反応 #974783

反応方程式

methyl 2-(trifluoromethyl)-3,3,3-trifluoropropionate

Methyl 2-(trifluoromethyl)-3,3,3-trifluoropropionate

2,4-dinitrofluorobenzene

KF

18-crown-6-ether

KF

18-Crown-6-ether

HCl

→

titled compound

2-(2,4-Dinitro-phenyl)-3,3,3-trifluoro-2-trifluoromethyl-propionic Acid Methyl Ester

溶媒

sulfolane

Et2O

反応条件

後処理

1. 1
   workup.ADDITIONAfter the addition
2. 2
   workup.ADDITIONpump addition over 14 h
3. 3
   workup.ADDITIONpump addition at 12 h
4. 4
   workup.ADDITIONAfter addition
5. 5
   workup.ADDITIONthe reaction mix
6. 6
   その他The layers were separated
7. 7
   洗浄the organic layer was washed with brine
8. 8
   乾燥dried over Na2SO4
9. 9
   ろ過filtered
10. 10
    濃縮concentrated under vacuum
11. 11
    洗浄The crude was eluted on a silica gel column with EtOAc/hexanes gradient

実験手順

A mixture of 7.08 g (38.07 mmol) 2,4-dinitrofluorobenzene, 2.43 g (41.88 mmol) KF, and 0.58 g (2.21 mmol) 18-crown-6-ether in 37 ml sulfolane was added 4.00 g (19.04 mmol) methyl 2-(trifluoromethyl)-3,3,3-trifluoropropionate dropwise over about 7 h via syringe pump. After the addition was complete, another 2.43 g KF, 0.58 g 18-Crown-6-ether were added and then 4.00 g Methyl 2-(trifluoromethyl)-3,3,3-trifluoropropionate were added dropwise over 12 h. The next day, repeated additions using same amounts and setting syringe pump addition over 14 h. The following day, the additions were again repeated, this time using half the amounts as above additions and setting syringe pump addition at 12 h. After addition was completed, the reaction mix was cooled to RT and diluted into Et2O and 0.5N aqueous HCl. The layers were separated, and the organic layer was washed with brine, dried over Na2SO4, filtered and concentrated under vacuum. The crude was eluted on a silica gel column with EtOAc/hexanes gradient, to yield the titled compound, as a yellow solid.

出典