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{{chembox {{chembox
| Watchedfields = changed
| verifiedrevid = 399909481 | verifiedrevid = 413471213
| ImageFile1 = Ph2AsCl.png | ImageFile1 = Ph2AsCl.png
| ImageSize1 = 150 | ImageSize1 = 150
| ImageFile2 = Ph2AsCl-from-xtal-1962-hydrogens-HF-3-21G-3D-CM-cartoon-balls-stroke-5px.png | ImageFile2 = Ph2AsCl-from-xtal-1962-hydrogens-HF-3-21G-3D-CM-cartoon-balls-stroke-5px.png
| ImageSize2 = 250 | ImageSize2 = 250
⚫ | IUPACName = diphenylchloroarsenic, chlorodiphenylarsane, sneezing gas
| PIN = Diphenylarsinous chloride
| OtherNames = diphenylchlorarsine
⚫ | OtherNames = diphenylchlorarsine, diphenylchloroarsenic, chlorodiphenylarsane, sneezing gas
| Section1 = {{Chembox Identifiers | Section1 = {{Chembox Identifiers
| Abbreviations = Ph<sub>2</sub>AsCl | Abbreviations = Ph<sub>2</sub>AsCl
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 12306 | ChemSpiderID = 12306
| InChI1 = 1/C12H10AsCl/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H | InChI1 = 1/C12H10AsCl/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H
Line 18: Line 19:
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = YHHKGKCOLGRKKB-UHFFFAOYSA-N | StdInChIKey = YHHKGKCOLGRKKB-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|??}}
| CASNo = 712-48-1 | CASNo = 712-48-1
| UNII_Ref = {{fdacite|correct|FDA}}
⚫ | PubChem = 12836
| UNII = 1H39V3559B
⚫ | SMILES = Cl(C1=CC=CC=C1)C2=CC=CC=C2
⚫ | PubChem = 12836
| InChI = 1/C12H10AsCl/c14/h1-10H
⚫ | SMILES = Cl(C1=CC=CC=C1)C2=CC=CC=C2
⚫ }}
⚫ | Section2 = {{Chembox Properties
⚫ | Formula = C<sub>12</sub>H<sub>10</sub>AsCl
⚫ | MolarMass = 264.59 g mol<sup>−1</sup>
}} }}
⚫ | Section2 = {{Chembox Properties
⚫ | Formula = C<sub>12</sub>H<sub>10</sub>AsCl
⚫ | MolarMass = 264.59&nbsp;g mol<sup>−1</sup>
| Appearance = colorless crystalline solid
| Density = 1.55 g/cm<sup>3</sup>
| MeltingPtC = 42
| BoilingPtC = 307.2
| MagSus = -145.5·10<sup>−6</sup> cm<sup>3</sup>/mol
⚫ }}
}} }}


'''Diphenylchloroarsine''' ('''DA''') is the ] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>AsCl. This odorless, toxic liquid was once used as harassing agent. It is also an intermediate in the preparation of other organoarsenic compounds. The molecule consists of a pyramidal ] center attached to two ] rings and one ]. '''Diphenylchloroarsine''' ('''DA''') is the ] with the formula (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>AsCl. It is highly toxic and was once used in ]. It is also an intermediate in the preparation of other organoarsenic compounds. The molecule consists of a pyramidal ] center attached to two ] rings and one ]. It was also known as '''sneezing oil''' during ] by the Allies.


==Preparation and structure==
⚫ ==Uses==
It was first produced in 1878 by the German chemists ] (1847–1916) and Wilhelm La Coste (1854–1885).<ref>As early as 1875, Michaelis found diphenylchlorarsine as a side-product in a reaction to produce monophenylarsenic chloride: {{cite journal |last1=Michaelis |first1=A. |title=Ueber aromatische Arsenverbindungen |journal=Berichte der Deutschen Chemischen Gesellschaft |date=1875 |volume=8 |issue=2 |pages=1316–1317 |url=https://babel.hathitrust.org/cgi/pt?id=iau.31858002458770;view=1up;seq=416 |trans-title=On aromatic arsenic compounds |language=German |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</ref><ref>{{cite journal |last1=La Coste |first1=W. |last2=Michaelis |first2=A. |title=Ueber Mono- und Diphenylarsenverbindungen |journal=Berichte der Deutschen Chemischen Gesellschaft |date=1878 |volume=11 |issue=2 |pages=1883–1887 |url=https://babel.hathitrust.org/cgi/pt?id=iau.31858002458846;view=1up;seq=499 |trans-title=On mono- and di-phenyl arsenic compounds |language=German |doi=10.1002/cber.187801102177}} See ''Diphenylarsenchlorür'' on p. 1885.</ref> It is prepared by the reduction of ] with ]. An idealized equation is shown:<ref>{{ cite journal |author1=Blicke, F. F. |author2=Smith, F. D. | title = Action of Aromatic Grignard Reagents on Arsenic Trioxide | journal = Journal of the American Chemical Society | year = 1929 | volume = 51 | issue = 5 | pages = 1558–1565 | doi = 10.1021/ja01380a038 }}</ref>
Diphenylchlorarsine was first used as a chemical weapon on the Western front during the trench warfare of ]
⚫ :Ph<sub>2</sub>AsO<sub>2</sub>H + SO<sub>2</sub> + HCl → Ph<sub>2</sub>AsCl + H<sub>2</sub>SO<sub>4</sub>
<ref>{{cite book |title= First World War|last= Gilbert|first= Martin|year= 1995|publisher= HarperCollins|isbn= 0006376665}}</ref> It belongs to the class of chemicals classified as vomiting agents. Other such agents are ] (DC) and ] (DM, adamsite).<ref>{{cite web |url= http://emedicine.medscape.com/article/833391-overview |title= CBRNE - Vomiting Agents - Dm, Da, Dc |author= Christopher P Holstege, Jennifer S Boyle |date= Nov 26, 2008 }}</ref>
The process adopted by ], the "sodium process", for the production of DA for chemical warfare purposes, employed a reaction between ] and ] in the presence of ].<ref>An Historical Sketch of Edgewood Arsenal. p 66</ref><ref name=":0" />


The German process, used in the first war, applied at Hochstam-Main, used the ] between ] and ]. The acidified product was ] and then neutralized. The salt was condensed again by the Sandmeyer reaction and reduced again, the final product was then acidified, resulting in DA.<ref name=":0">CHEMICAL CORPS CHEMICAL AND RADIOLOGICAL LABORATORIES. Army Chemical Center Maryland. Project: 4-72-05-005. 25 October, 1954</ref>
⚫ It is a useful ] in the preparation of other diphenylarsenic compounds, e.g. by reactions with ]s:

⚫ :RMgBr + (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>AsCl → (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>AsR + MgBrCl
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.<ref>{{cite journal | author = Trotter, J. | title = Stereochemistry of Arsenic. IV. Chlorodiphenylarsine | journal = Canadian Journal of Chemistry | year = 1962 | volume = 40 | issue = 8 | pages = 1590–1593 | doi = 10.1139/v62-241 }}</ref>

⚫ ==Uses==
⚫ It is a useful ] for the preparation of other diphenylarsenic compounds, e.g. by reactions with ]s:
:RMgBr + (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>AsCl → (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>AsR + MgBrCl
:(R = ], ]) :(R = ], ])


===Chemical warfare===
==Safety==
Diphenylchlorarsine was used as a chemical weapon on the Western front during the trench warfare of ].<ref>{{cite book | title = The First World War—A Complete History | last = Gilbert | first = M. | year = 1995 | publisher = HarperCollins | isbn = 0805047344 | url-access = registration | url = https://archive.org/details/firstworldwarsec00mart }}</ref> It belongs to the class of chemicals classified as vomiting agents. Other such agents are ] (DC) and ] (DM, Adamsite).<ref>{{cite web | url = http://emedicine.medscape.com/article/833391-overview | title = CBRNE - Vomiting Agents - Dm, Da, Dc |author1=Holstege, C. P. |author2=Boyle, J. S. | publisher = Medscape | date = 2008-11-26 }}</ref> 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 {{lang|de|Maskenbrecher}} (mask breaker), together with other substances with similar effects, such as Adamsite, ], and ].{{Citation needed|date=February 2013}} This gas did not actually penetrate masks any better than other gases.<ref>, 1918, Chapter IX.</ref>
⚫ Diphenylchlorarsine is known to cause ], ], ], ], and ]. ] and ] are negotiating remediation of stocks of a variety of organoarsenic weapons stored in northeastern China including chlorodiphenylarsine.<ref>{{cite web |url= http://www.nti.org/db/china/acwpos.htm |title= Abandoned Chemical Weapons (ACW) in China |date= 02/06/2004 }}</ref>

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.<ref name=":0" />

==Toxicity==
⚫ Diphenylchlorarsine is known to cause ], ], ], ], and ]. ] and ] are negotiating remediation of stocks of a variety of organoarsenic weapons, including diphenylchlorarsine, dumped in northeastern China after Japan's numerous invasions of China.<ref>{{ cite web | url = http://www.nti.org/db/china/acwpos.htm | title = Abandoned Chemical Weapons (ACW) in China | date = February 6, 2004 | url-status = dead | archiveurl = https://web.archive.org/web/20080704151015/http://www.nti.org/db/china/acwpos.htm | archivedate = July 4, 2008 }} </ref>

==See also==
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== References == == References ==
{{reflist}} {{reflist}}

{{Chemical agents}}


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