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{{chembox {{chembox
| Watchedfields = changed
| verifiedrevid = 406362547
| Name = Phenyldichloroarsine | Name = Phenyldichloroarsine
| ImageFile = Phenyldichloroarsine.svg | ImageFileL1 = Phenyldichloroarsine.svg
| ImageSize = 110px | ImageSizeL1 = 115px
| ImageName = Skeletal formula | ImageAltL1 = Skeletal formula of phenyldichloroarsine
| ImageFile1 = Phenyldichloroarsine-3D-balls.png | ImageFileR1 = Phenyldichloroarsine molecule ball.png
| ImageSize1 = 190px | ImageSizeR1 = 130px
| ImageName1 = Ball-and-stick model | ImageAltR1 = Ball-and-stick model of the phenyldichloroarsine molecule
| PIN = Phenylarsonous dichloride
| IUPACName = dichloro-phenylarsane
⚫ | OtherNames = Dichlorophenylarsane<br>Dichloro(phenyl)arsine
| SystematicName =
⚫ |Section1={{Chembox Identifiers
⚫ | OtherNames = Dichloro(phenyl)arsine
⚫ | Section1 = {{Chembox Identifiers
| Abbreviations = PD (NATO) | Abbreviations = PD (NATO)
| CASNo_Ref = {{cascite|correct|??}}
| CASNo = 696-28-6 | CASNo = 696-28-6
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = KK93BBF49U
| EINECS = 211-791-9 | EINECS = 211-791-9
| EINECSCASNO =
| PubChem = 12762 | PubChem = 12762
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 12238 | ChemSpiderID = 12238
| SMILES = Cl(Cl)c1ccccc1 | SMILES = Cl(Cl)c1ccccc1
⚫ | StdInChI=1S/C6H5AsCl2/c8-7(9)6-4-2-1-3-5-6/h1-5H
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
⚫ | StdInChIKey = UDHDFEGCOJAVRE-UHFFFAOYSA-N
⚫ | StdInChI =1S/C6H5AsCl2/c8-7(9)6-4-2-1-3-5-6/h1-5H
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
⚫ | StdInChIKey = UDHDFEGCOJAVRE-UHFFFAOYSA-N
| RTECS = CH5425000 | RTECS = CH5425000
| MeSHName = | MeSHName =
| ChEBI = | ChEBI =
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG = | KEGG =
⚫ }}
| ATCCode_prefix =
⚫ |Section2={{Chembox Properties
| ATCCode_suffix =
⚫ | Formula = C<sub>6</sub>H<sub>5</sub>AsCl<sub>2</sub>
| ATC_Supplemental =}}
⚫ | MolarMass = 222.9315 <nowiki>g/mol</nowiki>
⚫ | Section2 = {{Chembox Properties
⚫ | Appearance = Colorless liquid
⚫ | Formula = C<sub>6</sub>H<sub>5</sub>AsCl<sub>2</sub>
⚫ | Density = 1.65&nbsp;g/cm<sup>3</sup> (at 20&nbsp;°C)
⚫ | MolarMass = 222.9315 <nowiki></nowiki>
| MeltingPtC = -20
⚫ | Appearance = Colorless gas or liquid
| MeltingPt_notes =
⚫ | Density = 1.65 g/cc (at 20 °C)
| MeltingPt = -20 °C | BoilingPtC = 252 to 255
| Melting_notes = | BoilingPt_notes =
| BoilingPt = 252-255 °C | Solubility = Reacts
| Boiling_notes =
| Solubility = insoluable
| SolubleOther = acetone, ether, benzene | SolubleOther = acetone, ether, benzene
| Solvent = | Solvent =
| LogP = 3.060 | LogP = 3.060
| VaporPressure = .033 | VaporPressure = 0.033
| HenryConstant = 3.00E-05 atm-m3/mole | HenryConstant = 3.00E-05&nbsp;atm·m<sup>3</sup>/mole
| AtmosphericOHRateConstant = 1.95E-12 cm3/molecule-sec | AtmosphericOHRateConstant = 1.95E-12&nbsp;cm<sup>3</sup>/molecule·s
| pKa = | pKa =
| pKb = }} | pKb = }}
| Section3 = {{Chembox Structure |Section3={{Chembox Structure
| CrystalStruct = | CrystalStruct =
| Coordination = | Coordination =
| MolShape = }} | MolShape = }}
| Section4 = {{Chembox Thermochemistry |Section4={{Chembox Thermochemistry
| DeltaHf = | DeltaHf =
| DeltaHc = | DeltaHc =
| Entropy = | Entropy =
| HeatCapacity = }} | HeatCapacity = }}
| Section5 = {{Chembox Pharmacology |Section5={{Chembox Pharmacology
| AdminRoutes = | AdminRoutes =
| Bioavail = | Bioavail =
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| Legal_AU = | Legal_AU =
| Legal_CA = | Legal_CA =
| PregCat = | Pregnancy_category =
| PregCat_AU = | Pregnancy_AU =
| PregCat_US = }} | Pregnancy_US = }}
| Section6 = {{Chembox Explosive |Section6={{Chembox Explosive
| ShockSens = | ShockSens =
| FrictionSens = | FrictionSens =
| ExplosiveV = | DetonationV =
| REFactor = }} | REFactor = }}
| Section7 = {{Chembox Hazards |Section7={{Chembox Hazards
| ExternalMSDS = | ExternalSDS =
| EUClass =
| EUIndex =
| MainHazards = Flammability, incapacitation, blistering | MainHazards = Flammability, incapacitation, blistering
| NFPA-H = 4 | NFPA-H = 4
| NFPA-F = 1 | NFPA-F = 1
| NFPA-R = 0 | NFPA-R = 0
| NFPA-O = | NFPA-S =
| RPhrases = | HPhrases =
| SPhrases = | PPhrases =
| RSPhrases = | GHS_ref =
| FlashPt = 16 °C | FlashPtC = 16
| Autoignition = | AutoignitionPtC =
| ExploLimits = | ExploLimits =
| LD50 =2,500 mg - min/m<sup>3</sup> | LD50 =2,500&nbsp;mg·min/m<sup>3</sup>
| PEL = 0.5 mg/m<sup>2</sup>}} | PEL = 0.5&nbsp;mg/m<sup>2</sup>}}
| Section8 = {{Chembox Related |Section8={{Chembox Related
| OtherAnions = | OtherAnions =
| OtherCations = | OtherCations =
| OtherFunctn = | OtherFunction =
| Function = | OtherFunction_label =
| OtherCpds = | OtherCompounds =
}}
}} }}
⚫ '''Phenyldichloroarsine''', also known by its wartime name '''phenyl Dick'''<ref>{{cite journal | vauthors = Wood JR | title = Chemical Warfare-A Chemical and Toxicological Review | journal = American Journal of Public Health and the Nation's Health | volume = 34 | issue = 5 | pages = 455–60 | date = May 1944 | pmid = 18015982 | pmc = 1625133 | doi = 10.2105/AJPH.34.5.455 }}</ref> and its ] abbreviation '''PD''', is an ] ] vesicant and vomiting agent developed by Germany and France for use as a ] agent during ]. The agent is known by multiple synonyms and is technically classified as a vesicant, or ].
⚫ }}
⚫ '''Phenyldichloroarsine''', ] abbreviation PD, is an ] ] vesicant and vomiting agent developed by Germany for use as a ] agent during ]. The agent is known by multiple synonyms and is technically classified as a vesicant, or ].


==History== ==History==
PD was prepared during 1917–18 in Germany and France, during World War II it was prepared in Germany.
German chemists weaponized the first organic arsenical, ] (MD), during ] between 1917 and 1918.<ref name=emed>Fitzgerald, Geoffrey M. and Vollmer, Timothy. "", ''emedicine'' via '']'', June 19, 2006, accessed December 22, 2008.</ref> Phenyldichloroarsine and another ], ] were soon added to the German arsenal.<ref name=emed/><ref name=uiuc>Miller, Tyson A. "", '']'', Group Presentation, August 27, 2002, accessed December 22, 2008.</ref>


==Chemical characteristics== ==Chemical characteristics==
===General=== ===General===
Phenyldichloroarsine is an odorless, colorless substance that can form ] upon contact with water.<ref name=leikin/> The reaction with water is very slow, the substance sinks, and the reaction is considered non-hazardous.<ref name=hazmat>Pohanish, Richard P. ''HazMat Data'', (), Wiley-IEEE, 2005, pp. 895-96, (ISBN 0471726109).</ref> Another product of ] is phenylarsenious acid, which is a severe ] to the ] and ].<ref name=leikin/> Most often found in a liquid state, the chemical is an organic dithiol-arsenical.<ref name=leikin>Leikin, Jarrold B. and McFee, Robin B. ''Handbook of Nuclear, Biological, and Chemical Agent Exposures'', (), Informa Health Care, 2007, pp. 356-57, (ISBN 142004477X).</ref> In an impure state, phenyldichloroarsine may have a slight brown color, in its purest form though there is no color and the substance has an oily texture.<ref name=ledgard/> An impure solution of PD also emits a characteristically unpleasant ] or ]-like odor, which is detectable at .1 ppm.<ref name=ellison>Ellison, Hank D. ''Handbook of Chemical and Biological Warfare Agents'', (), CRC Press, 2007, p. 156, (ISBN 0849314348).</ref> Phenyldichloroarsine is an odorless, colorless substance that can form ] upon contact with water.<ref name=leikin/> The reaction with water is very slow, the substance sinks, and the reaction is considered non-hazardous.<ref name=hazmat>{{cite book | vauthors = Pohanish RP | title = HazMat Data | url = https://books.google.com/books?id=3Tbl2W8j-3oC&q=Phenyldichloroarsine&pg=PA895 | publisher = Wiley-IEEE | date = 2005 | pages = 895–96 | isbn = 0471726109 }})</ref> Another product of ] is phenylarsenious acid, which is a severe ] to the ] and ].<ref name=leikin>{{cite book | vauthors = Leikin JB, McFee RB | title = Handbook of Nuclear, Biological, and Chemical Agent Exposures | url = https://books.google.com/books?id=iB5pdQCKOZIC&q=Phenyldichloroarsine+chemical+weapon&pg=PA356 | publisher = Informa Health Care | date = 2007 | pages = 356–57 | isbn = 978-1420044775 }})</ref> In an impure state, phenyldichloroarsine may have a slight brown color, in its purest form though there is no color and the substance has an oily texture.<ref name=ledgard/> An impure solution of PD also emits a characteristically unpleasant ] or ]-like odor, which is detectable at 0.1&nbsp;ppm.<ref name=ellison>{{cite book | vauthors = Ellison HD | title = Handbook of Chemical and Biological Warfare Agents | url = https://books.google.com/books?id=E58GAKMgcR4C&q=Phenyldichloroarsine&pg=PA156 | publisher = CRC Press | date = 2007 | pages = 156 | isbn = 978-0849314346}}</ref>


Phenyldichloroarsine is one of four organic arsenicals, the other three are ] (L), ] (MD),and ] (ED).<ref name=emed/> PD is considered an ] of lewisite.<ref name=armyrept/> At its ], -20 °C, PD becomes a ] solid mass.<ref name=hills>Hills, Terry. ''The Illustrated Dictionary of Organic Chemistry'', (), Lotus Press, Tokyo: 2007, p. 149, (ISBN 8189093517).</ref> The compound has a ] between the ] and the arsenic and two ]s between the arsenic and the ].<ref name=manahan>Manahan, Stanley E. ''Industrial Ecology: Environmental Chemistry and Hazardous Waste'', (), CRC Press, 1999, p. 189, (ISBN 1566703816).</ref> Phenyldichloroarsine is one of four organic arsenicals, the other three are ] (L), ] (MD), and ] (ED).<ref name=emed>{{cite web | vauthors = Fitzgerald GM, Vollmer T | url = http://emedicine.medscape.com/article/832158-overview | title = CBRNE - Vesicants, Organic Arsenicals: L, ED, MD, PD, HL | work = emedicine | publisher = ] | date = 19 June 2006 | access-date = December 22, 2008 }}</ref> PD is considered an ] of lewisite.<ref name=armyrept/> At its ], -20&nbsp;°C, PD becomes a ] solid mass.<ref name=hills>{{cite book | vauthors = Hills T | title = The Illustrated Dictionary of Organic Chemistry | url = https://books.google.com/books?id=j4VHUen3bTYC&q=Phenyldichloroarsine&pg=PA149 | publisher = Lotus Press | location = Tokyo | date = 2007 | pages = 149 | isbn = 978-8189093518 }}</ref> The compound has a ] between the ] and the arsenic and two ]s between the arsenic and the ].<ref name=manahan>{{cite book | vauthors = Manahan SE | title = Industrial Ecology: Environmental Chemistry and Hazardous Waste | url = https://books.google.com/books?id=_-GDMkpoA4YC&q=Phenyldichloroarsine&pg=PA189 | publisher = CRC Press | date = 1999 | pages = 189 | isbn = 1566703816 }}</ref>


===Synthesis=== ===Synthesis===
Phenyldichloroarsine is produced by reacting ] with ]. Anhydrous ] acts as a ] in this reaction.<ref name=ledgard>Ledgard, Jared. ''A Laboratory History of Chemical Warfare Agents'', (), Lulu.com, 2006, pp. 127-29, (ISBN 1411694325).</ref> Phenyldichloroarsine is produced by reacting ] with ]. Anhydrous ] acts as a ] in this reaction.<ref name=ledgard>{{cite book | vauthors = Ledgard J | title = A Laboratory History of Chemical Warfare Agents | url = https://books.google.com/books?id=atU4GuKE8x0C&q=Phenyldichloroarsine+chemical+weapon&pg=PA127 | publisher = Lulu.com | date = 2006 | pages = 127–29 | isbn = 1411694325 }}</ref>


==Uses== ==Uses==
Phenyldichloroarsine is useful as a ] agent and is classified as a ] or a vomiting/].<ref name=cashman/> It was used as a weapon during World War I, where it showed itself as less effective than other vomiting agents.<ref name=cashman>Cashman, John R. ''Emergency Response Handbook for Chemical and Biological Agents and Weapons'', (), CRC Press, 2008, pp. 215-19, (ISBN 1420052659).</ref> The Japanese may also have used phenyldichloroarsine along with ]s and lewisite in China during ].<ref name=verwey>Verwey, Wil D. ''Riot Control Agents and Herbicides in War: Their Humanitarian, Toxicological, Ecological, Military, Polemological, and Legal Aspects'', (), BRILL, 1977, p. 273, (ISBN 9028603360).</ref> Phenyldichloroarsine is an arsenical vesicant which is most often mixed with other mustard agents for use in chemical warfare.<ref name=emed2/> This does not increase the severity of its effects but does tend to confuse exposure diagnosis.<ref name=emed2>Dire, Daniel J. "", ''emedicine'' via '']'', December 21, 2007, accessed December 22, 2008.</ref> Phenyldichloroarsine is an obsolete ] agent and is classified as a ] or a vomiting/].<ref name=cashman/> It was used as a weapon during World War I, where it showed itself as less effective than other vomiting agents.<ref name=cashman>{{cite book | vauthors = Cashman JR | title = Emergency Response Handbook for Chemical and Biological Agents and Weapons | url = https://books.google.com/books?id=S4PW-5qHUU8C&q=Phenyldichloroarsine+chemical+weapon&pg=PA215 | publisher = CRC Press | date = 2008 | pages = 215–19 | isbn = 978-1420052657 }}</ref> Phenyldichloroarsine is an arsenical vesicant which can be mixed with mustard agents for use in chemical warfare.<ref name=emed2>{{cite web | vauthors = Dire DJ | url = http://emedicine.medscape.com/article/832060-overview | title = CBRNE - Vesicants, Mustard: Hd, Hn1-3, H] | work = emedicine | publisher = ] | date = 21 December 2007 | access-date = 22 December 2008 }}</ref>

PD was developed for use in wet environments, because of its tendency to persist in cool and shaded areas.<ref name=byrnes/> Phenyldichloroarsine can have a persistence lasting anywhere from 2 to 7 days under usual environmental conditions.<ref name=ledgard/> In open areas, it is more useful as a vomiting agent but in closed-in areas, such as basements, trenches and caves, it is highly effective because of its "extreme" vapor density.<ref name=byrnes/> Phenyldichloroarsine has also been used by banks and other high-security facilities to defend against security breaches.<ref name=ledgard/> PD was developed for use in wet environments, because of its tendency to persist in cool and shaded areas.<ref name=byrnes/> Phenyldichloroarsine can have a persistence lasting anywhere from 2 to 7 days under usual environmental conditions.<ref name=ledgard/> In open areas, it is more useful as a vomiting agent but in closed-in areas, such as basements, trenches and caves, it is highly effective because of its "extreme" vapor density.<ref name=byrnes/> Phenyldichloroarsine has also been used by banks and other high-security facilities to defend against security breaches.<ref name=ledgard/>


==Biological effects== ==Biological effects==
PD damages the eyes, lungs, throat and nasal membranes.<ref name=byrnes/> PD immediately affects the eyes and blindness can result, though it requires high doses.<ref name=ledgard/> It also induces nausea and vomiting, an inhalation of as little as 5-50 milligrams can induce severe vomiting.<ref name=ledgard/> Long-term exposure to PD can cause systemic damage by replacing calcium with ], extensive ] damage can also result.<ref name=byrnes/> Due to PD being easily recognized in the field and a relatively fast rate for decontamination procedures to become effective, the chemical is not as useful as other blister agents.<ref name=ledgard/> The blistering resultant from PD exposure may also be delayed, for as little as 30 minutes,<ref name=armyrept>O'Connor,, Richard J., McGown, Evelyn L., Dill, Kilian. "", Department of Chemistry - '']'' for ], Letterman Army Institute of Research, August 1986, accessed December 22, 2008.</ref> or as long as 32 hours depending upon the concentration of the dose.<ref name=ledgard/> PD damages the eyes, lungs, throat and nasal membranes.<ref name=byrnes/> PD immediately affects the eyes and blindness can result, though it requires high doses.<ref name=ledgard/> It also induces nausea and vomiting, an inhalation of as little as 5-50 milligrams can induce severe vomiting.<ref name=ledgard/> Long-term exposure to PD can cause systemic damage by replacing calcium with ], extensive ] damage can also result.<ref name=byrnes/> Due to PD being easily recognized in the field and a relatively fast rate for decontamination procedures to become effective, the chemical is not as useful as other blister agents.<ref name=ledgard/> The blistering resultant from PD exposure may also be delayed, for as little as 30 minutes,<ref name=armyrept>{{cite web | vauthors = O'Connor RJ, McGown EL, Dill K | url = https://apps.dtic.mil/sti/pdfs/ADA175296.pdf | archive-url = https://web.archive.org/web/20110522043858/http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA175296&Location=U2&doc=GetTRDoc.pdf | url-status = live | archive-date = May 22, 2011 | title = Interaction of Phenyldicholoroarsine with Biological Molecules | work = Department of Chemistry - ] for ], Letterman Army Institute of Research | date = August 1986 | access-date = 22 December 2008 }}</ref> or as long as 32 hours depending upon the concentration of the dose.<ref name=ledgard/>


The molecular toxicology of PD is not well understood,<ref name=armyrept/> but a 1986 U.S. Army-sponsored report did shed some light on that area. The Army report showed that PD penetrated the ] membrane and interacted with something inside the cell. The study also found that ] was not responsible for "holding" the PD in its bond with the erythrocytes (red blood cells), instead ] was found to be a more likely interacting with PD inside the cell .<ref name=armyrept/><ref name=byrnes>Byrnes, Mark E. et al. ''Nuclear, Chemical, and Biological Terrorism: Emergency Response and Public Protection'', (), CRC Press, 2003, p. 57, (ISBN 1566706513).</ref> The molecular toxicology of PD is not well understood,<ref name=armyrept/> but a 1986 U.S. Army-sponsored report did shed some light on that area. The Army report showed that PD penetrated the ] membrane and interacted with something inside the cell. The study also found that ] was not responsible for "holding" the PD in its bond with the erythrocytes (red blood cells), instead ] was found to be a more likely interacting with PD inside the cell .<ref name=armyrept/><ref name=byrnes>{{cite book | vauthors = Byrnes ME, King DA, Tierno Jr PM | title = Nuclear, Chemical, and Biological Terrorism: Emergency Response and Public Protection | url = https://books.google.com/books?id=jOcXcdJuovgC&q=Phenyldichloroarsine+chemical+weapon&pg=PA57 | publisher = CRC Press | date = 2003 | pages = 57 | isbn = 1566706513 }}</ref>


==See also== == See also ==
*] *]
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==References== == References ==
{{reflist}} {{reflist}}


{{Chemical warfare}} {{Chemical warfare}}


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