Citric Acid → 3-({[(Tert-butoxy)carbonyl]amino}methyl)-5-nitrobenzoic acid

HRID 964487Notes

Reaction equation

HRID 964487 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH2:14][NH2:15])[CH:7]=[C:8]([CH:13]=1)[C:9]([O:11]C)=[O:10])([O-:3])=[O:2].[OH-].[Na+].[O:18](C(OC(C)(C)C)=O)[C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C(O)(C)(C)C.O>[C:22]([O:21][C:19]([NH:15][CH2:14][C:6]1[CH:7]=[C:8]([CH:13]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)[C:9]([OH:11])=[O:10])=[O:18])([CH3:25])([CH3:24])[CH3:23]

Participants

7

Reactant 4

HCID 311Citric AcidHCID 14798Sodium HydroxideHCID 90495Di-tert-butyl dicarbonateHCID 19077132Methyl 3-(aminomethyl)-5-nitrobenzoate

Product 1

HCID 190771343-({[(Tert-butoxy)carbonyl]amino}methyl)-5-nitrobenzoic acidYield 88%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6386tert-ButanolSolvent

Procedure

A solution of methyl 5-nitro-3-aminomethybenzoate (1980 mg, 9.4 mmol) in 1N NaOH (28 mL, 28 mmol) and tert-BuOH (20 mL) was stirred at r.t. for 10 hours and then added BOC2O (4100 mg, 18.8 mmol) and stirred for 17 hours. The reaction mixture was added hexanes (50 mL) and water (50 mL). The aqueous layer was acidified with 5% citric acid aq. and extracted with CH2 Cl2 (2×70 mL). The CH2Cl2 layers were combined and washed with water (50 mL). The organic layer was evaporated to give the desired compound (2450 mg, 88%): 1H NMR (300 MHz, DMSO-d6) δ 13.725 (s, 1H), 8.476 (s, 1H), 8.307 (s, 1H), 8.216 (s, 1H), 7.639 (t, J=5.7 Hz, 1H), 4.398 (d, J=5.7 Hz, 2H), 1.385 (s, 9H); 13C NMR (300 MHz, DMSO-d6) δ 165.5, 155.9, 147.9, 143.5, 133.6, 132.5, 125.4, 122.2, 78.3, 42.6, 28.2.

Workup

  1. extractionextracted with CH2 Cl2 (2×70 mL)
  2. washwashed with water (50 mL)
  3. customThe organic layer was evaporated

Sources & evidence

ORD record
ord-991de5e9c97e490b943c2a4013aaa6de
Source dataset
uspto-grants-1998_06
Patent number
US05770380

Reaction notes

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