Phenacyl chloride

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Phenacyl chloride
Chloroacetophenone.svg
Phenacyl-chloride-3D-balls.png
Names
Preferred IUPAC name
2-Chloro-1-phenylethan-1-one
Other names
2-Chloro-1-phenylethanone
α-Chloroacetophenone
2-Chloroacetophenone
Chloromethyl phenyl ketone
Phenyl chloromethyl ketone
CN
Weeping gas [1]
Mace
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.007.757 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C8H7ClO/c9-6-8(10)7-4-2-1-3-5-7/h1-5H,6H2
  • c1ccc(cc1)C(=O)CCl
Properties
C8H7ClO
Molar mass 154.59 g·mol−1
Appearancewhite to gray crystalline solid [2]
Odor pungent and irritating [2]
Density 1.324 g/cm3
Melting point 54 to 56 °C (129 to 133 °F; 327 to 329 K)
Boiling point 244.5 °C (472.1 °F; 517.6 K)
insoluble
Vapor pressure 0.005 mmHg (20 °C) [2]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Combustible [2]
GHS labelling: [3]
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg
Danger
H300, H311+H331, H315, H318, H334, H335
P280, P301+P310+P330, P302+P352+P312, P304+P340+P311, P305+P351+P338+P310
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
1
0
Flash point 88 °C (190 °F; 361 K)
Lethal dose or concentration (LD, LC):
417 mg/m3 (rat, 15 min)
600 mg/m3 (mouse, 15 min)
465 mg/m3 (rabbit, 20 min)
490 mg/m3 (guinea pig, 30 min)
159 mg/m3 (human, 20 min)
850 mg/m3 (human, 10 min) [4]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 0.3 mg/m3 (0.05 ppm) [2]
REL (Recommended)
TWA 0.3 mg/m3 (0.05 ppm) [2]
IDLH (Immediate danger)
15 mg/m3 [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Phenacyl chloride, also commonly known as chloroacetophenone, is a substituted acetophenone. It is a useful building block in organic chemistry. Apart from that, it has been historically used as a riot control agent, where it is designated CN. [5] It should not be confused with cyanide, another agent used in chemical warfare, which has the chemical structure CN−. Chloroacetophenone is thermally stable, and is the only tear agent that is distillable at ambient conditions.

Contents

Preparation

Chloroacetophenone was first synthetized by Graebe in 1871 by passing chlorine into boiling acetophenone. [6]

Phenacyl chloride is readily available and was first prepared by chlorination of acetophenone vapour. [7] It may also be synthesized by the Friedel-Crafts acylation of benzene using chloroacetyl chloride, with an aluminium chloride catalyst: [8]

Preparation of phenacyl chloride.png

Riot control agent

It was investigated, but not used, during the First and Second World Wars (it was used as a "green agent" by the former Japanese military during the Sino-Japanese War).

Because of its significantly greater toxicity, [9] it has largely been supplanted by CS gas. Even though CN is still supplied to paramilitary and police forces in a small pressurized aerosol known as “Mace” or tear gas, its use is falling as pepper spray both works and disperses more quickly than CN and is less toxic than CN.

The term "Mace" came into being because it was the brand-name invented by one of the first American manufacturers of CN aerosol sprays. Subsequently, in the United States, Mace became synonymous with tear-gas sprays in the same way that Kleenex has become strongly associated with facial tissues (a phenomenon known as a genericized trademark).

Like CS gas, this compound irritates the mucous membranes (oral, nasal, conjunctival and tracheobronchial). Sometimes it can give rise to more generalized reactions such as syncope, temporary loss of balance and orientation. [9] More rarely, cutaneous irritating outbreaks have been observed and allergic contact permanent dermatitis. [5]

At high concentrations, CN may cause corneal epithelial damage and chemosis. It has also accounted for at least five deaths, which have resulted from pulmonary injury and/or asphyxia. [10]

TRPA1 (Transient Receptor Potential-Ankyrin 1) ion channel expressed on nociceptors (especially trigeminal) has been implicated as the site of action for CN, in vivo and in vitro. [11] [12]

Related Research Articles

<span class="mw-page-title-main">Methyl isocyanate</span> Chemical compound

Methyl isocyanate (MIC) is an organic compound with the molecular formula CH3NCO. Synonyms are isocyanatomethane and methyl carbylamine. 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 an extremely toxic and irritating compound, it is very hazardous to human health. MIC was the principal toxicant involved in the Bhopal gas disaster, which eventually killed around 20,000 people in total as per official figures. It is also a very potent lachrymatory agent.

<span class="mw-page-title-main">CS gas</span> Chemical compound

The compound 2-chlorobenzalmalononitrile (also called o-chlorobenzylidene malononitrile; chemical formula: C10H5ClN2), a cyanocarbon, is the defining component of tear gas commonly referred to as CS gas, which is used as a riot control agent.

<span class="mw-page-title-main">Chloroethane</span> Chemical compound commonly known as ethyl chloride

Chloroethane, commonly known as ethyl chloride, is a chemical compound with chemical formula CH3CH2Cl, once widely used in producing tetraethyllead, a gasoline additive. It is a colorless, flammable gas or refrigerated liquid with a faintly sweet odor.

<span class="mw-page-title-main">Vinyl chloride</span> Chemical compound

Vinyl chloride is an organochloride with the formula H2C=CHCl. It is also called vinyl chloride monomer (VCM) or chloroethene. This colorless compound is an important industrial chemical chiefly used to produce the polymer, poly(vinyl chloride) (PVC). Vinyl chloride monomer is among the top twenty largest petrochemicals (petroleum-derived chemicals) in world production. The United States remains the largest vinyl chloride manufacturing region because of its low-production-cost position in chlorine and ethylene raw materials. China is also a large manufacturer and one of the largest consumers of vinyl chloride. Vinyl chloride is a flammable gas that has a sweet odor and is carcinogenic. It can be formed in the environment when soil organisms break down chlorinated solvents. Vinyl chloride that is released by industries or formed by the breakdown of other chlorinated chemicals can enter the air and drinking water supplies. Vinyl chloride is a common contaminant found near landfills. Before the 1970s, vinyl chloride was used as an aerosol propellant and refrigerant.

<span class="mw-page-title-main">Riot control</span> Measures taken against unlawful or violent crowds of people

Riot control measures are used by law enforcement, military, paramilitary or security forces to control, disperse, and arrest people who are involved in a riot, unlawful demonstration or unlawful protest.

<i>p</i>-Phenylenediamine Chemical compound

p-Phenylenediamine (PPD) is an organic compound with the formula C6H4(NH2)2. This derivative of aniline is a white solid, but samples can darken due to air oxidation. It is mainly used as a component of engineering polymers and composites like kevlar. It is also an ingredient in hair dyes and is occasionally used as a substitute for henna.

Mace is the brand name of an early type of aerosol self-defense spray invented by Alan Lee Litman in the 1960s. The first commercial product of its type, Litman's design packaged phenacyl chloride (CN) tear gas dissolved in hydrocarbon solvents into a small aerosol spray can, usable in many environments and strong enough to act as a deterrent and incapacitant when sprayed in the face.

<span class="mw-page-title-main">CR gas</span> Chemical compound

CR gas or dibenzoxazepine (chemical name dibenz[b,f][1,4]oxazepine, is an incapacitating agent and a lachrymatory agent. CR was developed by the British Ministry of Defence as a riot control agent in the late 1950s and early 1960s. A report from the Porton Down laboratories described exposure as "like being thrown blindfolded into a bed of stinging nettles", and it earned the nickname "firegas".

Cyanogen chloride is a highly toxic chemical compound with the formula CNCl. This linear, triatomic pseudohalogen is an easily condensed colorless gas. More commonly encountered in the laboratory is the related compound cyanogen bromide, a room-temperature solid that is widely used in biochemical analysis and preparation.

<span class="mw-page-title-main">Tear gas</span> Non-lethal chemical weapon

Tear gas, also known as a lachrymator agent or lachrymator, sometimes colloquially known as "mace" after the early commercial self-defense spray, is a chemical weapon that stimulates the nerves of the lacrimal gland in the eye to produce tears. In addition, it can cause severe eye and respiratory pain, skin irritation, bleeding, and blindness. Common lachrymators both currently and formerly used as tear gas include pepper spray, PAVA spray (nonivamide), CS gas, CR gas, CN gas, bromoacetone, xylyl bromide and Mace.

<span class="mw-page-title-main">Immediately dangerous to life or health</span> Exposure to dangerous levels of airborne contaminants

The term immediately dangerous to life or health (IDLH) is defined by the US National Institute for Occupational Safety and Health (NIOSH) as exposure to airborne contaminants that is "likely to cause death or immediate or delayed permanent adverse health effects or prevent escape from such an environment." Examples include smoke or other poisonous gases at sufficiently high concentrations. It is calculated using the LD50 or LC50. The Occupational Safety and Health Administration (OSHA) regulation defines the term as "an atmosphere that poses an immediate threat to life, would cause irreversible adverse health effects, or would impair an individual's ability to escape from a dangerous atmosphere."

<span class="mw-page-title-main">Ethylbenzene</span> Hydrocarbon compound; precursor to styrene and polystyrene

Ethylbenzene is an organic compound with the formula C6H5CH2CH3. It is a highly flammable, colorless liquid with an odor similar to that of gasoline. This monocyclic aromatic hydrocarbon is important in the petrochemical industry as a reaction intermediate in the production of styrene, the precursor to polystyrene, a common plastic material. In 2012, more than 99% of ethylbenzene produced was consumed in the production of styrene.

Ethylenediamine (abbreviated as en when a ligand) is the organic compound with the formula C2H4(NH2)2. This colorless liquid with an ammonia-like odor is a basic amine. It is a widely used building block in chemical synthesis, with approximately 500,000 tonnes produced in 1998. Ethylenediamine is the first member of the so-called polyethylene amines.

<span class="mw-page-title-main">Malononitrile</span> Organic compound with formula CH2(CN)2

Malononitrile is an organic compound nitrile with the formula CH2(CN)2. It is a colorless or white solid, although aged samples appear yellow or even brown. It is a widely used building block in organic synthesis.

Benzyl chloride, or α-chlorotoluene, is an organic compound with the formula C6H5CH2Cl. This colorless liquid is a reactive organochlorine compound that is a widely used chemical building block.

<span class="mw-page-title-main">Hexamethylene diisocyanate</span> Chemical compound

Hexamethylene diisocyanate (HDI) is the organic compound with the formula (CH2)6(NCO)2. It is classified as an diisocyanate. It is a colorless liquid. It has sometimes been called HMDI but this not usually done to avoid confusion with Hydrogenated MDI.

<span class="mw-page-title-main">Hexachloroethane</span> Chemical compound

Hexachloroethane (perchloroethane) is an organochlorine compound with the chemical formula (CCl3)2. It is a white or colorless solid at room temperature with a camphor-like odor. It has been used by the military in smoke compositions, such as base-eject smoke munitions.

<span class="mw-page-title-main">Chloroacetyl chloride</span> Chemical compound

Chloroacetyl chloride is a chlorinated acyl chloride. It is a bifunctional compound, making it a useful building block chemical.

<span class="mw-page-title-main">Chloroacetaldehyde</span> Chemical compound

Chloroacetaldehyde is an organic compound with the formula ClCH2CHO. Like some related compounds, it is highly electrophilic reagent and a potentially dangerous alkylating agent. The compound is not normally encountered in the anhydrous form, but rather as the hemiacetal (ClCH2CH(OH))2O.

References

  1. ↑ Verma, K.S. Cengage Physical Chemistry Part 1 Archived 2021-05-06 at the Wayback Machine , Illustration 5.65
  2. 1 2 3 4 5 6 7 NIOSH Pocket Guide to Chemical Hazards. "#0119". National Institute for Occupational Safety and Health (NIOSH).
  3. ↑ GHS: GESTIS 037810
  4. ↑ "alpha-Chloroacetophenone". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  5. 1 2 Treudler, R.; Tebbe, B.; Blume-Peytavi, U.; Krasagakis, K.; Orfanos, C. E. (1999). "Occupational contact dermatitis due to 2-chloracetophenone tear gas". British Journal of Dermatology. 140 (3): 531–534. doi:10.1046/j.1365-2133.1999.02724.x. PMID   10233281. S2CID   45123933.
  6. ↑ Graebe, C. (1871), Ueber eine neue Klasse von Alkoholen. Ber. Dtsch. Chem. Ges., 4: 34-35.
  7. ↑ "Ketones of the aromatic group". Journal of the Chemical Society, Abstracts. 34: 419. 1878. doi: 10.1039/CA8783400392 .
  8. ↑ Levin, N.; Hartung, W. H. (1955). "ω-Chloroisonitrosoacetophenone". Organic Syntheses .; Collective Volume, vol. 3, p. 191
  9. 1 2 Ballantyne, B.; Swanston, D. W. (1978). "The comparative acute mammalian toxicity of 1-chloroacetophenone (CN) and 2-chlorobenzylidene malononitrile (CS)". Archives of Toxicology. 40 (2): 75–95. doi:10.1007/BF01891962. PMID   350195. S2CID   35150415.
  10. ↑ Blain, P. G. (2003). "Tear Gases and Irritant Incapacitants: 1-Chloroacetophenone, 2-Chlorobenzylidene Malononitrile and Dibenz[b,f]-1,4-Oxazepine". Toxicological Reviews. 22 (2): 103–110. doi:10.2165/00139709-200322020-00005. PMID   15071820. S2CID   21164652.
  11. ↑ doi=10.1096/fj.08-117812
  12. ↑ doi=10.1016/j.taap.2008.04.005
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