Diphenylchloroarsine (DA) is the

organoarsenic compound 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 fungic ...

with the formula (C₆H₅)₂AsCl. It is highly toxic and was once used in

chemical warfare Chemical warfare (CW) involves using the toxic properties of chemical substances as weapons. This type of warfare is distinct from nuclear warfare, biological warfare and radiological warfare, which together make up CBRN, the military acronym ...

. 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 In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6 H5, and is often represented by the symbol Ph. Phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen ...

rings and one

chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride salts ...

. It was also known as sneezing oil during

World War I World War I (28 July 1914 11 November 1918), often abbreviated as WWI, was one of the deadliest global conflicts in history. Belligerents included much of Europe, the Russian Empire, the United States, and the Ottoman Empire, with fightin ...

by the Allies.

Preparation and structure

It was first produced in 1878 by the German chemists

August Michaelis August Michaelis (26 December 1847 – 31 January 1916) was a German people, German chemist and discovered the Michaelis–Arbuzov reaction. Michaelis studied at the University of Göttingen and University of Jena and became professor for chemist ...

(1847–1916) and Wilhelm La Coste (1854–1885). It is prepared by the reduction of diphenylarsinic acid with

sulfur dioxide Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic activ ...

. An idealized equation is shown: :Ph₂AsO₂H + SO₂ + HCl → Ph₂AsCl + H₂SO₄ The process adopted by

Edgewood Arsenal Aberdeen Proving Ground (APG) (sometimes erroneously called Aberdeen Proving ''Grounds'') is a U.S. Army facility located adjacent to Aberdeen, Harford County, Maryland, United States. More than 7,500 civilians and 5,000 military personnel work a ...

for the production of DA for chemical warfare purposes employed a reaction between

chlorobenzene Chlorobenzene is an aromatic organic compound with the chemical formula C6H5Cl. This colorless, flammable liquid is a common solvent and a widely used intermediate in the manufacture of other chemicals. Uses Historical The major use of chlorob ...

and

arsenic trichloride 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 o ...

in the presence of

sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...

. 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.

Uses

It is a useful

reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...

for the preparation of other diphenylarsenic compounds, e.g. by reactions with

Grignard reagent A Grignard reagent or Grignard compound is a chemical compound with the general formula , where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride and phenylmagnesium bromide ...

s: :RMgBr + (C₆H₅)₂AsCl → (C₆H₅)₂AsR + MgBrCl :(R =

alkyl In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloalk ...

aryl In organic chemistry, an aryl is any functional group or substituent derived from an aromatic ring, usually an aromatic hydrocarbon, such as phenyl and naphthyl. "Aryl" is used for the sake of abbreviation or generalization, and "Ar" is used as ...

)

Chemical warfare

Diphenylchlorarsine was used as a chemical weapon on the Western front during the trench warfare of

. It belongs to the class of chemicals classified as vomiting agents. Other such agents are

diphenylcyanoarsine Diphenylcyanoarsine, also called Clark 2 (Chlor-Arsen-Kampfstoff 2, being the successor of Clark 1) by the Germans, was discovered in 1918 by Sturniolo and BellinzoniSturniolo, G. und Bellinzoni, G. (1919); ''Boll. chim. pharm.'', 58, 409–410 an ...

(DC) and diphenylaminechlorarsine (DM, Adamsite). 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 (mask breaker), together with other substances with similar effects, such as Adamsite, diphenylarsincyanide, and diphenylaminarsincyanide. This gas did not actually penetrate masks any better than other gases.

Safety

Diphenylchlorarsine is known to cause

sneezing A sneeze (also known as sternutation) is a semi-autonomous, convulsive expulsion of air from the lungs through the nose and mouth, usually caused by foreign particles irritating the nasal mucosa. A sneeze expels air forcibly from the mouth and ...

coughing A cough is a sudden expulsion of air through the large breathing passages that can help clear them of fluids, irritants, foreign particles and microbes. As a protective reflex, coughing can be repetitive with the cough reflex following three phas ...

headache Headache is the symptom of pain in the face, head, or neck. It can occur as a migraine, tension-type headache, or cluster headache. There is an increased risk of depression in those with severe headaches. Headaches can occur as a result ...

salivation Saliva (commonly referred to as spit) is an extracellular fluid produced and secreted by salivary glands in the mouth. In humans, saliva is around 99% water, plus electrolytes, mucus, white blood cells, epithelial cells (from which DNA can be e ...

, and

vomiting Vomiting (also known as emesis and throwing up) is the involuntary, forceful expulsion of the contents of one's stomach through the mouth and sometimes the Human nose, nose. Vomiting can be the result of ailments like Food-poisoning, foo ...

China China, officially the People's Republic of China (PRC), is a country in East Asia. It is the world's most populous country, with a population exceeding 1.4 billion, slightly ahead of India. China spans the equivalent of five time zones and ...

and

Japan Japan ( ja, 日本, or , and formally , ''Nihonkoku'') is an island country in East Asia. It is situated in the northwest Pacific Ocean, and is bordered on the west by the Sea of Japan, while extending from the Sea of Okhotsk in the north ...

are negotiating remediation of stocks of a variety of organoarsenic weapons, including

chlorodiphenylarsine 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 ...

, dumped in northeastern China after Japan's numerous invasions of China.

References

{{Chemical agents Chemical weapons Organoarsenic chlorides Vomiting agents Phenyl compounds Arsenic(III) compounds

Preparation and structure

Uses

Chemical warfare

Safety

See also

References