| 95% |
With sulfuryl dichloride; acetic acid at -20℃; for 3h; |
|
| 92% |
With sulfuryl dichloride; acetic acid at -40 - 35℃; for 5h; |
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| 86.6% |
With sulfuryl dichloride; acetic acid at -20 - 35℃; for 2.5h; |
1
Step 1 : A solution of 1,2-dimethyldisulfane (79.6 g, 75 ml, 846 mmol, Eq: 1.00) in acetic acid (102 g, 96.7 ml, 1.69 mol, Eq: 2) was cooled to -20° C (mixture solidified), start dropwise addition of sulfuryl dichloride (354 g, 212 ml, 2.62 mol, Eq: 3.1) (after 1-2 ml it forms an orange solution). After complete addition stirring was continued at -20 °C for 1.5 h. Removed the cooling bath and let the reaction reach ambient temperature (gas evolution). Stirring was continued at 35 °C for 1 h. Removed the acetyl chloride at 40 °C and 150 mbar at the rotary evaporator and the residue was purified by distillation (bp. 55 °C at 53 mbar) to give the methanesulfinic chloride (144.3 g, 1.46 mol, 86.6 % yield) as a light yellow liquid. |
| 79% |
With sulfuryl dichloride; acetic acid; sodium hydroxide In water at -20℃; Schlenk technique; |
Step 1: Synthesis of Methylsulfinyl chloride (34)
A Schlenk flask equipped with a dropping funnel and connected to a gas washing bottle filled with aconcentrated aqueous solution of sodium hydroxide was charged with dimethyl disulfide (5.3 mL,60 mmol) and glacial acetic acid (6.9 mL, 120 mmol), and the mixture was cooled at -20 °C and stirredvigorously. Sulfuryl chloride (freshly distilled, 15.1 mL, 186 mmol) was added dropwise at thistemperature over a period of 20 min (strong gas evolution),13 and the mixture was stirred at -20 °C overnight.14 The mixture was warmed at room temperature, and stirred at this temperature for 2 h (gasevolution). The Schlenk flask was purged with nitrogen gas for 20 min,15 and the mixture wasconcentrated at 40 °C under reduced pressure (200 mbar). The residue was purified by fractionaldistillation (micro distillation apparatus with a Vigreux column). Yield: 9.39 g (79%). |
| 77.8% |
With sulfuryl dichloride; acetic acid In dichloromethane at -25 - 20℃; Inert atmosphere; |
1.1.2.1 (1) Preparation of Compound HS-A
Dimethyl disulfide (228 g), acetic acid (290 g), dichloromethane (1140 mL) were sequentially added to a 3 L reaction flask, and the mixture was evaporated. The internal temperature of the reaction liquid is about -25 °C, and the tail gas absorption device (absorption of alkali liquid) is connected, and sulfuryl chloride (1012 g) is added dropwise to the reaction system. At the end of 2.5 hours, the stirring was continued for 2 hours. The temperature was raised and stirred at room temperature overnight. The dichloromethane and the by-product acetyl chloride in the reaction liquid were distilled off with a water pump to obtain a yellow transparent concentrate. The concentrate was distilled under reduced pressure with a water pump to obtain 371.1 g of a yellow transparent liquid, yield 77.8%. |
| 48% |
With sulfuryl dichloride; acetic acid at -20 - 35℃; for 3.5h; |
13.1 Step 1: Methanesulfinic Chloride 13b
The compound 204 1,2-dimethyldisulfane (3.4 g, 36 mmol) was dissolved in 11 acetic acid (4.34 g, 72 mmol), and then 205 sulfonyl chloride (14.6 g, 108 mmol) was slowly added dropwise at -20° C. The reaction solution was stirred at -20° C. for 30 minutes, and slowly warmed up to room temperature and stirred for 2 hours, and then at 35° C. for another 1 hour. The mixture was concentrated in vacuo to remove volatile components and to obtain 206 methanesulfinic chloride 13b (6 g), yield 48%. |
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With chlorine; acetic acid at 0℃; |
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With chlorine; acetic acid In dichloromethane |
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With acetic anhydride; chlorine In dichloromethane |
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With chlorine; acetic acid at -15 - -10℃; |
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With acetic anhydride; chlorine |
|
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With chlorinating agent In acetic anhydride at -10℃; |
|
| 100 % Spectr. |
With sulfuryl dichloride; trimethylsilyl acetate at 0 - 20℃; for 0.5h; |
|
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With sulfuryl dichloride; acetic anhydride |
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With sulfuryl dichloride; acetic acid at -40 - 35℃; |
|
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With sulfuryl dichloride; acetic acid |
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With sulfuryl dichloride; acetic acid at -20 - 20℃; for 3h; Inert atmosphere; |
1.1 Synthesis of 3: (Step 1 & 2)
Dimethyldisulfide 1 (5 g, 53 mmol) and acetic acid (6 mL, 106 mmol) weremixed under nitrogen atmosphere and cooled to- 20 °C. Sulfuryl chloride (13 mL, 159 mmol)was added dropwise with stirring. The mixture was then stirred for 1 hour at -20 °C andafterwards allowed to come to room temperature and continued for another two hours. Acetylchloride was distilled off from the reaction mixture. Crude methanesulfinyl chloride 2 obtained20 was used in the next step without further purification. To a solution of chloramine T (14.95 g, 53 mmol) in dry toluene (220 mL) wasadded a solution ofmethanesulfinyl chloride 2 (5.2 g, 53 mmol) in dry toluene (10 mL) at 0 °C.The resulting suspension was heated at 80 oc for 2 hours with stirring. After cooling, the solidwas filtered off and washed with dry toluene (1 00 mL ). The filtrate was evaporated in vacuo and25 the crude mixture was purified through silica gel chromatography to obtain 3 as off white solid.1H NMR (300 MHz, CDCh): o 7.85- 7.91 (m, J = 8.42 Hz, 2H), 7.31- 7.38 (m, J = 8.23 Hz,2H), 3.78 (s, 3H), 2.45 (s, 3H). |
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With sulfuryl dichloride; acetic acid at -20 - 25℃; for 3h; |
A.2 Scheme A
Step 2: To a mixture of dimethyldisulfide (10 g, 106 mmol) and acetic acid (12 mL, 212 mmol) at -20 °C was added sulfuryl chloride (26 mL, 318 mmol) dropwise. The mixture was stirred at -20 °C for 1 h then warmed to room temperature and stirred for an additional 2 h. The volitiles were removed by distillation to afford methanesulfmyl chloride A4 which was taken to the next step without further purification. |
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With sulfuryl dichloride; acetic acid at -20 - 20℃; for 2.5h; Inert atmosphere; |
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With sulfuryl dichloride; acetic acid at -20 - 20℃; for 3h; Inert atmosphere; |
10.1 methanesulfinic chloride
To a stirred solution of 1,2-dimethyldisulfane (5.4 g, 57.3 mmol) in acetic acid (6.5 mL) was added sulfuryl dichloride (14.07 ml, 172 mmol) dropwise at -20 °C under N2 atmosphere. After the addition was finished, the reaction was stirred at -20 °C for 1 h, warmed to RT, and stirred for another 2 h. Then acetyl chloride was distilled off from the reaction mixture to afford the crude title compound (4.9 g, 49.7 mmol), which was used in the next step without further purification. |
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With sulfuryl dichloride; acetic acid at -20 - 20℃; for 5h; |
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| 20.5 g |
With sulfuryl dichloride; acetic acid at -20 - 20℃; for 3h; |
5.A Step A:
Preparation of N-[(4-methylphenyl)sulfonyl]methanesulfonimidoyl chloride
To a solution of dimethyl disulfide (20 g, 212 mmol) in acetic acid (25 ml), at -20° C. was added sulfuryl chloride (51.5 ml, 638 mmol) dropwise. The reaction mixture was stirred at -20° C. for 1 h, warmed to room temperature and stirred for 2 h. The reaction mixture was concentrated under reduced pressure to provide the intermediate compound methanesulfinyl chloride as a pale-yellow oil (20.5 g). |
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With sulfuryl dichloride; acetic acid at -20 - 20℃; for 2.5h; Inert atmosphere; |
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With sulfuryl dichloride; acetic acid at -20 - 35℃; for 6.5h; |
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With sulfuryl dichloride; acetic acid at -20 - 35℃; for 4h; |
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