Dimethylformamide → HCID 178509774, compound

HRID 549476Notes

Reaction equation

HRID 549476 reaction equation
C[N:2]([CH:4]=O)C.[Cl:6][C:7]1[CH:8]=[CH:9][C:10]2[C:23]3[N:22]=[C:21]([C:24]4[C:29](Br)=[CH:28][CH:27]=[CH:26][C:25]=4Br)[NH:20][C:19]=3[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:11]=2[CH:12]=1.[C:32]([Cu])#[N:33].[OH-].[NH4+]>C(OCC)(=O)C.O>[Cl:6][C:7]1[CH:8]=[CH:9][C:10]2[C:23]3[N:22]=[C:21]([C:24]4[C:29]([C:4]#[N:2])=[CH:28][CH:27]=[CH:26][C:25]=4[C:32]#[N:33])[NH:20][C:19]=3[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:11]=2[CH:12]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 14923Ammonium HydroxideHCID 178418546HCID 178418546, compoundHCID 178477840HCID 178477840, compound

Product 1

HCID 178509774HCID 178509774, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a DMF (300 mL) solution of 32 g (65.7 mmol) of 6-chloro-2-(2,6-dibromophenyl)-1H-phenanthro[9,10-d]imidazole from Step 5 was added 14.7 g of CuCN. The reaction was stirred overnight at 80° C., cooled down to room temperature, poured into a mixture of 1.5 L of water, 1.5 L of ethyl acetate and 200 mL of concentrated ammonium hydroxide and stirred 1 hr at room temperature. The aqueous layer was extracted with ethyl acetate and the combined organic layers were washed with 10% ammonium hydroxide, water, brine, dried over sodium sulphate and volatiles were removed under reduced pressure. The residue was swished in toluene (2×200 mL) and ethyl acetate (1 L). The obtained solid was purified by flash chromatography on silica gel in 5 portions using a gradient of 60% to 80% to 100% of ethyl acetate/hexane to afford 19.9 g of 2-(6-chloro-1H-phenanthro[9,10-d]imidazol-2-yl)isophthalonitrile as a pale yellow solid. 1H NMR (400 MHz, DMSO): δ 14.32 (s, 1H), 9.0-8.9 (m, 2H), 8.55-8.45 (m, 4H), 7.99 (t, 1H), 7.85-7.78 (m, 2H), 7.72 (t, 1H).

Workup

  1. temperaturecooled down to room temperature
  2. stirringstirred 1 hr at room temperature
  3. extractionThe aqueous layer was extracted with ethyl acetate
  4. washthe combined organic layers were washed with 10% ammonium hydroxide, water, brine
  5. dry with materialdried over sodium sulphate and volatiles
  6. customwere removed under reduced pressure
  7. customThe obtained solid was purified by flash chromatography on silica gel in 5 portions

Sources & evidence

ORD record
ord-1c5edad38c7e497783a78d9df3f2db9d
Source dataset
uspto-grants-2011_05
Patent number
US07943649B2

Reaction notes

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