Methanol → Methyl 3-(hydroxymethyl)-5-nitrobenzoate

HRID 391433Notes

Reaction equation

HRID 391433 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]([CH:11]=[C:12]([N+:14]([O-:16])=[O:15])[CH:13]=1)[C:8](O)=[O:9])=[O:4].O1CCCC1.CO>C(OCC)(=O)C>[OH:9][CH2:8][C:7]1[CH:6]=[C:5]([CH:13]=[C:12]([N+:14]([O-:16])=[O:15])[CH:11]=1)[C:3]([O:2][CH3:1])=[O:4]

Participants

5

Reactant 3

HCID 887MethanolHCID 8028TetrahydrofuranHCID 747761,3-Benzenedicarboxylic acid, 5-nitro-, 1-methyl ester

Product 1

HCID 10703703Methyl 3-(hydroxymethyl)-5-nitrobenzoate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

3-(Methoxycarbonyl)-5-nitrobenzoic acid (20.0 g, 88.9 mmol) was combined with tetrahydrofuran (150 mL) and cooled to 0° C. To this solution was added a 1 M borane tetrahydrofuran complex (178 mL, 178 mmol) cautiously over 15 min and the reaction mixture allowed to warm to room temperature overnight. The mixture was cooled to 0° C., treated with excess methanol and concentrated in vacuo to afford to afford a precipitate which was dissolved in ethyl acetate, washed with concentrated sodium bicarbonate (2×), then brine (2×), dried over sodium sulfate, and concentrated to afford 18.2 g (97%) which was used without further purification. 1H-NMR (CDCl3, 300 MHz) δ 8.70 (s, 1H), 8.39 (s, 1H), 8.30 (s, 1H), 4.84 (s, 2H), 3.95 (s, 3H). Mass spec.: 212.06 (MH)+.

Workup

  1. additionTo this solution was added a 1 M borane tetrahydrofuran complex (178 mL, 178 mmol) cautiously over 15 min
  2. temperatureto warm to room temperature overnight
  3. temperatureThe mixture was cooled to 0° C.
  4. concentrationconcentrated in vacuo
  5. customto afford
  6. customto afford a precipitate which
  7. washwashed with concentrated sodium bicarbonate (2×)
  8. dry with materialbrine (2×), dried over sodium sulfate
  9. concentrationconcentrated
  10. customto afford 18.2 g (97%) which
  11. customwas used without further purification

Sources & evidence

ORD record
ord-3752639b813f480c805a2a8aa5a56f14
Source dataset
uspto-grants-2013_02
Patent number
US08383821B2

Reaction notes

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