Water → HCID 14012328, compound

HRID 2375580Notes

Reaction equation

HRID 2375580 reaction equation
[CH2:1]([NH:4][C:5](=[O:18])[C:6]([C:16]#[N:17])=[N:7][NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[F:15])[CH2:2][CH3:3].[Cl-].[Al+3].[Cl-].[Cl-].O.[OH-].[Na+]>C1(C)C=CC=CC=1.C(Cl)(Cl)Cl>[NH2:17][C:16]1[C:14]2[C:9](=[C:10]([F:15])[CH:11]=[CH:12][CH:13]=2)[N:8]=[N:7][C:6]=1[C:5]([NH:4][CH2:1][CH2:2][CH3:3])=[O:18]

Participants

7

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 6451240Aluminum(III) ChlorideHCID 86613095HCID 86613095, compound

Product 1

HCID 14012328HCID 14012328, compoundYield 3.6%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6212ChloroformSolvent2×

Conditions

Temperature
90 °C

Procedure

To a suspension of N-propyl-2-cyano-2-[(2-fluorophenyl)hydrazono]acetamide (11.1 g, 44.71 mmol) in toluene (275 mL) was added aluminum chloride (20.90 g, 156.74 mmol). The mixture was stirred at 90° C. for 2.5 hours. The reaction mixture was cooled to 0° C., and then diluted with chloroform (1 L). A small amount of water was added to quench the reaction at 0° C. Aqueous sodium hydroxide (750 mL, 20% w/v solution) was poured into the mixture slowly at 0° C., and the mixture stirred at ambient temperature for one hour. A precipitate was formed gradually. The mixture was diluted with chloroform (2 L) until all of the precipitate was dissolved, washed twice with water, dried through magnesium sulfate, and concentrated to a volume of approximately 200 mL to leave a suspension of the product. The title compound as a light beige solid (11.06 g) was collected by filtration and washed with methylene chloride (50 mL×2), methanol (50 mL) and hexane (100 mL×2). The mother liquor was concentrated, and purified by flash chromatography using a gradient of ethyl acetate in hexane to give an additional 400 mg of the title compound as a beige solid. 1H NMR (300 MHz, CDCl3) δ 8.55 (br, 1H), 7.55-7.70 (m, 2H), 3.49 (m, 2H), 1.71 (m, 2H), 1.03 (t, J=7.4 Hz, 3H) MS APCI, m/z=249 (M+H) HPLC 1.30 min.

Workup

  1. temperatureThe reaction mixture was cooled to 0° C.
  2. customto quench
  3. customthe reaction at 0° C
  4. stirringthe mixture stirred at ambient temperature for one hour
  5. customA precipitate was formed gradually
  6. dissolutionwas dissolved
  7. washwashed twice with water
  8. dry with materialdried through magnesium sulfate
  9. concentrationconcentrated to a volume of approximately 200 mL
  10. customto leave
  11. additiona suspension of the product
  12. filtrationThe title compound as a light beige solid (11.06 g) was collected by filtration
  13. washwashed with methylene chloride (50 mL×2), methanol (50 mL) and hexane (100 mL×2)
  14. concentrationThe mother liquor was concentrated
  15. custompurified by flash chromatography

Sources & evidence

ORD record
ord-11289835ecec4f81a96657b6361356d4
Source dataset
uspto-grants-2008_12
Patent number
US07465795B2

Reaction notes

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