Methyl acetoacetate

116.12

116.12

506727

203-299-8

CW4I82QAX1

1086

1993

DTXSID9026716

Colorless liquid

29183000

43.4

0

APHA: ≤20 Liquid

1.0762 g/cm³ @ Temp: 20 °C

27-28 °C

171.7 °C

158 °F

n 20/D 1.419(lit.)

H2O: 460 g/L (20 ºC)

2-8°C

Vapour pressure, kPa at 20°C: 0.17

Relative vapour density (air = 1): 4.0

LD50 orally in rats: 3.0 g/kg (Smyth, Carpenter)

1.3-14.2%(V)

Agreeable odor

Henry's Law constant: 2.7X10-7 atm-cu m/mole at 25 °C /Estimated

Conversion factor (wt/vol): 1 ppm = 4.74 mg/cu m|Slight decomposition between 169-171 °C; give a deep red color with ferric chloride|Hydroxyl radical reaction rate constant: 3.25X10-13 cu cm/molecule sec at 25 °C

Very slightly soluble in water.

Esters, Sulfate Esters, Phosphate Esters, Thiophosphate Esters, and Borate Esters

METHYL ACETOACETATE is 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

536 °F (USCG, 1999)|536 °F (280 °C)|280 °C

1993

1

36

26

AK5775000

Xi

Separated from oxidants.

MAA and EAA are stable liquids

P264, P280, P305+P351+P338, P33, P313

H319

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational exposure 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, aquatic, and plant life; and conformance with environmental and public health regulations.

OPDYKE DL J; MONOGRAPHS ON FRAGRANCE RAW MATERIALS. METHYL ACETOACETATE; FOOD COSMET TOXICOL 16 (SUPPL 1): 815 (1978). A REVIEW WITH 12 REFERENCES ON METHYL ACETOACETATE INCL TOXICITY, IRRITATION, SENSITIZATION & NUTRITION.|EPA/Office of Pollution Prevention and Toxics; High Production Volume (HPV) Challenge Program's Robust Summaries and Test Plans. Available from: http://www.epa.gov/chemrtk/viewsrch.htm on Methyl acetoacetate as of November 2, 2004.|The U.S. high production volume (HPV) chemicals are those which are manufactured in or imported into the United States in amounts equal to or greater than one million pounds per year. Robust Summaries include health effects, ecotoxicity data, and environmental fate information for selected chemicals. EPA/Office of Pollution Prevention and Toxics; High Production Volume (HPV) Challenge Program's Robust Summaries and Test Plans. Available from: http://www.epa.gov/chemrtk/viewsrch.htm on Methyl acetoacetate as of November 2, 2004.

Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: 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 hazard indoors, outdoors or in sewers. Those substances designated with a (P) may polymerize explosively when heated or involved in a fire. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water. Substance may be transported hot. For hybrid vehicles, ERG Guide 147 (lithium ion batteries) or ERG Guide 138 (sodium batteries) should also be consulted. If molten aluminum is involved, refer to ERG Guide 169. (ERG, 2016)|Combustible. Above 77 °C explosive vapour/air mixtures may be formed.

|Warning|H319: Causes serious eye irritation [Warning Serious eye damage/eye irritation]|P264, P280, P305+P351+P338, and P337+P313|H319 (94.88%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]|Aggregated GHS information provided by 1955 companies from 7 notifications to the ECHA C&L Inventory.|H227: Combustible liquid [Warning Flammable liquids]|P210, P261, P264, P271, P280, P304+P340, P305+P351+P338, P312, P337+P313, P370+P378, P403+P233, P403+P235, P405, and P501

Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: As an immediate precautionary measure, isolate spill or leak area for at least 50 meters (150 feet) in all directions. LARGE SPILL: Consider initial downwind evacuation for at least 300 meters (1000 feet). FIRE: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2016)

Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area). All equipment used when handling the product must be grounded. Do not touch or walk through spilled material. Stop leak if you can do it without risk. Prevent entry into waterways, sewers, basements or confined areas. A vapor-suppressing foam may be used to reduce vapors. Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers. Use clean, non-sparking tools to collect absorbed material. LARGE SPILL: Dike far ahead of liquid spill for later disposal. Water spray may reduce vapor, but may not prevent ignition in closed spaces. (ERG, 2016)

Respirator, chemical safety goggles, rubber boots and heavy rubber gloves. (USCG, 1999)|Wear appropriate chemical protective gloves, boots and goggles.

FIRE HAZARD: Moderate, when exposed to heat or flame.

Explosive limits , vol% in air: 1.4-14.5

... /Use/ foam, carbon dioxide, dry chemical.|If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Use "alcohol" foam, dry chemical or carbon dioxide.

If material not on fire and not involved in fire: Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. Build dikes to contain flow as necessary. Use water spray to knock-down vapors.|Personnel protection: Avoid breathing vapors. Keep upwind. ... Do not handle broken packages unless wearing appropriate personal protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water.|SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit 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.

Methyl... acetoacetate may be irritating /to eyes and skin/.

Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Ventilation. Collect leaking and spilled liquid in sealable containers as far as possible. Wash away remainder with plenty of water.

Separated from oxidants.

No indication can be given about the rate at which a harmful concentration of this substance in the air is reached on evaporation at 20 °C.

The substance is irritating to the eyes and respiratory tract. Exposure could cause lowering of consciousness.

NO open flames. Above 77 °C use a closed system and ventilation.

Use ventilation, local exhaust or breathing protection.

Protective gloves.

Wear safety goggles.

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. Methyl acetoacetate is produced, as an intermediate or a final product, by process units covered under this subpart.

| 2 - Materials that, under emergency conditions, can cause temporary incapacitation or residual injury.| 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.

Oxygenated organic compounds, including methyl acetoacetate, were measured in condensed smoke of small (bench-scale) fires of ponderosa pine sapwood, needles, bark, litter, duff, and humus under three types of fire conditions, smoldering, self-sustaining smoldering, and flaming (1). Mean emission factors for methyl acetoacetate were found to range from not detected for a smoldering fire of humus to 0.77 g/kg for a smoldering wood fire(1).

LD50 Rat oral 3.0 g/kg|LD50 Rabbit dermal >10 mL/mg|LD50 Rat (male) oral 2.58 g/kg (95% Confidence interval: 2.23 -2.98 g/kg)|LD50 Rat (female) oral 3.37 g/kg (95% Confidence interval: 2.92 -3.90 g/kg)|For more Non-Human Toxicity Values (Complete) data for METHYL ACETOACETATE (7 total), please visit the HSDB record page.

Methyl acetoacetate was found in the condensed smoke of fires of ponderosa pine sapwood, needles, bark, litter, duff, and humus(1).

Methyl acetoacetate's production and use as a solvent for cellulose ethers and esters and in organic synthesis(1) may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 1.0(SRC), determined from a structure estimation method(2), indicates that methyl acetoacetate is expected to have very high mobility in soil(SRC). Volatilization of methyl acetoacetate from moist soil surfaces is expected to be slow(SRC) given an estimated Henry's Law constant of 2.7X10-7 atm-cu m/mole(SRC), derived from its vapor pressure of 0.892 mm Hg(3), and water solubility, 5X10+5 mg/L(4). A base-catalyzed second-order hydrolysis rate constant of 0.57 L/mole-sec(SRC) was estimated using a structure estimation method(5); this corresponds to half-lives of 140 and 14 days at pH values of 7 and 8, respectively(5). Methyl acetoacetate would be expected to hydrolyze in moist soil under basic conditions(SRC). Methyl acetoacetate is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 0.892 mm Hg(3). One screening test observed 78% biodegradation of methyl acetoacetate in 14 days(6); although this study was not specific to soil, it suggests that biodegradation in soil may be rapid(SRC).|AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 1.0(SRC), determined from a structure estimation method(2), indicates that methyl acetoacetate is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected to be slow(3) based upon an estimated Henry's Law constant of 2.7X10-7 atm-cu m/mole(SRC), derived from its vapor pressure of 0.892 mm Hg(4), and water solubility, 5X10+5 mg/L(5). A base-catalyzed second-order hydrolysis rate constant of 0.57 L/mole-sec(SRC) was estimated using a structure estimation method(6); this corresponds to half-lives of 140 and 14 days at pH values of 7 and 8, respectively(6). According to a classification scheme(7), an estimated BCF of 3.1(SRC), from an estimated log Kow of -0.69(8) and a regression-derived equation(9), suggests the potential for bioconcentration in aquatic organisms is low(SRC).|ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), methyl acetoacetate, which has a vapor pressure of 0.892 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase methyl acetoacetate 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 5 days(SRC), calculated from its rate constant of 3.25X10-13 cu cm/molecule-sec at 25 °C(3). Methyl acetoacetate does not absorb light with wavelengths >290 nm(4) and is not expected to be susceptible to direct photolysis by sunlight(SRC).

The rate constant for the vapor-phase reaction of methyl acetoacetate with photochemically-produced hydroxyl radicals has been reported as 3.25X10-13 cu cm/molecule-sec at 25 °C(1). This corresponds to an atmospheric half-life of about 5 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(2). A base-catalyzed second-order hydrolysis rate constant of 0.57 L/mole-sec(SRC) was estimated using a structure estimation method(3); this corresponds to half-lives of 140 and 14 days at pH values of 7 and 8, respectively(3). Methyl acetoacetate is not expected to be susceptible to direct photolysis by sunlight(SRC), since it does not absorb light with wavelengths >290 nm(4).

An estimated BCF of 3.1 was calculated for methyl acetatoactate(SRC), using an estimated log Kow of -0.69(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC).

Using a structure estimation method based on molecular connectivity indices(1), the Koc for methyl acetoacetate can be estimated to be 1.0(SRC). According to a classification scheme(2), this estimated Koc value suggests that methyl acetoacetate is expected to have very high mobility in soil.

The Henry's Law constant for methyl acetoacetate is estimated as 2.7X10-7 atm-cu m/mole(SRC) derived from its vapor pressure, 0.894 mm Hg(1), and water solubility, 5X10+5 mg/L(2). This Henry's Law constant indicates that methyl acetoacetate is expected to volatilize slowly from water surfaces(3). Methyl acetoacetate's estimated Henry's Law constant indicates that volatilization from moist soil surfaces may occur(SRC). Methyl acetoacetate is not expected to volatilize from dry soil surfaces(SRC) based upon its vapor pressure(1).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 1,872 workers (336 of these are female) are potentially exposed to methyl acetoacetate in the US(1). Occupational exposure to methyl acetoacetate may occur through inhalation and dermal contact with this compound at workplaces where methyl acetoacetate is produced or used(SRC). The general population may be exposed to methyl acetoacetate via inhalation of ambient air containing wood smoke(SRC).

Like other esters, /methyl acetoacetate/ is potentially skin-absorbable.

Although... similar to other acetates, hydrolysis and metabolic degradation occur rapidly, especially since acetoacetic acid is a common mammalian metabolite.

May be harmful by inhalation, ingestion, or skin absorption. Causes eye irritation. May cause skin irritation. (USCG, 1999)

INHALATION: Call for medical aid. Remove to fresh air. If not breathing, give aritificial respiration. If breathing is difficult, give oxygen. EYES: Flush eyes with copious amounts of water for at least 15 minutes. SKIN: Wash with soap and copious amounts of water. (USCG, 1999)

Fresh air, rest. Refer for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower.

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

Basic treatment: Establish a patent airway. Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with normal saline during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Cover skin burns with dry sterile dressings after decontamination ... . /Poison A and B/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in respiratory arrest. Positive pressure ventilation techniques with a bag valve mask device may be beneficial. Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start an IV with D5W /SRP: "To keep open", minimal flow rate/. Use lactated Ringer's if signs of hypovolemia are present. Watch for signs of fluid overload. Consider drug therapy for pulmonary edema ... . For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Poison A and B/

acetoacetic acid methyl ester

The substance can be absorbed into the body by inhalation of its vapour.

Cough. Dizziness. Drowsiness. Headache. Sore throat.

Redness. Pain.

/Available as/ liquid grades, assay 98%

Agriculture, forestry, fishing and hunting|Butanoic acid, 3-oxo-, methyl ester: ACTIVE|Total U.S. annual production of MAA and EAA combined is estimated to be 6000-7000 metric tons.

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