Cacodyl

Cacodyl
Names
IUPAC name
Tetramethyldiarsane
Other names
Tetramethyldiarsenic(As—As)
Tetramethyldiarsine
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.006.766
EC Number 207-440-4
Properties
C4H12As2
Molar mass 209.98 g·mol−1
-99.9·10−6 cm3/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

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.

Cacodyl is also the name of the functional group or radical (CH3)2As.

Preparation

A mixture of dicacodyl and cacodyl oxide ((CH3)2As—O—As(CH3)2) was first prepared by Cadet by the reaction of potassium acetate with arsenic trioxide. A subsequent reduction yields a mixture of several methylated arsenic compounds including dicacodyl. The reaction forming the oxide is something like:

A far better synthesis was later developed which started from the dimethyl arsine chloride and dimethyl arsine:

History

Jöns Jakob Berzelius coined the name kakodyl (later modified to cacodyl in English) for the dimethylarsinyl radical, (CH3)2As, from the Greek kakodes (evil-smelling) and hyle (matter).[1]

It was investigated by Edward Frankland and (over six years) by Robert Bunsen and is considered the earliest organometallic compound ever discovered (even though arsenic is not a true metal).

From it other compounds were made, such as cacodyl fluoride, chloride, et cetera. One compound, cacodyl cyanide, was particularly awful. In Bunsen's words "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".

Work on cacodyl led Bunsen to the postulation of "methyl radicals" as part of the then-current radical theory.

Applications

Cacodyl was used to try to prove the radical theory of Berzelius, which resulted in a wide use of cacodyl in research laboratories. Afterward interest in the toxic, malodorous compound decreased. During World War I the use of cacodyl as poison gas was considered, but it was never used in the war. Inorganic chemists discovered the properties of cacodyl as a ligand for transition metals.

References

  1. ↑ Berzelius, J. J. (1839). Jahresberichte über die Fortschritte der physischen Wissenschaften. 18: 487. Missing or empty |title= (help)
  • John H. Burns and Jürg Waser (1957). "The Crystal Structure of Arsenomethane". J. Am. Chem. Soc. 79 (4): 859–864. doi:10.1021/ja01561a020.
  • Seyferth, Dietmar (2001). "Cadet's Fuming Arsenical Liquid and the Cacodyl Compounds of Bunsen". Organometallics. 20 (8): 1488&ndash, 1498. doi:10.1021/om0101947.
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