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CHEMICAL PROBLEMS 2019 no. 1 (17) ISSN 2221-8688
UOT 547.74/75, 547.741
SYNTHESIS OF 2,3-DITHIOFENIL DERIVATIVES OF PYRROL ON THE BASIS OF 2,2-THIONINE
A.M. Maharramov*, P. Akay**, I.M. Akhmedov*, A.S. Safarova*, M.M. Qurbanova*,
E.Z. Huseynov*, S.A. Musayeva*
*Baku State University 23, Z. Khalilov str., AZ-1148 Baku, Azerbaijan; e-mail: [email protected] **Middle East Technical University 06800, Ankara,Turkey
Received 05.01.2019
It is known that pyrrole and its derivatives are a part of many important natural compounds. Polymeric semiconductors also were obtained on the basis of 2,5-dithienyl-pyrrole electropolymerization and its derivatives. The work deals with the synthesis of 2,3-dithiophenyl-1H-pyrroles by the reaction of 2,2'-thionine with various enamines.
Keywords: pyrrol, 2,2'-thionine, pyrrole derivative, 2,3-dithiophenyl-1H-pyrroles,enamines Doi.org/10.32737/2221-8688-2019-1-100-104
INTRODUCTION
Pyrrol and its derivatives hold a specific place between the five-membered heterocyclic compounds [1,2]. It is known that the pyrrol ring is a part of the composition of many important physiologically active natural organic compounds - chlorophyll, hemoglobin, vitamin B12, Crisprine A, Lettowainthine, Lamellarin D. Note that interest in pyrrole compounds is based on their antibacterial, antimicrobial, antidiabetic, etc. properties.
At present, a five-membered optical active pyrrole derivative "Lipitor" is the most widely used drug to decrease the amount of cholesterol in the blood [4].
Compounds containing porphyrin, phthalocyanine and BDP (bordipyrrolometane dyes) fragments which are synthesized on the basis of pyrrole are indispensable specific materials for preparation of sensors and photonstyl ators in the optical electronics and electrical industry [5,6]. Recently, many
articles have been devoted to the synthesis and electrolysis of 2.5-dithiophene derivatives of pyrroles in the production of semiconductor polymers. Due to the effect of weak electric current these polymers change colors into red, green, and blue and thus play a crucial role in the development of internet and television technology [7,8].
The main objective of the article is to study the synthesis and structure of derivatives of the 2,3-dithiophene especially as there is no sufficient information about the subject in the literature.
The 2,3-dithiophene of pyrrole is obtained from the condensation of 2,2'-thionine with various enamins at high temperature.
Thiophene-2-aldehyde was synthesized in the presence of the 2,2'-thionine thiamine hydrochloride catalyst by using the known method in the literature.
r~\_c_H + r~\_c_H tlliamine-HCl / \—C-CH-
^Ol CH
o
(I)
The structure of this substance was proved with H1-NMR spectroscopy. Two doublets was detected at 4.35 and 6.0 pp.m for the CH-OH fragment. Six protons of two thiophene rings was detected at 4.35 and 6.0
pp.m chemical shift as singlet and doublet peaks.The three enamins that we used as starting materials were also synthesized according to the following scheme [9].
H3C-
R=
O
O
R + NH4OAC
H-
-H3 (II); CO2C2H5 (m); CN (IV).
CH
R
H
The structure and purity of the synthesized enamines (II-IV) were explored by the NMR-spectroscopy and the TLC method. The 2,3-
dithiophene derivatives of the pyrolyte were synthesized by condensation of 2,2'-thionine with enamines at 140 ° C in acetic acid.
r h ho
R ,HOH R'
V v:
-oac
H 'hHO
H
R'
-oac
O CH3
H^ ^C'
O
H
R OH R'
v:
HO
H
%
-H-O
R^/HOH ^R' R^ o R'
' "" H
R'
H H
h-oac
R H OHR'
H R'
R
R R'
H-O
^^t^R' H3C N
H3C' "N'
H
R'
(V-VII)
+
Compounds (V-VII) were provided with H1 and C13 NMR spectroscopy. (VI) In the pyrrole spectrum CH3 protons of the CO2C2H5 fragment consist of triplet which were detected at lpp.m (J = 7.0 Hz), and CH2 protons at 4.04 pp.m (J = 7.0Hz) as a quartet. The methyl
radical of the pyrrole ring was observed as a singlet at 2,5 pp.m , and proton NH was observed as wide peak at the 8.30 pp.m. The six protons of the two thiophenes were observed as a multiplet at 6.80- 7.30 pp.m. (Fig. 1).
■ ■ I ■ ■ ■ ■ I ■ ■ ■ ■ I ■ ■ ■ ■ I ■ ■ ■ ■ I ■ ■ ■ ■ I ■—■ ■ I............I..........I-——r---1........ . ■ ■ 1 1 I....... I......I ■ ■ ■ ■ I ■ • ■ ■ I ■ ■ ■ ■ I-
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4,0 3.5 3,0 2.5 2.0 1.5 1.0 0.5 0.0 pptn
Figure 1. H1NMR spectroscopy of 2,3-dithiophene-4-etylcarbocsilate-5-methyl-1H-pyrrole Pyrrole compound (VI) was also observed at 12.90 and 12.69 pp.m areas, but
13
studied by C NMR spectroscopy. As seen in OCH2 carbon atom at 58.30 pp.m. The carbon
the spectrum (Picture 2), (5) compound atom of C=O group's carbon atom was
contains 16 carbon atoms. Carbon atoms of observed at 164.10 pp.m weak area. pyrrole ring's and CO2C2H5, CH3 radicals were
13
Figure 2. C NMR spectroscopy of 2,3-dithiophene-4-etylcarbocsilate-5-methyl-1H-pyrrole
13
C NMR spectroscopy of the pyrrole and two thiophene rings was observed in the following area (m.h.):112.18, 114.11, 122.12, 123.56,
123.83, 124.86, 125.54, 125.90, 127.34, 132.65, 134.66, 135.21.
(V-VII) pyrrole compounds were proved by H1 and C13 NMR spectroscopy
EXPERIMENTAL PART
The H1 and C13 NMR spectroscopy of the synthesized compounds were studied in the Bruker DPX400 (CDCh) and their cleaning
was investigated by UB light (k = 254nm) on the thin layer.
The synthesis of 2,2-thionine.
Thiaminehydrochloride salt 1.68 (5mmol), 4.2 ml (30 mmol) triethylamine and 8.9 ml (100 mmol) thiophene 2-aldehyde were placed in 25 ml flask, then added to 30 ml anhydrousethyl, left it stirring under condenser for 24 h at the room temperature. At the end of the reaction the mixture was filtered and the precipitation washed through cold ethanol, then left it to dry.
Note that 10 q compound was obtained in the yield of 78 % (melting point 39°C) H1 NMR spectroscopy for (CDCh): 5, 4,35 d (CH), 6.0 d (OH), 6.90 d (1H), 7.10 m (2H), 4.40 d (1H), 7.70 dd (2H).
The synthesis of 2,3-dithiophene-4-acetoxy-5-methyl-1H-pyrrole (V).
1q (0.1 mol) Pluorine-P, 2.24 q (0.1 mol)2,2'-thionine and 3.08 q (0.4 mol) ammoniumacetate were placed in a 25 ml flask, then left it to reflux at the 140°C for 2 h. Upon completion, the mixture left it to remain at room temperature, then 30 ml ethylacetate was added, washed with water and 5% NaHCO3. After that, MgSO4 used to dry water. Ethylacetate was evaporated and 2.15 q 75% liquid compound obtained. (V) H1 NMR spektroscopy for (CDO3): 5, 1.80 s (CH3), 2.50 s (COCH3), 6.80 d (2H, HC=), 6.90 s (1H, HC=), 7.00 m (2H, HC=), 7.30 d
(1H, HC=), 9.00 s (1H, NH). C13 (CDCls): 14.47 (CH3), 30.00 (CDCH3), 113.97, 123.01, 123.67, 124.45, 126.89, 127.11, 127.36, 129.48, 133.57, 135.93, 136.32, 196.46 (C=O).
The synthesis of 2,3-dithiophene-4-ethylcarboxylate-5-methyl-1H-pyrrole (VI).
The same prosedure was used for (VI) where 73% liquid was synthesized. H1 NMR (CDO3) : 5, 1.00 t (3H, CH3, J=7Hz), 2.50 S (3H,CH3), 4.00 Kv (2H, COCH2, J = 7,00Hz), 6.70-7.30 m (6H, HC=), 8.30 S (1H, NH).
C13(CDCl3) : 12.59, 12.90, 58.34, 112.81, 114.11, 122.11, 123.35, 123.38, 124.86, 125.54, 125.89, 127.34, 132.64, 134.66, 135.21, 164.11 (C=O).
The synthesis of 2,3-dithiophene-4-nitryl-5-methyl-1H-pyrrole (VII)
(1.7q) Pyrrole derivative (78%) (VII) was synthesized from the mixture of 2,2' thionine (2.24q), 1-methyl, 2-amine acronitrile (0.68 g), ammonium acetate (3.08g) and 10 ml of vinegar acid by using the same prosedure. H1 NMR (CDCl3): 5, 2,40 S (3H, CH3), 6.907.20 m (6H, HC=), 8.80-8.90 m (1H, NH). C13(CDCl3) : 5, 13.30, 93.94, 116.45, 122.81, 125.32, 125.85, 127.15, 127.33, 128.25, 129.05, 132.07, 133.46, 137.89, 138.06.
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2,2'- TiONiN OSASINDA 2,3-DiTiOFENiL PiRROL TÖRdMOLdRIMN SiNTEZi
A.M. Mdhdrrdmov*, P. Akay**, i.M. dhmsdov*, A.§. Sdfzrova*, M.M. Qurbanova*,
S.A. Musayeva*, E.Z. Hüseynov*
*Baki Dövldt Universiteti AZ1148 Baki, Z.Xdlilov küg., 23; e-mail: [email protected] **Orta Dogu Texniki Universiteti 06800, Ankara, Türkiyd
Pirrol vd onun tördmdldri vacib tdbii birld^mdldrin tdrkibind daxildir. Eyni zamanda 2,5-ditienil-pirrol vd onun tördmdhri dsasinda yarimkegirici polimer pirrollar sintez olunub. 2,2'-tioninin müxtdlif enaminldrld reaksiyasi dsasinda 2,3-ditiofenil-1H-pirrollarin alinmasina hdsr olunub. Agar sözfor: pirrol, tionin, enamin, 2,3-ditiofenil-1H-pirrollar
СИНТЕЗ 2,3-ДИТИОФЕНИЛПРОИЭВОДНЫХПИРРОЛА НА ОСНОВЕ 2,2-ТИОНИНА
А.М. Магеррамов*, П. Акай**, И.М. Ахмедов*, А.Ш. Сафарова*, М.М. Курбанова*,
Е.З. Гусейнов*, С^.Мусаева*
*Бакинский Государственный Университет AZ1148 Баку, ул. З.Халилова, 23; e-mail: [email protected] **Ближневосточный Технический Университет 06800, Анкара, Турция
Пиррол и его производные входят в состав многих важных природных соединений. На основе электрополимеризации 2,5-дитиенил-пиррола и их производных получены также полимерные полупроводники. Работа посвящена синтезу 2,3-дитиофенил-1Н-пирроловреакцией 2,2'-тионина с различными енаминами.
Ключевые слова: пиррол, тионин, 2,3-дитиофенил-1Н-пирролы, енамин
