Dimethylformamide → HCID 20033696, compound

HRID 231687Notes

Reaction equation

HRID 231687 reaction equation
Br[C:2]1[CH:6]=[CH:5][S:4][C:3]=1[S:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][CH3:15])=[CH:10][CH:9]=1.C([Li])CCC.CCCCCC.CN(C)[CH:29]=[O:30]>CCOCC>[CH3:15][O:14][C:11]1[CH:12]=[CH:13][C:8]([S:7][C:3]2[S:4][CH:5]=[CH:6][C:2]=2[CH:29]=[O:30])=[CH:9][CH:10]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8058HexaneHCID 20033702HCID 20033702, compoundHCID 178418339Butyllithium

Product 1

HCID 20033696HCID 20033696, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of 3-bromo-2-(4-methoxyphenylthio)thiophene (12.77 g, 0.042 mol) in anhydrous ether (100 ml) cooled to -78° C. was added dropwise over 1 hour. 1.55M n-butyl lithium in hexane (28.7 ml, 0.045 mol) under nitrogen atmosphere. The solution was stirred at -78° C. for another hour and then the temperature was allowed to rise to -30° C. over 1/4 hour. The temperature was lowered to -60° C. and dry dimethylformamide (6.2 g, 0.085 mol) was added over 5 minutes. The cooling bath was removed and the temperature was allowed to rise to 15° C. over 3/4 hour. The mixture was cooled to -20° C. and acidified by slowly adding 3NHCl (40 ml). The ether layer was separated and washed with saturated NaCl, saturated NaHCO3 and again with saturated NaCl. The solution was dried, filtered and concentrated in vacuo. A quantitative recovery of an amber oil which solidified to a waxy yellow solid was obtained. The product recrystallized from n-butyl chloride-hexane, mp 58°-60° C. The structure and purity were confirmed by NMR, mass spectral analysis and elemental analyses.

Workup

  1. additionwas added dropwise over 1 hour
  2. waitto rise to -30° C. over 1/4 hour
  3. customwas lowered to -60° C.
  4. customThe cooling bath was removed
  5. waitto rise to 15° C. over 3/4 hour
  6. temperatureThe mixture was cooled to -20° C.
  7. additionby slowly adding 3NHCl (40 ml)
  8. customThe ether layer was separated
  9. washwashed with saturated NaCl, saturated NaHCO3 and again with saturated NaCl
  10. customThe solution was dried
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customwas obtained
  14. customThe product recrystallized from n-butyl chloride-hexane, mp 58°-60° C

Sources & evidence

ORD record
ord-80faff47068d494ba27136d9ab6d361a
Source dataset
uspto-grants-1989_07
Patent number
US04847289

Reaction notes

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