Fluorescent Signaling of Oxone by Desulfurization of Thioamide

Abstract

The chemosignaling of the oxidant Oxone by selective desulfurization of a thioamide was investigated. Pyrene-thioamide was efficiently converted to its amide analogue by reaction with Oxone, resulting in a pronounced fluorescent turn-on type signaling. Selective signaling of Oxone in aqueous solution was possible in the presence of representative alkali and alkaline earth metal ions, as well as common anions.

Efficient synthesis of pyrene-1-carbothioamides and carboxamides. Tunable solid-state fluorescence of pyrene-1-carboxamides

“…14,15,36,37 Furthermore, the reaction of Oxone® with N,N-diethyl-1-pyrene-carboxamide was applied for uorescence sensing of this oxidant. 24 We found that Oxone® reacts smoothly with thioamides 1a-j in acetonitrile-water at room temperature to afford the corresponding amides 2a-j in high yields (86-100%, Scheme 1).…”

“…12,[14][15][16] Moreover, these compounds were used in the synthesis of polymers with tunable luminescent properties 17 and in the labelling of nucleosides. 7,8,[18][19][20][21][22] In contrast to amides, pyrene-1-carbothioamides are only weakly uorescent 23,24 because of the internal quenching effect of the thiocarbonyl group. Since some chemical species desulfurize thioamides (e.g.…”

“…The amides can then be transformed into thioamides via a reaction with Lawesson reagent. 17,23,24 In this paper we report an efficient method of synthesis of primary and secondary pyrene-1-carbothioamides directly from pyrene via a Friedel-Cras-type reaction with potassium thiocyanate and organic isothiocyanates, respectively. The thioamides were then desulfurized into the corresponding amides using Oxone®.…”

Electronic Effect on the Molecular Motion of Aromatic Amides: Combined Studies Using VT-NMR and Quantum Calculations

“…We added oxalyl chloride to a mixture of pyrene-1-carboxylic acid and 1-naphthoic acid in methylene chloride and added dimethyl formamide after approximately 1–2 drops [ 23 ] ( Scheme S1 ). The mixture was stirred at room temperature to maintain the reaction for approximately 4 h. Once the reaction was completed, the methylene chloride was evaporated, and 1 h of vacuum was performed.…”

Thionation of the 2‐λ5‐Phosphaquinolin‐2‐one Scaffold with Lawesson's Reagent

“…Coumarin, as well as other related fluorescent carbonyl‐containing systems, exhibit red‐shifted emissions and decreased quantum yields upon thionation with LR. Additionally, in many cases the thio form can be converted back to the respective oxo form through various means, a transformation which often shows a turn‐on fluorescence response [5,7–9] . Similarly, non‐aromatic aminophosphonic esters have been converted to their respective thio forms as well [10–12] .…”