Amidoxime-Functionalized (9,10-Dioxoantracen-1-yl)hydrazones

Abstract

New (9,10-dioxoanthracen-1-yl)hydrazones containing amidoxime fragments were synthesized by the interaction of corresponding hydrazones of malonodinitrile, ethyl cyanacetate, ethyl acetoacetate, and acetylacetone with hydroxylamine in boiling dioxane in the presence of sodium acetate. It was established that the reaction of N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)carbonohydrazonoyldicyanide 1 with NH 2 OH leads to the formation of 2-(2-(9,10-dioxo-9,10-dihydroanthracen-1yl)hydrazinylidene)-N' 1 ,N' 3-dihydroxymalonimidamide 2 as the major product, and 3-amino-2-(2-(9,10-dioxo-9,10dihydroanthracen-1-yl)hydrazinylidene)-3-(hydroxyimino)propanamide 3 as a minor product. The 1 H, 13 C NMR and LC-MS data showed that the interaction of 9,10dioxoanthracenylhydrazone of acetylacetone 5 by hydroxylamine is accompanied with the elimination of the acetyl fragment formed 1-[2-(2-(hydroxyimino) propylidene)hydrazinyl]anthracene-9,10-dione 9. Possible mechanisms for the formation of amidoximes 3 and 9 are proposed. Quantum-chemical DFT calculations of the Gibbs free energy (D G) to determine conformational advantage of Z-or E-isomers for the amidoxime form of the derivatives 2,3,7-9 were carried out using the M06-2X hybrid method with 6-311++G(d, p) basis set and the SMD solvation model in DMSO.

Sonogashira Cross‐Coupling Reaction of Bromocyanofluoro Pyridine Compounds: Access to 5‐ and 6‐Alkynylfluoropyridinamidoximes Scaffolds

“…Amidoximes have also been reported to be powerful pharmacophores in the identification of lead compounds towards the discovery of new synthetic drugs and prodrugs, with significant biological activity [8] . In particular, the use of amidoximes as antioxidant, [9] antimycotic, [10] antibacterial, [11] antimicrobial, [12] antileishmanial, [13] antihypertensive, [14] and antithrombotic [15] agents has become widespread. On the other hand, amidoxime derivatives also exhibit promising histone deacetylase (HDACs) inhibitory activity for cancer therapy, [16] as well as anesthetic properties [17] .…”