542-88-1

Basic information

• Product Name: BIS(CHLOROMETHYL)ETHER
• Synonyms: alpha,alpha’-dichlorodimethylether;alpha,alpha'-Dichlorodimethyl ether;BCME;bis(chloromethyl);bis-chloromethyl;Bis-CME;Chloro(chloromethoxy) methane;chloro(chloromethoxy)methane
• CAS NO: 542-88-1
• Molecular Formula: C₂H₄Cl₂O
• Molecular Weight: 114.95856
• EINECS: 208-832-8
• Product Categories: Organics;pharmacetical;Miscellaneous Reagents
• Mol File: 542-88-1.mol

Chemical Properties

• Melting Point: 171℃
• Boiling Point: 106℃
• Flash Point: 75℃
• Appearance: /
• Density: 1.267
• Vapor Pressure: 1.1mmHg at 25°C
• Refractive Index: 1.44433
• Storage Temp.: -20°C Freezer
• Solubility: Soluble in alcohol, ether (Weast, 1986), benzene (Hawley, 1981), and other solvents including acetone and chloroform.
• Water Solubility: decomposes. 2.2 g/100 mL
• CAS DataBase Reference: BIS(CHLOROMETHYL)ETHER(CAS DataBase Reference)
• NIST Chemistry Reference: BIS(CHLOROMETHYL)ETHER(542-88-1)
• EPA Substance Registry System: BIS(CHLOROMETHYL)ETHER(542-88-1)

Safety Data

• Hazard Codes: T+
• Statements: 10-36/37/38-40-26-24-22-45
• Safety Statements: 26-36/37/39-45-53
• RIDADR: 2249
• HazardClass: 6.1(a)
• PackingGroup: I
• Hazardous Substances Data: 542-88-1(Hazardous Substances Data)

Usage

Uses

1. Used in Anion-Exchange Quaternary Resins:
BCME is used as an intermediate in the production of anion-exchange quaternary resins. However, its use as a chloromethylation reagent in the industry is being discontinued due to its high carcinogenic properties.
2. Used in the Formation of Ether Linked Dimers:
BCME serves as a reagent in the formation of ether-linked dimers, which are essential in various chemical processes.
3. Used in Paints and Varnish Production:
In the past, BCME was used to make paints and varnish, as well as a solvent for these applications. However, its use in these industries has been highly restricted due to its hazardous nature.
4. Used in Polymers, Resins, and Textiles Production:
BCME was previously utilized in the production of several types of polymers, resins, and textiles. However, its use in these areas is now highly restricted, and only small quantities are produced for use in enclosed systems to make other chemicals.
5. Impurity Formation during Chloromethyl Methyl Ether Production:
Small quantities of BCME may be formed as an impurity during the production of chloromethyl methyl ether. It can pose exposure risks when the latter compound comes into contact with traces of water in the presence of hydrogen or hydroxyl ions.
Chemical Properties:
BCME is a colorless, volatile liquid with a strong, unpleasant odor.
It dissolves easily in water but degrades rapidly and readily evaporates into the air.
BCME is toxic and poses a significant fire risk, with vapors much denser than air and a flash point below 0°F.
It is insoluble in water and denser than water.

Air & Water Reactions

Highly flammable. Insoluble in water. Reacts with water to form hydrochloric acid & formaldehyde.

Reactivity Profile

DICHLORODIMETHYL ETHER is incompatible with the following: Acids, water [Note: Reacts with water to form hydrochloric acid & formaldehyde.] .

Hazard

A carcinogen. Toxic by ingestion.

Health Hazard

BCME is a highly toxic and carcinogeniccompound. The inhalation toxicity and car cinogenicity of this compound are greatestamong the haloethersExposure to its vapors can cause irritationof the eyes, nose, and throat in humans. Theprimary target organ is the lungs. Inhalationof 100 ppm of this compound in air for afew minutes can cause death to humans.Irritation of the eyes can be moderate tosevere and conjunctival. The acute oral anddermal toxicity of this compound, however,is moderate and comparable to that of bis(2-chloroethyl)etherLC50 value, inhalation (rats): 33 mg (7ppm)/m3/7 hrLD50 value, oral (rats): 210 mg/kg (NIOSH1986)Tests on animals have confirmed the car cinogenic action of BCME. It is carcinogenicby inhalation and by subcutaneous and skinapplications. In humans it can produce lungcancer — a fact that is now well established.Tests on rats indicate that exposure to 0.1-ppm concentrations in air for 6 hours per dayfor 6 months produced tumors in the noseand lungs. Subcutaneous and skin applicationsproduced tumors at the site of application.

Health Hazard

Acute toxicity is high by ingestion, inhalation, and skin irritation. Small quantities may cause death or permanent injury after very short exposure. Chloromethyl ether is an alkylating agent which is a recognized human carcinogen. There is a strong association between industrial exposure and excess lung cancer.

Health Hazard

Exposures to bis(chloromethyl) ether cause irritation to the skin, eyes, throat, and lungs, and in cases of severe exposures cause damage to the lungs (swelling and bleeding) and death. Breathing low concentrations will cause coughing and nose and throat irritation.

Fire Hazard

Container may explode in heat of fire. When heated to decomposition, BIS(CHLOROMETHYL)ETHER emits very toxic fumes of chlorides. Decomposed by water to hydrochloric acid and formaldehyde. Avoid water: hydrolyzes very rapidly (half life 10-40 seconds) on contact with water. Avoid decomposing heat, powerful oxidizers, areas of high fire hazard and moist air.

Potential Exposure

Exposure to bis(chloromethyl)ether may occur in industry and in the laboratory. This substance can form spontaneously in warm moist air by the combination of formaldehyde and hydrogen chloride. This compound is used as an alkylating agent in the manufacture of polymers; as a solvent for polymerization reactions; in the preparation of ion exchange resins; and as an intermediate for organic synthesis. Haloethers, primarily α-chloromethyl ethers, represent a category of alkylating agents of increasing concern due to the establishment of a causal relationship between occupational exposure to two agents of this class and lung cancer in the United States and abroad. The cancers are mainly oat cell carcinomas. Potential sources of human exposure to BCME appear to exist primarily in areas including: (1) its use in chloromethylating (crosslinking) reaction mixtures in anion-exchange resin production; (2) segments of the textile industry using formaldehydecontaining reactants and resins in the finishing of fabric and as adhesive in the laminating and flocking of fabrics; and (3) the nonwoven industry which uses as binders, thermosetting acrylic emulsion polymers comprising methylol acrylamide, since a finite amount of formaldehyde is liberated on the drying and curing of these bonding agents. NIOSH has confirmed the spontaneous formation of BCME from the reaction of formaldehyde and hydrochloric acid in some textile plants and is now investigating the extent of possible worker exposure to the carcinogen. However, this finding has been disputed by industrial tests in which BCME was not formed in air by the reaction of textile systems employing hydrochloric acid and formaldehyde.

Carcinogenicity

Bis(chloromethyl) ether (BCME) is known to be human carcinogens based on sufficient evidence of carcinogenicity from studies in humans.

Source

sym-Dichloromethyl ether may form as an intermediate by-product when form-aldehyde reacts with chloride ions under acidic conditions (Frankel et al., 1974; Tou and Kallos, 1974a; Travenius, 1982). Tou and Kallos (1974) reported that the reactants (formaldehyde and chloride ions) must be in concentrations of mg/L to form sym-dichloromethyl ether at concentrations of μg/L. Chloromethyl methyl ether may contain 1 to 8% sym-dichloromethyl ether as an impurity (Environment Canada, 1993a).

Environmental fate

Chemical/Physical. Reacts rapidly with water forming HCl and formaldehyde (Fishbein, 1979; Tou et al., 1974). Tou et al. (1974) reported a hydrolysis half-life of 38 sec for sym-dichloromethyl ether at 20 °C. Anticipated products from the reaction of sym-dichloromethyl ether with ozone or OH radicals in the atmosphere, excluding the decomposition products formaldehyde and HCl, are chloromethyl formate and formyl chloride (Cupitt, 1980).

Shipping

UN2249 Dichlorodimethyl ether, symmetrical, Hazard class: 6.1; Labels: 6.1—Poisonous materials, 3— Flammable liquid.

Toxicity evaluation

No information is available on the transport and partitioning of BCME in the environment. Due to the relatively short half-life in both air and water, it is unlikely that significant partitioning between media or transport occurs. Primary process for BCME degradation in air is believed to be reaction with photochemically generated hydroxyl radicals to yield chloromethyl formate ClCHO, formaldehyde, and HCl. Atmospheric half-life due to reaction with hydroxyl radicals is estimated to be 1.36 h. Hydrolysis in the vapor phase is found to be slower with an estimated half-life of 25 h. BCME is rapidly hydrolyzed in water to yield formaldehyde and HCl, and the hydrolysis rate constant is estimated to be 0.018 s-1at 20°C, which is equal to a half-life of ～35 s. No information is available on the fate of BCME in soil. It is probable that BCME would rapidly degrade upon contact with moisture in soil. Due to its high volatile nature, it is not expected that BCME would persist in soil for significant periods.

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. Decomposes on contact with water, moist air, and heat, forming corrosive hydrochloric acid, hydrogen chloride, and formaldehyde vapors. May form shocksensitive compounds on contact with oxidizers, peroxides, and sunlight. Attacks many plastics.

Waste Disposal

Incineration, preferably after mixing with another combustible fuel. Care must be exercised to assure complete combustion to prevent the formation of phosgene. An acid scrubber is necessary to remove the halo acids produced.

InChI:InChI=1/C2H2Cl4O/c3-1(4)7-2(5)6/h1-2H

Upstream product

• 67-56-1 methanol 
• 100-97-0 hexamethylenetetramine 
• 107-30-2 chloromethyl methyl ether 
• 353-49-1 fluoroformyl chloride 
• 67-68-5 dimethyl sulfoxide 
• 7647-01-0 hydrogenchloride 
• 50-00-0 formaldehyd 
• 7664-93-9 sulfuric acid 
• 7790-94-5 chlorosulfonic acid 
• 10025-87-3 trichlorophosphate 
• 7446-70-0 aluminium trichloride 
• 115-10-6 Dimethyl ether 
• 7782-50-5 chlorine 
• 505-22-6 1,3-dioxane 

Downstream Products

• 16089-85-3 1,3-bis(pyridinium)-2-oxapropane dichloride 
• 75-44-5 phosgene 
• 42818-11-1 bis-(3,4-dimethyl-phenoxymethyl)-ether 
• 42818-09-7 bis<4-methylphenoxy)methyl> ether 
• 607-50-1 1,1'-dinaphthylmethane 
• 1667-10-3 4,4'-bis(chloromethyl)biphenyl 
• 623-25-6 p-Xylylene dichloride 
• 40207-05-4 3-(chloromethyl)-4-methylbenzoic acid 
• 824-55-5 2,4-dimethyl-benzyl chloride 
• 101-76-8 4,4'-dichlorodiphenylmethane 
• 104-83-6 1-Chloro-4-(chloromethyl)benzene 
• 54777-65-0 4-acetamidobenzyl chloride 
• 4957-14-6 4,4'-dimethyldiphenylmethane 
• 104-82-5 4-Methylbenzyl chloride 

Relevant articles and documents

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Reactivity of [WCl6] with Ethers: A Joint Computational, Spectroscopic and Crystallographic Study

The reactions of [WCl6] with a series of ethers have been performed in chlorinated solvent and elucidated by means of analytical, spectroscopic and DFT methods. The addition of tetrahydropyran (thp) or 1,4-dioxane to [WCl6] resulted in the reversible formation of the adducts WCl6···L [L = thp (1a), 1,4-dioxane (1b)], detected in solution by NMR spectroscopy. The reaction of [WCl6] with thp in a molar ratio of 1:2 in chloroform at reflux afforded [WOCl4(thp)] (2a), which was isolated in 51 % yield. [WOCl4(OMe2)] (2b) and [WOCl3(OMe2)2] (3a) were isolated in yields of 53 and 18 %, respectively, from the reaction of [WCl6] with an excess of dimethyl ether. [WOCl3(OEt2)2] (3b) was the only identified metal compound produced from the reaction of [WCl6] and OEt2(1:2 molar ratio). According to NMR studies, the oxide ligand in 2a,b and 3a,b was generated by double C–O bond cleavage involving one equivalent of organic reactant. The 1:1 reaction of [WCl6] with 1,2-diethoxyethane led to [WCl5(κ1-OCH2CH2OEt)] (4) and a minor amount of [WCl4(κ2-EtOCH2CH2OEt)] (5). The aryl oxide compound [WCl5(OPh)] (6) was prepared in 62 % yield from the reaction of [WCl6] and anisole by selective Csp3–O bond activation. The prolonged heating of a mixture of [WCl6] and diphenyl ether in 1,2-dichloroethane led to the isolation of the WVcomplex [WCl5(OPh2)] (7). The molecular structures of 2a and 3a were ascertained by X-ray diffraction.

GLYCOSIDE COMPOUND, METHOD FOR PRODUCING THIOETHER, ETHER, METHOD FOR PRODUCING ETHER, METHOD FOR PRODUCING GLYCOSIDE COMPOUND, METHOD FOR PRODUCING NUCLEIC ACID

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The present invention refers to a process for the preparation of fluoromethyl 2,2,2-trifluoro-1-(trifluoromethyl) ethyl ether (sevoflurane) which includes a step that consists of reacting hexafluoroisopropanol with a formaldehyde equivalent selected among paraformaldehyde or 1,3,5-trioxane, a chlorinating agent selected from the group consisting of oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, sulfuryl chloride and thionyl chloride, and a strong acid selected from the group consisting of concentrated or fuming sulfuric acid resulting in the formation of the intermediate sevochlorane which is converted to sevoflurane in a second step which consists of reacting sevochlorane with an alkali metal fluoride, or a linear or branched chain tetra-alkyl quarternary ammonium fluoride in the presence of a sub-stoichiometric quantity of an alkali metal iodide, or a linear or branched alkyl chain tetra-alkyl quarternary ammonium iodide, preferably in a solvent.

Process for halomethyl ethers of hydroxyiminomethyl quaternary pyridinium salts

A halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl)-2-oxapropane is prepared by adding a pyridinealdoxime to a bis-halomethylether in such a manner that the bis-halomethylether is maintained in excess throughout the addition. This procedure produces the halide salt of a 1-(hydroxyiminomethyl-1-pyridino)-3-(halomethyl)-2-oxapropane in high yield and purity, which facilitates its use as an intermediate in the manufacture of an asymmetrically substituted 1,3-di (1-pyridino)-2-oxapropane, a class of compounds that are generally useful antidotes to various toxic agents. A prominent member of the class is the dimethylsulfonate salt of 1-(2-hydroxyiminomethyl-1-pyridino)-3-(4-carbamoyl-1-pyridino)-2-oxapropane. The use of mercaptoalkyl-functionalized polymers is disclosed as a preferred metal ion scavenger for a final purification step in the manufacture of these compounds.