Isoamyl Nitrite → 5-Bromo-6-(4-chloro-phenyl)-3-trifluoromethyl-pyrazine-2-carboxylic acid methyl ester
Reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10]([C:11]([F:14])([F:13])[F:12])=[N:9][C:8](N)=[C:7]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][CH:17]=2)[N:6]=1)=[O:4].C(ON=O)CC(C)C.C[Si](C)(C)[Br:33].C(=O)(O)[O-].[Na+]>BrCBr>[CH3:1][O:2][C:3]([C:5]1[C:10]([C:11]([F:14])([F:13])[F:12])=[N:9][C:8]([Br:33])=[C:7]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][CH:17]=2)[N:6]=1)=[O:4]Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 0 °C
Procedure
To a suspension of 2.11 g 5-amino-6-(4-chloro-phenyl)-3-trifluoromethyl-pyrazine-2-carboxylic acid methyl ester in 20 ml dibromomethane was added 1.59 g isoamylnitrite and the mixture was cooled to 0° C. To the resulting suspension was added 2.922 g trimethylbromosilane and the mixture was stirred at 0° C. for 10 min (no conversion by HPLC) and at room temperature for 3 h. To the dark reaction mixture was added another 1.59 g isoamylnitrite and the mixture was stirred at room temperature for 6 h. The dark reaction mixture was pored onto ice and ca 20 ml 10% sodium bicarbonate and the product was extracted with dichloromethane (2.64 g raw material which crystallized) and purified by chromatography on silica gel (20 g hep:EE=9:1 to 1:1) to yield 2.290 g of the title compound as white crystals. MS (M+H at 396.8 and 394.9).
Workup
- customTo the dark reaction mixture
- stirringthe mixture was stirred at room temperature for 6 h
- customThe dark reaction mixture
- extractionthe product was extracted with dichloromethane (2.64 g raw material which crystallized)
- custompurified by chromatography on silica gel (20 g hep:EE=9:1 to 1:1)
Sources & evidence
- ORD record
- ord-0a8c97580b204972bd1e313ca2a6edab
- Source dataset
- uspto-grants-2012_01
- Patent number
- US08088920B2
Reaction notes
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