Generation of Trityl Radicals by Nucleophilic Quenching of Tris(2,3,5,6‐tetrathiaaryl)methyl Cations and Practical and Convenient Large‐Scale Synthesis of Persistent Tris(4‐carboxy‐2,3,5,6‐tetrathiaaryl)methyl Radical

Abstract

Tris(2,3,5,6-tetrathiaaryl)methyl cations, which were generated from the corresponding triarylmethanols in the presence of strong acids, underwent reaction with nucleophiles to give trityl radicals, as the product of a one-electron reduction of the carbocation. Depending on the nature of the nucleophile, the only byproducts were either diamagnetic quinone methides or asymmetrical monosubstituted trityl radicals. Herein, we report a protocol for the large-scale synthesis of the Finland trityl, which has the advantage of high overall yield and reproducibility.

Dynamic nuclear polarisation by thermal mixing: quantum theory and macroscopic simulations

“…We prepared tris (8-deutero [1,3]dithiol-4-yl)methanol using D 4 -methanol in place of diethyl carbonate. 33,34 .…”

Synthesis, Characterization, and Nanoencapsulation of Tetrathiatriarylmethyl and Tetrachlorotriarylmethyl (Trityl) Radical Derivatives—A Study To Advance Their Applicability as in Vivo EPR Oxygen Sensors

“…10,40,42 HBF 4 (54 % in Et 2 O, 10 mL, 37.0 mmol) was added to a solution of 1,2,4,5-tetra(tertbutylthio)benzene (1) (16.0 g, 37.2 mmol) in toluene (500 mL). The mixture was stirred for 30 min at RT.…”

“…Compound 2b (3.49 g, 11.7 mmol), n-BuLi (4.7 mL, 11.7 mmol) and methyl chloroformate (0.3 mL, 3.9 mmol) in dry Tris [8-ethoxycarbonyl-2,2,6,6-tetramethylbenzo [1,2-d:4,5-d']bis( [1,3]dithiole)-4-yl]methanol (4). 23,40 Compound 3a (500 mg, 0.57 mmol) and TMEDA (0.85 mL, 5.7 mmol) were mixed in dry n-hexane (5 mL) under argon atmosphere and cooled to 0 °C. A solution of 2.5 M n-BuLi in hexane (2.3 mL, 5.7 mmol) was added dropwise over 30 min and the mixture was stirred at RT 30 for 3.5 h. Anhydrous toluene (10 mL) was added and the reaction mixture was allowed to stir for an additional 1 h, then added slowly via syringe to cold (-25 °C, cooling bath temperature) diethyl carbonate (3.42 mL, 28.3 mmol) diluted with toluene (5 mL).…”

Development and Application of Spin Traps, Spin Probes, and Spin Labels

“…In most cases, trityls are not so easy to synthesize, but recently a convenient way of preparing Finland trityl (Rogozhnikova et al, 2013) and diversely substituted trityls were proposed (Scheme 8A), which is based on the quenching of tris(2,3,5,6-tetrathiaaryl)methyl cations by C-, N-, P-, and S-nucleophiles (Scheme 8B) (Tormyshev et al, 2014). The authors found that C-, N-, P-, and S-nucleophiles react with symmetrical tris(2,3,5,6-tetrathiaaryl)methyl cations generated from the corresponding triarylmethanols by strong acids.…”

“…(B) Synthesis of monofunctional TAMs by nucleophilic quenching of triarylmethyl cation generated from diamagnetic triarylmethanols. (A) Adapted with permission fromRogozhnikova et al (2013).…”