Diphenylchlorarsine

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Diphenylchlorarsine
Ph2AsCl.png
Ph2AsCl-from-xtal-1962-hydrogens-HF-3-21G-3D-CM-cartoon-balls-stroke-5px.png
Names
Preferred IUPAC name
Diphenylarsinous chloride
Other names
diphenylchlorarsine, diphenylchloroarsenic, chlorodiphenylarsane, sneezing gas
Identifiers
3D model (JSmol)
AbbreviationsPh2AsCl
ChemSpider
ECHA InfoCard 100.010.839 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C12H10AsCl/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H Yes check.svgY
    Key: YHHKGKCOLGRKKB-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C12H10AsCl/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H
    Key: YHHKGKCOLGRKKB-UHFFFAOYAA
  • Cl[As](C1=CC=CC=C1)C2=CC=CC=C2
  • Cl[As](c1ccccc1)c2ccccc2
Properties
C12H10AsCl
Molar mass 264.59 g mol−1
Appearancecolorless crystalline solid
Density 1.55 g/cm3
Melting point 42 °C (108 °F; 315 K)
Boiling point 307.2 °C (585.0 °F; 580.3 K)
-145.5·10−6 cm3/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Diphenylchloroarsine (DA) is the organoarsenic compound with the formula (C6H5)2AsCl. It is highly toxic and was once used in chemical warfare. It is also an intermediate in the preparation of other organoarsenic compounds. The molecule consists of a pyramidal As(III) center attached to two phenyl rings and one chloride. It was also known as sneezing oil during World War I by the Allies.

Contents

Preparation and structure

It was first produced in 1878 by the German chemists August Michaelis (1847–1916) and Wilhelm La Coste (1854–1885). [1] [2] It is prepared by the reduction of diphenylarsinic acid with sulfur dioxide. An idealized equation is shown: [3]

Ph2AsO2H + SO2 + HCl → Ph2AsCl + H2SO4

The process adopted by Edgewood Arsenal, the "sodium process", for the production of DA for chemical warfare purposes, employed a reaction between chlorobenzene and arsenic trichloride in the presence of sodium. [4] [5]

The German process, used in the first war, applied at Hochstam-Main, used the Sandmeyer reaction between phenyldiazonium chloride and sodium arsenite. The acidified product was reduced and then neutralized. The salt was condensed again by the Sandmeyer reaction and reduced again, the final product was then acidified, resulting in DA. [5]

The structure consists of pyramidal As centre. The As-Cl distance is 2.26 A and the Cl-As-C and C-As-C angles are 96 and 105°, respectively. [6]

Uses

It is a useful reagent for the preparation of other diphenylarsenic compounds, e.g. by reactions with Grignard reagents:

RMgBr + (C6H5)2AsCl → (C6H5)2AsR + MgBrCl
(R = alkyl, aryl)

Chemical warfare

Diphenylchlorarsine was used as a chemical weapon on the Western front during the trench warfare of World War I. [7] It belongs to the class of chemicals classified as vomiting agents. Other such agents are diphenylcyanoarsine (DC) and diphenylaminechlorarsine (DM, Adamsite). [8] Diphenylchlorarsine was sometimes believed to penetrate the gas masks of the time and to cause violent sneezing, forcing removal of the protecting device. The Germans called it Maskenbrecher (mask breaker), together with other substances with similar effects, such as Adamsite, diphenylarsincyanide, and diphenylaminarsincyanide.[ citation needed ] This gas did not actually penetrate masks any better than other gases. [9]

DA (military code and acronym for diphenylchloroarsine) is a precursor to DC (diphenylcyanoarsine), generated by the reaction of an aqueous solution of sodium cyanide and DA (DC process, NaCN method), with cyanide being used in excess of 5%, for military purposes. [5]

Toxicity

Diphenylchlorarsine is known to cause sneezing, coughing, headache, salivation, and vomiting. China and Japan are negotiating remediation of stocks of a variety of organoarsenic weapons, including chlorodiphenylarsine, dumped in northeastern China after Japan's numerous invasions of China. [10]

See also

Related Research Articles

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

Arsenic trichloride is an inorganic compound with the formula AsCl3, also known as arsenous chloride or butter of arsenic. This poisonous oil is colourless, although impure samples may appear yellow. It is an intermediate in the manufacture of organoarsenic compounds.

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

Triphenylarsine is the chemical compound with the formula As(C6H5)3. This organoarsenic compound, often abbreviated AsPh3, is a colorless crystalline solid that is used as a ligand and a reagent in coordination chemistry and organic synthesis. The molecule is pyramidal with As-C distances of 1.942–1.956 Å and C-As-C angles of 99.6–100.5°.

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

Triphenylstibine is the chemical compound with the formula Sb(C6H5)3. Abbreviated SbPh3, this colourless solid is often considered the prototypical organoantimony compound. It is used as a ligand in coordination chemistry and as a reagent in organic synthesis.

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

Tetraphenylphosphonium chloride is the chemical compound with the formula [(C6H5)4P]Cl, abbreviated Ph4PCl or PPh4Cl or [PPh4]Cl, where Ph stands for phenyl. Tetraphenylphosphonium and especially tetraphenylarsonium salts were formerly of interest in gravimetric analysis of perchlorate and related oxyanions. This colourless salt is used to generate lipophilic salts from inorganic and organometallic anions. Thus, [Ph4P]+ is useful as a phase-transfer catalyst, again because it allows inorganic anions to dissolve in organic solvents.

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

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Arsenicals are chemical compounds that contain arsenic. In a military context, the term arsenical refer to toxic arsenic compounds that are used as chemical warfare agents. This include blister agents, blood agents and vomiting agents. Historically, they were used extensively as insecticides, especially lead arsenate.

Organoarsenic chemistry is the chemistry of compounds containing a chemical bond between arsenic and carbon. A few organoarsenic compounds, also called "organoarsenicals," are produced industrially with uses as insecticides, herbicides, and fungicides. In general these applications are declining in step with growing concerns about their impact on the environment and human health. The parent compounds are arsane and arsenic acid. Despite their toxicity, organoarsenic biomolecules are well known.

Ethyldichloroarsine, sometimes abbreviated as "ED" and "CY" and also known as ethyl Dick, is an organoarsenic compound with the formula CH3CH2AsCl2. This colourless volatile liquid is a highly toxic obsolete vesicant or blister agent that was used during World War I in chemical warfare. The molecule is pyramidal with the Cl-As-Cl and C-As-Cl angles approaching 90° (see image). Ethyldichloroarsine has high chronic toxicity, similar to lewisite.

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

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

Phenyldichloroarsine, also known by its wartime name phenyl Dick and its NATO abbreviation PD, is an organic arsenical vesicant and vomiting agent developed by Germany and France for use as a chemical warfare agent during World War I. The agent is known by multiple synonyms and is technically classified as a vesicant, or blister agent.

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

Phenylsodium C6H5Na is an organosodium compound. Solid phenylsodium was first isolated by Nef in 1903. Although the behavior of phenylsodium and phenyl magnesium bromide are similar, the organosodium compound is very rarely used.

<span class="mw-page-title-main">Lewisite 2</span> Chemical compound

Lewisite 2(L-2) is an organoarsenic chemical weapon with the formula AsCl(CH=CHCl)2. It is similar to lewisite 1 and lewisite 3 and was first synthesized in 1904 by Julius Arthur Nieuwland. It is usually found as a mixture of 2-chlorovinylarsonous dichloride (lewisite 1) as well as bis(2-chloroethenyl) arsinous chloride (lewisite 2) and tris(2-chlorovinyl)arsine (lewisite 3). Pure lewisite 1 is an oily, colorless liquid, however, the impure mixture can appear amber to black with an odor distinct to geraniums.

References

  1. ↑ As early as 1875, Michaelis found diphenylchlorarsine as a side-product in a reaction to produce monophenylarsenic chloride: Michaelis, A. (1875). "Ueber aromatische Arsenverbindungen" [On aromatic arsenic compounds]. Berichte der Deutschen Chemischen Gesellschaft (in German). 8 (2): 1316–1317. doi:10.1002/cber.187500802125. From p. 1317: "Der zweite neben Phenylarsenchlorid gebildete weisse Körper ist noch nicht untersucht, er ist wahrscheinlich Diphenylarsenchlorid, … " (The second white substance that formed beside phenylarsenic chloride has still not been investigated, it's probably diphenylarsenic chloride, … ) In 1878, Michaelis confirmed that it was indeed diphenylarsenic chloride.(La Coste & Michaelis, 1878), p. 1885
  2. ↑ La Coste, W.; Michaelis, A. (1878). "Ueber Mono- und Diphenylarsenverbindungen" [On mono- and di-phenyl arsenic compounds]. Berichte der Deutschen Chemischen Gesellschaft (in German). 11 (2): 1883–1887. doi:10.1002/cber.187801102177. See Diphenylarsenchlorür on p. 1885.
  3. ↑ Blicke, F. F.; Smith, F. D. (1929). "Action of Aromatic Grignard Reagents on Arsenic Trioxide". Journal of the American Chemical Society. 51 (5): 1558–1565. doi:10.1021/ja01380a038.
  4. ↑ An Historical Sketch of Edgewood Arsenal. p 66
  5. 1 2 3 CHEMICAL CORPS CHEMICAL AND RADIOLOGICAL LABORATORIES. Army Chemical Center Maryland. Project: 4-72-05-005. 25 October, 1954
  6. ↑ Trotter, J. (1962). "Stereochemistry of Arsenic. IV. Chlorodiphenylarsine". Canadian Journal of Chemistry. 40 (8): 1590–1593. doi:10.1139/v62-241.
  7. ↑ Gilbert, M. (1995). The First World War—A Complete History . HarperCollins. ISBN   0805047344.
  8. ↑ Holstege, C. P.; Boyle, J. S. (2008-11-26). "CBRNE - Vomiting Agents - Dm, Da, Dc". Medscape.
  9. ↑ Gas and Flame in Modern Warfare, 1918, Chapter IX.
  10. ↑ "Abandoned Chemical Weapons (ACW) in China". February 6, 2004. Archived from the original on July 4, 2008.
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