Ethyl bromoacetate → HCID 22034120, compound

HRID 1634542Notes

Reaction equation

HRID 1634542 reaction equation
Br[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[N:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[CH:14]([C:17]1[C:22]([CH3:23])=[CH:21][C:20]([CH3:24])=[CH:19][C:18]=1[CH3:25])[C:15]#[N:16].C(=O)([O-])[O-].[K+].[K+].CC(C)([O-])C.[K+]>CS(C)=O.[NH4+].[Cl-]>[NH2:16][C:15]1[C:14]([C:17]2[C:22]([CH3:23])=[CH:21][C:20]([CH3:24])=[CH:19][C:18]=2[CH3:25])=[C:9]2[N:8]([C:2]=1[C:3]([O:5][CH2:6][CH3:7])=[O:4])[CH:13]=[CH:12][CH:11]=[CH:10]2

Participants

7

Reactant 4

HCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 220341262-(2-Pyridinyl)-2-(2,4,6-trimethylphenyl)ethanenitrileHCID 23665647Potassium tert-butoxide

Product 1

HCID 22034120HCID 22034120, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
0 °C

Procedure

Slowly add dropwise ethyl bromoacetate (23 mL; 0.21 mol) over a 3-hour period to a mixture of 2-(2-pyridinyl)-2-(2,4,6-trimethylphenyl)-ethanenitrile (22.3 g; 0.094 mol) and potassium carbonate (78 g; 0.57 mol) suspended in DMSO (100 mL). Stir the mixture for 1 day, pout into on aqueous NH4Cl solution (ca. 1 L), and extract with 3×200 mL of Et2O. Wash the combined extracts with saturated brine, dry over Na2SO4, filter, and concentrate in vacuo. Dissolve the residue in THF (200 mL), cool to 0° C. and add slowly in portions potassium t-butoxide (12 g; 0.11 mol) over a 10-minute period, After 30 minutes at 0° C., dilute the mixture with aqueous NH4Cl and extract with 2×150 mL of 50% Et2O in hexane. Wash the combined extracts with saturated brine, dry over Na2SO4, filter, concentrate in vacuo, and purify by column chromatography on silica gel (eluent: 5 to 10% EtOAc in hexane) to obtain the title compound as an oil: 1H NMR (400 MHz, CDCl3) δ 1.47 (t, 3 H), 2.06 (s, 6 H), 2.35 (s, 3 H), 4.46 (br q, 2 H), 6.6 (br t, 1 H), 6.75 (d, 1 H), 6.9 (br t, 1 H), 7.00 (s, 2 H), 9.4 (1 H).

Workup

  1. extractionpout into on aqueous NH4Cl solution (ca. 1 L), and extract with 3×200 mL of Et2O
  2. washWash the combined extracts with saturated brine
  3. dry with materialdry over Na2SO4
  4. filtrationfilter
  5. concentrationconcentrate in vacuo
  6. dissolutionDissolve the residue in THF (200 mL)
  7. extractionextract with 2×150 mL of 50% Et2O in hexane
  8. washWash the combined extracts with saturated brine
  9. dry with materialdry over Na2SO4
  10. filtrationfilter
  11. concentrationconcentrate in vacuo
  12. custompurify by column chromatography on silica gel (eluent: 5 to 10% EtOAc in hexane)

Sources & evidence

ORD record
ord-28ddb0c31383471299ea6501e6344bab
Source dataset
uspto-grants-2003_01
Patent number
US06506762B1

Reaction notes

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