Cacodylic acid

Last updated
Cacodylic acid
Cacodylic acid.svg
Cacodylic-acid-3D-balls.png
Names
Preferred IUPAC name
Dimethylarsinic acid
Other names
Dimethylarsenic acid, Cacodylic acid, Hydroxydimethylarsine oxide, Arsecodile, Ansar, Silvisar, Phytar 560, DMAA, UN 1572
Identifiers
3D model (JSmol)
1736965
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.000.804 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 200-883-4
130562
KEGG
PubChem CID
RTECS number
  • CH7525000
UNII
UN number 1572
  • InChI=1S/C2H7AsO2/c1-3(2,4)5/h1-2H3,(H,4,5) Yes check.svgY
    Key: OGGXGZAMXPVRFZ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C2H7AsO2/c1-3(2,4)5/h1-2H3,(H,4,5)
    Key: OGGXGZAMXPVRFZ-UHFFFAOYAP
  • O=[As](O)(C)C
Properties
C2H7AsO2
Molar mass 137.9977 g/mol
AppearanceWhite 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
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
H301, H331, H410
P261, P264, P270, P271, P273, P301+P310, P304+P340, P311, P321, P330, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 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):
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 [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

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

Contents

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. [4] 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". [5]

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]

(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. [9] Arsenic is classified as a Group-A carcinogen. [9]

See also

Related Research Articles

<span class="mw-page-title-main">Arsine</span> Chemical compound

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".

<span class="mw-page-title-main">Realgar</span> Arsenic sulfide mineral

Realgar, also known as ″arsenic blende″, ″ruby sulphur″ or ″ruby of arsenic″, is an arsenic sulfide mineral with the chemical formula α-As4S4. It is a soft, sectile mineral occurring in monoclinic crystals, or in granular, compact, or powdery form, often in association with the related mineral, orpiment. It is orange-red in color, melts at 320 °C, and burns with a bluish flame releasing fumes of arsenic and sulfur. Realgar is soft with a Mohs hardness of 1.5 to 2 and has a specific gravity of 3.5. Its streak is orange colored. It is trimorphous with pararealgar and bonazziite.

<span class="mw-page-title-main">Cacodyl</span> Chemical compound

Cacodyl, also known as dicacodyl or tetramethyldiarsine, (CH3)2As–As(CH3)2, is an organoarsenic compound that constitutes a major part of "Cadet's fuming liquid" (named after the French chemist Louis Claude Cadet de Gassicourt). It is a poisonous oily liquid with an extremely unpleasant garlicky odor. Cacodyl undergoes spontaneous combustion in dry air.

<span class="mw-page-title-main">Arsenic trioxide</span> Chemical compound (industrial chemical and medication)

Arsenic trioxide is an inorganic compound with the formula As
2
O
3
. As an industrial chemical, its major uses include the manufacture of wood preservatives, pesticides, and glass. It is sold under the brand name Trisenox among others when used as a medication to treat a type of cancer known as acute promyelocytic leukemia. For this use it is given by injection into a vein.

<span class="mw-page-title-main">Cacodyl oxide</span> Chemical compound

Cacodyl oxide is a chemical compound of the formula [(CH3)2As]2O. This organoarsenic compound is primarily of historical significance since it is sometimes considered to be the first organometallic compound synthesized in relatively pure form.

<span class="mw-page-title-main">Diphenylchlorarsine</span> Chemical compound

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.

<span class="mw-page-title-main">Arsenic tribromide</span> Chemical compound

Arsenic tribromide is an inorganic compound with the formula AsBr3, it is a bromide of arsenic. Arsenic is a chemical element that has the symbol As and atomic number 33. This pyramidal molecule is the only known binary arsenic bromide. AsBr3 is noteworthy for its very high refractive index of approximately 2.3. It also has a very high diamagnetic susceptibility. The compound exists as colourless deliquescent crystals that fume in moist air.

<span class="mw-page-title-main">1,2-Bis(dimethylarsino)benzene</span> Chemical compound

1,2-Bis(dimethylarsino)benzene (diars) is the organoarsenic compound with the formula C6H4(As(CH3)2)2. The molecule consists of two dimethylarsino groups attached to adjacent carbon centers of a benzene ring. It is a chelating ligand in coordination chemistry. This colourless oil is commonly abbreviated "diars."

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.

<span class="mw-page-title-main">Cadet's fuming liquid</span> Mixture of organoarsenic compounds

Cadet's fuming liquid was a red-brown oily liquid prepared in 1760 by the French chemist Louis Claude Cadet de Gassicourt (1731-1799) by the reaction of potassium acetate with arsenic trioxide. It consisted mostly of dicacodyl (((CH3)2As)2) and cacodyl oxide (((CH3)2As)2O).

<span class="mw-page-title-main">Methyldichloroarsine</span> Chemical compound

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.

<span class="mw-page-title-main">Disodium methyl arsonate</span> Chemical compound

Disodium methyl arsenate (DSMA) is the organoarsenic compound with the formula CH3AsO3Na2. It is a colorless, water-soluble solid derived from methanearsonic acid. It is used as a herbicide. Tradenames include Metharsinat, Arrhenal, Disomear, Metharsan, Stenosine, Tonarsan, Tonarsin, Arsinyl, Arsynal, and Diarsen.

Arsenic biochemistry refers to biochemical processes that can use arsenic or its compounds, such as arsenate. Arsenic is a moderately abundant element in Earth's crust, and although many arsenic compounds are often considered highly toxic to most life, a wide variety of organoarsenic compounds are produced biologically and various organic and inorganic arsenic compounds are metabolized by numerous organisms. This pattern is general for other related elements, including selenium, which can exhibit both beneficial and deleterious effects. Arsenic biochemistry has become topical since many toxic arsenic compounds are found in some aquifers, potentially affecting many millions of people via biochemical processes.

Radical theory is an obsolete scientific theory in chemistry describing the structure of organic compounds. The theory was pioneered by Justus von Liebig, Friedrich Wöhler and Auguste Laurent around 1830 and is not related to the modern understanding of free radicals. In this theory, organic compounds were thought to exist as combinations of radicals that could be exchanged in chemical reactions just as chemical elements could be interchanged in inorganic compounds.

<span class="mw-page-title-main">Disodium hydrogen arsenate</span> Chemical compound

Disodium hydrogen arsenate is the inorganic compound with the formula Na2HAsO4.7H2O. The compound consists of a salt and seven molecules of water of crystallization although for simplicity the formula usually omits the water component. The other sodium arsenates are NaH2AsO4 and Na3AsO4, the latter being called sodium arsenate. Disodium hydrogen arsenate is highly toxic. The salt is the conjugate base of arsenic acid. It is a white, water-soluble solid.

<span class="mw-page-title-main">Methylarsonic acid</span> Chemical compound

Methylarsonic acid is an organoarsenic compound with the formula CH3AsO3H2. It is a colorless, water-soluble solid. Salts of this compound, e.g. disodium methyl arsonate, have been widely used in as herbicides and fungicides in growing cotton and rice.

<span class="mw-page-title-main">Arsinic acid</span>

Arsinic acids are organoarsenic compounds with the formula R2AsO2H. They are formally, but not actually, related to arsinic acid, a hypothetical compound of the formula H2AsO2H. Arsinic acids are monoprotic, weak acids. They react with sodium sulfide to give the dithioarinates R2AsS2Na. Arsinic acids are related to phosphinic acids (R2PO2H.).

<span class="mw-page-title-main">Cacodyl cyanide</span> Chemical compound

Cacodyl cyanide is a highly toxic organoarsenic compound discovered by Robert Bunsen in the 1840s. It is very volatile and flammable, as it shares the chemical properties of both arsenic and cyanide.

An arsinide, arsanide, dihydridoarsenate(1−) or arsanyl compound is a chemical derivative of arsine, where one hydrogen atom is replaced with a metal or cation. The arsinide ion has formula AsH−2. It can be considered as a ligand with name arsenido or arsanido. Few chemists study arsanyl compounds, as they are both toxic and unstable. The IUPAC names are arsanide and dihydridoarsenate(1−). For the ligand the name is arsanido. The neutral −AsH2 group is termed arsanyl.

<span class="mw-page-title-main">Arsenic compounds</span> Chemical compounds containing arsenic

Compounds of arsenic resemble in some respects those of phosphorus which occupies the same group (column) of the periodic table. The most common oxidation states for arsenic are: −3 in the arsenides, which are alloy-like intermetallic compounds, +3 in the arsenites, and +5 in the arsenates and most organoarsenic compounds. Arsenic also bonds readily to itself as seen in the square As3−
4
ions in the mineral skutterudite. In the +3 oxidation state, arsenic is typically pyramidal owing to the influence of the lone pair of electrons.

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. 1 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. 1 2 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