Cesium dithiolate based syntheses of keto-functionalized thio-crown ethers employing the novel building block 1,3-dimercaptoacetone. Molecular structures of 2,5,9,12-tetrathia-7-oxo-(13)-m-benzenophane and 1,4,7,10,13-pentathiacyclohexadecan-15-one

• Published in: Journal of organic chemistry Vol. 58; no. 21; pp. 5624 - 5627
• Main Authors: Edema, Jilles J. H, Buter, Jan, Schoonbeek, Franck S, Meetsma, Auke, van Bolhuis, Fre, Kellogg, Richard M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.10.1993; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Organic compounds; Physical Sciences; Physics; Preparations and properties; Science & Technology; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; 1,3,6,9,11,14-HEXATHIACYCLOHEXADECANE 16S6; 1,4,7-TRITHIACYCLONONANE; THIOETHER CHEMISTRY; MACROCYCLIC COMPLEXES; 2,5,8-TRITHIA -ORTHO-BENZENOPHANE TT OB; SILVER(I) COMPLEXES; COORDINATION; CRYSTAL; LIGAND; UNITS; Cesium Carbonates; Molecular structure; Thiolate; Experimental study; X ray diffraction; Macrocycle; Sulfur crown compound; Sulfur heterocycle; Cyclization; Bicyclic compound; Aromatic compound; DMF; Crystalline structure
• DOI: 10.1021/jo00073a019
• ISSN: 0022-3263

Cyclization of the bis cesium thiolate (generated in situ) of 1,3-dimercaptoacetone (1) with alpha,omega-dihalides in DMF affords the corresponding cyclic thioethers in good yields, providing an efficient alternative route to keto-functionalized thio-crown ethers. A previously suggested dimeric structure for 1 is supported by NMR spectra, which also allow distinction between cis and trans isomers of 1. Equilibration between the isomers can also be followed by NMR. The molecular structures of two specific thio-crown ethers have been determined by X-ray crystallography. Crystal data for 2,5,9,12-tetrathia-7-oxo-(13)-m-benzenophane (8) at 130 K: triclinic, space group P-1; a = 7.230(1) angstrom, b = 8.690(1) angstrom, c = 13.253(1) angstrom, alpha = 83.153(7)-degrees, beta = 84.257(6)-degrees, gamma = 85.575(6)-gamma, Z = 2, mu(Mo Kalpha) = 5.5 cm-1, R = 0.029 (R(w) = 0.041) for 3082 reflections (I greater-than-or-equal-to 2.5sigma(I)). Crystal data for 1,4,7,10,13-pentathiacyclohexadecan-15-one (9) at 140 K: monoclinic, space group P2(1)/a; a = 16.558(1) angstrom, b = 5.399(1) angstrom, c = 16.734(1) angstrom, beta = 90.28(5)-degrees, Z = 4, mu(Mo Kalpha) = 7.3 cm-1, R = 0.048 (R(w) = 0.66) for 3021 reflections (I greater-than-or-equal-to 3sigma(I)).