Tri thiocarbonates

Under similar conditions, perfluoroalkyl iodides react with alkyl phosphates to give fluorinated phosphine oxides, phosphinates, and phosphines [54 (equation 49) The product formed depends upon the stoichiometry and type of iodide used. When sodium alkyl trithiocarbonates are used as substrates, perfluoroalkyl tri-thiocarbonates ate formed [55]. 

Kohlen-schwarz, n. carbon black charcoal black, -schwefelwasserstoffsaure, /, (tri)-thiocarbonic acid (H2CS1). -spat, m. anthraconite whewellite, -spitze,/. carbon point, -staub, m. coal dust charcoal dust, -stick-stoff, m. cyanogen, -stickstoffsaure, /, car-bazotic acid (picric acid), -stoff, m. carbon,... 

Sulfkohlensaure, /. sulfocarbonic acid (tri-thiocarbonic acid) thionocarbonic acid (HOCSOH). 

In 1863 Husemann prepared an intermediate, to which he assigned the formula C2H4S, by the action of sodium sulfide on ethylene bromide. From it he obtained the cyclic dimer, dithiane, by distillation. Mans-feld (1886) reinvestigated the intermediate and concluded that it is a polymer. As a reminder of the significance of the term polymer at that time it is to be noted, however, that Mansfeld suggested the cyclic trimeric formula for the intermediate, which is now known to be a linear polymer. Other polymers prepared similarly by Husemann (1863) include methylene sulfide (—CH2—S—)a and methylene tri-thiocarbonate (—CH2—S—CS—S—) . Neither was recognized as a polymer, and neither has since been investigated from this standpoint. 

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. 

In the alditol series, examples of acetobrominolysis of O-isopropyl-idene groups of derivatives of D-mannitol and D-iditol were given by McCasland and coworkers.i . i i Thus, the D-mannitol trithioearbonate derivative 157 gave the 1,6-dibromo derivative 158 (yield 55%).160 The same bromation with ring-opening was described for the D-iditol tri-thiocarbonate analog (yield 77%). 

Referring to the cationic polymerization of spiro tetrathioorthocarbonates, a five-membered spiro compound, l,4,6,9-tetrathiaspiro[4.4)nonane (129) quantitatively gave polyethylene sulfide) with the complete extrusion of ethylene tri-thiocarbonate as found in the corresponding oxygen counterpart. [103] A six-membered spiro compound, l,5,7,ll-tetrathiaspiro[5.5]undeeane (130), did not... 

A general account of this area is available.1158 These complexes include di- and tri-thiocarbonates (OCS2, SCS2 ), unsaturated alkene systems (R2C=CS2 ), and dithiocarbimates (RN=CS ). K2CS3 can be prepared as a yellow solid by adding CS2 to an alcoholic solution of KOH which has been saturated with H2S,1159 and as a solution in DMF by adding KOH to CS "60 Relatively few cobalt complexes of these localized dithiols are known (Table 98). 

In the case of mercurated tiglic acid adducts (12), the erythro product is obtained with aqueous Na2S, and an ionic mechanism has been proposed with an intermediate carboxylate enolate (25). Sodium tri-thiocarbonate and, especially, 1,3-propanedithiol exhibit a preference for retention of configuration leading to the erythro isomer. Such sulfur-containing reagents are probably capable of intramolecular hydrogen atom delivery as illustrated schematically in (26), and they also promote demercuration by an ionic mechanism. 

The di- or tri-thiocarbonate (74.8) is cyclized by first treating it with allyloxalyl chloride to give the IV-oxalyl derivative which is not isolated in a pure state but is warmed with triethyl phosphite at 40-85 °C to give the ring system of isocephem (or iso-oxacephem) antibiotics which are synthesized by a broadly similar route. 

The episulfides (82), (83), (84), and (87) react readily with potassium methylxanthate in methanol at room temperature to give crystalline tri-thiocarbonate derivatives. Assuming attack at the primary position,the reaction from (84) may be formulated as follows. 

Aq.-alc. lead (II) acetate added dropwise to an ethanolic soln. of dodecyl mercaptan, triethylamine, and excess CSg, refluxed overnight didodecyl tri-thiocarbonate. Y 88%. Also isolation of intermediates s. M. Kiessel and D. Braun, B. 98, 1350 (1965). 

Tetrathio-D-iditol (520) has been synthesized from l,2 5,6-di-0-iso-propylidene-3,4-dithio-D-iditol 3,4-dithiocarbonate or the corresponding 3,4-tri-thiocarbonate by the sequence of reactions shown in Scheme 99. ... 

For trivially named thioacids and their Se and Te analogues the following convention holds (di, tri)thiocarbonic, thioformic, thioacetic, thioben-zoic, etc., acid systematic treatment of such acids follows from Table 8. 

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