1-(4,5-Dimethoxy-2-nitrophenyl)ethanone

(1) A mixture of 1-(3, 4-dimethoxyphenyl)ethan-1-one 11 (180 g, 1.0 mol), HOAc (1.5 L) was stirred and heated to 60°C. When the solid dissolved, 65percent HNO3 (110 mL, 1.5 mol) was added over 30 min and the mixture was stirred for another 3 h to give a yellow solution. The reaction mixture was poured slowly into ice-water (5 L) while stirring constantly. The yellow solid formed was filtered off and washed with cold water (600 mL × 2), dried at 60°C for 4 h to give crude product 12 (210 g). The crude 12 (210 g) was stirred and heated with EtOAc : petroleum ether= 1:1 (v:v) (800 mL) at reflux for 2 h then cooled to room temperature, the resulting solid was filtered off and washed with EtOAc : petroleum ether = 1:1 (v:v) (100 mL × 2), dried at 50°C for 4 h to afford 12(193.7 g, 86percent) as a yellow solid; mp 131.3−133.1° C (Lit.10 130−132°C). 1H NMR (400 MHz, DMSO-d6): δ 2.52 (s, 3H), 3.90 (s, 3H), 3.93(s, 3H), 7.23 (s, 1H), 7.64 (s, 1H). MS (ESI): m/z = 226.1 [M+ H]+, 473.2 [2M + Na]+.1-(3, 4-dimethoxyphenyl)ethan-1-one (10 g) was added to acetic anhydride (30 mL). After the solution was cooled to 0 °C, a mixture of nitric acid (200 mL) and acetic anhydride (10 mL) were added dropwise. Upon completion of the addition, the reaction solution was stirred for 4 hours, poured into 1 L of ice water, filtered, washed with water and dried to obtain 1-(4, 5-dimethoxy-2-nitrophenyl)ethan-1-one (8 g, 67percent).General procedure: To a solution of 3, 4-di(1H, 1H, 2H, 2H, 3H, 3H-perfluoroheptyloxy)acetophenone (2.14 g, 3.18 mmol) in diethyl ether (10 mL), HNO3 (15 mL) was carefully added dropwise at 0 °C. The solution was subsequently stirred at 0 °C for 5 h. The solution was added to ice water (100 mL) and the solution was extracted with ethyl acetate (40 mL x 2). The organic layer was washed with 5percent NaHCO3 (50 mL x 3) and dried over MgSO4. After concentrating the solution using a rotary evaporator, the residue was purified by recrystallization with ethanol to yield 1.38 g (1.92 mmol, 60percent) of 4g as yellow needle crystals.3, 4-dimethoxyacetophenone (15 g; 83.2 mmol) was added in small amounts to well stirred, ice-cooled nitric acid (sp gr 1.42; 90 ml) over a period of 1 hr. The final mixture was stirred for one further hour and then poured onto 400 g of crushed ice. When the ice had melted the resulting yellow solid was filtered off, air-dried and recrystallized from ethanol (9.5 g; 50.7percent yield).

Molecular Weight:225.20
XLogP3:1.4
Hydrogen Bond Acceptor Count:5
Rotatable Bond Count:3
Exact Mass:225.06372245
Monoisotopic Mass:225.06372245
Topological Polar Surface Area:81.4
Heavy Atom Count:16
Complexity:275
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes