Nitric Acid → Butanoic acid, 4-(4-formyl-2-methoxy-5-nitrophenoxy)-, methyl ester

HRID 33987

Reaction equation

HRID 33987 reaction equation
[CH3:1][O:2][C:3](=[O:18])[CH2:4][CH2:5][CH2:6][O:7][C:8]1[CH:13]=[CH:12][C:11]([CH:14]=[O:15])=[CH:10][C:9]=1[O:16][CH3:17].[N+:19]([O-])([OH:21])=[O:20].O>C(OC(=O)C)(=O)C>[CH3:1][O:2][C:3](=[O:18])[CH2:4][CH2:5][CH2:6][O:7][C:8]1[CH:13]=[C:12]([N+:19]([O-:21])=[O:20])[C:11]([CH:14]=[O:15])=[CH:10][C:9]=1[O:16][CH3:17]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 962WaterHCID 10753291Methyl 4-(4-formyl-2-methoxyphenoxy)butanoate

Product 1

HCID 11033807Butanoic acid, 4-(4-formyl-2-methoxy-5-nitrophenoxy)-, methyl esterYield 62%

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent2×

Procedure

A solution of the keto-ester (48)(20.00 g, 79.3 mmol) in acetic anhydride (80 mL) was added dropwise to a stirring solution of HNO3 (400 mL) and Ac2O (80 mL) at 0° C. After stirring for 2.5 hours the reaction mixture was poured into iced water (3 L) and allowed to stand at 4° C. for a further 16 hours. The precipitate was collected by filtration and dried under vacuum to provide the nitro compound (49) as a yellow crystalline solid (14.52 g, 62%). Melting Point 70-73° C. 1H NMR (250 MHz, CDCl3) δ 10.4 (s, 2H), 7.61 (s, 1H), 7.40 (s, 1H), 4.21 (t, J=6.2 Hz, 2H), 4.00 (s, 3H), 3.71 (s, 3H), 2.58 (t, J=7.1 Hz, 2H), 2.23 (pent, J=6.3 Hz, 2H). 13C NMR (67.8 MHz, CDCl3) 188.2 (C1), 173.7 (C12), 153.8 (Cquat.), 152.1 (Cquat.), 144.1 (Cquat.), 125.8 (Cquat.), 110.2 (C6), 108.5 (C3), 69.0 (C9), 57.0 (C8), 52.2 (C13), 30.6 (C11), 24.4 (C10). IR (cm−1) 3571, 3485, 2951, 1725, 1689, 1573, 1329, 1172, 1064, 1002, 936, 896, 858, 820, 766, 738, 688, 624. MS (M+1) 298.0. Anal. Calcd for C13H15NO7: C, 52.53; H, 5.09; N, 4.71. Found: C, 52.80; H, 5.03; N, 4.75.

Workup

  1. waitto stand at 4° C. for a further 16 hours
  2. filtrationThe precipitate was collected by filtration
  3. customdried under vacuum

Sources & evidence

ORD record
ord-d15a5165251245e5adaa94945b28ea16
Source dataset
uspto-grants-2008_09
Patent number
US07429658B2

Linked notes

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