Hydrochloric Acid → 1-Bromo-3-methoxy-5-methylbenzene
Reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5](N)=[C:4]([O:10][CH3:11])[CH:3]=1.Cl.N([O-])=O.[Na+].[PH2](O)=O>O.C(OCC)(=O)C.C(O)(=O)C>[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([O:10][CH3:11])[CH:3]=1Participants
8
Reactant 4
Product 1
Reagents, catalysts & solvents 3
Conditions
- Temperature
- 0 °C
Procedure
In a 250 mL round bottom flask, 4-bromo-2-methoxy-6-methyl-phenylamine (5.8 g, 26.84 mmol) was charged with acetic acid (49 mL) and concentrated HCl (5.6 mL). Sodium nitrite (2.19 g, 31.78 mmol) in 7 mL water was added to the mixture dropwise at 0° C. The reaction mixture was stirred at 0° C. for 30 minutes. 50% Hypophosphorous acid (56.5 mL) was added at 0° C. The reaction mixture was stirred at 0° C., and warmed up to room temperature overnight. Ethyl acetate was then added, followed by washing with saturated NaHCO3 solution. The organic layer was concentrated and purified (silica gel, 100% hexane) to give a pale liquid (5.12 g, 95%). 1H NMR (300 MHz, CDCl3): δ 6.97 (s, 1H), 6.87 (s, 1H), 6.64 (s, 1H), 3.80 (s, 3H), 2.36 (s, 3H).
Workup
- stirringThe reaction mixture was stirred at 0° C.
- temperaturewarmed up to room temperature overnight
- washby washing with saturated NaHCO3 solution
- concentrationThe organic layer was concentrated
- custompurified (silica gel, 100% hexane)
Sources & evidence
- ORD record
- ord-097bc055f61f4d0e901e94e13c96dcd2
- Source dataset
- uspto-grants-2012_12
- Patent number
- US08334295B2
Reaction notes
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