Ammonia → 2-(2',3'-Difluoro-4'-propoxybiphenyl-4-yl)-5-methylselenophene

HRID 1873412Notes

Reaction equation

HRID 1873412 reaction equation
[Li][CH2:2]CCC.[F:6][C:7]1[C:12]([F:13])=[C:11]([O:14][CH2:15][CH2:16][CH3:17])[CH:10]=[CH:9][C:8]=1[C:18]1[CH:23]=[CH:22][C:21]([C:24]2[Se:25][CH:26]=[CH:27][CH:28]=2)=[CH:20][CH:19]=1.CI.[Cl-].[NH4+].N>C(OCC)C>[F:6][C:7]1[C:12]([F:13])=[C:11]([O:14][CH2:15][CH2:16][CH3:17])[CH:10]=[CH:9][C:8]=1[C:18]1[CH:23]=[CH:22][C:21]([C:24]2[Se:25][C:26]([CH3:2])=[CH:27][CH:28]=2)=[CH:20][CH:19]=1

Participants

7

Reactant 5

HCID 222AmmoniaHCID 6328Methyl iodideHCID 25517Ammonium ChlorideHCID 59456297HCID 59456297, compoundHCID 178418339Butyllithium

Product 1

HCID 594563062-(2',3'-Difluoro-4'-propoxybiphenyl-4-yl)-5-methylselenophene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

2.0 ml (11.8 mmol) of TMP are initially introduced at −15° C. in 15 ml of diethyl ether, and 7.0 ml (11.1 mmol, 15% soln. in hexane) of n-BuLi are metered in. After 25 min, a solution of 3.5 g (9.3 mmol) of 2-(2′,3′-difluoro-4′-propoxybiphenyl-4-yl)selenophene in 35 ml of diethyl ether is metered in, and the mixture is stirred at RT for 45 min. The batch is cooled to −70° C., and 3.0 ml (48.2 mmol) of methyl iodide are added. The mixture is warmed to RT and stirred for 3 h. Sat. ammonium chloride soln. and conc. ammonia soln. are added successively, and the mixture is briefly stirred vigorously. 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:toluene=1:1). The further purification is carried out by digestion in ethanol and recrystallisation from n-heptane/toluene (2:1). 2-(2′,3′-Difluoro-4′-propoxybiphenyl-4-yl)-5-methylselenophene is obtained as a solid having an m.p. of 143° C.

Workup

  1. temperatureThe batch is cooled to −70° C.
  2. temperatureThe mixture is warmed to RT
  3. stirringstirred for 3 h
  4. additionare added successively
  5. stirringthe mixture is briefly stirred vigorously
  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:toluene=1:1)
  12. customThe further purification
  13. customrecrystallisation from n-heptane/toluene (2:1)

Sources & evidence

ORD record
ord-b5b52ff7d69d4b5e996c848e7fc76114
Source dataset
uspto-grants-2012_11
Patent number
US08304036B2

Reaction notes

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