Sulfuric Acid → 6-Bromo-7-methylquinoline

HRID 655224Notes

Reaction equation

HRID 655224 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[CH:4][C:3]=1[CH3:9].[N+]([C:13]1[CH:18]=CC=C[CH:14]=1)([O-])=O.S(=O)(=O)(O)O>C(O)C(O)CO>[Br:1][C:2]1[CH:7]=[C:6]2[C:5](=[CH:4][C:3]=1[CH3:9])[N:8]=[CH:18][CH:13]=[CH:14]2

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 7416NitrobenzeneHCID 233594-Bromo-3-methylaniline

Product 1

HCID 579110186-Bromo-7-methylquinoline

Reagents, catalysts & solvents 1

HCID 753GlycerolSolvent

Procedure

A mixture of 20 g of 4-bromo-3-methyl-phenylamine, 6.6 g of ferrous sulfate, 40.8 g of propane-1,2,3-triol, 8.12 g of nitrobenzene and 23 ml of concentrated sulfuric acid were heated gently. After the first vigorous reaction, the mixture was heated to reflux for 3 h and then evaporated to remove the excess nitrobenzene. To the solution was added saturated NaHCO3 to pH 8 and the solution was filtered and extracted with dichloromethane. The dichloromethane layers were combined and dried over Na2SO4 and concentrated. The solid was purified via flash column chromatography to give yellow solid which was washed with petroleum ether to return the title compound (7.5 g, 65%). NMR (CDCl3, 300 MHz) δ 8.89 (m, 1H), 8.04 (m, 2H), 7.96 (s, 1H), 7.36 (m, 1H), 2.60 (s, 3H).

Workup

  1. temperaturewere heated gently
  2. customAfter the first vigorous reaction
  3. temperaturethe mixture was heated
  4. temperatureto reflux for 3 h
  5. customevaporated
  6. customto remove the excess nitrobenzene
  7. additionTo the solution was added saturated NaHCO3 to pH 8
  8. filtrationthe solution was filtered
  9. extractionextracted with dichloromethane
  10. dry with materialdried over Na2SO4
  11. concentrationconcentrated
  12. customThe solid was purified via flash column chromatography
  13. customto give yellow solid which
  14. washwas washed with petroleum ether

Sources & evidence

ORD record
ord-0e571b6610d144f483983302cdaf2a50
Source dataset
uspto-grants-2011_12
Patent number
US08071581B2

Reaction notes

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