A facile and sustainable protocol to the preparation of aryl iodides using stable arenediazonium bis(trifluoromethylsulfonyl)imide salts via the telescopic process

Abstract

The preparation of aryl iodides in a telescopic reaction using tert‐butyl nitrite as a diazotization reagent and a mixture of bis(trifluoromethane) sulfonamide and glacial acetic acid as a mild acidic agent in ethanol followed by iododediazoniation with tetraethylammonium iodide in water was investigated. The current method has other advantages such as minimized waste by avoiding solvent for the purification of products in diazotization step, simple experimental procedure, and good yield of the sterically hindered aryl amines, metal and strong acid‐free waste and environmentally benign conditions. The noteworthy features of this study are the preparation of stable arenediazonium bis(trifluoromethylsulfonyl)imide salts that can be used with no significant loss activity after 1 week and bis(trifluoromethane)sulfonamide was recovered in high yields from reactions.

Arene diazonium saccharin intermediates: a greener and cost-effective alternative method for the preparation of aryl iodide

“…2,6-dimethylaniline, 2,6-diethylaniline, and 2,6diisopropylaniline 3(d-f) were isolated in 67%, 40%, 42% yields, respectively as expected ( Table 1, entry 4-6) [6]. All known products showed an identical melting point and NMR spectra to those in the literature (See Supplementary Material) [4]. Complete or partial recovering of the catalyst and reagents are very important in the industrial processes due to minimizing the waste, as well as lower raw material, energy, and waste disposal costs.…”

“…2,6-dimethylaniline, 2,6-diethylaniline, and 2,6diisopropylaniline 3(d-f) were isolated in 67%, 40%, 42% yields, respectively as expected (Table 1, entry 4-6) [6]. All known products showed an identical melting point and NMR spectra to those in the literature (See Supplementary Material) [4]. a Reaction conditions: TBN (0.30 mL,~2.3 mmol), aniline derivatives 1(a-l) (2.0 mmol), glacial acetic acid (0.12 mL, 2.1 mmol), Sac-H (0.37 g, 2.0 mmol), TEAI (0.52 g, 2.0 mmol), solvent (H2O/EtOH 1:1 v/v, 5 mL); total reaction time (2 h).…”

“…Based on our previous works [4,5], the glacial acetic acid and TBN together with Sac-H were slowly stirred in ethanol at low temperatures (an ice bath). After 5 min, aniline 1a was slowly added at the same temperature.…”

“…In continuation of our previous work [4] and application of saccharin [5][6][7], we encouraged to investigate the potential of saccharin for the synthesis of the aryl iodides through in situ formation the arene diazonium saccharin salts which to the best of our knowledge has not been presented to date. According to the current strategy, aryl iodides are formed from diazotization of in situ generated arene diazonium salts which are in turn formed from aniline derivatives and tert-butyl nitrite (TBN) in the presence of saccharin.…”

Transition-Metal-Catalyzed C–H Activation Reactions for the Creation and Modification of Organic Fluorophores

“…76 Of the aryl halides, aryl chlorides are usually the cheapest and most easily accessible, but they are, at times, poorly active in palladium-catalyzed cross-coupling reactions due to their slower rate of oxidative addition (Scheme 16). [77][78][79][80] Although the incorporation of electronwithdrawing groups may enhance the rate of oxidative addition in the cross-coupling reaction, electron-withdrawing groups may also quench the emission efficiency of fluorescent molecules. Thus, the necessity of prefunctionalization of the starting materials lowers the atom-economy of palladium-catalyzed cross-coupling reactions.…”