Bis(Chloromethyl) Ether

HCID 10967CAS 542-88-1

Basic information

Standard SMILES
ClCOCCl
InChIKey
HRQGCQVOJVTVLU-UHFFFAOYSA-N
Molecular formula
C2H4Cl2O
Average molar mass
114.96 g/mol
Monoisotopic mass
113.96392011

Overview

Bis(chloromethyl) ether is a clear liquid with a strong unpleasant odor. It does not occur naturally. It dissolves easily in water, but degrades rapidly and readily evaporates into air. In the past, it was used to make several types of polymers, resins, and textiles, but its use is now highly restricted. Only small quantities of bis(chloromethyl) ether are produced in the United States. The small quantities that are produced are only used in enclosed systems to make other chemicals. However, small quantities of bis(chloromethyl) ether may be formed as an impurity during the production of another chemical, chloromethyl methyl ether.

Names & identifiers

Preferred name
Bis(Chloromethyl) Ether
IUPAC
chloro(chloromethoxy)methane
English name
Dimethyl-1,1-dichloroether
Molecular formula
C2H4Cl2O
Molecular weight
0

Names & synonyms

BIS(CHLOROMETHYL) ETHER542-88-1Chloro(chloromethoxy)methaneBis(chloromethyl)etherChloromethyl ethersym-Dichloromethyl etherMethane, oxybis[chloro-Oxybis(chloromethane)Dichloromethyl etherEther, bis(chloromethyl)Dichlorodimethyl etherMonochloromethyl Ether
Show more names
sym-Dichloro-dimethyl etherDichlordimethylaetherBis-CMEOxybis[chloromethane]RCRA waste number P0161,1'-Dichlorodimethyl etherDimethyl-1,1'-dichloroetherMethane, oxybis(chloro-

Database identifiers

CAS
542-88-1
PubChem CID
10967
DTXSID
DTXSID8020173
ChEMBL
CHEMBL3185875
ChEBI
CHEBI:82270
UNII
77382IHE37
EC Number
208-832-8
Nikkaji
J3.293J

Properties

Computed structural properties

XLogP
1.5
Topological polar surface area
9.2 Ų
Hydrogen bond donors
0
Hydrogen bond acceptors
1
Rotatable bonds
2
Heavy atoms
5

Experimental & physicochemical properties

Chemical Classes · 3 items

Hazardous Air Pollutants (HAPs)

Other Classes -> Halogenated Ethers

Carcinogens

SpringerMaterials PropertiesSchoenflies notation
PesticidesPesticide -> EPA IRIS
LogP · 2 items

log Kow = 1.04

1.05

OdorSuffocating odor
Density · 6 items

1.315 at 68 °F (EPA, 1998) - Denser than water; will sink

1.323 g/cu cm at 15 °C

Density: 1.315 at 20 °C/4 °C

Relative density (water = 1): 1.3

1.32

1.323 @ 15°C

Physicochemical properties

Melting point
-41.5 °C · -41.5 °C
Boiling point
105 °C · 105°C
Density
1.315 at · 1.315 at 20°C
vapor density
4 · 4
Flash point
19 ° · <19°
color
Volatile liquid

Safety & regulation

GHS classification

GHS Classification · 6 items

Danger

H225: Highly Flammable liquid and vapor [Danger Flammable liquids]

P203, P210, P233, P240, P241, P242, P243, P260, P262, P264, P270, P271, P280, P284, P301+P317, P302+P352, P303+P361+P353, P304+P340, P316, P318, P320, P321, P330, P361+P364, P370+P378, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)

Danger

H225 (100%): Highly Flammable liquid and vapor [Danger Flammable liquids]

P203, P210, P233, P240, P241, P242, P243, P260, P262, P264, P270, P271, P280, P284, P301+P317, P302+P352, P303+P361+P353, P304+P340, P316, P318, P320, P321, P330, P361+P364, P370+P378, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)

Hazard information

Regulatory Information · 3 items

Hazard Traits - Carcinogenicity; Dermatotoxicity; Ocular Toxicity; Respiratory Toxicity

Bis(chloromethyl) ether: Does not have an individual approval but may be used as a component in a product covered by a group standard. It is not approved for use as a chemical in its own right.

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

DOT LabelPoison Flammable Liquid
Fire Hazards · 3 items

Container may explode in heat of fire. When heated to decomposition, it 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. (EPA, 1998)

· HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames.

Highly flammable. Vapour/air mixtures are explosive.

Fire Potential · 2 items

A dangerous fire hazard.

This chemical is a flammable liquid.

Health Hazards · 2 items

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. (EPA, 1998)

· TOXIC; may be fatal if inhaled, ingested or absorbed through skin.

Hazards Summary · 4 items

Bis(chloromethyl) ether is a clear liquid with a strong unpleasant odor. It does not occur naturally. It dissolves easily in water, but degrades rapidly and readily evaporates into air. In the past, it was used to make several types of polymers, resins, and textiles, but its use is now highly restricted. Only small quantities of bis(chloromethyl) ether are produced in the United States. The small quantities that are produced are only used in enclosed systems to make other chemicals. However, small quantities of bis(chloromethyl) ether may be formed as an impurity during the production of another chemical, chloromethyl methyl ether.

Bis(chloromethyl)ether (BCME) is no longer used commercially in the United States. In humans, acute (short-term) exposure to BCME may cause skin, mucous membrane, and respiratory tract irritation. Chronic bronchitis, chronic cough, and impaired respiratory function have been observed in humans following chronic (long-term) inhalation exposure. Several occupational studies have reported increased incidences of lung cancer among exposed workers. Animal studies indicate that BCME is a potent carcinogen with a short latency period. Increased incidences of respiratory tract tumors have been reported in rodents exposed by inhalation. EPA has classified BCME as a Group A, known human carcinogen.

A corrosive substance that can cause pulmonary edema; [ICSC] Bis(chloromethyl) ether and Chloromethyl methyl ether (technical grade) are listed in Table 18-3 as substances that are known human carcinogens (IARC Group 1) after occupational exposure causing lung cancer (oat cell). [Siemiatycki, p. 327]

The major hazards encountered in the use and handling of bis(chloromethyl) ether stem from its toxicologic properties and flammability. Exposure to this highly volatile, colorless liquid may occur via inhalation, ingestion, or dermal absorption from activities associated with its use as a chemical intermediate and in laboratory research. In addition, conflicting evidence exists for its spontaneous formation from formaldehyde and chloride ions (eg, hydrochloric acid (HCL) in moist air. Bis(chloromethyl) ether vapor is severely irritating to the skin, mucous membranes, and eyes. More importantly, this substance is a confirmed human carcinogen. As an OSHA regulated carcinogen, bis(chloromethyl) ether operations are prohibited in open vessels, and must employ the use of exhaust fans, protective equipment and clothing, warning signs, and labels. While mechanical ventilation must be used to minimize exposure, full body protective clothing and gloves also should be used on entering areas of potential exposure. Further, those employed in handling operations should wear full face supplied-air respirators of the continuous flow or pressure-demand type. Workers should remove and leave protective clothing and equipment at the end of the work shift for decontamination, and shower before dressing in street clothes. Smoking, drinking, application of cosmetics, and presence of food should be prohibited in the work area. Bis(chloromethyl) ether is a particularly dangerous fire hazard. In addition to being easily ignited by sparks or flames (flash point: <19 °C, closed cup), when heated to decomposition, this substance can emit hydrogen chloride fumes. Also, upon standing, this substance can form peroxides. If the substance is then heated, it can detonate. For small fires involving bis(chloromethyl) ether, extinguish with dry chemical, CO2, water spray, or foam, and for large fires use water spray, fog, or foam. Runoff from fire control water may give off poisonous gases and cause water pollution. Storage of bis(chloromethyl) ether should be in a cool, dry area, away from acids, oxidizers, or any sources of ignition (eg, open flames, hot plates). Adding antioxidants and keeping containers electrically grounded will reduce explosion potential. Containers of bis(chloromethyl) ether may be shipped via road and water (forbidden on passenger aircraft and railcar), and should be affixed with labels stating, "Poison". Before transporting bis(chloromethyl) ether, the regulatory requirements of the DOT should be consulted. For large spills of bis(chloromethyl) ether first isolate the hazard area and deny entry. Keeping upwind and staying out of low areas, use water spray to reduce vapor. Runoff should be prevented by diking. Protective clothing and a positive pressure breathing apparatus should be worn for all remedial operations. If the spill is in an enclosed space, ventilate before entering. Bis(chloromethyl) ether is a potential candidate for liquid injection, rotary kiln, and fluidized bed forms of incineration. Another method of treatment leading to the decomposition of bis(chloromethyl) ether is to inject it with ammonia in an aqueous or methanol solution. Prior to implementing land disposal of waste residue, consult with environmental regulatory agencies for guidance. Under RCRA, when bis(chloromethyl) ether becomes a waste, it must be managed according to federal and/or state hazardous waste regulations.

Safety & protection

Fire Fighting · 2 items

Move container from fire area if you can do so without risk. Fight fire from maximum distance. Dike fire control water for later disposal; do not scatter the material.

Use water spray, powder, alcohol-resistant foam, carbon dioxide. In case of fire: keep drums, etc., cool by spraying with water. NO direct contact with water.

First Aid Measures · 4 items

Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer immediately for medical attention.

Wear protective gloves when administering first aid. First rinse with plenty of water for at least 15 minutes, then remove contaminated clothes and rinse again. Refer immediately for medical attention .

Rinse with plenty of water for several minutes (remove contact lenses if easily possible). Refer immediately for medical attention.

Rinse mouth. Do NOT induce vomiting. Refer immediately for medical attention.

Accidental Release Measures · 2 items

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area.

First Aid · 2 items

Note: Chloromethyl ether is a recognized human carcinogen.

General First Aid:

Safe StorageFireproof. Dry. Cool. Separated from food and feedstuffs. Store only in original packaging.
Firefighting Hazards · 1 item

Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Storage containers and parts of containers may rocket great distances, in many directions.

Toxicology

Toxicological InformationCDC-ATSDR Toxicological Profile
Cancer SitesRespiratory
Interactions · 4 items

... /Administration/ to skin of single dose of 1 mg ... dissolved in 0.1 mL benzene, followed by thrice weekly applications of acetone solution of 0.025 mg in 0.1 mL mixed phorbol esters from croton oil 14 days after initiation treatment ... 2 mice had squamous cell carcinomas, 1 with metastases to lung. Median survival time ... 474 days. /Controls for this experiment not discussed in this review./

... /Skin administration/ of ... a single dose of 1 mg bis(chloromethyl) ether dissolved in 0.1 mL benzene, followed by thrice weekly applications of acetone solution of 0.025 mg in 0.1 mL mixed phorbol esters from croton oil 14 days after initiation treatment, yielded papillomas in 5/20 female mice, first papilloma ... at 76 days. No tumors were seen in a control group /of mice/ which received /1 mg bis(chlormethyl) ether dissolved in 0.1 mL benzene/ as initiator and no promoting treatment.

... Pre-treatment /of mouse skin/ with 0.15 mg benzo(a)pyrene in 0.1 mL benzene solution, followed 2 wk later by thrice weekly applications of bis(chloromethyl) ether (2 mg in 0.1 mL phorbol esters) ... papillomas ... in 13/20 mice, 12 ... progressed to carcinomas. Latent period ... 98 days ... /Controls for this experiment not discussed in this review./

A possible prophylactic effect of ascorbic acid was studied in a group of 77 workers occupationally exposed to bis(chloromethyl) ether. ... The effect of prophylactic treatment was assessed by cytogenetic analysis of chromosome aberrations, of blastic transformation and mitotic index in peripheral lymphocytes. Blood samples were taken at the beginning and end of 5 mo ascorbic acid prophylaxis. ... Administration of ascorbic acid in daily doses of 1 g, 5 days/wk, decreased the frequency of aberrant cells from 3.73% to 2.13% and increased the percent of blastic transformation from 59.15 to 67.26 and mitotic index from 1.04 to 1.42. ... Smoking habits had no clear-cut effect on detected changes. Thus, the risk of genetic injury, if assessed by the frequency of chromosome aberrations in peripheral lymphocytes, was considerably reduced after ascorbic acid prophylaxis in workers occupationally exposed to halogenated ethers.

Target OrgansCancer, Respiratory (From the Nose to the Lungs)
Environmental Fate · 3 items

TERRESTRIAL FATE: Bis(chloromethyl) ether hydrolyzes rapidly in water(1-2). As a result, adsorption, leaching, volatilization and biodegradation in moist soil are not expected to be important environmental fate processes(SRC). Bis(chloromethyl) ether is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 29.4 mm g at 25 °C(3).

AQUATIC FATE: Bis(chloromethyl) ether hydrolyzes rapidly in water(1-2). As a result, adsorption to suspended solids and sediment, biodegradation, volatilization, and bioconcentration are not expected to be important fate processes in aquatic systems(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), bis(chloromethyl) ether, which has a vapor pressure of 29.4 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase bis(chloromethyl) ether is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 22 days(SRC), calculated from its rate constant of 7.1X10-11 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Bis(chloromethyl) ether does not contain chromophores that absorb at wavelengths >290 nm(4) and, therefore, is not expected to be susceptible to direct photolysis by sunlight(SRC). Bis(chloromethyl) ether is reported to hydrolyze in humid air with half-lives of at least 18 hours(5) and >25 hours(6). However, results suggest that the hydrolysis is surface catalyzed and, therefore, may not represent the true half-life in atmospheric room air or outside air(7).

Adverse EffectsDermatotoxin - Skin burns.

Regulatory information

RCRA Requirements · 1 item

P016; As stipulated in 40 CFR 261.33, when bis(chloromethyl)ether, as a commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or a manufacturing chemical intermediate, becomes a waste, it must be managed according to federal and/or state hazardous waste regulations. Also defined as a hazardous waste is any container or inner liner used to hold this waste or any residue, contaminated soil, water, or other debris resulting from the cleanup of a spill, into water or on dry land, of this waste. Generators of small quantities of this waste may qualify for partial exclusion from hazardous waste regulations (40 CFR 261.5(e)).

Atmospheric Standards · 1 item

Listed as a hazardous air pollutant (HAP) generally known or suspected to cause serious health problems. The Clean Air Act, as amended in 1990, directs EPA to set standards requiring major sources to sharply reduce routine emissions of toxic pollutants. EPA is required to establish and phase in specific performance based standards for all air emission sources that emit one or more of the listed pollutants. Bis(chloromethyl)ether is included on this list.

CERCLA Reportable Quantities · 2 items

Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 10 lb or 4.54 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV.D.3.b).

Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Chloromethyl ether is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 100 lbs.

Clean Water Act Requirements · 2 items

For the maximum protection of human health from the potential carcinogenic effects of exposure to bis(chloromethyl) ether through ingestion of contaminated water and contaminated aquatic organisms, the ambient water concentrations should be zero, based on the nonthreshold assumption for this chemical. However, zero level may not be attainable at the present time. Therefore, the levels which may result in incremental increase of cancer risk over the lifetime are estimated at 10-5, 10-6, and 10-7. The corresponding recommended criteria are 37.6 x 10-6 ug/L, 3.76 x 10-6 ug/L, and 0.376 x 10-6 ug/L, respectively. If these estimates are made for consumption of aquatic organisms only, excluding consumption of water, the levels are 18.4 x 10-3 ug/L, 1.84 x 10-3 ug/L, and 0.184 x 10-3 ug/L, respectively.

Toxic pollutant designated pursuant to section 307(a)(1) of the Federal Water Pollution Control Act and is subject to effluent limitations. /Chloroalkyl ethers/

DHS Chemicals of Interest (COI) · 4 items

Chloromethyl ether

1

1000

Toxic chemical that can be released at a facility.

State Drinking Water Guidelines · 3 items

(FL) FLORIDA 10 ug/L

(MN) MINNESOTA 0.002 ug/L

(NH) NEW HAMPSHIRE 0.00016 ug/L

Safety data

ridadr
UN 2249
Toxicity
LD50 orl-rat: 210 mg/kg AIHAAP 30,470,69
hazard_class
6.1
packing_group
I

Chemistry & industry

Pharmacology

Biological Half-LifeNo reports found; [TDR, p. 191]
Metabolism/MetabolitesThe hydrolysis products of BCME are formaldehyde and hydrochloric acid (HCl).

Uses & manufacturing

Uses · 6 items

In the past, BCME was used for chloromethylation and as an alkylating agent in the manufacture of polymers. BCME is no longer used commercially in the United States. It is used as a research chemical and lab reagent.

Used in the past to make polymers, resins, and textiles; Currently, only small amounts are used in enclosed systems in the chemical industry. [ACGIH]

Regulated as a carcinogen; See 29CFR1910.1003;

Historical uses of BCME include crosslinking of cellulose, preparation of styrene and other polymers, surface treatment of vulcanized rubber to increase adhesion, and manufacture of flame-retardant fabrics.

Intermediate for ion-exchange resins; laboratory reagent.

... No longer used for chloromethylation in industry; however, it is used as the monitoring indicator for chloromethyl ether, because of its greater stability in workroom air.

ImpuritiesOne ... "commercial" /grade/ ... contained traces of carbonyl-containing impurity.
U.S. Production · 3 items

(1977) AT LEAST 4.54X10+7 G

(1982) NOT PRODUCED COMMERCIALLY IN USA

ALTHOUGH BIS(CHLOROMETHYL) ETHER MAY BE PRODUCED IN UNITED STATES AS CHEM INTERMEDIATE, NO EVIDENCE WAS FOUND THAT IT IS PRODUCED ON A COMMERCIAL SCALE FOR SALE TO OTHERS. ... SALES ... LIMITED TO LAB QUANTITIES.

Methods of ManufacturingBis(chloromethyl) ether is produced by reacting paraformaldehyde and chlorosulfonic acid in sulfuric acid (65%) under permanent cooling at temperatures between 26-28 °C; the reaction is controlled to prevent any hydrochloric acid formation.
Formulations/PreparationsOne ... "commercial" /grade/ ... was > 99% pure.
Use ClassificationChemical Classes -> Nitrosamines/ethers/alcohols

Related reactions

30 records

Linked notes

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