109-77-3 Usage
Chemical Description
Different sources of media describe the Chemical Description of 109-77-3 differently. You can refer to the following data:
1. Malononitrile is a compound with the formula CH2(CN)2.
2. Malononitrile is a versatile reagent used in organic synthesis, while the other three chemicals are derivatives synthesized and studied in the article.
3. Malononitrile is a versatile reagent used in organic synthesis.
Description
Malonitrile is an aliphatic nitrile. It can release cyanide through
either chemical or biological transformation. Malonitrile was
used decades ago for treating certain forms of mental illness.
Chemical Properties
Different sources of media describe the Chemical Properties of 109-77-3 differently. You can refer to the following data:
1. Malononitrile may polymerize violently on prolonged heating at 130°C or at lower
temperatures on contact with strong bases.
2. Solidified melt
3. Malononitrile is a white powder or colorless,
odorless crystalline substance.
Uses
Different sources of media describe the Uses of 109-77-3 differently. You can refer to the following data:
1. In organic synthesis.
2. Malononitrile is an important building block for the syntheses of pharmaceuticals (e.g. triamterene, adenine and methotrexate), thiamin (vitamin B1), pesticides dyestuffs for color photography and synthetic fibers (e.g. vinylidene cyanide). Product Data Sheet
3. The chemical properties of malononitrile are determined by the nucleophilicity of the malononitrile anion, formed by deprotonation with relatively weak bases and by the two electrophilic cyano groups.
4. Malononitrile is used in organic synthesis.
Definition
ChEBI: A dinitrile that is methane subtituted by two cyano groups.
Production Methods
Malononitrile is prepared by continuous introduction of preheated acetonitrile and
cyanogen chloride into a tube reactor until the reaction mixture reaches a temperature
of approximately 780°C.
General Description
A white-colored crystalline solid. Denser than water and soluble in water. Toxic by ingestion and may severely irritate skin and eyes. May polymerize violently if exposed to temperatures above 266°F. Used to make other chemicals.
Air & Water Reactions
Soluble in water.
Reactivity Profile
Malononitrile is a white, low-melting powder (m. p. 30.5° C), toxic, combustible. Violent polymerization on contact with strong bases (sodium hydroxide, potassium hydroxide) or when heated above 130° C. When stored at 70-80° C for 2 months, spontaneous explosion (decomposition) occurred [Bretherick, 5th ed., 1995, p. 394].
Hazard
Toxic by ingestion and inhalation.
Health Hazard
Different sources of media describe the Health Hazard of 109-77-3 differently. You can refer to the following data:
1. Metabolized by body to cyanide and thiocyanate; effects of inhalation of toxic fumes will be related to cyanide. Causes brain and heart damage related to lack of cellular oxygen. It is classified as extremely toxic. Probable oral lethal dose for humans is 5-50 mg/kg, or between 7 drops and 1 teaspoonful, for a 70 kg (150 lb.) person.
2. In the late 1940's, malononitrile was used experimentally in the treatment of
schizophrenia and depression. Patients were given an iv infusion of 5% malononi-trile for 10-69 min. The total dose during such treatments was 1-6 mg/kg and
treatments were given 2-3 times/wk. Ten to twenty min after beginning infusion,
all patients experienced tachycardia. In addition, redness, nausea, vomiting,
headache, shivering, muscle spasms, and numbness were reported with varying
frequency.
3. Malononitrile is a highly toxic compound by all toxic routes. Its acute toxicity is somewhat greater than that of the aliphatic mononitriles, propionitrile, and butyronitrile. The increased toxicity may be attributed to the greater degree of reactivity in the molecule arising from two- CN functional groups. The acute toxic symptoms in test animals have not been well documented. An intraperitoneal dose of 10 mg/kg was lethal to rats. LD50 value, intravenous (rabbits): 28 mg/kg LD50 value, oral (mice): 19 mg/kg Malononitrile is an eye irritant. The irritation from 5 mg in 24 hours was severe in rabbits’ eyes. There is no report of teratogenic and carcinogenic action in animals or humans.
Fire Hazard
When heated to decomposition, Malononitrile emits highly toxic fumes (cyanide). May polymerize violently on prolonged heating. Avoid heat. Hazardous polymerization may occur, at prolonged heating at 266F or contact with strong bases at lower temperatures.
Industrial uses
Malononitrile is used primarily as an intermediate in the synthesis of drugs and
vitamins (thiamine). It has also been employed in the manufacture of photosensitizes,
acrylic fibers and dyestuffs and as an oil-soluble polar additive in lubricating
oil.
Malononitrile was used formerly in treatment of various forms of mental illness
such as alteration of psychic functions and schizophrenic
disorders.
Safety Profile
Poison by ingestion,
skin contact, subcutaneous, intravenous, and
intraperitoneal routes. A severe eye irritant.
Combustible when exposed to heat or
flame. Polymerizes violently when heated to
130°C or on contact with strong base. May
spontaneously explode when stored at
70-80°C. To fight fire, use water, fog, spray,
foam. When heated to decomposition it
emits toxic fumes of NOx and CN-. See also
NITRILES.
Potential Exposure
Malononitrile is used in organic synthesis; as a lubricating oil additive; for thiamine synthesis;
for pteridine-type anticancer agent synthesis; and in the
synthesis of photosensitizers, acrylic fibers, and dyestuffs.
It has also been used in the treatment of various forms
of mental illness. It has been used as a leaching agent for
gold
Environmental Fate
When heated to decomposition, nitriles may release cyanide.
Malonitrile appears to decompose rapidly in contact with soil
and sediment.
Metabolism
The in vitro metabolsim of malononitrile has been described by Stern et al.
In the presence of thiosulphate, brain, liver and kidney slices metabolized malononitrile
to thiocyanate. The formation of thiocyanate from malononitrile and
thiosulphate was greatest in the presence of liver slices, lowest in brain, and
intermediate with kidney slices. The liver enzyme system was saturated at a
concentration of 3.3 mM malononitrile and a pH optimum of 7.0. This enzyme system was inhibited by cysteine and glutathione and inactivated by boiling. Stern
et al indicated that thiosulphate increased cyanide and thiocyanate formed
from malononitrile in tissue slices.
Shipping
UN2647 Malononitrile, Hazard Class: 6.1;
Labels: 6.1-Poisonous materials. UN3439 Nitriles, solid,
toxic, n.o.s., Hazard Class: 6.1; Labels: 6.1-Poisonous
materials, Technical Name Required
Purification Methods
Crystallise the nitrile from water, EtOH, *benzene or chloroform. Distil it in a vacuum from, and store over, P2O5. [Bernasconi et al. J Am Chem Soc 107 7692 1985, Gratenhuis J Am Chem Soc 109 8044 1987, Beilstein 2 IV 1892.]
Toxicity evaluation
The acute toxicity of malonitrile and related alkyl nitriles is
thought to be due to release of cyanide through metabolism of
the parent compound. Signs of acute malonitrile intoxication
including dyspnea, ataxia, and convulsions are similar to those
noted with acute cyanide intoxication. The onset and duration
indicate that these nitriles require metabolism to elicit toxicity.
Cyanide and thiocyanate have both been found in urine and
blood after malonitrile exposure.
Incompatibilities
Incompatible with strong bases. May
polymerize violently on prolonged heating @ 129C, or in
contact with strong bases at lower temperatures. Nitriles
may polymerize in the presence of metals and some metal
compounds. They are incompatible with acids; mixing
nitriles with strong oxidizing acids can lead to extremely
violent reactions. Nitriles are generally incompatible with
other oxidizing agents such as peroxides and epoxides. The
combination of bases and nitriles can produce hydrogen
cyanide. Nitriles are hydrolyzed in both aqueous acid and
base to give carboxylic acids (or salts of carboxylic acids).
These reactions generate heat. Peroxides convert nitriles to amides. Nitriles can react vigorously with reducing agents.
Acetonitrile and propionitrile are soluble in water, but
nitriles higher than propionitrile have low aqueous solubility. They are also insoluble in aqueous acids.
Waste Disposal
Generators of waste containing this contaminant (≥100 kg/mo) must conform to EPA
regulations governing storage, transportation, treatment,
and waste disposal
Check Digit Verification of cas no
The CAS Registry Mumber 109-77-3 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,0 and 9 respectively; the second part has 2 digits, 7 and 7 respectively.
Calculate Digit Verification of CAS Registry Number 109-77:
(5*1)+(4*0)+(3*9)+(2*7)+(1*7)=53
53 % 10 = 3
So 109-77-3 is a valid CAS Registry Number.
109-77-3Relevant articles and documents
-
Ardis et al.
, p. 1305 (1950)
-
Cyanocarbon Acids: Direct Evidence That Their Ionization Is Not an Encounter-Controlled Process and Rationalization of the Unusual Solvent Isotope Effects
Hojatti, M.,Kresge, A. J.,Wang, W.-H.
, p. 4023 - 4028 (1987)
The rate of exchange of the acidic hydrogen of tert-butylmalononitrile was examined by using as a tracer, and the process was found not to be inhibited by hydronium ions in dilute aqueous hydrochloric acid solutions.This rules out the Swain-Grunwald mechanism for this reaction under these conditions.The bromination of malonitrile was investigated under conditions where reprotonation of the dicyanomethyl carbanion and its reaction with bromine occur at comparable rates, and the bromination reaction was found to have a specific rate twice that for reprotonation.Reprotonation therefore cannot be a diffusion-controlled process, and malonitrile is not a "normal" acid.The unusually large solvent kinetic isotope effects found for these cyanocarbon acid ionization reactions are explained by postulating that the transferring hydrogen and its positive charge are becoming associated with a solvent cluster rather than with a single water molecule.The thermodynamic acidity constant of malonitrile was determined to be 11.41 in aqueous solution at 25 deg C.
Preparation method of malononitrile and malononitrile prepared by preparation method
-
Paragraph 0056-0103, (2021/05/01)
The invention relates to the technical field of chemical synthesis methods, particularly to a malononitrile preparation method and malononitrile prepared thereof. The malononitrile preparation method comprises the following steps: mixing cyanoacetamide, a catalyst and a solvent, heating, refluxing, and introducing phosgene to synthesize malononitrile, wherein the mass ratio of the cyanoacetamide to the catalyst to the solvent is (2.5-3.5):(0.005-0.02):(7.5-10.5), the solvent is any one of dichloromethane, dichloroethane or methylbenzene, and the catalyst is any one or more of diethylamine, N,N-dimethylformamide or pyridine. According to the invention, cyanoacetamide is adopted to synthesize malononitrile in one step under the action of phosgene, wherein the required raw materials are cheap and easy to obtain, the synthetic reaction steps are few, harsh conditions are avoided, the operation is simple, stable and good in controllability, and the yield of the prepared malononitrile can reach 93% or above and is far higher than that of malononitrile obtained through other process schemes; and the preparation method is low in three-waste treatment cost, and has objective economic benefit.
Preparation method of malononitrile
-
Paragraph 0044-0051, (2020/07/24)
The invention discloses a preparation method of an important organic synthesis raw material malononitrile, which comprises the following steps: performing a reaction on chloroacetonitrile and hydrogencyanide as raw materials in a tubular reactor, and separating the reaction product by condensation and negative pressure distillation to obtain the malononitrile. The method has the advantages of mild reaction conditions, simple separation and purification process, high product yield and purity, energy saving, environmental protection and low cost.
Synthetic method of malononitrile
-
Paragraph 0011-0030, (2020/01/08)
The invention belongs to the technical field of organic synthesis, and provides a malononitrile synthesis method. The synthetic method comprises the following steps: adding dichloromethane and sodiumcyanide into a reaction kettle at a molar ratio of (1: 1)-(3: 1), slowly adding a catalyst into the reaction kettle under stirring and heating conditions, controlling the temperature in the reaction kettle to be 90 DEG C, and carrying out thermal preservation reaction for 5-9 hours after feeding is finished; after the reaction is finished, adding deionized water into an obtained reaction product to wash an organic phase for a plurality of times, separating out the organic phase, drying the organic phase, and rectifying to obtain malononitrile; wherein the catalyst is a composition of aluminumtrichloride and tetrabutylammonium bromide. According to the method, the malononitrile product is directly synthesized by taking cheap dichloromethane as a raw material through a one-step method, theprocess route is simple, and the cost is low.
