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| | CROTONALDEHYDE Basic information |
| | CROTONALDEHYDE Chemical Properties |
| Melting point | −76 °C(lit.) | | Boiling point | 104 °C(lit.) | | density | 0.853 g/mL at 20 °C(lit.) | | vapor density | 2.41 (vs air) | | vapor pressure | 32 mm Hg ( 20 °C) | | refractive index | n20/D 1.437 | | Fp | 48 °F | | storage temp. | 2-8°C | | solubility | Miscible with alcohol, benzene, gasoline, kerosene, solvent naphtha, and toluene (Hawley, 1981) | | form | Colorless liquid | | color | Colourless | | Odor Threshold | 0.023ppm | | Water Solubility | Soluble in water. (150g/L) at 20°C. | | Sensitive | Air Sensitive | | Merck | 13,2624 | | BRN | 1209254 | | Henry's Law Constant | 1.92 x 10-5 atm?m3/mol (Buttery et al., 1971) | | Exposure limits | NIOSH REL: TWA 2 ppm (6 mg/m3), IDLH 50 ppm; OSHA PEL: TWA 2
ppm; ACGIH TLV: ceiling 0.3 ppm (adopted). | | Stability: | Air sensitive. Highly flammable. Readily forms explosive mixtures with air. May polymerize in the presence of acids, alkalies or amines. Uncontrolled polymerisation may lead to a rapid temperature rise. Incompatible with acids, bases, amines, strong oxidizing agents, butadiene, ketones, oxygen. May contain a stabilizer. | | LogP | 0.6 at 25℃ | | CAS DataBase Reference | 4170-30-3(CAS DataBase Reference) | | IARC | 3 (Vol. 63) 1995 | | EPA Substance Registry System | Crotonaldehyde (4170-30-3) |
| | CROTONALDEHYDE Usage And Synthesis |
| Description | Crotonaldehyde is a clear, colorless to straw-colored liquid with
a strong suffocating odor. It is highly flammable and produces
toxic vapors at room temperature. Crotonaldehyde is found
naturally in emissions of some vegetation and volcanoes; many
foods contain crotonaldehyde in small amounts. Crotonaldehyde
is an important environmental pollutant. It is formed
during combustion of carbon-containing fuels and other
materials. Lipari et al. calculated an emission of 140–2700
metric tons of crotonaldehyde per year in the United States due
to burning of wood in fireplaces, based on the consumption of
firewood. Concentrations of 0.02–17 mgm-3 were measured in
automobile exhausts; however, surprisingly low concentrations
of crotonaldehyde in the range of 1.1–2.1 μgm-3 were found
near highways at a distance of 1 m. In addition, relatively high
amounts of 72–228μg of crotonaldehyde are formed from each
smoked cigarette. Crotonaldehyde is evidently also formed
during biological degradation of organic material such as
plants. In exhausts of house garbage compost plants, amounts
of 2.9 mgm-3 were measured. Strongly varying concentrations
of crotonaldehyde are reported to occur in food, e.g., in fish
(71–1000 μg kg-1), in meat (10–270 μg kg-1), and in fruits and
vegetables (1–100 μg kg-1). Crotonaldehyde was also found in
alcoholic beverages like wine (0.3–1.24 mg l-1) or whisky (30–
210 μg l-1). Crotonaldehyde is an important industrial chemical
(e.g., for the synthesis of tocopherol (vitamin E), the food
preservative sorbic acid, and the solvent 3-methylbutanol), but
it is also a contaminant and by-product in various chemical
processes. | | Chemical Properties | colourless liquid | | Chemical Properties | Crotonaldehyde is water-white (turns paleyellow on contact with air) with an irritating, pungent, suffocating odor. | | Physical properties | Clear, colorless to straw-colored liquid with a pungent, irritating, suffocating odor. An odor
threshold concentration of 23 ppbv was reported by Nagata and Takeuchi (1990). Katz and Talbert
(1930) reported experimental detection odor threshold concentrations ranged from 180 to 570
μg/m3 (63 to 200 ppbv). | | Uses | manufacture of butyl alcohol, butyraldehyde, methoxybutyraldehyde, sorbic acid, maleic acid, crotonic acid, crotyl alcohol. In polymer chemistry: manufacture of resins and polyvinyl acetals, solvent for polyvinyl chloride, rubber antioxidant, increases rubber strength with ketones. In preparation of insecticides and fertilizers. In production of flavors. | | Uses | Crotonaldehyde is used in organic synthesis, in the manufacture
of butyl alcohol and butyraldehyde, and as a warning
agent in fuel gases. It is also used in the manufacture of nbutanol
and sorbic acid as well as in the production of
flavoring agents, surface-active agents, textiles, and insecticidal
compounds. | | Uses | Intermediate for the production of
scorbic acid; formerly used in the manufacture
of n-butyl alcohol; formed during the combustion
of fossil fuels | | Definition | Commercial crotonaldehyde is the trans isomer. | | General Description | A clear colorless to straw colored liquid with a penetrating pungent odor. Flash point 55°F. Density 7.1 lb / gal. Very toxic by inhalation. May polymerize with the release of heat under exposure to heat or contamination. If polymerization takes place inside a container, the container may rupture violently. Less dense than water. Vapors heavier than air. | | Air & Water Reactions | Highly flammable. Slightly soluble in water. | | Reactivity Profile | CROTONALDEHYDE can react violently with strong oxidizing reagents, e.g., reaction with conc. nitric acid leads to instantaneous ignition [Andrussow, L., Chim. Ind. (Paris), 1961, 86, p. 542]. In contact with strong acids or bases CROTONALDEHYDE will undergo an exothermic condensation reaction. Reaction with 1,3-butadiene is particularly violent [Greenlee, K. W., Chem. Eng. News, 1948, 26, p. 1985]. Crotonaldehyde may rapidly polymerize with ethyl acetoacetate (Soriano, D.S. et al. 1988. Journal of Chemical Education 65:637.). | | Hazard | An animal carcinogen. Irritating to
eyes, skin, and upper respiratory tract irritant.
Flammable, dangerous fire risk. Explosive limits
in air 2.9–15.5% by volume. Questionable carcinogen. | | Health Hazard | CROTONALDEHYDE is an extreme eye, respiratory, and skin irritant and can cause corneal damage. A 15 minute exposure at 4.1 ppm is highly irritating to the nose and upper respiratory tract and causes tearing. Brief exposure at 45 ppm proved very disagreeable with prominent eye irritation. | | Fire Hazard | Flammable/combustible material; may be ignited by heat, sparks or flames. Vapor may travel to a source of ignition and flash back. Container may explode in heat of fire. Vapor explosion and poison hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Readily converted by oxygen to hazardous peroxides and acids and is incompatible with caustics, ammonia, organic amines, mineral acids, and strong oxidizers. Readily resinifies to dimer when pure and slowly oxidizes to crotonic acid. Altered by light and air. Hazardous polymerization may occur. Polymerization may take place at high temperatures. | | Safety Profile | Suspected carcinogen
with experimental carcinogenic data. Poison
by ingestion and inhalation. Mutation data
reported. An eye, skin, and mucous
membrane irritant. A lachrymating material
that can cause corneal burns and is very
dangerous to the eyes. Caution: Keep away
from heat and open flame. Keep container
closed. Use with adequate ventilation.
Extremely irritating to eyes, slim, mucous
membranes. When necessary, the
lachrymatory effect of the vapors may be
counteracted by ammonia fumes.
Dangerous fire hazard when exposed to heat
or flame; can react with oxidizing materials.
To fight fire, use alcohol foam, CO2, dry
chemical. Reacts violently with 1,3
butadlene. Violent hypergolic reaction with
concentrated nitric acid. When heated to
decomposition it emits acrid smoke and
fumes. See also ALDEHYDES. | | Potential Exposure | Crotonaldehyde is used as a warning agent in fuel gases and gas line leaks; as solvent; in Crotonaldehyde 935 chemical warfare; as an intermediate in the manufacture of n-butanol and crotonic and sorbic acids; in resin and rubber antioxidant manufacture; also used as a solvent in mineral oil purification; as an alcohol denaturant. | | Carcinogenicity | Similar to acrolein, crotonaldehyde
is suspected of having tumorigenic activity and
of involvement in the metabolism of N-nitrosopyrrolidine
. Nevertheless, it has been proven that crotonaldehyde
does have a carcinogenic effect on rats. Indeed,
crotonaldehyde and nitrosopyrrolidine (a metabolite of
crotonaldehyde) induced neoplastic lesions in the liver,
hepatocellular carcinomas, neoplastic nodules, and liver
damage when administered orally to rats over long periods
of time. | | Source | Reported in gasoline-powered automobile exhaust at concentrations ranging from 100 to
900 ppb (quoted, Verschueren, 1983).
Gas-phase tailpipe emission rates from California Phase II reformulated gasoline-powered
automobiles with and without catalytic converters were 1.17 and 114 mg/km, respectively
(Schauer et al., 2002).
Schauer et al. (2001) measured organic compound emission rates for volatile organic
compounds, gas-phase semi-volatile organic compounds, and particle phase organic compounds
from the residential (fireplace) combustion of pine, oak, and eucalyptus. The gas-phase emission
rates of crotonaldehyde were 276 mg/kg of pine burned, 177 mg/kg of oak burned, and 198 mg/kg
of eucalyptus burned. | | Environmental fate | Biological. Heukelekian and Rand (1955) reported a 10-d BOD value of 1.30 g/g which is
56.8% of the ThOD value of 2.29 g/g.
Chemical/Physical. Slowly oxidizes in air forming crotonic acid (Windholz et al., 1983). At
elevated temperatures, crotonaldehyde may polymerize (NIOSH, 1997).
Crotonaldehyde undergoes addition of water across the CH=CH bond yielding 3-
hydroxybutanal (Kollig, 1995).
At an influent concentration of 1,000 mg/L, treatment with GAC resulted in effluent
concentration of 544 mg/L. The adsorbability of the carbon used was 92 mg/g carbon (Guisti et
al., 1974). | | Shipping | UN1143 Crotonaldehyde or Crotonaldehyde, stabilized, Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable liquid, Inhalation Hazard Zone B. | | Toxicity evaluation | Crotonaldehyde (steric form not reported) has been identified
as a volatile emission product from the arboreous plant
Chinese arborvitae. It has also been detected in gases emitted
from volcanoes. (E)-Crotonaldehyde is emitted to the atmosphere
from the combustion of wood and in exhaust from
gasoline and diesel engines. It is also released to the environment
from tobacco smoke, polymer combustion, and turbine
exhaust.
(E)-Crotonaldehyde has been detected in drinking water
and wastewater, and in human milk and expired air. If released
to soil, (E)-crotonaldehyde will have very high mobility.
Volatilization of (E)-crotonaldehyde may be important from
moist and dry soil surfaces. Biodegradation studies suggest that
(E)-crotonaldehyde may be biodegradable in soil and water,
especially in anaerobic conditions. (E)-Crotonaldehyde readily
polymerizes; therefore, if it is released to soil or water in a spill
situation, a significant fraction may polymerize. If released to
water, (E)-crotonaldehyde may not adsorb to suspended solids
and sediment. | | Incompatibilities | Vapors may form explosive mixture with air. A strong reducing agent. Readily converted by oxygen to peroxides and acids; heat or contact with alkalis and many other substances may cause polymerization. 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, nonoxidizing mineral acids; ammonia, organic amines; aliphatic amines; aromatic amines; 1,3-butadiene, strong bases. Liquid attacks some plastics, rubber, and coatings | | Waste Disposal | 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. May be absorbed on vermiculite and burned in open incinerator or dissolved in solvent and sprayed into incinerator |
| | CROTONALDEHYDE Preparation Products And Raw materials |
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