反応 #63801

反応方程式

7-chloro-1,3,4,5-tetrahydro-3-(methoxycarbonyl)-4-(4-methoxyphenyl)-2H-1-benzazepin-2-one

potassium hexamethyldisilazide

triethyl phosphite

→

title compound

収率 94.4%

7-Chloro-1,3,4,5-tetrahydro-3-hydroxy-3-(methoxycarbonyl)-4-(4-methoxyphenyl)-2H-1-benzazepin-2-one

収率 94.4%

溶媒

hexane

tetrahydrofuran

反応条件

後処理

1. 1
   その他anhydrous oxygen gas was rapidly bubbled through the resulting solution
2. 2
   workup.STIRRINGto stir for an additional hour
3. 3
   その他Oxygenation
4. 4
   その他the reaction was quenched by the addition of 50 ml of acetic acid
5. 5
   濃縮The reaction mixture was then concentrated
6. 6
   workup.DISSOLUTIONthe residue dissolved in ethyl acetate
7. 7
   洗浄The organic solution was washed successively with 1N hydrochloric acid, saturated sodium bicarbonate, and brine
8. 8
   乾燥dried over anhydrous sodium sulfate
9. 9
   その他Concentration of the dried organic solution afforded a solid which

実験手順

A solution of 7-chloro-1,3,4,5-tetrahydro-3-(methoxycarbonyl)-4-(4-methoxyphenyl)-2H-1-benzazepin-2-one (15 g, 41.7 mmole) in 780 ml of tetrahydrofuran was cooled to -78° C. and 147 ml (167 mmole in tetrahydrofuran) of potassium hexamethyldisilazide solution was added. After stirring for 1 hour, 28.7 ml of triethyl phosphite (166.7 mmole) was added and anhydrous oxygen gas was rapidly bubbled through the resulting solution. The reaction temperature was then raised to 0° C. and allowed to stir for an additional hour. Oxygenation was then discontinued and the reaction was quenched by the addition of 50 ml of acetic acid. The reaction mixture was then concentrated and the residue dissolved in ethyl acetate. The organic solution was washed successively with 1N hydrochloric acid, saturated sodium bicarbonate, and brine and then dried over anhydrous sodium sulfate. Concentration of the dried organic solution afforded a solid which, upon trituration in hexane, gave 14.8 g of the title compound.

出典