(2,4-Dichlorophenyl)hydrazine monohydrochloride → HCID 22171031, compound

HRID 2376238Notes

Reaction equation

HRID 2376238 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:9](O)=[CH:10][C:11](=O)[CH2:12][CH2:13][C:14]([OH:16])=[O:15])[CH:5]=[CH:6][C:7]=1[Cl:8].[Li].Cl.[Cl:21][C:22]1[CH:27]=[C:26]([Cl:28])[CH:25]=[CH:24][C:23]=1[NH:29][NH2:30]>CCO>[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[N:29]([C:23]3[CH:24]=[CH:25][C:26]([Cl:28])=[CH:27][C:22]=3[Cl:21])[N:30]=[C:11]([CH2:12][CH2:13][C:14]([OH:16])=[O:15])[CH:10]=2)[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

5

Reactant 3

HCID 2723905(2,4-Dichlorophenyl)hydrazine monohydrochlorideHCID 3028194LithiumHCID 68875341HCID 68875341, compound

Product 1

HCID 22171031HCID 22171031, compoundYield 33%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a round-bottom flask was added 6-(3,4-dichloro-phenyl)-6-hydroxy-4-oxo-hex-5-enoic acid bis-lithium salt (9.48 g, 31.3 mmol, 1.0 equiv), 2,4-dichloro-phenyl hydrazine hydrochloride (6.66 g, 31.3 mmol, 1.0 equiv) and EtOH (250 mL) under nitrogen. The mixture was stirred at room temperature for 24 h. The solvent was removed, and the crude residue was partitioned between 5% HCl and diethyl ether (200 mL each). The layers were separated, and the aqueous layer was extracted with diethyl ether (2×100 mL). The combined organic layers were washed with water (100 mL) then brine (100 mL), dried (Na2SO4), and concentrated under reduced pressure. Purification by flash chromatography (25% ethyl acetate/dichloromethane) afforded the title intermediate (4.5 g, 33%). HPLC: Rt=3.04 (Method A). MS (ESI): mass calculated for C18H12Cl4N2O2, 427.97; m/z found, 429/431 [M+H]+. 1H NMR (500 MHz, DMSO-d6): 12.20 (br s, 1H), 7.82 (d, J=2.2 Hz, 1H), 7.68 (d, J=8.5 Hz, 1H), 7.61-7.59 (m, 2H), 7.50 (d, J=2.2 Hz, 1H), 7.05 (dd, J=8.2, 1.9 Hz, 1H), 6.73 (s, 3H), 2.88 (t, J=7.4 Hz, 2H), 2.64 (t, J=7.4 Hz, 2H).

Workup

  1. customThe solvent was removed
  2. customthe crude residue was partitioned between 5% HCl and diethyl ether (200 mL each)
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with diethyl ether (2×100 mL)
  5. washThe combined organic layers were washed with water (100 mL)
  6. dry with materialbrine (100 mL), dried (Na2SO4)
  7. concentrationconcentrated under reduced pressure
  8. customPurification by flash chromatography (25% ethyl acetate/dichloromethane)

Sources & evidence

ORD record
ord-07bd7a6172ef438980eeb46bb6c0f86d
Source dataset
uspto-grants-2008_12
Patent number
US07465808B2

Reaction notes

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