反応 #1552065

反応方程式

n-BuLi

H2SO4

Methyl ethyl ketone

2-bromo-N-methyl-N-phenylaniline

→

desired compound

収率 57.0%

9-Ethyl-9,10-dimethyl-9,10-dihydroacridine

収率 57.0%

溶媒

THF

反応条件

後処理

1. 1
   温度to warm to room temperature
2. 2
   workup.STIRRINGstirred overnight under argon
3. 3
   その他After quenching with saturated ammonium chloride
4. 4
   抽出the reaction was extracted with Et2O
5. 5
   洗浄washed with brine and water
6. 6
   乾燥dried over anhydrous MgSO4
7. 7
   その他the solvent evaporated under reduced pressure
8. 8
   その他To the neat residue thus obtained
9. 9
   workup.STIRRINGthe mixture stirred at room temperature for 1 h under argon
10. 10
    抽出After dilution with 30 mL DI H2O, the reaction was extracted with Et2O (5×50 mL)
11. 11
    洗浄washed with brine and water
12. 12
    乾燥dried over anhydrous MgSO4
13. 13
    その他the solvent was evaporated under reduced pressure
14. 14
    その他The residue was purified by flash column chromatography

実験手順

A flame-dried two-necked flask was charged with 2-bromo-N-methyl-N-phenylaniline (1.0 g, 3.8 mmol) and 100 mL dry THF under argon and cooled to −78° C. in a dry ice-acetone bath. 2.6 mL of a 1.6 M solution of n-BuLi in hexanes (4.16 mmol) was added dropwise over 5 minutes and the reaction stirred at −78° C. under argon for 1 h. Methyl ethyl ketone (0.302 g, 4.2 mmol) was added in one portion to the reaction mixture at −78° C., the reaction allowed to warm to room temperature and stirred overnight under argon. After quenching with saturated ammonium chloride, the reaction was extracted with Et2O, the organic layers combined, washed with brine and water and dried over anhydrous MgSO4 and the solvent evaporated under reduced pressure. To the neat residue thus obtained was added 2 mL of concentrated H2SO4 under argon and the mixture stirred at room temperature for 1 h under argon. After dilution with 30 mL DI H2O, the reaction was extracted with Et2O (5×50 mL), the organic layers were combined, washed with brine and water and dried over anhydrous MgSO4, and the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography using hexanes as the eluent to yield 0.57 g (57%) of the desired compound as a clear oil. 1H NMR (400 MHz, CHCl3) δ 1.66 (dd, J=6.8 Hz, J=0.8 Hz, 3H), 1.78 (t, J=1.2 Hz, 3H), 3.10 (s, 3H), 5.49 (m, 1H), 6.66 (m, 3H), 7.18 (m, 6H). 13C NMR (100 MHz, CHCl3) δ 14.2, 15.2, 16.5, 24.2, 39.2, 39.6, 113.8, 114.1, 117.1, 117.4, 122.4, 124.4, 125.7025.9, 128.0, 128.2, 128.5, 128.8, 128.9, 130.6, 131.5, 136.4, 140.4, 144.3, 145.8, 146.9, 149.2, 149.4. HRMS (ESI) calc for C17H19N [M+H]+ 238.1590, found 238.1587. IR (KBr plate) 692 (m), 747 (m), 1345 (m), 1444 (m), 1499 (s), 1592 (s), 1602 (s), 2918 (m), 3024 (m) cm−1.

出典