Hydrochloric Acid → HCID 86232772, compound

HRID 554185Notes

Reaction equation

HRID 554185 reaction equation
[Br:1][C:2]1[N:6]([S:7]([C:10]2[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=2)(=[O:9])=[O:8])[CH:5]=[C:4]([C:18](OC)=[O:19])[CH:3]=1.[H-].C([Al+]CC(C)C)C(C)C.Cl>O1CCCC1.C1(C)C=CC=CC=1>[Br:1][C:2]1[N:6]([S:7]([C:10]2[CH:11]=[CH:12][C:13]([O:16][CH3:17])=[CH:14][CH:15]=2)(=[O:8])=[O:9])[CH:5]=[C:4]([CH:18]=[O:19])[CH:3]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 21225700Diisobutylaluminumhydride2×HCID 66924628HCID 66924628, compound

Product 1

HCID 86232772HCID 86232772, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution (30 mL) of methyl 5-bromo-1-[(4-methoxyphenyl)sulfonyl]-1H-pyrrole-3-carboxylate (3.00 g) in tetrahydrofuran was cooled to −78° C., a 1.5 mol/l solution (11.0 mL) of diisobutylaluminum hydride in toluene was added dropwise over 15 min, and the mixture was further stirred at −78° C. for 1 hr. A 1.5 mol/l solution (5.0 mL) of diisobutylaluminum hydride in toluene was added, and the mixture was stirred at −78° C. for 15 min, and at 25° C. for 2 hr. 1 mol/l Hydrochloric acid (40 mL) was added to the reaction mixture, and the mixture was stirred at 25° C. for 15 min and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. A solution (30 mL) of the residue in acetonitrile was cooled to 0° C., tetra-n-propylammonium perruthenate (281 mg), N-methylmorpholine N-oxide (1.41 g) and molecular sieves 4A powder (1.5 g) were added, and the mixture was stirred at room temperature for 1.5 hr. The reaction mixture was concentrated under reduced pressure, and the residue was suspended in ethyl acetate and filtered through celite. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=9:1→1:1) to give the title compound as a brown oil (yield 2.07 g, 75%).

Workup

  1. stirringthe mixture was stirred at −78° C. for 15 min
  2. waitat 25° C. for 2 hr
  3. stirringthe mixture was stirred at 25° C. for 15 min
  4. extractionextracted with ethyl acetate
  5. washThe extract was washed with saturated brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. temperatureA solution (30 mL) of the residue in acetonitrile was cooled to 0° C.
  9. additiontetra-n-propylammonium perruthenate (281 mg), N-methylmorpholine N-oxide (1.41 g) and molecular sieves 4A powder (1.5 g) were added
  10. stirringthe mixture was stirred at room temperature for 1.5 hr
  11. concentrationThe reaction mixture was concentrated under reduced pressure
  12. filtrationfiltered through celite
  13. concentrationThe filtrate was concentrated under reduced pressure
  14. customthe residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=9:1→1:1)

Sources & evidence

ORD record
ord-acb46d89b1f54202a4cc7b0fd0864a6b
Source dataset
uspto-grants-2011_11
Patent number
US08048909B2

Reaction notes

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