Felix Odame

The Formation of 2,2,4-Trimethyl-2,3-dihydro-1H-1,5-Benzodiazepine from 1,2-Diaminobenzene in the Presence of Acetone

In an attempt to synthesize a 2-substituted benzimidazole from the reaction of o-phenylenediamine and isophthalic acid in the presence of acetone and ethanol under microwave irradiation, a salt of the isophthalate ion and 2,2,4-trimethyl-2,3-dihydro-1H-1,5-benzodiazepin-5-ium ion was obtained. The condensation of two moles of acetone with the amine groups resulted in the formation of the benzodiazepine which crystallized as an iminium cation forming a salt with the isophthalate anion. The formation of benzodiazepine was also confirmed by performing the reaction of o-phenylenediamine with excess acetone in ethanol under conventional heating conditions. The compounds were characterized by NMR, FTIR, HRMS and microanalysis as well as X-ray crystallography. The reaction mechanism leading to the formation of benzodiazepine is also discussed.

Metal-mediated reactions towards the synthesis of a novel deaminolysed bisurea, dicarbamolyamine

Abstract A new selective cobalt acetate tetrahydrate or cerium nitrate hexahydrate mediated cleavage of the C–N bond of a benzoyl isothiocyanate derivative to give (carbamoylamino)methanethioamide is presented. The cleavage of the C–N could not be achieved in the absence of thione. The novel silver-mediated conversion of a thione to the carbonyl was achieved on 1-((benzamido)formyl)urea and replicated on (carbamoylamino)methanethioamide to give the deaminolyzed bisurea (dicarbamolyamine). The compounds were characterized by IR, NMR, microanalysis and GC–MS. The single crystal X–ray diffraction studies of the crystal structures of compounds I, II, III and V is discussed. Graphical Abstract

DFT Study of the Reaction Mechanism of N-(Carbomylcarbamothioyl) Benzamide Felix Odame

The reaction mechanism for the formation of N-(carbomylcarbamothioyl)benzamide has been successfully computed with the B3LYP/6-31g(d) functional and basis set and compared with 1H NMR monitoring of the progress of the reaction with time. The reaction is proposed to proceed through two transition states: Ts1 (the rate-determining step) with highly unstable species (with a requisite orientation for the reaction to proceed), and Ts2 with a lower energy leading to the product. Computation of the reaction pathway was also carried out using the B3PW91/6-31G(d), M06/6-31G(d) and Wb97XD/6- 31G(d) functionals and basis set. These results do not present a clear reaction pathway compared to that given by the B3LYP/6-31G(d).