Dichloromethane → 8-Fluoro-6-methylphenanthridine

HRID 2224629Notes

Reaction equation

HRID 2224629 reaction equation
I[C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].FC(F)(F)S(O[C:15]1[CH:20]=[CH:19][C:18]([F:21])=[CH:17][C:16]=1[C:22](=O)[CH3:23])(=O)=O.C(=O)([O-])[O-].[Na+].[Na+].ClCCl>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CN(C)C=O>[F:21][C:18]1[CH:19]=[CH:20][C:15]2[C:16](=[C:22]([CH3:23])[N:4]=[C:3]3[C:2]=2[CH:8]=[CH:7][CH:6]=[CH:5]3)[CH:17]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 119952-IodoanilineHCID 597176142-Acetyl-4-fluorophenyl trifluoromethanesulfonate

Product 1

HCID 224823738-Fluoro-6-methylphenanthridineYield 27%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

1H NMR and TLC and no starting material was present (2-iodoaniline). 2-Acetyl-4-fluorophenyl trifluoromethanesulfonate (7.9 g, 28 mmol) was added to the reaction mixture, along with aqueous sodium carbonate (2 M, 61 mL, 122 mmol) and additional [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (1.0 g, 1.22 mmol) and N,N-dimethylformamide (50 mL). The reaction mixture was degassed several times and heated at 85° C. for 18 hours. The mixture was cooled to room temperature and poured into water (250 mL). The suspension was extracted with diethyl ether (2×250 mL). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated in vacuo to give a brown oil. Purification by column chromatography (1:4 ethyl acetate:hexane) gave the product as a pale yellow solid (1.33 g, 27% ).

Workup

  1. customThe reaction mixture was degassed several times
  2. temperatureThe mixture was cooled to room temperature
  3. additionpoured into water (250 mL)
  4. extractionThe suspension was extracted with diethyl ether (2×250 mL)
  5. dry with materialThe combined organic extracts were dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give a brown oil
  9. customPurification by column chromatography (1:4 ethyl acetate:hexane)

Sources & evidence

ORD record
ord-32d051dcfba44ee28513e73f8714f83f
Source dataset
uspto-grants-2008_05
Patent number
US07378427B2

Reaction notes

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