Ammonia → HCID 59456261, compound

HRID 1873418Notes

Reaction equation

HRID 1873418 reaction equation
[CH2:1]([Li])CCCCC.[F:8][C:9]1[CH:10]=[C:11]([C:20]2[CH:25]=[CH:24][C:23]([CH2:26][CH2:27][CH3:28])=[CH:22][CH:21]=2)[CH:12]=[CH:13][C:14]=1[C:15]1[Se:16][CH:17]=[CH:18][CH:19]=1.CI.N>C1COCC1.CC(OC)(C)C.[Cl-].[NH4+]>[F:8][C:9]1[CH:10]=[C:11]([C:20]2[CH:21]=[CH:22][C:23]([CH2:26][CH2:27][CH3:28])=[CH:24][CH:25]=2)[CH:12]=[CH:13][C:14]=1[C:15]1[Se:16][C:17]([CH3:1])=[CH:18][CH:19]=1

Participants

8

Reactant 4

HCID 222AmmoniaHCID 6328Methyl iodideHCID 59456313HCID 59456313, compoundHCID 178506865HCID 178506865, compound

Product 1

HCID 59456261HCID 59456261, compound

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 15413tert-Butyl methyl etherSolventHCID 25517Ammonium ChlorideSolvent

Procedure

3.5 ml (20.6 mmol) of TMP are initially introduced at −20° C. in THF, and 7.7 ml (19.3 mmol, 2.5 M in hexane) of n-HexLi are metered in. After 25 min at this temperature, a solution of 5.5 g (16.0 mmol) of 2-(3-fluoro-4′-propylbiphenyl-4-yl)selenophene in 50 ml of THF is added. When the addition is complete, the batch is warmed to RT over the course of 45 min and left at this temperature for 20 min. The solution is cooled to −70° C., and 13.6 g (95.8 mmol) of methyl iodide are added. The reaction mixture is warmed to RT and stirred for 20 h. The solution is diluted with MTBE, and sat. ammonium chloride soln. and conc. ammonia soln. are added successively. The mixture is stirred vigorously for a few minutes, and the organic phase is separated off. The aqueous phase is extracted with MTBE, and the combined organic phases washed successively with water, 2 N hydrochloric acid and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to dryness. The crude product is purified by chromatography. The further purification is carried out by recrystallisation from n-heptane. 2-(3-Fluoro-4′-propylbiphenyl-4-yl)-5-methylselenophene is obtained as a solid having an m.p. of 97° C.

Workup

  1. additionWhen the addition
  2. waitleft at this temperature for 20 min
  3. temperatureThe solution is cooled to −70° C.
  4. temperatureThe reaction mixture is warmed to RT
  5. additionare added successively
  6. stirringThe mixture is stirred vigorously for a few minutes
  7. customthe organic phase is separated off
  8. extractionThe aqueous phase is extracted with MTBE
  9. washthe combined organic phases washed successively with water, 2 N hydrochloric acid and sat. sodium chloride soln
  10. customThe solution is dried
  11. concentrationconcentrated to dryness
  12. customThe crude product is purified by chromatography
  13. customThe further purification
  14. customis carried out by recrystallisation from n-heptane

Sources & evidence

ORD record
ord-291ebeaee73d44c18d5d1b2a4dc5fec5
Source dataset
uspto-grants-2012_11
Patent number
US08304036B2

Reaction notes

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