Organoarsenic compounds synthesis

Although now essentially obsolete for the treatment of human diseases because of their toxicities, organoarsenic compounds were the first synthetic organic pharmaceutical agents and were widely used in the early 1900s. The first pharmaceutical application was that of atoxyl (the sodium salt of 4-aminophenylarsinic acid), which was used to treat sleeping sickness. The synthesis of Salvarsan by Dr. Paul Ehrlich in 1907 was a development that may be considered the beginning of modem chemotherapy (chemical treatment of disease). Salvarsan was widely used for the treatment of syphilis. Toxic effects of Salvarsan included jaundice and encephalitis (brain inflammation). 

There have been several reviews that provide a comprehensive coverage of the synthesis and reactivity of organoarsenic compounds that contain tricoordinate arsenic with an As-N The acyclic aminoarsines,... 

The synthesis and reactivity of organoarsenic compounds that contain As-O bonds has been extensively reviewed. Because of space limitations, the extensive chemistry associated with As-O bonded systems cannot be covered. Instead, the highlights of the chemistry will be presented here and the reader is referred to the reviews for the vast quantity of more detailed information. These highlights have been grouped according to the more common classes of As O bonded compounds that serve as precursors to many of the compounds discussed in earher sections of this review. 

In the present review, the methods of synthesis of organoarsenic compounds will be surveyed. Typical and recent methods have been selected from a large number of reported methods. 

The pyrolysis of organoarsenic compounds containing the arsenyl moiety has some limited preparative applications [arsenyl (As=0) by analogy with phosphoryl (P=0)]. The compounds are based on the arsonic acid RAs(0)(0H)2, the arsinic acid R2As(0)0H and the arsine oxide R3As=0 structures. The acids are in interesting contrast with the phosphorus series. The phosphonic and phosphinic esters are prepared from the phosphorus(III) precursors via the Arbuzov synthesis. This synthetic route fails with the arsenic analogues, and further, if an alkyl halide or a salt is added in the pyrolysis of arsonic or arsinic acid esters a retro-Arbuzov reaction takes place . ... 

Yamamoto, Y. Akiba, K.-Y. In Chemistry of Organic Arsenic, Antimony and Bismuth Compounds, Patai, S. Ed. Wiley New York, 1994 Chapter 21, Synthesis of Organoarsenic Compounds, pp 813-882. 

Research on organoarsenic compounds up to 1993 has been previously reviewed and the following works should be consulted by readers requiring detailed information. The review of Cullen and Reimer is an all-encompassing treatise of arsenic compounds (species) in the environment and includes sections on basic chemistry, biotransformations, and environmental behavior. Chemical aspects, including synthesis, are the focus of the review by Edmonds et The review of arsenic in marine organisms, published in 1997adequately summarizes the relevant... 

Arsine is the simplest compound of arsenic. It is used in the semiconductor industry and has a use in the synthesis of organoarsenic compounds. It may be ingested or inhaled accidentally or deliberately. Arsine binds to the haemoglobin of red blood cells, causing them to be destroyed by the body, resulting in haemolytic anaemia, haemoglobinuria and subsequent nephropathy with renal failure. 

The compound 10,10 -oxybisphenoxarsine (OBPA) is a unique organoarsenic antimicrobial. The powerful antimicrobial properties of organoarsenics had long been recognized, and there is plentiful treatment of the synthesis of organoarsenic derivatives in the literature. OBPA is used primarily in the plastics industry, where its high temperature stability and low vapor pressure make it the leading industrial antimicrobial in this market (30). 

Discuss the historical aspects of organometallic compound toxicity, including organoarsenicals used as pharmaceutical agents, gasoline antiknock additives, and compounds used in applications such as catalysis and chemical synthesis. 

The first significant organoarsenical dmg was synthesized by Pierre Antoine Bechamp (1816-1908) by chemically reacting arsenic acid with aniline [16,17]. Bechamp isolated a colorless compound that he regarded as an anilide of arsenic acid (Fig. 2a). Some 40 years after its initial synthesis, Wolferstan Thomas in Liverpool demonstrated the trypanocidal activity of atoxyl [18] and a few years later it was also used in the treatment of syphilis [19]. Hence, Bechamp s anilide began to be used to treat disease. At the same time, Ferdinand Blumenthal described... 

Relatively few applications of optically active tertiary arsines to asymmetric synthesis have been reported by comparison with the extensive work with phosphines . Authoritative accounts of the synthesis and stereochemistry of compounds of Group V elements are available other reviews cover the subject up until 1979 . For general treatments of organoarsenic chemistry up until 1976, including optically active compounds, two important works are available . Of related interest is an article on stereochemical aspects of phosphorus chemistry and another published in this series on optically active phosphines preparation, uses and chiroptical properties . On matters concerning the intricacies of resolutions work, the reader should consult Reference 21, especially Chapter 7, which is entitled Experimental Aspects and Art of Resolutions. 

---