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Upstream product

• 31886-99-4 tetramethylcyclobutadiene*aluminum trichloride 
• 15795-42-3 N-sulfinyl-4-methylaniline 
• 503-17-3 dimethylacetylene 
• 24886-73-5 1-Azidoadamantane 
• 28895-02-5 3,4-dimethyl-2,5-hexanedione 
• 106-49-0 p-toluidine 

Relevant academic research and scientific papers

Oxidative nitrene transfer from azides to alkynes via Ti(ii)/Ti(iv) redox catalysis: Formal [2+2+1] synthesis of pyrroles

Catalytic oxidative nitrene transfer from azides with the early transition metals is rare, and has not been observed without the support of redox noninnocent spectator ligands. Here, we report the formal [2+2+1] coupling of azides and alkynes via TiII/TiIV redox catalysis from simple Ti halide imido precatalysts. These reactions yield polysubstituted N-alkyl pyrroles, including N-benzyl protected pyrroles and rare examples of very electron rich pentaalkyl pyrroles. Mechanistic analysis reveals that [2+2+1] reactions with bulky azides have different mechanistic features from previously-reported reactions using azobenzene as a nitrene source.

Electrochemical oxidation and EPR spectroscopy of radical cations of N-substituted 2,3,4,5-Tetramethylpyrroles

Electrochemical oxidation of 19 N-substituted 2,3,4,5-tetramethylpyrroles has been studied in acetonitrile and dichloromethane by means of slow cyclic voltammetry and coulometry. The first oxidation consumes one electron and occurs within the potential range 0.60-0.94 V in acetonitrile and 0.78-1.17 V in dichloromethane (vs. SCE). Twelve in situ generated primary radical cations were sufficiently stable at lowered temperature in dichloromethane for EPR measurement and showed well resolved HFS. The g-values (≈2.0026) and the coupling constants of 2,5-methyls (aH≈1.5 mT), 3,4-methyls (aH≈0.35 mT), and of the pyrrole nitrogen (aN≈0.42 mT) are very proximate for all 12 radical cations. It can be concluded, with support from quantum chemical calculations, that the odd electron is localised entirely on the pyrrole ring in the a2 HOMO of the parent molecule. Despite the odd electron distribution, the stability of the radical cations depends on the particular substituent attached to the pyrrole nitrogen. Acta Chemica Scandinavica 1998.

Benzvalene and Dewar Benzene Type Sulfinamides

The reaction of cyclobutadiene aluminum halide ? complexes with N-arylsulfinylamines leads, depending on the substitution pattern of the phenyl ring, to either bicyclic (Dewar benzene type) or tricyclic sulfinamides, the latter being formed via an intramolecular Friedel-Crafts reaction of an intermediate cyclobutenyl cation.A similar reaction of aluminum halide ? complex 1 with N-tert-butylsulfinylamine affords both a bicyclic and a tricyclic (benzvalene type) sulfinamide.