Bromide ion → HCID 14751115, compound

HRID 1649771Notes

Reaction equation

HRID 1649771 reaction equation
[CH2:1]([O:3][C:4](=[O:8])[CH2:5][C:6]#[N:7])[CH3:2].[O-]CC.[Na+].[Br-].Br[CH2:15][CH2:16][CH2:17][S:18][C:19]1[CH:29]=[CH:28][C:22]([C:23]([O:25][CH2:26][CH3:27])=[O:24])=[CH:21][CH:20]=1>C(O)C>[C:6]([CH:5]([C:4]([O:3][CH2:1][CH3:2])=[O:8])[CH2:15][CH2:16][CH2:17][S:18][C:19]1[CH:29]=[CH:28][C:22]([C:23]([O:25][CH2:26][CH3:27])=[O:24])=[CH:21][CH:20]=1)#[N:7]

Participants

6

Reactant 4

HCID 259Bromide ionHCID 7764Ethyl cyanoacetateHCID 2723922Sodium ethoxideHCID 14751114HCID 14751114, compound

Product 1

HCID 14751115HCID 14751115, compoundYield 71.4%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Ethylcyanoacetate (6.30 g, 55.7 mmoles) was added to a solution of sodium ethoxide (50 mmoles) in ethanol (25 mL) and refluxed 15 minutes. After cooling, the mixture was treated with bromide, 1A, (7.68 g, 25.3 mmoles) as a solution in ethanol (25 mL) and refluxed for 6 hours. The mixture was filtered, and the filtrate was treated with acetic acid to pH 7.0 and was evaporated to a viscous residue. The residue was partitioned between water (50 mL) and ether (50 mL), and the ether phase collected. The aqueous phase was washed with 4 volumes (50 mL) of ether, and the combined ether fractions were dried (CaSO4) and filtered. The filtrate was evaporated in vacuo, and the residue chromatographed (400 g silica, 3:1 hexane/ethyl acetate) to yield 6.06 g (70%) of the title compound, 1B, as a pale yellow oil. NMR (DMSO-d6) δ1.17 (t, 3H, CH3 of benzoate ether), 1.7 (m, 2H, CH2CH2 --CH2), 1.95 (m, 2H, CH2 --CH2CH2 --S), 1.28 (t, 3H, CH3 of acetate ester), 3.1 (m, 2H, CH2 --S), 4.15 (m, 1H, CH), 4.15 (q, 2H, CH2 of benzoate ester), 4.28 (q, 2H, CH2 of acetate ester), 7.4 (d, 2H, benzoate H's ortho to S), 7.85 (d, 2H, benzoate H's ortho to carbonyl). Compound 1B was used in the next reaction without further purification.

Workup

  1. temperaturerefluxed 15 minutes
  2. temperatureAfter cooling
  3. temperaturerefluxed for 6 hours
  4. filtrationThe mixture was filtered
  5. additionthe filtrate was treated with acetic acid to pH 7.0
  6. customwas evaporated to a viscous residue
  7. customThe residue was partitioned between water (50 mL) and ether (50 mL)
  8. customthe ether phase collected
  9. washThe aqueous phase was washed with 4 volumes (50 mL) of ether
  10. dry with materialthe combined ether fractions were dried (CaSO4)
  11. filtrationfiltered
  12. customThe filtrate was evaporated in vacuo
  13. customthe residue chromatographed (400 g silica, 3:1 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-bc4c37219695477ea2ae17059fa9bd38
Source dataset
uspto-grants-1990_05
Patent number
US04921836

Reaction notes

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