Venylether pentafluorosulfenyl method using sulfur hexafluoride as pentafluorosulfenyl source and pentafluorosulfenyl product
By using sulfur hexafluoride as a pentafluorosulfur group source, combined with a photocatalyst and a specific solvent, the pentafluorosulfurization reaction is carried out in the photo reactor, and the pentafluorosulfurization problem in the prior art is solved, a safe, economical and gentle reaction is achieved, and substrate compatibility is expanded.
Patent Information
- Application Number
- CN202411685038.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-22
- Publication Date
- 2025-02-25
AI Technical Summary
It is difficult to effectively synthesize the pentafluorosulfide of the alkenyl ether compound in the prior art, and the traditional methods have problems such as high cost, safety risks and limitations in substrate expansion.
Sulfur hexafluoride is used as the pentafluorosulfur source, combined with a photocatalyst and a specific solvent, and a replacement reaction is carried out in a photoreactor to achieve pentafluorosulfurization of the alkenyl ether.
The safe, economical and gentle progress of the pentafluorosulfation reaction was achieved, the substrate compatibility was expanded, and a new route was provided for the synthesis of related drug molecular derivatives.
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Figure CN119504536A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic chemical synthesis, and in particular to a method for pentafluorosulfanylation of enether using sulfur hexafluoride as a pentafluorosulfanylation source and a pentafluorosulfanylation product. Background Art
[0002] The pentafluorosulfonyl group structure is a unique octahedral structure around the sulfur atom. Due to its large steric hindrance and high chemical stability, it has broad development potential in the field of optoelectronic materials. In addition, the pentafluorosulfonyl group has more significant lipophilicity and electron-withdrawing properties than the trifluoromethyl group, which is of great significance for the synthesis and development of fluorine-containing drugs. The methods for synthesizing small molecules containing pentafluorosulfonyl groups are currently relatively limited, mainly limited to pentafluorosulfonylation reagents or photoredox methods.
[0003] In 2018, Hans-Achim Wagenknech's group proposed the first photocatalytic redox method to convert it into pentafluorosulfonylated α-methylstyrene and α-phenylstyrene simply using light. This work addresses the challenge of precisely activating sulfur hexafluoride with a photoredox catalyst that designs a continuous electron transfer cycle that allows styrene to capture the generated pentafluorosulfonyl group. (ChemCatChem 2018, 10, 2955–2961)
[0004] In 2019, Hans-Achim Wagenknech's group described the use of SF 6 As pentafluorosulfonylating agent, a one-step photoredox method was used to prepare SF 5 Ether compounds with ortho-substituents. (Angew.Chem.Int.Ed.2020,59,300–303)
[0005] In 2021, Hans-Achim Wagenknech's group reported a one-step synthesis of perfluorosulfonylated oxygen-containing heterocyclic compounds from α-substituted olefins, and the proposed mechanism was supported by theoretical calculations, which not only provided insights in the pentafluorosulfonylation step, but also fully complied with Baldwin's cyclization rules. The synthesized oxygen heterocyclic compounds cannot be simply prepared by other synthetic methods, and their structural complexity is relatively high, which greatly expands the scope of pentafluorosulfonylated building blocks and has important application value in medicine and materials chemistry. (Chem.Eur.J.2021,27,8088–8093)
[0006] In 2021, Qing Fengling's research group developed SF 5 A new synthesis method for SF 5 The free radical addition reaction of Cl with diazo compounds was successfully used to synthesize a series of α-SF5 Carbonyl compounds and dehydroepiandrosterone derivatives. (Angew.Chem.Int.Ed.2021,60,15271–15275) Summary of the invention
[0007] The technical problem to be solved by the present invention is how to pentafluorosulfurize an olefin ether compound.
[0008] The present invention solves the above technical problems through the following technical means:
[0009] A method for pentafluorosulfurization of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source comprises the following steps: placing a photocatalyst and an olefin ether compound in a reaction device, replacing air in the reaction device with sulfur hexafluoride gas, adding a solvent and methanol in the sulfur hexafluoride gas atmosphere, and sealing the reaction device and placing it in a photoreactor for reaction to obtain an olefin ether pentafluorosulfurization product; wherein the solvent is a mixture of one or more of isopropyl ether, DCE, acetonitrile, DCM, toluene, dioxane, 2-methyltetrahydrofuran, THF, PhCl, and MTBE; and during the reaction, the wavelength of the light source used is 355-375 nm.
[0010] Preferably, the olefin ether compound is (vinyloxy)methylbenzene 4-(vinyloxy)methyl-1,1-biphenyl 2-(Vinyloxy)methylnaphthalene Meiyan alcohol enether One of them.
[0011] Preferably, the photocatalyst is 10-phenylphenothiazine.
[0012] Preferably, the wavelength of the light source is 365 nm.
[0013] Preferably, the mass ratio of the photocatalyst to the olefinic ether compound is 11:25-42.
[0014] Preferably, the volume ratio of the solvent to methanol is 1:0.8.
[0015] Preferably, the usage ratio of the olefin ether compound and methanol is 25-42 mg:0.8 ml.
[0016] Preferably, during the reaction process, the power of the photoreactor is 10W.
[0017] Preferably, the reaction temperature is 20°C and the reaction time is 24 hours.
[0018] The present invention also provides a pentafluorosulfonated compound, which is prepared by the pentafluorosulfonation method of enether using sulfur hexafluoride as a pentafluorosulfonyl source.
[0019] The present invention also provides a method for synthesizing pentafluorothioacetaldehyde, comprising mixing the pentafluorothiolated compound with trifluoroacetic acid, stirring and reacting the mixture, and obtaining the pentafluorothioacetaldehyde after post-treatment.
[0020] Preferably, the usage ratio of the pentafluorosulfurized compound to trifluoroacetic acid is 0.2 mmol:1 ml.
[0021] The invention also provides an application of sulfur hexafluoride as a pentafluorosulfur source for pentafluorosulfurization of enether.
[0022] Preferably, the method comprises the following steps: placing a photocatalyst and an olefinic ether compound in a reaction device, replacing the air in the reaction device with sulfur hexafluoride gas, adding a solvent and methanol in the sulfur hexafluoride gas atmosphere, and placing the sealed reaction device in a photoreactor for reaction to obtain an olefinic ether pentafluorosulfurization product; wherein the solvent is a mixture of one or more of isopropyl ether, DCE, acetonitrile, DCM, toluene, dioxane, 2-methyltetrahydrofuran, THF, PhCl, and MTBE; and during the reaction, the wavelength of the light source used is 355-375 nm.
[0023] The advantages of the present invention are:
[0024] When synthesizing a series of pentafluorosulfonated derivatives, traditional conversion strategies are often limited by the need to pre-prepare expensive fluorination reagents and reliance on highly toxic substances. These problems not only drive up costs, but also pose safety risks. In addition, although Hans-Achim Wagenknech's research group previously proposed the use of 10-phenylphenolthiazine as a photocatalyst to achieve pentafluorosulfonation of sulfur hexafluoride, this method uses a common free radical scavenger such as diphenylethylene, which is relatively limited to the expansion of heterocyclic activated substrates, and the substrate expansion is only limited to the scope of nucleophilic reagents. The present invention proposes an innovative method that cleverly selects sulfur hexafluoride as a fluorination reagent to achieve the safe, economical, and mild pentafluorosulfonation of heteroatom-activated heteroolefin compounds, while showing a wide range of substrate compatibility. In addition, compared with the synthesis of other pentafluorosulfonyl functional groups The method has the advantage that it can realize the synthesis of some related drug molecule derivatives, and the substrate is subsequently transformed to synthesize a simpler pentafluorosulfenyl acetaldehyde building block, and the building block can be widely transformed, and a series of reactions such as witig reaction and amination reaction can be tried, which provides a new route for the synthesis of pentafluorosulfenyl molecules. In addition, the reaction also provides a new idea for the synthesis of acetal compounds, and provides a new idea and path for the synthesis of raw materials for the selective transformation of acetals, thereby providing a greener and more efficient method for chemical synthesis in this field.
[0025] The invention uses sulfur hexafluoride as a safe and cheap pentafluorosulfurization reagent to react with specific olefinic ether substances to prepare high value-added organic pentafluorosulfur group-containing small molecules. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 is the H NMR spectrum of the product in Example 11 of the present invention;
[0027] Figure 2 is the NMR carbon spectrum of the product in Example 11 of the present invention;
[0028] Figure 3 is the NMR fluorine spectrum of the product in Example 11 of the present invention;
[0029] Figure 4 is the H NMR spectrum of the product in Example 12 of the present invention;
[0030] Figure 5 is the NMR carbon spectrum of the product in Example 12 of the present invention;
[0031] Figure 6 is the NMR fluorine spectrum of the product in Example 12 of the present invention;
[0032] Figure 7 is the H NMR spectrum of the product in Example 14 of the present invention;
[0033] Figure 8 is the NMR carbon spectrum of the product in Example 14 of the present invention;
[0034] Fig. 9 This is the NMR fluorine spectrum of the product in Example 14 of the present invention.
[0035] Fig.10 is the H NMR spectrum of the product in Example 1 of the present invention;
[0036] Fig.11 is the NMR carbon spectrum of the product in Example 1 of the present invention;
[0037] Fig.12 This is the NMR fluorine spectrum of the product in Example 1 of the present invention. DETAILED DESCRIPTION
[0038] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. 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.
[0039] Unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources.
[0040] If no specific techniques or conditions are specified in the examples, they can be carried out according to the techniques or conditions described in the literature in the art or according to the product instructions.
[0041] Example 1
[0042] A method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source comprises the following steps:
[0043] (1) Preparation of photocatalyst-reducing agent raw material solution: Place an A615 polytetrafluoroethylene magnetic stirrer in a Schlenk tube with a volume of 10 mL, then weigh 11 mg of the photocatalyst PTH 10-phenylphenothiazine and 26.8 mg of the raw material (vinyloxy)methylbenzene and place them in the Schlenk tube. Screw on the polytetrafluoroethylene stopcock to seal the tube mouth and connect the tube cavity with the branch tube mouth. Take a high vacuum three-way gas valve with a stopper, and connect its interfaces to the Schlenk tube, vacuum pump and sulfur hexafluoride gas respectively. Connect the Schlenk tube and the vacuum pump, and extract the air in the tube (for more than 3 seconds); connect the sulfur hexafluoride gas and the Schlenk tube, and put in sulfur hexafluoride gas (for more than 3 seconds). One set of extraction and exhaust is a ventilation cycle. Repeat the ventilation three times and stay in the exhaust state so that there is a positive pressure of pure sulfur hexafluoride gas in the tube. Place the Schlenk tube in a -78°C environment, extract the gas in the tube (for more than 3 seconds); add sulfur hexafluoride gas (for more than 10 seconds), and one set of extraction and deflation is a ventilation cycle. Repeat the ventilation twice and stay in the deflation state for 15 seconds. Open the Schlenk tube stopcock, quickly add 1 ml of solvent isopropyl ether and 0.8 ml of methanol in the sulfur hexafluoride gas atmosphere, close the stopcock, and keep the Schlenk tube connected to the sulfur hexafluoride gas for 30 seconds. Close the stopcock to completely seal the Schlenk tube lumen, and disconnect the vacuum pump and sulfur hexafluoride gas.
[0044] (2) Reaction conditions: Place the sealed Schlenk tube in a parallel light reactor, adjust the light source wavelength to 365 nm, power to 10 W, and temperature to 20 °C, and react for 24 h.
[0045] (3) Reaction treatment: Open the Schlenk tube and detect the reaction product by TLC after the bubbles disappear completely.
[0046] Reaction result: 45% isolation yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6-Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane, its NMR spectrum is as follows Figure 10-12 As shown, the NMR data are as follows:
[0047] 1 H NMR (500 MHz, CDCl 3 )δ7.41–7.31(m,5H),5.06(t,J=5.1Hz,1H),4.69(d,J=11.4Hz,1H),4.60(d,J=11.4Hz,1H),3.85(pd,J=8.3,3.8Hz,2H),3.42(s,3H).
[0048] 13 C NMR (126 MHz, CDCl 3 )δ136.90,128.80,128.24,128.02,98.63(p,J=5.2Hz),72.07(p,J=12.5Hz),69.23,53.96.
[0049] 19 F NMR (471 MHz, CDCl 3 )δ85.23–82.58(m),67.92(dt,J=147.4,8.4Hz).
[0050] Example 2
[0051] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source is different from Example 1 only in that DCE is used in (1) instead of the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0052] Reaction result: 47% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0053] Example 3
[0054] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that acetonitrile is used in (1) instead of the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0055] Reaction result: 51% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0056] Example 4
[0057] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that DCM is used in (1) instead of the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0058] Reaction result: 43% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0059] Example 5
[0060] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that toluene is used in (1) instead of the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0061] Reaction result: 46% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0062] Example 6
[0063] A method for pentafluorosulfurization of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that dioxane is used in (1) to replace the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0064] Reaction result: 58% fluorine spectrum yield, the substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0065] Example 7
[0066] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that 2-methyltetrahydrofuran is used in (1) to replace the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0067] Reaction result: 70% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0068] Example 8
[0069] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that THF is used in (1) instead of the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0070] Reaction result: 77% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0071] Example 9
[0072] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that PhCl is used in (1) to replace the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0073] Reaction result: 86% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0074] Example 10
[0075] A method for pentafluorosulfuration of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that MTBE is used in (1) instead of the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0076] Reaction result: 50% fluorine spectrum yield, substrate 1 (2-(benzyloxy)-2-methoxyethyl) pentafluoro-λ 6-Sulfane(2-(benzyloxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane.
[0077] Comparative Example 1
[0078] The only difference from Example 1 is that DMF is used in (1) instead of the isopropyl ether in Example 1, and the remaining steps are the same as those in Example 1.
[0079] Reaction results: Substrate 1 was obtained, and only a trace amount of fluorine was obtained.
[0080] Embodiment 11
[0081] A method for pentafluorosulfurization of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, the difference from Example 1 being that 42 mg of 4-(vinyloxy)methyl-1,1-biphenyl is used in (1) to replace 26.8 mg of (vinyloxy)methylbenzene in Example 1, and the remaining steps are the same as those in Example 1.
[0082] Reaction result: 55% isolation yield, substrate 2 (2-([1,1'-biphenyl]-4-methoxy)-2-methoxyethyl) pentafluoro-λ 6 -Sulfane(2-([1,1'-biphenyl]-4-ylmethoxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane, its NMR spectrum is as follows Figure 1-3 The specific data are as follows:
[0083] 1 H NMR(500MHz,Chloroform-d)δ7.67–7.57(m,4H),7.45(q,J=7.6Hz,4H),7.39–7.34(m,1H),5.09( t,J=5.0Hz,1H),4.74(d,J=11.4Hz,1H),4.64(d,J=11.4Hz,1H),3.97–3.80(m,2H),3.44(s,3H).
[0084] 13 C NMR (126MHz, Chloroform-d) δ141.22,140.86,135.94,128.95,128.47,127.56,127.46,127.26,98.71(p,J=5.3Hz),72.12(p,J=12.4Hz)),68.98,54.00.
[0085] 19 F NMR (471MHz, Chloroform-d) δ85.20–83.02 (m), 68.01 (dt, J = 147.3, 8.4Hz).
[0086] Example 12
[0087] A method for pentafluorosulfurization of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, the difference from Example 1 being that 36.8 mg of 2-(vinyloxy)methylnaphthalene is used in step (1) to replace 26.8 mg of (vinyloxy)methylbenzene in Example 1, and the remaining steps are the same as those in Example 1.
[0088] Reaction result: 34% isolation yield, substrate 3 pentafluoro (2-methoxy-2- (naphthalene-2-methoxy) ethyl) -λ 6 -Sulfonepentafluoro(2-methoxy-2-(naphthalen-2-ylmethoxy)ethyl)-λ 6 -sulfane, its NMR spectrum is as follows Figure 4-6 The specific data are as follows:
[0089] 1 H NMR(500MHz,Chloroform-d)δ7.90–7.78(m,4H),7.55–7.44(m,3H),5.10(t,J=5.1Hz ,1H),4.85(d,J=11.6Hz,1H),4.76(d,J=11.6Hz,1H),3.98–3.77(m,2H),3.44(s,3H).
[0090] 13 C NMR(126MHz,Chloroform-d)δ134.26,133.24,133.12,128.43,127.96,127.76, 126.77,126.19,125.70,98.56(p,J=5.3Hz),72.01(p,J=12.4Hz),69.23,53.93.
[0091] 19 F NMR (471MHz, Chloroform-d) δ87.25–80.86 (m), 68.01 (dt, J = 147.4, 8.3Hz).
[0092] Embodiment 13
[0093] A method for synthesizing pentafluorothioacetaldehyde The method of Example 1 is first carried out to obtain product 1, and then product 1 is added to 2 ml of trifluoroacetic acid and stirred for 12 hours. After the reaction is completed, it is neutralized with a saturated sodium carbonate solution to neutrality, and then extracted with dichloromethane to obtain a dichloromethane solution of pentafluorothioacetaldehyde.
[0094] Embodiment 14
[0095] A method for pentafluorosulfurization of olefin ethers using sulfur hexafluoride as a pentafluorosulfur source, which differs from Example 1 only in that 40.8 mg of 1-(2,2-dimethyl-3-(vinyloxy)propyl)-3-methylbenzene olefin ether is used in (1) to replace 26.8 mg of (vinyloxy)methylbenzene in Example 1, and the remaining steps are the same as those in Example 1.
[0096] Reaction results: 46% isolation yield, the substrate 4 (2-(2,2-dimethyl-3-(m-tolyl)propoxy)-2-methoxyethyl)pentafluoro-λ was obtained 6 -sulfane(2-(2,2-dimethyl-3-(m-tolyl)propoxy)-2-methoxyethyl)pentafluoro-λ 6 -sulfane, its NMR spectrum is as follows Figure 7-9 The specific data are as follows:
[0097] 1 H NMR (500 MHz, CDCl 3 )δ7.17(t,J=7.5Hz,1H),7.04(d,J=7.6Hz,1H),7.00–6.88(m,2H),4.92(t,J=5.0Hz,1H),3.82(pd,J=8.4,5. 0Hz, 2H), 3.42 (s, 3H), 3.33 (d, J = 8.5Hz, 1H), 3.11 (d, J = 8.5Hz, 1H), 2.62–2.50 (m, 2H), 0.92 (d, J = 5.8Hz, 6H).
[0098] 13 C NMR (126 MHz, CDCl 3 )δ138.58,137.40,131.51,127.80,127.74,126.86,99.43(p,J=5.0Hz),72.16(p,J=12.6Hz),54.21,44.92,35.63,24.69,24.53,21.52.
[0099] 19 F NMR (471 MHz, CDCl3 )δ85.39–82.15(m),67.86(dt,J=147.2,8.4Hz).
[0100] Comparative Example 2
[0101] Compared with the synthesis method and catalytic method of Qing Fengling's research group, this article uses α-diazocarbonyl compounds and pentafluorosulfuryl chloride reagents to construct pentafluorosulfur compounds. (Angew.Chem.Int.Ed.2021,60,15271–15275)
[0102] (1) Operation steps: In a glove box, add K 3 PO 4 (31.8 mg, 0.15 mmol), and then sealed with a lid. Then DCM (1 mL) and SF 5 Cl (0.15 M in n-hexane, 1 mL, 0.15 mmol) was added to the reaction mixture, followed by a solution of the diazo compound (0.1 mmol) in DCM (1 mL) and stirred for 3 hours. After the reaction was complete, the air in the vial was carefully evacuated with a needle. The solvent was removed in vacuo.
[0103] (2) Comparison: The fluorination reagents of the present invention are all sulfur hexafluoride, which is low in price, suitable for a variety of substrates, and the solvent is easy to separate. The α-diazocarbonyl compound used in the comparative example requires multi-step synthesis, and a large amount of toxic reagents and low temperatures of 0°C and -78°C are used in the synthesis process. The preparation is cumbersome, costly, and time-consuming. In addition, the reagent needs to be stored under nitrogen conditions, and the storage conditions are relatively harsh, which is not conducive to application.
[0104] Table 1
[0105]
[0106]
[0107] Comparative Example 3
[0108] The only difference from Example 1 is that allyl alcohol is used in (1) instead of the methanol in Example 1, and the remaining steps are the same as those in Example 1.
[0109] Reaction results: only trace fluorine spectrum yield, no related products were obtained.
[0110] Comparative Example 4
[0111] The only difference from Example 1 is that 3-butyn-1-ol is used in (1) to replace the methanol in Example 1, and the remaining steps are the same as those in Example 1.
[0112] Reaction results: Only a trace amount of fluorine spectrum yield was obtained, and no related products were obtained.
[0113] Comparative Example 5
[0114] The only difference from Example 1 is that in (1), a 460nm blue light wavelength is used instead of the 365nm light source wavelength in Example 1, and the remaining steps are the same as those in Example 1.
[0115] Reaction results: only trace fluorine spectrum yield, no related products were obtained.
[0116] Comparative Example 6
[0117] The only difference from Example 1 is that in (1), a 440nm blue light wavelength is used instead of the 365nm light source wavelength in Example 1, and the remaining steps are the same as those in Example 1.
[0118] Reaction results: only 6% fluorine spectrum yield was obtained.
[0119] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for pentafluorosulfurization of enethers using sulfur hexafluoride as a pentafluorosulfur source, characterized in that: The following steps are involved: A photocatalyst and an olefinic ether compound are placed in a reaction device, the air in the reaction device is replaced by sulfur hexafluoride gas, a solvent and methanol are added in the sulfur hexafluoride gas atmosphere, and the sealed reaction device is placed in a photoreactor for reaction to obtain an olefinic ether pentafluorosulfuration product; wherein the solvent is a mixture of one or more of isopropyl ether, DCE, acetonitrile, DCM, toluene, dioxane, 2-methyltetrahydrofuran, THF, PhCl, and MTBE; and during the reaction, the wavelength of the light source used is 355-375 nm.
2. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to claim 1, characterized in that: The olefin ether compound is (vinyloxy)methylbenzene 4-(vinyloxy)methyl-1,1-biphenyl 2-(Vinyloxy)methylnaphthalene Meiyan alcohol enether One of them.
3. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to claim 1, characterized in that: The photocatalyst is 10-phenylphenothiazine.
4. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to claim 1, characterized in that: The wavelength of the light source is 365 nm.
5. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to claim 1, characterized in that: The mass ratio of the photocatalyst to the olefinic ether compound is 11:25-42.
6. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to claim 1, characterized in that: The volume ratio of the solvent to methanol is 1:0.
8.
7. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to claim 1, characterized in that: The usage ratio of the olefin ether compound and methanol is 25-42 mg:0.8 ml.
8. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to claim 1, characterized in that: During the reaction, the power of the photoreactor was 10W.
9. The method for pentafluorosulfurization of enether using sulfur hexafluoride as a pentafluorosulfur source according to any one of claims 1 to 8, characterized in that: The reaction temperature is 20°C and the reaction time is 24 hours.
10. A pentafluorosulfurized compound, characterized in that: The invention is prepared by the pentafluorosulfurization method of enether using sulfur hexafluoride as a pentafluorosulfur source as described in any one of claims 1 to 9.
11. A method for synthesizing pentafluorothioacetaldehyde, characterized in that: The method comprises mixing the pentafluorothiolated compound as claimed in claim 10 with trifluoroacetic acid, stirring the mixture for reaction, and obtaining the pentafluorothioacetaldehyde after post-treatment.
12. The method for synthesizing pentafluorothioacetaldehyde according to claim 11, characterized in that: The usage ratio of the pentafluorosulfurized compound to trifluoroacetic acid is 0.2 mmol:1 ml.
13. Use of sulfur hexafluoride as a pentafluorosulfenyl source for pentafluorosulfenylation of ethers.