Tetrahydrofuran → 1-Hydroxy-2-naphthoic acid

HRID 1354848Notes

Reaction equation

HRID 1354848 reaction equation
[N+](C1C=CC(N(C([C:19]2[C:28]3[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=3)[CH:22]=[CH:21][C:20]=2O)=O)C2C=CC=CC=2)=CC=1)([O-])=O.NN.C(Cl)Cl.[CH3:35][OH:36].[NH4+].[OH-:38].C1C[O:42]CC1>CO.[Ni]>[OH:36][C:35]1[C:24]2[C:23](=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH:22]=[CH:21][C:20]=1[C:19]([OH:42])=[O:38]

Participants

7

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 9321HydrazineHCID 21104204HCID 21104204, compoundHCID 21896990Dichloromethane methanol ammonium hydroxide

Product 1

HCID 68441-Hydroxy-2-naphthoic acidYield 96%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

To a stirred solution of 385 (8.11 mmol) in a mixture of THF and MeOH (1:1, v/v, 100 mL) was added Raney nickel (˜2 mL, 50% suspension in water). Hydrazine (N2H4, 32.0 mmol, 4 equiv) was added in portions over a period of 30 minutes. Once effervescence had ceased, TLC analysis (15:2:0.1, CH2Cl2/MeOH/NH4OH) indicated complete conversion of the starting material to a compound that had lower Rf than the starting material (stained spontaneously with PMA/Ce stain without requiring heating). The suspension was diluted with THF (100 mL) and filtered through a pad of Celite on a fritted funnel. The supernatant was concentrated to yield 1-hydroxy-[2]naphthoic acid-(4-amino-anilide) (111) (7.8 mmol, 96% yield) as a dark purple solid. 1H NMR (400 MHz, DMSO-d6) δ=5.06 ppm (br s, 2H), 6.57 (br d, 2H, J=9 Hz), 7.29 (br d, 2H, J=9 Hz), 7.39 (d, 1H, J=9 Hz), 7.53 (app. td, 1H, J=1, 8 Hz), 7.62 (app. td, 1H, J=1, 7 Hz), 7.86 (d, 1H, J=8 Hz), 8.05 (d, 1H, J=9 Hz), 8.26 (d, 1H, J=8 Hz), 10.13 (br s, 1H). LC-MS: m/e 279.2 [M+1]+.

Workup

  1. temperaturewithout requiring heating)
  2. filtrationfiltered through a pad of Celite on a fritted funnel
  3. concentrationThe supernatant was concentrated

Sources & evidence

ORD record
ord-ca3c8fb982214933b29b65aa3f0905c0
Source dataset
uspto-grants-2007_05
Patent number
US07223759B2

Reaction notes

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