反応 #1485077

反応方程式

1-boc-piperazine

Cs2CO3

rac-2,2′bis(diphenylphosphino)-1,1′-binaphthyl

compound 24

4-Bromo-1,2-dinitrobenzene

→

compound 25

収率 78.0%

tert-Butyl 4-(3,4-dinitrophenyl)piperazine-1-carboxylate

収率 78.0%

溶媒

toluene

反応条件

後処理

1. 1
   その他the air in the flask was removed
2. 2
   workup.STIRRINGThe reaction mixture was further stirred at room temperature for 0.5 h
3. 3
   workup.ADDITIONEthyl acetate (50 mL) was added to the mixture at room temperature
4. 4
   洗浄washed with H2O (15 mL) and brine (10 mL)
5. 5
   乾燥dried over Na2SO4
6. 6
   その他evaporated
7. 7
   その他The brown oily material was chromatographed on a silica column
8. 8
   洗浄eluting with hexanes:ethyl acetate (30:70)

実験手順

To an oven-dried flask, 1-boc-piperazine (1.59 g, 8.5 mmol), Cs2CO3 (2.91 g, 8.93 mmol), Pd2(dba)3 (0.72 g, 0.78 mmol), rac-2,2′bis(diphenylphosphino)-1,1′-binaphthyl (0.44 g, 0.71 mmol), toluene (6 mL) and compound 24 (1.76 g, 7.14 mmol) were added. While stirring the reaction mixture at room temperature, the air in the flask was removed and replaced by N2. This process was repeated three times. The reaction mixture was further stirred at room temperature for 0.5 h. Ethyl acetate (50 mL) was added to the mixture at room temperature, washed with H2O (15 mL) and brine (10 mL), dried over Na2SO4, and evaporated. The brown oily material was chromatographed on a silica column, eluting with hexanes:ethyl acetate (30:70), and then changing to (40:60), yielding compound 25. Yield: 78%, yellow solid. IR (KBr, cm−1) 3073 (Ar—H), 1683 (CO), 1528, 1432 (C═C), 1226 (C—N), 1151 (C-0); 1H NMR (500 MHz, CDCl3) δ 1.48 (9H, s, OC(CH3)3), 3.02 (m, 4H, 2CH2), 3.58 (m, 4H, 2CH2), 7.17 (dd, J=2.6, 8.8 Hz, 1H, H-6), 7.24 (d, J=2.5 Hz, 1H, H-2), 7.71 (d, J=8.5 Hz, 1H, H-4). 13C NMR (125.7 MHz, CDCl3) δ 28.30 (OC(CH3)3), 48.24 (CH2), 51.39 (CH2), 80.12 (OC(CH3)3), 124.23 (C-2), 124.92 (C-6), 127.49 (C-5), 128.17 (C-4), 141.62 (C-3), 146.94 (C-1), 154.60 (CO). Anal. Calcd for C15H20N4O6: C, 51.13; 11, 5.72; N, 15.90%. Found: C, 51.07; H, 5.78; N, 15.82%.

出典