Metal-Free Synthesis of S-Aryl Dithiocarbamates: A Direct Approach from Anilines and Secondary Amines in the Presence of tert-Butyl Nitrite

Abstract

A simple and efficient method was developed for the preparation of S-aryl dithiocarbamates from anilines, carbon disulfide, and amines in acetonitrile–water. The reactions proceeded at room temperature in the absence of catalysts, and the desired products were obtained in good to excellent yields. Simple operations, easy access to reactants, catalyst-free conditions, and high product yields are key benefits of this method.

Keywords

dithiocarbamates - anilines - amines - metal-free reaction - diazo compounds

Publication History

Received: 03 January 2025

Accepted after revision: 28 January 2025

Accepted Manuscript online:
28 January 2025

Article published online:
13 March 2025

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• 28 Phenyl Piperidine-1-carbodithioate (3a); Typical Procedure PhNH₂ (1a, 100 mg, 1.07 mmol, 1 equiv) was dissolved 3:1 MeCN–H₂O (2 mL) at 0 °C. tert-Butyl nitrite (2.15 mmol, 2 equiv) was added to the solution, and mixture was stirred at 0 °C for 30 min. In a second round-bottomed flask, piperidine (2a, 1.61 mmol, 1.5 equiv) was dissolved in 3:1 MeCN–H₂O (2 mL). CS₂ (2.68 mmol, 2.5 equiv) was added to the solution at 0 °C, and the mixture was stirred at 0 °C for 5 min. The resulting dithiocarbamic acid solution was added to the flask containing the diazonium salt, and the mixture was stirred for 90 min at r.t. until the reaction was complete (TLC). The mixture was then diluted with EtOAc and washed with H₂O. The organic layer was dried (Na₂SO₄) and concentrated, and the residue was purified by column chromatography [silica gel (230–400 mesh), 0.5% EtOAc–hexane] to give a white solid; yield: 212 mg (83%); R_f = 0.6. ¹H NMR (500 MHz, CDCl₃): δ = 7.49–7.42 (m, 5 H), 4.29 (s, 2 H), 4.00 (s, 2 H), 1.75 (s, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 196.0, 137.1, 131.6, 129.9, 128.9, 53.1, 51.9, 26.1, 25.3, 24.1.