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.
Highlights
Dithiocarbamates (DTCs) are important precursors for a wide range of chemical applications,[1] such as intermediates in the chemical synthesis of biologically active compounds and natural products,[2,3] as ligands in coordination chemistry to stabilize various transition metals,[4] and as initiators in the vulcanization of rubber and in the synthesis of polymers by reversible addition-fragmentation (RAFT) processes.[5]
In this article we show that para-substituted N,N-diphenyl DTCs can be synthesized by addition of CS2 to the corresponding metal amide, generated in situ from N-benzamide derivatives
Para-Substituted N,N-diphenylamines were synthesized from the diphenylbenzamide 1 (Scheme 1)
Summary
Dithiocarbamates (DTCs) are important precursors for a wide range of chemical applications,[1] such as intermediates in the chemical synthesis of biologically active compounds and natural products,[2,3] as ligands in coordination chemistry to stabilize various transition metals,[4] and as initiators in the vulcanization of rubber and in the synthesis of polymers by reversible addition-fragmentation (RAFT) processes.[5]. DTCs have been used to anchor a variety of functional molecules and polymers[7,8] onto metal surfaces, such as peptides,[6] carbohydrates,[9] DNA,[10] and cancer-targeting ligands.[11]. DTCs have intriguing potential as interconnects for molecular electronics, because of their extended conjugation. Wessels et al first demonstrated this possibility using bisDTC ligands as molecular junctions between Au nanoparticles, with large increases in overall conductivity relative to dithiol spacers.[12] Surface spectroscopy studies on DTC monolayers further established a high charge transport across aromatic DTCs assembled on Au.[13] Advances in this research area may be supported by developing a practical synthesis of DTCs attached to π-conjugated systems with tunable electronic structures
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