Hydrochloric Acid → 6-Iodoisoquinoline-1,3(2h,4h)-dione

HRID 2236568Notes

Reaction equation

HRID 2236568 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8]([O:12][Si](C(C)(C)C)(C)C)=[N:7][C:6]([O:20][Si](C(C)(C)C)(C)C)=[CH:5]2.C([Li])(C)(C)C.[I:33]I.Cl>O1CCCC1.CS(C)=O.CO.O>[I:33][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8](=[O:12])[NH:7][C:6](=[O:20])[CH2:5]2

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 807IodineHCID 593000576-Bromo-1,3-bis-(tert-butyl-dimethyl-silanyloxy)-isoquinolineHCID 178418306HCID 178418306, compound

Product 1

HCID 112661716-Iodoisoquinoline-1,3(2h,4h)-dioneYield 55.6%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 8028TetrahydrofuranSolventHCID 22242641Methanol--water (1/1)Solvent

Procedure

An amount of 6-bromo-1,3-bis{[tert-butyl(dimethyl)silyl]oxy}isoquinoline (15.0 g, 32.0 mmol) in 100 mL of anhydrous tetrahydrofuran is cooled to −78° C. and then 47 mL (80.0 mmol) of tert-butyllithium (1.7 M in pentane) is added slowly with stirring. After stirring at this temperature for 2 hr, 12.0 g (48 mmol) of fresh iodine crystal is quickly add into the mixture, and stirred at this temperature for additional 5 h. The dry-ice bath is removed, and the reaction mixture is allowed to warm up to room temperature and stirred over weekend. Evaporating the brown solution yielded brown oil. The reaction mixture is acidified with 48 mL of 2 M HCl solution and stirred at room temperature for 1 h. The mixture is filtered to give light tan solid. The solid is dissolved in hot DMSO, then 20% MeOH/H2O solution is added to give a precipitate. The precipitate is collected and washed successively with water, methanol, ether and hexane to afford 5.1 g (55.6% yield) of off-white solid: MS (ESI) m/z 286.08 (M−H)−1

Workup

  1. stirringAfter stirring at this temperature for 2 hr
  2. stirringstirred at this temperature for additional 5 h
  3. customThe dry-ice bath is removed
  4. stirringstirred over weekend
  5. customEvaporating the brown solution
  6. customyielded brown oil
  7. stirringstirred at room temperature for 1 h
  8. filtrationThe mixture is filtered
  9. customto give light tan solid
  10. customto give a precipitate
  11. customThe precipitate is collected
  12. washwashed successively with water, methanol, ether and hexane

Sources & evidence

ORD record
ord-9d496f98eadf4365a205616aa41cd4ce
Source dataset
uspto-grants-2010_05
Patent number
US07713994B2

Reaction notes

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