Carbon oxysulfide

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 ... 

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.

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... 

In the reaction of 1 with carbon oxysulfide, the dithiadisiletane 61 was isolated. Here, the corresponding intermediate loses carbon monoxide to... 

The meso-ionic 1,3-oxazol-S-ones show an incredible array of cycloaddition reactions. Reference has already been made to the cycloaddition reactions of the derivative 50, which are interpreted as involving cycloaddition to the valence tautomer 51. In addition, an extremely comprehensive study of the 1,3-dipolar cycloaddition reactions of meso-ionic l,3-oxazol-5-ones (66) has been undertaken by Huisgen and his co-workers. The 1,3-dipolarophiles that have been examined include alkenes, alkynes, aldehydes, a-keto esters, a-diketones, thiobenzophenone, thiono esters, carbon oxysulfide, carbon disulfide, nitriles, nitro-, nitroso-, and azo-compounds, and cyclopropane and cyclobutene derivatives. In these reactions the l,3-oxazol-5-ones (66)... 

The method described is adapted from the procedures of Kym 3 and Engelhardt, Latschinoff, and Malyscheff.4 Thio-benzoic acid has been prepared by the reaction of benzoyl chloride with potassium sulfide,4 hydrogen sulfide in pyridine,6 6 and magnesium bromide hydrosulfide.7 It is formed from dibenzoyl disulfide with potassium hydrosulfide,4 potassium hydroxide,4 8 and ammonia.9 It is also formed from dibenzoyl sulfide, from phenyl benzoate, and from benzoic anhydride with alcoholic potassium hydrosulfide.4 It has been obtained from dibenzoyl sulfide and hydrogen sulfide,10 carbon oxysulfide and phenyl-magnesium bromide,11 12 dibenzyl disulfide and sodium ethoxide,13 benzyl chloride and sulfur in the presence of potassium hydroxide,14 and benzylthiosulfuric acid and alkali.18 16... 

Heating cyclic mono-, di- or tri-thiocarbonates, usually in the presence of base, gives thiiranes and carbon dioxide, carbon oxysulfide or carbon disulfide respectively. The methiodide salts of 2-methylimino-l,3-oxathiolanes are converted to thiiranes with high stereoselectivity, except for 5-aryl-substituted oxathiolanes (Scheme 146) (80LA1779). Flash vacuum thermolysis of l,3-oxathiolan-5-ones causes loss of carbon dioxide and nearly quantitative formation of thiiranes of inverted configuration (Scheme 147) (80JA744). For example, thermolysis of c/s-2,4-diphenyl-1,3-oxathiolan-5-one gives trans-2,4-diphenyl-thiirane. 

An example of the use of carbon oxysulfide is the reported preparation of aliphatic polyureas. 

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