ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 9, pp. 2080–2086. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © N.A. Anisimova, E.I. Khristoforova, Yu.G. Trishin, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 9, pp. 1499–
1505.
To the 85th Anniversary of birthday of late Yu.G. Gololobov
Cyclocondensation of Ethylenediamine with Acetone
and Methyl Ethyl Ketone as a Synthetic Route
to 14-Membered Azamacrocyclic Compounds
N. A. Anisimova, E. I. Khristoforova, and Yu. G. Trishin
St. Petersburg State Technological University of Plant Polymers, ul. Ivana Chernykh 4, St. Petersburg, 198095 Russia
e-mail: trish@YT4470.spb.edu
Received July 17, 2015
Abstract—14-Membered azamacrocyclic compounds, substituted 1,4,8,11-tetraazacyclotetradeca-4,11-diene
and 1,4,8,11-tetraazacyclotetradeca-4,14-diene containing azomethine cycle and amine nitrogen atoms, were
obtained as a mixture of trans- and cis-isomers by reacting ethylenediamine with acetone and methyl ethyl
ketone. More stable trans-isomers were isolated individually by vacuum distillation.
Keywords: cyclocondensation, ethylenediamine, acetone, methyl ethyl ketone, azamacrocyclic compounds
DOI: 10.1134/S1070363215090108
Azamacrocyclic compounds are important objects
of supramolecular chemistry [1] due in particular to
their wide spectrum of practically important properties.
So, they tend to form discotic liquid crystals [2] and
exhibit selective binding of metal cations and anions,
acting as artificial anion receptors [3]. Metal
complexes of macrocyclic Schiff bases are charac-
terized by unusual magnetic and optical properties [4,
5], as well as by catalytic activity in redox reactions
and inhibitory activity towards auto-oxidation
reactions [6, 7]. Some of them show biological activity
and are potential drugs. For example, complexes of 14-
membered azamacrocycle exhibit antibacterial activity
and are available for the use as analogs of antifungal
drug Fluconazole [8].
unsuccessful due to their ability to hydrolysis and aldol-
crotonic condensation [10, 11]. However, azamacro-
cyclic ligand we obtained was a stable compound. This
fact prompted us to investigate the possibility of
azamacrocycles synthesis by reacting ethylenediamine
with acetone and other aliphatic ketones, by passing the
intermediate step of producing their perchlorate salts
or metal complexes, wherefrom free ligands can be
prepared by the action of alkali solution [12, 13] or by
reaction with potassium cyanide [14, 15], respectively.
Cyclocondensation of ethylenediamine with acetone
and methyl ethyl ketone was found to form 14-mem-
bered azamacrocyclic compounds as a mixture of
trans- and cis-isomers: 5,7,7,12,14,14-hexamethyl-1,4,8,11-
tetraazacyclotetradeca-4,11-diene 1a, 5,7,7,12,12,14-
hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,14-diene
1b and 7,14-dimethyl-5,7,12,14-tetraethyl-1,4,8,11- tetra-
azacyclotetradeca-4,11-diene 2a, 7,12-dimethyl-5,7,12,14-
tetraethyl-1,4,8,11-tetraazacyclotetradeca-4,14-diene
2b, respectively. Reacting ethylenediamine with acetone
in a ratio of 1 : 2 under reflux in ethanol for 10 h
resulted in the formation of trans- (1a) and cis-isomers
In this regard, the development of new methods for
the synthesis of macrocyclic nitrogen-containing
compounds is an urgent task.
Recently, we obtained [LNi]2+Cl2 complex (L was
5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetra-
deca-4,11-diene) via reaction of nickel(II) trisethylene-
diaminate complex with acetone and alongside the
complex free ligand L was isolated in a 35% yield of
[9]. It should be noted that attempts to synthesize
aliphatic diene ligands as free Schiff bases have been
1
(1b) in a ratio of 1.3 : 1.0. By H NMR, the reaction
was not complicated by side transformations (Fig. 1).
The total yield of compounds 1a and 1b was 63%.
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