Methyl iodide → Propanedinitrile, 2-[(methylamino)(methylthio)methylene]-

HRID 1414887Notes

Reaction equation

HRID 1414887 reaction equation
[H-].[Na+].[C:3](#[N:7])[CH2:4][C:5]#[N:6].[CH3:8][N:9]=[C:10]=[S:11].[CH3:12]I>CN(C)C=O>[C:5]([C:4]([C:3]#[N:7])=[C:10]([S:11][CH3:12])[NH:9][CH3:8])#[N:6]

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 8010MalononitrileHCID 11167Methyl isothiocyanateHCID 24758Sodium hydride

Product 1

HCID 3640288Propanedinitrile, 2-[(methylamino)(methylthio)methylene]-

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

Sodium hydride (50% oil dispersion, 9.6g) was added portionwise to a solution of malononitrile (13.21 g) in dry dimethylformamide (150 ml). The mixture was stirred at 0° for 10 minutes and then to it was added dropwise a solution of methyl isothiocyanate (14.62 g) in dimethylformamide, maintaining the reaction temperature below 40°. The dark red solution was stirred for 45 minutes and a solution of methyl iodide (28.4 g) in dimethylformamide (25 ml) was then added. The reaction mixture was stirred vigorously for 20 minutes and then poured on to crushed ice (500 ml). The crude product (26 g, m.p. 115°) was filtered off and taken up in hot ethanol-ether (3:1, 600 ml). Filtration and cooling furnished 1,1-dicyano-2-methylthio-2-methylaminoethylene m.p. 119°-120°. Further recrystallisation from water gave a sample of m.p. 120°-121°. (Found: C, 46.7; H, 4.6; N, 27.1; S, 20.8; C6H7N3S requires: C, 47.0; H, 4.4; N, 27.4; S, 20.9:)

Workup

  1. temperaturemaintaining the reaction temperature below 40°
  2. stirringThe dark red solution was stirred for 45 minutes
  3. stirringThe reaction mixture was stirred vigorously for 20 minutes
  4. additionpoured on
  5. filtrationThe crude product (26 g, m.p. 115°) was filtered off
  6. filtrationFiltration
  7. temperaturecooling

Sources & evidence

ORD record
ord-f107b27e24ba44fe9934b504412f2ffb
Source dataset
uspto-grants-1977_01
Patent number
US04002759

Reaction notes

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