vestichИзвестия Национальной академии наук Беларуси. Серия химических наукProceedings of the National Academy of Sciences of Belarus, Chemical Series1561-83312524-2342The Republican Unitary Enterprise Publishing House "Belaruskaya Navuka"10.29235/1561-8331-2018-54-2-168-179vestich-318Research ArticleОРГАНИЧЕСКАЯ ХИМИЯORGANIC CHEMISTRYСИНТЕЗ (E,E)-АЗОМЕТИНОКСИМОВ НА ОСНОВЕ ОКСИМА 4-АМИНОАЦЕТОФЕНОНАSYNTHESIS OF (E,E)-AZOMETHINEOXIMES BASED ON 4-AMINOACETOPHENONE OXIMEДикусарЕ. А.DikusarE. A.

Дикусар Евгений Анатольевич – канд. хим. наук, ст. науч. сотрудник.

ул. Сурганова, 13, 220072, Минск.

Evgenij A. Dikusar – Ph. D. (Chemistry), Senior researcher.

13, Surganov Str., 220072, Minsk.

dikusar@ifoch.bas-net.byФилипповичЛ. Н.FilippovichL. N.

Филиппович Людмила Николаевна – канд. хим. наук, науч. сотрудник.

ул. Сурганова, 13, 220072, Минск.

Liudmila N. Filippovich – Ph. D. (Chemistry), Researcher.

13, Surganov Str., 220072, Minsk.

luda1977@list.ruШахабС. Н.ShahabS. N.

Шахаб Сиямак Насер – канд. хим. наук, профессор Российской академии естествознания, вед. науч. сотрудник.

ул. Сурганова, 13, 220072, Минск. 

Siyamak N. Shahab – Ph. D. (Chemistry), Professor of the Russian Academy of Natural History, Senior researcher.

13, Surganov Str., 220072, Minsk.

siyamak@tut.byПеткевичС. К.PetkevichS. K.

Петкевич Сергей Константинович – канд. хим. наук, ст. науч. сотрудник.

ул. Сурганова, 13, 220072, Минск.

Sergej K. Petkevich – Ph. D. (Chemistry), Senior researcher.

13, Surganov Str., 220072, Minsk.

petkevich@ifoch.bas-net.byСтёпинС. Г.StepinS. G.

Стёпин Святослав Генрихович – канд. хим. наук, доцент кафедры органической химии.

пр-т Фрунзе, 27, 210023, Витебск.  

Svjatoslav G. Stepin – Ph. D. (Chemistry), Associate Professor, Department of Organic Chemistry.

17, Frun- ze Ave., 210023, Vitebsk. 

stepins@tut.byИнститут физико-органической химии, Национальная академия наук Беларуси.БеларусьInstitute of Physical Organic Chemistry, National Academy of Sciences of Belarus.BelarusИнститут физико-органической химии, Национальная академия наук Беларуси.БеларусьInstitute of Physical Organic Chemistry, National Academy of Sciences of Belarus/BelarusИнститут физико-органической химии, Национальная академия наук Беларуси.БеларусьInstitute of Physical Organic Chemistry, National Academy of Sciences of Belarus.BelarusИнститут физико-органической химии, Национальная академия наук Беларуси .БеларусьInstitute of Physical Organic Chemistry, National Academy of Sciences of Belarus .BelarusВитебский государственный ордена Дружбы народов медицинский университет.БеларусьVitebsk State Order of Peoples’ Friendship Medical University .Belarus201823062018542168179Copyright © Дикусар Е.А., Филиппович Л.Н., Шахаб С.Н., Петкевич С.К., Стёпин С.Г., 20182018Дикусар Е.А., Филиппович Л.Н., Шахаб С.Н., Петкевич С.К., Стёпин С.Г.Dikusar E.A., Filippovich L.N., Shahab S.N., Petkevich S.K., Stepin S.G.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vestichem.belnauka.by/jour/article/view/318

Оксим 4-аминоацетофенона является удобным и доступным реагентом для химической модификации замещенных ароматических альдегидов с целью получения лигандов для комплексообразования с переходными металлами. Взаимодействием оксима 4-аминоацетофенона с альдегидами ванилинового ряда, в среде кипящего абсолютного метанола в присутствии каталитических количеств ледяной уксусной кислоты были синтезированы (E,E)-азометины с выходами 70–85 %. Взаимодействием 4-аминоацетофенона с 9-фенантренкарбальдегидом, ферроценкарбальдегидом, 5-фенилизоксазол-3-карбальдегидом и 5-(п-толил)изоксазол-3-карбальдегидом были получены соответствующие (E,E)-азометиноксимы c выходом 77–84 %. Ацилированием оксима (E)-1-{4-(E)-бензо[d][1,3]диоксол-5-илметиленаминофенил}этан-1-она хлорангидридом 4,5-дихлоризотиазол-3-карбоновой кислоты в растворе сухого диэтилового эфира в присутствии триэтиламина был синтезирован соответствующий сложный эфир с вы- ходом 84 %. Путем квантово-химических расчетов с использованием метода DFT с применением уровня теории B3LYP1/MIDI, программного пакета GAMESS и базисного набора MIDI установлены наиболее термодинамически устойчивые изомеры ряда синтезированных соединений. При расчетах проводили оптимизацию всех геометрических параметров до достижения минимумов полных электронных энергий (E,E)-, (E,Z)-(Z,E)- и (Z,Z)-азометиноксимов.

4-Aminoacetophenone oxime is convenient and accessible reagent for chemical modification of substituted aromatic aldehydes to produce ligands for complexation with transition metals. By the reaction of 4-aminoacetophenone oxime with aldehydes vanillyl series by boiling in absolute methanol in the presence of catalytic amounts of glacial acetic acid, (E,E)-azomethyneoximes with 70–85 % yields were synthesized. By the reaction of 4-aminoacetophenone oxime with 9-phenanthrene carboxaldehyde, ferrocene carboxaldehyde, 5-phenylisoxazole-3-carboxaldehyde and 5-(p-tolyl)isoxazole- 3-carboxaldehyde, corresponding (E,E)-azomethineoximes with 77–84 % yield were obtained. By acylation of the (E)-1-{4-(E)-benzo[d][1,3]dioxol-5-ylmethyleneaminophenyl}ethan-1-one oxime in a solution of dry diethyl ester in the presence of triethylamine, corresponding ester was synthesized with 84 % yield. By quantum chemical calculations using DFT method using level B3LYP1 / MIDI using the theory GAMESS software package and a MIDI basic set, we defined the most thermodynamically stable isomers of the synthesized compounds. In the process of calculations a full optimization of all geometric parameters to achieve a minimum total energy (E,E)-, (E,Z)-, (Z,E)- and (Z,Z)-azomethineoximes was carried out.

4-аминоацетофененоксим 4-аминоацетофенонаальдегиды9-фенантренкарбальдегидфер- роценкарбальдегид5-фенилизоксазол-3-карбальдегид5-(р-толил)изоксазол-3-карбальдегид(EE)-азометиноксимыкрасителиквантово-химические расчетымоделирование4-aminoacetophenone4-aminoacetophenone oximealdehydes9-phenanthrene carboxaldehydeferrocene carboxaldehyde5-phenylisoxazole-3-carboxaldehyde5-(p-tolyl)isoxazole-3-carboxaldehyde(EE)-azomethineoximescolourantesquantum-chemical calculationsmodelingБелорусский республиканский фонд фундаментальных исследований (гранты Х 15СО-006 и Х 16–021).Belarusian Republican Foundation for Fundamental Research (grants № Х 15СО-006 and Х 16–021).ReferencesZhao, L. 1-(4-{[(E)-4-Methylbenzylidene]amino}phenyl)ethanone oxime / L. Zhao, S. W. Ng // Acta Crystall. Sec. E. Struct. Reports Online. – 2010. – Vol. 66, № 10. – P. o2473. DOI: 10.1107/s1600536810034598Zhao L., Ng S. W. 1-(4-{[(E)-4-Methylbenzylidene]amino}phenyl)ethanone oxime. 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The authors declare that there are no conflicts of interest present.