Ammonia → 5-Bromosalicylamide

HRID 1991553Notes

Reaction equation

HRID 1991553 reaction equation
[Br:1][C:2]1[CH:10]=[C:6]([C:7](O)=[O:8])[C:5]([OH:11])=[CH:4][CH:3]=1.OS(O)(=O)=O.[NH3:17]>C(O)CCC.CO>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([OH:11])=[C:6]([CH:10]=1)[C:7]([NH2:17])=[O:8]

Participants

6

Reactant 3

HCID 222AmmoniaHCID 1118Sulfuric AcidHCID 69725-Bromosalicylic acid

Product 1

HCID 728765-BromosalicylamideYield 82%

Reagents, catalysts & solvents 2

HCID 2631-ButanolSolvent2×HCID 887MethanolSolvent2×

Procedure

To a stirred solution of 5-Bromosalicyclic acid (30 g, 135.5 mmol) in n-butylalcohol (60 mL) was added H2SO4 (95.6%, 289 μL, 5.42 mmol) in a 100 ml round bottom flask connected by a Dean-Stark trap/reflux condenser that was filled with 12 ml of n-butylalcohol. After heated to reflux for 2 days, the reaction was cooled down to R.T. and concentrated to give a pale yellow oil. The mixture was added 50 mL MeOH, followed by NH3 in MeOH (7 N, 116 mL). The reaction was stirred at R.T. for another 2 days, monitored by HPLC. After the reaction complete, it was concentrated to give a white solid. The crude solid was washed with small amount of EtOAc and hexane to afford 24 g of the product as a white crystalline solid (82% yield). 1H NMR (CDCl3) δ 12.15 (s, 1H), 7.54 (m, 2H), 6.97 (d, J=12 Hz, 1H), 6.00 (broad, 2H).

Workup

  1. temperaturetrap/reflux condenser that
  2. temperatureAfter heated
  3. temperatureto reflux for 2 days
  4. concentrationconcentrated
  5. customto give a pale yellow oil
  6. customAfter the reaction complete
  7. concentrationit was concentrated
  8. customto give a white solid
  9. washThe crude solid was washed with small amount of EtOAc and hexane

Sources & evidence

ORD record
ord-97f3a81385b14de18924ca948ab4d75e
Source dataset
uspto-grants-2010_01
Patent number
US07645780B2

Reaction notes

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