A method for preparing an organosulfur ether compound
By enabling the addition reaction of thiophenol compounds with olefins under blue light irradiation in the presence of an alkalizing agent and an iron catalyst, the problems of reactor corrosion and environmental hazards caused by halogen participation were solved, and high-yield organic sulfide compounds were prepared.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANJING TECH UNIV
- Filing Date
- 2024-04-12
- Publication Date
- 2026-05-26
AI Technical Summary
In existing methods for preparing organosulfur compounds, reactions involving halogens are prone to corroding reactors and causing environmental damage, and the yields are low.
The addition reaction of thiophenols with olefins in the presence of an alkalizing agent and an iron catalyst, under blue light irradiation, avoids the involvement of halogens and generates organosulfur ether compounds.
This method improves the preparation process under environmentally friendly conditions, achieving a yield of 65%, reducing costs, and simplifying the preparation process, thus providing a new method for synthesizing organosulfur ether compounds.
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Figure CN118515519B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis and relates to a method for preparing organothioether compounds, particularly a method for synthesizing thioethers by reacting substituted thiophenols and alkenes under blue light catalysis under alkaline iron catalysis. Background Technology
[0002] With the development of modern science, sulfur-containing compounds have been widely used in pesticides, pharmaceuticals, chemical dyes, and functional materials. Organic sulfur also has effects on the human body; sulfur deficiency can lead to various degenerative diseases, increased stress, and depression. Organic sulfur compounds are also powerful antioxidants and detoxifiers, helping to excrete heavy metals from the body. When the body is injured, organic sulfur promotes circulation in the injured area, utilizing nutrients to repair the wound. Organic sulfur also has antiseptic and cleansing effects in the digestive tract, simultaneously aiding liver function and promoting metabolism, preventing toxin accumulation. In organic compounds, sulfur atoms mostly exist as CS bonds, most commonly in thiols and thioethers. Currently, organic thioether compounds are mainly produced through the reaction of thiols with halogen-substituted aromatic hydrocarbons. The presence of halogens in this reaction can corrode reactors and is environmentally harmful. Summary of the Invention
[0003] Purpose of the invention: The technical problem to be solved by the present invention is to provide a new method for preparing organosulfur ether compounds that does not rely on halogen reactions, is more reactor- and environmentally friendly, and can improve yield and reduce cost.
[0004] To achieve the above objectives, the technical solution of this invention is as follows: Using thiophenol compounds and olefins as raw materials, an alkalizing agent and a catalyst are reacted together in a solvent under blue light irradiation at room temperature to obtain the product. The reaction formula is as follows:
[0005]
[0006] In the formula, R 1 It is selected from any one of hydrogen, C1-C6 alkyl, alkoxy, trifluoromethyl, and halogen;
[0007] R 2 R 3 Selected from C1-C6 alkyl groups respectively.
[0008] or R 2 With R 3 They form a ring, together constituting -(CH2). n - where n = 1, 2, 3 or 7,
[0009] or R 2 With R 3They form a ring, together constituting -(CH2). m -O-(CH2) n - where m = 1 or 2, n = 1 or 2.
[0010] Specifically, the thiophenol compounds are selected from any one of thiophenol, 4-methylthiophenol, 4-trifluoromethylthiophenol, and 4-methoxythiophenol.
[0011] Specifically, the olefin is selected from any one of cyclohexene, 3,6-dihydrofuran, and cyclopropene.
[0012] Specifically, the molar ratio of thiophenol compounds to olefins is 1:1 to 1:3.
[0013] Specifically, the catalyst is an iron catalyst, selected from any one of FeCl3, FeCl2, FeBr3, FeO, FeBr2, and Fe2O3.
[0014] Specifically, the amount of the catalyst used accounts for 1-10% of the molar amount of the thiophenol compound.
[0015] Specifically, the alkalizing agent is a tert-butanol salt, selected from any one of potassium tert-butoxide, lithium tert-butoxide, and sodium tert-butoxide.
[0016] Specifically, the amount of alkalizing agent used is 2-2.5 times the molar amount of thiophenol compounds.
[0017] Specifically, the blue light wavelength is 450-480nm and the power is 3-60W.
[0018] Specifically, the reaction temperature is 25-30℃ and the reaction time is 2-6 hours.
[0019] Beneficial effects:
[0020] This invention provides a novel method for preparing organosulfur compounds. It utilizes tert-butanol salts to abstract a hydrogen atom from the S-position of R-thiophene, generating an R-thiophene anion. Under light irradiation, the R-thiophene anion loses electrons to produce an R-thiophene radical. This radical then reacts with an olefin compound via iron ion catalysis to yield an organosulfur ether compound. This method is rationally designed, does not rely on halogen reactions, is relatively reactor- and environmentally friendly, achieves a yield of up to 65%, and is cost-effective. It provides a new method for the synthesis of organosulfur ether compounds and has promising industrial applications. Attached Figure Description
[0021] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.
[0022] Figure 1 It is the product obtained in Example 1. 1 H NMR spectrum.
[0023] Figure 2 It is the product obtained in Example 1. 13 C10 NMR spectrum.
[0024] Figure 3 It is the product obtained in Example 7. 1 H NMR spectrum.
[0025] Figure 4 It is the product obtained in Example 7. 13 C10 NMR spectrum. Detailed Implementation
[0026] The present invention can be better understood from the following embodiments.
[0027] Example 1
[0028]
[0029] Ferric chloride (1.6 mg, 0.01 mmol), potassium tert-butoxide (44.9 mg, 0.4 mmol), and 4-methylthiophenol (24.8 mg, 0.2 mmol) were added to a reaction tube equipped with a magnetic flux. After purging with argon, 20.5 μL of cyclohexene dissolved in 2 mL of acetonitrile was added to the reaction tube under an argon atmosphere. The reaction was irradiated with blue light at room temperature for 6 h. After the reaction was confirmed to be complete by TLC, it was subjected to silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to give a colorless oily liquid Ia 26.5 mg, yield 65%. 1 See the HNMR spectrum. Figure 1 The product 13 The C NMR spectrum is shown below. Figure 2 .
[0030] 1 H NMR(400MHz,Chloroform-d)δ7.36(dd,J=19.3,7.8Hz,2H),7.11(d,J=7.9Hz,2H),3.60-3.47(s,1H),2.3 3(s,J=3.9Hz,3H),2.09-1.85(d,2H),1.81-1.51(d,2H),1.35-1.18(d,6H),HRMS(ESI)[M+H]calculated for[C 13 H 19 S] + 207.1129, found 207.1130.
[0031] Example 2
[0032]
[0033] Ferric chloride (1.6 mg, 0.01 mmol), potassium tert-butoxide (44.9 mg, 0.4 mmol), and 4-methoxythiophenol (14.0 mg, 0.1 mmol) were added to a reaction tube equipped with a magnetic ion. After purging with argon, 20.5 μL of cyclohexene dissolved in 2 mL of THF was added to the reaction tube under an argon atmosphere. The reaction was irradiated with blue light at room temperature for 6 h. After the reaction was confirmed to be complete by TLC, it was subjected to silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to give a colorless oily liquid Ib 27.3 mg, yield 62%.
[0034] HRMS(ESI)[M+H]calculated for[C 13 H 17 OS] + 221.0922, found 221.0924.
[0035] Example 3
[0036]
[0037] Ferric chloride (1.6 mg, 0.01 mmol), potassium tert-butoxide (56.1 mg, 0.5 mmol), and 4-trifluoromethylthiophenol (35.6 mg, 0.2 mmol) were added to a reaction tube equipped with a magnetic spool. After purging with argon, 18.2 μL of 3,6-dihydropyran dissolved in 2 mL of toluene was added to the reaction tube under an argon atmosphere. The reaction was irradiated with blue light at room temperature for 6 h. After the reaction was confirmed to be complete by TLC, it was subjected to silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to give a colorless oily liquid I-c 33.3 mg, yield 64%.
[0038] HRMS(ESI)[M+H]calculated for[C 12 H 12 F3OS] + 263.0483, found 263.0486.
[0039] Example 4
[0040]
[0041] Ferric chloride (3.2 mg, 0.02 mmol), potassium tert-butoxide (44.9 mg, 0.4 mmol), and thiophenol (22.0 mg, 0.2 mmol) were added to a reaction tube equipped with a magnetic spool. After purging with argon, 20.5 μL of cyclohexene dissolved in 2 mL of DCM was added to the reaction tube under an argon atmosphere. The reaction was irradiated with blue light at room temperature for 3 h. After the reaction was confirmed to be complete by TLC, it was subjected to silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to give a colorless oily liquid Ie 23.2 mg, yield 61%.
[0042] HRMS(ESI)[M+H]calculated for[C 14 H 15 S] + 193.0816, found 193.0817.
[0043] Example 5
[0044]
[0045] Ferric chloride (3.2 mg, 0.02 mmol), potassium tert-butoxide (44.9 mg, 0.4 mmol), and 4-bromothiophenol (37.8 mg, 0.2 mmol) were added to a reaction tube equipped with a magnetic spool. After purging with argon, 41.0 μL of cyclohexene dissolved in 2 mL of CH3CN was added to the reaction tube under an argon atmosphere. The reaction was carried out at room temperature under blue light for 5 h. After the reaction was confirmed to be complete by TLC, it was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to give 23.2 mg of a colorless oily liquid If, with a yield of 64%.
[0046] HRMS(ESI)[M+H]calculated for[C 12 H 14 BrS] + 270.9921, found 270.9926.
[0047] Example 6
[0048]
[0049] Ferric chloride (3.2 mg, 0.02 mmol), potassium tert-butoxide (44.9 mg, 0.4 mmol), and 4-chlorothiophenol (43.4 mg, 0.3 mmol) were added to a reaction tube equipped with a magnetic ion. After purging with argon, 31.0 μL of cyclohexene dissolved in 2 mL of THF was added to the reaction tube under an argon atmosphere. The reaction was irradiated with blue light at room temperature for 3 h. After the reaction was confirmed to be complete by TLC, it was subjected to silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to give 1 g of colorless oily liquid, 41.0 mg, with a yield of 61%.
[0050] HRMS(ESI)[M+H]calculated for[C 12 H 14 ClS] + 226.0426, found 226.0429.
[0051] Example 7
[0052]
[0053] Ferric chloride (3.2 mg, 0.02 mmol), potassium tert-butoxide (44.9 mg, 0.4 mmol), and 4-methylthiophenol (37.2 mg, 0.3 mmol) were added to a reaction tube equipped with a magnetic flux. After purging with argon, 31.0 μL of cyclopentene dissolved in 2 mL of THF was added to the reaction tube under an argon atmosphere. The reaction was irradiated with blue light at room temperature for 4 h. After the reaction was confirmed to be complete by TLC, it was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to give a colorless oily liquid. The product yield was 38.4 mg / h, 67%. 1 The H NMR spectrum is shown in [reference]. Figure 3 The product 13 The C NMR spectrum is shown below. Figure 4 .
[0054] 1 H NMR(400MHz,Chloroform-d)δ7.36(dd,J=19.3,7.8Hz,2H),7.11(d,J=7.9Hz,2H),3.60-3.47(s,1H),2.3 3(s,J=3.9Hz,3H),2.09-1.85(d,2H),1.81-1.51(d,2H),1.35-1.18(d,4H),HRMS(ESI)[M+H]calculated for[C 12 H 17 S] + 193.0973, found 193.0976.
[0055] This invention provides a method for preparing organosulfur ether compounds. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.
Claims
1. A method for preparing an organosulfur ether compound, characterized in that, The product is obtained by an addition reaction of thiophenolic compounds and olefins with an alkalizing agent and a catalyst in a solvent under blue light irradiation at room temperature. The reaction formula is as follows: ； In the formula, R 1 It is selected from any one of hydrogen, C1-C6 alkyl, alkoxy, trifluoromethyl, and halogen; R 2 With R 3 They form a ring, together constituting -(CH2). n - , where n=2 or 3, Or R 2 With R 3 They form a ring, together constituting -(CH2). m -O- (CH2) n - where m=1, n=1; The catalyst is selected from either FeCl3 or FeBr3; The alkalizing agent is selected from any one of potassium tert-butoxide, lithium tert-butoxide, and sodium tert-butoxide.
2. The method for preparing the organosulfur ether compound according to claim 1, characterized in that, The thiophenol compounds mentioned are selected from any one of thiophenol, 4-methylthiophenol, 4-trifluoromethylthiophenol, and 4-methoxythiophenol.
3. The method for preparing the organosulfur ether compound according to claim 1, characterized in that, The olefin is selected from either cyclohexene or cyclopentene.
4. The method for preparing the organosulfur ether compound according to claim 1, characterized in that, The molar ratio of thiophenols to olefins is 1:1 to 1:
3.
5. The method for preparing the organosulfur ether compound according to claim 1, characterized in that, The amount of the catalyst used is 1-10% of the molar amount of the thiophenol compound.
6. The method for preparing the organosulfur ether compound according to claim 1, characterized in that, The amount of the alkalizing agent is 2-2.5 times the molar amount of the thiophenol compound.
7. The method for preparing the organosulfur ether compound according to claim 1, characterized in that, The blue light wavelength is 450-480nm and the power is 3-60W.
8. The method for preparing the organosulfur ether compound according to claim 1, characterized in that, The addition reaction time is 2-6 h.