Dimethylformamide → HCID 86761038, compound

HRID 1990839Notes

Reaction equation

HRID 1990839 reaction equation
Br[C:2]1[CH:3]=[C:4](OCC)[C:5]([O:8][CH3:9])=[N:6][CH:7]=1.BrC1N=C(OC)[C:17]([O:22]CC)=[CH:16]C=1.[Li]CCCC.CN([CH:33]=[O:34])C.[Cl-].[NH4+]>C1COCC1>[CH2:17]([O:22][C:7]1[C:2]([CH:33]=[O:34])=[CH:3][CH:4]=[C:5]([O:8][CH3:9])[N:6]=1)[CH3:16]

Participants

7

Reactant 5

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 666174095-Bromo-3-ethoxy-2-methoxypyridineHCID 866076326-Bromo-3-ethoxy-2-methoxypyridineHCID 178418339Butyllithium

Product 1

HCID 86761038HCID 86761038, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a 3:2 mixture of 5-bromo-3-ethoxy-2-methoxy-pyridine and 6-bromo-3-ethoxy-2-methoxy-pyridine (1.0 g, 4.31 mmol, 1.0 equiv) in anhydrous THF (20 mL) was added at −78° C. under Ar a solution of n-BuLi (3.23 mL, 5.17 mmol, 1.2 equiv, 1.6 M solution in hexane). After stirring for 1 h, anhydrous DMF (0.7 mL, 9.05 mmol, 2.1 equiv) was added and the reaction mixture stirred for an additional 30 min. A sat. solution of ammonium chloride (20 mL) was added and the solution extracted with ethyl acetate (3×50 mL). The combined organic phases were dried over MgSO4, the solvent removed by evaporation under reduced pressure and the crude material purified by twice recrystallization from isopropanol yielding 0.35 g (75%) of the title compound. 1H NMR (300 MHz, CDCl3): δ 1.50 (t, J=7.0 Hz, 3H), 4.11 (s, 3H), 4.15 (q, J=7.0 Hz, 2H), 7.46 (d, J=1.9 Hz, 1H), 8.19 (d, J=1.9 Hz, 1H), 9.93 (s, 1H). 13C NMR (75 MHz, CDCl3): δ 14.44, 54.67, 64.59, 113.72, 127.59, 144.29, 144.31, 158.80, 189.66. MS (ISP): 181.8 [M+H]+.

Workup

  1. stirringthe reaction mixture stirred for an additional 30 min
  2. extractionthe solution extracted with ethyl acetate (3×50 mL)
  3. dry with materialThe combined organic phases were dried over MgSO4
  4. customthe solvent removed by evaporation under reduced pressure
  5. customthe crude material purified by twice recrystallization from isopropanol yielding 0.35 g (75%) of the title compound

Sources & evidence

ORD record
ord-d98b01d0614c4c4cba5b68e0fb26833c
Source dataset
uspto-grants-2010_01
Patent number
US07645753B2

Reaction notes

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