Trifluoroacetic acid → 1-[Di(methoxycarbonyl)-methyl]-4-nitronaphthalene-2-carboxylic acid

HRID 366800Notes

Reaction equation

HRID 366800 reaction equation
FC(F)(F)C(O)=O.[CH3:8][O:9][C:10]([CH:12]([C:38]([O:40][CH3:41])=[O:39])[C:13]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:16]([N+:23]([O-:25])=[O:24])=[CH:15][C:14]=1[C:26]([O:28]CC1C=CC(OC)=CC=1)=[O:27])=[O:11].C1(OC)C=CC=CC=1>O>[CH3:8][O:9][C:10]([CH:12]([C:38]([O:40][CH3:41])=[O:39])[C:13]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:16]([N+:23]([O-:25])=[O:24])=[CH:15][C:14]=1[C:26]([OH:28])=[O:27])=[O:11]

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 7519AnisoleHCID 108140884-Methoxybenzyl 1-[di(methoxycarbonyl)methyl]-4-nitronaphthalene-2-carboxylate

Product 1

HCID 105215641-[Di(methoxycarbonyl)-methyl]-4-nitronaphthalene-2-carboxylic acidYield 93.1%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
20 °C

Procedure

Trifluoroacetic acid (36 mL) was added in one portion to a mixture of 5 (9.20 g, 19.7 mmol) and anisole (12.16 g, 20 mmol), and the resulting solution was stirred at 20° C. for 10 min and then diluted with cold water (800 mL). The precipitated semi-solid was collected, dissolved in EtOAc and the solution was washed with water, dried (Na2SO4) and then concentrated under reduced pressure below 30° C. The residue was triturated with iPr2O to provide a crude product, which was recrystallised from EtOAc/iPr2O/petroleum ether/AcOH (1drop) to give 1-[di(methoxycarbonyl)-methyl]-4-nitronaphthalene-2-carboxylic acid (6) (6.37 g, 93%), mp 153-154° C. (dec.). 1H NMR [(CD3)2SO] δ 14.1 (br s, 1H, CO2H), 8.62 (s, 1H, H-3), 8.36 (d, J=8.2 Hz, 1H, H-5), 8.30 (d, J=8.7 Hz, 1H, H-8), 7.92 (br t, J=7.6 Hz, 1H, H-6), 7.84 (br t, J=7.7 Hz, 1H, H-7), 6.65 (s, 1H, ArCH), 3.63 (s, 6H, 2×CO2CH3). Anal. Calculated for C16H13NO8 : C, 55.3; H, 3.8; N, 4.0. Found: C, 55.4; H, 3.8; N, 3.7%.

Workup

  1. customThe precipitated semi-solid was collected
  2. dissolutiondissolved in EtOAc
  3. washthe solution was washed with water
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated under reduced pressure below 30° C
  6. customThe residue was triturated with iPr2O
  7. customto provide a crude product, which
  8. customwas recrystallised from EtOAc/iPr2O/petroleum ether/AcOH (1drop)

Sources & evidence

ORD record
ord-5574bf5cfec1438ea2d0263925216af6
Source dataset
uspto-grants-2000_10
Patent number
US06130237

Reaction notes

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