Methyl 4-benzylsulfanyl-5-nitrothiophene-3-carboxylate → (4-Benzylsulfanyl-5-nitro-thiophen-3-yl)-methanol

HRID 552098Notes

Reaction equation

HRID 552098 reaction equation
[CH2:1]([S:8][C:9]1[C:10]([C:17](OC)=[O:18])=[CH:11][S:12][C:13]=1[N+:14]([O-:16])=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].C([Al+]CC(C)C)C(C)C>ClCCl>[CH2:1]([S:8][C:9]1[C:10]([CH2:17][OH:18])=[CH:11][S:12][C:13]=1[N+:14]([O-:16])=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 851124Methyl 4-benzylsulfanyl-5-nitrothiophene-3-carboxylateHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 59168797(4-Benzylsulfanyl-5-nitro-thiophen-3-yl)-methanol

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Methyl 4-(benzylthio)-5-nitrothiophene-3-carboxylate (5 g, 16.2 mmol) in dichloromethane (150 mL) at −40° C. was reacted with diisobutylaluminum hydride (1 M in dichloromethane, 36 mL, 2.2 equivalents) added dropwise. The reaction was stirred for 15 minutes after complete addition, quenched with 10% aqueous sodium potassium tartrate solution and stirred at 25° C. for 1 hour. The organic layer was separated, filtered through Celite® (diatomaceous earth) and the filtrate was concentrated under reduced pressure. The resulting oil was purified by flash chromatography on silica gel with a Biotage-40s column eluting with 2:98 methanol/dichloromethane to give [4-(benzylthio)-5-nitrothien-3-yl]methanol as an oil, (4.32 g, 95%). 1H NMR (300 MHz, CDCl3) ppm 4.21 (s, 2 H), 4.39 (s, 2 H), 7.11 (m, 3 H), 7.23 (m, 2 H) 7.40 (s, 1 H).

Workup

  1. additionadded dropwise
  2. additionafter complete addition
  3. customquenched with 10% aqueous sodium potassium tartrate solution
  4. stirringstirred at 25° C. for 1 hour
  5. customThe organic layer was separated
  6. filtrationfiltered through Celite® (diatomaceous earth)
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe resulting oil was purified by flash chromatography on silica gel with a Biotage-40s column
  9. washeluting with 2:98 methanol/dichloromethane

Sources & evidence

ORD record
ord-6222150b35044304b6a0a4241f838de0
Source dataset
uspto-grants-2011_05
Patent number
US07951800B2

Reaction notes

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