CN115385835B - Synthesis method of selenate compound - Google Patents
Synthesis method of selenate compound Download PDFInfo
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- CN115385835B CN115385835B CN202210988198.3A CN202210988198A CN115385835B CN 115385835 B CN115385835 B CN 115385835B CN 202210988198 A CN202210988198 A CN 202210988198A CN 115385835 B CN115385835 B CN 115385835B
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- 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
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- 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
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention relates to the technical field of organic synthetic chemistry, in particular to a method for synthesizing a selenate compound, which comprises the following reaction steps: under the existence of a photocatalyst, aromatic aldehyde and diselenide compound are stirred and reacted under the condition of a certain temperature and the irradiation of a light source to obtain the diselenide compound. Compared with the traditional synthesis method, the method has mild reaction conditions and can be smoothly carried out at room temperature; the method uses cheap and easily available initial raw materials, and has wide substrate application range, high yield and good functional group compatibility; meanwhile, the method disclosed by the invention uses visible light as an energy source and has the characteristics of low cost, sustainability and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of organic synthetic chemistry, in particular to a method for synthesizing a selenate compound.
Background
Selenium is a necessary trace element for human body and participates in important physiological process of human body. Meanwhile, the antioxidant is a powerful antioxidant and is beneficial to removing redundant free radicals in human bodies. Selenium-containing compounds are also important organic synthetic reagents, often applied to various organic reactions, and can also be applied to research of material science and pharmacy. Thus, the synthesis of selenium-containing compounds has received extensive attention from 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).
Among the various selenium-containing compounds, selenate (selenoester) is a class of non-essential compounds, which are widely present in natural compounds and are also very important intermediates in organic synthesis. Thus, chemists have devoted considerable effort to develop methods for synthesizing selenate (Baldassari, L.L.; ludtke, D.S. chem. Eur. J.2021,27, 8656-8667). In the reported methods for synthesizing selenate compounds, selenium-containing anion compounds are generally used for addition of acid anhydride, acid chloride, carboxylic acid, aldehyde, etc. However, these methods have drawbacks such as the use of metal reagents to produce selenium nucleophiles, the difficulty of treatment with the metal reagents, and the greater environmental pollution. The reaction conditions are harsh, and the substrate compatibility is poor. Therefore, a new reaction system which is simple and convenient to operate, high in safety performance, high in yield, wide in applicability and relatively green is still required to be developed to construct the selenate compound.
Disclosure of Invention
The present invention is directed to a method for synthesizing selenate compounds, which solves the problems set forth in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a synthesis method of a selenate compound comprises the following reaction steps: in an organic solvent, taking aromatic aldehyde with a structure shown in a formula (I) and diselenide with a structure shown in a formula (II) as reaction raw materials, carrying out reaction under irradiation of visible light in the presence of a photocatalyst, 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 a diselenide compound with a structure shown in a formula (III);
the reaction equation is shown as follows:
wherein the compound of the formula (I) is aromatic aldehyde, ar is selected from naphthyl, furyl, 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 formula (II) is diaryl diselenide or dialkyl diselenide, R1 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 aromatic aldehyde of the structure of formula (I) to diselenide of the structure of formula (II) is from 1:0.5 to 1:1, preferably 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 organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, dichloromethane, chloroform, ethyl acetate, acetonitrile, tetrahydrofuran and carbon tetrachloride, and preferably dichloromethane.
Preferably, the reaction time is 10h-30h.
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 (10-200): and 1, collecting eluent, and spin-evaporating the solvent to obtain the selenate compound shown in the formula (III).
Compared with the prior art, the invention has the beneficial effects that:
(1) The method can be carried out at room temperature, and has the advantages of simple operation, mild reaction conditions, good functional group compatibility and high product yield.
(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, and can obtain the target product only by one step, 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 synthesis method of a selenate compound comprises the following reaction steps: the reaction steps are as follows: in an organic solvent, taking aromatic aldehyde with a structure shown in a formula (I) and diselenide with a structure shown in a formula (II) as reaction raw materials, carrying out reaction under irradiation of visible light in the presence of a photocatalyst, 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 a diselenide compound with a structure shown in a formula (III);
the reaction equation is shown as follows:
wherein the compound of the formula (I) is aromatic aldehyde, ar is selected from naphthyl, furyl, 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 diaryl diselenide or dialkyl diselenide, R1 is selected from C1-C10 straight-chain or branched-chain alkyl, benzyl and 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;
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 organic solvent is dichloromethane.
Example 1:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with benzaldehyde (0.2 mmol), diphenyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=100:1), 44 mg of target compound is obtained, the yield is 85%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.95–7.83(m,2H),7.65–7.58(m,3H),7.53–7.40(m,5H)； 13 C NMR(100MHz,CDCl 3 ):δ193.2,138.9,136.1,134.1,129.6,129.2,129.0,127.9,125.8.
example 2:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 4-methylbenzaldehyde (0.2 mmol), diphenyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=80:1), 50 mg of target compound is obtained, the yield is 90%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.80(d,J＝8.4Hz,2H),7.60–7.55(m,2H),7.42–7.36(m,3H),7.25(d,J＝8.2Hz,2H),2.40(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ192.5,144.8,136.4,135.8,129.3,129.8,129.0,127.3,125.7,21.5.
example 3:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 4-methoxybenzaldehyde (0.2 mmol), diphenyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 Protection, placing a 23W white compact fluorescent lamp at a distance of 1 cm from the reaction tube, and roomAfter the reaction was completed, the solvent was removed from the organic phase 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=100:1) to give 48 mg of the objective compound in 83% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.92–7.89(m,2H),7.63–7.57(m,2H),7.45–7.37(m,3H),6.99–6.94(m,2H),3.88(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ191.3,164.5,136.1,131.3,130.0,129.3,129.1,126.0,114.4,55.7.
example 4:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 4-chlorobenzaldehyde (0.2 mmol), diphenyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=110:1), 54 mg of target compound is obtained, the yield is 92%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.90–7.86(m,2H),7.62–7.56(m,2H),7.49–7.39(m,5H)； 13 C NMR(100MHz,CDCl 3 ):δ192.8,140.4,137.0,136.4,130.1,129.3,129.1,128.7,125.7.
example 5:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 4-nitrobenzaldehyde (0.2 mmol), diphenyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=50:1), 55 mg of target compound is obtained, the yield is 90%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ8.35(d,J＝8.2Hz,2H),8.10(d,J＝8.1Hz,2H),7.51–7.40(m,2H),7.31–7.25(m,3H)； 13 CNMR(100MHz,CDCl 3 ):δ192.1；151.1,143.3,136.5,131.5,129.7,128.2,125.2,124.1.
example 6:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 2-furaldehyde (0.2 mmol), diphenyl diselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=80:1), 43 mg of target compound is obtained, the yield is 85%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.52-7.45(m,3H),7.33-7.26(m,3H),7.12-7.09(m,1H),6.49-6.43(m,1H)； 13 C NMR(100MHz,CDCl 3 ):δ182.0,151.8,147.0,136.8,129.7,129.5,125.0,115.6,113.2.
example 7:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 2-thiophenecarboxaldehyde (0.2 mmol), diphenyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=100:1), 49 mg of target compound is obtained, the yield is 92%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.82(d,J＝4.0Hz,1H),7.65(d,J＝5.3Hz,1H),7.59–7.55(m,2H),7.40–7.38(m,3H),7.13(t,J＝4.6Hz,1H)； 13 C NMR(100MHz,CDCl 3 )δ183.2,142.5,136.1,133.0,131.9,129.1,128.7,127.8,125.4.
example 8:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with 1-naphthaldehyde (0.2 mmol), diphenyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 Protecting, placing a 23W white compact fluorescent lamp at a distance of 1 cm from the reaction tube, reacting at room temperature for 20 hours, and removing solvent from the organic phase by rotary evaporatorPurifying the residue with silica gel column (silica gel size 200-300 mesh, eluent petroleum ether/ethyl acetate=90:1) to obtain 58 mg of target compound with 93% yield,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ8.58(d,J＝8.4Hz,1H),8.21(d,J＝7.2Hz,1H),8.08(d,J＝8.4Hz,1H),7.93(d,J＝7.6Hz,1H),7.70–7.68(m,2H),7.63–7.47(m,6H)； 13 C NMR(100MHz,CDCl 3 ):δ195.5,136.4,136.2,133.9,133.7,129.5,129.1,128.5,128.4,128.3,127.3,127.3,127.0,125.5,124.7.
example 9:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with benzaldehyde (0.2 mmol), dimethyl diselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=120:1), the target compound is obtained, the yield is 81 percent,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.90–7.81(m,3H)7.65–7.59(m,2H),2.42(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ195.0,139.2,134.0,129.5,127.8,5.9.
example 10:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with benzaldehyde (0.2 mmol), bis (4-chlorophenyl) diselenide (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=100:1), 51 mg of target compound is obtained, the yield is 87%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.94–7.91(m,2H),7.62(d,J＝10.0Hz,1H),7.52–7.46(m,4H),7.40–7.36(m,2H)； 13 C NMR(100MHz,CDCl 3 ):δ192.9,138.8,137.6,136.7,135.0,130.0,129.5,127.6,124.3.
example 11:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with benzaldehyde (0.2 mmol), bis (4-methylphenyl) diselenide (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=100:1), 51 mg of target compound is obtained, the yield is 92%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 )δ7.89(d,J＝7.4Hz,2H),7.65(t,J＝7.4Hz,1H),7.51(t,J＝7.3Hz,4H),7.26(d,J＝7.4Hz,2H),2.41(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ193.8,140.1,138.6,136.7,133.9,130.3,129.2,127.0,122.1,21.8.
example 12:
the reaction equation is shown as follows:
a10 ml reaction tube equipped with a magnetic stirrer was charged with benzaldehyde (0.2 mmol), dithienyldiselenether (0.1 mmol), ir (p-CF) 3 ppy) 3 (0.002 mmol) in dichloromethane (2 ml) and N was charged after addition 2 The protection is carried out, a 23 watt white compact fluorescent lamp is placed at a position which is 1 cm away from a reaction tube, the reaction is carried out for 20 hours at room temperature, after the reaction is completed, an organic phase is subjected to solvent removal by a rotary evaporator, the residue is purified by a silica gel column (the silica gel specification is 200 meshes-300 meshes, the eluent is petroleum ether/ethyl acetate=80:1), 49 mg of target compound is obtained, the yield is 91%,
the nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.91(d,J＝8.4Hz,2H),7.65–7.60(m,2H),7.55–7.50(m,2H),7.31–7.27(m,1H),7.19–7.15(m,1H)； 13 C NMR(100MHz,CDCl 3 ):δ192.6,137.7,137.1,134.0,132.8,129.0,127.9,127.5,119.0.
in summary, the present invention provides a method for synthesizing selenate compounds in the presence of a photocatalyst Ir (p-CF) 3 ppy) 3 In the presence of visible light irradiation, aromatic aldehyde and diselenide react to obtain a diselenide compound. The method has the advantages of cheap and easily obtained initial raw materials, 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 (5)
1. A synthesis method of a selenate compound is characterized in that: the reaction steps are as follows: in an organic solvent, taking aromatic aldehyde with a structure shown in a formula (I) and diselenide with a structure shown in a formula (II) as reaction raw materials, carrying out reaction under irradiation of visible light in the presence of a photocatalyst, 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 a diselenide compound with a structure shown in a formula (III);
the reaction equation is shown as follows:
wherein the compound of the formula (I) is aromatic aldehyde, ar is selected from naphthyl, furyl, 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 diaryl diselenide or dialkyl diselenide, R1 is selected from C1-C10 straight-chain or branched-chain alkyl, benzyl and 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;
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 organic solvent is dichloromethane.
2. The method for synthesizing a selenate compound according to claim 1, wherein: the molar ratio of the aromatic aldehyde with the structure shown in the formula (I) to the diselenide with the structure shown in the formula (II) is 1:0.5-1:1.
3. The method for synthesizing a selenate compound according to claim 2, wherein: the molar ratio of the aromatic aldehyde with the structure shown in the formula (I) to the diselenide with the structure shown in the formula (II) is 1:0.5.
4. The method for synthesizing a selenate compound according to claim 1, wherein: the reaction time is 10-30 h.
5. The method for synthesizing a selenate compound according to claim 1, wherein: 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 (10-200): and 1, collecting eluent, and spin-evaporating the solvent to obtain the selenate compound shown in the formula (III).
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| CN112608262A (en) * | 2021-01-12 | 2021-04-06 | 西北大学 | Oxalic acid diselenide ester compound and synthesis method and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112608262A (en) * | 2021-01-12 | 2021-04-06 | 西北大学 | Oxalic acid diselenide ester compound and synthesis method and application thereof |
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