Malononitrile → HCID 72697075, compound

HRID 573568Notes

Reaction equation

HRID 573568 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[Br:10][C:11]1[CH:12]=[C:13]([C:17](=O)[CH3:18])[CH:14]=[CH:15][CH:16]=1.[C:20](#[N:24])[CH2:21][C:22]#[N:23]>C(O)(=O)C>[Br:10][C:11]1[CH:12]=[C:13]([C:17](=[C:21]([C:20]#[N:24])[C:22]#[N:23])[CH3:18])[CH:14]=[CH:15][CH:16]=1

Participants

5

Reactant 3

HCID 8010MalononitrileHCID 13838HexamethyldisilazaneHCID 165023'-Bromoacetophenone

Product 1

HCID 72697075HCID 72697075, compoundYield 102.4%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Conditions

Temperature
70 °C

Procedure

To a stirred solution of acetic acid (30 mL) at RT was added hexamethyldisilazane (13.09 mL, 62.8 mmol) dropwise over 10 min, maintaining temperature below 40° C. The resulting solution was then added dropwise to a solution of 1-(3-bromophenyl)ethanone (6.68 mL, 50.2 mmol) and malononitrile (6.33 mL, 100 mmol) in acetic acid (30 mL) and the mixture heated to 70° C. under nitrogen overnight. The reaction mixture cooled to RT and partitioned between water and toluene (ca. 150 mL each). The aqueous layer was separated and re-extracted with toluene (ca. 100 mL). The combined organic layer was dried over MgSO4 and solvent removed in vacuo, to afford the title compound (12.7 g) which was carried over to next step without further purification. LCMS (A) m/z: 247/249 [M+1]+, Rt 1.18 min (acidic).

Workup

  1. temperaturemaintaining temperature below 40° C
  2. temperatureThe reaction mixture cooled to RT
  3. custompartitioned between water and toluene (ca. 150 mL each)
  4. customThe aqueous layer was separated
  5. extractionre-extracted with toluene (ca. 100 mL)
  6. dry with materialThe combined organic layer was dried over MgSO4 and solvent
  7. customremoved in vacuo

Sources & evidence

ORD record
ord-af2f591947a747f798b4be57bbc518be
Source dataset
uspto-grants-2015_05
Patent number
US09029545B2

Reaction notes

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