Triethylamine → HCID 21075810, compound

HRID 1373976Notes

Reaction equation

HRID 1373976 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[C:6]3[N:15]([NH:16][CH:17]([CH3:19])[CH3:18])[C:14]([CH2:20][CH2:21][CH3:22])=[N:13][C:7]=3[C:8]([NH2:12])=[N:9][C:10]=2[CH:11]=1.[CH2:23](N(CC)CC)[CH3:24]>C(O)CC.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]>[CH:17]([NH:16][N:15]1[C:6]2[C:5]3[CH:4]=[CH:3][C:2]([CH:23]=[CH2:24])=[CH:11][C:10]=3[N:9]=[C:8]([NH2:12])[C:7]=2[N:13]=[C:14]1[CH2:20][CH2:21][CH3:22])([CH3:19])[CH3:18]

Participants

5

Reactant 2

HCID 8471TriethylamineHCID 69177518HCID 69177518, compound

Product 1

HCID 21075810HCID 21075810, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 10311-PropanolSolvent

Conditions

Temperature
100 °C

Procedure

A suspension of 7-bromo-N1-isopropyl-2-propyl-1H-imidazo[4,5-c]quinoline-1,4-diamine (1.71 g, 4.72 mmol) in 34 mL of 1-propanol was placed under an atmosphere of nitrogen. The mixture was treated with triethylamine (1.25 mL, 9.44 mmol) and then the headspace of the flask was evacuated and back-filled with nitrogen (3×). The reaction mixture was treated with potassium vinylfluoroborate (0.695 g, 5.19 mmol) and dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium (II) dichloromethane adduct (0.069 g, 0.094 mmol) and the head-space purged and backfilled as before. The reaction was heated to 100° C. After 16 h, the reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. The residue was dissolved in 50 mL of CHCl3 and washed with 5% Na2CO3 solution (15 mL). There was a thick emulsion that did not fully separate. The organic portion was washed with H2O (15 mL) resulting in another slowly separating emulsion. The combined aqueous washes were back extracted with CHCl3 (15 mL). The combined organic extracts were washed with brine (15 mL), dried over Na2SO4, filtered and concentrated under reduced pressure to yield an orange solid. The solid was purified by chromatography (SiO2, 20% (80:18:2 CHCl3:MeOH:NH4OH) in CHCl3) to yield N1-isopropyl-2-propyl-7-vinyl-1H-imidazo[4,5-c]quinoline-1,4-diamine (0.92 g) as a tan solid.

Workup

  1. customthe headspace of the flask was evacuated
  2. additionback-filled with nitrogen (3×)
  3. customthe head-space purged
  4. temperaturethe reaction mixture was cooled to ambient temperature
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in 50 mL of CHCl3
  7. washwashed with 5% Na2CO3 solution (15 mL)
  8. customdid not fully separate
  9. washThe organic portion was washed with H2O (15 mL)
  10. customresulting in
  11. customanother slowly separating emulsion
  12. extractionThe combined aqueous washes were back extracted with CHCl3 (15 mL)
  13. washThe combined organic extracts were washed with brine (15 mL)
  14. dry with materialdried over Na2SO4
  15. filtrationfiltered
  16. concentrationconcentrated under reduced pressure
  17. customto yield an orange solid
  18. customThe solid was purified by chromatography (SiO2, 20% (80:18:2 CHCl3:MeOH:NH4OH) in CHCl3)

Sources & evidence

ORD record
ord-0a979be8d04144c2b6ff9187653d749d
Source dataset
uspto-grants-2007_01
Patent number
US07163947B2

Reaction notes

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