Names | |
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Preferred IUPAC name Diphenylarsinous chloride | |
Other names diphenylchlorarsine, diphenylchloroarsenic, chlorodiphenylarsane, sneezing gas | |
Identifiers | |
3D model (JSmol) | |
Abbreviations | Ph2AsCl |
ChemSpider | |
ECHA InfoCard | 100.010.839 |
PubChem CID | |
UNII | |
CompTox Dashboard (EPA) | |
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Properties | |
C12H10AsCl | |
Molar mass | 264.59 g mol−1 |
Appearance | colorless 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). |
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.
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]
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]
It is a useful reagent for the preparation of other diphenylarsenic compounds, e.g. by reactions with Grignard reagents:
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]
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 diphenylchlorarsine, dumped in northeastern China after Japan's numerous invasions of China. [10]
Arsine (IUPAC name: arsane) is an inorganic compound with the formula AsH3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in the semiconductor industry and for the synthesis of organoarsenic compounds. The term arsine is commonly used to describe a class of organoarsenic compounds of the formula AsH3−xRx, where R = aryl or alkyl. For example, As(C6H5)3, called triphenylarsine, is referred to as "an arsine".
Copper(I) chloride, commonly called cuprous chloride, is the lower chloride of copper, with the formula CuCl. The substance is a white solid sparingly soluble in water, but very soluble in concentrated hydrochloric acid. Impure samples appear green due to the presence of copper(II) chloride (CuCl2).
Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.
The Sandmeyer reaction is a chemical reaction used to synthesize aryl halides from aryl diazonium salts using copper salts as reagents or catalysts. It is an example of a radical-nucleophilic aromatic substitution. The Sandmeyer reaction provides a method through which one can perform unique transformations on benzene, such as halogenation, cyanation, trifluoromethylation, and hydroxylation.
1,1'-Carbonyldiimidazole (CDI) is an organic compound with the molecular formula (C3H3N2)2CO. It is a white crystalline solid. It is often used for the coupling of amino acids for peptide synthesis and as a reagent in organic synthesis.
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.
Organomercury chemistry refers to the study of organometallic compounds that contain mercury. Typically the Hg–C bond is stable toward air and moisture but sensitive to light. Important organomercury compounds are the methylmercury(II) cation, CH3Hg+; ethylmercury(II) cation, C2H5Hg+; dimethylmercury, (CH3)2Hg, diethylmercury and merbromin ("Mercurochrome"). Thiomersal is used as a preservative for vaccines and intravenous drugs.
Organocadmium chemistry describes the physical properties, synthesis, reactions, and use of organocadmium compounds, which are organometallic compounds containing a carbon to cadmium chemical bond. Cadmium shares group 12 with zinc and mercury and their corresponding chemistries have much in common. The synthetic utility of organocadmium compounds is limited.
Bis(benzene)chromium is the organometallic compound with the formula Cr(η6-C6H6)2. It is sometimes called dibenzenechromium. The compound played an important role in the development of sandwich compounds in organometallic chemistry and is the prototypical complex containing two arene ligands.
Diphenyl diselenide is the chemical compound with the formula (C6H5)2Se2, abbreviated Ph2Se2. This yellow-coloured solid is the oxidized derivative of benzeneselenol. It is used as a source of the PhSe unit in organic synthesis.
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°.
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.
Phenylarsonic acid is the chemical compound with the formula C6H5AsO(OH)2, commonly abbreviated PhAsO3H2. This colourless solid is an organic derivative of arsenic acid, AsO(OH)3, where one OH group has been replaced by a phenyl group. The compound is a buffering agent and a precursor to other organoarsenic compounds, some of which are used in animal nutrition, e.g. 4-hydroxy-3-nitrobenzenearsonic acid.
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.
Methyldichloroarsine, sometimes abbreviated "MD" and also known as methyl Dick, is an organoarsenic compound with the formula CH3AsCl2. This colourless volatile liquid is a highly toxic vesicant that has been used in chemical warfare.
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.
Diphenylphosphine oxide is an organophosphorus compound with the formula (C6H5)2P(O)H. It is a white solid that soluble in polar organic solvents.
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.
Lewisite 3(L-3) is an organoarsenic chemical weapon like lewisite 1 and lewisite 2 first synthesized in 1904 by Julius Arthur Nieuwland. It is usually found as a mixture of 2-chlorovinylarsonous dichloride as well as bis(2-chloroethenyl) arsinous chloride and tris(2-chlorovinyl)arsine. Pure lewisite 1 is an oily, colorless liquid, however, the impure mixture can appear amber to black with an odor distinct to geraniums.