Hydrochloric Acid → HCID 136331493, compound

HRID 484415Notes

Reaction equation

HRID 484415 reaction equation
[C:1]([CH:4]1[CH2:13][C:12](=O)[C:11]2[C:6](=[CH:7][C:8](Cl)=[CH:9][C:10]=2Cl)[NH:5]1)([OH:3])=[O:2].[ClH:17].[NH2:18][OH:19].N1C=CC=C[CH:21]=1.[ClH:26]>CO>[Cl:17][C:10]1[CH:9]=[C:8]([Cl:26])[CH:7]=[C:6]2[C:11]=1[C:12](=[N:18][OH:19])[CH2:13][CH:4]([C:1]([O:3][CH3:21])=[O:2])[NH:5]2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 443297Hydroxyamine hydrochlorideHCID 15168442HCID 15168442, compound

Product 1

HCID 136331493HCID 136331493, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

To a solution of 2-carboxy-5,7-dichloro-4-oxo-1,2,3,4-tetrahydroquinoline (Example 1) (14.85 g, 57.1 mmol) in methanol (300 ml) was added hydroxylamine hydrochloride (4.17 g, 60.0 mmol) followed by dry pyridine (4.85 ml, 60.0 mmol) and the resulting mixture was heated at reflux under an atmosphere of nitrogen for 2 hours. The mixture was then cooled, and a solution of methanol saturated with hydrogen chloride (50 ml) was added and the reaction was stirred at room temperature under an atmosphere of nitrogen for 17 hours. The solvent was removed in vacuo and the residue was partitioned between water (300 ml) and diethyl ether (300 ml). The aqueous phase was further extracted with diethyl ether (2×300 ml) and the combined organic layers were washed with 0.5M aqueous citric acid solution (1×200 ml), saturated hydrogen sodium bicarbonate solution (2×200 ml), brine (1×200 ml), then dried (MgSO4) and the solvent was removed under vacuum to give the title compound (15.1 g) as a brown solid (m.p. 216°-217° C.); δ (360 MHz, DMSO) 2.79 (1H, dd, J=15.4 and 6.1 Hz, CHAHBCHC), 3.25 (1H, dd, J=15.4 and 5.8 Hz, CHAHBCHC), 3.64 (3H, s, CO2CH3), 4.23 (1H, m, CHAHBCHC), 6.70 (1H, d, J=2.1 Hz, 6-H or 8-H), 6.82 (1H, d, J=2.1 Hz, 6-H or 8-H), 7.01 (1H, br, s, NH), 11.41 (1H, s, NOH); m/e 288 (M+), 213 (100%); Found: C, 45.75; H, 3.50; N, 9.51; C11H10Cl2N2O3 requires C, 45.70; H, 3.49; N, 9.69%.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureat reflux under an atmosphere of nitrogen for 2 hours
  3. temperatureThe mixture was then cooled
  4. customThe solvent was removed in vacuo
  5. customthe residue was partitioned between water (300 ml) and diethyl ether (300 ml)
  6. extractionThe aqueous phase was further extracted with diethyl ether (2×300 ml)
  7. washthe combined organic layers were washed with 0.5M aqueous citric acid solution (1×200 ml), saturated hydrogen sodium bicarbonate solution (2×200 ml), brine (1×200 ml)
  8. dry with materialdried (MgSO4)
  9. customthe solvent was removed under vacuum

Sources & evidence

ORD record
ord-4d85584877cd4a1ba03e6deeaa20ff14
Source dataset
uspto-grants-1993_07
Patent number
US05231102

Reaction notes

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