Alkylation of the SCS linkage. Towards lipophilic mono- and ditopic heavy-metal receptors containing trithiane building blocks. Molecular structure of cis-2,4,6-tribenzyl-1,3,5-trithiane
✍ Scribed by Jilles J. H. Edema; Marcel Hoogenraad; Franck S. Schoonbeek; Richard M. Kellogg; Huub Kooijman; Anthony L. Spek
- Publisher
- Elsevier Science
- Year
- 2010
- Tongue
- English
- Weight
- 594 KB
- Volume
- 112
- Category
- Article
- ISSN
- 0165-0513
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✦ Synopsis
Abstract
Reaction of 1,3,5‐trithiane with BuLi in THF at ‐ 50°C, followed by reaction with an equivalent amount of alkyl halide [n‐hexyl (a), benzyl (b), n‐dodecyl (c)] affords the corresponding lipophilic alkyl trithianes in moderate to good yields (25‐75%). Reactions with xylylene dibromides (ortho, meta, para) proceeded analogously to afford potentially ditopic ligands in reasonable overall yields (30‐50%). Alkylation of 1,3,5‐trithiane with excess alkyl halide results in the stereoselective formation of all‐cis di‐ or trisubstituted trithianes.
Investigation of the complexation behavior of these alkylated trithianes with Ag^+^ was done by means of conductometric titrations of AgO~3~SCF~3~ in MeCN and THF. The molecular structure of 2,4,6‐tribenzyl‐1,3,5‐trithiane (4b) has been determined by X‐ray crystallography. Crystal data for 4b: trigonal, space group R‐3 with a = b = 13.2287(7), c = 20.9177(2) Å, Z = 6, R = 0.030 (R~w~ = 0.034) for 1564 reflections.