Sulfuric Acid → 8-Bromo-4-methylquinoline

HRID 2374172Notes

Reaction equation

HRID 2374172 reaction equation
[Br:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].S(=O)(=O)(O)O.[CH:14]([C:16]([CH3:18])=O)=[CH2:15].[OH-].[Na+]>C(O)(=O)C.O>[CH3:18][C:16]1[C:5]2[C:3](=[C:2]([Br:1])[CH:8]=[CH:7][CH:6]=2)[N:4]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 6570Methyl vinyl ketoneHCID 119922-BromoanilineHCID 14798Sodium Hydroxide

Product 1

HCID 153799098-Bromo-4-methylquinoline

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

2-Bromoaniline (5.16 g, 30 mmol) dissolved in acetic acid and conc. sulfuric acid was treated with a solution of methyl vinyl ketone in acetic acid. The reaction mixture heated to 90° C. for 14 h. The cooled mixture was poured into water and basified with sodium hydroxide and extracted into EtOAc. The organics were dried over Na2SO4, and concentrated the purified by SGC (Combiflash 0-100% EtOAc: hexanes over 30 minutes) followed by recrystallization from hot hexanes furnished 4-methyl-8-bromoquinoline (2.3 g). 1H NMR (CDCl3) δ 8.92 (d, 1H), 8.08 (d,1H), 8.01 (d,1H), 7.45 (t,1H), 7.32 (d,1H), 2.71 (s, 3H).

Workup

  1. extractionextracted into EtOAc
  2. dry with materialThe organics were dried over Na2SO4
  3. concentrationconcentrated the
  4. custompurified by SGC (Combiflash 0-100% EtOAc: hexanes over 30 minutes)
  5. customfollowed by recrystallization from hot hexanes

Sources & evidence

ORD record
ord-fe770b77b80a4e4f9565ca3795157d67
Source dataset
uspto-grants-2008_12
Patent number
US07462600B2

Reaction notes

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