Thiete dioxides rearrangement

Thermolysis of Thiet Dioxides, In the vapour phase at 400 °C or in solution at 220 °C, thiet 1,1-dioxide (80) gave the cyclic sulphinate (81), the intermediate vinylsulphene in this rearrangement (Scheme 12) being... 

Thiabicyclo[3.1.0]hex-3-ene synthesis, 4, 784 9-Thiabicyclo[3.3.1]nonane 9,9-dioxide bond angles, 7, 409 5-Thiabicyclo-2-pentene, 1,2,3,4-tetrakis(trifiuoromethyl)-rearrangement, 7, 153 2H-l,2-Thiaborin dibenzo fused, 1, 658 1-Thia[2.2.2]cyclazines, 4, 479 5-Thia[2.3.3]cyclazines, 4, 481 Thiacyclobutadienes — see lH-1 A -Thietes... 

Mass spectrometry was applied in conjunction with thermolysis studies leading mainly to sulfines and rearranged products with four-membered sulfoxides and to a loss of sulfur dioxide with sulfones The fragmentation pattern of thietes under electron impact can be explained by the sequential loss of the elements of sulfur monoxide and oxygen from an intervening cyclic sulfmate intermediate . ... 

Dittmer et al. to be as shown in Scheme 13. The final product 223 resulting from intermediate 224 via CO expulsion and subsequent proton rearrangement is more likely than the reverse-reaction sequence. Thiete 1,1-dioxide... 

An iron tetracarbonyl complex (295) ° and a platinum bis(triphenylphosphine) complex of thiete 1,1-dioxide have been prepared. Platinum complexes of 3-phenyl- and 3-(p-bromophenyl) thiete 1,1-dioxide also have been prepared. No complex was obtained with the 3-t-butyl derivative. The pale-yellow, crystalline iron complex decomposes in refluxing hexane in the presence of excess sulfone to Fe2S2(CO)9, indicating a drastic structural rearrangement. Other carbon-containing fragments were not observed. The bis(triphenylarsine)platinum complex of 3-02-bromophenyl) thiete sulfone is decomposed photochemically to the thiete sulfone. The same result is achieved on treatment of the complex with tetra-cyanoethylene. ... 

Reactions.—Condensation of thiet sulphone with 2 moles of halogeno-hydrazones, RC(Cl)=NNHPh, gives isoimidazoles (113). Cycloaddition of thiet sulphone to cyclopentadiene occurs with an exofendo ratio of 0.25. 2,4-Diphenylthiet dioxide is hydrolysed to dibenzyl sulphone with base, but rearranges to the isomeric sulphinate 3,5-diphenyl-1,2-oxathiolen 2-oxide with concentrated sulphuric acid. Treatment of 4-phenyl-2i/-thiet 1,1-dioxide with KOH in ethanol gives 3-ethoxy-2-phenylthietan 1,1 -dioxide. ... 

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