Ammonia → 2-Methyl-5-(4-propylphenyl)selenophene

HRID 1873406Notes

Reaction equation

HRID 1873406 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[Se:11][CH:12]=[CH:13][CH:14]=2)=[CH:6][CH:5]=1)[CH2:2][CH3:3].[Li][CH2:16]CCC.CI.[Cl-].[NH4+].N>C(OCC)C>[CH3:16][C:12]1[Se:11][C:10]([C:7]2[CH:8]=[CH:9][C:4]([CH2:1][CH2:2][CH3:3])=[CH:5][CH:6]=2)=[CH:14][CH:13]=1

Participants

7

Reactant 5

HCID 222AmmoniaHCID 6328Methyl iodideHCID 25517Ammonium ChlorideHCID 594563182-(4-Propylphenyl)selenopheneHCID 178418339Butyllithium

Product 1

HCID 594562832-Methyl-5-(4-propylphenyl)selenophene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-70 °C

Procedure

3.0 g (12.0 mmol) of 2-(4-propylphenyl)selenophene are initially introduced in 30 ml of diethyl ether, and 9.4 ml (15.0 mmol, 15% soln. in hexane) of n-BuLi are metered in rapidly. The mixture is heated under reflux for 30 min and subsequently cooled to −70° C. 3.0 ml (48.2 mol) of methyl iodide are added in one portion, and the mixture is warmed to RT and stirred for 3 h. Sat. ammonium chloride soln. and conc. ammonia soln. are added, and the batch 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 with 2 N hydrochloric acid and sat. sodium chloride soln. and dried using sodium sulfate. The solution is concentrated to dryness, and the residue is purified by column chromatography (SiO2, n-heptane:EtOAc=20:1→10:1→5:1). The further purification is carried out by flash chromatography (SiO2 RP-18, ACN:water=9:1); 2-methyl-5-(4-propylphenyl)selenophene is obtained as a colourless solid (m.p. 31° C.).

Workup

  1. temperatureThe mixture is heated
  2. temperatureunder reflux for 30 min
  3. temperaturethe mixture is warmed to RT
  4. additionare added
  5. stirringthe batch is stirred vigorously for a few minutes
  6. customThe organic phase is separated off
  7. extractionthe aqueous phase is extracted with MTBE
  8. washThe combined organic phases are washed with 2 N hydrochloric acid and sat. sodium chloride soln
  9. customand dried
  10. concentrationThe solution is concentrated to dryness
  11. customthe residue is purified by column chromatography (SiO2, n-heptane:EtOAc=20:1→10:1→5:1)
  12. customThe further purification

Sources & evidence

ORD record
ord-bb1a79b4464344f79d0876a47570d6cf
Source dataset
uspto-grants-2012_11
Patent number
US08304036B2

Reaction notes

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