反応 #1552064

ord-9d79118d34cf4d8789f18c0764a3de03

反応方程式

[H-].[Na+]
NaH
[H-].[Na+]
NaH
COS(=O)(=O)OC
dimethyl sulfate
Brc1ccccc1Nc1ccccc1
2-bromo-N-phenylaniline
C1COCCOCCOCCOCCO1
15-crown-5
[Br-].[K+]
KBr
CN(c1ccccc1)c1ccccc1Br
2-Bromo-N-methyl-N-phenylaniline

反応条件

温度
0°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    温度After refluxing for 20 h under argon the reaction
  2. 2
    抽出extracted with Et2O (5×50 mL)
  3. 3
    洗浄washed thoroughly with saturated sodium bicarbonate (3×25 mL), brine and water
  4. 4
    乾燥dried over MgSO4
  5. 5
    その他the solvent evaporated under reduced pressure
  6. 6
    その他The resulting oil was purified by flash column chromatography
  7. 7
    洗浄elution
  8. 8
    その他to yield 2.5 g (80%)

実験手順

A flame-dried two-neck round bottom flask was charged with 2-bromo-N-phenylaniline (3 g, 12.2 mmol), 0.1 mL 15-crown-5, 200 mL dry THF and 50 mL dimethoxyethane under argon. The solution was cooled to 0° C. in an ice bath, 0.6 g of a 60 wt % dispersion of NaH in mineral oil (0.36 g NaH, 15 mmol) was added to the reaction mixture in small portions under argon and 1.4 mL dimethyl sulfate (1.89 g, 15 mmol) was added via syringe. After refluxing for 20 h under argon the reaction was poured carefully onto 500 g ice and extracted with Et2O (5×50 mL). The organic layers were combined, washed thoroughly with saturated sodium bicarbonate (3×25 mL), brine and water, dried over MgSO4 and the solvent evaporated under reduced pressure. The resulting oil was purified by flash column chromatography using gradient elution, starting with 100% hexanes and progressing to 30% dichloromethane in hexanes to yield 2.5 g (80%)-of a clear oil. 1H NMR (400 MHz, CHCl3) δ 3.22 (s, 3H), 6.56 (d, J=7.6 Hz, 2H), 6.75 (t, J=7.6 Hz, 1H), 7.15 (m, 3H), 7.25 (dd, J=8.0 Hz, J=2.0 Hz, 1H), 7.32 (td, J=7.6 Hz, J=1.2 Hz, 1H), 7.66 (dd, J=8.0 Hz, J=1.6 Hz, 1H). 13C NMR (100 MHz, CHCl3) δ 39.1, 113.5, 117.8, 124.4, 127.9, 128.4, 129.1, 129.2, 130.6, 134.3, 147.0, 148.7. HRMS (ESI) calc for C13H12BrN [M+H]+ 262.0226, found 262.0234. IR (KBr plate) 654 (s), 691 (s), 748 (s), 872 (s), 1139 (s), 1137 (s), 1273 (s), 1346 (s), 1438 (m), 1467 (s), 1499 (s), 1580 (s), 1601 (s), 2813 (m), 2824 (s), 3058 (m), 3089 (m) cm−1.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US08999722B2uspto-grants-2015_04