Vinylidene chloride → 7-Chloro-2-methyl-8-(2,2,2-trichloroethyl)quinoxaline

HRID 505235Notes

Reaction equation

HRID 505235 reaction equation
C(ON=O)(C)(C)C.[Cl:8][C:9]([Cl:11])=[CH2:10].[Cl:12][C:13]1[C:14](N)=[C:15]2[C:20](=[CH:21][CH:22]=1)[N:19]=[CH:18][C:17]([CH3:23])=[N:16]2.[NH4+].[Cl-:26]>C(#N)C.[Cu](Cl)Cl.CCOC(C)=O>[Cl:12][C:13]1[C:14]([CH2:10][C:9]([Cl:26])([Cl:11])[Cl:8])=[C:15]2[C:20]([N:19]=[CH:18][C:17]([CH3:23])=[N:16]2)=[CH:21][CH:22]=1

Participants

8

Reactant 4

HCID 6366Vinylidene chlorideHCID 10906Tert-Butyl nitriteHCID 25517Ammonium ChlorideHCID 668833186-Chloro-3-methylquinoxalin-5-amine

Product 1

HCID 668820407-Chloro-2-methyl-8-(2,2,2-trichloroethyl)quinoxalineYield 56%

Reagents, catalysts & solvents 3

HCID 24014Cupric ChlorideCatalystHCID 6342AcetonitrileSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Tert-butylnitrite (2.74 g, 26.60 mmol, 1.5 equiv) was added to a suspension of copper(II) chloride (2.86 g, 21.28 mmol, 1.2 equiv) in anhydrous acetonitrile (25 ml). 1,1-Dichloroethene (25.8 g, 266 mmol, 15 equiv) and a solution of 6-chloro-3-methyl-quinoxalin-5-ylamine (3.43 g, 17.74 mmol) in anhydrous acetonitrile (16 ml) were added. After 4 hours at room temperature, concentrated aqueous NH4Cl solution and EtOAc were added. The mixture was filtered and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified via flash chromatography (gradient of hexane/EtOAc 100:0 to 90:10) to afford the title compound (3.08 g, 56%) as an oil. 1H NMR (400 MHz, CDCl3): δ=8.71 (s, 1H), 8.02 (d, J=8.8 Hz, 1H), 7.74 (d, J=8.8 Hz, 1H), 4.98 (s, 2H), 2.77 (s, 3H). MS (ES+): 310 (M+H)+.

Workup

  1. filtrationThe mixture was filtered
  2. extractionextracted with EtOAc
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified via flash chromatography (gradient of hexane/EtOAc 100:0 to 90:10)

Sources & evidence

ORD record
ord-a159d9c857e24c428de49b07c9cda041
Source dataset
uspto-grants-2010_08
Patent number
US07781438B2

Reaction notes

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