Unsaturated Thiacrown Ethers:  Synthesis, Physical Properties, and Formation of a Silver Complex

Abstract

The 6-, 9-, 12-, 15-, 18-, 21-, 24-, and 27-membered unsaturated thiacrown ethers 1-8 were formed by reaction of cis-1,2-dichloroethylene with sodium sulfide in acetonitrile. Crystal structures of 4-8 were determined by X-ray crystallography, and it was found that all sulfur atoms of 5-8 direct to the inside of the ring (endodentate). All of the ORTEP drawings show that there are cavities in these molecules, and the cavity sizes in 4-8 were 1.76, 2.34, 3.48, 4.43, and 5.36 A, respectively. The UV spectra of 4-8 showed absorption maximums at the range of 255-276 nm in acetonitrile, and the absorption maximums of 4-8 were found to shift to longer wavelengths by changing the solvent from acetonitrile to cyclohexane. The cyclic voltammograms of 4-8 indicate that the larger unsaturated thiacrown ethers were oxidized more easily than the smaller systems, and unsaturated thiacrown ethers were oxidized more easily than corresponding saturated systems. The reaction of 4 with silver trifluoroacetate in acetone afforded the colorless complex Ag(I)(C2H2S)5(CF3COO) 9. The crystal structure of 9 was determined by X-ray analysis, and it was found that three of the five sulfur atoms bonded to the silver atom.

Molecular Transformations of Unsaturated Thiacrown Ethers

“…Three sulfur atoms of 4 are oriented to the inside of the ring (endodentate) in the crystalline state similar to the crystal structure of 1. 8 The bond lengths and angles of 4 are almost normal. The bond length of S(1)-O(1) and angles of O(1)-S(1)-C(1) and O(1)-S(1)-C(10) of 4 are 1.50 Å and 106.5°and 105.9°, respectively, and the S-C and CdC bond lengths and the C-S-C and S-C-C angles of 4 (S-C: 1.74-1.77 Å; CdC: 1.33-1.34 Å; C-S-C: 99.5-106.6°; S-C-C: 121.7-132.0°) are almost the same as those of 1.…”

Unique effects of sulfur and water on the syntheses of thiaheterocycles

“…On the contrary, halogenated alkenes or alkynes treated with inorganic sulfides also produced desirable thiaheterocyclic compounds [10][11][12][13]. Especially in recent years, important progress has been achieved in the research on unsaturated thiacrown ethers [14,15], which have been studied in a variety of fields [16][17][18][19][20][21][22][23]. However, many reactions were carried out with the participation of catalysts or additives and usually under rigorous conditions.…”

Synthesis, structure, and complexation behavior of 14‐ and 28‐membered partially unsaturated thiacrown ethers

“…• C in dimethyl sulfoxide (DMSO)-d 6 to show new signals on the 1 H NMR spectra assignable to Z-E-isomerized products 7 and 8 and ring-reduced seven-membered cyclic compound 9. The changes in the 1 H NMR spectra of the olefin protons of 3 are shown in Fig.…”