Dimethylformamide → HCID 22918435, compound

HRID 1376768Notes

Reaction equation

HRID 1376768 reaction equation
I[C:2]1[CH:27]=[CH:26][CH:25]=[CH:24][C:3]=1[NH:4][C:5]1[CH:6]=[C:7]2[C:12](=[O:13])[NH:11][C:9](=[O:10])[C:8]2=[CH:14][C:15]=1[NH:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1I.[Cu][C:29]#[N:30].[CH3:31][N:32](C=O)C>C(OCC)(=O)C.O.Cl.[Fe](Cl)(Cl)Cl>[C:31]([C:2]1[CH:27]=[CH:26][CH:25]=[CH:24][C:3]=1[NH:4][C:5]1[CH:6]=[C:7]2[C:12](=[O:13])[NH:11][C:9](=[O:10])[C:8]2=[CH:14][C:15]=1[NH:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:29]#[N:30])#[N:32]

Participants

8

Reactant 3

HCID 6228DimethylformamideHCID 22918357HCID 22918357, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 22918435HCID 22918435, compound

Reagents, catalysts & solvents 4

HCID 24380Iron chloride (FeCl3)CatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 581 mg (1 mmol) of 4,5-bis(2-iodoanilino)phthalimide and 197 mg (2.2 mmol) of copper(I) cyanide in DMF is stirred for 6 hours at 130°-140° C., the dark-brown solution changing into a dark-yellow suspension. The reaction mixture is cooled to 80° C. and diluted with 8 ml ethyl acetate. After further cooling to 60°-70° C., a solution of 467 mg (2.88 mmol) of iron(III) chloride in 1.6 ml of water and 300 μl of concentrated hydrochloric acid is added dropwise and the mixture is stirred for 30 minutes. 2 ml of water and Hyflo Super Cel® (kieselguhr from Fluka, Buchs, Switzerland) are added to the reaction mixture which is then filtered through Hyflo Super Gel® and the phases are separated. The aqueous phase is extracted once with ethyl acetate and the combined organic phases are washed twice with water, once with saturated sodium hydrogen carbonate solution and twice more with water, dried over magnesium sulfate and concentrated by evaporation. The resulting oily brown crystal mixture is chromatographed on silica gel with ethyl acetate/hexane 2:3. The product fractions are concentrated by evaporation and crystallized from boiling dichloromethane, yielding the title compound in the form of pale-yellow crystals: FAB-MS: 380 (M+ +H), m.p.: 279°-280° C.

Workup

  1. temperatureAfter further cooling to 60°-70° C.
  2. filtrationis then filtered through Hyflo Super Gel®
  3. customthe phases are separated
  4. extractionThe aqueous phase is extracted once with ethyl acetate
  5. washthe combined organic phases are washed twice with water, once with saturated sodium hydrogen carbonate solution and twice more with water
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated by evaporation
  8. customThe resulting oily brown crystal mixture is chromatographed on silica gel with ethyl acetate/hexane 2:3
  9. concentrationThe product fractions are concentrated by evaporation
  10. customcrystallized

Sources & evidence

ORD record
ord-774ec9cbc12249d19a069f5b830a6995
Source dataset
uspto-grants-1997_09
Patent number
US05663336

Reaction notes

Loading…