Trithiolanes

Trithiolane, 3,5-dimethyl-biological activity, 6, 895 occurrence, 6, 895 reactions... 

Tile behavior of /3-moiiooxo derivatives of 4-chlomaiioiies (27) toward morpholine was rather complex (98JOC9840). Tlius, the proposed thio-ketoiie 5-sulhde intermediates 28 would dimerize into either 1,2,4,5-tetrathianes 29 in a two-step manner or to 1,3,4,5,6-oxatetrathiocins 30 by a [5 + 3] cycloaddition. Meanwhile, the formation of oxadithiins 31 and 1,2,4-trithiolanes 32 is suggestive of the disproportionation of 28 into the thioke-tones 33 and the thioketone 5 -disulhdes 34. Tlie oxadithiins 31 correspond to a Diels-Alder dimer of 33, and the 1,2,4-trithiolanes 32 correspond to cycloadducts of 33 and 34. 

Tliiobenzophenone 5-sulfide (35) was successfully generated by a cycloreversion of the 1,2,4-trithiolane 36 at 60°C or by a sulfur transfer from thiiranes to tliiobenzophenone (87JA902 97T939).Tlie thioketone 5-sulfide... 

Thiaziridines,145 thiiranes,167 and elemental sulfur168 (in the presence of Ph3P) can react with a thioketone to give thiosulfines then trapped as 1,2,4-trithiolane. 

In solution aliphatic and aromatic sulfines combine with aromatic and aliphatic thiones to yield 1,2,4-oxadithiolanes.169,170 Cycloadducts with only aromatic substituents could not be obtained, since the conjugation energy of aromatic sulfine drives the equilibrium to the reactant side.170 Thiobenzophe-none- and thiofluorenone-sulfines react with 3 to afford 1,2,4-trithiolanes.171 This is interpreted by assuming that 1,2,4-oxadithiolanes are formed in a first step, hence converted to 1,2,4-trithiolane. 

In the case of 1,2,4-trithiolanes, both els and trans isomers are obtained with a different reaction mechanism involving a molecule of thioketone and a molecule of thiosulfine.50... 

Lenthionine has the characteristic shiitake flavor. It is formed from the precursor, lentinic acid 14 by complex reactions involving a C-S lyase enzyme.30 Cyclic polysulfides occur in other Basidiomycete mushrooms (Genus Micromp-hale and Colly bid), in some red alga, and in seeds of Parkia speciosa. The latter contain lenthionine and 1,2,4-trithiolane (1,2,4-trithiacyclopentane) 17 as well as compounds with 4, 5, or 6 sulfur atoms.31 These seeds are valued in Indonesia for a unique, onion-like odor. Djenkolic acid and dichrostachinic acid S -[(2-carboxy-2-hydroxyethylsulfonyl)-methyl]cysteine are converted by a C-S lyase enzyme to cyclic polysulfides djenkolic acid yields 1,2,4-trithiolane and 1,2,4,6-tetrathiepane the latter is also formed from dichrostachinic acid.32... 

Trithiolane, see Phorate Tubaic acid, see Rotenone Valeraldehyde, see Cyclohexanol, Pentane... 

Tirey et al. (1993) evaluated the degradation of phorate at three different temperatures. When oxidized at temperatures of 200, 250, and 275 °C, the following reaction products were identified by GC/MS ethanol, ethanethiol, methyl mercaptan, 1,2,4-trithiolane, 1,1-thiobisethane, 1,1 -(methylenebis(thio))bisethane, 1,3,5-trithiane, 0,0-diethyl-5-pentenyl phosphorodithioic acid, ethylthioacetic acid, diethyl disulfide, 2,2 -dithiobisethanol, ethyl-(1-methylpropyl) disulfide, sulfur dioxide, carbon monoxide, carbon dioxide, sulfuric acid, and phosphine. 

A number of unusual cyclic polysulfides showing antibiotic activity against bacteria and fungi have been isolated from the red alga Chondria aalifomica ( ) and from the mushroom Lentinue edodes ( ). Both 34 (1,2,4,6-tetrathiepane) and 35 (1,2,3,5,6-pentathiepane or lenthionine) have been isolated from both sources, while 1,2,3,4,5,6 -hexathiepane, 36, was obtained from the mushroom and 27 (1,2,4-trithiolane), 2 (1,2,4-trithiolane 4-oxide),... 

The six possible five-membered monocyclic rings containing three oxygen or sulfur atoms in 1,2, and 4 positions are shown in (1) to (6). Examples of each ring system are known, although 1,2,4-trioxolane (1) and 1,2,4-trithiolane (2) are the only parent rings that have been synthesized and characterized. The other systems are found as derivatives of the parent ring, with 1,4,2-dioxa-thiolanes and 1,2,4-oxadithiolanes only reported in the form of S-oxides. 

With advances in technology, theoretical methods have gained importance as a powerful tool. 1,2,4-Trioxolanes have attracted the most interest, undoubtedly because of their pivotal role in the mechanism of the ozonolysis of alkenes. Apart from 1,2,4-trithiolane (2) nothing has been reported for the other five-membered rings (3)-(6) or their derivatives. 

Trioxolanes remain the most studied ring system by microwave spectroscopy and recently, 1,2,4-trithiolane also became the subject of attention. In all cases, isotopically labelled derivatives were made which have very different rotational constants. These aid assignment of structures and also provide useful tools for looking at the mechanism of the ozonolysis reaction. Rotational constants for the parent compounds and their calculated dipole moments are given in Table 3. 

Table 3 Ground state rotational constants and dipole moments for 1,2,4-trioxolanes and 1,2,4-trithiolane.

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