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{{Chembox |
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{{Chembox |
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| Watchedfields = changed |
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| verifiedrevid = 399485097 |
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| verifiedrevid = 433275081 |
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| ImageFileR1 = Cacodyl-from-xtal-1988-3D-balls.png |
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| ImageFile1 = Cacodyl Structural Formula V.3.svg |
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| ImageSizeR1 = 121 |
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| ImageNameR1 = Ball and stick model of cacodyl |
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| ImageName1 = Structural formula of cacodyl |
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| ImageFileL2 = Cacodyl-from-xtal-1988-3D-balls.png |
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| ImageFileL1 = Struktur Kakodyl.png |
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| ImageNameL2 = Ball and stick model of cacodyl |
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| ImageSizeL1 = 121 |
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| ImageFileR2 = Cacodyl-3D-vdW.png |
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| ImageNameL1 = Structural formula of cacodyl |
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| ImageNameR2 = Space-filling model of cacodyl |
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| IUPACName = Tetramethyldiarsane |
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| PIN = Tetramethyldiarsane |
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| OtherNames = Tetramethyldiarsenic(''As''—''As'')<br /> |
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| OtherNames = Tetramethyldiarsenic(''As''—''As'')<br /> |
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Bis(dimethylarsenic)(''As''—''As'')<br /> |
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Tetramethyldiarsine |
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Tetramethyldiarsine |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo = 471-35-2 |
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| CASNo = 471-35-2 |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo_Ref = {{cascite|correct|??}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| PubChem = 79018 |
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| UNII = 11N299093L |
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| PubChem_Ref = {{Pubchemcite|correct|PubChem}} |
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| ChemSpiderID = 71351 |
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| PubChem = 79018 |
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| ChemSpiderID = 71351 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| EINECS = 207-440-4 |
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| SMILES = ((C)C)(C)C |
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| EINECS = 207-440-4 |
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| SMILES = ((C)C)(C)C |
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| SMILES1 = C(C)(C)C |
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| SMILES1 = C(C)(C)C |
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| StdInChI = 1S/C4H12As2/c1-5(2)6(3)4/h1-4H3 |
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| StdInChI = 1S/C4H12As2/c1-5(2)6(3)4/h1-4H3 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| InChI = 1/C4H12As2/c1-5(2)6(3)4/h1-4H3 |
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| InChI = 1/C4H12As2/c1-5(2)6(3)4/h1-4H3 |
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| StdInChIKey = RSKPLCGMBWEANE-UHFFFAOYSA-N |
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| StdInChIKey = RSKPLCGMBWEANE-UHFFFAOYSA-N |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| InChIKey = RSKPLCGMBWEANE-UHFFFAOYAG}} |
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| InChIKey = RSKPLCGMBWEANE-UHFFFAOYAG}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C = 4 |
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| C=4 | H=12 | As=2 |
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| MagSus = -99.9·10<sup>−6</sup> cm<sup>3</sup>/mol |
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| H = 12 |
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}} |
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| As = 2 |
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|Section3={{Chembox Hazards |
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| ExactMass = 209.937093218 g mol<sup>−1</sup>}} |
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| Section3 = {{Chembox Hazards |
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| MainHazards = |
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| MainHazards = |
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| FlashPt = |
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| FlashPt = |
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| Autoignition = }} |
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| AutoignitionPt = }} |
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}} |
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}} |
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'''Cacodyl''', '''dicacodyl''', '''tetramethyldiarsine''', '''alkarsine''' or minor part of the "]" (after the French chemist ]) (CH<sub>3</sub>)<sub>2</sub>As—As(CH<sub>3</sub>)<sub>2</sub> is a poisonous oily liquid with a garlicky odor. Cacodyl undergoes spontaneous combustion in dry air. |
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'''Cacodyl''', also known as '''dicacodyl''' or '''tetramethyldiarsine''', (CH<sub>3</sub>)<sub>2</sub>As–As(CH<sub>3</sub>)<sub>2</sub>, is an ] compound that constitutes a major part of "]" (named after the French chemist ]). It is a poisonous oily liquid with an extremely unpleasant garlicky odor. Cacodyl undergoes ] in dry air.<ref>{{cite journal |
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| title = Cadet's Fuming Arsenical Liquid and the Cacodyl Compounds of Bunsen |
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| first = Dietmar |
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| last = Seyferth |
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| journal = Organometallics |
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| year = 2001 |
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| volume = 20 |
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| issue =8 |
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| pages = 1488–1498 |
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| doi = 10.1021/om0101947 |
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| doi-access = free |
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}}</ref> |
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'''Cacodyl''' is also the name of the ] or ] (CH<sub>3</sub>)<sub>2</sub>As. |
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==Preparation== |
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==Preparation== |
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Cacodyl oxide is prepared by the reaction of ] with ]. |
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A mixture of dicacodyl and cacodyl oxide ((CH<sub>3</sub>)<sub>2</sub>As–O–As(CH<sub>3</sub>)<sub>2</sub>) was first prepared by Cadet by the reaction of ] with ]. A subsequent reduction yields a mixture of several methylated arsenic compounds including dicacodyl. |
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The global reaction (mass balance) corresponding to the oxide formation is the following: |
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:4 CH<sub>3</sub>CO<sub>2</sub>K + As<sub>2</sub>O<sub>3</sub> → As<sub>2</sub>(CH<sub>3</sub>)<sub>4</sub> + 2 K<sub>2</sub>CO<sub>3</sub> + 2 CO<sub>2</sub> |
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: {{chem2|4 CH3COOK + As2O3 → ((CH3)2As)2O + 2 K2CO3 + 2 CO2}} |
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A subsequent reduction or ] of the substance under the reaction conditions yields a mixture of several methylated arsenic compounds. |
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A far better synthesis was developed which started from the dimethyl arsine chloride and dimethyl arsine. |
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A more efficient synthesis was later developed which started from the dimethyl arsine chloride and dimethyl arsine: |
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: {{chem2|As(CH3)2Cl + As(CH3)2H → As2(CH3)4 + HCl}} |
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:As(CH<sub>3</sub>)<sub>2</sub>Cl + As(CH<sub>3</sub>)<sub>2</sub>H → As<sub>2</sub>(CH<sub>3</sub>)<sub>4</sub> + HCl |
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==History== |
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==History== |
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] coined the name '''kakodyl''' (later changed to cacodyl) for the dimethylarsinyl radical, (CH<sub>3</sub>)<sub>2</sub>As, from the Greek kakodes (evil-smelling) and hyle (matter).<ref>{{cite journal |
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] coined the name '''kakodyl''' (later modified to cacodyl in English) for the dimethylarsinyl radical, (CH<sub>3</sub>)<sub>2</sub>As, from the Greek ''κακώδης kakōdēs'' ("evil-smelling") and ὕλη ''hylē'' ("matter").<ref>{{cite journal|author=Berzelius|first=Jöns Jacob|author-link=Jöns Jacob Berzelius|year=1841|title=Kakodyl|url=https://zs.thulb.uni-jena.de/receive/jportal_jparticle_00317596|journal=Jahresberichte über die Fortschritte der Physischen Wissenschaften|volume=20|pages=526–539}}</ref> |
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| title = |
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| author = Berzelius, J. J. |
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| journal = Jahresber. |
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| year = 1839 |
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| volume = 18 |
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| issue = |
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| pages = 487 |
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}}</ref> |
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It was investigated by ] and ] and is considered one of the earliest ] compounds ever discovered. It was originally made from ] distilled with ]. |
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It was investigated by ] and (for over six years) by ] and is considered the earliest ] compound ever discovered (even though arsenic is not a true metal). |
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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''". |
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From it other compounds were made, such as cacodyl fluoride, ], et cetera. One compound, ], 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''". |
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Work on cacodyl led Bunsen to the postulation of ] ]. |
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Work on cacodyl led Bunsen to the postulation of "methyl radicals" as part of the then-current ]. |
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==Use== |
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==Applications== |
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Cacodyl was used to prove the radical theory of Berzelius, which resulted in a wide use of cacodyl in research laboratories. After the radical theory was established, the interest in the toxic substance with the literally evil smell decreased. During ] the use of cacodyl as ] was considered, but it was never used in the war. The inorganic chemists discovered the properties of cacodyl as ligand for transition metals. |
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Cacodyl was used to try to prove the ] of ], which resulted in a wide use of cacodyl in research laboratories. Afterward interest in the toxic, malodorous compound decreased. During ] the use of cacodyl as a ] was considered, but it was never used in the war. Inorganic chemists discovered the properties of cacodyl as a ] for transition metals. |
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==See also== |
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* ] |
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==References== |
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==References== |
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| pages = 859–864 |
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| pages = 859–864 |
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| doi = 10.1021/ja01561a020 |
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| doi = 10.1021/ja01561a020 |
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| hdl = 1911/18207 |
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| url = https://scholarship.rice.edu/bitstream/1911/18207/1/3079641.PDF |
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| hdl-access = free |
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}} |
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*{{cite journal |
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| ⚫ |
| title = Cadet's Fuming Arsenical Liquid and the Cacodyl Compounds of Bunsen |
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| ⚫ |
| first = Dietmar |
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| ⚫ |
| last = Seyferth |
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| ⚫ |
| journal = Organometallics |
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| ⚫ |
| year = 2001 |
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| ⚫ |
| volume = 20 |
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| ⚫ |
| issue =8 |
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| ⚫ |
| pages = 1488–1498 |
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| ⚫ |
| doi = 10.1021/om0101947 |
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| url = http://pubs.acs.org/cgi-bin/abstract.cgi/orgnd7/2001/20/i08/abs/om0101947.html}} |
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