Benzyllithium from methylated benzylamine and its ammonium salt via naphthalene-catalyzed carbon-nitrogen bond reductive cleavage

Abstract

The reaction of N,N-dimethylbenzylamine with lithium powder and a catalytic amount of naphthalene, followed by addition of different electrophiles, gave the expected reaction products in low yield. However, yields could be improved by using the corresponding ammonium salt instead of the amine. When N,N,N-trimethylbenzylammonium iodide was submitted to the naphthalene-catalyzed lithiation process, followed by reaction with several electrophiles, the expected reaction products were obtained in moderate to good yields.

Insights into the Transport of Aqueous Quaternary Ammonium Cations: A Combined Experimental and Computational Study

“…The reaction scheme for the synthesis of labeled cations is shown in Scheme . A white precipitate was formed by adding ethanol and washed, following a procedure described elsewhere . The resulting salts were dissolved in water and passed through an anion exchange resin column to convert them to the hydroxide form.…”

Ni-Catalyzed Iterative Alkyl Transfer from Nitrogen Enabled by the In Situ Methylation of Tertiary Amines

“…N,N,N-Trimethyl-1-phenylmethanaminium iodide (1a). 37 The reaction was performed with 16 mmol of amine in 16 mL ethyl acetate. 1a was recrystallized to afford white needle-like crystals (4.2 g, 96%); mp: 176−177 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 7.66 (d, J = 7.9 Hz, 2H), 7.49−7.40 (m, 3H), 5.05 (s, 2H), 3.40 (s, 9H); 13 37 The reaction was performed with 16 mmol of amine in 16 mL ethyl acetate.…”

“…37 The reaction was performed with 16 mmol of amine in 16 mL ethyl acetate. 1a was recrystallized to afford white needle-like crystals (4.2 g, 96%); mp: 176−177 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 7.66 (d, J = 7.9 Hz, 2H), 7.49−7.40 (m, 3H), 5.05 (s, 2H), 3.40 (s, 9H); 13 37 The reaction was performed with 16 mmol of amine in 16 mL ethyl acetate. 1c was isolated as a white solid (3.7 g, 77%); mp: 157−158 °C; 1 37 The reaction was performed with 16 mmol of amine in 16 mL ethyl acetate.…”

“…1-(4-(tert-butyl)phenyl)-N,N,N-trimethylmethanaminium iodide (1m). 37 The reaction was performed with 7.0 mmol of amine in 7 mL ethyl acetate. 1m was isolated as a white solid (1.7 g, 73%); mp: 211−212 °C.…”

“…4.1.1.2. N,N,N-Trimethyl-1-(p-tolyl)methanaminium iodide (1b) 37. The reaction was performed with 7.1 mmol of amine in 7 mL ethyl acetate.…”