Malononitrile

Malononitrile is an organic compound nitrile with the formula CH2(CN)2. It is a colorless or white solid, although aged samples appear yellow or even brown. It is a widely used building block in organic synthesis.

Malononitrile
Names
IUPAC name
Malononitrile
Preferred IUPAC name
Propanedinitrile
Other names
  • Malonodinitrile
  • Cyanoacetonitrile
  • Dicyanomethane
  • Malonic dinitrile
Identifiers
  • 109-77-3 Y
3D model (JSmol)
  • Interactive image
773697
ChEBI
  • CHEBI:33186 Y
ChemSpider
  • 13884495 Y
ECHA InfoCard 100.003.368
EC Number
  • 203-703-2
1303
MeSH dicyanmethane
  • 8010
RTECS number
  • OO3150000
UNII
  • EBL1KKS93J Y
UN number 2647
  • DTXSID6021907
  • InChI=1S/C3H2N2/c4-2-1-3-5/h1H2 Y
    Key: CUONGYYJJVDODC-UHFFFAOYSA-N Y
  • N#CCC#N
Properties
CH2(CN)2
Molar mass 66.063 g·mol−1
Appearance Colourless or white solid
Odor Sweet
Density 1.049 g/cm3
Melting point 30–32 °C (86–90 °F; 303–305 K)
Boiling point 220 °C (428 °F; 493 K)
133 g/L (20 °C (68 °F; 293 K))
Thermochemistry[citation needed]
110.29 J⋅K−1⋅mol-1
130.96 J⋅K−1⋅mol-1
187.7 to 188.1 kJ⋅mol−1
−1654.0 to −1654.4 kJ⋅mol−1
Hazards
GHS labelling:
Signal word
Danger
H300, H311+H331, H317, H319, H410
P261, P264, P270, P271, P272, P273, P280, P301+P310+P330, P302+P352+P312, P304+P340+P311, P305+P351+P338, P333+P313, P337+P313, P362, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
4
1
1
Flash point 86 °C (187 °F; 359 K)
365 °C (689 °F; 638 K)
Lethal dose or concentration (LD, LC):
LD50 (median dose)
  • 19 mg/kg (oral, mouse)
  • 14 mg/kg (oral, rat)
  • 350 mg/kg (dermal, rat)
LC50 (median concentration)
0.51 mg/L (inhalation, dust/mist, 4h)
NIOSH (US health exposure limits):
PEL (Permissible)
none
REL (Recommended)
TWA 3 ppm (8 mg/m3)
IDLH (Immediate danger)
N.D.
Related compounds
Related alkanenitriles
Related compounds
Malonic acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Preparation and reactions

It can be prepared by dehydration of cyanoacetamide. Most commonly malononitrile is produced by the gas-phase reaction of acetonitrile and cyanogen chloride:

NCCl + CH3CN → NCCH2CN + HCl

About 20,000,000 kilograms (20,000 LT) are produced annually (2007). Important outlets include the synthesis of thiamine, the drug triamterene and minoxidil, and the dyes disperse Yellow 90 and disperse Blue 354.

Malononitrile is relatively acidic, with a pKa of 11 in water. This allows it to be used in the Knoevenagel condensation, for example in the preparation of CS gas:

Despite its relative obscurity, Malononitrile is very useful in several reactions, the prime example being a suitable starting reagent for the Gewald reaction, where the nitrile condenses with a ketone or aldehyde in the presence of elemental sulfur and a base to produce a 2-aminothiophene.

Interstellar occurrence

Due to its permanent dipole moment (i.e., 3.735 ± 0.017 D), malononitrile was detected in spectral emissions coming from interstellar cloud TMC-1 through the QUIJOTE line survey conducted with the Yebes 40 m radio telescope.

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