Sodium Iodide → HCID 10727305, compound

HRID 1359435Notes

Reaction equation

HRID 1359435 reaction equation
[H-].[Na+].[C:3]([CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])#[N:4].Br[CH:12]1[CH2:16][CH2:15][O:14][CH:13]1[O:17][CH3:18].[I-].[Na+]>CN(C=O)C.O>[CH2:9]([O:8][C:6](=[O:7])[CH:5]([C:3]#[N:4])[CH:12]1[CH2:16][CH2:15][O:14][CH:13]1[O:17][CH3:18])[CH3:10]

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 7764Ethyl cyanoacetateHCID 24758Sodium hydrideHCID 18183066HCID 18183066, compound

Product 1

HCID 10727305HCID 10727305, compoundYield 15.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Sodium hydride (95%, 30.32 g, 1.2 mol) was suspended in anhydrous DMF (350 ml) in a 2 L, 3-necked flask and ethyl cyanoacetate (136 ml, 1.2 mol) was added dropwise with stirring under argon over 1 h. After a further 15 min, 3-bromo-2-methoxytetrahydrofuran (75 g, 0.41 mol) was added, followed by sodium iodide (2 g) and then the solution was heated with vigorous stirring at 140° C. for 20 h under argon. After cooling, water (200 ml) was added and the solution was concentrated on a rotary evaporator to about 300 ml. More water (200 ml) was added and the crude product was extracted into diethylether (4×500 ml). The combined extracts were dried (Na2SO4), filtered and evaporated. Distillation of the residue under reduced pressure through a Vigreaux column afforded a colourless liquid (13.28 g, 15%). The cut b. p. 90-110° C./0.4 mmHg was taken; Rf (in A), 0.45, 0.36; stains yellow with anisaldehyde/H+; δH(d6-DMSO) 5.00 (0.75 H, m, mixt. of trans-2-H), 4.89 (0.25 H, d J2.1, cis-2-H), 4.29-4.19 (2 H, 2 q, cis/trans-CH2), 4.06-3.83 (2 H, 2 m, cis/trans-5-H), 3.39 (0.75 H, s, MeO), 3.36 (0.75 H, s, MeO), 3.35 (0.75 H, s, MeO), 3.31 (0.75 H, s, MeO), 2.78-2.70 (1 H, m, cis/trans-3-H), 2.30-1.71 (2 H, 2 m, 2×cis/trans-4-H) ppm; m/z (EI) 213.1002 (M+; Calc. for C10H15NO4, 213.1023).

Workup

  1. additionwas added dropwise
  2. waitAfter a further 15 min
  3. temperaturethe solution was heated
  4. stirringwith vigorous stirring at 140° C. for 20 h under argon
  5. temperatureAfter cooling
  6. concentrationthe solution was concentrated on a rotary evaporator to about 300 ml
  7. additionMore water (200 ml) was added
  8. extractionthe crude product was extracted into diethylether (4×500 ml)
  9. dry with materialThe combined extracts were dried (Na2SO4)
  10. filtrationfiltered
  11. customevaporated
  12. distillationDistillation of the residue under reduced pressure through a Vigreaux column

Sources & evidence

ORD record
ord-e7b1f8447a124816bb5f1e5bae676093
Source dataset
uspto-grants-2003_07
Patent number
US06600028B1

Reaction notes

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