Malononitrile → [1-(3-Methoxyphenyl)ethylidene]propanedinitrile

HRID 573545Notes

Reaction equation

HRID 573545 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[C:10](#[N:14])[CH2:11][C:12]#[N:13].[CH3:15][C:16]([C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([O:24][CH3:25])[CH:19]=1)=O>C(O)(=O)C>[CH3:25][O:24][C:20]1[CH:19]=[C:18]([C:16](=[C:11]([C:10]#[N:14])[C:12]#[N:13])[CH3:15])[CH:23]=[CH:22][CH:21]=1

Participants

5

Reactant 3

HCID 8010MalononitrileHCID 114603-MethoxyacetophenoneHCID 13838Hexamethyldisilazane

Product 1

HCID 247355[1-(3-Methoxyphenyl)ethylidene]propanedinitrileYield 100.9%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Conditions

Temperature
70 °C

Procedure

To a stirred solution of acetic acid (60 mL) was added hexamethyldisilazane (26.2 mL, 125 mmol) dropwise over 30 min with temperature kept below 40° C. throughout addition. This resulting solution was subsequently added to a stirred solution of malononitrile (13.50 g, 204 mmol) and 3-methoxyacetophenone (13.71 mL, 100 mmol) in acetic acid (30 mL). The final reaction mixture heated to 70° C. under nitrogen for 16 h. The reaction mixture was cooled to RT, partitioned between toluene and water (150 mL each). The aqueous layer was separated and re-extracted with toluene (2×60 mL). The combined organic layer was dried over Na2SO4 and solvent removed in vacuo, to afford the title compound (20 g). LCMS (A) m/z: 199 [M+1]+, Rt 1.20 min (acidic).

Workup

  1. additionkept below 40° C. throughout addition
  2. customThe final reaction mixture
  3. temperatureThe reaction mixture was cooled to RT
  4. custompartitioned between toluene and water (150 mL each)
  5. customThe aqueous layer was separated
  6. extractionre-extracted with toluene (2×60 mL)
  7. dry with materialThe combined organic layer was dried over Na2SO4 and solvent
  8. customremoved in vacuo

Sources & evidence

ORD record
ord-57683380c43049ebb8e76570d90c2b9a
Source dataset
uspto-grants-2015_05
Patent number
US09029545B2

Reaction notes

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