シアノ酢酸 エチル

Nitrogen Compounds -> Nitriles

Reactive agents - 1st degree

Colorless liquid

Colorless to pale straw-colored liquid

Very soluble in ethyl ether, ethanol

Soluble in ammonia water, aqueous solution of alkalies; miscible with alcohol, ether

In water, 2.0X10+4 mg/L at 25 °C

230 °F (NFPA, 2010)

230 °F

205 °C

BP: 206.00 °C at 750 mm Hg; 152.8 °C at 100 mm Hg; 133.8 °C at 40 mm Hg; 119.8 °C at 20 mm Hg; 106.0 °C at 10 mm Hg; 93.5 °C at 5 mm Hg; 67.8 °C at 1.0 mm Hg

When heated to decomposition or on contact with acid or acid fumes, it emits highly toxic fumes of /cyanides/.

Hazardous decomposition products formed under fire conditions. - Carbon oxides, nitrogen oxides (NOx)

0.03 [mmHg]

VP: 1 mm Hg at 67.8 °C

3.88X10-2 mm Hg at 25 °C

This chemical does not meet GHS hazard criteria for 74.7% (204 of 273) of all reports.

Warning

H302 (21.2%): Harmful if swallowed [Warning Acute toxicity, oral]

P261, P264, P270, P271, P280, P301+P317, P302+P352, P304+P340, P317, P321, P330, P362+P364, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 273 reports by companies from 11 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Chemical: Acetic acid, cyano-, ethyl ester

Acetic acid, 2-cyano-, ethyl ester is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Acetic acid, 2-cyano-, ethyl ester are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)

Status: Active Update: 17-07-2018 https://echa.europa.eu/registration-dossier/-/registered-dossier/14515

Acetic acid, cyano-, ethyl ester: Does not have an individual approval but may be used under an appropriate group standard

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

ETHYL CYANOACETATE is both a nitrile and an ester. Esters react with acids to liberate heat along with alcohols and acids. Strong oxidizing acids may cause a vigorous reaction that is sufficiently exothermic to ignite the reaction products. Heat is also generated by the interaction of esters with caustic solutions. Flammable hydrogen is generated by mixing esters with alkali metals and hydrides. 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.

This action promulgates standards of performance for equipment leaks of Volatile Organic Compounds (VOC) in the Synthetic Organic Chemical Manufacturing Industry (SOCMI). The intended effect of these standards is to require all newly constructed, modified, and reconstructed SOCMI process units to use the best demonstrated system of continuous emission reduction for equipment leaks of VOC, considering costs, non air quality health and environmental impact and energy requirements. Ethyl cyanoacetate is produced, as an intermediate or a final product, by process units covered under this subpart.

/GUIDE 156: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE/WATER-SENSITIVE)/ Fire or Explosion: Combustible material: may burn but does not ignite readily. Substance will react with water (some violently) releasing flammable, toxic or corrosive gases and runoff. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapors may travel to source of ignition and flash back. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated or if contaminated with water.

/GUIDE 156: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE/WATER-SENSITIVE)/ Health: TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. Contact with molten substance may cause severe burns to skin and eyes. Reaction with water or moist air will release toxic, corrosive or flammable gases. Reaction with water may generate much heat which will increase the concentration of fumes in the air. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

/GUIDE 156: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE/WATER-SENSITIVE)/ Public Safety: CALL Emergency Response Telephone Number ... As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas.

/GUIDE 156: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE/WATER-SENSITIVE)/ Protective Clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.

For more DOT Emergency Guidelines (Complete) data for ETHYL CYANOACETATE (8 total), please visit the HSDB record page.

1 - Materials that, under emergency conditions, can cause significant irritation.

1 - Materials that must be preheated before ignition can occur. Materials require considerable preheating, under all ambient temperature conditions, before ignition and combustion can occur.

1 - Materials that in themselves are normally stable but that can become unstable at elevated temperatures and pressures.

Carbon dioxide, dry chemical

Water or foam may cause frothing.

Suitable extinguishing media: Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

Special protective equipment for fire-fighters: Wear self contained breathing apparatus for fire fighting if necessary.

Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation.

Soak up with inert absorbent material and dispose of as hazardous waste. Keep in suitable, closed containers for disposal.

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal and plant life; and conformance with environmental and public health regulations.

SRP: The scientific literature for the use of contact lenses by industrial workers is inconsistent. The benefits or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.

Avoid contact with skin and eyes. Avoid inhalation of vapor or mist.

Choose body protection according to the amount and concentration of the dangerous substance at the work place.

Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.

Excerpt from ERG Guide 151 [Substances - Toxic (Non-Combustible)]:

Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).

For prolonged or repeated contact use protective gloves.

Face shield and safety glasses.

Antidotes to cyanide poisoning include hydroxocobalamin and sodium nitrite, which release the cyanide from the cytochrome system, and rhodanase, which is an enzyme occurring naturally in mammals that combines serum cyanide with thiosulfate, producing comparatively harmless thiocyanate. Oxygen therapy can also be administered. (L97)

Exposure to high levels of cyanide for a short time harms the brain and heart and can even cause coma, seizures, apnea, cardiac arrest and death. Chronic inhalation of cyanide causes breathing difficulties, chest pain, vomiting, blood changes, headaches, and enlargement of the thyroid gland. Skin contact with cyanide salts can irritate and produce sores. (L96, L97)

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 4(SRC), determined from a structure estimation method(2), indicates that ethyl cyanoacetate is expected to have very high mobility in soil(SRC). Volatilization of ethyl cyanoacetate from moist soil surfaces is expected to be a moderate fate process(SRC) given an estimated Henry's Law constant of 2.9X10-7 atm-cu m/mole(SRC), based upon its vapor pressure, 3.88X10-2 mm Hg(3), and water solubility, 2.0X10+4 mg/L(4). Ethyl cyanoacetate is not expected to volatilize from dry soil surfaces(SRC) based upon its vapor pressure(4). A 68% of its theoretical BOD in 28 days in the Japanese MITI test(5) indicates that biodegradation may be an important environmental fate process in soil(SRC).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 4(SRC), determined from a structure estimation method(2), indicates that ethyl cyanoacetate is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon an estimated Henry's Law constant of 2.9X10-9 atm-cu m/mole(SRC), derived from its vapor pressure, 3.9X10-2 mm Hg(4), and water solubility, 2.0X10+4 mg/L(5). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 4 months and 2.7 years, respectively(SRC). According to a classification scheme(6), an estimated BCF of 3(SRC), from an estimated log Kow of 0.02(7) and a regression-derived equation(8), suggests the potential for bioconcentration in aquatic organisms is low(SRC). A 68% of its theoretical BOD in 28 days in the Japanese MITI test(9) indicates that biodegradation may be an important environmental fate process in water(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), ethyl cyanoacetate, which has a vapor pressure of 3.88X10-2 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase ethyl cyanoacetate is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 6 days(SRC), calculated from its rate constant of 1.7X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Ethyl cyanoacetate does not contain chromophores that absorb at wavelengths >290 nm(4), and therefore is not expected to be susceptible to direct photolysis by sunlight(SRC).

Ethyl cyanoacetate is the ethyl ester of cyanoacetic acid. Ethyl cyanoacetate hydrolyzes rapidly under neutral and alkaline conditions to cyanoacetic acid and ethanol ... , while in acid pH the half life is considerably longer. It also is likely that unspecific esterases in the body catalyze the hydrolysis to cyanoacetic acid and ethanol ... As the acid and the ester have different physical chemical properties due to their chemical nature, effects that are related to the acidity of the acid (e.g. ecotoxicity data, local irritating effects) have to be assessed separately. The environmental and toxicokinetic distribution can however be expected to range in a similar order of magnitude due to the similar polarity, vapor pressure and log Kow. ... Human Health. From the physical chemical properties of both cyanoacetic acid and ethyl cyanoacetate it can be expected that both substances will be moderately absorbed by all exposure routes. A relatively even distribution between tissues and also to embryonic tissues of pregnant rats was observed after oral administration of cyanoacetic acid. A similar behavior can be expected for ethyl cyanoacetate. Ethyl cyanoacetate is likely to be metabolized by unspecific esterases of different tissues, in particular in the liver to cyanoacetic acid and ethanol. While no mortality and no signs of toxicity were observed in a 7-hour vapor inhalation study in rats with saturated vapors of cyanoacetic acid, the 4-hour LC50 in rats for an aerosol of 50% cyanoacetic acid in water was 1900 mg/cu m. The most prominent symptoms were signs of severe irritation of eyes, mouth and respiratory tract. In a 1-hour inhalation study with ethyl cyanoacetate at the maximum attainable aerosol concentration of 7380 mg/cu m the only substance related findings were reversible signs of irritation of the eyes and the upper respiratory tract. For cyanoacetic acid a dermal LD50 > 2000 mg/kg bw in rabbits was reported. In this study with limited documentation local irritant effects on the skin and some systemic effects (dyspnea, behavioral changes) were reported, indicating a possible systemic toxicity after dermal exposure. For ethyl cyanoacetate a dermal LD50 > 1000 and > 2000 mg/kg bw was reported in rabbits and rats, respectively ... . No treatment related findings except for slight local skin irritation in the study in rabbits were observed. An acute oral LD50 value in rats of 1010 mg/kg bw has been reported for cyanoacetic acid. Symptoms including dyspnea, labored breathing, apathy and staggered gait were observed from doses of 1000 mg/kg bw and necropsy revealed local effects in the stomach. Only systemic effects similar to those reported for cyanoacetic acid were observed with ethyl cyanoacetate at a limit dose of 2000 mg/kg bw in rats. Cyanoacetic acid was corrosive to rabbit skin ... and eyes ... while ethyl cyanoacetate was not irritating to rabbit skin ... and moderately irritating to rabbit eyes... . Based on the results of the inhalation toxicity studies, cyanoacetic acid can be regarded as highly irritating to the mucous membranes of the respiratory tract while ethyl cyanoacetate only had a slight irritant effect on the respiratory tract. Both substances were not skin sensitizing in a Buehler test in guinea pigs ... . One 90-day oral (gavage) study in rats ... has been conducted with ethyl cyanoacetate at doses of 0, 100, 300 and 1000 mg/kg bw/day. The NOAEL in this study was 100 mg/kg bw/day for female rats and 300 mg/kg bw/day for male rats. A significant dose related reduction in hemoglobin values was observed at dose levels of 300 and 1000 mg/kg bw/day in female animals. In males of the 1000 mg/kg bw/day dose group increased urine volume and reversible pathological changes in liver (chronic peribiliary inflammation) and adrenals (vacuolization in the zona fasciculata of the adrenals) were observed. An additional examination of sperm counts and sperm motility in high dosed males revealed an apparently treatment related decrease in the percentage of motile sperms and sperm counts in the epididymis (changes within 2 standard deviations of the historical control data, no significant changes in organ weights or pathological findings in testes or epididymis). No effects were observed on female sex organs and estrous cycle. Both cyanoacetic acid and ethyl cyanoacetate were not mutagenic in the standard Ames assay in bacteria with and without metabolic activation. Neither Salmonella typhimurium TA102 nor E. coli WP2 were tested in these Ames tests, however, this is an acceptable restriction, because it can be assumed that neither cyanoacetic acid nor ethyl cyanoacetate has oxidizing or cross-linking potential, which may be detected by TA102 or E. coli WP2. Ethyl cyanoacetate did not show any clastogenic activity in the in vitro cytogenetic assay with V79 Chinese Hamster lung cells in the presence and absence of a metabolic activation system. All tests with ethyl cyanoacetate were conducted according to OECD or EC guidelines and GLP. For both substances, there is no structural alert for genotoxicity. In conclusion, from the available information, there is no indication of a genotoxic potential of the substances, both for gene mutations and chromosomal aberrations. No data are available on carcinogenicity. No specific studies on fertility are available for cyanoacetic acid or ethyl cyanoacetate. In a 90-day oral gavage study ... with ethyl cyanoacetate that included a histopathological evaluation of the gonads as well as additional investigations on sperm motility and sperm counts a NOAEL for these fertility related endpoints of 300 mg/kg bw/day was derived. A decrease of sperm motility and epididymal sperm counts observed in this study at 1000 mg/cu m (LOAEL) were not accompanied by significant reductions in testicular, epididymal, ovary or uterus weights, or any histopathological findings in these organs. Moreover, these effects are observed together with systemic toxicity. In a developmental toxicity study with ethyl cyanoacetate ... the NOAEL for embryotoxic or fetotoxic effects was 100 mg/kg bw/day based on an increase in minor skeletal anomalies in litters of the 300 and 1000 mg/kg bw/day dose groups and a reduced mean fetal weight at 1000 mg/kg bw/day. The NOAEL for maternal toxicity in this study was 300 mg/kg bw/day. Maternal toxicity in this study was however, only defined based on clinical signs, body weight development and macroscopic organ changes. Therefore it can not be excluded that the observed developmental effects are due to maternal toxicity. Studies on repeated dose toxicity and developmental toxicity conducted with ethyl cyanoacetate are considered relevant for cyanoacetic acid as well, as the ester will be rapidly metabolized to cyanoacetic acid and ethanol and its toxicity is likely to be mediated predominantly by cyanoacetic acid. Furthermore the study of the ester represents a "worst case" assumption for the acid as it can be assumed that the slightly more lipophilic ethyl ester is more readily absorbed than the corresponding acid and the maximum applicable dose of the ester is not limited by local irritation to mucous membranes. Therefore the ester can be administered at higher dose levels and is assumed to have a better bioavailability than the acid.

Organic nitriles decompose into cyanide ions both in vivo and in vitro. Consequently the primary mechanism of toxicity for organic nitriles is their production of toxic cyanide ions or hydrogen cyanide. Cyanide is an inhibitor of cytochrome c oxidase in the fourth complex of the electron transport chain (found in the membrane of the mitochondria of eukaryotic cells). It complexes with the ferric iron atom in this enzyme. The binding of cyanide to this cytochrome prevents transport of electrons from cytochrome c oxidase to oxygen. As a result, the electron transport chain is disrupted and the cell can no longer aerobically produce ATP for energy. Tissues that mainly depend on aerobic respiration, such as the central nervous system and the heart, are particularly affected. Cyanide is also known produce some of its toxic effects by binding to catalase, glutathione peroxidase, methemoglobin, hydroxocobalamin, phosphatase, tyrosinase, ascorbic acid oxidase, xanthine oxidase, succinic dehydrogenase, and Cu/Zn superoxide dismutase. Cyanide binds to the ferric ion of methemoglobin to form inactive cyanmethemoglobin. (L97)

/AQUATIC SPECIES/ Acute toxicity data for 3 trophic levels of the aquatic environment are available for ethyl cyanoacetate ... . A 96 h LC50 of 59 mg/L was derived (Danio rerio). This test was conducted under flow-through conditions to ensure stability of the test concentration. The 48 hr EC50 for Daphnia magna was ... 471 mg/L for ethyl cyanoacetate (nominal concentration). The 72 hr ErC50 /median effective concentration for growth rate/ for algae (Scenedesmus subspicatus) was 142 mg/L (72 hr EbC50 /median effective concentration for biomass/ 72.4 mg/L) and the NOEC based on growth rate was 17 mg/L for ethyl cyanoacetate. It can reasonably be assumed that hydrolysis of the ester occurred in this study and the acid and the lowered pH have contributed considerably to the toxicity. Therefore the data of the ester are relevant for cyanoacetic acid as well.

/PLANTS/ No growth inhibition of ethyl cyanoacetate to terrestrial plants in soil was observed up to concentrations of >100 mg/kg soil (dry weight) and no toxicity to Eisenia fetida /(earthworm)/ was observed at concentrations of 1000 mg ethyl cyanoacetate /kg soil (dry weight) after 14 days of exposure.

Using a structure estimation method based on molecular connectivity indices(1), the Koc of ethyl cyanoacetate can be estimated to be 4(SRC). According to a classification scheme(2), this estimated Koc value suggests that ethyl cyanoacetate is expected to have very high mobility in soil.

This action promulgates standards of performance for equipment leaks of Volatile Organic Compounds (VOC) in the Synthetic Organic Chemical Manufacturing Industry (SOCMI). The intended effect of these standards is to require all newly constructed, modified, and reconstructed SOCMI process units to use the best demonstrated system of continuous emission reduction for equipment leaks of VOC, considering costs, non air quality health and environmental impact and energy requirements. Ethyl cyanoacetate is produced, as an intermediate or a final product, by process units covered under this subpart.

Ethyl cyanoacetate is likely to be metabolized by unspecific esterases of different tissues, in particular in the liver to cyanoacetic acid and ethanol.

Organic nitriles are converted into cyanide ions through the action of cytochrome P450 enzymes in the liver. Cyanide is rapidly absorbed and distributed throughout the body. Cyanide is mainly metabolized into thiocyanate by either rhodanese or 3-mercaptopyruvate sulfur transferase. Cyanide metabolites are excreted in the urine. (L96)

From the physical chemical properties of both cyanoacetic acid and ethyl cyanoacetate it can be expected that both substances will be moderately absorbed by all exposure routes. A relatively even distribution between tissues and also to embryonic tissues of pregnant rats was observed after oral administration of cyanoacetic acid. A similar behavior can be expected for ethyl cyanoacetate.

Used in organic synthesis of pharmaceuticals and dyes; [Hawley]

Organic synthesis, pharmaceuticals, dyes.

The most important application of cyanoacetates is in the field of adhesives. /Cyanoacetates/

2023: 52,654 lb

Acetic acid, cyano-, ethyl ester is listed as a High Production Volume (HPV) chemical (65FR81686). Chemicals listed as HPV were produced in or imported into the U.S. in >1 million pounds in 1990 and/or 1994. The HPV list is based on the 1990 Inventory Update Rule. (IUR) (40 CFR part 710 subpart B; 51FR21438).

Production volumes for non-confidential chemicals reported under the Inventory Update Rule. [Table#4166]

Production volume for non-confidential chemicals reported under the 2006 Inventory Update Rule. Chemical: Acetic acid, 2-cyano-, ethyl ester. Aggregated National Production Volume: 1 to < 10 million lbs.

Made by the interaction of sodium cyanide and chloroacetic acid and subsequent esterification of the cyanoacetic acid formed.

... Cyanidation of sodium chloroacetate followed by acidification of the sodium cyanoacetate solution. Cyanoacetic acid is isolated by extraction with an organic solvent and evaporation of the solvent, whereas the cyanoacetates are obtained by mineral acid-catalyzed esterification with subsequent azeotropic removal of water. /Cyanoacetates/

Esterification of cyanoacetic acid with ethanol; reaction of an alkali cyanide and chloroacetic ethyl ester.

Computer and Electronic Product Manufacturing

Acetic acid, 2-cyano-, ethyl ester: ACTIVE

Method of purification: Vacuum distillation.

Ethyl cyanoacetate is the ethyl ester of cyanoacetic acid. Ethyl cyanoacetate hydrolyzes rapidly under neutral and alkaline conditions to cyanoacetic acid and ethanol (and so it does under most physiological and environmental conditions), while in acid pH the half life is considerably longer. It also is likely that unspecific esterases in the body catalyze the hydrolysis to cyanoacetic acid and ethanol, as it has been shown for the structurally related ethyl acetate, which is rapidly hydrolyzed in vitro and in vivo by various esterases to yield ethanol and acetic acid. Ethanol is a physiological substance that is metabolized via physiological pathways. Ethanol (CAS. 64-17- 5) was evaluated within the OECD HPV Chemicals Programme. It can be assumed that for most endpoints cyanoacetic acid will be the common metabolite that determines the toxicity of both substances. Furthermore the production and use pattern of both, ester and acid, are comparable. As the acid and the ester have different physical chemical properties due to their chemical nature, effects that are related to the acidity of the acid (e.g. ecotoxicity data, local irritating effects) have to be assessed separately. The environmental and toxicokinetic distribution can however be expected to range in a similar order of magnitude due to the similar polarity, vapor pressure and log Kow. The biodegradation behavior is also expected to be comparable as the ester is probably cleaved and the metabolites further degraded.