Ammonia → 2-(4'-Ethyl-3-fluorobiphenyl-4-yl)-5-methylselenophene

HRID 1873428Notes

Reaction equation

HRID 1873428 reaction equation
[Li][CH2:2]CCC.[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].CI.[Cl-].[NH4+].N>C(OCC)C>[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]([CH3:2])=[CH:23][CH:24]=3)=[C:16]([F:25])[CH:15]=2)=[CH:12][CH:13]=1)[CH3:7]

Participants

7

Reactant 5

HCID 222AmmoniaHCID 6328Methyl iodideHCID 25517Ammonium ChlorideHCID 594563342-(4'-Ethyl-3-fluorobiphenyl-4-yl)selenopheneHCID 178418339Butyllithium

Product 1

HCID 594563122-(4'-Ethyl-3-fluorobiphenyl-4-yl)-5-methylselenophene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

5.5 ml (32.3 mmol) of TMP are initially introduced at −15° C. in 20 ml of diethyl ether, and 20.0 ml (31.8 mmol, 15% soln. in hexane) of n-BuLi are metered in. After 30 min, a solution of 10.0 g (30.4 mmol) of 2-(4′-ethyl-3-fluorobiphenyl-4-yl)selenophene in 80 ml of diethyl ether is added. When the addition is complete, the batch is warmed to RT and stirred for 90 min. The solution is cooled to −70° C., and 10.0 ml (0.16 mol) of methyl iodide are added. The reaction mixture is warmed to RT and stirred for 20 h. Sat. ammonium chloride soln. and conc. ammonia soln. are added successively, and the mixture is stirred vigorously for a few minutes. The organic phase is separated off, and the aqueous phase is extracted with MTBE. The combined organic phases are 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 column chromatography (SiO2, n-heptane:toluene=95:5). The further purification is carried out by recrystallisation from n-heptane. 2-(4′-Ethyl-3-fluorobiphenyl-4-yl)-5-methylselenophene is obtained as a solid having an m.p. of 121° C.

Workup

  1. additionWhen the addition
  2. temperatureThe solution is cooled to −70° C.
  3. temperatureThe reaction mixture is warmed to RT
  4. stirringstirred for 20 h
  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 are 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 column chromatography (SiO2, n-heptane:toluene=95:5)
  13. customThe further purification
  14. customis carried out by recrystallisation from n-heptane

Sources & evidence

ORD record
ord-5de6e593a1f440c494ae168bd43f8c54
Source dataset
uspto-grants-2012_11
Patent number
US08304036B2

Reaction notes

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