670-54-2

Basic information

• Product Name: Tetracyanoethylene
• Synonyms: 1,1,2,2-Tetracyanoethene;1,1,2,2-Tetracyanoethylene;delta(sup2,2’)-bimalononitrile;delta2,2'-Bimalononitrile;Ethene, tetracyano-;Ethylene, tetracyano-;Tetracyanoethene;Tetracyanoαthylen(ausderSchmelze)
• CAS NO: 670-54-2
• Molecular Formula: C₆N₄
• Molecular Weight: 128.09
• EINECS: 211-578-0
• Product Categories: Acceptors (Charge Transfer Complexes);Charge Transfer Complexes for Organic Metals;Functional Materials;TCNQ Derivatives;organic compound
• Mol File: 670-54-2.mol
• Article Data: 54

Chemical Properties

• Melting Point: 197-199 °C(lit.)
• Boiling Point: 223 °C
• Flash Point: 223°C
• Appearance: White to beige-brown/Crystalline Powder, Crystals or Chunks
• Density: 1,348 g/cm3
• Vapor Pressure: 0.117mmHg at 25°C
• Refractive Index: 1.5600
• Storage Temp.: 2-8°C
• Water Solubility: hydrolyzes
• Sensitive: Moisture Sensitive
• Merck: 14,9195
• BRN: 1679885
• CAS DataBase Reference: Tetracyanoethylene(CAS DataBase Reference)
• NIST Chemistry Reference: Tetracyanoethylene(670-54-2)
• EPA Substance Registry System: Tetracyanoethylene(670-54-2)

Safety Data

• Hazard Codes: T+
• Statements: 20/21-28-23/24
• Safety Statements: 28-36/37-45-28A-22-1
• RIDADR: UN 2811 6.1/PG 1
• WGK Germany: 3
• RTECS: KM7300000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 670-54-2(Hazardous Substances Data)

Usage

Chemical Description

Different sources of media describe the Chemical Description of 670-54-2 differently. You can refer to the following data:
1. Tetracyanoethylene is a highly reactive organic compound used in the synthesis of various organic compounds.
2. Tetracyanoethylene is a highly reactive organic compound used in organic synthesis and as a building block for other chemicals.

Description

Tetracyanoethylene (TCNE) is a crystalline solid with a melting point of 200 °C. DuPont researchers prepared it in 1957 by treating dibromomalononitrile with copper in boiling benzene. TCNE is an excellent electron acceptor and has been used to prepare organic superconductors. Tetracyanoethylene is a chemical compound of cyanide. It is used to prepare numerous organic superconductors, usually by serving as a single electron oxidant of an organic electron donor. Such charge-transfer salts are sometimes called Bechgaard salt.

Chemical Properties

white to beige-brown crystalline powder, crystals

Uses

Different sources of media describe the Uses of 670-54-2 differently. You can refer to the following data:
1. In the synthesis of spiro Compounds, in modified Diels-Alder reactions, as aromatizing agent: Longone, Smith, Tetrahedron Lett. 1962, 205.
2. Used for postfunctional addition to polyphenylacetylene derivatives to change the oxygen permeability. As reactant for Regioselective [2+2] cycloaddition reaction for production of BODIPY dyes2 and TCBD derivatives, Thermal addition reaction with alkynes, One-pot reactions with nucleophilic reagents forming aromatic cyanovinyl compounds, Synthesis of cobalt tetracyanoethylene films, Biotransformation by Botrytis cinerea.
3. Used for postfunctional addition to polyphenylacetylene derivatives to change the oxygen permeabilityReactant for: Regioselective [2+2] cycloaddition reaction for production of BODIPY dyes and TCBD derivativesThermal addition reaction with alkynesOne-pot reactions with nucleophilic reagents forming aromatic cyanovinyl compoundsSynthesis of cobalt tetracyanoethylene filmsBiotransformation by Botrytis cinerea

Definition

The first member of a class of compounds called cyanocarbons.

Synthesis Reference(s)

Organic Syntheses, Coll. Vol. 4, p. 877, 1963The Journal of Organic Chemistry, 45, p. 5113, 1980 DOI: 10.1021/jo01313a019

Hazard

Hydrolyzes in moist air to hydrogen cyanide.

Purification Methods

Crystallise it from chlorobenzene, dichloroethane, or dichloromethane [Hall et al. J Org Chem 52 5528 1987]. Storeitat0oina desiccator over NaOH pellets. (It slowly evolves HCN on exposure to moist air CARE.) It can also be sublimed at 120o under vacuum. Also purify it by repeated sublimation at 120-130o/0.5mm. [Frey et al. J Am Chem Soc 107 748 1985, Traylor & Miksztal J Am Chem Soc 109 2778 1987, Fatiadi Synthesis 249 1986, Synthesis 749 1967, Beilstein 2 IV 1245.]

InChI:InChI=1/C6N4/c7-1-5(2-8)6(3-9)4-10

Upstream product

• 98451-46-8 3-(2,2-Di-p-tolyl-vinyl)-cyclobutane-1,1,2,2-tetracarbonitrile 
• 100155-14-4 1-Methyl-3,3,4,4-tetracyan-2,3,4,4a-tetrahydro-phenanthren 
• 1885-23-0 dibromomalononitrile 
• 71-43-2 benzene 
• 7791-25-5 sulfuryl dichloride 
• 7782-50-5 chlorine 
• 2448-55-7 tetracyano-1,4-dithiine 
• 7440-09-7 potassium 
• 7439-93-2 lithium 
• 7440-23-5 sodium 
• 82849-49-8 dimethyl 2,2-dicyanoethene-1,1-dicarboxylate 
• 95765-38-1 [3-[1-Dimethylamino-meth-(Z)-ylidene]-bicyclo[2.2.1]hept-(2Z)-ylidenemethyl]-dimethyl-amine 
• 492-97-7 2,2'-Bithiophene 
• 73662-59-6 C₁₃H₁₀ClNO*C₆N₄ 

Downstream Products

• 69155-29-9 4,5-Dimethyl-4-cyclohexen-1,1,2,2-tetracarbonitril 
• 102184-64-5 4-oxo-3,4-diphenylbutane-1,1,2,2-tetracarbonitrile 
• 340169-68-8 bis-(3-phenyl-[1,2,4]thiadiazol-5-yl)-butenedinitrile 
• 57459-16-2 (3-phenyl-[1,2,4]thiadiazol-5-yl)-ethenetricarbonitrile 
• 16969-45-2 pyridin-1-ium 
• 65032-86-2 1-Benzyl-1,4,5,6-tetrahydro-pyridine-3-carboxylic acid amide 
• 102118-43-4 2,3,3-Tricyano-4-(5-methyl-1,1-dioxo-2-phenyl-1,2-dihydro-1λ⁶-[1,2]thiazin-3-yl)-butyronitrile 
• 102118-46-7 2,3,3-Tricyano-4-[2-(4-methoxy-phenyl)-5-methyl-1,1-dioxo-1,2-dihydro-1λ⁶-[1,2]thiazin-3-yl]-butyronitrile 
• 20484-50-8 TCNE-1-Phenylpyrrol-Komplex 
• 100604-20-4 (3aS,5R,6S,6aR)-2-<2,3,3a,5,6,6a-Hexahydro-6-hydroxy-5-(hydroxymethyl)furo<2,3-d>oxazol-2-yliden>cyanessigsaeure-methylester 
• 1824-97-1 methyl β-D-xylofuranoside 
• 70086-48-5 4-Phenyl-3,8a-dihydro-naphthalene-1,1,2,2-tetracarbonitrile 
• 102118-44-5 4-[2-(4-Chloro-phenyl)-5-methyl-1,1-dioxo-1,2-dihydro-1λ⁶-[1,2]thiazin-3-yl]-2,3,3-tricyano-butyronitrile 
• 94074-32-5 (4-chloro-anilino)-ethenetricarbonitrile 

Relevant articles and documents

Effect of external pressure and solvent on the equilibrium constant of the Diels-Alder reaction of 9-chloroanthracene with tetracyanoethylene

The effect of external pressure and solvent on the equilibrium constant of the Diels-Alder reaction of tetracyanoethylene with 9-chloroanthracene at 25°C was studied. The molar reaction volume is strongly solvent-dependent, cm3/mol: -11.3±1.0 in ?-xylene, -14.9±1.0 in toluene, -20.6±1.5 in 1,2-dichloroethane, -22.6±1.5 in ethyl acetate, and -24.2±1.5 in acetonitrile.

Structure of Spurs in γ-Irradiated Alcohol Matrices Determined by Electron Spin-Echo Method

Paramagnetic relaxation rates of radiation-generated tetracyanoethylene anion radicals (TCNE(1-)) and chemically prepared TCNE(1-) in the glassy matrices of ethanol, 1-propanol and 1-butanol, and radiation-generated CH3CHOH radicals in neat ethanol matrices have been measured by an electron spin-echo method for elucidating the detailed structure of spurs generated in the alcohol matrices γ-irradiated at 77 K.The local concentrations of hydroxyalkyl radicals generated in pair with TCNE(1-) or CH3CHOH radicals in isolated spurs were determined by analyzing the rates of excitation transfer from the magnetically excited TCNE(1-) or CH3CHOH radicals to the hydroxylakyl radicals.Comparison of the local concentrations of CH3CHOH radicals in ethanol matrices with and without solute tetracyanoethylene reveaked that the average number of ion pairs in a spur is close to unity.The distribution function of the distance r between TCNE(1-) and the paired hydroxyalyl radical, φ(r), was derived from relaxation kinetics of TCNE(1-), and was found to be expressed by φ(r)=3 exp(-r6/r06)(2?3/2r03).The average distances between TCNE(1-) and the paired hydroxyalkyl radicals were determined from the local concentrations of the hydroxyalkyl radicals, and were about 5 nm for all the alcohol matrices.

Reactivity Variation of Tetracyanoethylene and 4-Phenyl-1,2,4-Triazoline-3,5-Dione in Cycloaddition Reactions in Solutions

The reasons for the very high reactivity and variability of reactivity of two dienophiles, tetracyanoethylene (1) and 4-phenyl-1,2,4-triazoline-3,5-dione (2), in the Diels–Alder reactions were considered. The data on the rate of reactions with anthracene (3), benzanthracene (4) and dibenzanthracene (5) in 14 solvents over a range of temperatures and high pressures, data on the change in the enthalpy of solvation of reagents, transition state, and adducts in the forward and backward reactions, and the enthalpies of these reactions in solution were obtained. Strong π-acceptor dienophile 1 has sharply reduced reactivity in reactions in π-donor aromatic solvents. It was observed that the π-acceptor properties of dienophile 1 disappear upon passage to the transition state and adduct. Large solvent effects on the reaction rate can be predicted for all types of reactions involving tetracyanoethylene. Very high reactivity of dienophiles 1 and, especially, 2 can be useful to catch such carcinogenic impurities such as 3–5 and neutralize them by transformation into less dangerous adducts.

Why can the activation volume of the cycloadduct decomposition in isopolar retro-diels-alder reactions be negative?

Rate constants of the Diels-Alder cycloaddition reaction of anthracene with tetracyanoethylene, enthalpy of solution of reactants and adduct, enthalpy of the reaction in solution, enthalpy and entropy of activation of the forward and retro-Diels-Alder reactions were determined in 14 solvents. Temperature and pressure effects on the rate of the decomposition of the adduct formed from 9-chloroanthracene and tetracyanoethylene were studied. Since the electrostriction effect can be excluded from the consideration of the isopolar Diels-Alder reaction, negative values of the activation volume in the retro-Diels-Alder reactions can be caused by the different possibilities of penetration of the solvent molecules to large steric branched structures of the transition states and adducts.