.29(t,J＝7.4 Hz,2H),7.21(t,J＝7.4 Hz,1H),7.17(d,J＝7.1 Hz,2H),7.03(d,J＝8.7Hz,2H),3.86(s,3H),3.06–3.02(m,3H),2.92-2.88(m,1H)；13C NMR(CDCl3,125 MHz,ppm):162.0,138.9,134.5,128.7,128.5,126.7,126.0,114.8,58.5,55.6,28.3；HRMS calc.forC15H17O2S(M+H)+,261.0949；found,261.0951.
experimental example 23:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), benzylthiophenol 2n (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction for 16h under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 35.9mg of yellow oily solid, and the yield is 73%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.31(d,J＝8.8 Hz,2H),7.28-7.26(m,1H),7.25–7.23(m,2H),6.98(d,J＝6.5 Hz,2H),6.92(d,J＝8.8 Hz,2H),4.12(d,J＝12.5 Hz,1H),3.96(d,J＝12.5 Hz,1H),3.84(s,3H)；13C NMR(CDCl3,125 MHz,ppm):162.1,133.6,130.4,129.3,128.5,128.2,126.4,114.4,63.8,55.5；HRMS calc.forC14H15O2S(M+H)+,247.0793；found,247.0791.
experimental example 24:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), n-butylmercaptan 2o (0.2mmol), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under illumination of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 33.9mg of yellow oily solid, and the yield is 80%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.57(d,J＝8.7 Hz,2H),7.03(d,J＝8.7 Hz,2H),3.86(s,3H),2.86–2.72(m,2H),1.68–1.57(m,2H),1.48–1.40(m,2H),0.92(t,J＝7.3 Hz,3H)；13C NMR(CDCl3,125 MHz,ppm):161.9,134.9,126.0,114.7,57.2,55.5,24.3,21.9,13.7；HRMS calc.for C11H17O2S(M+H)+,213.0949；found,213.0951.
experimental example 25:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol,128.4mg), methyl thioglycolate 2p (0.2mmol,21.2mg), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 31.9mg of yellow oily solid, and the yield is 70%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.55(d,J＝8.8 Hz,2H),6.96(d,J＝8.8 Hz,2H),3.80(d,J＝13.6 Hz,1H),3.79(s,3H),3.63(s,3H),3.57(d,J＝13.6 Hz,1H)；13C NMR(CDCl3,125 MHz,ppm):164.2,161.5,132.8,125.2,113.9,60.6,54.6,51.7；HRMS calc.for C10H13O4S(M+H)+,229.0535；found,229.0537.
experimental example 26:
in a 15mL reaction tube, p-methyl phenyl azo methyl sulfone 1b (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction at 25 ℃ for 16h under the irradiation of a 3W blue LED lamp. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 32.0mg of yellow oily solid, and the yield is 74%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.57–7.55(m,2H),7.46(d,J＝8.2 Hz,2H),7.40–7.35(m,3H),7.19(d,J＝7.9 Hz,2H),2.29(s,3H)；13C NMR(CDCl3,125MHz,ppm):145.8,142.5,141.7,130.9,130.1,129.3,125.0,124.7,21.4；MS(EI)；[M+H]+:217.2.
experimental example 27:
m-methyl phenyl azo methyl sulfone 1c (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence to a 15mL reaction tube, mixed uniformly, and then stirred for reaction at a reaction temperature of 25 ℃ for 16h under the irradiation of a 3W blue LED lamp. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 31.1mg of yellow oily solid, and the yield is 72%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.67–7.62(m,2H),7.49–7.43(m,4H),7.42(d,J＝7.7 Hz,1H),7.33(t,J＝7.6 Hz,1H),7.24(d,J＝7.5 Hz,1H),2.38(s,3H)；13C NMR(CDCl3,125 MHz,ppm):145.7,145.4,139.6,132.0,131.0,129.3,129.1,125.0,124.8,122.0,21.4；MS(EI)；[M+H]+:217.2.
experimental example 28:
in a 15mL reaction tube, m-tolylazomethylsulfonylmethane 1c (0.6mmol,118.8mg), p-methylphenylthiol 2b (0.2mmol,24.8mg), 1mL acetonitrile and 1mL water were added in this order, mixed well, and then reacted with stirring under a 3W blue LED lamp at a reaction temperature of 25 ℃ for 16 hours. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 30.4mg of yellow oily solid, and the yield is 66%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.53(d,J＝8.2 Hz,2H),7.47(s,1H),7.39(d,J＝7.8 Hz,1H),7.32(t,J＝7.6 Hz,1H),7.25(d,J＝6.5 Hz,2H),7.23(d,J＝7.5 Hz,1H),2.37(s,3H),2.37(s,3H)；13C NMR(CDCl3,125 MHz,ppm):145.6,142.6,141.5,139.5,131.8,130.0,129.1,125.0,124.9,121.9,21.4,21.4；HRMS calc.forC14H15OS(M+H)+,231.0844；found,231.0845.
experimental example 29:
in a 15mL reaction tube, o-tolylazomethylsulfonyl 1d (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction for 16h under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 29.4mg of yellow oily solid, and the yield is 68%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.95–7.94(m,1H),7.61–7.59(m,2H),7.46–7.43(m,3H),7.41(d,J＝7.5 Hz,1H),7.37–7.35(m,1H),7.17(d,J＝7.3Hz,1H),2.36(s,3H)；13C NMR(CDCl3,125 MHz,ppm):144.6,142.9,135.8,131.1,131.0,131.0,129.3,127.2,125.9,124.8,18.6；MS(EI)；[M+H]+:217.1.
experimental example 30:
in a 15mL reaction tube, p-methyl phenyl azo methyl sulfone 1b (0.6mmol), p-methyl thiophenol 2b (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 32.2mg of yellow oily solid, and the yield is 70%.
Number of obtained product spectraAccording to the following steps:1H NMR(CDCl3,500 MHz,ppm):7.51(d,J＝8.2 Hz,4H),7.25(d,J＝8.0 Hz,4H),2.36(s,6H)；13C NMR(CDCl3,125 MHz,ppm):142.6,141.5,130.0,124.9,21.4；MS(EI)；[M+H]+:231.1.
experimental example 31:
in a 15mL reaction tube, arylazomethylsulfonylmethane 1b (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL were added in this order, mixed well, and then stirred under the irradiation of a 3W blue LED lamp at a reaction temperature of 25 ℃ for reaction for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extracts are combined, after the extracts are dried by anhydrous sodium sulfate, the extracts are concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 27.5mg of yellow oily solid, and the yield is 68%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.66–7.64(m,4H),7.48–7.43(m,6H)；13C NMR(CDCl3,125 MHz,ppm):145.2,131.1,129.3,124.8；MS(EI)；[M+H]+:203.1.
experimental example 32:
p-fluorobenzene azomethylsulfone 1b (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL are sequentially added into a 15mL reaction tube, uniformly mixed, and then stirred for reaction for 16h under the irradiation of a 3W blue LED lamp at the reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 29.9mg of yellow oily solid, and the yield is 68%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.70–7.59(m,4H),7.50–7.44(m,3H),7.15(t,J＝8.6 Hz,2H)；13C NMR(CDCl3,125 MHz,ppm):164.3(d,J＝250.4Hz),145.4,141.2,131.2,129.4,127.2(d,J＝8.9Hz),124.7,116.8,116.7(d,J＝22.4Hz)；MS(EI)；[M+H]+:221.1.
experimental example 33:
1g (0.6mmol) of p-chlorobenzoylmethylsulfone, 1mL (0.2mmol) of thiophenol 2a, 1mL of acetonitrile and 1mL of water were sequentially added to a 15mL reaction tube, mixed uniformly and then stirred for reaction at 25 ℃ under the irradiation of a 3W blue LED lamp for 16 h. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 34.0mg of yellow oily solid, and the yield is 72%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.64–7.62(m,2H),7.58(d,J＝8.5 Hz,2H),7.49–7.46(m,3H),7.43(d,J＝8.5 Hz,2H)；13C NMR(CDCl3,125 MHz,ppm):145.4,144.3,137.3,131.4,129.6,129.5,126.1,124.7；MS(EI)；[M+H]+:237.0.
experimental example 34:
1g (0.6mmol) of p-chlorobenzoylmethylsulfone, 1mL (0.2mmol) of p-methylthiophenol 2b, 1mL of acetonitrile and 1mL of water are sequentially added into a 15mL reaction tube, uniformly mixed and then stirred for reaction for 16h under the irradiation of a 3W blue LED lamp at the reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extracts are combined, after the extracts are dried by anhydrous sodium sulfate, the extracts are concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by a mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 33.5mg of yellow oily solid, and the yield is 67%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.57–7.55(m,2H),7.51(d,J＝8.2 Hz,2H),7.43–7.42(m,2H),2.37(s,3H)；13C NMR(CDCl3,125 MHz,ppm):144.4,142.1,142.1,137.1,130.2,129.6,126.0,125.0,21.4；MS(EI)；[M+H]+:251.0.
experimental example 35:
p-bromophenylazo methylsulfone (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile (1 mL) and water (1 mL) are sequentially added into a 15mL reaction tube, uniformly mixed, and then stirred and reacted for 16h under the irradiation of a 3W blue LED lamp at the reaction temperature of 25 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times each time, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 30.8mg of yellow oily solid, and the yield is 55%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.64–7.62(m,2H),7.59(d,J＝8.6 Hz,2H),7.51(d,J＝8.6 Hz,2H),7.48–7.46(m,3H)；13C NMR(CDCl3,125 MHz,ppm):145.2,144.8,132.6,131.4,129.5,126.3,125.6,124.7；MS(EI)；[M+H]+:281.2.
experimental example 36:
in a 15mL reaction tube, p-cyanobenzazomethylsulfonyl 1i (0.6mmol), thiophenol 2a (0.2mmol), acetonitrile 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction at 25 ℃ for 16h under the irradiation of a 3W blue LED lamp. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated to be solvent-free by vacuum (0.08Mpa) to obtain a crude product, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and the silica gel column flash column chromatography is carried out to obtain the sulfoxide product of the embodiment, wherein the sulfoxide product is 28.2mg of yellow oily solid, and the yield is 62%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.79–7.73(m,4H),7.68–7.64(m,2H),7.51–7.49(m,3H)；13C NMR(CDCl3,125 MHz,ppm):151.2,144.5,133.0,132.0,129.8,125.0,124.9,117.7,114.7；MS(EI)；[M+H]+:228.1.
experimental example 37:
in a 15mL reaction tube, p-methoxyphenylazomethylsulfone 1a (0.6mmol), thiophenol 2a (0.2mmol), tetrahydrofuran 1mL and water 1mL are added in sequence, mixed uniformly, and then stirred for reaction for 16h under the irradiation of a 60W blue LED lamp at a reaction temperature of 30 ℃. After TLC detection is carried out until the reaction is finished, ethyl acetate is added for extraction, 3 times of extraction are carried out for 3 times, the extraction liquid is combined, after the extraction liquid is dried by anhydrous sodium sulfate, the extraction liquid is concentrated under reduced pressure of vacuum (0.08Mpa) until no solvent is obtained, a crude product is obtained, then the crude product is washed by mixed eluent of petroleum ether and ethyl acetate with the volume ratio of 5:1, and silica gel column flash column chromatography is carried out, so that the sulfoxide product of the embodiment is 34.8mg of yellow oily solid, and the yield is 75%.
The product profile data obtained were:1H NMR(CDCl3,500 MHz,ppm):7.62-7.60(m,2H),7.58-7.56(m,2H),7.47-7.43(m,3H),6.96(d,J＝8.9 Hz,2H),3.82(s,3H)；13C NMR(CDCl3,125MHz,ppm):162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:233.2.
other technical features which are the same as or similar to those of formula III obtained by oxidative coupling reaction induced by visible light under air and light reaction conditions using compounds represented by formula I and II as starting materials are one of the embodiments of the present invention, and the technical features of the above-described embodiments can be arbitrarily combined, and in order to meet the requirements of patent laws, patent practice rules and examination guidelines, all possible combinations of the technical features of the above-described embodiments are not described.
The above embodiment is only one implementation form of the method for preparing sulfoxide compounds based on photocatalysis provided by the invention, and other variations of the scheme provided by the invention, such as adding or reducing components or steps therein, or applying the invention to other technical fields similar to the invention, belong to the protection scope of the invention.
Claims (6)
1. A method for preparing asymmetric sulfoxide compounds by light induction is characterized by comprising the following steps:
adding a compound shown as a general formula I and a compound shown as a general formula II into a reactor, adding a mixture of an organic solvent and water as a reaction solvent, communicating the reactor with air, and reacting at room temperature for 16-40 hours under the irradiation of a visible light lamp;
after the TLC thin-layer chromatography plate detection reaction is finished, adding purified water, then extracting, combining extract liquor, drying the extract liquor, concentrating and purifying the extract liquor to obtain a compound shown as a general formula III, namely the asymmetric sulfoxide compound, wherein the reaction formula is as follows:
wherein R is1Is an ester group, cyano, alkoxy, aryl, heteroaryl, fluoro, chloro, bromo, or C1-C4 alkyl;
R2is aryl, heteroaryl, cycloalkyl, alkyl or allyl;
the organic solvent is acetonitrile, ethanol and tetrahydrofuran.
2. The method for preparing asymmetric sulfoxide compounds by photo-stimulation according to claim 1, wherein: the molar ratio of the compound of formula I to the compound of formula II is 3: 1.
3. The method for preparing asymmetric sulfoxide compounds by photo-stimulation according to claim 1, wherein: the mixing ratio of the organic solvent acetonitrile/water is 1: 1.
4. The method for preparing the asymmetric sulfoxide compound by photocatalysis according to claim 1, characterized in that: the light source illuminated by the visible light lamp is a blue LED lamp with power of 3w-60w, a white LED lamp with power of 3w-60w or a green LED lamp with power of 3w-60 w.
5. The method for preparing the asymmetric sulfoxide compound by photocatalysis according to claim 1, characterized in that: the room temperature is 20-30 ℃.
6. The method for preparing the asymmetric sulfoxide compound by light induction according to claim 1, wherein: the concrete treatment after the extraction liquid combination is as follows: drying the extract liquid by anhydrous sodium sulfate, carrying out vacuum decompression concentration treatment on the extract liquid by 0.06-0.10Mpa to obtain a crude product without containing an organic solvent, and then carrying out column chromatography treatment on the crude product by a silica gel column to obtain the asymmetric sulfoxide compound, wherein the column chromatography separation and purification treatment is washing by a mixed eluent of petroleum ether and ethyl acetate according to the volume ratio of 5: 1.
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