Dimethylformamide → ethyl 4-(5-bromo-3-nitropyridin-2-yl)tetrahydro-2H-pyran-4-carboxylate
Reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N+:13]([O-:15])=[O:14])[C:5]([CH2:8][C:9]([O:11][CH3:12])=[O:10])=[N:6][CH:7]=1.[H-].[Na+].Br[CH2:19][CH2:20][O:21][CH2:22][CH2:23]Br.[NH4+].[Cl-].[CH3:27]N(C=O)C>CCOC(C)=O>[Br:1][C:2]1[CH:3]=[C:4]([N+:13]([O-:15])=[O:14])[C:5]([C:8]2([C:9]([O:11][CH2:12][CH3:27])=[O:10])[CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)=[N:6][CH:7]=1Participants
Reactant 5
Product 1
Reagents, catalysts & solvents 1
Procedure
To a stirred solution of methyl 2-(5-bromo-3-nitropyridin-2-yl)acetate (2.0 g, 7.27 mmol) in DMF (15 mL) was added sodium hydride (0.384 g, 16.00 mmol) portionwise over 5 min (solution turns dark blue). The reaction was stirred at rt for 15 min and then 2-bromoethyl ether (1.69 mL, 7.27 mmol) was added via syringe over 1 min. The reaction was stirred at rt for 16 h. After this time 0.2 g of NaH was added and the reaction was stirred at rt for 14 h. The reaction was treated with saturated aqueous NH4Cl (60 mL) and EtOAc (300 mL). The separated organic layer was washed with 1.0M aqueous LiCl (60 mL) and then dried over MgSO4, filtered and evaporated in vacuo. Column chromatography (hexane:EtOAc, 1:0 to 1:1) gave ethyl 4-(5-bromo-3-nitropyridin-2-yl)tetrahydro-2H-pyran-4-carboxylate as a dark brown oil.
Workup
- stirringThe reaction was stirred at rt for 16 h
- stirringthe reaction was stirred at rt for 14 h
- washThe separated organic layer was washed with 1.0M aqueous LiCl (60 mL)
- dry with materialdried over MgSO4
- filtrationfiltered
- customevaporated in vacuo
Sources & evidence
- ORD record
- ord-fdaaa6832b9d4c3c9cf48e3ab957baab
- Source dataset
- uspto-grants-2014_07
- Patent number
- US08765940B2
Reaction notes
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