Phenacyl chloride

Last updated
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 Carl 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 CN's significantly greater toxicity, [9] CN has largely been supplanted for military use 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, CN's use is falling because 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 short-term killed 4,000–8,000 people and caused permanent injury and premature deaths to approximately 6 lakhs. 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 the lachrymatory agent commonly referred to as CS gas, a tear gas which is used as a riot control agent, and is banned for use in warfare due to the 1925 Geneva Protocol.

Chloromethane, also called methyl chloride, Refrigerant-40, R-40 or HCC 40, is an organic compound with the chemical formula CH3Cl. One of the haloalkanes, it is a colorless, sweet-smelling, flammable gas. Methyl chloride is a crucial reagent in industrial chemistry, although it is rarely present in consumer products, and was formerly utilized as a refrigerant. Most chloromethane is biogenic.

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

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<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 polyvinyl 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.

<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

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Tear gas, also known as a lachrymatory 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, chloropicrin and Mace.

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

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

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

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

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

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<span class="mw-page-title-main">Propylene glycol dinitrate</span> Chemical compound

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

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

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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". Berichte der deutschen chemischen Gesellschaft. 4 (1): 34–35. doi:10.1002/cber.18710040116. ISSN   0365-9496.
  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 ; Collected Volumes, 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. Bibcode:1978ArTox..40...75B. 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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