Potassium Carbonate → t-Butyl ethyl (2,4-dinitronaphthalen-1-yl)malonate

HRID 431729Notes

Reaction equation

HRID 431729 reaction equation
C([O-])([O-])=O.[K+].[K+].Cl[C:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]([N+:18]([O-:20])=[O:19])=[CH:10][C:9]=1[N+:21]([O-:23])=[O:22].[C:24]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])(=[O:31])[CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27]>C1COCC1>[N+:21]([C:9]1[CH:10]=[C:11]([N+:18]([O-:20])=[O:19])[C:12]2[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:8]=1[CH:25]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:24]([O:32][C:33]([CH3:36])([CH3:34])[CH3:35])=[O:31])([O-:23])=[O:22]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 169871-Chloro-2,4-dinitronaphthaleneHCID 96345tert-Butyl ethyl malonate

Product 1

HCID 11452450t-Butyl ethyl (2,4-dinitronaphthalen-1-yl)malonateYield 78.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

K2CO3 (4.04 g, 29.22 mmol) was added to a solution of 1-chloro-2,4-dinitronaphthalene (6.04 g, 23.91 mmol) and t-butyl ethyl malonate (5.0 g, 26.50 mmol) in THF (50 mL), and the mixture was heated reflux overnight. The mixture was cooled and filtered, then the filtrate was concentrated under reduced pressure. Flash chromatography (20-50% AcOEt-Petroleum ether gradient elution) afforded t-butyl ethyl (2,4-dinitronaphthalen-1-yl)malonate (7.6 g, 54%) as a pale red solid. M.p. 86-88° C.; 1H NMR (CDCl3, 500 MHz) δ 8.65 (s, 1H), 8.55 (dd, 0.5, 8.5, 1H), 8.36 (dd, 0.5, 9.0, 1H), 7.89 (dt, 1.0, 8.0, 1H), 7.81 (dt, 1.5, 9.0, 1H), 5.64 (s, 1H), 4.26 (q, 7.0, 2H), 1.44 (s, 9H), 1.24 (t, 7.0, 3H); IR (neat) 2980, 1745, 1537, 1368, 1346, 1306, 1253, 1147, 1027, 850, 832, 801, 774, 761 cm−1. FABMS (NBA) m/z 405 (M+H+, 5).

Workup

  1. temperaturethe mixture was heated
  2. temperaturereflux overnight
  3. temperatureThe mixture was cooled
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. washFlash chromatography (20-50% AcOEt-Petroleum ether gradient elution)

Sources & evidence

ORD record
ord-c72f337d4fe748be88c9b2631c84dedf
Source dataset
uspto-grants-2003_12
Patent number
US06660742B2

Reaction notes

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