High‐Impact Sulfur Compounds: Constitutional and Configurational Assignment of Sulfur‐Containing Heterocycles

Abstract

To unambiguously identify their structures and to evaluate their organoleptic properties, several constitutional und configurational isomers of dialkyl-tetrathianes and dialkyl-pentathiepanes were synthesized by two different synthetic protocols, and separated by preparative gas chromatography. Raman and NMR spectroscopy were used to differentiate between the constitutional 3,6-dialkyl-1,2,4,5-tetrathiane and the 4,6-dialkyl-1,2,3,5-tetrathiane isomers. Furthermore, cis- and trans-isomers of 3,6-dialkyl-1,2,4,5-tetrathianes were distinguished by temperature-dependent NMR experiments. Static, quantum-chemical simulations of the NMR spectra for these cis- and trans-isomers were calculated in the gas layer in order to confirm our experimental assignments. In addition, the assignment of 4,7-alkyl-1,2,3,5,6-pentathiepanes were deducted from their Raman spectra. Dialkyl-tetrathianes and dialkyl-pentathiepanes are interesting components to be used in flavor applications due to their unique olfactory impact and facets.

Thiosilane‐ and Organoselenosilane‐Mediated Novel Access to 3,7‐Disubstituted‐1,2,5‐ trithiepanes and ‐1,2,5‐dithiaselenepanes

“…3, 2, 3, 2, 9, 24.0, 30.9, 31.2, 32.7, 33.0, 41.2, 115.4, 137.4 3, 2, 3, 2,. A mixture of two diastereoisomers (75%); 1 H NMR (200 MHz, CDCl 3 ) δ ppm: 0.85-0.96 (m, 6H), 1.24-1.65 (m, 12H), 2.64-3.33 (m, 6H); 13 C NMR (50 MHz, CDCl 3 ) δ ppm: 13.…”

“…Found: C,61.34;H,6.34. (3S,2,. The product was purified by flash column chromatography (petroleum ether/diethyl ether 15:1) to give 2g.…”

“…2,50.2,70.1,73.2,127.7,128.1,128.4,137.8;MS m/z (%): 392 (M + ·, 2), 301 (1), 284 (1), 195 (2), 147 (9), 105 (5), 91 (100).…”

“…2,34.3,46.8,47.1,71.7,72.1,117.1,134.6;MS m/z (%): 292 (M + ·, 2), 235 (32), 177 (8), 105 (18), 97 (100), 73 (64), 55 (71). (1,2,bis(methylene) Dibutyrate (2i).…”

“…Polysulfurated heterocycles represent as well an interesting class of compounds for their physical and chemical properties and synthetic utility [2]. Several cyclic polysulfides of different ring size have been isolated from marine bacteria, and a profile of the pharmaceutical and agrochemical properties was investigated [3].…”