Organoarsenic chemistry

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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.

Contents

History

Cacodyl (tetramethyldiarsine) was one of the first organoarsenic compounds. Cacodyl Structural Formula V.3.svg
Cacodyl (tetramethyldiarsine) was one of the first organoarsenic compounds.

Surprising for an area now considered of minor importance, organoarsenic chemistry played a prominent role in the history of the field of chemistry. The oldest known organoarsenic compound, the foul smelling cacodyl was reported in "cacodyl" (1760) and is sometimes classified as the first synthetic organometallic compound. The compound Salvarsan was one of the first pharmaceuticals, earning a Nobel prize for Paul Ehrlich. Various other organoarsenic compounds formerly found use as antibiotics (Solarson) or other medical uses. [2]

Synthesis and classification

Arsenic typically occurs in the oxidation states (III) and (V), illustrated by the halides AsX3 (X = F, Cl, Br, I) and AsF5. Correspondingly, organoarsenic compounds are commonly found in these two oxidation states. [3]

The hydroxyarsenic compounds are known: [3]

Organoarsenic(V) compounds and uses

Arsenic(V) compounds typically feature the functional groups RAsO(OH)2 or R2AsO(OH) (R = alkyl or aryl). Biomethylation of arsenic compounds starts with the formation of methanearsonates. Thus, trivalent inorganic arsenic compounds are methylated to give methanearsonate. S-adenosylmethionine is the methyl donor. The methanearsonates are the precursors to dimethylarsonates, again by the cycle of reduction (to methylarsonous acid) followed by a second methylation. [4] This dimethyl compound is cacodylic acid ((CH3)2AsO2H), figures prominently throughout the chemistry of organoarsenic compounds. In contrast, the dimethylphosphonic acid is less significant in the corresponding chemistry of phosphorus. Cacodylic acid arises from the methylation of arsenic(III) oxide. Phenylarsonic acids can be accessed by the reaction of arsenic acid with anilines, the so-called Bechamp reaction.

The monomethylated acid, methanearsonic acid (CH3AsO(OH)2), is a precursor to fungicides (tradename Neoasozin) in the cultivation of rice and cotton. Derivatives of phenylarsonic acid (C6H5AsO(OH)2) are used as feed additives for livestock, including 4-hydroxy-3-nitrobenzenearsonic acid (3-NHPAA or Roxarsone), ureidophenylarsonic acid and p-arsanilic acid. These applications are controversial as they introduce soluble forms of arsenic into the environment.

Compounds of arsenic(V) containing only organic ligands are rare, the pre-eminent member being the pentaphenyl derivative As(C6H5)5. [5]

Organoarsenic(III) compounds and uses

Most such compounds are prepared by alkylation of AsCl3 and its derivatives using organolithium and Grignard reagents. [5] For example, the series trimethylarsine ((CH3)3As), dimethylarsenic chloride ((CH3)2AsCl), and methylarsenic dichloride (CH3AsCl2) is known. Reduction of the chloride derivatives with hydride reducing reagents affords the corresponding hydrides, such as dimethylarsine ((CH3)2AsH) and methylarsine (CH3AsH2). Similar manipulations apply to other organoarsenic chloride compounds.

An important route to dimethylarsenic compounds begin with reduction of cacodylic acid (see above):

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

A variety of heterocycles containing arsenic(III) are known. These include arsole, the arsenic analogue of pyrrole, and arsabenzene, the arsenic analogue of pyridine.

Symmetrical organoarsenic(III) compounds, e.g. trimethylarsine and triphenylarsine, are commonly used as ligands in coordination chemistry. They behave like phosphine ligands, but are less basic. The diarsine C6H4(As(CH3)2)2, known as diars, is a chelating ligand. Thorin is an indicator for several metals.

Organoarsenic(I) compounds and uses

Least significant in terms of commercial uses and numbers are the organoarsenic(I) compounds. The anti-syphylic drugs Salvarsan and Neosalvarsan are representative of this class. These compounds typically feature three bonds to As, but only As-As single bonds.

Arsaalkenes and arsaalkynes

Following the pattern described by the double bond rule, compounds with As=As, As=C, and As≡C bonds are rare. They are observed in the gas phase but as liquids or solids, considerable steric protection is required to inhibit their conversion to oligomers.

Chemical warfare

Organoarsenic compounds, especially those featuring As-Cl bonds, have been used as chemical weapons, especially during World War I. Infamous examples include "Lewisite" (chlorovinyl-2-arsenic dichloride) and "Clark I" (chlorodiphenylarsine). Phenyldichloroarsine is another one.

In nature

As arsenic is toxic to most life forms and it occurs in elevated concentration in some areas several detoxification strategies have evolved. Inorganic arsenic and its compounds, upon entering the food chain, are progressively metabolized to a less toxic form of arsenic through a process of methylation. [6] Organoarsenic compounds arise via biomethylation of inorganic arsenic compounds, [7] via processes mediated by enzymes related to vitamin B12. [8] For example, the mold Scopulariopsis brevicaulis produces significant amounts of trimethylarsine if inorganic arsenic is present. [9] The organic compound arsenobetaine, a betaine, is found in some marine foods such as fish and algae, and also in mushrooms in larger concentrations. The average person's intake is about 10-50 µg/day. Values about 1000 µg are not unusual following consumption of fish or mushrooms. But there is little danger in eating fish because this arsenic compound is nearly non-toxic. [10] Arsenobetaine was first identified in the Western rock lobster [11] [12]

Saccharides bound to arsenic, collectively known as arsenosugars, are found especially in seaweeds. Arsenic containing lipids are also known. [13] Although arsenic and its compounds are toxic for humans, one of the first synthetic antibiotics was Salvarsan, the use of which has long been discontinued.

The only polyarsenic compound isolated from a natural source is arsenicin A, found in the New Caledonian marine sponge Echinochalina bargibanti. [14]

Organoarsenic compounds may pose significant health hazards, depending on their speciation. Arsenous acid (As(OH)3) has an LD50 of 34.5 mg/kg (mice) whereas for the betaine (CH3)3As+CH2CO2− the LD50 exceeds 10 g/kg. [10]

Representative compounds

Some illustrative organoarsenic compound are listed in the table below:

OrganoarsenicR Molar mass CAS number Properties
10,10'-oxybis-10H-Phenoxarsine 10,10'-oxybis-10H-PhenoxarsinePic.svg 502.231858-36-6
Triphenylarsine Phenyl TriphenylarsinePic.svg 306.23603-32-7 Melting point 58-61 °C
Phenyldichloroarsine phenyl, chlorine Phenyldichloroarsine.svg 222.93696-28-6
Roxarsone Roxarsone.png 263.04121-19-7
Arsenobetaine ArsenobetainePIC.svg 64436-13-1
Arsenicin A Arsenicin A.png 389.76925705-41-5 Melting point 182 to 184 °C (360 to 363 °F)
Representative organoarsenic compounds [15] [14]

Nomenclature

The naming of cyclic organoarsenic compounds is based on an extension of the Hantzsch–Widman nomenclature system [16] approved by IUPAC, as summarized below: [17]

Ring sizeUnsaturated ring Saturated ring
3ArsireneArsirane
4ArseteArsetane
5ArsoleArsolane
6ArsinineArsinane
7ArsepineArsepane
8ArsocineArsocane
9ArsonineArsonane
10ArsecineArsecane

Because of its similarity to the English slang word "arsehole" (in common use outside North America), the name "arsole" has been considered a target of fun, a "silly name", [18] [19] and one of several chemical compounds with an unusual name. However, this "silly name" coincidence has also stimulated detailed scientific studies. [20]

See also

Related Research Articles

<span class="mw-page-title-main">Organometallic chemistry</span> Study of organic compounds containing metal(s)

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.

In the chemical sciences, methylation denotes the addition of a methyl group on a substrate, or the substitution of an atom by a methyl group. Methylation is a form of alkylation, with a methyl group replacing a hydrogen atom. These terms are commonly used in chemistry, biochemistry, soil science, and the biological sciences.

<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">Phosphorus trichloride</span> Chemical compound

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

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">Arsenous acid</span> Chemical compound

Arsenous acid (or arsenious acid) is the inorganic compound with the formula H3AsO3. It is known to occur in aqueous solutions, but it has not been isolated as a pure material, although this fact does not detract from the significance of As(OH)3.

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

<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">Arsenic trichloride</span> Chemical compound

Arsenic trichloride is an inorganic compound with the formula AsCl3, also known as arsenous chloride or butter of arsenic. This poisonous oil is colourless, although impure samples may appear yellow. It is an intermediate in the manufacture of organoarsenic compounds.

<span class="mw-page-title-main">Organolead chemistry</span>

Organolead chemistry is the scientific study of the synthesis and properties of organolead compounds, which are organometallic compounds containing a chemical bond between carbon and lead. The first organolead compound was hexaethyldilead (Pb2(C2H5)6), first synthesized in 1858. Sharing the same group with carbon, lead is tetravalent.

Trimethylarsine (abbreviated TMA or TMAs) is the chemical compound with the formula (CH3)3As, commonly abbreviated AsMe3 or TMAs. This organic derivative of arsine has been used as a source of arsenic in microelectronics industry, a building block to other organoarsenic compounds, and serves as a ligand in coordination chemistry. It has distinct "garlic"-like smell. Trimethylarsine had been discovered as early as 1854.

<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."

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

Trimethylolpropane phosphite, C2H5C(CH2O)3P, is a phosphite ester used as a ligand in organometallic chemistry. Trimethylolpropane phosphite is sometimes abbreviated to EtCage. It is a white solid that is soluble in organic solvents. It is also highly toxic.

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

Arsenobetaine is an organoarsenic compound that is the main source of arsenic found in fish. It is the arsenic analog of trimethylglycine, commonly known as betaine. The biochemistry and its biosynthesis are similar to those of choline and betaine.

Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.

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.

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

Pentamethylarsenic (or pentamethylarsorane)is an organometalllic compound containing five methyl groups bound to an arsenic atom with formula As(CH3)5. It is an example of a hypervalent compound. The molecular shape is trigonal bipyramid.

<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">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. ↑ Seyferth, Dietmar (2001). "Cadet's Fuming Arsenical Liquid and the Cacodyl Compounds of Bunsen". Organometallics. 20 (8): 1488–1498. doi: 10.1021/om0101947 .
  2. ↑ Singh, R. Synthetic Drugs. Mittal Publications (2002). ISBN   817099831X
  3. 1 2 Grund, S. C.; Hanusch, K.; Wolf, H. U. "Arsenic and Arsenic Compounds". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_113.pub2.
  4. ↑ Styblo, M.; Del Razo, L. M.; Vega, L.; Germolec, D. R.; LeCluyse, E. L.; Hamilton, G. A.; Reed, W.; Wang, C.; Cullen, W. R.; Thomas, D. J. (2000). "Comparative toxicity of trivalent and pentavalent inorganic and methylated arsenicals in rat and human cells". Archives of Toxicology . 74 (6): 289–299. doi:10.1007/s002040000134. PMID   11005674. S2CID   1025140.
  5. 1 2 Elschenbroich, C. "Organometallics" (2006) Wiley-VCH: Weinheim. ISBN   978-3-527-29390-2
  6. ↑ Reimer, K. J.; Koch, I.; Cullen, W. R. (2010). Organoarsenicals. Distribution and transformation in the environment. Metal Ions in Life Sciences. Vol. 7. Cambridge: RSC publishing. pp. 165–229. doi:10.1039/9781849730822-00165. ISBN   978-1-84755-177-1. PMID   20877808.
  7. ↑ Dopp, E.; Kligerman, A. D.; Diaz-Bone, R. A. (2010). Organoarsenicals. Uptake, metabolism and toxicity. Metal Ions in Life Sciences. Vol. 7. Cambridge: RSC publishing. pp. 231–265. doi:10.1515/9783110436600-012. ISBN   978-1-84755-177-1. PMID   20877809.
  8. ↑ Toshikazu Kaise; Mitsuo Ogura; Takao Nozaki; Kazuhisa Saitoh; Teruaki Sakurai; Chiyo Matsubara; Chuichi Watanabe; Ken'ichi Hanaoka (1998). "Biomethylation of Arsenic in an Arsenic-rich Freshwater Environment". Applied Organometallic Chemistry. 11 (4): 297–304. doi:10.1002/(SICI)1099-0739(199704)11:4<297::AID-AOC584>3.0.CO;2-0.
  9. ↑ Bentley, Ronald; Chasteen, Thomas G. (2002). "Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth". Microbiology and Molecular Biology Reviews. 66 (2): 250–271. doi:10.1128/MMBR.66.2.250-271.2002. PMC   120786 . PMID   12040126.
  10. 1 2 Cullen, William R.; Reimer, Kenneth J. (1989). "Arsenic speciation in the environment". Chemical Reviews. 89 (4): 713–764. doi:10.1021/cr00094a002. hdl: 10214/2162 .
  11. ↑ Francesconi, Kevin A.; Edmonds, John S. (1998). "Arsenic Species in Marine Samples" (PDF). Croatica Chemica Acta. 71 (2): 343–359. Archived from the original (PDF) on 2008-03-09.
  12. ↑ John S. Edmonds; Kevin A. Francesconi; Jack R. Cannon; Colin L. Raston; Brian W. Skelton & Allan H. White (1977). "Isolation, crystal structure and synthesis of arsenobetaine, the arsenical constituent of the western rock lobster panulirus longipes cygnus George". Tetrahedron Letters. 18 (18): 1543–1546. doi:10.1016/S0040-4039(01)93098-9.
  13. ↑ Alice Rumpler; John S. Edmonds; Mariko Katsu; Kenneth B. Jensen; Walter Goessler; Georg Raber; Helga Gunnlaugsdottir; Kevin A. Francesconi (2008). "Arsenic-Containing Long-Chain Fatty Acids in Cod-Liver Oil: A Result of Biosynthetic Infidelity?". Angew. Chem. Int. Ed. 47 (14): 2665–2667. doi:10.1002/anie.200705405. PMID   18306198.
  14. 1 2 Mancini, Ines; Guella, Graziano; Frostin, Maryvonne; Hnawia, Edouard; Laurent, Dominique; Debitus, Cecile; Pietra, Francesco (2006). "On the First Polyarsenic Organic Compound from Nature: Arsenicin a from the New Caledonian Marine SpongeEchinochalina bargibanti". Chemistry: A European Journal. 12 (35): 8989–94. doi:10.1002/chem.200600783. PMID   17039560.
  15. ↑ "Home". sigmaaldrich.com.
  16. ↑ "Revision of the Extended Hantzsch-Widman System of Nomenclature for Heteromonocycles" at IUPAC, retrieved 29 Sept 2008
  17. ↑ Nicholas C. Norman (1998). Chemistry of arsenic, antimony, and bismuth. Springer. p. 235. ISBN   978-0-7514-0389-3 . Retrieved 15 March 2011.
  18. ↑ Richard Watson Todd (25 May 2007). Much ado about English: up and down the bizarre byways of a fascinating language. Nicholas Brealey Publishing. p. 138. ISBN   978-1-85788-372-5 . Retrieved 15 March 2011.
  19. ↑ Paul W May, Molecules with Silly or Unusual Names, publ. 2008 Imperial College Press, ISBN   978-1-84816-207-5(pbk). See also the Web page "Molecules with Silly or Unusual Names" at the School of Chemistry, University of Bristol, (retrieved 29 Sept 2008)
  20. ↑ M. P. Johansson; J. Juselius (2005). "Arsole Aromaticity Revisited". Lett. Org. Chem. 2 (5): 469–474. doi:10.2174/1570178054405968. Using quantum chemical methodology, we reinvestigate the aromaticity of the much debated arsole, using the newly developed gauge-including magnetically induced currents (GIMIC) method. GIMIC provides a quantitative measure of the induced ring current strength, showing arsole to be moderately aromatic.
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