Diethyl Malonate

Other Classes -> Esters, Other

Flammable agents - 2nd degree

log Kow = 0.96

0.96

0.96

0.96

Sweet ester odor

Slightly aromatic, pleasant odor

Aroma of ripe fruit, peach, cut grass

1.0551 g/cu cm at 20 °C

Density (at 20 °C): 1.06 g/cm³

Relative density of the vapour/air-mixture at 20 °C (air = 1): 1.00

1.053-1.056

1.055 @ 20°C

Colorless liquid

Clear, colorless liquid

This chemical does not meet GHS hazard criteria for 2.7% (69 of 2532) of reports.

Warning

H319 (96.9%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]

P264+P265, P280, P305+P351+P338, and P337+P317 (click each P-code to see the statement)

Aggregated GHS information provided per 2532 reports by companies from 18 notifications to the ECHA C&L Inventory.

Warning

Chemical: Propanedioic acid, diethyl ester

Regulation (EC) No 1831/2003 (amended)

Propanedioic acid, 1,3-diethyl ester is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Propanedioic acid, 1,3-diethyl 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: 06-04-2023 https://echa.europa.eu/registration-dossier/-/registered-dossier/5774

Diethyl malonate: 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.)

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

2 - Materials that must be moderately heated or exposed to relatively high ambient temperatures before ignition can occur. Materials would not under normal conditions form hazardous atmospheres with air, but under high ambient temperatures or under moderate heating could release vapor in sufficient quantities to produce hazardous atmospheres with air.

0 - Materials that in themselves are normally stable, even under fire conditions.

Eye Irrit. 2A (96.9%)

Flammable liquids - Category 4

Flammable agents - 2nd degree

Eye irritation in rabbits: moderately irritating.

A skin irritant.

Conditions to avoid: Heat, flames and sparks. Incompatible materials: Acids, Bases, Oxidizing agents, Reducing agents

can react with oxidizing materials.

Fresh air, rest. Seek medical attention if you feel unwell.

Rinse and then wash skin with water and soap.

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Give one or two glasses of water to drink. Seek medical attention if you feel unwell.

Water may be used to blanket fire.

To fight fire, use water to blanket fire, foam, CO2, dry chemical.

Extinguishing media: Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide. Advice for firefighters: Wear self-contained breathing apparatus for firefighting if necessary. Further information: Use water spray to cool unopened containers.

ACCIDENTAL RELEASE MEASURES; Personal precautions, protective equipment and emergency procedures: Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided. Methods and materials for containment and cleaning up: Contain spillage, and then collect with an electrically protected vacuum cleaner or by wet-brushing and place in container for disposal according to local regulations. Keep in suitable, closed containers for disposal.

SRP: 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 air, soil or water; effects on animal, aquatic and plant life; and conformance with environmental and public health regulations. If it is possible or reasonable use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination.

Product: This combustible material may be burned in a chemical incinerator equipped with an afterburner and scrubber. Offer surplus and non-recyclable solutions to a licensed disposal company. Contaminated packaging: Dispose of as unused product.

Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment. Collect leaking liquid in sealable containers. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations.

Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands.

Avoid inhalation of vapor or mist. Keep away from sources of ignition - No smoking. Take measures to prevent the build up of electrostatic charge.

ACCIDENTAL RELEASE MEASURES; Personal precautions, protective equipment and emergency procedures: Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided.

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

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.

EC50; Species: Pimephales promelas (Fathead Minnow) age 33 days, length 14 mm, weight 0.036 g; Conditions: freshwater, flow through, 25.4 °C (23.5-27.7 °C), pH 7.42 (7.35-7.45), hardness 44.0 mg/L CaCO3, alkalinity 45.0 mg/L CaCO3, dissolved oxygen 87.6 mg/L (73.7-102 mg/L); Concentration: 20900 ug/L for 24 hr; Effect: behavior, loss of equilibrium /99% purity/

EC50; Species: Pimephales promelas (Fathead Minnow) age 33 days, length 14 mm, weight 0.036 g; Conditions: freshwater, flow through, 25.4 °C (23.5-27.7 °C), pH 7.42 (7.35-7.45), hardness 44.0 mg/L CaCO3, alkalinity 45.0 mg/L CaCO3, dissolved oxygen 87.6 mg/L (73.7-102 mg/L); Concentration: 15600 ug/L for 48 hr; Effect: behavior, loss of equilibrium /99% purity/

LC50; Species: Pimephales promelas (Fathead Minnow) age 33 days, length 14 mm, weight 0.036 g; Conditions: freshwater, flow through, 25.4 °C (23.5-27.7 °C), pH 7.42 (7.35-7.45), hardness 44.0 mg/L CaCO3, alkalinity 45.0 mg/L CaCO3, dissolved oxygen 87.6 mg/L (73.7-102 mg/L); Concentration: 23500 ug/L for 24 hr /99% purity/

LC50; Species: Pimephales promelas (Fathead Minnow) age 33 days, length 14 mm, weight 0.036 g; Conditions: freshwater, flow through, 25.4 °C (23.5-27.7 °C), pH 7.42 (7.35-7.45), hardness 44.0 mg/L CaCO3, alkalinity 45.0 mg/L CaCO3, dissolved oxygen 87.6 mg/L (73.7-102 mg/L); Concentration: 16600 ug/L for 48 hr /99% purity/

For more Ecotoxicity Values (Complete) data for Diethyl malonate (7 total), please visit the HSDB record page.

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 10(SRC), determined from a structure estimation method(2), indicates that diethyl malonate is expected to have very high mobility in soil(SRC). Volatilization of diethyl malonate from moist soil surfaces may occur(SRC) given an estimated Henry's Law constant of 2.0X10-6 atm-cu m/mole(SRC), derived from its vapor pressure, 0.19 mm Hg(3), and water solubility, 2.0X10+4 mg/L(4). In chemical stimulant studies simulating chemical warfare agents, diethyl malonate deposited to dry soil and foliar surfaces was rapidly lost through volatilization processes with observed half-lives on soil of about 2 hours (fast) to 5-16 hours (residual material)(4); foliar half-lives ranged from 1 to 242 hours(5). Two screening studies found diethyl malonate to be readily biodegradable(6,7). An 86% of theoretical BOD in two weeks using activated sludge in the Japanese MITI test(6) suggests that biodegradation is an important environmental fate process in soil(SRC).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 10(SRC), determined from a structure estimation method(2), indicates that diethyl malonate 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 2.0X10-6 atm-cu m/mole(SRC), derived from its vapor pressure, 0.19 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 23 and 173 days, respectively(SRC). According to a classification scheme(6), an estimated BCF of 3(SRC), from its log Kow of 0.96(7) and a regression-derived equation(2), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Two screening studies found diethyl malonate to be readily biodegradable(8,9). An 86% of theoretical BOD in two weeks using activated sludge in the Japanese MITI test(8) suggests that biodegradation is an important environmental fate process in water(SRC). Diethyl malonate hydrolyzes readily in neutral and alkaline water, but slowly in acidic water(10). Respective hydrolysis half-lives at pH 4, pH7 and pH 9 are <10% after 5 days (50 °C), 137.5 hr (25 °C) and <2.4 hr (50 °C)(10).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), diethyl malonate, which has a vapor pressure of 0.19 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase diethyl malonate 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 3.1 days(SRC), calculated from its rate constant of 3.4X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Diethyl malonate contains chromophores that absorb at wavelengths >290 nm(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).

Diethyl malonate is reported found in pineapple, bilberry, Cape gooseberry, cognac, malt whiskey, apple brandy, grape brandy port cider, sherry, and red wine, white and strawberry wines. It is used as a flavor additive in alcoholic beverages, baked goods, frozen dairy, gelatins, puddings, hard candy, non-alcoholic beverages and soft candy(1).

Safe in the present practices of use and concentration. Ingredient, concentration, and use information are available in documents discoverable at https://cir-reports.cir-safety.org

IDENTIFICATION AND USE: Diethyl malonate is used in chemical synthesis. It is also used in food, beverages, and in fragrances. HUMAN STUDIES: A maximization test was reported in 23 volunteers. 4% of the test substance in petrolatum produced no sensitization reactions. Tested at 4% in petrolatum it produced no irritation after a 48-hr closed-patch test on human subjects. ANIMAL STUDIES: Diethyl malonate causes moderate irritation to rabbit's eyes and is non-irritating to rabbit's skin. Application of 0.005 mL of undiluted diethyl malonate to the rabbit cornea caused severe burning. Diethyl malonate fed to rats for 90 days at more than 100 times the equivalent of the human daily dietary intake (averaging 35.93 mg/kg bw per day for males and 41.14 mg/kg bw per day for females) had no adverse effects. The maximum time for inhalation of the concentrated vapor of diethyl malonate by rats without deaths was found to be 8 hr. Mutagenicity test in Salmonella typhimurium TA98, TA 100, TA 1535, TA 1537, TA 1538 was negative with and without activation at concentrations of 8, 40, 200, 1000, 5000 ug/plate 5000 ug/plate (maximal concentration).

Cough.

Redness.

Redness.

No acute symptoms expected.

EPA has released the Interactive Chemical Safety for Sustainability (iCSS) Dashboard. The iCSS Dashboard provides an interactive tool to explore rapid, automated (or in vitro high-throughput) chemical screening data generated by the Toxicity Forecaster (ToxCast) project and the federal Toxicity Testing in the 21st century (Tox21) collaboration. /The title compound was tested by ToxCast and/or Tox21 assays/[USEPA; ICSS Dashboard Application; Available from, as of August 9, 2018: http://actor.epa.gov/dashboard/]

Using a structure estimation method based on molecular connectivity indices(1), the Koc of diethyl malonate can be estimated to be 10(SRC). According to a classification scheme(2), this estimated Koc value suggests that diethyl malonate is expected to have very high mobility in soil(SRC).

Diethyl malonate is reportedly found in pineapple, bilberry, Cape gooseberrys, grapes and strawberries(1). Diethyl malonate is present in guava fruit, melon, concord grape, pineapple, and blackberry(2). The related diester (dimethyl malonate) occurs in pineapple, bananas and blackberries(3).

/HUMAN EXPOSURE STUDIES/ Tested at 4% in petrolatum it produced no irritation after a 48-hr closed-patch test on human subjects.

/HUMAN EXPOSURE STUDIES/ A maximization test was reported in 23 volunteers. 4% of the test substance in petrolatum produced no sensitization reactions.

Hydrolysis of diethyl malonate would produce ethanol and malonic acid, which is a relatively strong acid and acts as an inhibitor of enzymes, including succinic dehydrogenase.

Diethyl malonate was hydrolyzed by adipose-tisue lipase and to the monoester by alpha-chymotrypsin.

A shower decontamination bench model has been used to assess quantitatively the importance of several variables (water pressure and temperature, surfactant concentration in the decontamination fluid, nozzle type, and shower time) on decontamination of nontoxic chemical warfare-agent simulants diethyl malonate and thickened diethyl malonate from pig skin in vitro. Diethyl malonate was validated as a simulant for 1,2,2-trimethylpropyl methylphosphonofluoridate (soman) by comparison of the skin penetration and decontamination of radiolabeled diethyl malonate to the radiolabeled phosphonofluoridate in shower decontamination trials of pig skin in vitro. Percutaneous penetration of diethyl malonate was significantly greater than that of the phosphonofluoridate during the 15-min period after application. However, both were less than 0.1% of the applied dose. Showering or thickener had no significant effect on the percutaneous penetration of diethyl malonate or the phosphonofluoridate. Most of the phosphonofluoridate removed by showering or scrubbing the skin was inactivated. The quantity of intact 1,2,2-trimethylpropyl methylphosphonofluoridate that penetrated through the skin was below the detection limit of the enzymatic analysis. There was no statistically significant difference between the phosphonofluoridate and diethyl malonate in efficacy of shower decontamination. The presence of thickener did not have a significant effect on decontamination efficacy.

The in vitro distribution and fate of [(14)C]diethyl malonate and [(14)C]diisopropyl fluorophosphate were evaluated on normal and heat-treated pig skin. The extent of hydrolysis from the skin surface, skin, and receptor fluid was determined. A significant skin-mediated hydrolysis (15-35% of applied dose) was observed for diethyl malonate in normal skin, but not in heat-treated skin. These results indicated that a heat labile process (e.g., enzymatic hydrolysis) was in part responsible for the degradation of diethyl malonate after topical application to normal skin. Heat treatment tripled the skin penetration of diisopropyl fluorophosphate and reduced the amount of recovered hydrolysis product, diisopropyl phosphoric acid. Enzymatic and spontaneous hydrolysis, as well as impurity, accounted for the presence of degradation product.

CIR ingredient: Diethyl Malonate

Used to make barbiturates and pigments and as a flavoring; [Hawley] Used to make agrochemicals and industrial chemicals; [eChemPortal: SIDSUNEP]

Dimethyl and diethyl malonates are widely used for the production of vitamins, pharmaceuticals, agrochemicals, fragrances, and dyes.

Manufacture of barbiturates.

Table: Reported uses (ppm): [Table#8510]

Diethyl malonate was used to investigate Knoevenagel condensation reactions in microreactor using zeolite catalysts obtained by grafting amino groups onto NaX and CsNaX zeolites. It may be used in the synthesis of diethyl benzylidenemalonate by base catalyzed Knoevenagel condensation with benzaldehyde. It may be used in the synthesis of a-aryl malonates

In some cases, the use of conventional GC/FTIR technique is limited due to its lower detectability to micro-components in organic mixtues in comparison to GC/MS. In this paper, an integration of LG/GC using retention gap technique with partially concurrent solvent evaporation, as a efficient chromatographic system for sample preconcentration and preseparation, was coupled into FTIR system in order to overcome the detectability problems of GC/FTIR analysis. The applicability of the on-line LG-GC/FTIR method is demonstrated by analysis of the isomers of divinylbenzene in purified diethyl malonate under conditions of hexane/dichloromethane (85:15) used as mobile phase in LC, solvent evaporation temperature of 75 degrees C and inlet pressure of 0.20MPa etc.

2023: 7,000,000 - <8,500,000 lb

Non-confidential 2016 Chemical Data Reporting (CDR) information on the production and use of chemicals manufactured or imported into the United States. Chemical: Diethyl malonate:

By passing hydrogen chloride into cyanoacetic acid dissolved in absolute alcohol with subsequent distillation.

Carbon Monoxide Process. According to this process, dimethyl, diethyl, and diisopropyl malonates are produced by a dicobalt octacarbonyl-catalyzed reaction of chloroacetates (methyl, ethyl, or isopropyl) with carbon monoxide in the presence of the appropriate alcohol. In the case of diethyl malonate the reaction is conducted at around 100 °C and 18 bar at pH 5.7. Ethyl acetate is formed as a major byproduct. After completion of the reaction, sodium chloride and catalyst are separated. The alcohol and the low-boiling components are distilled off and the nonconverted chloroacetate recovered by distillation. The crude ethyl malonate obtained is purified by redistillation.

Reacting chloroacetic acid to cyanoacetic acid using sodium cyanide and subsequent saponification; malonic acid if finally esterified by azeotropic distillation with ethanol in benzene.

Fragrance Ingredients

Flavouring Agent -> FLAVOURING_AGENT -> JECFA Functional Classes

Flavoring Agents -> JECFA Flavorings Index

Flavouring Agent -> FLAVOURING_AGENT -> JECFA Functional Classes

Flavouring Agent -> FLAVOURING_AGENT -> JECFA Functional Classes

Flavouring Agent -> FLAVOURING_AGENT -> JECFA Functional Classes

All Other Basic Organic Chemical Manufacturing

Propanedioic acid, 1,3-diethyl ester: ACTIVE

Diethyl malonate is diethyl ester of malonic acid. Acylation of diethyl malonate using magnesium chloride and triethylamine is reported. K2CO3-catalyzed 1,4-addition reaction of diethyl malonate with various substituted 1,2-allenic ketones yields polyfunctionalized beta,gamma-unsaturated enones.