Hypervalent Iodine(III) Sulfonate Mediated Synthesis of α‐Thiocynanatoketones in a Task‐Specific Ionic Liquid [bmim]SCN

Abstract

The task-specific ionic liquid (TSIL) and 1-n-butyl-3-methylimidazolium thiocynanate, ([bmim]SCN) were used as the medium as well as the reactant for the synthesis of a-thiocynanatoketones by the reaction with a-sulfonyloxy aryl ketones. Significant rate enhancements and improved yields have been observed.

Experimental Study on the Solubility of Carbon Dioxide in Nitrate and Thiocyanate-Based Ionic Liquids

“…The studied ILs were synthesized and prepared in our laboratory. [Omim]­[SCN] and [Hmim]­[SCN] were prepared by an anion exchange reaction using [Omim]­[Cl], [Hmim]­[Cl], and KSCN. , [Omim]­[Cl] was synthesized according to the method described in literature . The preparation methods were explained in our previous works. , The structures of the ILs were checked with nuclear magnetic resonance (NMR) spectroscopy and the NMR spectrum of the ILs are shown in the Supporting Information.…”

“…[Omim][SCN] and [Hmim][SCN] were prepared by an anion exchange reaction using [Omim][Cl], [Hmim]-[Cl], and KSCN. 20,21 [Omim][Cl] was synthesized according to the method described in literature. 22 The preparation methods were explained in our previous works.…”

An environmentally benign way to synthesize 2-thiocyano-1,3-dicarbonyl compounds with high antifungal activity: a key role of solvent

“…8,33 Nowadays, oxidative thiocyanation has emerged as a thriving field since it does not require pre-functionalization. Thus, direct thiocyanation of ketones was performed using various chemical oxidants (Scheme 1, a): Selectfluor™, 34 bromodimethyl sulfonium bromide, 35 pyridinium hydrobromide perbromide, 36 I 2 O 5 , 37 iodine/MeOH, 38 hypervalent iodine( iii ) sulfonate, 39 [hydroxy(tosyloxy)iodo] benzene, 40 (dichloroiodo)benzene, 41 CAN, 42 oxone, 43 H 2 O 2 /graphene oxide, 44 K 2 S 2 O 8 /Cu( ii ), 45 CuBr 2 /Al 2 O 3 , 33 anhydrous AlCl 3 , 46 anhydrous iron( iii ) chloride, 47 and N -bromosuccinimide. 48 α-Thiocyano ketones were also obtained from acrylic acids.…”

α-Selective C(sp3)–H Thio/Selenocyanation of Ketones with Elemental Chalcogen

“…As such, a number of methods for the construction of α-thiocyanato ketones have been developed. A traditional synthetic strategy involved the nucleophilic substitution reaction between α-halogen ketones and nucleophilic “SCN” sources such as NaSCN, KSCN, and NH 4 SCN (Scheme a) . Obviously, it suffered from poor atom economy and the formation of a large amount of inorganic salt waste, as well as the use of prefunctionalized starting materials.…”