CN109810030A - A kind of visible light promotes the preparation method of asymmetric sulfoxide compound - Google Patents
A kind of visible light promotes the preparation method of asymmetric sulfoxide compound Download PDFInfo
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Abstract
The invention belongs to synthetic organic chemical arts, and in particular to a kind of preparation method of asymmetric sulfoxide compound, especially a kind of method for synthesizing asymmetric sulfoxide compound based on visible light catalytic.General formula I compound represented and general formula II compound represented are added in reactor, the mixture that organic solvent and water is added is reaction dissolvent, and reactor is communicated with air, it is seen that under light light irradiation, react at room temperature 16-40 hours.TLC chromatographic sheet detects after the reaction was completed, pure water is added, then it extracts, combining extraction liquid, after dry extract liquor, concentration carried out to extract liquor and purifying to obtain general formula III compound represented be asymmetric sulfoxide compound, reaction condition of the present invention is mild, clean energy, does not need strong oxidizer, improves the safety of reaction；It avoids polluting using metal reagent, has saved reaction cost.
Description
Technical field
The invention belongs to synthetic organic chemical arts, and in particular to a kind of preparation method of asymmetric sulfoxide compound,
Especially a kind of method that asymmetric sulfoxide compound is synthesized based on visible light catalytic.
Background technique
Asymmetric sulfoxide is extremely valuable organic structure skeleton, it is not only largely present in natural products and pharmacological activity
In molecule, and it can also be used to construct various important chemicals and therapeutic agent, such as antiulcer, the medicines such as antimycotic and anti arteriosclerosis
Object (J.Nat.Prod., 2008,71,2036；J.Nat.Prod.,2002,65,935；J.Nat.Prod.,2010,73,
1306).Representative marketed drug containing sulfoxide skeleton structure such as is used to treat the drug esomeprazole of stomach
(A.Aktiebolag, US5877192A, 1998) and the drug modafinil for being clinically used for treatment hypnosia and apositia
(L.L.Lafon, US4927855A,1990).Diversity and significant biological function due to its structure, the synthesis of sulfoxide
The extensive concern of synthetic organic chemist and pharmacy man are attracted.
Traditional sulfoxide synthetic method depends on the oxidation reaction of thioether, such reaction is generally using stoichiometry
High price iodine or peroxide are oxidant, utilize the catalysis of the salt such as various transition metal such as iron, vanadium, copper, titanium, cobalt, magnesium, silver and zinc
Effect promotes sulfide oxidation (reaction equation 1).Obviously, these methods are related to using some toxic metals reagents and harmful oxidation
Agent, this causes to generate a large amount of waste, pollutes environment.Another problem that prior synthesizing method faces is that most of sulfoxide can quilt
Excessive oxidation is at sulfone.
Reaction equation 1
Due to cleaning, cheap and reproducible advantage, it is seen that light has always been considered as being the ideal energy for promoting organic synthesis conversion.
In recent years, after especially 2008, it is seen that light has become the mild and strong conjunction for constructing various important organic compounds
At tool.In visible light catalytic field, uses oxygen or air to be catalyzed sulfide oxidation by photochemical catalyst for oxidant and sent out
Transform into for be effectively synthesized the method for sulfoxide (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).But these reactions are required through the cumbersome previously prepared sulfide compound of operation sequence.
Recently, directlying adopt thiophenol or the mercaptan of commercialization, there are reports to synthesize sulfoxide.Such as visible light promotes
Alkene and thiophenol oxidation sulfoxidation building β-carbonyl sulfoxide and sulfone (reaction equation 2) (Green Chem., 2014,16,
3986；Chem.Commun.,2017,53,10463；Green Chem.,2017,19,3520).2018, Lee report was visible
Light promotes silver nitrate catalysis process to construct diaryl sulphoxide and diaryl sulfone, and this method utilizes aryl diazonium salts and aryl thiophenol
For raw material, 3 equivalent potassium peroxydisulfates are oxidant, the pyridine of 3 equivalents be additive (reaction equation 3) (Org.Lett.2018,20,
764).But there is also some disadvantages for the type light-catalyzed reaction, such as substrate spectrum is narrow (is confined to alkene or is confined to
Aryl thiophenol), using inorganic oxidizer of metallic catalyst and equivalent, limit their extensive uses in organic synthesis.
Reaction equation 2
Reaction equation 3
Summary of the invention
The object of the present invention is to provide a kind of methods for preparing asymmetric sulfoxide compound based on Photocatalysis.This method
Overcome prior art disadvantage, use the extensive arylazo methyl sulfone of substrate spectrum and aromatic series thiophenol or aliphatic mercaptan for
Raw material does not use photochemical catalyst using air as oxidant, efficiently synthesizes asymmetric sulfoxide compound under light at room temperature photograph.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
The present invention provides a kind of methods that photoinduction prepares asymmetric sulfoxide compound, using following steps: by general formula I institute
The compound and general formula II compound represented shown is added in reactor, and the mixture that organic solvent and water is added is to react molten
Agent, reactor are communicated with air, it is seen that under light light irradiation, are reacted at room temperature 16-40 hours.The detection of TLC chromatographic sheet has been reacted
Cheng Hou is added pure water, then extracts, combining extraction liquid, after dry extract liquor, carries out concentration to extract liquor and purifying is led to
Formula III compound represented is asymmetric sulfoxide compound, and reaction equation is as follows:
Wherein R1For ester group, cyano, alcoxyl, aryl, heteroaryl, fluorine, chlorine, bromine or the 1-4 carbon alkyl arbitrarily replaced；
R2For aryl, heteroaryl, naphthenic base, alkyl or the allyl arbitrarily replaced；
Further, in above-mentioned reaction, the molar ratio of general formula I compound represented and general formula II compound represented is 3:1.
Further, the organic solvent is acetonitrile, ethyl acetate, n,N-Dimethylformamide, methylene chloride, Isosorbide-5-Nitrae-
Dioxane, toluene, benzene, chloroform, 1,2- dichloroethanes, tetrahydrofuran, 1,2- dimethoxy-ethane or dimethyl sulfoxide, preferably second
Nitrile/water mixed solvent, the preferred 1:1 of acetonitrile/water mixed proportion.
Further, the light source that the visible lamp shines be the blue LED lamp of 3w-60w power, 3w-60w power it is white
The green LED lamp of color LED light or 3w-60w power, the preferably blue LED lamp of 3w power.
Further, the room temperature is 20-30 DEG C, preferably 25 DEG C.
Reaction provided by the invention is to carry out under air.
Further, the specific processing after the combining extraction liquid are as follows: extract liquor will extract after anhydrous sodium sulfate is dry
It takes liquid to handle by 0.06-0.10Mpa vacuum-concentrcted, obtains the crude product without organic solvent, then pass through silicagel column
Column Image processing is carried out to crude product and obtains asymmetric sulfoxide compound, wherein column chromatography for separation purification processes are according to volume
Mixtures of eluents than petroleum ether and ethyl acetate for 5:1 is rinsed.
In method provided by the invention, reaction process does not need plus any photochemical catalyst.
The utility model has the advantages that
1, the present invention is using in visible light catalytic operation synthesis sulfoxide compound in next step, and reaction condition is mild, clean energy, no
Strong oxidizer is needed, the safety of reaction is improved；
2, present invention reaction does not need photochemical catalyst, avoids polluting using metal reagent, has saved reaction cost；
3, reaction uses organic solvent and water mixed solvent, and reaction environment is friendly.
Specific embodiment
The present invention is further illustrated below by specific embodiment, it should be understood that the preparation side of the embodiment of the present invention
Method is only used for illustrating the present invention, rather than limiting the invention；Under the premise of present inventive concept, prepared by the present invention
The simple modifications of method belong to the present invention claims protection scope.
It should also be noted that each preferred technical characteristic of above-mentioned the method for the present invention and being detailed below
Each particular technique feature in embodiment can be combined, and the various combinations of all these technical characteristics are had by the present invention
All numberical ranges etc. of the numerical value disclosed in body as bound are all fallen within the scope of the present invention.
Experimental methods as used in the following examples are conventional method unless otherwise specified.
Material as used in the following examples, reagent are commercially available unless otherwise specified or by business ways
Material synthesis obtained by diameter.
Specific embodiments of the present invention are described in detail below with reference to technical solution, but process conditions are not limited only to these implementations
Example.
Embodiment 1:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 36.7mg, yield 79%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
Embodiment 2:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 30 degree of reaction temperature lower stirrings
16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, combining extraction liquid, extraction
Take liquid after anhydrous sodium sulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), slightly produced
The mixtures of eluents of object, the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, and silicagel column rapid column chromatography obtains
The present embodiment sulfoxide product is yellow oily solid 36.0mg, yield 78%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
Embodiment 3:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 20 degree of reaction temperature lower stirrings
16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, combining extraction liquid, extraction
Take liquid after anhydrous sodium sulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), slightly produced
The mixtures of eluents of object, the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, and silicagel column rapid column chromatography obtains
The present embodiment sulfoxide product is yellow oily solid 36.0mg, yield 78%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
Embodiment 4:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W green LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 19.5mg, yield 42%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
Embodiment 5:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), tetrahydrofuran 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W white led lamps, under 25 degree of reaction temperature
It is stirred to react 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid is taken, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry,
Crude product is obtained, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 22.7mg, yield 49%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
Embodiment 6:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), tetrahydrofuran 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, under 25 degree of reaction temperature
It is stirred to react 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid is taken, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry,
Crude product is obtained, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 17.2mg, yield 37%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
Embodiment 7:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), ethyl alcohol 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 17.6mg, yield 38%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
Embodiment 8:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), to methylbenzene phenyl-sulfhydrate 2b
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 40.4mg, yield 82%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ161.9,142.7,141.3,137.0,129.9,127.1,
124.8,114.8, 55.5,21.4；MS(EI)；[M+H]+:247.1.
Embodiment 9:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), o-methyl-benzene thiophenol 2c
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 39.4mg, yield 80%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ8.03-8.01(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):δ162.0,
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.
Embodiment 11:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), o-methoxythiophenol 2d
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 43.0mg, yield 82%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.94-7.92(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):δ116.7,
115.5,136.6, 133.3,132.0,127.5,124.5,121.5,114.4,111.0,55.7,55.4；HRMS
calc.for C14H15O3S(M+H)+, 263.0742；found,263.0745.
Experimental example 12:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), to methoxybenzenethiol 2e
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 42.5mg, yield 81%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ161.8,137.0,126.9,
114.7,55.5；HRMS calc.for C14H15O3S(M+H)+,263.0742；found,263.0746.
Experimental example 13:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), 3,4- dimethoxy benzenethiols
2f (0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, under 25 degree of reaction temperature
It is stirred to react 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, is merged
Extract liquor, extract liquor pass through extract liquor and are concentrated under reduced pressure into vacuum (0.08Mpa) without molten after anhydrous sodium sulfate is dry
Agent obtains crude product, and the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, and silicagel column is quick
Column chromatography, obtains the present embodiment sulfoxide product, is yellow oily solid 38.6mg, yield 66%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ161.9,151.3,149.9,137.1,137.0,
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 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), 4- hydroxyl base benzenethiol 2g
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 40.2mg, yield 81%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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)13C
NMR (CDCl3,125 MHz,ppm):δ162.0,160.3,135.2,133.9,127.7,127.1,116.7,114.9,
55.5；HRMS calc.for C13H13O3S(M+H)+,249.0585；found,249.0589.
Experimental example 16:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), to fluoro thiophenol 2h
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 38.5mg, yield 77%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62–7.58(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):δ164.2(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 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), to chlorothio-phenol 2i
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 36.2mg, yield 68%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.58–7.52(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):δ
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 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), to bromo thiophenol 2j
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 36.0mg, yield 58%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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)；13C
NMR (CDCl3,125 MHz,ppm):δ162.3,145.0,136.2,132.4,127.3,126.1,125.2,115.0,
55.6；HRMS calc.for C13H12BrO2S(M+H)+,310.9741；found,310.9743.
Experimental example 19:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), 2- sulfydryl -5- methyl-1,3,
4- thiadiazoles 2k (0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, reaction temperature
40h is stirred to react under 25 degree.It is detected with TLC to after the reaction was completed, ethyl acetate extraction, each 3mL, extraction 3 is then added
Secondary, combining extraction liquid, extract liquor passes through extract liquor and is concentrated under reduced pressure at vacuum (0.08Mpa) after anhydrous sodium sulfate is dry
It is extremely solvent-free, crude product is obtained, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silica gel
Column rapid column chromatography obtains the present embodiment sulfoxide product, is yellow oily solid 23.4mg, yield 46%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ162.9,
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 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol, 128.4mg), 2- sulfydryl benzo
Thiazole 2l (0.2mmol, 30.8mg), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, reaction temperature
40h is stirred to react under 25 degree of degree.It is detected with TLC to after the reaction was completed, ethyl acetate extraction, each 3mL, extraction 3 is then added
Secondary, combining extraction liquid, extract liquor passes through extract liquor and is concentrated under reduced pressure at vacuum (0.08Mpa) after anhydrous sodium sulfate is dry
It is extremely solvent-free, crude product is obtained, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silica gel
Column rapid column chromatography obtains the present embodiment sulfoxide product, is yellow oily solid 27.2mg, yield 47%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ178.7,162.9,153.8,
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 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol, 128.4mg), 2- benzene ethyl mercaptan
2m (0.2mmol, 27.6mg), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, reaction temperature 25
16h is stirred to react under degree.It being detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times,
Combining extraction liquid, extract liquor pass through extract liquor and are concentrated under reduced pressure into vacuum (0.08Mpa) after anhydrous sodium sulfate is dry
It is solvent-free, crude product is obtained, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column
Rapid column chromatography obtains the present embodiment sulfoxide product, is yellow oily solid 38.0mg, yield 73%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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=8.7
Hz,2H), 3.86(s,3H),3.06–3.02(m,3H),2.92-2.88(m,1H)；13C NMR(CDCl3,125 MHz,ppm):
δ 162.0,138.9,134.5,128.7,128.5,126.7,126.0,114.8,58.5,55.6,28.3；HRMS
calc.for C15H17O2S (M+H)+,261.0949；found,261.0951.
Experimental example 23:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzyl thiophenol 2n
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 35.9mg, yield 73%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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): δ162.1,133.6,130.4,129.3,128.5,128.2,126.4,114.4,63.8,55.5；HRMS
calc.for C14H15O2S (M+H)+,247.0793；found,247.0791.
Experimental example 24:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), n-butyl mercaptan 2o
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 33.9mg, yield 80%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ161.9,134.9,126.0,114.7,
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 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol, 128.4mg), thioacetic acid first
Ester 2p (0.2mmol, 21.2mg), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, reaction temperature
16h is stirred to react under 25 degree.It being detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times,
Combining extraction liquid, extract liquor pass through extract liquor and are concentrated under reduced pressure into vacuum (0.08Mpa) after anhydrous sodium sulfate is dry
It is solvent-free, crude product is obtained, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column
Rapid column chromatography obtains the present embodiment sulfoxide product, is yellow oily solid 31.9mg, yield 70%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ164.2,161.5,132.8,125.2,113.9,60.6,
54.6,51.7； HRMS calc.for C10H13O4S(M+H)+,229.0535；found,229.0537.
Experimental example 26:
In 15mL reaction tube, sequentially add to methyl benzeneazo methyl sulfone 1b (0.6mmol), benzenethiol 2a (0.2mmol), second
Nitrile 1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 32.0mg, yield 74%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.57–7.55(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,
125 MHz,ppm):δ145.8,142.5,141.7,130.9,130.1,129.3,125.0,124.7,21.4；MS(EI)；[M+
H]+: 217.2.
Experimental example 27:
In 15mL reaction tube, a methyl benzeneazo methyl sulfone 1c (0.6mmol), benzenethiol 2a (0.2mmol), second are sequentially added
Nitrile 1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 31.1mg, yield 72%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.67–7.62(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):δ145.7,145.4,139.6,132.0,131.0,129.3,
129.1, 125.0,124.8,122.0,21.4；MS(EI)；[M+H]+:217.2.
Experimental example 28:
In 15mL reaction tube, a methyl benzeneazo methyl sulfone 1c (0.6mmol, 118.8mg) is sequentially added, to methylbenzene phenyl-sulfhydrate
2b (0.2mmol, 24.8mg), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, reaction temperature 25
16h is stirred to react under degree.It being detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times,
Combining extraction liquid, extract liquor pass through extract liquor and are concentrated under reduced pressure into vacuum (0.08Mpa) after anhydrous sodium sulfate is dry
It is solvent-free, crude product is obtained, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column
Rapid column chromatography obtains the present embodiment sulfoxide product, is yellow oily solid 30.4mg, yield 66%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ145.6,
142.6,141.5, 139.5,131.8,130.0,129.1,125.0,124.9,121.9,21.4,21.4；HRMS
calc.for C14H15OS(M+H)+, 231.0844；found,231.0845.
Experimental example 29:
In 15mL reaction tube, o-methyl-benzene azo methyl sulfone 1d (0.6mmol), benzenethiol 2a (0.2mmol), second are sequentially added
Nitrile 1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 29.4mg, yield 68%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.95–7.94(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=
7.3 Hz,1H),2.36(s,3H)；13C NMR(CDCl3,125 MHz,ppm):δ144.6,142.9,135.8,131.1,
131.0,131.0,129.3,127.2,125.9,124.8,18.6；MS(EI)；[M+H]+:217.1.
Experimental example 30:
In 15mL reaction tube, sequentially add to methyl benzeneazo methyl sulfone 1b (0.6mmol), to methylbenzene phenyl-sulfhydrate 2b
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 32.2mg, yield 70%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3, 500 MHz, ppm): δ 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):δ142.6,141.5,130.0,
124.9,21.4；MS(EI)；[M+H]+:231.1.
Experimental example 31:
In 15mL reaction tube, arylazo methyl sulfone 1b (0.6mmol), benzenethiol 2a (0.2mmol), acetonitrile are sequentially added
1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 27.5mg, yield 68%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.66–7.64(m,4H),7.48 –
7.43(m,6H)；13C NMR(CDCl3,125 MHz,ppm):δ145.2,131.1,129.3,124.8；MS(EI)； [M+H]+:
203.1.
Experimental example 32:
In 15mL reaction tube, sequentially add to fluorobenzene azo methyl sulfone 1b (0.6mmol), benzenethiol 2a (0.2mmol), acetonitrile
1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 29.9mg, yield 68%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.70–7.59(m,4H), 7.50–
7.44 (m, 3H), 7.15 (t, J=8.6 Hz, 2H)；13C NMR(CDCl3, 125 MHz, ppm): δ 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:
In 15mL reaction tube, sequentially add to chlorobenzene azo methyl sulfone 1g (0.6mmol), benzenethiol 2a (0.2mmol), acetonitrile
1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 34.0mg, yield 72%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.64–7.62(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):δ145.4,144.3,137.3,131.4,129.6,129.5,126.1,124.7；MS(EI)；[M+H]+:237.0.
Experimental example 34:
In 15mL reaction tube, sequentially add to chlorobenzene azo methyl sulfone 1g (0.6mmol), to methylbenzene phenyl-sulfhydrate 2b
(0.2mmol), acetonitrile 1mL and water 1mL are uniformly mixed, then under the irradiation of 3W blue LED lamp, 25 degree of reaction temperature lower stirrings
React 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, merges extraction
Liquid, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa) extract liquor after anhydrous sodium sulfate is dry, obtains
To crude product, the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, silicagel column flash column
Analysis, obtains the present embodiment sulfoxide product, is yellow oily solid 33.5mg, yield 67%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.57–7.55(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):δ 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:
In 15mL reaction tube, sequentially add to bromobenzene azo methyl sulfone 1h (0.6mmol), benzenethiol 2a (0.2mmol), acetonitrile
1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 30.8mg, yield 55%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.64–7.62(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):δ145.2,144.8,132.6,131.4,129.5,126.3,125.6,124.7；MS(EI)；[M+H]+:281.2.
Experimental example 36:
In 15mL reaction tube, sequentially add to cyano benzeneazo methyl sulfone 1i (0.6mmol), benzenethiol 2a (0.2mmol), second
Nitrile 1mL and water 1mL is uniformly mixed, and then under the irradiation of 3W blue LED lamp, is stirred to react 16h under 25 degree of reaction temperature.Use TLC
Then ethyl acetate extraction is added to after the reaction was completed in detection, each 3mL is extracted 3 times, combining extraction liquid, and extract liquor passes through nothing
It is after aqueous sodium persulfate is dry, extract liquor is solvent-free by being concentrated under reduced pressure into vacuum (0.08Mpa), crude product is obtained, is then used
The mixtures of eluents of petroleum ether and ethyl acetate that volume ratio is 5:1 is rinsed, and silicagel column rapid column chromatography obtains the present embodiment Asia
Sulfone product is yellow oily solid 28.2mg, yield 62%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.79–7.73(m,4H),7.68 –
7.64(m,2H),7.51–7.49(m,3H)；13C NMR(CDCl3,125 MHz,ppm):δ151.2,144.5, 133.0,
132.0,129.8,125.0,124.9,117.7,114.7；MS(EI)；[M+H]+:228.1.
Experimental example 37:
In 15mL reaction tube, sequentially add to methoxybenzene azo methyl sulfone 1a (0.6mmol), benzenethiol 2a
(0.2mmol), tetrahydrofuran 1mL and water 1mL are uniformly mixed, then under the irradiation of 60W blue LED lamp, under 30 degree of reaction temperature
It is stirred to react 16h.It is detected with TLC to after the reaction was completed, ethyl acetate extraction is then added, each 3mL is extracted 3 times, is merged
Extract liquor, extract liquor pass through extract liquor and are concentrated under reduced pressure into vacuum (0.08Mpa) without molten after anhydrous sodium sulfate is dry
Agent obtains crude product, and the mixtures of eluents of the petroleum ether and ethyl acetate that are then 5:1 with volume ratio is rinsed, and silicagel column is quick
Column chromatography, obtains the present embodiment sulfoxide product, is yellow oily solid 34.8mg, yield 75%.
Products therefrom spectrum data are as follows:1H NMR(CDCl3,500 MHz,ppm):δ7.62-7.60(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(CDCl3,125
MHz,ppm):δ162.1,145.7,136.6,130.8,129.2,127.3,124.6,114.9,55.5；MS(EI)；[M+H]+:
233.2.
There are also it is other with the use of object shown in general formula I and II is starting material, under the conditions of air and illumination reaction, using can
Light-exposed induction carries out oxidative coupling reaction and obtains the identical or similar technical characteristic of object shown in general formula III to be all of the invention
One of embodiment, and each technical characteristic of embodiment described above can be combined arbitrarily, to meet Patent Law, patent
The requirement of detailed rules for the implementation and guidelines for examination, no longer to all possible combined implementation of each technical characteristic in above-described embodiment
Example is all described.
Above-described embodiment is one kind provided by the present invention based on the light-catalysed method for preparing sulfoxide compound
Way of realization, other deformations of provided scheme, increase and perhaps reduce composition therein or step or incite somebody to action according to the present invention
The present invention is all belonged to the scope of protection of the present invention for other technical fields close with the present invention.
Claims (6)
1. a kind of method that photoinduction prepares asymmetric sulfoxide compound, which is characterized in that use following steps:
General formula I compound represented and general formula II compound represented are added in reactor, organic solvent and water is added
Mixture is reaction dissolvent, and reactor is communicated with air, it is seen that under light light irradiation, is reacted at room temperature 16-40 hours；
TLC chromatographic sheet detects after the reaction was completed, and pure water is added, then extracts, combining extraction liquid, after dry extract liquor,
Carrying out concentration and purifying to extract liquor, to obtain general formula III compound represented be asymmetric sulfoxide compound, and reaction equation is such as
Under:
Wherein R1For ester group, cyano, alcoxyl, aryl, heteroaryl, fluorine, chlorine, bromine or the 1-4 carbon alkyl arbitrarily replaced；
R2For aryl, heteroaryl, naphthenic base, alkyl or the allyl arbitrarily replaced
A kind of light according to claim 1 promotes the method for preparing asymmetric sulfoxide compound, it is characterised in that: general formula
The molar ratio of I compound represented and general formula II compound represented is 3:1.
2. a kind of light according to claim 1 promotes the method for preparing asymmetric sulfoxide compound, it is characterised in that: institute
The organic solvent stated is acetonitrile, ethyl acetate, N,N-dimethylformamide, methylene chloride, 1,4- dioxane, toluene, benzene, chlorine
Imitative, 1,2- dichloroethanes, tetrahydrofuran, 1,2- dimethoxy-ethane or dimethyl sulfoxide, preferably acetonitrile/water mixed solvent, acetonitrile/
Water mixed proportion is 1:1.
3. the method that a kind of photocatalysis according to claim 1 prepares asymmetric sulfoxide compound, it is characterised in that: institute
The light source that the visible lamp stated shines is the white led lamps or 3w-60w power of the blue LED lamp of 3w-60w power, 3w-60w power
Green LED lamp, the preferred blue LED lamp of 3w power.
4. the method that a kind of photocatalysis according to claim 1 prepares asymmetric sulfoxide compound, it is characterised in that: institute
The room temperature stated is 20-30 DEG C, preferably 25 DEG C.
5. the method that a kind of photoinduction according to claim 1 prepares asymmetric sulfoxide compound, it is characterised in that: institute
The reaction stated is to carry out under air.
6. the method that a kind of photoinduction according to claim 1 prepares asymmetric sulfoxide compound, it is characterised in that: institute
Specific processing after stating combining extraction liquid are as follows: extract liquor passes through 0.06- after anhydrous sodium sulfate is dry, by extract liquor
The processing of 0.10Mpa vacuum-concentrcted, obtains the crude product without organic solvent, then carries out column to crude product by silicagel column
Image processing obtains asymmetric sulfoxide compound, and wherein column chromatography for separation purification processes are the petroleum for being 5:1 according to volume ratio
The mixtures of eluents of ether and ethyl acetate is rinsed.
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| CN110386885A (en) * | 2019-07-30 | 2019-10-29 | 曲阜师范大学 | A kind of visible light promotion β-carbonyl sulphones preparation method |
| CN112264103A (en) * | 2020-10-29 | 2021-01-26 | 山东大学 | Silver-based metal organic framework material and preparation method and application thereof |
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| CN107141248A (en) * | 2017-07-11 | 2017-09-08 | 曲阜师范大学 | A kind of method that visible light catalytic synthesizes the ketene compound of 3 sulfuryl loop coil three |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110386885A (en) * | 2019-07-30 | 2019-10-29 | 曲阜师范大学 | A kind of visible light promotion β-carbonyl sulphones preparation method |
| CN112264103A (en) * | 2020-10-29 | 2021-01-26 | 山东大学 | Silver-based metal organic framework material and preparation method and application thereof |
| CN112264103B (en) * | 2020-10-29 | 2022-01-25 | 山东大学 | Silver-based metal organic framework material and preparation method and application thereof |
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