反応 #2023547

反応方程式

isoamyl nitrite

dimethyl disulfide

4-bromo-2-nitroaniline

→

4-bromo-1-methylsulfanyl-2-nitro-benzene

収率 97.1%

反応条件

後処理

1. 1
   温度The reaction mixture was cooled to 25° C.
2. 2
   濃縮concentrated in vacuo
3. 3
   workup.DISSOLUTIONThe resulting residue was dissolved in ethyl acetate (300 mL)
4. 4
   洗浄The organic layer was washed successively with a 1N aqueous hydrochloric acid solution (1×300 mL)
5. 5
   乾燥a saturated aqueous sodium chloride solution (1×300 mL), dried over anhydrous magnesium sulfate
6. 6
   ろ過filtered
7. 7
   濃縮concentrated in vacuo Biotage chromatography (FLASH 40M, Silica, 6/1 to 5/1 hexanes/ethyl acetate)

実験手順

A solution of isoamyl nitrite (10.05 mL, 75 mmol) in dimethyl disulfide (49.5 mL, 550 mmol) at 25° C. was slowly treated with 4-bromo-2-nitroaniline (10.85 g, 50 mmol). The reaction was exothermic with gas evolution. The resulting brown reaction mixture was heated to 80-90° C. for 2 h, at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was cooled to 25° C. and then concentrated in vacuo. The resulting residue was dissolved in ethyl acetate (300 mL). The organic layer was washed successively with a 1N aqueous hydrochloric acid solution (1×300 mL) and a saturated aqueous sodium chloride solution (1×300 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo Biotage chromatography (FLASH 40M, Silica, 6/1 to 5/1 hexanes/ethyl acetate) afforded 4-bromo-1-methylsulfanyl-2-nitro-benzene (12.05 g, 97%) as a brown solid: EI-HRMS m/e calcd for C7H6BrNO2S (M+) 246.9372, found 246.9368.

出典