Ethanol → 3-Aminophthalic acid

HRID 1050727Notes

Reaction equation

HRID 1050727 reaction equation
[N+:1]([C:4]1[CH:12]=[CH:11][CH:10]=[C:6]([C:7]([OH:9])=[O:8])[C:5]=1[C:13]([OH:15])=[O:14])([O-])=O.C(O)C.[H][H]>CCOCC.[Pd]>[NH2:1][C:4]1[CH:12]=[CH:11][CH:10]=[C:6]([C:7]([OH:9])=[O:8])[C:5]=1[C:13]([OH:15])=[O:14]

Participants

6

Reactant 3

HCID 702EthanolHCID 690433-Nitrophthalic acidHCID 178418361HCID 178418361, compound3×

Product 1

HCID 794903-Aminophthalic acidYield 84%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 3283Diethyl EtherSolvent

Procedure

After a mixture of 10% Pd/C (2.5 g), 3-nitrophthalic acid (75.0 g, 355 mmol) and ethanol (1.5 L) was charged to a 2.5 L Parr hydrogenator under nitrogen, hydrogen was charged to the reaction vessel for up to 55 psi (379 kPa). The mixture was shaken for 13 hours while the hydrogen pressure was maintained at between 50 psi (245 kPa) and 55 psi (379 kPa). Hydrogen was released and the mixture was purged with nitrogen 3 times. The suspension was filtered through a celite bed and rinsed with methanol. The filtrate was concentrated in vacuum to yield a solid. The solid was suspended in ether and isolated by vacuum filtration. The solid was dried in vacuum to a constant weight to afford 54 g (84% yield) of 3-aminopthalic acid as a yellow product. The product in DMSO-d6 was characterized by a 1H NMR spectrum showing the following chemical shifts (δ in ppm): 3.17 (s, 2H), 6.67 (d, 1H), 6.82 (d, 1H), 7.17 (t, 1H), 8-10 (brs, 2H). The product in DMSO-d6 was characterized by a 13C-NMR spectrum showing the following chemical shifts (δ in ppm): 112.00, 115.32, 118.20, 131.28, 135.86, 148.82, 169.15, 170.09.

Workup

  1. additionwas charged to a 2.5 L Parr hydrogenator under nitrogen
  2. temperaturewas maintained at between 50 psi (245 kPa) and 55 psi (379 kPa)
  3. customthe mixture was purged with nitrogen 3 times
  4. filtrationThe suspension was filtered through a celite bed
  5. washrinsed with methanol
  6. concentrationThe filtrate was concentrated in vacuum
  7. customto yield a solid
  8. customisolated by vacuum filtration
  9. customThe solid was dried in vacuum to a constant weight

Sources & evidence

ORD record
ord-11ffbe7bf0914a7fb9460c21e79ed8e8
Source dataset
uspto-grants-2016_07
Patent number
US09387195B2

Reaction notes

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