Реакции гексаметилентетрамина (уротропина) с этилендиаминтетрауксусной кислотой. Молекулярная структура тригидрата диаммоний этилендиаминтетраацетата (NH4)2H2L∙3H2O

V. V. Semenov; B. I. Petrov; T. S. Pochekutova; N. M. Lazarev; N. V. Zolotareva; R. V. Rumyantsev; E. N. Razov

Authors

V. V. Semenov G.A. Razuvaev Institute of Organometallic Chemistry of the RAS
B. I. Petrov G.A. Razuvaev Institute of Organometallic Chemistry of the RAS
T. S. Pochekutova G.A. Razuvaev Institute of Organometallic Chemistry of the RAS
N. M. Lazarev G.A. Razuvaev Institute of Organometallic Chemistry of the RAS
N. V. Zolotareva G.A. Razuvaev Institute of Organometallic Chemistry of the RAS
R. V. Rumyantsev G.A. Razuvaev Institute of Organometallic Chemistry of the RAS
E. N. Razov Институт проблем машиностроения РАН – филиал Федерального государственного бюджетного научного учреждения «Федеральный исследовательский центр Институт прикладной физики РАН»

Keywords:

hexamethylenetetramine, ethylenediaminetetraacetic acid and its diammonium salt, molecular structure

Abstract

The interaction of ethylenediaminetetraacetic acid (H4L, EDTA) with hexamethylenetetramine (CH2)6N4 (HMTA) in aqueous medium leads to formation of hexamethylenetetraminium ethylenediaminetetraacetate monohydrate [(CH2)6N4H]+(H3L)-∙H2O (1) and diammonium ethylenediaminetetraacetate trihydrate (NH4)2H2L∙3H2O (2). The diammonium salt is obtained by reaction of 2 moles of aqueous ammonia solution formed by dissociation of HMTA in aqueous methanol medium to formaldehyde and ammonia and reaction of the latter with EDTA, yielding 32% after recrystallization. The reaction with the ratio NH3 : H4L equaling 4 : 1 does not lead to formation of pure products of tetra- or triammonium salts (NH4)nH4-nL∙mH2O (n = 3,4). The mixture is a triammonium salt with an unreacted acid. However, recrystallization from aqueous methanol gives a pure sample of the diammonium salt (NH4)2H2L∙3H2O. The structure of the synthesized complexes was investigated by IR spectroscopy and elemental analysis. The structure of complex 2 was proved by the X-ray method. The analysis has shown that the dianion of ethylenediaminetetraacetate in 2 is a zwitterion in which hydrogen atoms are located on nitrogen atoms and all four carboxyl groups are deprotonated. General regularities concerning the interaction of quadruple-butyric acids EDTA and OEDP with HMTA and aqueous ammonia have been revealed, and the analogy of the course of these reactions has been shown. It is established that the diammonium salts can be synthesized directly from acids and aqueous ammonia solutions.

Author Biographies

V. V. Semenov, G.A. Razuvaev Institute of Organometallic Chemistry of the RAS

доктор химических наук, ведущий научный сотрудник

B. I. Petrov, G.A. Razuvaev Institute of Organometallic Chemistry of the RAS

доктор химических наук, ведущий научный сотрудник

T. S. Pochekutova, G.A. Razuvaev Institute of Organometallic Chemistry of the RAS

научный сотрудник

N. M. Lazarev, G.A. Razuvaev Institute of Organometallic Chemistry of the RAS

кандидат химических наук, научный сотрудник

N. V. Zolotareva, G.A. Razuvaev Institute of Organometallic Chemistry of the RAS

кандидат химических наук, научный сотрудник

R. V. Rumyantsev, G.A. Razuvaev Institute of Organometallic Chemistry of the RAS

кандидат химических наук, научный сотрудник

E. N. Razov, Институт проблем машиностроения РАН – филиал Федерального государственного бюджетного научного учреждения «Федеральный исследовательский центр Институт прикладной физики РАН»

Institute of Mechanical Engineering Problems of the Russian Academy of Sciences – branch of the Federal State Budgetary Scientific Institution “Federal Research Center Institute of Applied Physics RAS”