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{{chembox {{Chembox
| Verifiedfields = changed
⚫ | verifiedrevid = 443670981
| Watchedfields = changed
⚫ | ImageFileL1 = cacodylic-acid-3D-sticks.png
⚫ | verifiedrevid = 459990955
| ImageSizeL1 = 120px
| ImageFileR1 = cacodylic-acid-tetrahedral.png | ImageFile = Cacodylic acid.svg
| ImageSizeR1 = 175px | ImageSize = 160px
| ImageAlt = Structural formula
⚫ | IUPACName = Dimethylarsinic acid
⚫ | ImageFile1 = cacodylic-acid-3D-balls.png
| ImageSize1 = 160px
| ImageAlt1 = Ball-and-stick model
| ImageCaption1 = ]<ref>{{ Cite journal | url = https://dx.doi.org/10.5517/ccx73mv | title = CSD Entry: CADYLA01 : Dimethylarsinic acid | website = ]: Access Structures | year = 2011 | publisher = ] | doi = 10.5517/ccx73mv | access-date = 2021-12-21 | last1 = Betz | first1 = R. | last2 = McCleland | first2 = C. | last3 = Marchand | first3 = H. }}</ref><ref name="Betz">{{ cite journal | title = The monoclinic polymorph of dimethylarsinic acid | first1 = R. | last1 = Betz | first2 = C. | last2 = McCleland | first3 = H. | last3 = Marchand | journal = ] | year = 2011 | volume = 67 | issue = 8 | pages = m1013 | doi = 10.1107/S1600536811025505 | pmid = 22090811 | pmc = 3212109 }}</ref>
⚫ | PIN = Dimethylarsinic acid
| OtherNames = Dimethylarsenic acid, Cacodylic acid, Hydroxydimethylarsine oxide, Arsecodile, Ansar, Silvisar, Phytar 560, DMAA, UN 1572 | OtherNames = Dimethylarsenic acid, Cacodylic acid, Hydroxydimethylarsine oxide, Arsecodile, Ansar, Silvisar, Phytar 560, DMAA, UN 1572
| Section1 = {{Chembox Identifiers |Section1={{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 2418 | ChemSpiderID = 2418
| UNII_Ref = {{fdacite|correct|FDA}} | UNII_Ref = {{fdacite|correct|FDA}}
Line 21: Line 26:
| CASNo_Ref = {{cascite|correct|CAS}} | CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 75-60-5 | CASNo = 75-60-5
| PubChem = 2513 | PubChem = 2513
| EINECS = 200-883-4 | EINECS = 200-883-4
| ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI_Ref = {{ebicite|changed|EBI}}
| ChEBI = 48765 | ChEBI = 29839
| RTECS = CH7525000 | ChEMBL = 1231644
| RTECS = CH7525000
| DrugBank_Ref = {{drugbankcite|correct|drugbank}} | DrugBank_Ref = {{drugbankcite|correct|drugbank}}
| DrugBank = DB02994 | DrugBank = DB02994
| UNNumber = 1572
| Gmelin = 130562
| Beilstein = 1736965
| SMILES = O=(O)(C)C | SMILES = O=(O)(C)C
| InChI = 1/C2H7AsO2/c1-3(2,4)5/h1-2H3,(H,4,5) | InChI = 1/C2H7AsO2/c1-3(2,4)5/h1-2H3,(H,4,5)
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| Formula = C<sub>2</sub>H<sub>7</sub>AsO<sub>2</sub> | Formula = C<sub>2</sub>H<sub>7</sub>AsO<sub>2</sub>
| MolarMass = 137.9977 g/mol | MolarMass = 137.9977 g/mol
| Appearance = White crystals or powder | Appearance = White crystals or powder
| Density = > 1.1 g/cm<sup>3</sup> | Odor = odorless
| Density = > 1.1 g/cm<sup>3</sup>
| MeltingPt = 192 - 198 °C | MeltingPtC = 192 to 198
| MeltingPt_notes =
| BoilingPt = > 200 °C | BoilingPt= >
⚫ | Solubility = 667 g/l
| pKa = 6.3 | BoilingPtC = 200
⚫ | Solubility = 66.7 g/100 ml
| SolubleOther = soluble in ], ] <br /> insoluble in ]
| pKa = 6
| MagSus = -79.9·10<sup>−6</sup> cm<sup>3</sup>/mol
}} }}
| Section3 = {{Chembox Hazards |Section3={{Chembox Structure
| CrystalStruct = triclinic,<ref>{{ cite journal | first1 = J. | last1 = Trotter | first2 = T. | last2 = Zobel | journal = ] | year = 1965 | pages=4466–4471 | title = 826. Stereochemistry of arsenic. Part XVI. Cacodylic acid | doi = 10.1039/JR9650004466 }}</ref> monoclinic<ref name="Betz" />
| EUClass = {{Hazchem T+}}
}}
⚫ | ExternalMSDS =
|Section7={{Chembox Hazards
⚫ | FlashPt =
| GHSPictograms = {{GHS06}}{{GHS09}}
| Autoignition =
| GHSSignalWord = Danger
| RPhrases = {{R26/27/28}}, {{R40}}
| HPhrases = {{H-phrases|301|331|410}}
| PPhrases = {{P-phrases|261|264|270|271|273|301+310|304+340|311|321|330|391|403+233|405|501}}
| NFPA-H = 4
| NFPA-F = 0
| NFPA-R = 0
⚫ | ExternalSDS =
⚫ | FlashPt =
| AutoignitionPt =
| LD50 = 23-100 mg/kg (rat and mouse, oral)
}} }}
}} }}


'''Cacodylic acid''' is the ] with the ] (CH<sub>3</sub>)<sub>2</sub>AsO<sub>2</sub>H. Derivatives of cacodylic acid, '''cacodylates''', were frequently used as ]s. For example, "]," one of the chemicals used during the ], is a mixture of cacodylic acid and sodium cacodylate. Sodium cacodylate is frequently used as a ] in the preparation and fixation of biological samples for ]. '''Cacodylic acid''' is an ] with the ] (CH<sub>3</sub>)<sub>2</sub>]O<sub>2</sub>H. With the formula R<sub>2</sub>As(O)OH, it is the simplest of the ]. It is a colorless solid that is soluble in water.

Neutralization of cacodylic acid with base gives '''cacodylate''' salts, e.g. '''sodium cacodylate'''. They are potent ]s. Cacodylic acid/sodium cacodylate is a ] in the preparation and fixation of biological samples for ] and in ].


== History == == History ==
⚫ In the 18th century it was found that combining ] ({{chem2|As2O3}}) and four equivalents of ] ({{chem2|CH3CO2K}}) gives a product called "]" which contains ], {{chem2|((CH3)2As)2O}} and ], {{chem2|((CH3)2As)2}}.
⚫ Significant early research into ]s was done by ] at the University of Marburg. Bunsen said of the compounds, "the smell of this body produces instantaneous tingling of the hands and feet, and even giddiness and insensibility...It is remarkable that when one is exposed to the smell of these compounds the tongue becomes covered with a black coating, even when no further evil effects are noticeable". His work in this field led to an increased understanding of the ].


Early research into "]s" was reported by ] at the ]. Bunsen said of the compounds,
⚫ Cacodyloxide, ((CH<sub>3</sub>)<sub>2</sub>As)<sub>2</sub>O, is often considered the first ] to be prepared synthetically.


⚫ <blockquote>"The smell of this body produces instantaneous tingling of the hands and feet, and even giddiness and insensibility... It is remarkable that when one is exposed to the smell of these compounds the tongue becomes covered with a black coating, even when no further evil effects are noticeable".</blockquote>
== Synthesis and reactions==
⚫ In the 18th century it was known that combining As<sub>2</sub>O<sub>3</sub> and four equivalents of ] (CH<sub>3</sub>CO<sub>2</sub>K) gives a product called "]" which contains ], ((CH<sub>3</sub>)<sub>2</sub>As)<sub>2</sub>O and ], ((CH<sub>3</sub>)<sub>2</sub>As).


His work in this field led to an increased understanding of the ].
⚫ Cacodylic acid can be reduced to dimethylarsine (III) derivatives, which are versatile intermediates for the synthesis of other organoarsenic compounds:<ref>Feltham, R. D.; Kasenally, A. and Nyholm, R. S., "A New Synthesis of Di- and Tri-Tertiary Arsines", Journal of Organometallic Chemistry, 1967, volume 7, 285-288.</ref><ref>Burrows, G. J. and Turner, E. E., "A New Type of Compound containing Arsenic", Journal of the Chemical Society Transactions, 1920, 1374-1383</ref>
:(CH<sub>3</sub>)<sub>2</sub>AsO<sub>2</sub>H + 2 Zn + 4 HCl → (CH<sub>3</sub>)<sub>2</sub>AsH + 2 ZnCl<sub>2</sub> + 2 H<sub>2</sub>O
:(CH<sub>3</sub>)<sub>2</sub>AsO<sub>2</sub>H + SO<sub>2</sub> + HI → (CH<sub>3</sub>)<sub>2</sub>AsI + SO<sub>3</sub> + H<sub>2</sub>O


⚫ Cacodyl oxide, {{chem2|((CH3)2As)2O}}, is often considered the first ] to be prepared synthetically.
⚫ == Health effects ==


Cacodylic acid and its salts were incorporated into ]s by a large variety of manufacturers under numerous brand names. APC Holdings Corp. sold cacodylic acid and its salts under the ] brand name.<ref name="Greene2005">{{cite book|author=Stanley A. Greene|title=Sittig's Handbook of Pesticides and Agricultural Chemicals|url=https://books.google.com/books?id=hAoKEHpyu6wC&pg=PA132|year=2005|publisher=William Andrew|isbn=978-0-8155-1903-4|page=132}}</ref> The variety Phytar 560G, a mixture of cacodylic acid and sodium cacodylate, was used during the ] as a ] under the name "]".<ref name="HerbicidesMedicine1994">{{cite book |author1=Committee to Review the Health Effects in Vietnam Veterans of Exposure to Herbicides |url=https://books.google.com/books?id=RjCHcoUE3B8C&pg=PA89 |title=Veterans and Agent Orange: Health Effects of Herbicides Used in Vietnam |author2=Institute of Medicine |publisher=National Academies Press |year=1994 |isbn=978-0-309-55619-4 |pages=89–90}}</ref>
Cacodylic acid is highly toxic by ingestion, inhalation, or skin contact. Once thought to be a byproduct of inorganic arsenic detoxification, it is now believed to have serious health consequences of its own. It has been shown to be ] in rodents, most often causing cleft palate but also fetal fatality at high doses. It has been shown to be genotoxic in human cells, causing ] and also decreased DNA production and shorter DNA strands. While not itself a strong carcinogen, cacodylic acid does promote tumors in the presence of carcinogens in organs such as the kidneys and liver.

==Reactions==
Cacodylic acid is a ] with a pK<sub>a</sub> of around 6.25.<ref>{{cite journal |vauthors=((Shin, T.-W.)), ((Kim, K.)), ((Lee, I.-J.)) |date=April 1997 |title=Spectrophotometric determination of the acid dissociation constants for cacodylic acid and p-Nitrophenol at elevated temperatures |journal=Journal of Solution Chemistry |volume=26 |issue=4 |pages=379–390 |doi=10.1007/BF02767677 |issn=0095-9782}}</ref>

⚫ Cacodylic acid can be reduced to dimethylarsine , which is a versatile intermediate for the synthesis of other organoarsenic compounds:<ref>{{cite journal|author1=Feltham, R. D. |author2=Kasenally, A. |author3=Nyholm, R. S. |title=A New Synthesis of Di- and Tri-Tertiary Arsines|journal=Journal of Organometallic Chemistry|year=1967|volume=7|issue=2|pages=285–288|doi=10.1016/S0022-328X(00)91079-9}}</ref><ref>Burrows, G. J. and Turner, E. E., "A New Type of Compound containing Arsenic", Journal of the Chemical Society Transactions, 1920, 1374-1383</ref>

:{{chem2|(CH3)2AsO2H + 2 Zn + 4 HCl → (CH3)2AsH + 2 ZnCl2 + 2 H2O}}

:{{chem2|(CH3)2AsO2H + SO2 + HI → (CH3)2AsI + SO3 + H2O}}

⚫ == Health effects ==
Cacodylic acid is highly toxic by ], ], or skin contact. The U.S. EPA states that all forms of arsenic are a serious risk to human health and the United States ] ranked arsenic as number 1 in its 2001 Priority List of Hazardous Substances at Superfund sites.<ref name="EPA1">{{cite web |url=https://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.highlight/abstract/6015 |title=Biogeochemistry of Arsenic in Contaminated Soils of Superfund Sites |last1=Dibyendu |first1=Sarkar |last2=Datta |first2=Rupali |date=2007 |website=EPA |publisher=United States Environmental Protection Agency |access-date=25 February 2018 |archive-url=https://web.archive.org/web/20200317143949/https://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.highlight/abstract/6015 |archive-date=17 March 2020 |url-status=dead}}</ref> Arsenic is classified as a Group-A ].<ref name="EPA1"/>


== See also == == See also ==
Line 72: Line 106:
* ] * ]
* ] * ]
* ]


== References == == References ==
{{reflist}}
<references/>

⚫ * {{cite journal | author = Kenyon, E. M.; Hughes, M. F. | title = A Concise Review of the Toxicity and Carcinogenicity of Dimethylarsenic Acid | journal = ] | volume = 160 | year = 2001 | issue = 1-3 | pages = 227–236 | doi = 10.1016/S0300-483X(00)00458-3}}
==Further reading==
⚫ * {{cite journal |author1=Kenyon, E. M. |author2=Hughes, M. F. | title = A Concise Review of the Toxicity and Carcinogenicity of Dimethylarsenic Acid | journal = ] | volume = 160 | year = 2001 | issue = 1–3 | pages = 227–236 | doi = 10.1016/S0300-483X(00)00458-3|pmid=11246143 |url=https://zenodo.org/record/1259985 }}
* Elschenbroich, C; Salzer, A. (1992) Organometallics, 2nd Edition * Elschenbroich, C; Salzer, A. (1992) Organometallics, 2nd Edition
⚫ *


== External links == == External links ==
* *
⚫ *


{{DEFAULTSORT:Cacodylic Acid}} {{DEFAULTSORT:Cacodylic Acid}}

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Latest revision as of 20:23, 25 November 2024

Cacodylic acid
Structural formula
Ball-and-stick model
Ball-and-stick model
Names
Preferred IUPAC name Dimethylarsinic acid
Other names Dimethylarsenic acid, Cacodylic acid, Hydroxydimethylarsine oxide, Arsecodile, Ansar, Silvisar, Phytar 560, DMAA, UN 1572
Identifiers
CAS Number
3D model (JSmol)
Beilstein Reference 1736965
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.000.804 Edit this at Wikidata
EC Number
  • 200-883-4
Gmelin Reference 130562
KEGG
PubChem CID
RTECS number
  • CH7525000
UNII
UN number 1572
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C2H7AsO2/c1-3(2,4)5/h1-2H3,(H,4,5)Key: OGGXGZAMXPVRFZ-UHFFFAOYSA-N
  • InChI=1/C2H7AsO2/c1-3(2,4)5/h1-2H3,(H,4,5)Key: OGGXGZAMXPVRFZ-UHFFFAOYAP
SMILES
  • O=(O)(C)C
Properties
Chemical formula C2H7AsO2
Molar mass 137.9977 g/mol
Appearance White crystals or powder
Odor odorless
Density > 1.1 g/cm
Melting point 192 to 198 °C (378 to 388 °F; 465 to 471 K)
Boiling point > 200 °C (392 °F; 473 K)
Solubility in water 66.7 g/100 ml
Solubility soluble in ethanol, acetic acid
insoluble in diethyl ether
Acidity (pKa) 6
Magnetic susceptibility (χ) -79.9·10 cm/mol
Structure
Crystal structure triclinic, monoclinic
Hazards
GHS labelling:
Pictograms GHS06: ToxicGHS09: Environmental hazard
Signal word Danger
Hazard statements H301, H331, H410
Precautionary statements P261, P264, P270, P271, P273, P301+P310, P304+P340, P311, P321, P330, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4 0 0
Lethal dose or concentration (LD, LC):
LD50 (median dose) 23-100 mg/kg (rat and mouse, oral)
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

Cacodylic acid is an organoarsenic compound with the formula (CH3)2AsO2H. With the formula R2As(O)OH, it is the simplest of the arsinic acids. It is a colorless solid that is soluble in water.

Neutralization of cacodylic acid with base gives cacodylate salts, e.g. sodium cacodylate. They are potent herbicides. Cacodylic acid/sodium cacodylate is a buffering agent in the preparation and fixation of biological samples for electron microscopy and in protein crystallography.

History

In the 18th century it was found that combining arsenic trioxide (As2O3) and four equivalents of potassium acetate (CH3CO2K) gives a product called "Cadet's fuming liquid" which contains cacodyl oxide, ((CH3)2As)2O and cacodyl, ((CH3)2As)2.

Early research into "cacodyls" was reported by Robert Bunsen at the University of Marburg. Bunsen said of the compounds,

"The smell of this body produces instantaneous tingling of the hands and feet, and even giddiness and insensibility... It is remarkable that when one is exposed to the smell of these compounds the tongue becomes covered with a black coating, even when no further evil effects are noticeable".

His work in this field led to an increased understanding of the methyl group.

Cacodyl oxide, ((CH3)2As)2O, is often considered the first organometallic compound to be prepared synthetically.

Cacodylic acid and its salts were incorporated into herbicides by a large variety of manufacturers under numerous brand names. APC Holdings Corp. sold cacodylic acid and its salts under the Phytar brand name. The variety Phytar 560G, a mixture of cacodylic acid and sodium cacodylate, was used during the Vietnam War as a defoliant under the name "Agent Blue".

Reactions

Cacodylic acid is a weak acid with a pKa of around 6.25.

Cacodylic acid can be reduced to dimethylarsine , which is a versatile intermediate for the synthesis of other organoarsenic compounds:

(CH3)2AsO2H + 2 Zn + 4 HCl → (CH3)2AsH + 2 ZnCl2 + 2 H2O
(CH3)2AsO2H + SO2 + HI → (CH3)2AsI + SO3 + H2O

Health effects

Cacodylic acid is highly toxic by ingestion, inhalation, or skin contact. The U.S. EPA states that all forms of arsenic are a serious risk to human health and the United States Agency for Toxic Substances and Disease Registry ranked arsenic as number 1 in its 2001 Priority List of Hazardous Substances at Superfund sites. Arsenic is classified as a Group-A carcinogen.

See also

References

  1. Betz, R.; McCleland, C.; Marchand, H. (2011). "CSD Entry: CADYLA01 : Dimethylarsinic acid". Cambridge Structural Database: Access Structures. Cambridge Crystallographic Data Centre. doi:10.5517/ccx73mv. Retrieved 2021-12-21.
  2. ^ Betz, R.; McCleland, C.; Marchand, H. (2011). "The monoclinic polymorph of dimethylarsinic acid". Acta Crystallogr. E. 67 (8): m1013. doi:10.1107/S1600536811025505. PMC 3212109. PMID 22090811.
  3. Trotter, J.; Zobel, T. (1965). "826. Stereochemistry of arsenic. Part XVI. Cacodylic acid". J. Chem. Soc.: 4466–4471. doi:10.1039/JR9650004466.
  4. Stanley A. Greene (2005). Sittig's Handbook of Pesticides and Agricultural Chemicals. William Andrew. p. 132. ISBN 978-0-8155-1903-4.
  5. Committee to Review the Health Effects in Vietnam Veterans of Exposure to Herbicides; Institute of Medicine (1994). Veterans and Agent Orange: Health Effects of Herbicides Used in Vietnam. National Academies Press. pp. 89–90. ISBN 978-0-309-55619-4.
  6. Shin, T.-W., Kim, K., Lee, I.-J. (April 1997). "Spectrophotometric determination of the acid dissociation constants for cacodylic acid and p-Nitrophenol at elevated temperatures". Journal of Solution Chemistry. 26 (4): 379–390. doi:10.1007/BF02767677. ISSN 0095-9782.
  7. Feltham, R. D.; Kasenally, A.; Nyholm, R. S. (1967). "A New Synthesis of Di- and Tri-Tertiary Arsines". Journal of Organometallic Chemistry. 7 (2): 285–288. doi:10.1016/S0022-328X(00)91079-9.
  8. Burrows, G. J. and Turner, E. E., "A New Type of Compound containing Arsenic", Journal of the Chemical Society Transactions, 1920, 1374-1383
  9. ^ Dibyendu, Sarkar; Datta, Rupali (2007). "Biogeochemistry of Arsenic in Contaminated Soils of Superfund Sites". EPA. United States Environmental Protection Agency. Archived from the original on 17 March 2020. Retrieved 25 February 2018.

Further reading

External links

Categories: