反応 #168263

反応方程式

cyclobutylmethanol

(S)-2-methylpropane-2-sulfinamide

cyclobutanecarbaldehyde

Dess-Martin periodinane

→

(S)—N-[(1E)-cyclobutylmethylidene]-2-methylpropane-2-sulfinamide

溶媒

dichloromethane

—

petroleum ether

—

petroleum ether

dichloromethane

反応条件

後処理

1. 1
   その他Into a 20-L 4-necked round-bottom flask was placed
2. 2
   その他quenched by the addition of 20 L of cold, saturated aqueous sodium bicarbonate solution
3. 3
   その他Solids were removed by filtration
4. 4
   洗浄washed with 5 L of dichloromethane
5. 5
   抽出The filtrate was extracted with dichloromethane
6. 6
   乾燥dried over anhydrous sodium sulfate
7. 7
   濃縮concentrated under vacuum
8. 8
   洗浄eluted with DCM
9. 9
   その他This resulted in 100 L of cyclobutanecarbaldehyde in dichloromethane
10. 10
    workup.STIRRINGThe resulting solution was stirred for 2 days at room temperature
11. 11
    その他Solids were removed by filtration
12. 12
    濃縮The filtrate was concentrated under vacuum
13. 13
    洗浄eluted with ethyl acetate/petroleum ether (1:5)

実験手順

Into a 20-L 4-necked round-bottom flask was placed a solution of cyclobutylmethanol (1000 g, 11.61 mol) in dichloromethane (10 L). This was followed by the addition of Dess-Martin periodinane (4683 g, 11.04 mol) in several batches at 10-15° C. over 120 min. The resulting solution was stirred for 2 h at room temperature and then quenched by the addition of 20 L of cold, saturated aqueous sodium bicarbonate solution. Solids were removed by filtration and washed with 5 L of dichloromethane. The filtrate was extracted with dichloromethane. The organic layers were combined, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column and eluted with DCM:PE (2:1). This resulted in 100 L of cyclobutanecarbaldehyde in dichloromethane and petroleum ether solution. Step 2: Into a 50-L barrel was placed cyclobutanecarbaldehyde in dichloromethane and petroleum ether (33 L of the solution described at the end of Step 1), (S)-2-methylpropane-2-sulfinamide (500 g, 4.13 mol) and copper sulfate (2 kg, 13.33 mol). The resulting solution was stirred for 2 days at room temperature. Solids were removed by filtration. The filtrate was concentrated under vacuum. The residue was applied onto a silica gel column and eluted with ethyl acetate/petroleum ether (1:5) to afford (S)—N-[(1E)-cyclobutylmethylidene]-2-methylpropane-2-sulfinamide.

出典