Über die Einwirkung von Verbindungen der Diazomethan‐Reihe auf Thionester. Über eine Synthese von Keten‐mercaptolen, ‐acetalchloriden und ‐thioacetalchloriden. Diphenyl‐diazomethan als „freies Radikal”︁

Thiiranes

“…Chloro-substituted aromatic thiiranes were obtained by conversion of aromatically substituted diazoalkanes with thiocarboxylic acid chlorides, thiophosgene, di- The following thiiranes were synthesized: Ar = CeH8, R = Cl and C6H6 (224); R = OC6H5 and SC6H6 (196); Ar, Ar = diphenylene, R = Cl and Cells ( 224), R = OCeHsand SC6H5 (195). The use of trithiocarbonates in an analogous process resulted in thiirane disulfides.…”

“…The use of trithiocarbonates in an analogous process resulted in thiirane disulfides. The synthesis covered: Ar = CeH6, R = C6H6 (195); Ar = p-CH3C6H4, R = p-CH3C6H4 ( 95).…”

“…Thiiranes were not obtained from the conversion of phenylbenzoyldiazomethane with thiophosgene, ethyl diazoacetate with thiobenzoyl chloride (224), diphenyldiazomethane with thiourea, thiobenzamide, ethyl dithiobenzoate, carbon disulfide, and phenylisothiocyanate ( 223), and from diazofluorene with phenylthiocarbonyl chloride (195).…”

Cleavage of the Carbon-Sulfur Bond in Divalent Sulfur Compounds.

“…c6h6 c6h6 at reflux temperatures; at lower temperatures the sulfide polymerizes, and apparently the alkylation reaction involves interaction of the polymer with benzene (399). Tetraarylethylene sulfides and some diarylethylene sulfides containing other negative groups lose sulfur on heating to about 200°C., or at much lower temperatures when heated with copper bronze (e.g., 356,364,365,393,394), the reaction leading in some cases to interesting ketene acetal derivatives. R R The driving force for the reaction is undoubtedly the tendency to form a conjugated system with the aromatic nuclei.…”

Thermal transformations of organic compounds of divalent sulfur

“…Thermal transformations of organic compounds of divalent sulfur 3-Chloro-2,2-diphenyl-3-X-thiiranes also cyclise into the corresponding benzothiophenes on heating. 128,129 Tetrafluorothiirane is distinguished by its high thermal stability. Its partial conversion into difluorothioformaldehyde, tetrafluoroethylene and a number of other products takes place only at 430 8C.…”