Sodium hydride → HCID 61633471, compound

HRID 2202091Notes

Reaction equation

HRID 2202091 reaction equation
[CH2:1]=[N:2][CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[H-].[Na+].[C:11]([C:13]1[CH:21]=[CH:20][C:16]([C:17](Cl)=[O:18])=[CH:15][CH:14]=1)#[N:12]>C1(C)C=CC=CC=1>[C:11]([C:13]1[CH:21]=[CH:20][C:16]([C:17]2[O:18][CH:1]=[N:2][C:3]=2[C:4]([O:6][CH2:7][CH3:8])=[O:5])=[CH:15][CH:14]=1)#[N:12]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 801724-Cyanobenzoyl chlorideHCID 12755258HCID 12755258, compound

Product 1

HCID 61633471HCID 61633471, compoundYield 36.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of ethyl 2-(methylideneamino)acetate (1.7 g, 14.77 mmol, 1.00 equiv) was added dropwise to a stirred mixture of sodium hydride (60%, 722 mg, 18.05 mmol, 1.22 equiv) in toluene (30 mL) at 5° C. The mixture was stirred at room temperature for 30 min. 4-cyanobenzoyl chloride (3 g, 18.12 mmol, 1.22 equiv) was then added dropwise at 5° C. The reaction was stirred at room temperature for 12 h then quenched with 30 mL of ice-water mixture. The resulting mixture was extracted with 2×15 mL of ethyl acetate. The combined organic layers was washed with 1×30 mL of brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was purified on a silica gel column eluted with 0-30% of ethyl acetate in petroleum ether to give 1.3 g (36%) of ethyl 5-(4-cyanophenyl)oxazole-4-carboxylate as a red solid. 1H-NMR (300 MHz, CDCl3): δ 8.29-8.26 (m, 2H), 8.00 (s, 1H), 7.91-7.77 (m, 2H), 4.48-4.41 (m, 2H), 1.46-1.41 (t, J=7.2 Hz, 3H) ppm.

Workup

  1. stirringThe reaction was stirred at room temperature for 12 h
  2. customthen quenched with 30 mL of ice-water mixture
  3. extractionThe resulting mixture was extracted with 2×15 mL of ethyl acetate
  4. washThe combined organic layers was washed with 1×30 mL of brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated under vacuum
  7. customThe residue was purified on a silica gel column
  8. washeluted with 0-30% of ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-ceef97db976040aa8cd2f8e3f61987aa
Source dataset
uspto-grants-2016_06
Patent number
US09365527B2

Reaction notes

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