Abstract
Oxidation-sensitive N,N-diaryl dithiocarbamates (DTCs) are synthesized in good yields by the generation of metal amide salts from N-benzoyl precursors, followed by addition of CS2. para-Substituted diphenylamines are prepared by electrophilic aromatic substitution of diphenylbenzamide and saponification. Deacylation of electron-rich species such as bis(p-dimethylaminophenyl)benzamide is challenging because of the oxidative sensitivity of the anionic intermediate but could be achieved in good yield by using n-BuLi to generate a hemiaminal adduct, prior to acidification. The N,N-diaryl DTCs are stable as alkali salts and can be used to produce densely packed monolayers on gold surfaces.
GRAPHICAL ABSTRACT
Notes
a Conversion determined by 1H NMR.
b Isolated yield.
a 1.0–2.5 equiv.
b Isolated yields unless stated otherwise.
c Hydrochloride salt, neutralized with one equivalent of n-BuLi or dimsyl-Li.
d Reaction conditions: (i) 50 °C for 5 h, then −78 °C; (ii) CS2 (5–10 equiv), warmed to rt.
e Yield after a single precipitation.