Chemistry:Cacodylic acid
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 | |
| Names | |
|---|---|
| Preferred IUPAC name
Dimethylarsinic acid | |
| Other names
Dimethylarsenic acid, Cacodylic acid, Hydroxydimethylarsine oxide, Arsecodile, Ansar, Silvisar, Phytar 560, DMAA, UN 1572
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| Identifiers | |
3D model (JSmol)
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| 1736965 | |
| ChEBI | |
| ChEMBL | |
| ChemSpider | |
| DrugBank | |
| EC Number |
|
| 130562 | |
| KEGG | |
PubChem CID
|
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| RTECS number |
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| UNII | |
| UN number | 1572 |
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| |
| Properties | |
| C2H7AsO2 | |
| Molar mass | 137.9977 g/mol |
| Appearance | White crystals or powder |
| Odor | odorless |
| Density | > 1.1 g/cm3 |
| Melting point | 192 to 198 °C (378 to 388 °F; 465 to 471 K) |
| Boiling point | > 200 °C (392 °F; 473 K) |
| 66.7 g/100 ml | |
| Solubility | soluble in ethanol, acetic acid insoluble in diethyl ether |
| Acidity (pKa) | 6 |
| -79.9·10−6 cm3/mol | |
| Structure | |
| triclinic,[3] monoclinic[2] | |
| Hazards | |
| Safety data sheet | External MSDS |
| GHS pictograms |  
|
| GHS Signal word | Danger |
| H301, H331, H410 | |
| P261, P264, P270, P271, P273, P301+310, P304+340, P311, P321, P330, P391, P403+233, P405, P501 | |
| NFPA 704 (fire diamond) | |
| Lethal dose or concentration (LD, LC): | |
LD50 (median dose)
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23-100 mg/kg (rat and mouse, oral) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
 verify (what is   ?)
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| Infobox references | |
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 As
2O
3 and four equivalents of potassium acetate (CH
3CO
2K) gives a product called "Cadet's fuming liquid" which contains cacodyl oxide, ((CH
3)
2As)
2O and cacodyl, ((CH
3)
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, ((CH
3)
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.[4] The variety used in Vietnam (as Agent Blue) was Phytar 560G.[5] "Agent Blue", a mixture of cacodylic acid and sodium cacodylate was used during the Vietnam War as a defoliant.
Reactions
Cacodylic acid is a weak acid with a pKa of around 6.25.[6]
Cacodylic acid can be reduced to dimethylarsine , which is a versatile intermediate for the synthesis of other organoarsenic compounds:[7][8]
- (CH
3)
2AsO
2H + 2 Zn + 4 HCl → (CH
3)
2AsH + 2 ZnCl
2 + 2 H
2O
- (CH
3)
2AsO
2H + SO
2 + HI → (CH
3)
2AsI + SO
3 + H
2O
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.[9] Arsenic is classified as a Group-A carcinogen.[9]
See also
References
- ↑ Betz, R.; McCleland, C.; Marchand, H. (2011). CSD Entry: CADYLA01 : Dimethylarsinic acid. Cambridge Crystallographic Data Centre. doi:10.5517/ccx73mv. https://dx.doi.org/10.5517/ccx73mv. Retrieved 2021-12-21.
- ↑ 2.0 2.1 Betz, R.; McCleland, C.; Marchand, H. (2011). "The monoclinic polymorph of dimethylarsinic acid". Acta Crystallogr. E 67 (8): m1013. doi:10.1107/S1600536811025505. PMID 22090811.
- ↑ Trotter, J.; Zobel, T. (1965). "826. Stereochemistry of arsenic. Part XVI. Cacodylic acid". J. Chem. Soc.: 4466–4471. doi:10.1039/JR9650004466.
- ↑ Stanley A. Greene (2005). Sittig's Handbook of Pesticides and Agricultural Chemicals. William Andrew. p. 132. ISBN 978-0-8155-1903-4. https://books.google.com/books?id=hAoKEHpyu6wC&pg=PA132.
- ↑ 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. https://books.google.com/books?id=RjCHcoUE3B8C&pg=PA89.
- ↑ "Spectrophotometric determination of the acid dissociation constants for cacodylic acid and p-Nitrophenol at elevated temperatures". Journal of Solution Chemistry 26 (4): 379–390. April 1997. doi:10.1007/BF02767677. ISSN 0095-9782.
- ↑ 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.
- ↑ Burrows, G. J. and Turner, E. E., "A New Type of Compound containing Arsenic", Journal of the Chemical Society Transactions, 1920, 1374-1383
- ↑ 9.0 9.1 Dibyendu, Sarkar; Datta, Rupali (2007). "Biogeochemistry of Arsenic in Contaminated Soils of Superfund Sites". United States Environmental Protection Agency. https://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.highlight/abstract/6015.
Further reading
- Kenyon, E. M.; Hughes, M. F. (2001). "A Concise Review of the Toxicity and Carcinogenicity of Dimethylarsenic Acid". Toxicology 160 (1–3): 227–236. doi:10.1016/S0300-483X(00)00458-3. PMID 11246143. https://zenodo.org/record/1259985.
- Elschenbroich, C; Salzer, A. (1992) Organometallics, 2nd Edition
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