Ethyl Acetate → HCID 9946036, compound

HRID 1861016Notes

Reaction equation

HRID 1861016 reaction equation
C(OC(=O)[NH:7][CH2:8][CH2:9][S:10][C:11]1[CH:12]=[C:13]([C:25]2[NH:26][CH:27]=[CH:28][CH:29]=2)[C:14]2[C:15](=[O:24])[NH:16][C:17]3[C:22]=2[C:21]=1[C:20]([F:23])=[CH:19][CH:18]=3)(C)(C)C.C1C=C(Cl)C=C(C(OO)=[O:39])C=1.C(OCC)(=O)C>C1COCC1>[NH2:7][CH2:8][CH2:9][S:10]([C:11]1[CH:12]=[C:13]([C:25]2[NH:26][CH:27]=[CH:28][CH:29]=2)[C:14]2[C:15](=[O:24])[NH:16][C:17]3[C:22]=2[C:21]=1[C:20]([F:23])=[CH:19][CH:18]=3)=[O:39]

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 70297m-Chloroperbenzoic acidHCID 23550272HCID 23550272, compound

Product 1

HCID 9946036HCID 9946036, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of [2-[6-fluoro-2-oxo-3-(1H-pyrrol-2-yl)-1,2-dihydro-benzo[cd]indol-5-ylsulfanyl]-ethyl]-carbamic acid tert-butyl ester (from Example 39 above) (150 mg, 0.35 mmol) in THF (approximately 15 mL) was treated with mCPBA (Acros, 97 mg, 0.42 mmol, 75%) at 0° C. The reaction mixture was allowed to stir and warm up to room temperature overnight. The mixture was poured into ethyl acetate and washed successively with aqueous saturated Na2S2O3 and aqueous saturated K2CO3. The organic layer was dried over Na2SO4, filtered, concentrated and the residue was purified by HPLC (silica gel, 40% ethyl acetate in hexanes). The resulting intermediate was precipitated out of THF with excess of pentane. This material was then dissolved at 0° C. in 50% TFA in CH2Cl2 solution (10 mL) that contained H2O (0.5 mL) and stirred for 2 hours. Upon completion, the reaction mixture was diluted with ethyl acetate and extracted with aqueous ammonium hydroxide. The organic layer was dried over Na2SO4, filtered and concentrated to an orange solid. This solid was dissolved in THF and precipitated with excess of pentane to give 5-(2-amino-ethanesulfinyl)-6-fluoro-3-(1H-pyrrol-2-yl)-1H-benzo[cd]indol-2-one as an orange solid. (Yield 75 mg, 62%).

Workup

  1. washwashed successively with aqueous saturated Na2S2O3 and aqueous saturated K2CO3
  2. dry with materialThe organic layer was dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customthe residue was purified by HPLC (silica gel, 40% ethyl acetate in hexanes)
  6. customThe resulting intermediate was precipitated out of THF with excess of pentane
  7. dissolutionThis material was then dissolved at 0° C. in 50% TFA in CH2Cl2 solution (10 mL) that
  8. stirringstirred for 2 hours
  9. additionUpon completion, the reaction mixture was diluted with ethyl acetate
  10. extractionextracted with aqueous ammonium hydroxide
  11. dry with materialThe organic layer was dried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated to an orange solid
  14. dissolutionThis solid was dissolved in THF
  15. customprecipitated with excess of pentane

Sources & evidence

ORD record
ord-1c0fcdbd88f441bea68d48663baea49d
Source dataset
uspto-grants-2003_03
Patent number
US06531598B1

Reaction notes

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