2-Chloroacetophenone

Hazardous Air Pollutants (HAPs)

Toxic Gases & Vapors -> Tear Gas Agents

-> NIOSH Emergency Response Categories

IN VERY LOW CONCN IN AIR IT HAS AN ODOR RESEMBLING APPLE BLOSSOMS

Apple blossoms when dilutes; choking

Sharp, irritating odor

1.32 at 59 °F (USCG, 1999) - Denser than water; will sink

1.324 g/cu cm at 15 °C

Solid density at 20 °C = 1.318 g/cc; liquid density at 58 °C = 1.187 g/cc

1.3 g/cm³

Relative density of the vapour/air-mixture at 20 °C (air = 1): 1.0

1.32

Crystals from dilute alcohol, carbon tetrachloride, or light petroleum

Solid at 20 °C

Colorless to gray crystalline solid

White crystals

Plates from dilute alcohol; rhombic leaves from petroleum ether

less than 1 mg/mL at 66 °F (NTP, 1992)

Practically insoluble in water

Very soluble in ethanol, ethyl ether, benzene; soluble in acetone, petroleum ether

Soluble in carbon disulfide

Solubility in water, g/100ml at 25 °C: 1.64

Insoluble

244 °F (NTP, 1992)

244 °F

118 °C (closed cup)

244 °F (118 °C) (Closed cup)

118 °C c.c.

244 °F

441 to 442 °F at 760 mmHg (NTP, 1992)

247 °C

244-245 °C

472 °F

472 °F

133.7 °F (NTP, 1992)

56.5 °C

54-59 °C

134 °F

134 °F

Danger

H300 (100%): Fatal if swallowed [Danger Acute toxicity, oral]

P233, P260, P261, P262, P264, P264+P265, P270, P271, P272, P280, P284, P301+P316, P302+P352, P304+P340, P305+P354+P338, P316, P317, P319, P320, P321, P330, P332+P317, P333+P317, P342+P316, P361+P364, P362+P364, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 54 reports by companies from 7 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Danger

H301: Toxic if swallowed [Danger Acute toxicity, oral]

Chemical: Ethanone, 2-chloro-1-phenyl-

Hazard Traits - Dermatotoxicity; Ocular Toxicity; Respiratory Toxicity

2-Chloroacetophenone: Does not have an individual approval but may be used under an appropriate group standard

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.)

For information on chemical warfare tear gas agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)

· Combustible material: may burn but does not ignite readily.

· Combustible material: may burn but does not ignite readily.

Combustible. Gives off irritating or toxic fumes (or gases) in a fire.

For information on chemical warfare tear gas agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)

· TOXIC and/or CORROSIVE; inhalation, ingestion or skin contact with material may cause severe injury or death.

· TOXIC and/or CORROSIVE; inhalation, ingestion or skin contact with material may cause severe injury or death.

The main uses for 2-chloroacetophenone are in tear gas and in chemical Mace. It is a potent eye, throat, and skin irritant. Acute (short-term) inhalation exposure of humans causes burning of the eyes with lacrimation, some degree of blurred vision, possible corneal damage, irritation and burning of the nose, throat, and skin, and burning in the chest with dyspnea. Acute dermal exposure is irritating and can result in first, second, and third degree chemical burns in humans. Squamous hyperplasia of the nasal respiratory epithelium was reported in rats chronically exposed (long-term) via inhalation. EPA has not classified 2-chloroacetophenone with respect to potential carcinogenicity.

Alpha-chloroacetophenone can cause allergic contact dermatitis with cross-reactions to o-chlorobenzylidene malononitrile. [ACGIH] A lachrymator; [HSDB] With extremely high inhalational exposures, lower respiratory injury is possible. [Olson, p. 680]

3416 153

1697 153

1697 153

Schrempf A; Chemical mace- how dangerous is chloroacetophenone? Chem Unserer Zeit 12 (5): 146 (1978). A review, with 59 references, of the toxicology and chemistry of the lacrimator mace.

Hu H et al; J Am Med Assoc 262 (5): 660-663 (1989). The uses of tear gas, its toxicity, and treatment for exposure were reviewed. The two compounds most commonly used in recent years were identified as omega-chloroacetophenone and o-chlorobenzylidenemalononitrile. Previous reports and reviews of tear gas usage and exposure effects were considered.

Danto BL; Medical Problems and Criteria Regarding Use of Tear Gas by Police; Am J Forensic Med Pathol 8 (4): 317-22 (1987). This paper addresses the basic types of gas in terms of their chemistry, uses, and medical side effects and complications. Two types of gases namely, chloroacetophenone (CN) and orthochlorobenzylidenemalontrile (CS) are discussed in terms of basic properties, unique advantages, and possible harm to the body.

DHHS/NTP; Toxicology & Carcinogenesis Studies of 2-Chloroacetophenone in F344/N Rats and B6C3F1 Mice (Inhalation Studies) Technical Report Series No. 379 (1990) NIH Publication No. 90-2834

For information on chemical warfare tear gas agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)

Use water spray, powder, foam, carbon dioxide. In case of fire: keep drums, etc., cool by spraying with water.

- Chloroacetophenone (CN) is combustible.

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

Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Give one or two glasses of water to drink. Give a slurry of activated charcoal in water to drink. Refer for medical attention . Rest.

· 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.

· 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.

For information on chemical warfare tear gas agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)

General First Aid:

General First Aid:

(General first aid procedures)

· Wear positive pressure self-contained breathing apparatus (SCBA).

· Wear positive pressure self-contained breathing apparatus (SCBA).

Use water spray, powder, foam, carbon dioxide.

In case of fire: keep drums, etc., cool by spraying with water.

Personal protection: self-contained breathing apparatus. Sweep spilled substance into covered sealable, plastic containers. If appropriate, moisten first to prevent dusting. Carefully collect remainder. Then store and dispose of according to local regulations.

Ventilate area of spill. For small quantities, sweep onto paper or other suitable material, place in an appropriate container and burn in safe place (such as a fume hood). Large quantities may be reclaimed; however, if this is not practical, dissolve in a flammable solvent (such as alcohol) and atomize in a suitable combustion chamber equipped with an appropriate effluent gas cleaning device.

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.

By making package of alpha-chloroacetophenone in paper or other flammable material and burning in a suitable combustion chamber equipped with an appropriate effluent gas cleaning device. By dissolving alpha-chloroacetophenone in a flammable solvent (such as alcohol) and atomizing in a suitable combustion chamber equipped with an appropriate effluent gas cleaning device.

Personal protection: self-contained breathing apparatus. Sweep spilled substance into covered sealable, plastic containers. If appropriate, moisten first to prevent dusting. Carefully collect remainder. Then store and dispose of according to local regulations.

Respiratory

Eyes, skin, respiratory system

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 100(SRC), determined from a structure estimation method(2), indicates that 2-chloroacetophenone is expected to have high mobility in soil(SRC). Volatilization of 2-chloroacetophenone from moist soil surfaces is expected to be an important fate process(SRC) given an estimated Henry's Law constant of 3.5X10-6 atm-cu m/mole(SRC), using a fragment constant estimation method(3). 2-Chloroacetophenone is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 5.4X10-3 mm Hg at 20 °C(4). 2-Chloroacetophenone is expected to degrade based on limited reduction data studied in anaerobic sediments(5).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 100(SRC), determined from a structure estimation method(2), indicates that 2-chloroacetophenone is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon an estimated Henry's Law constant of 3.5X10-6 atm-cu m/mole(SRC), developed using a fragment constant estimation method(4). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 14 and 105, respectively(SRC). According to a classification scheme(5), an estimated BCF of 2(SRC), from an estimated log Kow of 1.93(6) and a regression-derived equation(7), suggests the potential for bioconcentration in aquatic organisms is low(SRC). 2-Chloroacetophenone is expected to undergo hydrolysis in the environment very slowly with hydrolysis products of hydrochloric acid and hydroacetophenone(8). 2-Chloroacetophenone is expected to degrade based on limited reduction data studied in anaerobic sediments(9).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 2-chloroacetophenone, which has a vapor pressure of 5.4X10-3 mm Hg at 20 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase 2-chloroacetophenone 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 7 days(SRC), calculated from its rate constant of 2.0X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). 2-Chloroacetophenone contains chromophores that absorb at wavelengths >290 nm (291 and 329 nm)(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).

The substance can be absorbed into the body by inhalation and by ingestion.

inhalation, ingestion, skin and/or eye contact

Chloroacetophenone (CN) can be absorbed by ingestion and inhalation. It may cause localized irritation of the gastrointestinal tract, respiratory tract, and upon contact with the skin or eyes.

Burning sensation. Cough. Sore throat. Nausea. Shortness of breath.

Redness. Pain.

Redness. Pain. Blurred vision. Partial loss of vision.

Burning sensation.

irritation eyes, skin, respiratory system; pulmonary edema

- Threshold concentrations: Immediate burning pain, spasmodic blinking (blepharospasm), tear production (lacrimation), eye redness, runny nose (rhinorrhea), coughing, sneezing, and pain, but usually no long term tissue damage.

The following link will take the user to the National Toxicology Program (NTP) Test Agent Search Results page, which tabulates all of the "Standard Toxicology & Carcinogenesis Studies", "Developmental Studies", and "Genetic Toxicity Studies" performed with this chemical. Clicking on the "Testing Status" link will take the user to the status (i.e., in review, in progress, in preparation, on test, completed, etc.) and results of all the studies that the NTP has done on this chemical.[Available from, as of August 23, 2013: http://ntp-apps.niehs.nih.gov/ntp_tox/index.cfm?fuseaction=ntpsearch.searchresults&searchterm=532-27-4]

2-Chloroacetophenone

Respiratory

3 x 10 ^-5 mg/m^3

Using a structure estimation method based on molecular connectivity indices(1), the Koc of 2-chloroacetophenone can be estimated to be 100(SRC). According to a classification scheme(2), this estimated Koc value suggests that 2-chloroacetophenone is expected to have high mobility in soil.

/HUMAN EXPOSURE STUDIES/ Four human volunteers were exposed to concentrations of 2-chloroacetophenone up to 350 mg/cu m until they could no longer tolerate the effects or until a maximum of 4 minute exposure was attained. 2-Chloroacetophenone was primarily a lachrymator. The subjects mainly complained of tingling of the nose and rhinorrhea, burning of the throat, eyes, and skin around the eyes, lacrimation, and some degree of blurred vision. Less frequent, but more severe symptoms included burning in the chest with difficulties in breathing and slight gagging with nausea. At post-exposure examinations, the only constant sign was a mild to moderate conjunctivitis. There was not any chest congestion or sign of obstruction at any time, and all signs had usually disappeared within 10 minutes.

/HUMAN EXPOSURE STUDIES/ /Investigators/ reported a brief sensitizing reaction in 5/9 male volunteers in a modified Draize test after uncovered application of 5 drops of a 1% solution of 2-chloroacetophenone in acetone. Most of those subjects sensitized to the 1% concentration had skin reactions when treated with a 0.1% concentration, but not with 0.01%. Most subjects cross-reacted to CS, although at a significantly decreased intensity.

/HUMAN EXPOSURE STUDIES/ Several volunteers experienced primary irritant dermatitis from high 2-chloroacetophenone concentrations in range-finding studies to obtain a proper concentration for patch testing. Generally, these reactions resolved within 1 week, leaving an area of hyperpigmentation, but vesicular dermatitis developed at the primary irritant site 14-21 days after the initial exposure in 2 of these volunteers who appeared to have allergic contact sensitivity to 2-chloroacetophenone by additional appropriate patch testing.

/HUMAN EXPOSURE STUDIES/ ... Patients ... sprayed in the eyes with chem mace ... at distance of 6-12 inches ... had injuries of epithelium of cornea & conjunctiva demonstrable by staining with fluorescein ... 9/12 healed in 72 hr. The other 3 had more extensive epithelial injury which took 14-21 days to heal completely ... in 1 eye a superficial stromal opacity ... /persisted/ for 5 months, but this was superficial and located peripherally in the cornea.

For more Human Toxicity Excerpts (Complete) data for 2-CHLOROACETOPHENONE (15 total), please visit the HSDB record page.

2-Chloroacetophenone's production and use as an intermediate in pharmaceuticals(1) and as an ingredient in chemical MACE (Methylchloroform chloro ACEtophenone)(2) may result in its release to the environment through various waste streams(SRC). Its use as a riot control gas(1) will result in its direct release to the environment(SRC).

ANAEROBIC: 2-Chloroacetophenone was reductively transformed in anaerobic sediments via electron transfer to form acetophenone and via hydride transfer to form 2-chloro-1-phenylethanol(1). An increase in temperature decreases the rate of degradation(1).

PURE CULTURE: Inoculation of a sterile solution (containing 6% glucose, 4% peptone, 4% yeast extract, 4% malt extract, and 100 mg 2-chloroacetophenone) with Cryptococcus macerans for a 2-day period yielded the corresponding chlorohydrin and 2-chloro-1-phenylethanol(1).

2-Chloroacetophenone (CN)

TR-379: Toxicology and Carcinogenesis Studies of 2-Chloroacetophenone (CASRN 532-27-4) in F344/N Rats and B6C3F1 Mice (Inhalation Studies) (1990 )

11/20/89

No Evidence

Equivocal Evidence

No Evidence

Section 8(a) of TSCA requires manufacturers of this chemical substance to report preliminary assessment information concerned with production, exposure, and use to EPA as cited in the preamble in 51 FR 41329. Effective date: 1/26/94; Reporting date: 3/28/94.

Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. 2-Chloroacetophenone is included on this list. Effective date: 1/26/94; Sunset date: 6/30/98.

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. 2-Chloroacetophenone is included on this list.

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 100 lb or 45.4 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).

2-Chloroacetophenone toxicity may be due to the alkylation and consequent inhibition of sulfhydryl-containing enzymes because inhibition of lactate dehydrogenase activity by 2-chloroacetophenone in vitro was not reversed by glutathione and because intravenous administration of sodium thiosulfate did not protect rats from lethal doses of 2-chloroacetophenone given by intraperitoneal injection.

Drugs that act locally on cutaneous or mucosal surfaces to produce inflammation; those that cause redness due to hyperemia are rubefacients; those that raise blisters are vesicants and those that penetrate sebaceous glands and cause abscesses are pustulants; tear gases and mustard gases are also irritants.

Gases that irritate the eyes, throat, or skin. Severe lacrimation develops upon irritation of the eyes.

2-Chloroacetophenone is primarily used as a riot-control agent (tear gas) and in Chemical Mace. It is also used as a pharmaceutical intermediate and formerly as an alcohol denaturant.

A lacrimator (tear gas) agent; [ACGIH]

For 2-chloroacetophenone (USEPA/OPP PC Code: 018001) there are 0 labels match. /SRP: Not registered for current use in the U.S., but approved pesticide uses may change periodically and so federal, state and local authorities must be consulted for currently approved uses./

... Alcohol denaturant (former use)

Pharmaceutical intermediate; riot control gas

Obsolete in military use, common in police agency mixtures of tear gas; principal ingredient in the riot agent under the tradename MACE /whose tradename is derived from the first letters of/ Methylchloroform chloro ACEtophenone

(1977) AT LEAST 4.99X10+6 G

(1981) 4.50X10+5 G (PRINCPL CUSTMS DISTS)

From chloroacetylchloride, benzene, and aluminum chloride.

Prepared by chlorination of acetophenone with selenium oxychloride

Acetophenone (alpha chlorination)

Chemical mace consists of a potent lacrimator, chloroacetophenone (0.9-1.2%) dissolved in a mixture of trichlorotrifluoroethane (70-80%), 1,1,1-trichloroethane (5%), and hydrocarbons resembling kerosene (approx 4%).

93% Purity grade

Ethanone, 2-chloro-1-phenyl-: ACTIVE

Chemical warfare agent with lacrimatory properties.