Z. S. Titova’s research while affiliated with A.E. Arbuzov Institute of Organic and Physical Chemistry and other places

Electrocarboxylation of the hydrazones (I) and subsequent treatment with methyl iodide (III) give the hydrazinocarboxylates (IV).

According to the data from photoelectron and UV spectroscopy, the molecules of N,N-dimethylmethane sulfenamide and N,N-diethylpropane-2-sulfenamide have a conformation with orthogonal orientation of nN and nS orbitals, while N,N-dimethylbenzene sulfenamide in the gas phase exists in conformational equilibrium of the planar and skewed conformers.

1. It is shown that a number of aryl and acylhydrazones can be electrochemically carboxylated in non-aqueous media (acetonitrile, DMF) to give α-hydrazino (or hydrazido) acids. 2. On passing from benzoyl to acetylhydrazones electrocarboxylation no longer occurs, probably because of the predominance in the acetylhydrazones of the EE′E″ form, in which the basicity of the imino nitrogen atom is lower than in the EE′Z″ form.

Conclusions On the basis of data obtained by methods of dipole moments and IR spectroscopy, it has been shown that these semicarbazones and thiosemicarbazones of aromatic aldehydes exist in solution in the EEE form, apparently stabilized by specific interaction NH2... N=C.

Die Umsetzung der Chlor-benzaldehyd-phenylhydrazone (I) mit den Aryl-phenylhydrazonen (III) zu den Hydrazidinen (IV) verläuft mit niedrigen Ausbeuten.

1. Reaction of C,N-diphenylnitrilimines with benzaldehyde arylhydrazones has given new representatives of the arylidenebenzhydrazidines. 2. In solution, 1,4-diaryl-2-benzylidenehydrazidines have a nonplanar structure, and can exist in two conformational forms.

1. A study has been made of the IR and PMR spectra of arylhydrazones of benzoyl chlorides and arylhydrazones of benzaldehydes. The changes inν NH of the arylhydrazones of benzoyl chlorides when the change is made from solutions to crystals can be explained by realization of a weak intramolecular hydrogen bond (INTRAHB) NH...Cl in the crystals. 2. In the 2-nitrophenylhydrazones of benzoyl chloride and benzaldehyde, there is an NH...O(O2N) INTRAHB. In proton-acceptor solvents (dioxane, Me CN, DMSO, hexametapol), the arylhydrazones of benzoylchlorides and the arylhydrazones of aromatic aldehydes in which the NH does not participate in an INTRAHB form an intermolecular H-bond with the solvent. The character of the intermolecular interactions of the arylhydrazone of benzoyl chloride) or specific (phenylhydrazone of benzaldehyde). 3. X-ray structure analysis of the phenylhydrazone of benzaldehyde does not reveal any intermolecular contacts shorter than the sum of the van der Waals radii.

When the 2,4-dinitrophenylhydrazones of acetone, diethyl ketone, and cyclohexanone are treated with Br2 in AcOH, they are converted to the corresponding perbromides, which possess fungicidal and bacteriostatic properties.

1.Coordination compounds of Co, Cu, and Ni with acetone acylhydrazones have been obtained and their structures have been studied by physicochemical methods. Acetone benzoylhydrazone and its substituted derivatives coordinate with Co(II), Ni(II), and Cu(II) ions from, their acetates in thea-hydroxyazine form, and acetone salicyloylhydrazone coordinates with Ni(II) and Co(n) in the hydrazone form and with Cu(II) in thea-hydroxyazine form.2.The stability constants of a number of complexes of acetone acylhydrazones in methanol have been calculated on the basis of their UV-spectroscopic characteristics.

1. The aroylhydrazones with intramolecular hydrogen bonding exist in acylhydrazone form with a high degree of electron delocalization. 2. The preferred form in nonpolar solution is an equilibrium mixture of three conformers of the salicyloylhydrazones of several different aldehydes, these differing in the degree of rotation around the amide N-C bond and in the type of H-bonding (-OH...O=C or N-H...-OH).