P-carbonyl sulfide

The highly ionic thaHic nitrate, which is soluble in alcohols, ethers, and carboxyhc acids, is also a very useful synthetic reagent. Oxidation of olefins, a,P-unsaturated carbonyl compounds, P-carbonyl sulfides, and a-nitrato ketones can aH be conveniently carried out in good yields (31,34—36). 

The Gassman indole synthesis involves an one-pot process in which hypohalite, a P-carbonyl sulfide derivative 2, and a base are added sequentially to an aniline or a substituted aniline 1 to provide 3-thioalkoxyindoles 3. Raney nickel-mediated desulfurization of 3 then produces the parent indole... 

Vargas RR, BecharaEJH, Marzorati L, Wladislaw B (1999) Asymmetric Sulfoxidation of a P-Carbonyl Sulfide Series by Chloroperoxidase. Tetrahedron Asym 10 3219... 

Health and Safety Factors. Carbonyl sulfide is dangerously poisonous, more so because it is practically odorless when pure. It is lethal to rats at 2900 ppm. Studies show an LD q (rat, ip) of 22.5 mg/kg. The mechanism of toxic action appears to iavolve breakdowa to hydrogea sulfide (36). It acts principally on the central nervous system with death resulting mainly from respiratory paralysis. Little is known regarding the health effects of subacute or chronic exposure to carbonyl sulfide a 400-p.g/m max level has been suggested until more data are available (37). Carbon oxysulfide has a reported inhalation toxicity in mice LD q (mouse) = 2900 ppm (37). 

Nitro sulfides are conveniently prepared by simply mixing carbonyl compounds, nitroal-kanes, and thiols in the presence of triethylamine.2 P-Nitro sulfide, which is used for synthesis of rf-biotin, is prepared by this procedure (Eq. 4.2).3... 

Peyton, T.O., Steel, R.V.,andMabey, W.R. Carbon disulfide, carbonyl sulfide literature review and environmental assessment, U.S. EPA Report PB-257-947/2,1976, 64 p. 

Zander, R., C. P. Rinsland, C. B. Farmer, J. Namkung, R. H. Norton, and J. M. Russell III, Concentrations of Carbonyl Sulfide and Hydrogen Cyanide in the Free Upper Troposphere and Lower Stratosphere Deduced from ATMOS/Spacelab 3 Infrared Solar Occultation Spectra, . /. Geophys. Res., 93, 1669-1678(1988). 

Kourtidis, K. A., R. Borchers, P. Fabian, and J. Harnisch, Carbonyl Sulfide (COS) Measurements in the Arctic Polar Vortex, Geophys. Res. Lett, 22, 393-396 (1995). 

To a heavy-walled, 2 liter suction flask is added a suspension of 9.3 gm (0.10 mole) of aniline in 150 ml of water containing 10 ml (0.088 mole) of 30% hydrogen peroxide. The flask is placed under reduced pressure and then pressurized to 5 psi with carbonyl sulfide. A snug-fitting rubber stopper and the clamped rubber tubing were sufficient to hold the pressure for 24 hr. The solid product precipitated and was isolated to yield 9.0 gm, m.p. 231°-232°C. 

Chengelis, C.P., and R.A. Neal. Studies of carbonyl sulfide toxicity Metabolism by carbonic anhydrase. Toxicol. Appl. Pharmacol. 55 198-202, 1980. 

Kettle A. J., Kuhn U., von Hobe M., Kesselmeier J., Liss P. S., and Andreae M. O. (2002) Comparing forward and inverse models to estimate the seasonal variation of hemisphere-integrated fluxes of carbonyl sulfide. Atmos. Chem. Phys. 2, 343-361. 

CO2 analogues such as allenes, ketenes, isocyanates, carbodiimides, and carbonyl sulfide also insert. Studies of insertion reactions of Cp2ZrR2 (R = Me, CH2Ph, Ph) show that the ease of insertion follows the series Me > Py CH2Ph and Ph2C=C=0>PhN=C=0>p-MeC6H4N=C=NC6H4Me-p>C02. The data have been reasonably interpreted as evidence for precoordination before insertion occurs. A four-center transition state similar to that depicted above for the thorium system is favored. 

The Wittig-Homer reaction between C-metallated a-phosphoryl sulfides and carbonyl compounds provides a common route to a,P-unsaturated sulfides, but one which usually results in poor yields of the desired product when enolisable ketones are used. Stephan et al. have investigated the role of boron trifluoride in promoting the Wittig-Horner reaction of enolisable ketones, which usually follows a two-step process the initial condensation of the anion followed by an elimination step. It was found that when the second step occurred at a slow rate then addition of boron triflouride was necessary for completion. ... 

P.S. Weiss, S.S. Andrews, J.E. Johnson, O.C. Zafiriou (1995). Photoproduction of carbonyl sulfide in South Pacific Ocean waters as a function of irradiation wavelength. Geophys. Res. Lett., 22, 215-218. 

Limited information is available on the biotransformation of carbon disulfide in humans, and the metabolic products of carbon disulfide are not completely known. In animals and humans the proposed metabolic pathways involved in the metabolism of carbon disulfide (Beauchamp et al. 1983) are depicted in Figure 2-3, reactions i-x. Reaction i has been demonstrated in in vivo animal studies and in in vitro assays. Reactions ii-v are proven by in vitro studies, while products of reactions vi-ix are the results of proposed metabolic pathways of carbon disulfide in animals and humans. Carbon disulfide is metabolized by cytochrome P-450 to an unstable oxygen intermediate (reaction i). The intermediate may either spontaneously degrade to atomic sulfur and carbonyl sulfide (reaction ii) or hydrolyze to form atomic sulfur and monothiocarbonate (reaction iii). The atomic sulfur generated in these reactions may either covalently bind to macromolecules (reaction iv) or be oxidized to products such as sulfate (reaction v). 

The metabolic formation of carbonyl sulfide from carbon disulfide was confirmed in an in vivo study (Dalvi and Neal 1978). After intraperitoneal injection of 14C-carbon disulfide in nonpretreated rats, carbonyl sulfide was excreted by the lung in greater quantities than carbon dioxide. Pretreatment with phenobarbital, however, resulted in a greater amount of excretion of carbon dioxide than carbonyl sulfide. In both experiments, excretion of 14C-carbonyl sulfide and carbon dioxide accounted for 14-43% of the total administered radioactivity, with about twice as much carbon dioxide. These results indicate that phenobarbital treatment caused induction of cytochrome P-450 which catalyzed the conversion of carbon disulfide to carbonyl sulfide faster in pretreated rats than in rats not pretreated with phenobarbital. The role of the cytochrome P-450 monooxygenase system in catalyzing carbonyl sulfide formation was also confirmed by in vitro studies (Dalvi et al. 1974, 1975). The rate of carbonyl sulfide formation was NADPH-dependent and increased with microsomes obtained from phenobarbital-treated rats. 

Hanst, P.L., L.L. Speller, D.M. Watts, J.W. Spence, and F.M. Miller, Infrared measurements of fluorocarbons, carbon tetrachloride, carbonyl sulfide, and other atmospheric trace gases. Air Pollution Control Assn J 24, 12, 1220, 1975. 

Maroulis, P.J., A.L. Torres, and A.R. Bandy, Atmospheric concentrations of carbonyl sulfide in the south-western and eastern United States. Geophys Res Lett 4, 510, 1977. 

Rinsland, C.P., R. Zander, E. Mahieu, P. Demoulin, A. Goldman, D. Ehhalt, and J. Rudolph, Ground-based infrared measurements of carbonyl sulfide total column abundances Long-term trends and variability. J Geophys Res 97, 5995, 1992. 

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