Directed synthesis of macrocyclic phenylene sulfides

Synthesis and Molecular Recognition of Water‐Soluble S6‐Corona[3]arene[3]pyridazines

“…The first S n ‐corona[ n ]arenes ( n =4, 5), then were known as cyclic ( p ‐phenylene sulfide)s, were obtained as by‐products from polymerization of p ‐dichlorobenzene and sodium sulfide 16. Selective synthesis of S 6 ‐corona[6]arene, a crystalline compound of a high melting point, was later reported respectively by Franke and Vögtle17 using p ‐bromothiophenolate and by Sergeev18 from the reaction of a dibrominated trimer with sodium sulfide. Oxidative polymerization of diphenyl disulfide also gives S 6 ‐corona[6]arene 19.…”

“…[15] Being different from 1,3-alternate heteracalixaromatics which form V-shaped clefts,c oronarenes contain ac ylindroid cavity.T he combination of heteroatoms and (het)arenes would advantageously generate almost limitedless diverse macrocycles of regulable cavity sizes and electronic features.W er eport herein ah ighly efficient synthesis of unprecedented water-soluble S 6 -corona [3]arene [3]pyridazines by one-pot nucleophilic aromatic substitution reaction (S N Ar) between diesters of 2,5dimercaptoterephthalate and 3,6-dichlorotetrazine followed consecutively by the inverse electron-demand Diels-Alder reaction of tetrazine moieties with an enamine and complete hydrolysis of diester functionality.T he resulting macrocycles acted as powerful synthetic receptors to interact selectively with electron-deficient guests in water, forming 1:1complexes with an association constant up to (1.18 AE 0.06) 10 5 m À1 .T he first S n -corona[n]arenes (n = 4, 5), then were known as cyclic (p-phenylene sulfide)s,w ere obtained as by-products from polymerization of p-dichlorobenzene and sodium sulfide. [16] Selective synthesis of S 6 -corona [6]arene,acrystalline compound of ahigh melting point, was later reported respectively by Franke and Vçgtle [17] using p-bromothiophenolate and by Sergeev [18] from the reaction of ad ibrominated trimer with sodium sulfide.O xidative polymerization of diphenyl disulfide also gives S 6 -corona [6]arene. [19] Except for its ringopening polymerization to prepare linear poly(p-phenylene sulfide)s, [19,20] no application of S 6 -corona [6]arene has been reported.…”

Synthesis, Structure, and Molecular Recognition of S6‐ and (SO2)6‐Corona[6](het)arenes: Control of Macrocyclic Conformation and Properties by the Oxidation State of the Bridging Heteroatoms

“…The first S n ‐corona[ n ]arenes ( n =4, 5), then termed cyclic oligo p‐ phenylene sulfides, were obtained and identified as a trace amount in by‐products from polymerization of p ‐dichlorobenzene and sodium sulfide in 1982 . Synthesis of cyclic hexameric p‐ phenylene sulfide was later reported by Vögtle and Sergeev, respectively, by using the reaction of p ‐bromothiophenolate and the reaction between a dibrominated trimer and sodium sulfide. Oxidative polymerization of diphenyl disulfide was also found to form cyclic hexameric p‐ phenylene sulfide effectively .…”

Synthesis and Molecular Recognition of Water‐Soluble S6‐Corona[3]arene[3]pyridazines

“…[16] Selective synthesis of S 6 -corona[6]arene,acrystalline compound of ahigh melting point, was later reported respectively by Franke and Vçgtle [17] using p-bromothiophenolate and by Sergeev [18] from the reaction of ad ibrominated trimer with sodium sulfide.O xidative polymerization of diphenyl disulfide also gives S 6 -corona[6]arene. [19] Except for its ringopening polymerization to prepare linear poly(p-phenylene sulfide)s, [19,20] no application of S 6 -corona[6]arene has been reported.…”