REACTIONS OF 3-AROYL-1H-PYRROLO[2,1-C][1,4]BENZOXASINE-1,2,4-TRIONES WITH GEWALD THIOPHENES Текст научной статьи по специальности «Химические науки»

ВЕСТНИК ПЕРМСКОГО УНИВЕРСИТЕТА

Том 9 Химия Вып. 4

УДК 547.745 +547.86+547.867.4 DOI: 10.17072/2223-1838-2019-4-416-421

Д.И. Пчелинцева1, Д.Н. Лукманова2, Я.И. Приходько2, П.Т. Павлов2, И.В. Машевская2, С. Чаудхари3

1 Пермский государственный аграрно-технологический университет имени академика Д.Н. Прянишникова, Пермь, Россия

2 Пермский государственный национальный исследовательский университет, Пермь, Россия

3 Малавийский национальный технологический институт, Джайпур, Индия

ВЗАИМОДЕЙСТВИЕ 3-АРОИЛ-Ш-ПИРРОЛО[2,1-с][1,4]БЕНЗОКСАЗИН-1,2,4-ТРИОНОВ

С ТИОФЕНАМИ ГЕВАЛЬДА

Исследованы реакции 3-ароил-1Н-пирроло[2,1-с][1,4]бензоксазин-1,2,4-трионов с рядом тиофенов Гевальда. Установлено, что в результате этих реакций образуются замещенные (2)')-этил 2(2,4-диоксо-3-(2-оксо-2Н-бензо[b][1,4]оксазин-3(4Н)-илиден)-4-арилбутанамидо)-тиофен-3-карбоксилат ы.

Ключевые слова: гетарено[е]пиррол-2,3-дионы; тиофены Гевальда; рециклизация

D.I. Pchelintseva1, D.N. Lukmanova2, J.I. Prikhodko2, P. T. Pavlov2, I.V. Mashevskaya2, S. Chaudhary3

1 Perm State Agro-Technological University, Perm, Russia

2 Perm State University, Perm, Russia

3 Malaviya National Institute of Technology, Jaipur, India

REACTIONS OF 3-AROYL-1#-PYRROLO[2,1-c][1,4]BENZOXASINE-1,2,4-TRIONES WITH

GEWALD THIOPHENES

The reactions of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with a number of Gewald thiophenes were studied. It was established that as a result of these reactions, substituted (Z)-ethyl 2(2,4-dioxo-3-(2-oxo-2H-benzo[b][1,4]oxazin-3(4H)-ylidene)-4-arylbutanamido)thiophene-3-carboxylates.

Keywords: hetareno[e]pyrrole-2,3-diones; Gewald's thiophenes; recyclization

© Пчелинцева Д.И., Лукманова Д.Н., Приходько Я.И., Павлов П.Т., Машевская И.В., Чаудхари С., 2019

nnenuH^ea ff.H., flyKMaHoea ff.H., npuxoôbKO KH., u dp.

Gewald's thiophenes [1] are widely used as convenient "building blocks" for the synthesis of condensed heterocycles.

It was previously discovered that reactions of these reagents with pyrroloquinoxalinetriones lead to pharmacologically active products [2], while the interaction of 3-aroyl-1H-pyrrolo [2,1-c][1,4]benzoxazine-1,2,4-triones with Gewald's thiophenes have not been previously studied.

It was found that in the reaction of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine- 1,2,4-triones with

a number of Gevald thiophenes, carried out by short boiling in anhydrous acetonitrile, gives the products of the initial nucleophilic addition of the reagent to the carbon atom at position 1 of the pyrrolbenzoxazintrione molecule, followed by the disclosure of the pyrroldione ring via the C:-N10 bond and the formation of recycling products -substituted (Z)-ethyl 2(2,4-dioxo-3-(2-oxo-2H-benzo [b] [1,4] oxazin-3 (4H)-ylidene)-4-arylbutan-amido)thiophene-3 -carboxylates (Illa-e)

R

nia-d

o

EtOOC

COPh

^ H

me O

EtOOC

1

Ar=Ph (Ia), 4-MeC6H4 (Ib); R=Rj=Me, Ar=4-MeC6H4 (IIa, IIIa), R=Ph, Rj=Me, Ar=4-MeC6H4 (IIb, IIIb), R=Me, Ri=Ph, Ar=4-MeC6H4 (IIc, IIIc), R= Ri=Ph, Ar=4-MeC6H4 (Ild, IlId)

Compounds III (a-e) are crystalline substances of orange color, insoluble in common organic solvents, insoluble in water and alkanes. They do not give a positive enols test (cherry color) with an alcoholic solution of iron (III) chloride.

The structure of the synthesized compounds was confirmed by the IR and NMR spectroscopy data.

The IR spectra of compounds III (a-e) contains bands of stretching vibrations of NH groups around 3209-3280 cm-1, carbonyl ester groups around 1774-1778 cm-1, carbonyl groups of the CONH side chain, C2=O, and aroyl fragments in the area of 1572-1656 cm-1, the band "amide II" around 1511-1530 cm-1.

B3auModeucmeue 3-apom-1H-nupporn[2,1-c][1,4]6eH30Kca3UH-1,2,4-mpuonoe.

In the :H NMR spectra of compounds III (a-e), in addition to the signals of aromatic protons and related groups, there are singlets of the proton of the amide NH group of the side chain in the region of 12.24-12.39 ppm, an extended singlet of the proton of the N1H group in the region of 14.04-14.12 ppm.

Experimantal data

IR spectra of the synthesized compounds were recorded on an FSM-1201 spectrophotometer in liquid paraffin. :H NMR spectra were recorded on a Bruker Avance III HD 400 spectrometer in DMSO-d6; HMDS was used as the internal standard. The identity of the synthesized compounds was confirmed by thin layer chromatography on Silufol plates, eluents — ethyl acetate, ethyl acetate-benzene, 1:5, chromatograms showed iodine vapor.

(Z)-Ethyl 2-(2,4-dioxo-3-(2-oxo-2H-benzo [b] [1,4] oxasine-3(4H)-ylidene)-4-(4-tolylbutanamido)-4,5-dimethylthiophene-3-carboxylate (IIIa)

To a solution of 0.005 mol of 3-(4-methylbenzoyl)- 1H-pyrrolo[2,1 -c][1,4]benzoxazine-1,2,4-trione [3], in anhydrous acetonitrile were added 0.005 mol of ethyl-2-amino-4,5-dimethylthiophene-3 -carboxylate [1], heated for 5-10 minutes, after which the reaction mixture was left for a day, the precipitate of compound (IIIa) was filtered off, recrystallized from anhydrous acetonitrile. Yield 84%, m.p. = 253-255 ° C. IR spectrum (FSM-120, liquid paraffin, v, cm-1): 3209, 3236 (NHCO, NH), 1775 (COO), 1689 (CONH), 1668 (COAr), 1579 wide C2 = O), 1521 (amide II). 'H NMR spectrum, 5, ppm: 1.37 t (3H, CH3), 1.39 t (3H, CH3), 2.36 s

(6H, 2CH3), 4.38 q (2H, CH2), 7.15-7.70 gr.s. (8H, 2C6H4), 12.30 s (1H, NHCO), 14.10 br.s. (1H, NH). Found, %: C 63.18; H 4.52; N 5.25. C28H24N2O7S. Calculated, %: C 63.15; H 4.54; N 5.26.

(Z)-Ethyl 2-(2,4-dioxo-3-(2-oxo-2H-benzo [b] [1,4] oxasine-3(4H)-ylidene)-4-(4-tolylbutanamido)-4-methyl-5-phenylthiophene-3-carboxylate (IIIb)

Synthesized similarly. Yield - 79%, T.nn. = 202-203°C.

IR spectrum (FSM-120, liquid paraffin, v, cm" 1): 3190, 3274 (NHCO, NH), 1775 (COO), 1680 (CONH), 1667 (COAr), 1572 m (C2 = O), 1511 (amide II). :H NMR spectrum, 5, ppm: 1.34 t (3H, CH3), 1.42 t (3H, CH3), 2.34 s (6H, 2CH3), 4.34 q (2H, CH2), 7.30-7.96 gr.s. (8H, 2C6H4), 12.32 s (1H, NHCO), 14.10 br.s. (1H, NH). Found, %: C 66.65; H 4.41; N 4.72. C33H26N2O7S. Calculated, %: C 66.66; H 4.41; N 4.71.

(Z)-Ethyl 2-(2,4-dioxo-3-(2-oxo-2H-benzo [b] [1,4] oxasine-3(4H)-ylidene)-4-(4-tolylbutanamido)-5-methyl-4-phenylthiophene-3-carboxylate (IIIc)

Synthesized similarly. Yield - 81%, m.p. = 230-232°C. IR spectrum (FSM-120, liquid paraffin, v, cm-1): 3175, 3230 (NHCO, NH), 1774 (COO), 1690 (CONH), 1658 (COAr), 1586 m (C2 = O), 1521 (amide II). :H NMR spectrum, 5, ppm: 0.73 t (3H, CH3), 2.01 t (3H, CH3), 2.33 s (6H, 2CH3), 3.94 q (2H, CH2), 7.10-7.76 gr.s. (8H, 2C6H4), 12.24 s (1H, NHCO), 14.04 br.s. (1H, NH). Found, %: C 66.65; H 4.43; N 4.71. C33H26N2O7S. Calculated, %: C 66.66; H 4.41; N 4.71.

(Z)-Ethyl 2-(2,4-dioxo-3-(2-oxo-2H-

benzo [b] [1,4] oxasine-3(4H)-ylidene)-4-(4-tolylbutanamido)-4,5-diphenylthiophene-3-carboxylate (IIId)

Synthesized similarly. Yield - 78%, m.p. = 263-265°C. IR spectrum (FSM-120, liquid paraffin, v, cm-1): 3212, 3280 (NHCO, NH), 1777 (COO), 1685 (CONH), 1656 (COAr), 1580 m (C2 = O), 1520 (amide II). :H NMR spectrum, 5, ppm: 0.77 t (3H, CH3), 1.29 t (3H, CH3), 2.35 s (6H, 2CH3), 3.98 q (2H, CH2), 7.04-7.84 gr.s. (8H, 2C6H4), 12.39 s (1H, NHCO), 14.12 br.s. (1H, NH). Found, %: C 69.53; H 4.29; N 4.27. C38H28N2O7S. Calculated, %: C 69.50; H 4.30; N 4.27.

(Z)-Ethyl 2-(2,4-dioxo-3-(2-oxo-3,4-dihydro-2H-benzo [b] [1,4] oxasine-3-yl)-4-(phenylbutanamido)-4,5,6,7-tetrahydrobenzo [b]thiophene-3-carboxylate (IIIe)

Synthesized similarly. Yield - 71%, m.p. = 230-232°C.

IR spectra (FSM-120, liquid paraffin, v, cm"1): 3210, 3230 (NHCO, NH), 1778 (COO), 1690 (CONH), 1665 (COAr), 1579 m (C2=O), 1530 (amide II). :H NMR spectrum, 5, ppm.: 1.70 gr.s. (4H, 2CH2), 2.79 s (2H, CH2), 4.04 q (2H, CH2), 7.14-7.79 gr.s. (8H, 2C6H4), 12.33 s (1H, NHCO), 14.10 s (1H, NH). Found, %: C 63.97; H 4.45; N 5.12. C29H24N2O7S. Calculated, %: C 63.96; H 4.44; N 5.14.

The study was carried out with the financial support of the Government of the Perm Area as part of the scientific project No S"26 /174.5

Библиографический список

1. K.Giewald, E.Schinke, H.Bottcher. 2-Aminotiophene aus methylenaktiven Nitrilen, Carbonylverbindungen und Schwefe// Chemische Berichte.1966. B. 99. P. 94-100.

2. Kotegov V.P ., Mashevskaya I.V., Pavlov P.T., Pchelintseva D.I. Synthesis and antidiabetic activity of products of the reaction between 3-aroylpyrrolo[1,2-a]quinoxaline- 1,2,4(5Н)-triones with Gewald's thiophenes // Bulletin of Perm University. Chemistry. 2015, Iss.4 (20). Pp. 66-77.

3. Maslivets A.N., Mashevskaya I.V., Smirnova L.I., Krasnykh O.P., Shurov S.N., Andreichikov Yu.S. Five-membered 2.3-dioxoheterocycles. Synthesis of 3-aroyl-1,2-dihydro-4H-pyrrolo [5,1-c][1,4]benzoxasine-1,2,4-triones and their reactions with water and alcohols // Russ. Journal of Organic Chemistry. 1992, Vol.25. Pp. 2545-2553.

References

1 K.Giewald, E.Schinke, H.Bottcher. 2-Aminotiophene aus methylenaktiven Nitrilen, Carbonylverbindungen und Schwefe// Chemische Berichte.1966. B. 99. P. 94-100.

2 V.P.Kotegov, Mashevskaya I.V., Pavlov P.T., Pchelintseva D.I. Synthesis and antidiabetic activity of products of the reaction between 3-aroylpyrrolo[1,2-a]quinoxaline- 1,2,4(5Н)-triones with Gewald's thiophenes // Bulletin of Perm University. Chemistry. 2015, Iss.4 (20). Pp. 66-77.

3 Maslivets A.N., Mashevskaya I.V., Smirnova L.I., Krasnykh O.P., Shurov S.N., Andreichikov Yu.S. Five-membered 2.3-dioxoheterocycles. Synthesis of 3-aroyl-1,2-dihydro-4H-pyrrolo [5,1-c][1,4]benzoxasine-1,2,4-triones and their reactions with water and alcohols // Russ. Journal of Organic Chemistry. 1992, Vol.25. Pp. 2545-2553.

Взаимодействие 3-ароил-1Н-пирроло[2,1-с][1,4]бензоксазин-1,2,4-трионов.

Об авторах

Пчелинцева Дарья Игоревна, аспирант

Пермский Государственный аграрно-технологический университет имени Академика Д.Н.Прянишникова

614045, г. Пермь, ул. Петропавловская, 23.

Лукманова Джамиля Наильевна, магистрант химического факультата Пермский государственный национальный исследовательский университет 614990, г. Пермь, ул. Букирева, 15. lukmanova.96@mail.ru

Приходько Ярослав Игоревич, аспирант химического факультета Пермский государственный национальный исследовательский университет 614990, г. Пермь, ул. Букирева, 15. j aroslavpr@mail. ги

Павлов Петр Тимофеевич,

кандидат химических наук, доцент кафедры

органической химии

Пермский государственный национальный исследовательский университет Россия, 614990, г. Пермь, ул. Букирева, 15.

Машевская Ирина Владимировна, доктор химических наук, профессор, декан химического факультета Пермский государственный национальный исследовательский университет 614990, г. Пермь, ул. Букирева, 15. mashevskaya-irina@mail. ги

About the authors

Pchelintseva Daria Igorevna, Ph.D. student

Perm State Agro-Technological University 614045, Perm, Petropavlovskaya St., 23

Lukmanova Dzhamilya Nailevna,

undergraduate chemical faculty

Perm State University

15, Bukireva st., Perm, Russia, 614990

lukmanova.96@mail.ru

Prikhodko Yaroslav Igorevich, graduate student in chemistry Perm State University 15, Bukireva st., Perm, Russia, 614990 j aroslavpr@mail. ru

Pavlov Pyotr Timofeevich,

candidate of chemistry, Associate Professor,

Department of Organic Chemistry

Perm State University

15, Bukireva st., Perm, Russia, 614990

Mashevskaya Irina Vladimirovna,

Doctor of Chemical Sciences, Professor, Dean of

the Faculty of Chemistry

Perm State University

15, Bukireva st., Perm, Russia, 614990

mashevskaya-irina@mail. ru

Сандип Чаудхари, Sandeep Chaudhary,

PhD, профессор Малавийского Национального PhD, Assistant Proffessor of the Deptartment of Технологического Института, Джайпур, Индия Chemistry,

302017, г. Джайпур, ул. Джавахарлала Неру Malaviya National Institute of Technology Jaipur

Jawahar Lal Nehru Marg, Jhalana Gram, Malviya Nagar, Jaipur, Rajasthan 302017, India

Информация для цитирования:

Пчелинцева Д.И., Лукманова Д.Н., Приходько Я.И., Павлов П.Т., Машевская И.В., Чаудхари С. Взаимодействие 3-ароил-1Н-пирроло[2,1-с][1,4]бензоксазин-1,2,4-трионов с тиофенами Гевальда // Вестник Пермского университета. Серия «Химия». 2019. Т. 9, вып. 4. С. 416-421. DOI: 10.17072/22231838-2019-4-416-421.

Pchelintseva D.I., Lukmanova D.N., Prikhodko Ia.I., Pavlov P.T., Mashevskaia I.V., Chaudkhari S. Vzaimodeistvie 3-aroil-1N-pirrolo[2,1-s][1,4]benzoksazin-1,2,4-trionov s tiofenami Gevalda [Reactions of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxasine-1,2,4-triones with Gewald thiophenes] // Vestnik Permskogo universiteta. Seriya «Khimiya» = Bulletin of Perm University. Chemistry. 2019. Vol. 9. Issue 4. P. 416-421 (in Russ.). D0I:10.17072/2223-1838-2019-4-416-421.