CN115010635B - Synthesis method of (E) -beta-selenenyl sulfone compound - Google Patents

Synthesis method of (E) -beta-selenenyl sulfone compound Download PDF

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CN115010635B
CN115010635B CN202210543786.6A CN202210543786A CN115010635B CN 115010635 B CN115010635 B CN 115010635B CN 202210543786 A CN202210543786 A CN 202210543786A CN 115010635 B CN115010635 B CN 115010635B
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CN115010635A (en
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刘功清
王永皓
姜有琴
张云倩
凌勇
赵育
明亮
习霞
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Nantong University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/34—Sulfur atoms
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a synthesis method of (E) -beta-selenovinyl sulfone compounds, which comprises the following reaction steps: in the presence of a photocatalyst and alkali, alkyne, sulfonyl chloride and diselenide react in three components by irradiation of visible light to obtain the (E) -beta-selenovinyl sulfone compound. The method has mild conditions and can be carried out at room temperature; the substrate has wide application range, high yield and good functional group compatibility. The method disclosed by the invention uses visible light as an energy source and has the characteristics of low cost, sustainability and environment friendliness. The invention realizes the difunctional of alkyne through one-step reaction, obtains the target compound, and has high economic utilization value.

Description

Synthesis method of (E) -beta-selenenyl sulfone compound
Technical Field
The invention relates to the technical field of organic synthetic chemistry, in particular to a synthetic method of (E) -beta-selenovinyl sulfone compounds.
Background
The organic selenium compound has very important application value in the fields of medicines, pesticides, synthesis and materials, and the selenium-containing compound has various pharmacological effects of resisting tumor, virus, inflammation, aging, cardiovascular diseases and the like. Thus, there has been a great deal of interest in synthesizing selenium-containing compounds by organic and pharmaceutical chemists ((a) Nogueira, c.w., zeni, g., rocha, J.B.T., chem.Rev.2004,104,6255-6286), (b) Hou, w., xu, h., j.med.chem.2022,65, 4436-4456), (c) Makhal, P, n., nandi, a., kaki, v.r. chemistry select2021,6, 663-679).
Alkenyl sulfone compounds are not only important reactants or intermediates in organic and pharmaceutical synthesis reactions, but also basic structural units of a plurality of bioactive molecules, and are widely applied to the synthesis of natural products, medicines and material molecules. Thus, in recent years, chemists have been devoted great effort to develop new alkenyl sulfone synthesis methods (Fang, y.; luo, z.; xu, x.rscoadv.2016, 6,59661-59676).
The alkyne is a cheap and easily available bulk chemical product and is also a basic raw material for organic synthesis, and the 1, 2-difunctional reaction of the alkyne can effectively introduce two functional groups in one step, thereby providing an effective strategy for constructing complex organic molecules. In view of the unique bioactivity and physicochemical properties of organic selenium compounds and alkenyl sulfones, the synthesis of seleno compounds based on alkyne bifunctional strategies has stimulated considerable research interest. For example, a previously prepared selenophenyl sulfonate (PhSeSO) is used in the presence of the free radical initiator AIBN or transition metal 2 Ph) addition of alkyne compounds can produce (E) -beta-seleno vinyl sulfone ((a) Back, T.G.); collins, s; kerr, R.G.J.Org.chem.1983,48,3077-3084; (b) Zhang, r.; xu, p.; wang, s. -y; ji, s. -j., j.org.chem.2019,84, 12324-12333). The three-component tandem reaction of arylsulfonyl hydrazides, diselenides and alkynes is also a common method of constructing (E) - β -selenovinylsulfones ((a) Liu, Y.; zheng, G.; zhang, Q.; li, Y.; zhang, Q.; J.Org. chem.2017,82, 2269-2275), (b) Sun, K.; wang, X.; fu, F.; zhang, C.; chen, Y.; liu, L.; green chem.2017,19,1490-1493; (c) Kong, X.; yu, K.; chen Q.; xu, B.; asian J.Org. Chem.2020,9, 1760-1764)). More recently Sun et al disclose aryl diazonium salts, diselenides, alkynes and bis (sulfur dioxide) -1, 4-diazabicyclo [2.2.2]Octane adducts (DABSO) four-component tandem reactions were synthesized as (E) - β -selenovinylsulfones (Sun, k.; shi, z.; liu, z.; luan, b.; zhu, j.; xue, y.; org.lett.2018,20, 6687-6690).
As described above, various methods for preparing (E) - β -seleno vinyl sulfone are disclosed in the prior art, but these methods have drawbacks such as the necessity of using selenosulfonate prepared in advance, the use of radical initiator and oxidizer with potential explosion hazard, the rigor of reaction conditions (high temperature conditions), and the low atom utilization rate of selenizing reagent. More importantly, many of the process regions and stereoselectivity are poor, resulting in mixtures of the Z/E type. Therefore, the development and use of the method with wide application range of cheap initial raw materials and mild reaction conditions for efficiently constructing the selenium vinyl sulfone compound have important theoretical significance and practical application value.
Disclosure of Invention
The invention aims to provide a synthesis method of (E) -beta-selenovinyl sulfone compounds, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: a synthetic method of (E) -beta-selenvinyl sulfone compounds comprises the following reaction steps: in an organic solvent, taking alkyne with a structure shown in a formula (I), sulfonyl chloride with a structure shown in a formula (II) and diselenide with a structure shown in a formula (III) as reaction raw materials, carrying out reaction under the existence of a photocatalyst and alkali under the irradiation of visible light, decompressing reaction liquid after the reaction is finished, removing the solvent to obtain a crude product, and purifying the crude product through column chromatography to obtain the (E) -beta-selenovinyl sulfone compound with a structure shown in a formula (IV);
the reaction equation is shown as follows:
wherein the compound of the formula (I) is alkyne, R1 is selected from C6-C10 alkyl, benzyl, 2-naphthyl, 2-furyl, 2-thienyl, phenyl and phenyl substituted by one or more substituents, and the substituents are selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl or trifluoromethoxy;
the compound of the formula (II) is sulfonyl chloride, R2 is selected from 2-naphthyl, 2-furyl, 2-thienyl, phenyl and phenyl substituted by one or more substituents, wherein the substituents are selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl or trifluoromethoxy;
the compound of formula (III) is diaryl diselenide or dialkyl diselenide, R3 is selected from C1-C10 straight-chain or branched-chain alkyl, benzyl, phenyl substituted by one or more substituents, wherein the substituents are selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, carboxyl and hydroxyl.
Preferably, the molar ratio of alkyne of the structure shown in formula (I) to sulfonyl chloride of the structure shown in formula (II) and diselenide of the structure shown in formula (III) is 1:1:0.5 to 1:1:1, preferably 1:1:0.5.
Preferably, the irradiation light source for the reaction is one of sunlight, a fluorescent lamp and an LED lamp, and preferably the fluorescent lamp.
Preferably, the catalyst for the reaction is Ir (ppy) 3 、Ir(p-CF 3 ppy) 3 、Ir(d-Fppy) 3 、[Ir{dFCF 3 ppy} 2 (bpy)]PF 6 、[Ir(dtbbpy)(ppy) 2 ](PF 6 ) 2 Any of them is preferably Ir (p-CF) 3 ppy) 3 。
Preferably, the base is potassium carbonate, sodium bicarbonate or potassium phosphate, preferably potassium phosphate.
Preferably, the organic solvent is at least one of N, N-dimethylformamide, dichloromethane, chloroform, ethyl acetate, acetonitrile, 1, 4-dioxane, tetrahydrofuran and carbon tetrachloride, and preferably acetonitrile.
Preferably, the reaction time is 30h-40h.
Preferably, after the reaction is finished, the reaction solution is concentrated under reduced pressure, the concentrate is separated by column chromatography, and a mixed solution of petroleum ether and ethyl acetate is used as an eluent, wherein the petroleum ether: the volume ratio of the ethyl acetate is (1-30): and 1, collecting eluent, and spin-evaporating the solvent to obtain (E) -beta-selenovinyl sulfone shown in a formula (IV).
Compared with the prior art, the invention has the beneficial effects that:
(1) The method can be carried out at room temperature, and has mild reaction conditions and good functional group compatibility.
(2) The invention uses visible light as energy source, has the characteristics of low cost, sustainability and environmental protection, and has the advantages of safety and easy operation.
(3) The invention uses cheap and easily available initial raw materials, can obtain target products only by one step, and obtains difunctional molecules, thereby having good application potential.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides the following technical scheme: a synthetic method of (E) -beta-selenvinyl sulfone compounds comprises the following reaction steps: in an organic solvent, taking alkyne with a structure shown in a formula (I), sulfonyl chloride with a structure shown in a formula (II) and diselenide with a structure shown in a formula (III) as reaction raw materials, carrying out reaction under the existence of a photocatalyst and alkali under the irradiation of visible light, decompressing reaction liquid after the reaction is finished, removing the solvent to obtain a crude product, and purifying the crude product through column chromatography to obtain the (E) -beta-selenovinyl sulfone compound with a structure shown in a formula (IV);
the reaction equation is shown as follows:
wherein the compound of the formula (I) is alkyne, R1 is selected from C6-C10 alkyl, benzyl, 2-naphthyl, 2-furyl, 2-thienyl, phenyl and phenyl substituted by one or more substituents, and the substituents are selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl or trifluoromethoxy;
the compound of the formula (II) is sulfonyl chloride, R2 is selected from 2-naphthyl, 2-furyl, 2-thienyl, phenyl and phenyl substituted by one or more substituents, wherein the substituents are selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl or trifluoromethoxy;
the compound of formula (III) is diaryl diselenide or dialkyl diselenide, R3 is selected from C1-C10 straight-chain or branched-chain alkyl, benzyl, phenyl substituted by one or more substituents, wherein the substituents are selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, carboxyl and hydroxyl.
Example 1:
the reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) was charged at room temperature 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=7:1) to give 72 mg of the objective compound in a yield of 87%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.60–7.55(m,2H),7.45–7.30(m,6H),7.28(t,J＝6.9Hz,2H),7.23–7.18(m,2H),7.14–7.09(m,2H),6.21(s,1H),2.35(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ157.0,143.1,138.5,136.4,135.0,131.3,130.6,129.4,128.2,128.0,127.2,127.1,125.7,21.3.
example 2:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 4-chlorophenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=6:1) to give 74 mg of the objective compound in 83% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.60–7.55(m,2H),7.50–7.40(m,3H),7.38–7.35(m,2H),7.30–7.25(m,2H),7.20–7.14(m,4H),6.22(s 1H),2.42(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ155.9,143.5,138.6,136.6,136.4,135.6,134.0,131.0,130.3,129.5,128.6,127.5,126.9,126.6,21.7.
example 3:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 4-nitrophenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=5:1) to give 73 mg of the objective compound in 80% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.59–7.51(m,4H),7.50–7.44(m,1H),7.42–7.36(m,4H),7.35–7.30(m,2H),7.25–7.20(m,2H),6.25(s,1H),2.21(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ153.9,144.3,139.5,138.2,136.5,131.2,130.4,130.3,130.0,129.1,127.4,127.0,118.35,112.8,21.8.
example 4
The reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 4-methylphenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=10:1) to give 76 mg of the objective compound in 89% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.60–7.55(m,2H),7.49–7.33(m,5H),7.18–7.10(m,6H),6.15(s,1H),2.42(s,3H),2.39(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ157.9,144.0,140.0,139.4,137.0,132.1,130.5,130.4,129.6,129.1,128.9,127.7,127.6,125.5,21.7,21.5.
example 5
The reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, 2-ethynylnaphthalene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=8:1) to give 84 mg of the objective compound in 91% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.85(d,J＝7.8,Hz,1H),7.80–7.72(m,2H),7.70–7.60(m,3H),7.58-7.52(m,2H),7.50–7.40(m,3H),7.36(d,J＝8.2,Hz,1H),7.30–7.26(m,2H),6.99(d,J＝8.1Hz,2H),6.31(s,1H),2.28(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ157.0,143.2138.3,136.5,133.0,132.4,132.0,130.4,129.4,128.2,128.1,127.7,127.5,127.3,127.1,126.9,126.5,126.2,125.9,21.6.
example 6
The reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 1-hexyne (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), addAfter that, a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was subjected to solvent removal by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=8:1) to give 67 mg of the objective compound in 85% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.66(d,J＝8.2Hz,2H),7.53(d,J＝7.0Hz,2H),7.44-7.33(m,3H),7.29(d,J＝8.0Hz,2H),5.88(s,1H),2.85(t,J＝7.9Hz,2H),2.44(s,3H),1.60-1.50(m,2H),1.38(q,J＝7.8Hz,2H),0.91(t,J＝7.4Hz,3H)； 13 C NMR(100MHz,CDCl 3 ):δ161.0,143.5,139.4,136.5,129.8,129.7,126.8,125.1,123.3,34.2,32.1,22.0,21.1,13.5.
example 7
The reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-chlorobenzenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) was charged at room temperature 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=6:1) to give 76 mg of the objective compound in 88% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.60–7.55(m,2H),7.50–7.39(m,3H),7.38–7.24(m,7H),7.22–7.19(m,2H),6.20(s,1H). 13 C NMR(100MHz,CDCl 3 ):δ158.9,140.5,139.4,136.6,134.6,130.4,130.1,129.2,128.4,128.5,126.9,125.5.
example 8
The reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-methoxyphenylsulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) was charged at room temperature 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=5:1) to give 70 mg of the objective compound in 82% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.59–7.52(m,2H),7.45–7.26(m,6H),7.25–7.15(m,4H),6.78–6.64(m,2H),6.15(s,1H),3.83(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ163.2,156.9,136.7,135.0,133.5,130.7,130.4,130.0,129.5,128.5,128.0,127.1,126.3,113.9,55.9.
example 9
The reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-cyanobenzenesulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) was charged at room temperature 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23W white compact fluorescent lamp was placed 1 cm from the reaction tube, reacted at room temperature for 30 hours, and after completion of the reaction, the organic phase was passed through a spin-on reactorThe solvent was removed by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size 200-300 mesh, eluent petroleum ether/ethyl acetate=4:1) to give 68 mg of the objective compound in 80% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.63–7.38(m,9H),7.38–7.23(m,3H),7.18–7.10(m,2H),6.15(s,1H)； 13 C NMR(100MHz,CDCl 3 ):δ160.8,145.8,136.8,133.9,132.2,130.5,130.0,128.5,128.3,128.0,126.5,124.1,117.4,116.5.
example 10
The reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), 2-naphthylsulfonyl chloride (0.2 mmol), diphenyldiselener (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=8:1) to give 74 mg of the objective compound in 82% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.89–7.78(m,3H),7.72(d,J＝8.1Hz,1H),7.65–7.44(m,5H),7.47–7.35(m,3H),7.29–7.10(m,5H),6.29(s,1H)； 13 C NMR(100MHz,CDCl 3 ):δ158.0,138.1,136.4,134.5,134.3,131.8,130.2,129.4,129.1,129.0,129.1,128.7,128.4,127.7,127.2,126.6,125.5,122.2.
example 11
The reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), 2-thienyl sulfonyl chloride (0.2 mmol), diphenyl diselenide (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=10:1) to give 66 mg of the objective compound in a yield of 81%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.66–7.56(m,2H),7.52(dd,J＝4.9,1.5Hz,1H),7.44-7.23(m,8H),7.11(dd,J＝3.8,1.5Hz,1H),6.87(dd,J＝4.9,4.1Hz,1H),6.20(s,1H)； 13 C NMR(100MHz,CDCl 3 ):δ158.3,143.0,136.8,134.6,133.0,133.2,130.3,129.5,128.5,128.4,127.5,126.9,125.7.
example 12:
the reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), bis (4-chlorophenyl) diselenide (0.1 mmol), ir (p-CF) was charged at room temperature 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube after the addition, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=15:1) to give the objective compound 74Milligrams, yield 83%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.50(d,J＝8.2Hz,2H),7.38-7.25(m,7H),7.17(d,J＝7.4Hz,2H),7.11(d,J＝8.0Hz,2H),6.24(s,1H),2.40(s,3H). 13 C NMR(100MHz,CDCl 3 ):δ156.1,143.5,138.6,137.6,136.9,134.3,130.5,129.4,129.2,128.7,128.0,127.4,126.5,125.1,21.7.
example 13:
the reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), bis (4-methoxyphenyl) diselenide (0.1 mmol), ir (p-CF) was charged at room temperature 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=5:1) to give 80 mg of the objective compound in a yield of 90%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.51(d,J＝8.2Hz,2H),7.33-7.25(m,5H),7.20(d,J＝7.9Hz,2H),7.14(d,J＝8.0Hz,2H),6.95(d,J＝8.3Hz,2H),6.13(s,1H),3.89(s,3H),2.40(s,3H), 13 C NMR(100MHz,CDCl 3 ):δ161.0,158.0,143.1,138.8,138.0,134.3,128.9,128.0,127.5,127.1,117.1,115.8,55.1,21.4
example 14:
the reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), dithienyldiselener (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=10:1) to give 74 mg of the objective compound in 88% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.58(d,J＝6.8Hz,1H),7.40-7.30(m,6H),7.22(d,J＝7.1Hz,2H),7.08(dd,J＝6.7,3.8Hz,3H),6.23(s,1H),2.40(s,3H). 13 C NMR(100MHz,CDCl 3 ):δ156.8,143.0,138.8,134.2,133.6,129.4,129.3,128.7,128.3,127.8,127.4,126.1,120.5,21.3
example 15:
the reaction equation is shown as follows:
into a 10 ml reaction tube equipped with a magnetic stirrer, phenylacetylene (0.2 mmol), p-toluenesulfonyl chloride (0.2 mmol), dimethyl diselenide (0.1 mmol), ir (p-CF) was charged at room temperature 3 ppy) 3 (0.002 mmol), K 3 PO 4 (0.2 mmol), acetonitrile (1 ml), a 23 w white compact fluorescent lamp was placed at a distance of 1 cm from the reaction tube, reacted at room temperature for 30 hours, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent: petroleum ether/ethyl acetate=6:1) to give 59 mg of the objective compound in a yield of 84%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.40–7.30(m,2H),7.35(t,J＝7.2Hz,1H),7.28(t,J＝7.9Hz,2H),7.14(d,J＝7.9Hz,4H),6.44(s,1H),2.44(s,3H),2.15(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ156.6,144.0,139.3,135.6,129.7,129.6,128.3,128.0,127.9,125.6,21.3,8.2.
in summary, the present invention provides a method for synthesizing (E) -beta-selenovinyl sulfone compounds, which comprises the steps of irradiating a photocatalyst Ir (p-CF 3 ppy) 3 And in the presence of alkali, alkyne, sulfonyl chloride and diselenide react in three components to obtain the difunctional molecule. The method has mild reaction conditions and high reaction yield of the obtained product, so that the synthesis method has good application prospects in organic synthesis and drug synthesis.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (1)

1. A method for synthesizing (E) -beta-selenvinyl sulfones compounds is characterized in that: the reaction steps are as follows: in an organic solvent, taking a compound with a structure shown in a formula (I), a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III) as reaction raw materials, carrying out reaction under the existence of a photocatalyst and alkali and irradiation of visible light, decompressing reaction liquid after the reaction is finished, removing the solvent to obtain a crude product, and purifying the crude product through column chromatography to obtain the (E) -beta-selenvinyl sulfone compound with a structure shown in a formula (IV);
the reaction equation is shown as follows:
wherein, in the compound of the formula (I), R1 is selected from C6-C10 alkyl, benzyl, 2-naphthyl, 2-furyl, 2-thienyl, phenyl and phenyl substituted by one or more substituents selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl or trifluoromethoxy;
in the compound of the formula (II), R2 is selected from 2-naphthyl, 2-furyl, 2-thienyl, phenyl and phenyl substituted by one or more substituents, wherein the substituents are selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl or trifluoromethoxy;
in the compound of the formula (III), R3 is selected from C1-C10 linear or branched alkyl, benzyl and phenyl substituted by one or more substituents selected from C1-C10 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, carboxyl and hydroxyl;
the photocatalyst is Ir (p-CF) 3 ppy) 3 The method comprises the steps of carrying out a first treatment on the surface of the The irradiation light source of the reaction is a fluorescent lamp; the alkali is potassium phosphate; the organic solvent is acetonitrile;
the mol ratio of the compound with the structure shown in the formula (I) to the compound with the structure shown in the formula (II) is 1:1:0.5-1:1:1;
the molar ratio of the compound with the structure shown in the formula (I) to the compound with the structure shown in the formula (II) is 1:1:0.5;
the reaction time is 30-40 h;
after the reaction is finished, the reaction solution is decompressed and concentrated, the concentrate is separated by column chromatography, and the mixed solution of petroleum ether and ethyl acetate is used as eluent, wherein the petroleum ether is as follows: the volume ratio of the ethyl acetate is (1-30): and 1, collecting eluent, and spin-evaporating the solvent to obtain (E) -beta-selenovinyl sulfone shown in a formula (IV).
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Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Direct Allylic C(sp3)-H Thiolation with Disulfides via Visible Light Photoredox Catalysis;Kim Jungwon 等;ACS Catalysis;第10卷(第11期);第6013-6022页 *
Electrochemical Oxidation-induced Difunctionalization of Alkynes and Alkenes with Sulfonyl Hydrazides: Facile Access to β-Selenovinyl Sulfones and β-Ketosulfones;Kong Xianqiang 等;Asian Journal of Organic Chemistry;第09卷(第11期);第1760-1764页 *
Photoinduced ynamide structural reshuffling and functionalization;Mohana Reddy Mutra 等;Nature Communications;第13卷;第1-14页 *
Reactions of amines with β-(phenylseleninyl)vinyl sulfones derived from the selenosulfonation of acetylenes. Formation of enamine sulfones;Back Thomas G. 等;Canadian Journal of Chemistry;第63卷(第08期);第2313-2318页 *
Synthesis of (E)-β-Selenovinyl Sulfones through a Multicomponent Regio- and Stereospecific Selenosulfonation of Alkynes with Insertion of Sulfur Dioxide;Sun Kai 等;Organic Letters;第20卷(第21期);第6687-6690页 *

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