Malononitrile

Last updated
Malononitrile
Malondinitrile Structural Formula V1.svg
Ball-and-stick model Malononitrile-3D-balls.png
Ball-and-stick model
Space-filling model Malononitrile-3D-spacefill.png
Space-filling model
Names
IUPAC name
Malononitrile [1]
Preferred IUPAC name
Propanedinitrile [1]
Other names
Malonodinitrile, Cyanoacetonitrile, Dicyanomethane, Malonic dinitrile [2]
Identifiers
3D model (JSmol)
773697
ChEBI
ChemSpider
ECHA InfoCard 100.003.368 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-703-2
1303
MeSH dicyanmethane
PubChem CID
RTECS number
  • OO3150000
UNII
UN number 2647
  • InChI=1S/C3H2N2/c4-2-1-3-5/h1H2 Yes check.svgY
    Key: CUONGYYJJVDODC-UHFFFAOYSA-N Yes check.svgY
  • N#CCC#N
Properties
CH2(CN)2
Molar mass 66.063 g·mol−1
AppearanceColourless or white solid [2]
Density 1.049 g cm−3
Melting point 32 °C; 89 °F; 305 K
Boiling point 220.1 °C; 428.1 °F; 493.2 K
13% (20 °C) [2] [ clarification needed ]
Thermochemistry
110.29 J K−1 mol−1
Std molar
entropy (S⦵298)
130.96 J K−1 mol−1
187.7 to 188.1 kJ mol−1
−1,654.0 to −1,654.4 kJ mol−1
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
H301, H311, H331, H410
P261, P273, P280, P301+P310, P311
Flash point 86 °C (187 °F; 359 K)
Lethal dose or concentration (LD, LC):
  • 19 mg kg−1(oral, mouse)
  • 350 mg kg−1(dermal, rat)
NIOSH (US health exposure limits):
PEL (Permissible)
none [2]
REL (Recommended)
TWA 3 ppm (8 mg/m3) [2]
IDLH (Immediate danger)
N.D. [2]
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).

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.

Contents

Preparation and reactions

It can be prepared by dehydration of cyanoacetamide. [3] This method is mainly practiced in China where environmental rules are lax. Most commonly malononitrile is produced by the gas-phase reaction of acetonitrile and cyanogen chloride: [4]

NCCl + CH3CN → NCCH2CN + HCl

About 20,000,000 kg 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. [4]

Malononitrile is relatively acidic, with a pKa of 11 in water. [5] This allows it to be used in the Knoevenagel condensation, for example in the preparation of CS gas:

CS-chemical-synthesis CS-Gas-Synthese.svg
CS-chemical-synthesis

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. [6]

Related Research Articles

<span class="mw-page-title-main">Sodium cyanide</span> Chemical compound

Sodium cyanide is a poisonous compound with the formula NaCN. It is a white, water-soluble solid. Cyanide has a high affinity for metals, which leads to the high toxicity of this salt. Its main application, in gold mining, also exploits its high reactivity toward metals. It is a moderately strong base.

Acetonitrile, often abbreviated MeCN, is the chemical compound with the formula CH3CN and structure H3C−C≡N. This colourless liquid is the simplest organic nitrile. It is produced mainly as a byproduct of acrylonitrile manufacture. It is used as a polar aprotic solvent in organic synthesis and in the purification of butadiene. The N≡C−C skeleton is linear with a short C≡N distance of 1.16 Å.

<span class="mw-page-title-main">Tetrahydrofuran</span> Cyclic chemical compound, (CH₂)₄O

Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is mainly used as a precursor to polymers. Being polar and having a wide liquid range, THF is a versatile solvent. It is an isomer of another solvent, butanone.

<span class="mw-page-title-main">Diazomethane</span> Simplest diazo compound and methylating agent

Diazomethane is an organic chemical compound with the formula CH2N2, discovered by German chemist Hans von Pechmann in 1894. It is the simplest diazo compound. In the pure form at room temperature, it is an extremely sensitive explosive yellow gas; thus, it is almost universally used as a solution in diethyl ether. The compound is a popular methylating agent in the laboratory, but it is too hazardous to be employed on an industrial scale without special precautions. Use of diazomethane has been significantly reduced by the introduction of the safer and equivalent reagent trimethylsilyldiazomethane.

Triethylamine is the chemical compound with the formula N(CH2CH3)3, commonly abbreviated Et3N. It is also abbreviated TEA, yet this abbreviation must be used carefully to avoid confusion with triethanolamine or tetraethylammonium, for which TEA is also a common abbreviation. It is a colourless volatile liquid with a strong fishy odor reminiscent of ammonia. Like diisopropylethylamine (Hünig's base), triethylamine is commonly employed in organic synthesis, usually as a base.

<span class="mw-page-title-main">Hexamethylphosphoramide</span> Chemical compound

Hexamethylphosphoramide, often abbreviated HMPA, is a phosphoramide (an amide of phosphoric acid) with the formula [(CH3)2N]3PO. This colorless liquid is used as a solvent in organic synthesis.

<span class="mw-page-title-main">Dimethylamine</span> Chemical compound

Dimethylamine is an organic compound with the formula (CH3)2NH. This secondary amine is a colorless, flammable gas with an ammonia-like odor. Dimethylamine is commonly encountered commercially as a solution in water at concentrations up to around 40%. An estimated 270,000 tons were produced in 2005.

<span class="mw-page-title-main">Phosphoryl chloride</span> Chemical compound

Phosphoryl chloride is a colourless liquid with the formula POCl3. It hydrolyses in moist air releasing phosphoric acid and fumes of hydrogen chloride. It is manufactured industrially on a large scale from phosphorus trichloride and oxygen or phosphorus pentoxide. It is mainly used to make phosphate esters.

<span class="mw-page-title-main">Cyanamide</span> Chemical compound featuring a nitrile group attached to an amino group

Cyanamide is an organic compound with the formula CN2H2. This white solid is widely used in agriculture and the production of pharmaceuticals and other organic compounds. It is also used as an alcohol-deterrent drug. The molecule features a nitrile group attached to an amino group. Derivatives of this compound are also referred to as cyanamides, the most common being calcium cyanamide (CaCN2).

<span class="mw-page-title-main">Succinonitrile</span> Chemical compound

Succinonitrile, also butanedinitrile, is a nitrile, with the formula of C2H4(CN)2. It is a colorless waxy solid which melts at 58 °C.

Benzyl chloride, or α-chlorotoluene, is an organic compound with the formula C6H5CH2Cl. This colorless liquid is a reactive organochlorine compound that is a widely used chemical building block.

<span class="mw-page-title-main">Ethylamine</span> Chemical compound

Ethylamine, also known as ethanamine, is an organic compound with the formula CH3CH2NH2. This colourless gas has a strong ammonia-like odor. It condenses just below room temperature to a liquid miscible with virtually all solvents. It is a nucleophilic base, as is typical for amines. Ethylamine is widely used in chemical industry and organic synthesis. It is a DEA list I chemical by 21 CFR § 1310.02.

<span class="mw-page-title-main">Hexafluoroacetone</span> Chemical compound

Hexafluoroacetone (HFA) is a chemical compound with the formula (CF3)2CO. It is structurally similar to acetone; however, its reactivity is markedly different. It a colourless, hygroscopic, nonflammable, highly reactive gas characterized by a musty odour. The most common form of this substance is hexafluoroacetone sesquihydrate (1.5 H2O), which is a hemihydrate of hexafluoropropane-2,2-diol (F
3C)
2C(OH)
2, a geminal diol.

<span class="mw-page-title-main">Crotonaldehyde</span> Chemical compound

Crotonaldehyde is a chemical compound with the formula CH3CH=CHCHO. The compound is usually sold as a mixture of the E- and Z-isomers, which differ with respect to the relative position of the methyl and formyl groups. The E-isomer is more common (data given in Table is for the E-isomer). This lachrymatory liquid is moderately soluble in water and miscible in organic solvents. As an unsaturated aldehyde, crotonaldehyde is a versatile intermediate in organic synthesis. It occurs in a variety of foodstuffs, e.g. soybean oils.

<span class="mw-page-title-main">Propargyl alcohol</span> Chemical compound

Propargyl alcohol, or 2-propyn-1-ol, is an organic compound with the formula C3H4O. It is the simplest stable alcohol containing an alkyne functional group. Propargyl alcohol is a colorless viscous liquid that is miscible with water and most polar organic solvents.

<span class="mw-page-title-main">Nitroethane</span> Chemical compound

Nitroethane is an organic compound having the chemical formula C2H5NO2. Similar in many regards to nitromethane, nitroethane is an oily liquid at standard temperature and pressure. Pure nitroethane is colorless and has a fruity odor.

<span class="mw-page-title-main">4-Nitroaniline</span> Chemical compound

4-Nitroaniline, p-nitroaniline or 1-amino-4-nitrobenzene is an organic compound with the formula C6H6N2O2. A yellow solid, it is one of three isomers of nitroaniline. It is an intermediate in the production of dyes, antioxidants, pharmaceuticals, gasoline, gum inhibitors, poultry medicines, and as a corrosion inhibitor.

<span class="mw-page-title-main">Ethenone</span> Organic compound with the formula H2C=C=O

Ethenone is the formal name for ketene, an organic compound with formula C2H2O or H2C=C=O. It is the simplest member of the ketene class. It is an important reagent for acetylations.

Glycolonitrile, also called hydroxyacetonitrile or formaldehyde cyanohydrin, is the organic compound with the formula HOCH2CN. It is the simplest cyanohydrin and it is derived from formaldehyde. It is a colourless liquid that dissolves in water and ether. Because glycolonitrile decomposes readily into formaldehyde and hydrogen cyanide, it is listed as an extremely hazardous substance. In January 2019, astronomers reported the detection of glycolonitrile, another possible building block of life among other such molecules, in outer space.

Propionitrile, also known as ethyl cyanide and propanenitrile, is an organic compound with the formula CH3CH2CN. It is a simple aliphatic nitrile. The compound is a colourless, water-soluble liquid. It is used as a solvent and a precursor to other organic compounds.

References

  1. 1 2 International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 902. doi:10.1039/9781849733069. ISBN   978-0-85404-182-4.
  2. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0378". National Institute for Occupational Safety and Health (NIOSH).
  3. ↑ Surrey, Alexander (1945). "Malononitrile". Organic Syntheses. 25: 63–64. doi:10.15227/orgsyn.025.0063.
  4. 1 2 Strittmatter, Harald; Hildbrand, Stefan; Pollak, Peter (2007). "Malonic Acid and Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a16_063.pub2. ISBN   978-3527306732.
  5. ↑ Evans pKa table
  6. ↑ Sabnis, R. W.; Rangnekar, D. W.; Sonawane, N. D. (1999). "2-Aminothiophenes By The Gewald Reaction". Journal of Heterocyclic Chemistry. 36 (2): 333–345. doi:10.1002/jhet.5570360203 . Retrieved 2007-07-18.
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