Cyclic Polysulfides Research Articles

Vibrational Spectra of Some Cyclic Polysulfides

Vibrational spectra and normal-coordinate analyses using a modified Urey-Bradley force field are reported for 1,2,3,5,6-pentathiepane (lenthionine), 1,3,5,7-tetrathiocane, and 1,2,3-trithiane. Characteristic Raman bands are identified for S-CH2-S and S-S-S functionalities in cyclic molecules.

Radical Ions, 78 [1, 2] The Oxidative Desulfuration of Organic Cyclic Polysulfides to Disulfide Radical Cations in AlCl3 /H2 CCl2 Solution

Organodisulfide radical cations R2S2'® and R2C2S2'® can be generated from aliphatic as well as aromatic cyclic polysulfides in A1C13/H2CC12 solutions and characterized by their ESR spectra. Examples presented are the oxidations of 1,2,3-trithiolanes to 1,2-dithiolane radical cations, in which energetically favored planarized 3 electron/2 center bonds - S a r e formed.

Structure-activity relationship of stress-inducing odorants in the rat

The stress for 12 sulfur-containing synthetized volatiles was evaluated in male Wistar rats and compared to that for fox-dropping extract concentrate. Stress behavior was analyzed by quantifying various stress responses in a standard open field and measuring the increase in plasma corticosterone concentration. Nine compounds induced stress-a dihydrothiazole, two cyclic polysulfides, five mercaptoketones, and a mercaptan. For the mercaptoketones, the following structure-activity relationships were observed. Size can vary considerably; the mercapto group can be either alpha or beta and either secondary or tertiary. The keto group is not essential, since a structurally related mercaptan remains active. The mercapto group is essential for activity in mercaptoketones, since conversion to a methyl sulfide resulted in a neutral response. This type of odorant could function as an allomone and may have potential in rat control as an area repellent.

Synthesis of cyclic polysulfides by the reaction of trimethylvinylsilane with S8 in the presence of Fe3(CO)12

Reaction of trimethylvinylsilane with S8 in the presence of Fe3(CO)12 yielded the following compounds: S2Fe2(CO)6, S2Fe3(CO)9, 1-trimethylsilyl-2,3,4,5,6-pentathiacycloheptane, 1,4-di(trimethylsilyl)-2,3,6-trithiacycloheptane, 1,4-di(trimethylsilyl)-2,3,6,7-tetrathiacyclooctane. An X-ray analysis was performed for the two latter polysulfides.

Collisional activation study of cyclic polysulfides

AbstractCyclic polysulfides isolated from higher plants, model compounds and their electron impact induced fragment ions have been investigated by various mass spectrometric methods. These species represent three sets of sulfur compounds: C3H6Sx (x=1−6), C2H4Sx (x=1−5) and CH2Sx (x=1−4). Three general fragmentation mechanisms are discussed using metastable transitions: (1) the unimolecular loss of structural parts (CH2S, CH2 and Sx); (2) fragmentations which involve ring opening reactions, hydrogen migrations and recyclizations of the product ions ([MCH3]+, [MCH3S]+, [MSH]+ and [MCS2]+˙); and (3) complete rearrangements preceding the fragmentations ([MS2H]+ and [MC2H4]+˙). The cyclic structures of [M]+˙ and of specific fragment ions have been investigated by comparing the collisional activation spectra of model ions. On the basis of these results the cyclic ions decompose via linear intermediates and then recyclizations of the product ions occur. The stabilities of the fragment ions have been determined by electron efficiency vs electron energy curves.

Reactions of olefins with elementary sulfur in the presence of triiron dodecacarbonyl

1. Dithiolane diiron hexacarbonyl complexes are formed in the reaction of S8 with Fe3(CO)12 in the presence of cyclohexene or 1-hexene. When cyclohexene is used, sulfur atoms are incorporated at the double bond to give cyclic polysulfides. 2. The structure of thiotriiron decarbonyl was investigated by means of x-ray diffraction analysis.

A simple, efficient synthesis of lenthionine and 1,2,4,6-tetrathiepane from dimethyl disulfide

A synthetic route to the important cyclic polysulfide, lenthlonine, and a related natural product is outlined.

Fluorinated Cyclic Polysulfides and Their Polymers

Fluorinated Cyclic Polysulfides and Their Polymers

The Reaction of Sulfur and Sulfur Compounds with Olefinic Substances. Part IX. The Reaction of Sulfur with 2,6-Dimethylocta-2,6-Diene

Abstract Farmer and Shipley showed that reaction of sulfur with 2,6-dimethylocta-2,6-diene (I) at 140° yields a cyclic monosulfide and a crosslinked polysulfide. No detailed investigation of the structures of these cyclic monosulfide or polysulfide products was undertaken, but it was deduced that the former contained 6-ethyl-2,2,6-trimethylthiaeyclohex-3-ene (VIII) and a compound having vinylidene unsaturation, CH2:CRR′, as apparently revealed by the infrared spectrum, and this has formed part of the evidence on which broad mechanistic conclusions have been based. This reaction has now been re-examined in greater detail; the compositions of the cyclic sulfide and crosslinked polysulfide fractions and their variation with time of reaction have been determined. Results and conclusions differing in important respects from those advanced by the earlier workers have been reached, as reported preliminarily elsewhere.