Oxysulfides

Red-emitting Y202S Eu3+ phosphors were developed especially for excitation with cathode rays [5.345], [5.346]. Production generally starts from mixed rare-earth oxides, which are fired with sodium carbonate and sulfur. The polysulfide formed 

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This type of synthesis, which was investigated by Cook and Heilbron (323) and Takahashi (393, 394) between 1947 and 1953, gives 5-aminothiazoles variously substituted in the 2-position by reacting an aminonitrile with salts and esters of dithioacids, carbon disulfide, carbon oxysulfide, and isothiocyanates under exceptionally mild conditions. 

By condensing carbon oxysulfide with o-aminOnitriles the corresponding 2-hydroxy-5-aminothiazoles can be obtained. In the presence of benzaldehyde or its substituted derivatives the reaction leads to 5-benzy-lideneaminothiazole derivatives (218) in good yields (Scheme 114 and Table 11.35) (393, 442). However, the reaction fails with or-amino acetonitrile (206), R = H (317). The 2-alkoxy analogs (220), R = Me, Et, Pr, Bu, vinyl, were similarly obtained from 219 and benzylideneamino acetonitrile (Scheme 115a) (393). 

Reactions were carried out by condensing the o-aminoacetonitrile with carbon oxysulfide in the presence of benzaldehyde or its substituted derivatives, in aicoho) as solvent. 

The reaction of ethyleneimine (and detivatives) with carbon oxysulfide yields 2-thiazohdinone [2682-49-7J (256,257). Carbon disulfide and ethyleneimine react to give 2-thiothia2ohdine (258—260). Carbon diselenide reacts with azitidines to form 2-selena2obdineselenones (261). 

Physica.1 Properties. Carbonyl sulfide [463-58-1] (carbon oxysulfide), COS, is a colorless gas that is odorless when pure however, it has been described as having a foul odor. Physical constants and thermodynamic properties are Hsted ia Table 1 (17,18). The vapor pressure has been fitted to an equation, and a detailed study has been made of the phase equiUbria of the carbonyl sulfide—propane system, which is important ia the purification of propane fuel (19,20). Carbonyl sulfide can be adsorbed on molecular sieves (qv) as a means for removal from propane (21). This approach has been compared to the use of various solvents and reagents (22). 

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). 

Carbon disulfide is essentially unreactive with water at room temperature, but above about 150°C in the vapor phase some reaction occurs forming carbonyl sulfide (carbon oxysulfide) [463-58-1] and hydrogen sulfide [7783-06-4]. Carbonyl sulfide is an intermediate in the hydrolysis reaction ... 

Cerium(III) oxysulfide [12442-45-4], is a high melting stable compound that precipitates out when steel is treated with a cerium-based metal... 

Va.t, or Agitated Leeching. Vat or agitated leaching usually extracts copper from oxide or mixed oxysulfide ores containing more... 

Upon thermolysis of xanthates (xanthogenates) 1 olefins 2 can be obtained, together with gaseous carbon oxysulfide COS 3 and a thiol RSH 4. This decomposition process is called the Chugaev reactionanother common transcription for the name of its discoverer is Tschugaejf. 

Kohlen-ozydvergiftung, /. carbon monoxide poisoning, -oxysulfid, n, carbon oxysulfide. -papier, n. carbon paper, -pres (s)stein, m, coal briquet, -puWer, n, coal powder, powdered coal charcoal powder, powdered charcoal, -puppe, /, (Elec.) carbon rod, -riick-stand, m. carbon residue, -sandstein, m. carboniferous sandstone. 

Radial distribution curves for carbon disulfide and carbon oxysulfide (treated by the usual method by Cross and Brockway11) are shown in Fig. 5. For carbon disulfide the maxima of the two peaks occur at 1.60 and 3.07 A. In this symmetrical linear molecule the C-S distance is just one-half the S-S distance the values found deviate from this ratio by 4%. Similarly in carbon oxysulfide the sum of two interatomic distances equals the third. The values C-S = 1.60 A. and O-S = 2.70 A. given by the two maxima differ by 1.10 A. 

Fig. B.—Radial distribution curves for carbon disulfide and carbon oxysulfide.

Treatment of the rhenium sulfide chlorides with an excess of chlorine at temperatures above 450°C results in formation of ReCls 140). Reduction between 350 and 500°C gives binary rhenium chalcogenides 139,262). Action of water vapor on rhenium sulfide chlorides at 350-500°C produces oxysulfides 139). 

Mild Y, Nakazato D, Ikuta H, Uchida T, Wakihara M (1995) Amorphous M0S2 as the cathode of Uthium secondary batteries. J Power Sources 54 508-510 Yufit V, Nathan M, Golodnitsky D, Peled E (2003) Thin-fihn Uthium and Uthium-ion batteries with electrochemicaUy deposited molybdenum oxysulfide cathodes. J Power Sources 122 169-173... 

Further, tungsten oxysulfide films, WOyS, have shown promising behavior as positive electrodes in microbatteries, unlike WS2 that is not suitable as cathode in lithium cells. Using amorphous thin films of WO1.05S2 and WO1.35S2.2 in the cell Li/LiAsFe, 1 M ethyl-methyl sulfone (EMS)/W03,Sz, Martin-Litas et al. [80] obtained current densities up to 37 xA cm between 1.6 and 3 V. In these cathode materials, 0.6 and 0.8 lithium per formula unit, respectively, could be intercalated and de-intercalated reversibly. 

Gonbeau D, Guimon C, Pfister-Guillouzo G, Levasseur A, Meunier G, Dormoy R (1991) XPS study of thin films of titanium oxysulfides. Surface Sci 254 81-89... 

Schmidt E, Meunier G, Levasseur A (1995) Electrochemical properties of new amorphous molybdenum oxysulfide thin films. Solid State Ionics 76 243-247... 

Carbomethoxybenzaldehyde, 30, 100 Carbon disulfide, 30, 57 Carbon oxysulfide, 32, 103 Carbon tetrachloride, 32, 27 Carbonylation, of pyrogallol-1,3-di-methyl ether with hexamethylenetetramine, 31, 92... 

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