A method for producing a pentafluorosulfuryl chloride gas

Abstract

The application provides a method for preparing a five fluorine sulfur chloro gas, and in particular, provides a method for preparing SF5Cl, characterized in that the method comprises the following steps: reacting a sulfur source with trichloroisocyanuric acid in the presence of an N-methyl pyrrolidone substance to obtain SF5Cl. The method is characterized in that N-methyl pyrrolidone is used as a catalyst, and the five fluorine sulfur chloro gas can be prepared at room temperature at low cost and high efficiency.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of fluorine chemistry, in particular, the present application provides a method for synthesizing pentafluorosulfur chloride gas (SF5Cl). The method uses N-methyl pyrrolidone as a catalyst for the first time, uses a mild oxidation system, and can be prepared at room temperature with low cost and high efficiency. BACKGROUND

[0002] Due to the unique properties of fluorine element, fluorine-containing organic compounds have been widely used in the fields of clinical diagnosis, drugs, pesticides and herbicides, corrosion-resistant polymers, liquid crystals, surfactants, etc. A series of organic functional groups containing carbon-fluorine bonds, such as trifluoromethyl (-CF3), difluoromethyl (-CHF2), etc., all play an important role in fluorine-containing functional molecules. Compared with trifluoromethyl, the pentafluorosulfur functional group (-SF5) has stronger electronegativity, greater liposolubility, and better thermal stability and chemical stability, and is also known as "super trifluoromethyl". There are mainly two methods for synthesizing compounds containing pentafluorosulfur functional groups at present. One is to obtain by addition reaction of pentafluorosulfur chloride (SF5Cl) or pentafluorosulfur bromide (SF5Br) with carbon-carbon double bond / carbon-carbon triple bond (for example, U.S. Patent No. 6,919,484B2 and 6,958,415B2); the other is to obtain by reaction of benzenethiol with chlorine gas and potassium fluoride (for example, U.S. Patent No. 8,399,720B2).

[0003] As an important reagent for synthesizing pentafluorosulfur functional groups, the synthesis of pentafluorosulfur chloride gas (SF5Cl) is relatively difficult, which usually requires extremely strong oxidizing, highly toxic gas raw materials with great safety hazards, high reaction temperature or long reaction time, difficult operation and low reaction yield. For example, U.S. Patent No. 3,035,890 uses sulfur powder and chlorine trifluoride gas (ClF3) to react at a temperature not higher than 105℃ for 4 hours, but the yield is not provided; U.S. Patent No. 3,035,892 uses dichloride disulfide (S2Cl2) and fluorine gas to react at -80℃ to -20℃ for 5 hours, with a yield of 13%; U.S. Patent No. 3,359,081 uses sulfur tetrafluoride (SF4), chlorine gas and cesium fluoride to react at 100℃ to 150℃ for 6 hours, with a yield of 75%; U.S. Patent No. 4,082,839 uses sulfur tetrafluoride (SF4), chlorine gas and nitrosyl fluoride (NOF) to react at room temperature for 16 hours, but the yield is not provided; Patent No. WO 2009152385 A2 uses sulfur powder, chlorine gas, liquid bromine and potassium fluoride to react at room temperature for 5-14 days, with a yield of 95%; Patent No. WO 2019229103 A1 uses sulfur powder, trichloroisocyanuric acid, potassium fluoride in acetonitrile solvent under the catalysis of trifluoroacetic acid at room temperature for 14 hours, but the yield is not provided, and the repeated yield of the example is 5%.

[0004] In summary, there is still a lack of a method for preparing SF5Cl under mild conditions (such as room temperature) with cheap and readily available raw materials. SUMMARY

[0005] The present application discloses a method for preparing SF5Cl under mild conditions (room temperature) with cheap and readily available solid oxidant trichloroisocyanuric acid and readily available raw materials. The process is simple to operate, easy to scale up, and has high practical value.

[0006] In a first aspect, the present application provides a method for preparing SF5Cl, which comprises:

[0007] reacting a sulfur source with trichloroisocyanuric acid in the presence of a catalyst to obtain SF5Cl;

[0008] wherein the catalyst is a compound of general formula I:

[0009]

[0010] wherein R, R1and R2are each independently selected from the group consisting of H, substituted or unsubstituted C1-C6alkyl; or any two of R, R1and R2together with the atoms to which they are attached form a substituted or unsubstituted 4-8 membered non-aromatic ring; wherein the substitution means that one or more hydrogen atoms of the group are replaced by a substituent selected from the group consisting of =O, halogen, C1-C4alkyl; preferably, the catalyst is selected from the group consisting of DMF, N-methylpyrrolidone, 2-methylpyrrolidone, N-methylsuccinamide, N,N-dimethylacetamide.

[0011] In another preferred embodiment, the reaction is carried out under an inert atmosphere.

[0012] In another preferred embodiment, the reaction is carried out under a nitrogen atmosphere.

[0013] In another preferred embodiment, the reaction is carried out at room temperature.

[0014] In another preferred embodiment, the reaction time is 12-60h.

[0015] In another preferred embodiment, the catalyst is selected from the group consisting of N-methylpyrrolidone, 2-methylpyrrolidone, N-methylsuccinamide, N,N-dimethylformamide, N,N-dimethylacetamide; preferably, the catalyst is N-methylpyrrolidone.

[0016] In another preferred embodiment, the reaction is carried out in a closed reaction vessel; preferably, the closed reaction vessel is selected from the group consisting of a PFA reaction bottle, or a glass reaction bottle.

[0017] In another preferred embodiment, the method further comprises: collecting the product with a negative pressure receiving bottle in communication with the reaction vessel after the reaction is completed.

[0018] In another preferred embodiment, the reaction is carried out in the presence of an alkali metal fluoride salt.

[0019] In another preferred embodiment, the alkali metal fluoride salt is selected from the group consisting of NaF, KF, or a combination thereof.

[0020] In another preferred embodiment, the reaction is carried out in an inert solvent; preferably, the inert solvent is acetonitrile.

[0021] In another preferred embodiment, the sulfur source is selected from the group consisting of elemental sulfur, disulfur dichloride, or a combination thereof.

[0022] In another preferred embodiment, the molar ratio of the sulfur source to trichloroisocyanuric acid is 1:5-20.

[0023] In another preferred embodiment, when the sulfur source is elemental sulfur, the molar ratio of the sulfur source to trichloroisocyanuric acid is 1:8-12.

[0024] In another preferred embodiment, when the sulfur source is disulfur dichloride, the molar ratio of the sulfur source to trichloroisocyanuric acid is 1:16-20.

[0025] In another preferred embodiment, the molar ratio of the sulfur source to the catalyst is 1:0.2-2, preferably 1:0.4-1.2.

[0026] In another preferred embodiment, the molar ratio of the sulfur source to the alkali metal fluoride salt is 1:10-40.

[0027] In another preferred embodiment, the molar ratio of the sulfur source to the alkali metal fluoride salt is 1:12-20.

[0028] In another preferred embodiment, the molar ratio of the sulfur source to the alkali metal fluoride salt is 1:25-35.

[0029] In another preferred embodiment, the reaction temperature is -20°C to 60°C; preferably, the reaction temperature is 0°C to 25°C.

[0030] It should be understood that, within the scope of the present application, each of the technical features described above and each of the technical features described in detail below (e.g., in the examples) can be combined with each other to form new or preferred technical solutions. Due to the limited space, they will not be listed one by one here. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 A schematic diagram of a SF5Cl receiving device under the method of the present application is shown. Detailed Implementation

[0032] Through long-term and in-depth research, the inventors discovered that using N-methylpyrrolidone as a catalyst in the reaction of sulfur source and trichloroisocyanuric acid can greatly promote the chlorination effect of trichloroisocyanuric acid in the reaction system. Based on the above discovery, the inventors completed this invention.

[0033] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

[0034] Experimental apparatus:

[0035] 1 The H NMR spectrum was determined using an Agilent-400 (400MHz) nuclear magnetic resonance spectrometer. 1 The internal standard for H NMR is TMS (δ 0.00) or CDCl3 (δ 7.26).

[0036] 13 The C NMR spectra were determined using a Bruker AM-400 (100.7 MHz) nuclear magnetic resonance spectrometer. 13 The internal standards for C NMR were CDCl3 (δ77.16), DMSO-d6 (δ39.52), CD3CN (δ1.32), and (CD3)2CO (δ29.84, 206.26).

[0037] 19 The F NMR spectrum was determined using an Agilent-400 (376MHz) nuclear magnetic resonance spectrometer. 19 The internal standard for F NMR is FCCl3 (δ 0.00), and the low field is positive.

[0038] LC-MS (ESI) spectra were determined using a Waters ACQUITY UPLC H-Class system and an ACQUITY QDa mass detector (eluent: 0.1% trifluoroacetic acid in water and acetonitrile). [Method: 7000 psi, flow rate = 0.6 ml / min. t = 0 min, 95% H2O; t = 0.10 min, 95% H2O; t = 1.20 min, 5% H2O; t = 2.00 min, 5% H2O; t = 2.50 min, 95% H2O. Total acquisition time = 2.50 min.] The spectra shown in the examples are UV absorption chromatograms, for which the corresponding mass spectra are not shown. The horizontal axis of the chromatograms is time (in min), and the vertical axis is absorption intensity. The three-digit number in the upper right corner of the chromatogram is the selected UV wavelength (in nm).

[0039] HRMS spectra were determined using a Finnigan MAT 8430 mass spectrometer.

[0040] Melting points were determined using a Bϋchi M-565 melting point apparatus.

[0041] Column chromatography used silica gel (300-400 mesh or 100-200 mesh) produced by Yantai Jiangyou Silica Gel Development Co., Ltd., and thin layer chromatography plates were produced by Yantai Jiangyou Silica Gel Development Co., Ltd., and the developing agents were ZF-7A portable UV detector, iodine tank, and alkaline potassium permanganate solution.

[0042] The reagents used were purchased from Wuhan Pharm Link Chemicals Co., Ltd., Shanghai Aladdin Bio-Chem Technology Co., Ltd. (Aladdin), TCI (Shanghai) Development Co., Ltd. (TCI), Shanghai Macklin Biochemical Technology Co., Ltd. (Macklin), Energy Chemical (Shanghai) Co., Ltd. (Energy Chemical), Alfa Aesar (China) Chemical Co., Ltd. (Alfa Aesar), Adamas, Shanghai Bide Pharmaceutical Technology Co., Ltd., Shanghai Tianlian Chemical Technology Co., Ltd., Shanghai Lingfeng Chemical Co., Ltd., and Shanghai Reagent Three Factory.

[0043] The solvents were purchased from Shanghai Macklin Biochemical Technology Co., Ltd. (Macklin) and Adamas, Shanghai Lingfeng Chemical Co., Ltd. without additional treatment and were used directly after purchase.

[0044] In the embodiments of the present application, the TCCA is trichloroisocyanuric acid, the NMP is N-methylpyrrolidone, the DMF is N,N-dimethylformamide, the DMAC is N,N-dimethylacetamide, and the DMSO is dimethyl sulfoxide.

[0045] Example 1:

[0046]

[0047] Spray-dried powdered potassium fluoride (40 mmol, 2.35 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 mL PFA reaction flask (A). Fine-grained sulfur (2.5 mmol, 80 mg) and trichloroisocyanuric acid (22.5 mmol, 5.2 g) were then added to the PFA reaction flask, which was capped with a rubber septum (Xinniwe RS121922). The system was purged with nitrogen three times, then evacuated to a negative pressure. Anhydrous acetonitrile (water content < 50 ppm, 12 mL) and trifluoroacetic acid (0.125 mmol, 14 mg dissolved in 0.5 mL of anhydrous acetonitrile) were added sequentially using a syringe at room temperature. The reaction was stirred at room temperature for 14 h.

[0048] After the reaction was stopped, CFCl3 internal standard and trifluoromethyltoluene internal standard (0.167 mmol) were added to the reaction system, and a sample was taken 19 F-NMR tracking showed that the amount of SF5Cl in the reaction solution was 0.125 mmol by fluorine spectrum integration, and the yield was 5%. 19 F-NMR (376 MHz): δ = 125.4 (4F, d, J = 150.4 Hz), 65.2 (1F, p, J = 150.4 Hz).

[0049] Example 2:

[0050]

[0051] Spray-dried powdered potassium fluoride (160 mmol, 9.3 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 250 mL PFA reaction flask (A). Fine-grained sulfur (10 mmol, 320 mg) and trichloroisocyanuric acid (90 mmol, 20.8 g) were then added to the PFA reaction flask, which was capped with a rubber septum. The system was purged with nitrogen three times, then evacuated to a negative pressure. Anhydrous acetonitrile (water content < 50 ppm, 48 mL) and trifluoroacetic acid (0.5 mmol, 57 mg dissolved in 2 mL of anhydrous acetonitrile) were added sequentially using a syringe at room temperature. The reaction was stirred at room temperature for 60 h.

[0052] After the reaction was stopped, CFCl3 internal standard and trifluoromethyltoluene internal standard (0.167 mmol) were added to the reaction system, and a sample was taken Figure 1The PFA reaction flask (A) was connected to a glass reaction receiving flask (B). Stopcock X was closed and the glass reaction receiving flask (B) was evacuated to negative pressure and cooled to -78°C in a dry ice-acetone bath. Stopcock X was then opened and the PFA reaction flask (A) was connected to the glass reaction receiving flask (B) and the gaseous product from the reaction flask (A) was frozen into the receiving flask (B) for 30 minutes. Stopcock X was closed again and 10 ml of super-dry acetonitrile was added to the receiving flask (B) and the crude product was dissolved in acetonitrile. The solution was allowed to warm to room temperature and 0.5 ml of the solution was taken and CFCl3 internal standard and 4-methylbenzenesulfonyl fluoride internal standard (0.025 mmol, 4.4 mg) were added, 19 F-NMR tracking gave a solution of SF5Cl of 0.6 mmol by fluorine spectrum integration. Yield: 6%. 19 F-NMR (376 MHz): δ = 125.4 (4F, d, J = 150.4 Hz), 65.2 (IF, p, J = 150.4 Hz).

[0053] Example 3:

[0054]

[0055] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200°C for 6 hours. After cooling to room temperature, the potassium fluoride was transferred to a 100 ml PFA reaction flask (A). Fine-grained sulphur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber bung. The system was evacuated and replaced with nitrogen three times, then evacuated to negative pressure. Super-dry acetonitrile (25 ml, water content < 50 ppm) was added at room temperature using a syringe and the reaction stirred at room temperature for 48 hours.

[0056] After the reaction was stopped, the gaseous product was frozen into the receiving flask (B) as described in [Example 2]. 10 ml of super-dry acetonitrile was added to the receiving flask (B) and the crude product was dissolved in acetonitrile. 0.5 ml of the solution was taken and CFCl3 internal standard and 4-methylbenzenesulfonyl fluoride internal standard (0.025 mmol, 4.4 mg) were added, 19 F-NMR tracking gave a solution of SF5Cl of 0.6 mmol by fluorine spectrum integration. Yield: 6%. 19 F-NMR (376 MHz): δ = 125.4 (4F, d, J = 150.4 Hz), 65.2 (IF, p, J = 150.4 Hz).

[0057] Example 4:

[0058]

[0059] Spray dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 ml PFA reaction flask (A). Fine grained sulphur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber bung. The system was purged with nitrogen three times, then the system was evacuated to a negative pressure and dry acetonitrile (25 ml, <50 ppm water) and N-methylpyrrolidone (2.5 mmol, 240 μΐ^) were added sequentially using a syringe at room temperature. The reaction was stirred at room temperature for 48 h.

[0060] The gaseous product was frozen into a receiving flask (B) following the procedure outlined in [Example 2]. To the receiving flask (B) was added 20 ml of dry acetonitrile and the crude product was dissolved in acetonitrile solution. 0.5 ml of the solution was taken and CFCl3 internal standard and 4-methylbenzenesulfonyl fluoride internal standard (0.025 mmol, 4.4 mg) were added, 19 F-NMR tracking gave a solution of SF5CI of 1.5 mmol by fluorine spectrum integration, yield: 30%. 19 F-NMR (376 MHz): δ = 125.4 (4F, d, J = 150.4 Hz), 65.2 (1F, p, J = 150.4 Hz).

[0061] Example 5:

[0062]

[0063] Spray dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 ml PFA reaction flask (A). Fine grained sulphur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber bung. The system was purged with nitrogen three times, then the system was evacuated to a negative pressure and dry acetonitrile (25 ml, <50 ppm water), TFA (0.5 mmol, 38 uL) and N-methylpyrrolidone (2.5 mmol, 240 μΐ^) were added sequentially using a syringe at room temperature. The reaction was stirred at room temperature for 48 h.

[0064] The gaseous product was frozen into a receiving flask (B) following the procedure outlined in [Example 2]. To the receiving flask (B) was added 20 ml of dry acetonitrile and the crude product was dissolved in acetonitrile solution. 0.5 ml of the solution was taken and CFCl3 internal standard and 4-methylbenzenesulfonyl fluoride internal standard (0.025 mmol, 4.4 mg) were added, 19F-NMR tracking, the amount of SF5Cl in solution was determined by fluorine spectrum integration to be 1.7 mmol, yield: 34%. 19 F-NMR (376 MHz): δ = 125.4 (4F, d, J = 150.4 Hz), 65.2 (IF, p, J = 150.4 Hz).

[0065] Example 6:

[0066]

[0067] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 ml PFA reaction flask. Fine-grained sulfur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber septum. The system was purged with nitrogen three times, then the system was evacuated to a negative pressure, and anhydrous acetonitrile (25 ml, water content < 50 ppm) and DMF (2.5 mmol, 193 μΐ^) were added sequentially at room temperature using a syringe. The reaction was stirred at room temperature for 48 h.

[0068] The gas product was condensed into a receiving flask (B) according to the procedure in [Example 2]. To the receiving flask (B) was added 20 ml of anhydrous acetonitrile, and the crude product was dissolved in acetonitrile solution. 0.5 ml of the solution was taken, and CFCl3 internal standard and 4-methylbenzenesulfonyl fluoride internal standard (0.025 mmol, 4.4 mg) were added, 19 F-NMR tracking, the amount of SF5Cl in solution was determined by fluorine spectrum integration to be 0.4 mmol, yield: 8%. 19 F-NMR (376 MHz): δ = 125.4 (4F, d, J = 150.4 Hz), 65.2 (IF, p, J = 150.4 Hz).

[0069] Example 7:

[0070]

[0071] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 hours. After returning to room temperature, the potassium fluoride was transferred to a 100 mL PFA reaction flask. Then, finely granulated sublimed sulfur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were added to the PFA reaction flask, and the flask was sealed with a rubber stopper. The system was purged with nitrogen three times, and then the system was evacuated to negative pressure. At room temperature, ultra-dry acetonitrile (25 mL, water content <50 ppm) and DMSO (2.5 mmol, 177 μL) were added sequentially using a syringe, and the reaction was stirred at room temperature for 48 hours.

[0072] After the reaction was stopped, CFCl3 internal standard was added to the reaction system. 19 F-NMR tracing of the reaction showed that no SF5Cl product was formed, yield: 0%.

[0073] Example 8:

[0074]

[0075] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 hours. After returning to room temperature, the potassium fluoride was transferred to a 100 mL PFA reaction flask (A). Then, finely granulated sublimed sulfur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were added to the PFA reaction flask, and the flask was sealed with a rubber stopper. The system was purged with nitrogen three times, and then the system was evacuated to negative pressure. At room temperature, ultra-dry acetonitrile (25 mL, water content <50 ppm) and N-methylpyrrolidone (2.5 mmol, 240 μL) were added sequentially using a syringe, and the reaction was stirred at room temperature for 48 hours.

[0076] Following the procedure in [Example 2], the gaseous product was frozen into receiving flask (B). 20 ml of ultra-dry acetonitrile was added to receiving flask (B) to dissolve the crude product into an acetonitrile solution. 0.5 ml of the solution was taken, and CFCl3 internal standard and 4-methylbenzenesulfonyl fluoride internal standard (0.025 mmol, 4.4 mg) were added. 19 F-NMR tracing and fluorine spectrum integration determined the amount of SF5Cl in the solution to be 1.5 mmol, yield: 30%. 19 F-NMR (376MHz): δ=125.4 (4F, d, J=150.4Hz), 65.2 (1F, p, J=150.4Hz).

[0077] Example 9:

[0078]

[0079] Spray dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 ml PFA reaction flask (A). Fine grained sulphur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber bung. The system was purged with nitrogen three times, then evacuated to a negative pressure. Anhydrous acetonitrile (25 ml, water content < 50 ppm) and 2-pyrrolidinone (2.5 mmol, 190 μL) were added sequentially using a syringe at room temperature. The reaction was stirred at room temperature for 48 h.

[0080] The gaseous product was condensed into a receiving flask (B) as described in [Example 2]. To the receiving flask (B) was added 20 ml of anhydrous dichloromethane and the crude product was dissolved in dichloromethane. A 0.5 ml aliquot of the solution was added to a solution of a CFCl3 internal standard and 4-methylbenzenesulphonyl fluoride internal standard (0.025 mmol, 4.4 mg), 19 F-NMR tracking gave a solution of SF5Cl of 0.4 mmol by fluorine spectrum integration. Yield: 8%. 19 F-NMR (376 MHz): δ = 125.4 (4F, d, J = 150.4 Hz), 65.2 (IF, p, J = 150.4 Hz).

[0081] Example 10:

[0082]

[0083] Spray dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 ml PFA reaction flask (A). Fine grained sulphur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber bung. The system was purged with nitrogen three times, then evacuated to a negative pressure. Anhydrous acetonitrile (25 ml, water content < 50 ppm) and N-methylsuccinamide (2.5 mmol, 283 mg dissolved in 1 ml of anhydrous acetonitrile) were added sequentially using a syringe at room temperature. The reaction was stirred at room temperature for 48 h.

[0084] The gaseous product was condensed into a receiving flask (B) as described in [Example 2]. To the receiving flask (B) was added 20 ml of anhydrous dichloromethane and the crude product was dissolved in dichloromethane. A 0.5 ml aliquot of the solution was added to a solution of a CFCl3 internal standard and 4-methylbenzenesulphonyl fluoride internal standard (0.025 mmol, 4.4 mg), 19F-NMR tracking, the amount of SF5Cl in solution was determined by fluorine spectrum integration to be 0.4 mmol, yield: 8%. 19 F-NMR (376 MHz): δ = 126.0 (4F, d, J = 150.4 Hz), 64.5 (IF, p, J = 150.4 Hz).

[0085] Example 11:

[0086]

[0087] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h, after which the potassium fluoride was transferred to a 100 ml PFA reaction flask (A). Fine-grained sublimed sulfur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber bung. The system was purged with nitrogen three times, after which the system was evacuated to a negative pressure and dry acetonitrile (25 ml, <50 ppm water content) and N,N-dimethylacetamide (2.5 mmol, 240 μΐ^) were added via syringe under ice-water cooling. The reaction was stirred for 1 h under ice-water cooling, after which the cooling bath was removed and the reaction was stirred at room temperature for 47 h.

[0088] The gas product was condensed into a receiving flask (B) according to the procedure in [Example 2]. To the receiving flask (B) was added 20 ml of dry n-hexane and the crude product was dissolved in n-hexane solution. 0.5 ml of the solution was taken and added to a trifluoromethylbenzene internal standard (0.1 mmol, 12.5 μΐ^), 19 F-NMR tracking, the amount of SF5Cl in solution was determined by fluorine spectrum integration to be 1.2 mmol, yield: 24%. 19 F-NMR (376 MHz): δ = 125.6 (4F, d, J = 150.4 Hz), 63.9 (IF, p, J = 150.4 Hz).

[0089] Example 12:

[0090]

[0091] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 mL PFA reaction flask (A). Fine-grained sulfur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was capped with a rubber septum. The system was purged with nitrogen three times, then evacuated to a negative pressure, and dry acetonitrile (25 mL, <50 ppm water) and N-methylpyrrolidone (2.5 mmol, 240 μί) were added sequentially via syringe while the system was cooled in an ice-water bath. The reaction was stirred for 1 h in the ice-water bath, then the cold bath was removed and the reaction was stirred at room temperature for 47 h.

[0092] The gaseous product was condensed into a receiving flask (B) according to the procedure described in [Example 2]. To the receiving flask (B) was added 20 mL of dry n-hexane and the crude product was dissolved in n-hexane. A 0.5 mL aliquot of the solution was taken and a trifluoromethylbenzene internal standard (0.1 mmol, 12.5 μί) was added, 19 F-NMR tracking determined that there was 2 mmol of SF5CI in solution by fluorine spectral integration. Yield: 40%. 19 F-NMR (376 MHz): δ = 125.6 (4F, d, J = 150.4 Hz), 63.9 (1F, p, J = 150.4 Hz).

[0093] Example 13:

[0094]

[0095] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 100 mL PFA reaction flask (A). Fine-grained sulfur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was capped with a rubber septum. The system was purged with nitrogen three times, then evacuated to a negative pressure, and dry acetonitrile (40 mL, <50 ppm water) and N-methylpyrrolidone (5 mmol, 480 μί) were added sequentially via syringe while the system was cooled in an ice-water bath. The reaction was stirred for 1 h in the ice-water bath, then the cold bath was removed and the reaction was stirred at room temperature for 47 h.

[0096] The gaseous product was condensed into a receiving flask (B) according to the procedure described in [Example 2]. To the receiving flask (B) was added 20 mL of dry n-hexane and the crude product was dissolved in n-hexane. A 0.5 mL aliquot of the solution was taken and a trifluoromethylbenzene internal standard (0.1 mmol, 12.5 μί) was added, 19F-NMR tracking, the amount of SF5Cl in solution was determined by fluorine spectrum integration to be 1.57 mmol, yield: 31%. 19 F-NMR (376 MHz): δ = 125.6 (4F, d, J = 150.4 Hz), 63.9 (1F, p, J = 150.4 Hz).

[0097] Example 14:

[0098]

[0099] Spray-dried powdered potassium fluoride (80 mmol, 4.7 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h, after which the potassium fluoride was transferred to a 100 ml PFA reaction flask (A). Fine-grained sublimed sulfur (5 mmol, 160 mg) and trichloroisocyanuric acid (45 mmol, 10.4 g) were then added to the PFA reaction flask, which was sealed with a rubber bung. The system was purged with nitrogen three times, after which the system was evacuated to a negative pressure and dry acetonitrile (40 ml, <50 ppm water content) and N-methylpyrrolidine (2.5 mmol, 240 μΐ^) were added sequentially using a syringe while the system was cooled in an ice-water bath. The reaction was stirred for 1 h in an ice-water bath, after which the cooling bath was removed and the reaction was stirred at room temperature for 47 h.

[0100] The gas product was condensed into a receiving flask (B) by reference to the procedure in [Example 2]. To the receiving flask (B) was added 20 ml of dry n-hexane and the crude product was dissolved in n-hexane solution. 0.5 ml of the solution was taken and added to a trifluoromethylbenzene internal standard (0.1 mmol, 12.5 μΐ^), 19 F-NMR tracking, the amount of SF5Cl in solution was determined by fluorine spectrum integration to be 3 mmol, yield: 60%. 19 F-NMR (376 MHz): δ = 125.6 (4F, d, J = 150.4 Hz), 63.9 (1F, p, J = 150.4 Hz).

[0101] Example 15:

[0102]

[0103] Spray-dried powdered potassium fluoride (160 mmol, 9.3 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 250 mL glass reaction flask (A). Fine-grained sublimed sulfur (10 mmol, 320 mg) and trichloroisocyanuric acid (90 mmol, 20.8 g) were then added to the glass reaction flask, which was capped with a rubber septum. The system was purged with nitrogen three times, then evacuated to a negative pressure, and anhydrous acetonitrile (80 mL, <50 ppm water) and N-methylpyrrolidone (5 mmol, 480 μί) were added sequentially via syringe while the system was cooled in an ice-water bath. The reaction was stirred in the ice-water bath for 1 h, then the cold bath was removed and the reaction was stirred at room temperature for 47 h.

[0104] The gaseous product was condensed into a receiving flask (B) according to the procedure in [Example 2]. To the receiving flask (B) was added 50 mL of anhydrous n-hexane and the crude product was dissolved in n-hexane. A 0.5 mL aliquot of the solution was taken and added to a solution of the trifluoromethylbenzene internal standard (0.1 mmol, 12.5 μί), 19 F-NMR tracking determined that there was 6.6 mmol of SF5CI in solution by fluorine spectral integration, yield: 66%. 19 F-NMR (376 MHz): δ = 125.6 (4F, d, J = 150.4 Hz), 63.9 (1F, p, J = 150.4 Hz).

[0105] Example 16:

[0106]

[0107] Spray-dried powdered potassium fluoride (320 mmol, 18.6 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 500 mL PFA reaction flask (A). Trichloroisocyanuric acid (180 mmol, 41.6 g) was then added to the PFA reaction flask, which was capped with a rubber septum. The system was purged with nitrogen three times, then evacuated to a negative pressure, and anhydrous acetonitrile (160 mL, <50 ppm water) was added via syringe while the system was cooled in an ice-water bath. Then, dithium dichloride (10 mmol, 800 μί) and N-methylpyrrolidone (10 mmol, 960 μί) were added sequentially via syringe. The reaction was stirred in the ice-water bath for 1 h, then the cold bath was removed and the reaction was stirred at room temperature for 47 h.

[0108] The gaseous product was condensed into a receiving flask (B) according to the procedure in [Example 2]. To the receiving flask (B) was added 50 mL of anhydrous n-hexane and the crude product was dissolved in n-hexane. A 0.5 mL aliquot of the solution was taken and added to a solution of the trifluoromethylbenzene internal standard (0.1 mmol, 12.5 μί), 19F-NMR tracking determined that 0.6 mmol of SF5Cl remained in the mother liquor, combined yield: 10.8 mmol, yield: 54%. 19 F-NMR tracking determined that 0.6 mmol of SF5Cl remained in the mother liquor, combined yield: 10.8 mmol, yield: 54%. 19 F-NMR (376 MHz): δ = 125.6 (4F, d, J = 150.4 Hz), 63.9 (IF, p, J = 150.4 Hz).

[0109] Example 17:

[0110]

[0111] Spray-dried powdered potassium fluoride (320 mmol, 18.6 g) was dried under vacuum (1-2 torr) at 200 °C for 6 h. After cooling to room temperature, the potassium fluoride was transferred to a 500 ml PFA reaction flask (A). Trichloroisocyanuric acid (180 mmol, 41.6 g) was then added to the PFA reaction flask, which was sealed with a rubber bung. The system was purged with nitrogen three times, then evacuated to a negative pressure and dry acetonitrile (140 ml, <50 ppm water content) was added using a syringe under an ice-water bath. The reaction was stirred for 20 min. Subsequently, a solution of disulfur dichloride (10 mmol, 800 μΐ^) in 20 ml dry acetonitrile was added using a syringe (added over 3 min at a rate of 7 ml / min) followed by N-methylpyrrolidine (10 mmol, 960 μΐ^). The reaction was stirred for 30 min under an ice-water bath, then the cold bath was removed and the reaction was stirred at room temperature for 47 h.

[0112] The gaseous product was condensed into a receiving flask (B) according to the procedure described in [Example 2]. To the receiving flask (B) was added 50 ml dry n-hexane and the crude product was dissolved in n-hexane. A 0.5 ml solution was taken and a trifluoromethylbenzene internal standard (0.1 mmol, 12.5 μΐ^) was added, 19 F-NMR tracking determined that 0.6 mmol of SF5Cl remained in the mother liquor, combined yield: 10.8 mmol, yield: 54%. 19 F-NMR (376 MHz): δ = 125.6 (4F, d, J = 150.4 Hz), 63.9 (IF, p, J = 150.4 Hz).

[0113] All documents referred to in the present application are incorporated herein by reference as if each were individually incorporated. In addition, it is to be understood that the application can be carried out by specifically different embodiments and that each disclosed embodiment can be implemented with or without the corresponding use of the other embodiments. Other embodiments will occur to those skilled in the art upon consideration of this disclosure or can be learned from practice of the application. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, and all changes coming within the meaning and equivalency range of the appended claims are intended to be embraced therein.

Claims

1. A method for preparing SF5Cl, characterized in that, The method includes: SF5Cl was obtained by reacting a sulfur source with trichloroisocyanuric acid in the presence of a catalyst. The catalyst is selected from the group consisting of N-methylpyrrolidone, 2-methylpyrrolidone, N-methylsuccinamide, N,N-dimethylformamide, and N,N-dimethylacetamide; and the reaction is carried out in the presence of an alkali metal fluoride salt; the sulfur source is selected from the group consisting of elemental sulfur, disulfur dichloride, or a combination thereof.

2. The method as described in claim 1, characterized in that, The catalyst is N-methylpyrrolidone.

3. The method as described in claim 1, characterized in that, The reaction is carried out in a closed reaction vessel.

4. The method as described in claim 3, characterized in that, The sealed reaction vessel is selected from the following group: PFA reaction flask or glass reaction flask.

5. The method as described in claim 1, characterized in that, The method further includes collecting the product using a negative pressure receiving bottle connected to the reaction vessel after the reaction is completed.

6. The method as described in claim 1, characterized in that, The alkali metal fluoride salts mentioned are selected from the group consisting of NaF, KF, or combinations thereof.

7. The method as described in claim 1, characterized in that, The reaction is carried out in an inert solvent.

8. The method as described in claim 7, characterized in that, The inert solvent is acetonitrile.

9. The method as described in claim 1, characterized in that, The molar ratio of the sulfur source to trichloroisocyanuric acid is 1:5-20.

10. The method as described in claim 1, characterized in that, The molar ratio of the sulfur source to the catalyst is 1:0.2-2.

11. The method as described in claim 1, characterized in that, The molar ratio of the sulfur source to the catalyst is 1:0.4-1.2.

Images