N-Formylmorpholine → 5-(4'-Ethyl-3-fluorobiphenyl-4-yl)selenophene-2-carbaldehyde

HRID 1873429Notes

Reaction equation

HRID 1873429 reaction equation
[Li]CCCC.[CH2:6]([C:8]1[CH:13]=[CH:12][C:11]([C:14]2[CH:19]=[CH:18][C:17]([C:20]3[Se:21][CH:22]=[CH:23][CH:24]=3)=[C:16]([F:25])[CH:15]=2)=[CH:10][CH:9]=1)[CH3:7].[CH:26](N1CCOCC1)=[O:27]>C1COCC1.ClCCl.Cl>[CH2:6]([C:8]1[CH:9]=[CH:10][C:11]([C:14]2[CH:19]=[CH:18][C:17]([C:20]3[Se:21][C:22]([CH:26]=[O:27])=[CH:23][CH:24]=3)=[C:16]([F:25])[CH:15]=2)=[CH:12][CH:13]=1)[CH3:7]

Participants

7

Reactant 3

HCID 20417N-FormylmorpholineHCID 594563342-(4'-Ethyl-3-fluorobiphenyl-4-yl)selenopheneHCID 178418339Butyllithium

Product 1

HCID 594563395-(4'-Ethyl-3-fluorobiphenyl-4-yl)selenophene-2-carbaldehyde

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

27.5 ml (0.16 mol) of TMP are initially introduced at −20° C. in 100 ml of THF, and 100 ml (0.16 mol, 15% soln. in hexane) of n-BuLi are metered in. After 30 min at this temperature, a solution of 50.2 g (0.15 mol) of 2-(4′-ethyl-3-fluorobiphenyl-4-yl)selenophene in 400 ml of THF is added. When the addition is complete, the batch is warmed to RT and left at this temperature for 30 min. The solution is cooled to −70° C., and 17.0 ml (0.17 mol) of N-formylmorpholine are added. The reaction mixture is warmed to RT and stirred for 1 h. the solution is diluted with a lot of dichloromethane, and 2 N hydrochloric acid is added. The mixture is washed with water, and the organic phase is separated off. The aqueous phase is extracted with dichloromethane, and the combined organic phases are washed with sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The residue is taken up in dichloromethane and purified by column chromatography (SiO2, toluene). The further purification is carried out by recrystallisation from toluene. 5-(4′-Ethyl-3-fluorobiphenyl-4-yl)selenophene-2-carbaldehyde is obtained as a brown solid.

Workup

  1. additionWhen the addition
  2. waitleft at this temperature for 30 min
  3. temperatureThe solution is cooled to −70° C.
  4. temperatureThe reaction mixture is warmed to RT
  5. additionis added
  6. washThe mixture is washed with water
  7. customthe organic phase is separated off
  8. extractionThe aqueous phase is extracted with dichloromethane
  9. washthe combined organic phases are washed with sat. sodium chloride soln
  10. customThe solution is dried
  11. concentrationconcentrated to dryness
  12. custompurified by column chromatography (SiO2, toluene)
  13. customThe further purification
  14. customis carried out by recrystallisation from toluene

Sources & evidence

ORD record
ord-68cd8e094b40407ca5bee448bcf52fc2
Source dataset
uspto-grants-2012_11
Patent number
US08304036B2

Reaction notes

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