Chloromethyl methyl ether

Chloromethyl methyl ether (CMME) is a compound with formula CH3OCH2Cl. It is a chloroalkyl ether. It is used as an alkylating agent and industrial solvent to manufacture the detergent dodecylbenzyl chloride, water repellents and ion-exchange resins. In organic synthesis, it is used for introducing the methoxymethyl (MOM) protecting group,[3] and is thus often called MOM-Cl or MOM chloride. It also finds application as a chloromethylating agent in some variants of the Blanc chloromethylation.

Chloromethyl methyl ether[1]
Names
IUPAC name
Chloro(methoxy)methane
Other names
MOM-Cl, CMME, MCD, Chlorodimethyl ether, Chloromethoxymethane, Dimethylchloroether, Methylchloromethyl ether
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.003.165
EC Number
  • 203-480-1
KEGG
RTECS number
  • KN6650000
UNII
UN number 1239
Properties
C2H5ClO
Molar mass 80.51 g·mol−1
Appearance Colorless liquid
Odor Irritating and acrid
Density 1.06 g/mL
Melting point −103.5 °C (−154.3 °F; 169.7 K)
Boiling point 55–57 °C (131–135 °F; 328–330 K)
reacts
Solubility Soluble in alcohol and diethylether
Vapor pressure 192 mmHg (21°C)[2]
Hazards
Main hazards Carcinogen & Irritant
Safety data sheet Safety Data Sheet Archived
GHS pictograms
GHS Signal word Danger
GHS hazard statements
 H225, H302, H312, H319, H332, H350
P201, P202, P210, P233, P240, P241, P242, P243, P261, P264, P270, P271, P280, P281, P301+312, P302+352, P303+361+353, P304+312, P304+340, P305+351+338, P308+313, P312, P322, P330, P337+313
NFPA 704 (fire diamond)
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. gasolineHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
3
3
2
Flash point 0 °C (32 °F; 273 K) (open cup)[2]
NIOSH (US health exposure limits):
PEL (Permissible)
 OSHA-Regulated Carcinogen, no PEL[2]
REL (Recommended)
 Carcinogenic[2]
IDLH (Immediate danger)
 N.D.[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

A convenient and reliable method to prepare chloromethyl methyl ether in situ is by combining dimethoxymethane and acetyl chloride, either neat or as a solution in an inert solvent like toluene, in the presence of zinc bromide (0.0001 equiv) as a catalytic Lewis acid.[4][5] This mixture affords a solution of chloromethyl methyl ether of high purity (>95%) in methyl acetate which can be used directly in many applications. A very similar method, using a high-boiling acyl chloride, can be used to prepare pure material. After simple distillation, this method yields >93% pure material with dimethoxymethane as the only contaminant.[6] In contrast, the classical procedure reported in Organic Syntheses employing formaldehyde, methanol and hydrogen chloride yields material contaminated with a significant amount of the dangerous bis(chloromethyl) ether and requires fractional distillation.[7]

The amount of time required to destroy residual chloromethyl methyl ether using various standard aqueous quench solutions (ammonium chloride solution, water, and sodium carbonate solution) has been measured. In all cases, a solution of chloromethyl methyl ether in toluene/methyl acetate was destroyed (to within detection limit) after vigorous stirring with the quench solution for 15 minutes.[5]

CMME is a known human carcinogen.[8] Chronic exposure can increase the incidence of respiratory cancers, including small cell carcinoma.[9] It is one of 13 chemicals regulated by the Occupational Safety and Health Administration despite not having an established permissible exposure limit.[10][11]

It is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.[12] It listed in Schedule 1 Part 1 of Canada's Prohibition of Certain Toxic Substances Regulations.[13]

References
  1. Sigma-Aldrich
  2. NIOSH Pocket Guide to Chemical Hazards. "#0129". National Institute for Occupational Safety and Health (NIOSH).
  3. Protective Groups in Organic Synthesis, T. W. Greene and P. G. M. Green, 3rd Edition, pages 27-33. ISBN 0-471-16019-9
  4. Synthesis of Alpha-Halo Ethers from Symmetric Acetals and In Situ Methoxymethylation of an Alcohol, Organic Syntheses, Vol. 84, No. 102 (2007)
  5. Berliner, Martin A.; Belecki, Katherine (November 2005). "Simple, Rapid Procedure for the Synthesis of Chloromethyl Methyl Ether and Other Chloro Alkyl Ethers 1". The Journal of Organic Chemistry. 70 (23): 9618–9621. doi:10.1021/jo051344g. ISSN 0022-3263. PMID 16268645.
  6. R.J. Linderman, M. Jaber, B.D. Griedel, J. Org. Chem. 1994, 59, 6499-6500.
  7. Monochloromethyl ether, Organic Syntheses I, 377
  8. bis(Chloromethyl) Ether and Technical-Grade Chloromethyl Methyl Ether CAS Nos. 542-88-1 and 107-30-2 Report on carcinogens, eleventh edition
  9. "Chloromethyl methyl ether". U.S. Environmental Protection Agency, Integrated Risk Information System. 7 March 2011. Accessed 3 May 2011.
  10. NIOSH Pocket Guide to Chemical Hazards
  11. Appendix B - Thirteen OSHA-Regulated Carcinogens
  12. "40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities" (PDF) (July 1, 2008 ed.). Government Printing Office. Archived from the original (PDF) on February 25, 2012. Retrieved October 29, 2011. Cite journal requires |journal= (help)
  13. http://laws-lois.justice.gc.ca/PDF/SOR-2012-285.pdf
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