3-Chloro-2-methylaniline → 2-(3-Chloro-2-methylphenyl)thiophene

HRID 2295851Notes

Reaction equation

HRID 2295851 reaction equation
[Cl:1][C:2]1[C:3]([CH3:9])=[C:4]([CH:6]=[CH:7][CH:8]=1)N.[S:10]1[CH:14]=[CH:13][CH:12]=[CH:11]1.N(OCCC(C)C)=O>>[Cl:1][C:2]1[C:3]([CH3:9])=[C:4]([C:11]2[S:10][CH:14]=[CH:13][CH:12]=2)[CH:6]=[CH:7][CH:8]=1

Participants

4

Reactant 3

HCID 68943-Chloro-2-methylanilineHCID 8030ThiopheneHCID 8053Isoamyl Nitrite

Product 1

HCID 132434162-(3-Chloro-2-methylphenyl)thiopheneYield 12.5%

Procedure

To a stirred solution of 50.0 g (0.353 mol) of 3-chloro-2-methylaniline in 100 g (1.19 mol) of thiophene was added dropwise 82.7 g (0.706 mol) of isoamyl nitrite during 0.5 hour. Upon complete addition, the reaction mixture was heated to reflux temperature, and stirred for 0.75 hour. The reaction mixture was then allowed to cool to ambient temperature, and stirring was continued for 16 hours. The reaction mixture was concentrated under reduced pressure to give a black residual oil. The oil was subjected to column chromatography on silica gel, eluting with heptane, then heptane:ethyl acetate (40:1). The appropriate fractions were combined to give a red oil which was subjected to distillation under reduced pressure using a Kugelrohr distilling system to give 9.2 g of 2-(3-chloro-2methylphenyl)thiophene, b.p. 78° C.±3° C./0.05 mm.

Workup

  1. additionUpon complete addition
  2. temperaturethe reaction mixture was heated
  3. temperatureto reflux temperature
  4. stirringstirring
  5. waitwas continued for 16 hours
  6. concentrationThe reaction mixture was concentrated under reduced pressure
  7. customto give a black residual oil
  8. washeluting with heptane
  9. customto give a red oil which
  10. distillationwas subjected to distillation under reduced pressure
  11. distillationdistilling system

Sources & evidence

ORD record
ord-255bf62e7fe343ae9bd42cce4591825a
Source dataset
uspto-grants-1984_01
Patent number
US04426524

Reaction notes

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