反応 #65938

反応方程式

Tetramethyltin

3 -(N-Allyl-N-n-propylamino)-5 -trifluoromethane sulfonyloxychroman

LiCl

2.6-di- t-butyl- 4-methylphenol

→

5-acetyl-3-(N-allyl-N-n-propylamino)chroman

収率 39.0%

溶媒

DMF

THF n-hexane

反応条件

後処理

1. 1
   その他The flask was evacuated
2. 2
   その他followed by inlet of CO (three times)
3. 3
   その他The solvent was evaporated
4. 4
   その他the residue was partitioned between aqueous NH3 (2M) and CH2Cl2 (3×15 mL)
5. 5
   乾燥the organic phases were dried (Na2SO4)
6. 6
   ろ過filtered
7. 7
   濃縮concentrated in vacuo

実験手順

3 -(N-Allyl-N-n-propylamino)-5 -trifluoromethane sulfonyloxychroman (0.28 g, 0.74 mmol), LiCl (0.097 g, 2.3 mmol), PdCl2 (dppf) (0.031 g, 0.04 retool) and 2.6-di- t-butyl- 4-methylphenol (0,005 g) were dissolved in DMF (5.0 mL) in a three-necked round-bottom flask (50 mL) with a magnetic stirrer. The flask was evacuated, followed by inlet of CO (three times). Tetramethyltin (0.12 mL, 0.89 mmol) was added and then the mixture was stirred under an atmosphere of CO (1 arm) at 120° C. (oilbath temp) for 4 hours. The solvent was evaporated, the residue was partitioned between aqueous NH3 (2M) and CH2Cl2 (3×15 mL) and the organic phases were dried (Na2SO4), filtered and concentrated in vacuo. Column chromatography on silica with THF-n-hexane (1:9) as eluent afforded 5-acetyl-3-(N-allyl-N-n-propylamino)chroman (0.078 g, 39% yield) as an oil. The base was precipitated from an ether solution by adding a slight excess of HCl (approx. 3M in ether). The crude salt was collected and dried in vacuo at 40° C. to give a white amorphous powder. Mp 125°-127° C. PdCl 2 (dppf)=dichloro[1,1'-bis(diphenylphosphino)-ferrocene] palladium (II).

出典