A method for synthesizing selenoester compounds promoted by visible light
By using aryl ketone acid and diselenate ether in organic solvents and reacting under visible light irradiation, the problem of using expensive reagents and harsh conditions in the existing synthetic selenium ester methods is solved, and efficient and green selenium ester compound synthesis is achieved.
Patent Information
- Application Number
- CN202410679473.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-29
- Publication Date
- 2025-05-09
- Estimated Expiration
- 2044-05-29
AI Technical Summary
The existing methods for synthesizing selenium esters have the disadvantage of using expensive transition metals, chemical oxidants and photocatalysts, and the reaction conditions are harsh and the substrate compatibility is poor.
Using a method of promoting visible light, aryl ketone acid and diselenate ether are used as reaction materials in an organic solvent, and the reaction is carried out by irradiation of visible light to obtain a selenium ester compound. This method does not require transition metals, chemical oxidants and photocatalysts, and is easy to operate and has mild reaction conditions.
It realizes efficient and green selenium ester compound synthesis, reduces production costs, reduces environmental pollution, has wide applicability and simple operation.
Smart Images
Figure QLYQS_1 
Figure BDA0004865190440000021 
Figure BDA0004865190440000031
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic synthetic chemistry, and in particular to a method for synthesizing a selenoester compound promoted by visible light. Background Art
[0002] Selenium is an essential biological trace element for the human body and is widely found in natural products, amino acids and proteins. Organic selenium compounds have unique biological activities and pharmacological effects, such as anti-inflammatory, antibacterial, antihypertensive, antioxidant, antiviral, antiparasitic and anti-radiation properties. Among various selenium-containing compounds, selenium esters are widely used in medicine, pesticides, etc., and their special structure can make some compounds have good physiological and pharmaceutical activities. Therefore, chemists have invested a lot of energy in developing methods for the synthesis of selenium esters (Chem. Eur. J. 2021, 27, 8656–8667). In the reported methods for synthesizing selenium ester compounds, selenium anion compounds are usually used to add acid anhydrides, acyl chlorides, carboxylic acids, aldehydes, etc. These methods reported in the literature have some disadvantages, such as the use of metal reagents to produce selenium nucleophiles, the difficulty of handling the metal reagents used, and the greater pollution to the environment. The reaction conditions are harsh and the substrate compatibility is poor.
[0003] In recent years, visible light-induced chemical reactions have gradually become a powerful synthetic strategy. Such reactions can usually produce active free radical intermediates under mild conditions, and then other chemical bonds are constructed. Aryl keto acids are a class of cheap, readily available and relatively stable compounds, which are usually used as acylating agents in chemical reactions. However, literature research shows that there are few reports on the method of synthesizing selenoester compounds from aryl keto acids and diselenides promoted by visible light. In the study of the mechanism of chromium-catalyzed olefin double acylation reaction under photoredox catalysis, Xiao Wenjing et al. added diphenyl diselenide to the reaction system to obtain a small amount of selenoester (ACS Catal. 2022, 12, 1879-1885). The reaction yield is low, the amount of diselenide is large, and a photocatalyst is required. Therefore, it is still necessary to develop a new reaction system that is simple to operate, has a high yield, is widely applicable, and is relatively green to construct selenoester compounds. Here, the present application utilizes the unique advantages of photochemistry in the field of synthesis to construct a green and efficient photocatalytic reaction to achieve the preparation of selenoester compounds. Summary of the invention
[0004] The object of the present invention is to provide a method for synthesizing a selenoester compound promoted by visible light to solve the problems raised in the above background technology.
[0005] To achieve the above object, the present invention provides the following technical solution: a method for synthesizing a selenoester compound promoted by visible light, comprising the following steps:
[0006] In an organic solvent, an aromatic keto acid compound having a structure as shown in formula (I) and a diselenide having a structure as shown in formula (II) are used as reaction raw materials, and the reaction is carried out under visible light irradiation under open and room temperature conditions. After the reaction is completed, the reaction solution is decompressed to remove the solvent to obtain a crude product, and the crude product is purified by column chromatography to obtain a selenoester compound having a structure as shown in formula (III). The reaction equation is shown below:
[0007]
[0008] Wherein, the compound of formula (I) is an aryl keto acid compound, Ar is naphthyl, furanyl, thienyl, isoxazolyl, phenyl, phenyl substituted with one or more substituents, and the substituents are halogen, alkyl, alkyl nitrogen, alkoxy, trifluoromethyl;
[0009] The compound of formula (II) is diaryl diselenide and dialkyl diselenide; the irradiation light source of the reaction is an LED lamp; and the organic solvent is acetonitrile.
[0010] Preferably, the molar ratio of the keto acid compound of the structure represented by formula (I) to the diselenide of the structure represented by formula (II) is 1:0.5 to 2:0.5, preferably 2:0.5.
[0011] Preferably, the organic solvent is any one of acetonitrile, cyclohexane, nitromethane, dichloroethane, toluene, ethyl acetate, acetone, hexafluoroisopropanol, chlorobenzene or xylene, preferably acetonitrile.
[0012] Preferably, the irradiation light source for the reaction is one of sunlight, fluorescent lamp, tungsten lamp, and LED lamp, preferably LED lamp.
[0013] Preferably, the reaction time is 24h-48h.
[0014] Preferably, after the reaction is completed, the reaction solution is concentrated under reduced pressure, and the concentrate is separated by column chromatography, using a mixed solution of petroleum ether and ethyl acetate as an eluent, wherein the volume ratio of petroleum ether:ethyl acetate is (200-1):1, and the eluate is collected, and the solvent is evaporated to obtain a selenoester compound with a structure shown in formula (III).
[0015] Compared with the prior art, the present invention has the following beneficial effects:
[0016] (1) The present invention does not require expensive transition metals, chemical oxidants and photocatalysts, has low cost, little environmental pollution, and is green and sustainable.
[0017] (2) The present invention can be carried out in air and at room temperature, with mild reaction conditions, simple operation, and a wide range of substrate applications.
[0018] (3) The present invention uses visible light as an energy source, which is safe and environmentally friendly. DETAILED DESCRIPTION
[0019] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0020] The present invention provides the following technical solution: a method for synthesizing a selenoester compound promoted by visible light, comprising the following steps:
[0021] In an organic solvent, an aromatic keto acid compound having a structure as shown in formula (I) and a diselenide having a structure as shown in formula (II) are used as reaction raw materials, and the reaction is carried out under visible light irradiation under open and room temperature conditions. After the reaction is completed, the reaction solution is decompressed to remove the solvent to obtain a crude product, and the crude product is purified by column chromatography to obtain a selenoester compound having a structure as shown in formula (III). The reaction equation is shown below:
[0022]
[0023] Wherein, the compound of formula (I) is an aryl keto acid compound, Ar is naphthyl, furanyl, thienyl, isoxazolyl, phenyl, phenyl substituted with one or more substituents, and the substituents are halogen, alkyl, alkyl nitrogen, alkoxy, trifluoromethyl;
[0024] The compound of formula (II) is diaryl diselenide and dialkyl diselenide; the irradiation light source of the reaction is an LED lamp; and the organic solvent is acetonitrile.
[0025] Example 1
[0026] The reaction equation is shown below:
[0027]
[0028] Into a 20 ml test tube equipped with a magnetic stirrer, phenylglyoxylic acid (1 mmol), Ph2Se2 (0.25 mmol), and CH3CN (2 ml) were added. After the addition, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent. The residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 70 / 1) to obtain 108 mg of the target compound with a yield of 83%.
[0029] The NMR spectrum data of the obtained product are:
[0030] 1H NMR (400MHz, CDCl3): δ.7.87(d,J=7.0Hz,1H),7.61–7.50(m,3H),7.42(t,J=7.7Hz,2H),7.38–7.35(m,2H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ193.5,138.5,136.4,134.0,129.4,129.1,129.0,127.4,125.8.
[0031] Example 2
[0032]
[0033] Into a 20 ml test tube equipped with a magnetic stirrer, 4-bromophenylglyoxylic acid (1 mmol), Ph2Se2 (0.25 mmol), and CH3CN (2 ml) were added. After the addition, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent. The residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 90 / 1) to obtain 134 mg of the target compound with a yield of 79%.
[0034] The NMR spectrum data of the obtained product are:
[0035] 1 H NMR (400MHz, CDCl3): δ7.72(d,J=8.5Hz,2H),7.56(d,J=8.6Hz,2H),7.51(dd,J=7.3,2.2Hz,2H),7.42–7.30(m,3H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ192.6,137.3,136.3,132.3,129.5,129.3,129.0,128.7,125.4.
[0036] Example 3
[0037]
[0038] Into a 20 ml test tube equipped with a magnetic stirrer, (2-furyl)glyoxylic acid (1 mmol), Ph2Se2 (0.25 mmol), and CH3CN (2 ml) were added. After the addition, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent. The residue was purified using a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 120 / 1) to obtain 105 mg of the target compound with a yield of 84%.
[0039] The NMR spectrum data of the obtained product are:
[0040] 1 H NMR (400MHz, CDCl3): δ7.56(d,J=1.7Hz,1H),7.51(dd,J=7.2,2.4Hz,2H),7.36–7.31(m,3H),7.14(d,J=3.6Hz,1H),6.51(dd,J=3.7,1.7Hz,1H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ180.9,151.8,146.7,136.4,129.4,129.2,124.8,115.3,112.9.
[0041] Example 4
[0042]
[0043] Into a 20 ml test tube equipped with a magnetic stirrer, 1-naphthoylcarboxylic acid (1 mmol), Ph2Se2 (0.25 mmol), and CH3CN (2 ml) were added. After the addition was completed, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was passed through a rotary evaporator to remove the solvent. The residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 110 / 1) to obtain 124 mg of the target compound with a yield of 80%.
[0044] The NMR spectrum data of the obtained product are:
[0045] 1 H NMR (400MHz, CDCl3): δ8.46(d,J=8.4Hz,1H),8.08(d,J=7.3Hz,1H),7.92(d,J=8.3Hz,1H),7.7 6(dd,J=7.9,1.6Hz,1H),7.56(d,J=2.4Hz,1H),7.50–7.39(m,4H),7.35(p,J=4.0,3.6Hz,3H).13 C{ 1 H}NMR (100MHz, CDCl3): δ195.4,136.3,136.2,134.0,133.6,133.3,129.5,129.3,129.2,128.4,128.3,127.3,127.0,125.3,124.6.
[0046] Example 5
[0047]
[0048] Into a 20 ml test tube equipped with a magnetic stirrer, 2-oxo-2-[3,5-(dichloro)phenyl]acetic acid (1 mmol), Ph2Se2 (0.25 mmol), and CH3CN (2 ml) were added. After the addition, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent. The residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 130 / 1) to obtain 124 mg of the target compound with a yield of 75%.
[0049] The NMR spectrum data of the obtained product are:
[0050] 1 H NMR (400MHz, CDCl3): δ7.69 (d, J = 1.8Hz, 2H), 7.52-7.46 (m, 3H), 7.39-7.32 (m, 3H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ191.5,141.0,136.2,136.0,133.4,129.6,125.6,125.0.
[0051] Example 6
[0052]
[0053] Into a 20 ml test tube equipped with a magnetic stirrer, 5-methyl-3-phenyl-4-isoxazole acyl carboxylic acid (1 mmol), Ph2Se2 (0.25 mmol), and CH3CN (2 ml) were added. After the addition was completed, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent. The residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 100 / 1) to obtain 123 mg of the target compound with a yield of 72%.
[0054] The NMR spectrum data of the obtained product are:
[0055] 1 H NMR (400MHz, CDCl3): δ7.56-7.53(m,2H),7.47-7.35(m,5H),7.33-7.26(m,3H),2.66(s,3H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ186.0,172.9,161.2,136.1,130.5,129.7,129.5,128.6,127.6,125.8,118.5,13.9.
[0056] Example 7
[0057]
[0058] Into a 20 ml test tube equipped with a magnetic stirrer, phenylglyoxylic acid (1 mmol), di(p-chlorophenyl) diselenide (0.25 mmol), and CH3CN (2 ml) were added. After the addition was completed, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 120 / 1) to obtain 126 mg of the target compound with a yield of 85%.
[0059] The NMR spectrum data of the obtained product are:
[0060] 1 H NMR (400MHz, CDCl3): δ7.88-7.81(m,2H),7.59-7.53(m,1H),7.47-7.39(m,4H),7.36-7.29(m,2H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ192.9,137.7,135.6,134.1,129.7,129.1,127.4,124.0.
[0061] Example 8
[0062]
[0063] Into a 20 ml test tube equipped with a magnetic stirrer, phenylglyoxylic acid (1 mmol), di(3,4,5-trimethylphenyl) diselenide (0.25 mmol), and CH3CN (2 ml) were added. After the addition was completed, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 150 / 1) to obtain 121 mg of the target compound with a yield of 80%.
[0064] The NMR spectrum data of the obtained product are:
[0065] 1 H NMR (400MHz, CDCl3): δ7.90 (d, J = 8.3Hz, 2H), 7.56-7.50 (m, 1H), 7.40 (t, J = 7.6Hz, 2H), 6.95 (s, 2H), 2.33 (s, 6H), 2.24 (s, 3H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ192.9,143.2,139.7,139.1,133.9,129.0,128.9,127.5,124.8,24.2,21.2.
[0066] Example 9
[0067]
[0068] Into a 20 ml test tube equipped with a magnetic stirrer, phenylglyoxylic acid (1 mmol), dibenzyl diselenide (0.25 mmol), and CH3CN (2 ml) were added. After the addition was completed, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 160 / 1) to obtain 107 mg of the target compound with a yield of 78%.
[0069] The NMR spectrum data of the obtained product are:
[0070] 1 H NMR (400MHz, CDCl3): δ7.85-7.79(m,2H),7.48(d,J=7.4Hz,1H),7.36(t,J=7.7Hz,2 H),7.29(d,J=7.3Hz,2H),7.21(t,J=7.5Hz,2H),7.14(d,J=7.3Hz,1H),4.26(s,2H). 13 C{1 H}NMR (100MHz, CDCl3): δ194.6,139.1,138.8,133.8,129.1,128.9,128.7,127.3,127.1,29.1.
[0071] Example 10
[0072]
[0073] Into a 20 ml test tube equipped with a magnetic stirrer, phenylglyoxylic acid (1 mmol), dimethyl diselenide (0.25 mmol), and CH3CN (2 ml) were added. After the addition was completed, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 130 / 1) to obtain 70 mg of the target compound with a yield of 70%.
[0074] The NMR spectrum data of the obtained product are:
[0075] 1 H NMR (400MHz, CDCl3): δ7.87-7.82(m,2H),7.55-7.49(m,1H),7.39(t,J=7.6Hz,2H),2.32(s,3H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ195.0,139.0,133.6,128.8,127.1,5.2.
[0076] Embodiment 11
[0077]
[0078] Into a 20 ml test tube equipped with a magnetic stirrer, phenylglyoxylic acid (1 mmol), diphenylethyl diselenide (0.25 mmol), and CH3CN (2 ml) were added. After the addition was completed, a fluorescent lamp was placed 2 cm away from the test tube. The reaction was allowed to proceed at room temperature for 48 hours under open conditions. After the reaction was completed, the organic phase was subjected to a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel specification was 200-300 mesh, and the eluent was petroleum ether / ethyl acetate = 100 / 1) to obtain 103 mg of the target compound with a yield of 71%.
[0079] The NMR spectrum data of the obtained product are:
[0080] 1H NMR (400MHz, CDCl3): δ7.84-7.80(m,2H),7.50(td,J=7.2,1.4Hz,1H),7.36(t,J =7.8Hz,2H),7.26-7.12(m,5H),3.24(dd,J=8.6,6.9Hz,2H),3.01-2.94(m,2H). 13 C{ 1 H}NMR (100MHz, CDCl3): δ194.8,141.1,139.1,133.7,128.8,128.6,128.5,127.2,126.5,36.9,26.7.
[0081] In summary, the present invention provides a method for synthesizing a selenoester compound promoted by visible light, wherein, under visible light irradiation, an aromatic keto acid and a diselenide undergo an intermolecular coupling reaction to obtain a selenoester compound. The present invention uses visible light as an energy source, has mild reaction conditions, and is green and environmentally friendly; it does not require strict exclusion of air and moisture, is simple to operate, has good functional group compatibility, and synthesizes a series of selenoesters under light-induced conditions, which has good application prospects.
[0082] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A method for synthesizing a selenoester compound promoted by visible light, characterized in that: The following steps are involved: In an organic solvent, an aromatic keto acid compound having a structure as shown in formula (I) and a diselenide having a structure as shown in formula (II) are used as reaction raw materials, and the reaction is carried out under visible light irradiation under open and room temperature conditions. After the reaction is completed, the reaction solution is decompressed to remove the solvent to obtain a crude product, and the crude product is purified by column chromatography to obtain a selenoester compound having a structure as shown in formula (III). The reaction equation is shown below: ; Wherein, the compound of formula (I) is an aryl keto acid compound, Ar is naphthyl, furanyl, thienyl, isoxazolyl, phenyl, phenyl substituted with one or more substituents, and the substituents are halogen, alkyl, alkyl nitrogen, alkoxy, trifluoromethyl; The compound of formula (II) is diaryl diselenide or dialkyl diselenide; the irradiation light source of the reaction is a fluorescent lamp; the organic solvent is acetonitrile; The molar ratio of the aromatic keto acid compound with the structure shown in formula (I) to the diselenide with the structure shown in formula (II) is 2:0.
5.
2. The method for synthesizing a selenoester compound promoted by visible light according to claim 1, characterized in that: The reaction time is 48h.
3. The method for synthesizing a selenoester compound promoted by visible light according to claim 1, characterized in that: After the reaction is completed, the reaction solution is concentrated under reduced pressure, and the concentrate is separated by column chromatography, using a mixed solution of petroleum ether and ethyl acetate as an eluent, wherein the volume ratio of petroleum ether:ethyl acetate is (200-1):1, and the eluate is collected, and the solvent is rotary evaporated to obtain a selenoester compound represented by formula (III).