Hydrochloric Acid → HCID 59157932, compound

HRID 1920523Notes

Reaction equation

HRID 1920523 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[CH:4][C:3]=1[I:9].Cl.[C:11]1(Cl)[C:17](=O)C(Cl)=C(Cl)[C:13](=O)[C:12]=1Cl.C(=O)/C=C/C>C(O)(C)C.CCOC(C)=O.[NH4+].[OH-]>[Br:1][C:2]1[CH:7]=[C:6]2[C:5](=[CH:4][C:3]=1[I:9])[N:8]=[C:12]([CH3:13])[CH:11]=[CH:17]2

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8371ChloranilHCID 447466CrotonaldehydeHCID 145483374-Bromo-3-iodoaniline

Product 1

HCID 59157932HCID 59157932, compound

Reagents, catalysts & solvents 3

HCID 3776IsopropanolSolvent2×HCID 8857Ethyl AcetateSolventHCID 14923Ammonium HydroxideSolvent

Procedure

To (4-bromo-3-iodophenyl)amine (11.93 g, 40 mmol) was added conc HCl (6 ml), p-chloranil (9.83 g, 1 equiv.) and isopropanol (20 ml) and the mixture was heated to reflux. A solution of crotonaldehyde (3.98 ml) in isopropanol (3.8 ml) was then added at a rate of 0.1 ml/min using a syringe pump and the mixture was stirred at reflux for another 40 min after the end of the addition. The mixture was cooled to r.t., diluted with EtOAc and 5% aq. NH4OH. The products were extracted in EtOAc and the organic layer was washed several times with water, brine, and dried over Na2SO4. The crude material was dissolved as much as possible in 300 ml boiling toluene and purified by flash chromatography on silica with a gradient of EtOAc/toluene 0 to 5%. The first product was 6-bromo-7-iodo-2-methylquinoline followed by its isomer 6-bromo-5-iodo-2-methylquinoline.

Workup

  1. temperaturethe mixture was heated to reflux
  2. temperatureat reflux for another 40 min
  3. additionafter the end of the addition
  4. extractionThe products were extracted in EtOAc
  5. washthe organic layer was washed several times with water, brine
  6. dry with materialdried over Na2SO4
  7. dissolutionThe crude material was dissolved as much as possible in 300 ml
  8. custompurified by flash chromatography on silica with a gradient of EtOAc/toluene 0 to 5%

Sources & evidence

ORD record
ord-02154a50f23349f3a0e9697d1000d3cd
Source dataset
uspto-grants-2012_05
Patent number
US08168815B2

Reaction notes

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