Chloroacetonitrile

Product features

Chloroacetonitrile, also known as "cyanide chloromethane" has its chemical formula being ClCH2CN and the molecular weight being 75.50. It is colorless and fuming liquid with the melting point being 38 ℃ and boiling point being 126~127 ℃ (decomposition), 30~32 ℃ (2.0kPa), the relative density being 1.1930 and the refractive index being 1.420225. It is soluble in ether, alcohol and hydrocarbons but insoluble in water. It is highly toxic. It can form adduct with aluminum trichloride and react with various kinds of reagents including phloroglucinol trimethylether, methoxyacetophenone, Grignard reagent and anhydrous hydrogen chloride. It can be obtained through the dehydration of chloroacetamide under the action of phosphorus pentoxide, or the reaction between excess amount of acetonitrile with chlorine at 460 ℃ as well as introducing ammonia gas into the ether solution of dichloro acetylene. Chloroacetonitrile can be used as a fumigant.
Fumigants refer to a kind of pesticides whose volatile vapor can be applied to poison and kill pests. Its gaseous molecules can enter into the body of the harmful organisms and exert toxic effects. It can also exist in forms being different from gas such as liquid, solid or compressed gaseous form. The usage dose can be calculated according to the volume of space fumigation place (unit: g/m 3). The applied concentration can be based on the fumigation period, the closeness extent of fumigation place and the amount of material as well as its absorption capability of fumigant vapor. It is suitable to be used in the closed or nearly closed conditions in places such as warehouse, tent, house, car, etc. In the case of large concentration of the object to be fumigated, it can effectively eliminate hidden pests or pathogens.
The fumigant vapor generally directly enters into the respiratory system through the skin or valve of the pests, thus penetrating into blood and cause the poisoning and death of pests. Its insecticidal effect is generally believed to be located in the chemical action on the enzyme. For example, methyl bromide can combine with thiol, causing gradually reversible or irreversible inhibitory effects on various kinds of enzymes inside the pest body. Phosphine can cause inhibition on the animal central nervous system, irritate the lungs and cause edema, resulting in swelling heart syndrome. Fumigants such as trichloroethane, dibromoethane and carbon tetrachloride are mainly narcotics while carbon dioxide mainly causes stifling effect.
This information is edited by Xiongfeng Dai from Chemicalbook.

Chemical Properties

It is colorless, transparent fuming liquid with a pungent choking smell. It is soluble in alcohol and ether.

Uses

1. It can be used as raw material of organic synthesis and analytical reagents.
2. It can be used as pharmaceutical intermediates, pesticides.

Production method

It can be obtained through: chloroacetic acid is reacted with ethanol to generate ethyl chloroacetate, which then generate chloroacetamide through reaction with ammonia; finally have dehydration to get it. Detailed process: add trichloroacetic acid to the ethanol; add under stirring of concentrated sulfuric acid; the stirring was stopped after heating reflux; have the reaction for 8-10 h, filter and wash with water, separate out the water layer to obtain ethyl chloroacetate. Add it to the ammonia of 0-2 ℃ with the temperature being not exceed 15 ℃; sir for 10 to 15 mins after finishing adding added, cool, stand, filtrate and dry to obtain the chloroacetamide. Then, to the chloroacetamide, add phosphorus pentoxide and perform thermal dehydration with heating and distilling chloroacetonitrile out simultaneously; finally perform distillation under reduced pressure to evaporate out all the chloroacetonitrile. The resulting crude product is hydrated using phosphorus pentoxide and magnesium sulfate with vacuum distillation to derive the finished products.

Category

Toxic substances.

Toxicity grading

Highly toxic.

Acute toxicity

Oral-rat LD50: 220 mg/kg; Oral-Mouse LD50: 139 mg/kg.

Irritation data

Skin-Rabbit 14 mg/24 hr mild; Eye-Rabbit 20 mg/24 hours of moderate.

Flammable and hazardous characteristics

Combustible upon fire with thermal decomposition into toxic nitrogen compounds, chloride and cyanide gas.

Storage characteristics

Treasury: ventilated and low-temperature and dry; store it separately from oxidants, acids and food additives.

Extinguishing agent

Dry powder, carbon dioxide and sand. pH extinguishing agent should be disabled.

Chemical Properties

A clear, colorless liquid. Pungent odor. Chloroacetonitrile [107-14-2], chloromethanenitrile, chloromethyl cyanide, ClCH2CN, Mr 75.50, bp 124 – 126℃, d204 1.1896, n20D 1.426, is a colorless liquid with pungent odor. It is miscible with hydrocarbons and ethanol; immiscible with water. Chloroacetonitrile can be selectively obtained by the photochemical chlorination of acetonitrile with chlorine in the presence of, for example, SnCl4. Another method is based on the dehydration of chloroacetamide with, e.g., phosphorous pentoxide. Chloroacetonitrile is used as an organic intermediate, e.g., in the synthesis of the cardiovascular drug guanethidine [36] and the insecticide fenoxycarb.

Uses

Fumigant, intermediate.

Uses

Chloroacetonitrile is used in the electrochemical synthesis of cyanoacetic acid with carbon dioxide. It is involved in phase-transfer-catalyzed Darzen's condensation reaction with cyclohexanone. It is also used as an eluent additive in thermospray liquid chromatography/mass spectrometry. Further, it is used to prepare polysubstituted pyrido[1,2-a]benzimidazole by reacting with other reactant such as malononitrile, aromatic aldehyde and pyridine.

Preparation

In a 3-L round-bottomed, threenecked flask fitted with an efficient mechanical stirrer, a reflux condenser, and a thermometer were placed phosphorus pentoxide (170 g, 1.2 mol), chloroacetamide 1423 (187 g, 2 mol), and dry technical grade trimethylbenzene (800 mL). The mixture was gently refluxed with vigorous stirring for 1 h. It was then allowed to cool to about 100 C° with continuous stirring, and the reflux condenser was replaced with a distillation head fitted with a thermometer and a water-cooled condenser. The crude product and part of the solvent were distilled at atmospheric pressure. The yield of crude product boiling at 124–128 C° was 121–131 g (80–87%). In order to obtain a pure product, the crude chloroacetonitrile was mixed with phosphorus pentoxide (10 g) and redistilled through an efficient packed fractionating column. The yield of pure chloroacetonitrile distilling at 123–124 C° was 93–106 g (62–70%).

Definition

ChEBI: Chloroacetonitrile is a nitrile.

General Description

A colorless liquid with a pungent odor. Flash point 118°F. Insoluble in water and denser than water. Hence, sinks in water. Very toxic by ingestion, inhalation and skin absorption. A lachrymator. Used to make other chemicals and as a fumigant.

Air & Water Reactions

Flammable. Insoluble in water and denser than water. Hence, sinks in water. Reacts with water and steam to produce toxic vapors of hydrogen chloride.

Reactivity Profile

Chloroacetonitrile reacts with water, steam, strong acids or acid fumes to produce toxic vapors of hydrogen chloride. When heated to decomposition, Chloroacetonitrile emits highly toxic fumes of hydrogen cyanide and hydrogen chloride [Sax, 2nd ed., 1963, p. 600].

Hazard

Irritant. Questionable carcinogen.

Health Hazard

TOXIC; may be fatal if inhaled, ingested or absorbed through skin. Inhalation or contact with some of these materials will irritate or burn skin and eyes. Fire will produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution.

Fire Hazard

HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion and poison hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.

Safety Profile

Poison by ingestion, skin contact, and intraperitoneal routes. Moderately toxic by inhalation. A skin irritant. Human mutation data reported. Questionable carcinogen with experimental tumorigenic data. Flammable liquid. See also NITRILES. When heated to decomposition it emits very toxic fumes of Cl-, NOx, and CN-.

Potential Exposure

A chlorinated haloacetonitrile used as a fumigant and as a manufacturing chemical intermediate for making other chemicals

Shipping

UN2668 Chloroaceto nitrile Hazard class: 6.1, Labels: 6.1-Poison Inhalation Hazard, 3-Flammable liquid Inhalation Hazard Zone B.

Purification Methods

Reflux it with P2O5 for one day, then distil it through a helices-packed column. Also purified by gas chromatography. [Beilstein 2 IV 492.] LACHRYMATOR, HIGHLY TOXIC.

Incompatibilities

Highly flammable, forms explosive mixture with air. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Reacts with water and steam, releasing toxic and corrosive vapors of hydrogen chloride. 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 low aqueous solubility. They are also insoluble in aqueous acids. with reducing agents. Acetonitrile and propionitrile are soluble in water, but nitriles higher than propionitrile have

Waste Disposal

Use a licensed professional waste disposal service to dispose of this material. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed.