1,2,3-Trithian

PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] (Vol 18) Hexamethyl-l,3,5-trithiane [828-26-2]... 

Compounds with active hydrogen add to the carbonyl group of acetone, often followed by the condensation of another molecule of the addend or loss of water. Hydrogen sulfide forms hexamethyl-l,3,5-trithiane probably through the transitory intermediate thioacetone which readily trimerizes. Hydrogen cyanide forms acetone cyanohydrin [75-86-5] (CH2)2C(OH)CN, which is further processed to methacrylates. Ammonia and hydrogen cyanide give (CH2)2C(NH2)CN [19355-69-2] ix.orn. 6<55i the widely used polymerization initiator, azobisisobutyronitrile [78-67-1] is made (4). 

Thermolysis of trithiane (69) or carbonate (70) at reduced pressure yields methylene-thiirane which is stable in cold, dilute solution (Scheme 152) (78JA7436, 78RTC214). A novel acenaphthylene episulfide is obtained by treatment of the six-membered sulfoxide (71) with acetic anhydride (Scheme 153) (68JA1676), and photolysis of (72) gives a low yield of episulfide (73 Scheme 154) (72JA521). Low yields may be due to the desulfurization of the thiiranes under the reaction conditions. 

Extension of these studies to medium rings produced interesting results (73). The mercuric acetate oxidation of 1-methyl-1-azacyclooctane (64), when worked up in the usual manner, gave no distillable material. When an equivalent amount of hydrochloric acid was added to the solution which had been saturated with hydrogen sulfide to precipitate the excess mercuric acetate and filtered, evaporation of the solution to dryness gave a solid which was subsequently identified as 2,4,6-tris(6 -methylaminohexyl)-trithiane trihydrochloride (65). Two plausible routes to the observed... 

The conformational preference of 1,3,5-trithiane-l-oxide has been determined in solution and in the solid state168. 13C and dynamic 1H NMR studies indicated that the S=0 bond is equatorial (182) in solution, as did molecular mechanics calculations. Surprisingly, the axial conformation (183) is preferred in the crystalline state. 

The molecular mechanics method314 has been applied to the calculation of conformational properties of the thiane, dithiane and trithiane oxide systems315, which are... 

The same preferences have been calculated315 and observed319 in the 1,2-dithiane oxide system. Although the chair forms are also more stable than the twist or boat in 1,3-, 1,4-dithianes and 1,3,5-trithianes, the preference of the oxygen is highly variable, depending on steric and electronic interactions. 

The addition of H2S to an aldehyde or ketone can result in a variety of products. The most usual product is the trithiane (8). ° ot-Hydroxy thiols (5) can be prepared from polychloro and polyfluoro aldehydes and ketones.Apparently, compounds 5 are stable only when prepared from these compounds, and not even for all of them. Thioketones (6) can be prepared from certain ketones, such as diaryl ketones, by treatment with H2S and an acid catalyst, usually HCl. They are often unstable and tend to trimerize (to 8) or to react with air. Thioaldehydes are even less stable and simple ones apparently have never been isolated, though t-BuCHS has been... 

This name applies to formation of 5. Names for formation of 6,7, and 8, are, respectively, thioxo-de-oxo-bisubstitution, dimercapto-de-oxo-bisubstitution, and carbonyl-trithiane transformation. 

Reaction of the anion derived from the tosyl imide of l,3,S-trithiane with alkyl iodides gives a mixture of the mono- and di- alkylated products, in which anti stereochemistry predominates. The analogous 1,3-dithiane derivative is only monoalkylated <96JCS(P1)313>. 

The anion from 1,3,5-trithiane hexaoxide has been silylated and thence converted into a sulfoxonium ylide <96CB161>. 

Chang and co-workers isolated strain Nocardia sp. CYKS2 from a dyeing industry wastewater using DBT as the sole sulfur source [27]. This strain also desulfurized DBT to the same product 2-HBP however, it had broader substrate specificity and was reported to desulfurize thiophenes, sulfides, and disulfides (Table 3) in addition to DBT. However, it did not desulfurize trithiane, thianthrene and 4,4 -thiodiphenol. The desulfurization experiments were conducted in batch with the rate reported as 0.279 mg-sulfur/L dispersion/h for DBT conversion. 

S-compounds (dibenzoth-iophene, dibenzothio-phene sulfone, thianthrene, dibenzothio-phene sulfoxide, and trithiane)... 

The resistance of the E14-S bond in cyclotrimetallathianes toward nucleophilic reagents, for example, water and alcohol,62 increases on going from the silicon compounds to the corresponding germanium and tin derivatives. This is due, most likely, to the fact that the reaction of less nucleophilic ylides with phenyl groups at the phosphorus atom with trithianes (R2MS)3 (M = Ge, Sn) occurs slowly and is impeded by several side processes. 

The pale yellow 2-diarylmethylene derivative of 1,3,5-trithiane 101 exhibits electrochromism, changing to the deep blue dication 102 upon electrochemical oxidation . 

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