Methyl isocyanate

Methyl isocyanate
Names
Preferred IUPAC name
Isocyanatomethane
Other names
Methyl isocyanate
methyl carbylamine
MIC
Identifiers
624-83-9 YesY
3D model (Jmol) Interactive image
ChEBI CHEBI:59059 YesY
ChemSpider 11727 YesY
ECHA InfoCard 100.009.879
6290
PubChem 12228
Properties
H3CNCO
Molar mass 57.051 g/mol
Appearance Colorless liquid
Odor Sharp, pungent odor[1]
Density 0.9230 g/cm3 at 27 °C
Melting point −45 °C (−49 °F; 228 K) [2]
Boiling point 38.3 °C (100.9 °F; 311.4 K) [2]
10% (15°C)[1]
Vapor pressure 57.7 kPa
Structure
2.8 D
Thermochemistry
−92.0 kJ·mol−1[2]
Hazards
F+ T+
R-phrases R12, R24/25, R26, R37/38, R41, R42/43, R63
S-phrases (S1/2), S26, S27/28, S36/37/39, S45, S63
NFPA 704
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g., gasoline) Health code 4: Very short exposure could cause death or major residual injury. E.g., VX gas Reactivity code 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g., fluorine Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
3
4
3
Flash point −7 °C (19 °F; 266 K)
534 °C (993 °F; 807 K)
Explosive limits 5.3–26%[2]
Lethal dose or concentration (LD, LC):
120 mg/kg (oral, mouse)
51.5 mg/kg (oral, rat)[3]
6.1 ppm (rat, 6 hr)
12.2 ppm (mouse, 6 hr)
5.4 ppm (guinea pig, 6 hr)
21 ppm (rat, 2 hr)[3]
US health exposure limits (NIOSH):
PEL (Permissible)
 TWA 0.02 ppm (0.05 mg/m3) [skin][1]
REL (Recommended)
 TWA 0.02 ppm (0.05 mg/m3) [skin][1]
IDLH (Immediate danger)
 3 ppm[1]
Related compounds
Related compounds
 Methyl isothiocyanate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
YesY verify (what is YesYN ?)
Infobox references

Methyl isocyanate (MIC) is an organic compound with the molecular formula CH3NCO. Synonyms are isocyanatomethane, methyl carbylamine, and MIC. Methyl isocyanate is an intermediate chemical in the production of carbamate pesticides (such as carbaryl, carbofuran, methomyl, and aldicarb). It has also been used in the production of rubbers and adhesives. As a highly toxic and irritating material, it is extremely hazardous to human health. It was the principal toxicant involved in the Bhopal disaster, which killed nearly 2,259 people initially and officially 3,787 people in total.[4][5][6][7][8][9][10]

Physical properties

Methyl isocyanate (MIC) is a colorless, lachrymatory (tearing agent), flammable liquid.[11] It is soluble in water to 6–10 parts per 100 parts, but it also reacts with water (see Reactions below).

Manufacture

Methyl isocyanate is usually manufactured by the reaction of monomethylamine and phosgene. For large scale production, it is advantageous to combine these reactants at higher temperature in the gas phase. A mixture of methyl isocyanate and two moles of hydrogen chloride is formed, but N-methylcarbamoyl chloride (MCC) forms as the mixture is condensed, leaving one mole of hydrogen chloride as a gas.

The methyl isocyanate is obtained by treating the MCC with a tertiary amine, such as N,N-dimethylaniline, or with pyridine[12] or by separating it by using distillation techniques.[13]

Methyl isocyanate is also manufactured from N-methylformamide and air. In the latter process, it is immediately consumed in a closed-loop process to make methomyl.[14] Other manufacturing methods have been reported.[15][16]

Reactions

Methyl isocyanate reacts readily with many substances that contain N-H or O-H groups. With water, it forms 1,3-dimethylurea and carbon dioxide with the evolution of heat (325 calories per gram of MIC):

At 25 °C, in excess water, half of the MIC is consumed in 9 min.;[17] if the heat is not efficiently removed from the mixture, the rate of the reaction will increase and rapidly cause the MIC to boil. If MIC is in excess, 1,3,5-trimethylbiuret is formed along with carbon dioxide.[11] Alcohols and phenols, which contain an O-H group, react slowly with MIC, but the reaction can be catalyzed by trialkylamines or dialkyltin dicarboxylate. Oximes, hydroxylamines, and enols also react with MIC to form methylcarbamates.[11] These reactions produce the products described below (Uses).

Ammonia, primary, and secondary amines rapidly react with MIC to form substituted ureas. Other N-H compounds, such as amides and ureas, react much more slowly with MIC.[18]

It also reacts with itself to form a trimer or higher molecular weight polymers. In the presence of catalysts, MIC reacts with itself to form a solid trimer, trimethyl isocyanurate, or a higher molecular weight polymer:

Sodium methoxide, triethyl phosphine, ferric chloride and certain other metal compounds catalyze the formation of the MIC-trimer, while the high-molecular-weight polymer formation is catalyzed by certain trialkylamines. Since the formation of the MIC trimer is exothermic (298 calories per gram of MIC), the reaction can lead to violent boiling of the MIC. The high-molecular-weight polymer hydrolyzes in hot water to form the trimethyl isocyanurate. Since catalytic metal salts can be formed from impurities in commercial grade MIC and steel, this product must not be stored in steel drums or tanks.[11]

Uses

Methyl isocyanate is an intermediate chemical in the production of carbamate pesticides (such as carbaryl, carbofuran, methomyl, and aldicarb and Bendiocarb). It has also been used in the production of rubbers and adhesives.

MIC is used in the synthesis of Fluzinamide, Caracemide, cloretazine, temozolomide & 1,1-diphenyl-2-propynyl n-methylcarbamate[19] (analog of Enpromate).

Hazards

Methyl isocyanate (MIC) is extremely toxic. The threshold limit value set by the American Conference on Government Industrial Hygienists is 0.02 ppm. MIC is toxic by inhalation, ingestion and contact in quantities as low as 0.4 ppm. Exposure symptoms includes coughing, chest pain, dyspnea, asthma, irritation of the eyes, nose and throat, as well as skin damage. Higher levels of exposure, over 21 ppm, can result in pulmonary or lung edema, emphysema and hemorrhages, bronchial pneumonia and death. Although the odor of methyl isocyanate cannot be detected at 5 ppm by most people, its potent lachrymal properties provide an excellent warning of its presence (at a concentration of 2–4 parts per million (ppm) subject's eyes are irritated, while at 21 ppm, subjects could not tolerate the presence of methyl isocyanate in air).[20]

Proper care must be taken to store methyl isocyanate because of its ease of exothermically polymerizing (see Reactions) and its similar sensitivity to water. Only stainless steel or glass containers may be safely used; the MIC must be stored at temperatures below 40 °C (104 °F) and preferably at 4 °C (39 °F).

The toxic effect of the compound was apparent in the Bhopal disaster, when around 42,000 kilograms (93,000 lb) of methyl isocyanate and other gases were released from the underground reservoirs of the Union Carbide India Limited (UCIL) factory, over a populated area on December 3, 1984, immediately killing thousands.

Extraterrestrial occurrence

On 30 July 2015, scientists reported that upon the first touchdown of the Philae lander on comet 67/P's surface, measurements by the COSAC and Ptolemy instruments revealed sixteen organic compounds, four of which were seen for the first time on a comet, including acetamide, acetone, methyl isocyanate and propionaldehyde.[21][22][23]

References

  1. 1 2 3 4 5 "NIOSH Pocket Guide to Chemical Hazards #0423". National Institute for Occupational Safety and Health (NIOSH).
  2. 1 2 3 4 Lide, David R., ed. (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. ISBN 0-8493-0487-3.
  3. 1 2 "Methyl isocyanate". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH).
  4. ↑ Methyl Isocyanate. Union Carbide F-41443A – 7/76. Union Carbide Corporation, New York 1976
  5. ↑ Operating Manual Part II. Methyl Isocyanate Unit. Union Carbide India Limited, Agricultural Products Division, 1979
  6. ↑ Broughton E (2005). "The Bhopal disaster and its aftermath: a review". Environmental Health. 4 (1): 6. doi:10.1186/1476-069X-4-6. PMC 1142333Freely accessible. PMID 15882472.
  7. ↑ Eckerman I (2001). "Chemical Industry and Public Health — Bhopal as an example" (pdf). MPH. Göteborg, Sweden: Nordic School of Public Health. 2001 (24). ISSN 1104-5701.
  8. ↑ Eckerman I (2004). The Bhopal Saga - Causes and Consequences of the World's Largest Industrial Disaster. India: Universities Press. ISBN 81-7371-515-7.
  9. ↑ Rosenberg J. "At 1984 - Huge Poison Gas Leak in Bhopal, India". About.com. Retrieved 2008-07-10.
  10. ↑ Eckerman I (2013). "Bhopal Gas Catastrophe 1984: Causes and Consequences". Reference Module in Earth Systems and Environmental Sciences. Elsevier. ISBN 978-0-12-409548-9.
  11. 1 2 3 4 Union Carbide Corporation "Methyl Isocyanate" Product Information Publication, F-41443, November 1967.
  12. ↑ US patent 2480088, Slocombe, R. J.; Hardy, E. E., "Process of Producing Carbamyl Chlorides", issued 1949-08-23, assigned to Monsanto
  13. ↑ FR patent 1400863, Merz, W., "Procédé et dispositif de préparation d'isocyanates d'alkyle", issued 1965-05-28, assigned to Bayer
  14. ↑ Chemical Week, "A fleeting existence for toxic-gas molecules" p. 9, June 12, 1985.
  15. ↑ DE patent 2828259, Giesselmann, G.; Guenther, K.; Fuenten, W., "Verfahren zur Herstellung von Methyl Isocyanate", issued 1980-01-10, assigned to Degussa
  16. ↑ "A safer method for making carbamates". Chemical Week. 1985b (20): 136. 1985.
  17. ↑ Castro EA, Moodie RB, Sansom PJ (1985). "The kinetics of hydrolysis of methyl and phenyl isocyanates". Journal of the Chemical Society, Perkin Transactions 2. 1985 (5): 737–742. doi:10.1039/P29850000737.
  18. ↑ March J (1985). Advanced Organic Chemistry (3rd ed.). New York: John Wiley & Sons. p. 802.
  19. ↑ Donald R Cassady, Robert D Dillard, Nelson R Easton U.S. Patent 3,436,402 (1966 to Lilly Co Eli).
  20. ↑ Kimmerle G, Eben A (1964). "Zur Toxizität von Methylisocyanat und dessen quantitativer Bestimmung in der Luft". Archiv für Toxikologie. 20 (4): 235–241. doi:10.1007/bf00577897.
  21. ↑ Jordans F (30 July 2015). "Philae probe finds evidence that comets can be cosmic labs". The Washington Post. Associated Press. Retrieved 30 July 2015.
  22. ↑ "Science on the Surface of a Comet". European Space Agency. 30 July 2015. Retrieved 30 July 2015.
  23. ↑ Bibring JP, Taylor MG, Alexander C, Auster U, Biele J, Finzi AE, Goesmann F, Klingehoefer G, Kofman W, Mottola S, Seidenstiker KJ, Spohn T, Wright I (31 July 2015). "Philae's First Days on the Comet - Introduction to Special Issue". Science. 349 (6247): 493. Bibcode:2015Sci...349..493B. doi:10.1126/science.aac5116. Retrieved 30 July 2015.
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