Malononitrile → Sodium

HRID 1712116Notes

Reaction equation

HRID 1712116 reaction equation
[Na:1].[C:2](#[N:6])[CH2:3][C:4]#[N:5].[CH2:7]([O:9][C:10]([N:12]=[C:13]=[S:14])=[O:11])[CH3:8]>C(O)C>[Na:1].[C:4]([C:3]([C:2]#[N:6])=[C:13]([NH:12][C:10]([O:9][CH2:7][CH3:8])=[O:11])[S-:14])#[N:5]

Participants

6

Reactant 3

HCID 8010MalononitrileHCID 85320Ethyl isothiocyanatoformateHCID 5360545Sodium

Product 2

HCID 5360545SodiumHCID 178473559HCID 178473559, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodium metal (1.01 g, 44 mmol) was dissolved in 40 mL of ethanol at ambient temperature. The resulting solution was cooled in an ice bath, and malononitrile (2.91 g, 44 mmol) was added. The ice bath was removed, and the mixture was stirred at ambient temperature for 30 minutes. After cooling to 0° C., ethoxycarbonylisothiocyanate (5.77 g, 44 mmol) was added, and the mixture was allowed to warm to ambient temperature overnight. The mixture was concentrated in vacuo, and the residue solidified upon repeated dilution with hexane and concentration in vacuo. The resulting yellow solids were collected and dried in vacuo, affording 10.74 g (100%) or sodium, 2,2-dicyano-1-ethoxycarbonylamino-ethenethiolate as a light yellow solid that contained 0.5 molar equiv. of ethanol as indicated by 1H NMR spectroscopy. 1H NMR (300 MHz, DMSO-d6) δ 4.36 (t, 0.5H, J=5.0 Hz (EtOH)), 4.03 (q, 2H, J=7.1 Hz), 3.43 (dq, 1H J=5.0, 6.7 Hz (EtOH)), 1.26 (t, 3H, J=7.3 Hz), 1.06 (t, 1.5H, J=7.0 Hz (EtOH)) ppm; MS (APCI, m/z): 197 [M−Na]−.

Workup

  1. temperatureThe resulting solution was cooled in an ice bath
  2. customThe ice bath was removed
  3. temperatureAfter cooling to 0° C.
  4. temperatureto warm to ambient temperature overnight
  5. concentrationThe mixture was concentrated in vacuo
  6. concentrationwith hexane and concentration in vacuo
  7. customThe resulting yellow solids were collected
  8. customdried in vacuo

Sources & evidence

ORD record
ord-1ed01987204a4f82b58bd11172d96fea
Source dataset
uspto-grants-2010_09
Patent number
US07790902B2

Reaction notes

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