Water → Ethyl (4-amino-2-nitronaphthalen-1-yl)acetate

HRID 431731Notes

Reaction equation

HRID 431731 reaction equation
[N+:1]([C:4]1[CH:13]=[C:12]([N+:14]([O-])=O)[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]=1[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])([O-:3])=[O:2].O>CCO>[NH2:14][C:12]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])=[C:4]([N+:1]([O-:3])=[O:2])[CH:13]=1

Participants

4

Reactant 2

HCID 962WaterHCID 11358597Ethyl (2,4-dinitronaphthalen-1-yl)acetate

Product 1

HCID 11460008Ethyl (4-amino-2-nitronaphthalen-1-yl)acetateYield 11.1%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Na2S (60%, 4.27 g, 32.87 mmol) was added to a refluxing solution of ethyl (2,4-dinitronaphthalen-1-yl)acetate (10.0 g, 32.87 mmol) in EtOH (200 mL) and stirred for 0.5 h. The mixture was poured into water (200 mL), concentrated and extracted with AcOEt (300 mL). The organic layer was washed with H2O (100 mL) and saturated aqueous NaCl (50 mL). The each aqueous layer was extracted with AcOEt (100 mL). The combined organic layer was washed with saturated aqueous NaCl (50 mL), dried (Na2SO4) and concentrated under reduced pressure. Flash chromatography (20% AcOEt-Petroleum ether) afforded ethyl (4-amino-2-nitronaphthalen-1-yl)acetate (1.0 g, 11%) as a dark purple solid. M.p. 93-100° C. (decomp.); 1H NMR (CDCl3, 500 MHz) δ 8.08 (d, 8.0, 1H), 7.86 (d, 7.5, 1H), 7.66 (t, 7.0, 1H), 7.62 (t, 7.0, 1H), 7.20 (s, 1H), 4.40 (brs, 2H), 4.26 (s, 2H), 4.20 (q, 7.0, 2H), 1.26 (t, 7.0, 3H); IR (neat) 3459, 3379, 3255, 2980, 1728, 1634, 1590, 1515, 1466, 1439, 1368, 1337, 1249, 1200, 1156, 1027, 841, 756 cm−1. FABMS (NBA) m/z 274 (M+).

Workup

  1. concentrationconcentrated
  2. extractionextracted with AcOEt (300 mL)
  3. washThe organic layer was washed with H2O (100 mL) and saturated aqueous NaCl (50 mL)
  4. extractionThe each aqueous layer was extracted with AcOEt (100 mL)
  5. washThe combined organic layer was washed with saturated aqueous NaCl (50 mL)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-2116951181c84d77a1bf5212f4ce3219
Source dataset
uspto-grants-2003_12
Patent number
US06660742B2

Reaction notes

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