Thiolane-1,1-dioxide

A long-range proton coupling, which was found to be transmitted by a sulfone group in thiolane dioxide systems292, is apparently facilitated by a nonbonding p-orbital on one of the sulfone oxygen atoms. This phenomenon is of interest for saturated cyclic systems. 

Thio-Claisen rearrangement 746-748 Thioketene 5-oxides photolysis of 878 reactions of 277 Thiolane dioxides formula of 382 NMR spectra of 460 reactions of 604 synthesis of 461 Thiolane oxides 747 formula of 382 IR spectra of 461 synthesis of 461, 462, 752 Thiolanes, photolysis of 881 Thiolene dioxides formula of 382 NMR spectra of 460 reactions of 464, 465 synthesis of 461 Thiolene oxides formula of 382 synthesis of 461, 746 Thiols... 

Catalytic hydrogenation of thiolene 1,1-dioxides to thiolane 1,1-dioxides 97UK463. 

Similarly, the most common method of preparing the substituted, fully unsaturated thiolane system, e.g. thiophene dioxides, is by direct oxidation of the readily available substituted thiophenes with hydrogen peroxide, perbenzoic acid and m-chloroperbenzoic acid280 283. Alternatively, thiophene dioxides are conveniently prepared via the double elimination methodology280 305 illustrated in equation 117. 

A few studies have been carried out on the parent four- and five-membered cyclic sulfones—for thietane 1,1-dioxide (30) by Scala and Colon65 and for thiolane 1,1-dioxide (sulfolane) (31) by Honda and coworkers66 and, later, by Schuchmann and von Sonntag67. In the former compound, the major photochemical process, in the vacuum UV range, is the initial production of a trimethylene (C3H6) biradical and S02 (equation 9). In both the solid- (77 K) and gas-phase photolyses, formation of a triplet biradical appears to be favored. As well as the expected cyclopropane and propylene, ethylene is also obtained during these photolyses, presumably by a cycloreversion process (equation 10). 

The order of decreasing Lewis basicity toward trimethylaluminum is thiane, thiolane, diethyl (or dimethyl) sulfide, thietane and 2-methylthiirane (67IC1461). Thietane can be protonated at -60 °C with fluorosulfonic acid in antimony pentafluoride-liquid sulfur dioxide the NMR spectrum shows bands at 8 7.40 (S—H) and 3.20-4.40 p.p.m. (C—H) (71JOC1121). 

Trivial names which have found use in this article are thiolane (for tetrahydrothiophene), sulfolane (for tetrahydrothiophene 1,1-dioxide) and sulfolene (for 2,5-dihydrothiophene 1,1-dioxide). As with usual practice, thienyl refers to the radical corresponding to phenyl in benzene chemistry, and thenyl is analogous to benzyl . 

Simple sulfolanes (thiolane 1-dioxides, tetrahydrothiophene 1,1-dioxides, 5) show a more uniform mode of fragmentation into a one- and 2 two-membered fragments they are cleaved into sulfur dioxide and two alkenes [75JOC1842 94JCS(P1)2301].1... 

AGstrain, 7, 419 (75JA5167, 79MI51400) lA6-Thiolane 1,1-dioxide 13C NMR, 7, 414 (80JOC4807)... 

To determine the three-dimensional structure of iV-phenylthiolano[3,4-rf]thiazolidine-2-thione 5,5-dioxide (13), an X-ray diffraction study was carried out. The thiazolidine ring is planar, while the thiolane ring has an envelope configuration, presumably the result of the effect of the thiazolidine ring portion (82CHE668). 

Treatment of the substituted aminosulfolene (253) with phenyl isothiocyanate in refluxing benzene-pyridine (2 1) gave the perhydrothieno[3,4-rf]imidazole-2-thione 5,5-dioxide (254) (82CHE328). Reaction of 4-halo-2-thiolene (or -thiolane) 1,1-dioxides with dithiocarbamates proceeded similarly to give perhydrothieno[3,4-[Pg.1011]

The overall reversibility of the process was shown by the recovery of 2-octanone when 2,2-bis(difluoroamino)octane was shaken with H2S04 at room temperature for 1 hr (17). In the presence of strong acids, aldehydes (RCHO) react to give bis(a-difluoroaminoalkyl)ethers [RCH-(NF2)OCH(NF2)R, 50-60% yield], and gem-bis(difluoroamino)alkanes [RCH(NF2)2, 20-40% yield] (108, 109). The reactions of HNF2 with a-hydroxyketones and a-/ -diketones in fuming sulfuric acid lead to difluoroamino-l,3-dioxa-2-thiolane-2,2-dioxides (215). 

Oxa-tricydo 4.3.2.0, undec-IO-ene E17f, 742 (2-Cl-tricycl.-thiolan-S,S-dioxid/ROR)... 

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