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| | Methyl formate Basic information |
| | Methyl formate Chemical Properties |
| Melting point | -100 °C (lit.) | | Boiling point | 32-34 °C (lit.) | | density | 0.974 g/mL at 20 °C (lit.) | | vapor density | 2.1 (vs air) | | vapor pressure | 32.91 psi ( 55 °C) | | refractive index | n20/D 1.343(lit.) | | Fp | −16 °F | | storage temp. | Store below +30°C. | | solubility | 300g/l | | form | Liquid | | color | Clear colorless | | PH | 4-5 (200g/l, H2O, 20℃) | | Odor | Pleasant; agreeable. | | Odor Threshold | 130ppm | | explosive limit | 5-23%(V) | | Odor Type | fruity | | Water Solubility | 300 G/L (20 ºC) | | λmax | λ: 259 nm Amax: 1.00
λ: 260 nm Amax: 0.70
λ: 265 nm Amax: 0.20
λ: 270 nm Amax: 0.04
λ: 310-400 nm Amax: 0.01 | | Merck | 14,6077 | | BRN | 1734623 | | Henry's Law Constant | 0.90 at 5.00 °C, 1.18 at 10.00 °C, 1.51 at 15.00 °C, 1.91 at 20.00 °C, 2.36 at 25.00 °C (column
stripping-UV, Kutsuna et al., 2005) | | Exposure limits | TLV-TWA 100 ppm (～250 mg/m3) (ACGIH,
MSHA, and OSHA); TLV-STEL 150 ppm
(～375 mg/m3) (ACGIH); IDLH 5000 ppm
(NIOSH). | | Stability: | Stable. Extremely flammable. Readily forms explosive mixtures with air. Note low flash point and very wide explosion limits. Incompatible with oxidizing agents. | | LogP | -0.21 at 25℃ | | CAS DataBase Reference | 107-31-3(CAS DataBase Reference) | | NIST Chemistry Reference | Methyl formate(107-31-3) | | EPA Substance Registry System | Methyl formate (107-31-3) |
| Hazard Codes | F+,Xn | | Risk Statements | 12-20/22-36/37 | | Safety Statements | 9-16-24-26-33 | | RIDADR | UN 1243 3/PG 1 | | WGK Germany | 1 | | RTECS | LQ8925000 | | Autoignition Temperature | 842 °F | | TSCA | Yes | | HS Code | 2915 13 00 | | HazardClass | 3 | | PackingGroup | I | | Hazardous Substances Data | 107-31-3(Hazardous Substances Data) | | Toxicity | LD50 orally in Rabbit: 1500 mg/kg LD50 dermal Rat > 4000 mg/kg | | IDLA | 4,500 ppm |
| | Methyl formate Usage And Synthesis |
| Description | Methyl Formate, also known as methyl methanoate, is the methyl ester of formic acid. The simplest example of an ester, it is a clear liquid with an ethereal odour, high vapor pressure, and low surface tension. It is an aromatic compound found in apples (Neubeller and Buchloh, 1986), and was identified as a volatile constituent in brewed, roasted, and dried coffee (Lovell et al., 1980); Methyl formate is used primarily to manufacture formamide, dimethylformamide, and formic acid. It is also used as a solvent for quick-drying finishes such as lacquers and in organic synthesis. | | Chemical Properties | Methyl formate is a colorless liquid with a pleasant odor. Its solubility in water is 230 g/l at 25 °C (Riddick et al., 1985), but it reacts slowly with water to form formic acid and methyl alcohol (DOT, 1984). It is soluble in ether, chloroform, and is miscible with ethanol (Lide, 2000). | | Physical properties | Clear, colorless, mobile liquid with a pleasant, etheral odor. An odor threshold concentration of
130 ppmv was reported by Nagata and Takeuchi (1990). | | Uses | Methyl formate is used primarily to manufacture formamide, dimethyl formamide, and formic acid. Because of its high vapor pressure, it is used for quick - drying finishes. It is also used as an insecticide and to manufacture certain pharmaceuticals. Foam Supplies, Inc. has trademarked Ecomate, which is used as a blowing agent for foam insulation, as a replacement for CFC, HCFC, or HFCs, with zero ozone depletion potential and < 25 global warming potential.
A historical use of methyl formate, which sometimes brings it attention, was in refrigeration. Before the introduction of less-toxic refrigerants, methyl formate was used as an alternative to sulfur dioxide in domestic refrigerators, such as some models of the famous GE Monitor Top. Owners of methyl formate refrigerators should keep in mind that, even though they operate below atmospheric pressure, if evidence of a leak develops, they should take measures to avoid exposure to the ether-smelling liquid and vapor. | | Uses | Methyl formate is used as a fumigant, as alarvicide for food crops, and as a solvent forcellulose acetate. | | Production Methods | In the laboratory, methyl formate can be produced by the condensation reaction of methanol and formic acid, as follows:
HCOOH + CH3OH → HCOOCH3 + H2O
Industrial methyl formate, however, is usually produced by the combination of methanol and carbon monoxide (carbonylation) in the presence of a strong base, such as sodium methoxide :
CH3OH + CO → HCOOCH3
This process, practiced commercially by BASF among other companies gives 96 % selectivity toward methyl formate, although it can suffer from catalyst sensitivity to water, which can be present in the carbon monoxide feedstock, commonly derived from synthesis gas. Very dry carbon monoxide is, therefore, an essential requirement. | | Definition | ChEBI: Methyl formate is a formate ester resulting from the formal condensation of formic acid with methanol. A low-boiling (31.5 ℃) colourless, flammable liquid, it has been used as a fumigant and larvicide for tobacco and food crops. It has a role as a polar aprotic solvent, a fumigant, an insecticide and a refrigerant. It is a formate ester, a methyl ester and a volatile organic compound. It is functionally related to a methanol. | | General Description | A clear colorless liquid with an agreeable odor. Flash point -27°F. Less dense than water Vapors heavier than air. | | Air & Water Reactions | Highly flammable. Water soluble. Reacts slowly with water to give formic acid, a corrosive material, and methanol, a flammable liquid. Both products are dissolved in the water. | | Reactivity Profile | Methyl formate reacts 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 with caustic solutions. Flammable hydrogen is generated by mixing with alkali metals and hydrides. | | Hazard | Flammable, dangerous fire and explosionrisk, explosive limits in air 5.9–20%. Eye, upperand lower respiratory tract irritant. | | Health Hazard | Inhalation causes irritation of mucous membranes. Prolonged inhalation can produce narcosis and central nervous symptoms, including some temporary visual disturbance. Contact with liquid irritates eyes and may irritate skin if allowed to remain. Ingestion causes irritation of mouth and stomach and central nervous system depression, including visual disturbances. | | Health Hazard | Methyl formate is a moderately toxic com pound affecting eyes, respiratory tract, andcentral nervous system. It is an irritant tothe eyes, nose, and lungs. Exposure to highconcentrations of its vapors in air may pro duce visual disturbances, irritations, narcoticeffects, and respiratory distress in humans.Such effects may be manifested at a 1-hourexposure to about 10,000-ppm concentration.Cats died of pulmonary edema from 2-hourexposure to this concentration
The acute oral toxicity of methyl formatewas low in test subjects. The symptoms werenarcosis, visual disturbances, and dyspnea.An oral LD50 value in rabbit is in the range1600 mg/kg.. | | Fire Hazard | Behavior in Fire: Vapor is heavier than air and may travel considerable distance to a source of ignition and flash back. | | Safety Profile | Moderately toxic by
ingestion. Inhalation of vapor can cause
irritation to nasal passages and conjunctiva,
optic neuritis, narcosis, retching, and death
from pulmonary irritation. Industrial
fatalities have occurred only with exposure
to high concentrations. Flammable liquid.
Very dangerous fire hazard when exposed to
heat or flame; can react vigorously with
oxidizing materials. Explosive in the form of
vapor when exposed to heat or flame.
Reacts with methanol + sodium methoxide
to form an explosive product. To fight fire,
use alcohol foam, CO2, dry chemical. When
heated to decomposition it emits acrid
smoke and irritating fumes. | | Potential Exposure | Methyl formate is used as a solvent;
as an intermediate in pharmaceutical manufacture; and
as a fumigant | | Environmental fate | Photolytic. Methyl formate, formed from the irradiation of dimethyl ether in the presence of
chlorine, degraded to carbon dioxide, water, and small amounts of formic acid. Continued
irradiation degraded formic acid to carbon dioxide, water, and hydrogen chloride (Kallos and Tou,
1977; Good et al., 1999).
A rate constant of 2.27 x 10-12 cm3/molecule?sec was reported for the reaction of methyl formate
and OH radicals in the atmosphere (Atkinson, 1989).
Chemical/Physical. Hydrolyzes slowly in water forming methanol and formic acid (NIOSH,
1997). Hydrolysis half-lives reported at 25 °C: 0.91 h at pH 9, 9.1 h at pH 8, 2.19 d at pH 7, and
21.9 d at pH 6 (Mabey and Mill, 1978). | | Purification Methods | Wash the formate with strong aqueous Na2CO3, dry it with solid Na2CO3 and distil it from P2O5. (Procedure removes free alcohol or acid.) [Beilstein 2 IV 20.] | | Incompatibilities | May form 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 slowly with water to form methanol
and formic acid. Contact with water, steam releases formic
acid. Compounds of the carboxyl group react with all
bases, both inorganic and organic (i.e., amines) releasing
substantial heat, water and a salt that may be harmful.
Incompatible with arsenic compounds (releases hydrogen
cyanide gas), diazo compounds, dithiocarbamates isocyanates, mercaptans, nitrides, and sulfides (releasing
heat, toxic, and possibly flammable gases), thiosulfates and
dithionites (releasing hydrogen sulfate and oxides of sulfur) | | Waste Disposal | Incineration; atomizing in a
suitable combustion chamber. | | References | Lee, Jae S., J. C. Kim, and Y. G. Kim. "Methyl formate as a new building block in C1 chemistry." Applied Catalysis 57.1 (1990): 1-30.
Handa, Yash Paul, et al. "Insulating Thermoplastic Foams Made With Methyl Formate-Based Blowing Agents." (2006).
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| | Methyl formate Preparation Products And Raw materials |
| Raw materials | Iridium | | Preparation Products | N,N-Dimethylformamide-->Formic acid-->Formamide-->Bensulfuron methyl-->METSULFURON METHYL-->1,2,4-Triazole-->Tribenuron methyl-->3,4-Dimethylpyrazole phosphate-->3,5-DIFLUOROPYRIDINE-4-CARBALDEHYDE-->2-Fluoropyridine-5-carboxaldehyde-->5-methoxy-2-(methylthio)pyrimidin-4-ol ,97%-->2,4-Dichloro-5-methoxypyrimidine-->2-Bromo-5-fomylthiazole-->DPX-T5648-->Nicarbazin-->Olaquindox-->Procymidone-->Imidazole-2-carboxaldehyde-->4-CHLORO-5-METHOXY-2-(METHYLSULFANYL)PYRIMIDINE-->N-Methylformamide-->Ethametsulfuron-methyl-->2,3-Quinoline dicarboxylic acid-->5-ETHYL-2-THIOURACIL-->4(1H)-Pyrimidinone, 2-methyl- (8CI,9CI)-->1,1-Dichlorodimethyl ether-->5-METHOXY-2-SULFANYL-4-PYRIMIDINOL-->1-Formylhomopiperazine-->Methyl 4-acetamido-5-chloro-2-methoxybenzoate-->2-[2-[4-[(4-ethoxyphenyl)methylamino]phenyl]vinyl]-5-(methoxycarbonyl)-1,3,3-trimethyl-3H-indolium chloride-->N-Formylmorpholine-->Methyl 2-amino-3,5-dibromobenzoate-->1,4-DIFORMYLPIPERAZINE-->pyrante |
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