- Identification of Degradation Products of Sea-Dumped Chemical Warfare Agent-Related Phenylarsenic Chemicals in Marine Sediment
-
Previously unknown phenylarsenic chemicals that originated from chemical warfare agents (CWAs) have been detected and identified in sediment samples collected from the vicinity of chemical munition dumpsites. Nontargeted screening by ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS) was used for detection of 14 unknown CWA-related phenylarsenic chemicals. Methylated forms of Clark I/II, Adamsite, and phenyldichloroarsine were detected in all analyzed sediment samples, and their identification was based on synthesized chemicals. In addition, other previously unknown CWA-related phenylarsenic chemicals were detected, and their structures were elucidated using MS/HRMS technique. On the basis of relative isotope ratios of protonated molecules and measures of exact masses of formed fragment ions, it could be concluded that some of these unknown chemicals contained a sulfur atom attached to an arsenic atom. In addition to that, some of the samples contained chemicals that had formed via addition of an OH group to the aromatic ring. However, it is not possible to say how these chemicals are formed, but the most plausible cause is activities of marine microbes in the sediment. To our knowledge, these chemicals have not been detected from sediment samples previously. Sensitive analytical methods are needed for these novel chemicals to assess the total CWA burden in marine sediments, and this information is essential for the risk assessment.
- Kiljunen, Harri,Niemikoski, Hanna,Ostin, Anders,Soderstrom, Martin,Vanninen, Paula
-
p. 4891 - 4899
(2020/08/07)
-
- New Reagents, XXXIV. (Diphenylarsino)methyllithium: Synthesis and Preparative Applications
-
(Diphenylarsino)methyl iodide (3) was synthesized for the first time (76 percent). (Diphenylarsino)methyllithium (2), stable at 20 deg C, is accessible from 3 (ca. 100 percent) by iodine-lithium exchange with butyl- or phenyllithium and by organoelement-lithium exchange with butyllithium from diphenylarsane (4d; 92 percent). 2, prepared from 4d, gives far better yields of (diphenylarsino)alkanes by the reaction with alkyl halides than 2, obtained from 3.To the contrary, no difference is observed in the reactivity of 2 from 3 or 4d towards aldehydes and ketones.
- Kauffmann, Thomas,Altepeter, Bruno,Klas, Norbert,Kriegesmann, Reinhard
-
p. 2353 - 2364
(2007/10/02)
-
- Photostimulated Reactions of Potassium Diphenylarsenide with Haloarenes by the SRN1 Mechanism
-
Photostimulated reactions of haloarenes with potassium diphenylarsenide (3) were studied in liquid ammonia. p-Chloro-, p-bromo-, and p-iodotoluenes gave four products: triphenylarsine, p-tolyldiphenylarsine, di-p-tolylphenylarsine and tri-p-tolylarsine.Similarly, with p-chloro, p-bromo-, and p-iodoanisole as substrates, four arsines were found as products: triphenylarsine, p-anisyldiphenylarsine, di-p-anisylphenylarsine and tri-p-anisylarsine. p-Chlorotoluene and p-bromoanisole are unreactive in the dark, but with 4-chlorobenzophenone there is a dark reaction, which is accelerated by light and inhibited by m-dinitrobenzene and oxygen.Withthe latter substrate, only the straightforward substitution product is formed.These reactions are believed to occur by the SRN1 mechanism, with an exstra feature of reversible coupling of aryl radicals with arside ions, which causes the scrambling of aryl rings.It is suggested that the low-lying ?* MO of the benzophenone moiety prevents C-As bond breaking in the radical anion intermediate in that case.
- Rossi, Roberto A.,Alonso, Ruben A.,Palacios, Sara M.
-
p. 2498 - 2502
(2007/10/02)
-
- Structural studies of derivatives of methinyltricobalt enneacarbonyls. I. The crystal structure of CH3CCo3(CO)8P(C6H5) 3
-
The crystal and molecular structure of CH3CCo3(CO)8P(C6H5) 3 has been determined by three-dimensional X-ray analysis. Crystals of the compound are monoclinic, space group C2h5-P21/c, with four molecules in a cell of dimensions a = 12.19 (2), b = 16.11 (2), c = 17.19 (4) ?; β = 120.0 (1)°. X-Ray data were collected by conventional film techniques using Co Kα radiation, the intensities of 2189 independent reflections being measured photometrically. The structure has been refined isotropically by modified full-matrix least-squares techniques to a conventional R factor of 0.099. The monomeric molecular structure closely resembles the parent compound CH3CCo3(CO)9 being based on a Co3 triangle. The P(C6H5)3 unit has simply replaced one of the equatorial carbonyl groups, causing small distortions in the remainder of the molecule. Co-Co bond lengths are in the range 2.490-2.510 (6) ?.
- Brice,Penfold,Robinson, Ward T.,Taylor, Susan R.
-
p. 362 - 367
(2008/10/08)
-