New Carbazole-Containing Chalcones and ... - Springer Link

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 4, pp. 530–536. © Pleiades Publishing, Ltd., 2011. Original Russian Text © R.V. Syutkin, G.G. Abashev, E.V. Shklyaeva, P.G. Kudryavtsev, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 4, pp. 532–537.

New Carbazole-Containing Chalcones and Pyrimidines Based Thereon: Synthesis and Electrochemical Study R. V. Syutkina, G. G. Abasheva, b, E. V. Shklyaevab, and P. G. Kudryavtsevc a

Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences, Perm, Russia

b

Institute of Natural Sciences, Perm State Universitety, ul. Genkelya 4, Perm, 614990 Russia e-mail: [email protected] c

“Trivektr” Scientific and Industrial Association Ltd., Perm, Russia Received January 5, 2009

Abstract—Condensations of aromatic carbo- and heterocyclic ketones and aldehydes in methanol gave new chalcones containing carbazole fragments, 1,3-diaryl(9-R-9H-carbazol-3-yl)prop-2-en-1-ones. Some of the synthesized chalcones reacted with guanidine sulfate to produce 2-amino-4,6-diarylpyrimidines that are promising materials for the design of light emitting diodes. Study on electrochemical polymerization of both chalcones and pyrimidines derived therefrom showed that almost all the examined substrates give rise to stable colored conjugated polymer films on the surface of working electrode under conditions of cyclic voltammetry.

DOI: 10.1134/S1070428011040117 and optical properties of the resulting polymer over a wide range [4]. Conjugated polymers containing chalcone fragments, in particular those having carbazole and thiophene rings, were not reported previously, though the synthesis of some carbazole-containing chalcones was described; however, these chalcones were synthesized for other purposes. For example, Zotti et al. [5] described the synthesis of fluorescent conjugated diarylcarbazolyldihydropyrazole systems, while Nagarajan and Perumal [6] reported on pyrazolylcarbazoles and carbazolylquinolines possessing a broad spectrum of biological activity. In addition,

Synthesis of new conducting organic polymers and study on their properties constitute a promising line in organic chemistry. Among conjugated polymers, an important place is occupied by those containing carbazole fragments as a part of the conjugation system. Such polymers attract strong interest due to their unique properties, specifically high thermal and chemical stability, high luminescence quantum yield, blue luminescence in organic light emitting diodes (OLED), and high hole conduction [1–3]. Introduction of various substituents and functional groups into carbazole rings makes it possible to vary electrophysical

Scheme 1. CHO DMF, POCl3, PhCl N

RBr, [Et3NBzl]+ Cl– 50% aq. NaOH, Me2CO

R III, IV

N H

N

Ac

AcBr, SnCl4 anhydrous CH2Cl2

R I, II

N R V, VI

I, III, V, R = Et; II, IV, VI, R = Bu.

530

NEW CARBAZOLE-CONTAINING CHALCONES

531

Scheme 2. O Ar

O

R2 = Me, R3 = H R

R1

O

KOH, MeOH

+ R

N

N

2

3

VII–X, XIV, XVI–XVIII O

Ar

Ar

R1 R2 = H, R3 = Me N R1 XI–XIII, XV 1

1

VII–XII, XVII, XVIII, R = Et; XIII–XV, R = Bu; VII, XII, XIV, XV, Ar = 2-thienyl;

VIII, XVI, Ar =

; IX, Ar = 4-BrC6H4; X, Ar = 4-MeC6H4; XI, Ar = ferrocenyl; XIII, XVII, Ar =

; N

N Et

Bu

O

XVIII, Ar =

.

.

N Et

chalcones are important as intermediate products in organic synthesis, e.g., in the preparation of various heterocyclic compounds [7], in particular of substituted pyrimidines [8]. The latter are electron-deficient heterocycles that attract interest from the viewpoint of their use as materials for molecular electronics [9]. In the present work we developed a procedure for the synthesis of chalcones containing carbazole, thiophene, and ferrocene fragments; the obtained compounds were converted into substituted pyrimidines; and polymerization of both initial chalcones and pyrimidines was studied. As starting compounds we used N-substituted carbazole-3-carbaldehydes III and IV and carbazol-3-yl methyl ketones V and VI which were prepared in turn by Vilsmeier–Haak formylation of N-alkylcarbazoles I and II or acylation of the latter with acetyl bromide according to the procedure described in [10]. N-Alkylcarbazoles I and II were synthesized by alkylation of carbazole under conditions of phase-transfer catalysis (Scheme 1). The second components in the synthesis of carbazole-containing chalcones (Scheme 2) were acetylferrocene prepared as described in [12] and

2-acetylthiophene which was obtained by acetylation of thiophene with acetic anhydride in the presence of phosphoric acid [13]. Several approaches were tested for the synthesis of chalcones [6, 7, 14–17]. The most appropriate procedure implied stirring of equimolar amounts of the corresponding carbonyl compounds in methanol in the presence of potassium hydroxide at room temperature over a period of 24 h [17]; only in the synthesis of ferrocene derivative, heating of the reaction mixture for 3 h under reflux was necessary. All chalcones VII–XVIII were not reported previously; their structure was confirmed by IR and 1H NMR spectroscopy. Compounds VII–XVIII characteristically displayed in the 1 H NMR spectra signals from protons in the CH=CHCO fragment with a large 1H–1H coupling constant (3J = ~15 Hz). In addition, some of the products were analyzed by gas chromatography– mass spectrometry (GC–MS). Structures containing both electron-deficient and electron-rich heterocyclic fragments are important in the design of various devices on the basis of conjugated polymers. Such polymers could possess both n- and p-type conductivity; therefore, some of the synthesized

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

SYUTKIN et al.

532

Scheme 3. Ar

O Ar'

Ar

Ar'

(NH2)2C=NH · H2SO4

Ar

N

NH

N

NH2 VIII, IX, XI, XII, XVIII

Ar =

N NH2

A

; XIX, Ar′ =

Ar'

H2O2

XIX–XXIII

; XX, Ar′ = 4-BrC6H4; XXI, Ar′ = ferrocenyl; XXII, Ar′ = 2-thienyl;

N

N

Et

Et

XXIII, Ar′ =

; N Et

N N NH2

chalcones, namely compounds VIII, IX, XI, XII, and XVIII were converted into 4,6-disubstituted pyrimidines XIX–XXIII having electron-donating groups (Scheme 3) via cyclization with guanidine sulfate in ethanol in the presence of 50% aqueous potassium hydroxide and subsequent oxidation of intermediate dihydropyrimidine A with hydrogen peroxide [8]. Pyrimidines XIX–XXIII were isolated as light yellow high-melting substances which decomposed on heating above 250°C. In the 1H NMR spectra of XIX–XXIII we observed a broadened signal from protons in the primary amino group (~5 ppm). The yields of XIX– XXIII were relatively poor (~25–30%), and they were isolated and purified by column chromatography. The newly synthesized compounds were studied by cyclic voltammetry. To compare the properties of the new chalcones and pyrimidines, cyclic voltammograms of the initial N-ethyl- and N-butylcarbazoles were also recorded. The oxidation and reduction potentials of alkylcarbazoles and their derivatives are given in table. The cyclic voltammograms generally displayed two oxidation peaks, though they were not always defined clearly.* The first oxidation peak corresponds to the formation of radical cation, and the second (at a higher potential) reflects the formation of dication. Almost in all cases, two reduction peaks were observed. As the number of cycles increased, the voltammograms were displaced, indicating oxidative linking of the monomers. The films formed on the working electrode surface were generally blue–green. * The images of the voltammograms are available from the authors upon request by e-mail.

In the course of cyclic voltammetry, N-alkylcarbazoles I and II, as well as all chalcones except for p-bromophenyl-substituted derivative IX, gave rise to stable colored polymeric films on the surface of working electrode; the polymeric molecules included alternating heterocyclic fragments, double bond, and carbonyl group. Chalcone XI showed on the voltammogram two strong peaks corresponding to reversible oxidation–reduction of the ferrocenyl fragment (Ea1 = 699.7, Ec1 = 610.8 mV) and a peak due to formation of N-ethylcarbazole radical cation (E2a = 1047.1 mV). Analogous peaks were observed on the voltammogram of pyrimidine XXI, but they were located at lower potentials (697.6 and 597.75 mV, respectively). Chalcone XI underwent polymerization most readily to produce a bright violet film, and the oxidation potential corresponding to the formation of radical cation was the lowest (Ea1 = 699.7 mV). Likewise, polymerization of chalcone VIII having two carbazole fragments readily occurred, and the polymeric film was bright green. Chalcone VIII was characterized by the lowest oxidation potential for the formation of radical cation among chalcones having two carbazole fragments; furthermore, its oxidation potential, as well as the oxidation potential of compound XVI, was lower than that of initial N-alkylcarbazole I or II. EXPERIMENTAL The 1H NMR spectra were measured on a Varian Mercury Plus-300 spectrometer from solutions in CDCl3 using hexamethyldisiloxane as internal reference. The progress of reactions and the purity of prod-



ucts were monitored by TLC (Silufol, Kavalier). The reaction mixtures were separated, and the products were purified, by column chromatography on silica gel (Silica gel 60, 0.060–0.2 mm; Lancaster). The cyclic voltammograms were obtained at room temperature using an IPC-compact potentiostat–galvanostat (Vol’taProm Ltd.) with a Modul’ EM-04 electrochemical sensor and a standard three-electrode cell equipped with a vitreous carbon working electrode, an ERL-02 platinum auxiliary electrode, and an EVL1M4 silver chloride reference electrode. Solutions of compounds under study with a concentration c of 10–3 M were prepared in anhydrous acetonitrile or its mixture (1 : 1) with anhydrous methylene chloride containing tetrabutylammonium chloride as supporting electrolyte (c = 0.1 M); scan rate 100 mV/s. Gas chromatographic–mass spectrometric analysis was performed on an Agilent GC 6890N MSD 5975B instrument; HP-5ms column, 30 × 0.25 mm, film thickness 0.25 μm; carrier gas helium; electron impact, 70 eV. The elemental compositions were determined on a LECO CHNS-932 analyzer.

Oxidation and reduction potentials of compounds I, II, VII– IX, XI–XIX, and XXI, determined by cyclic voltammetry (acetonitrile, 25°C)

9-Ethyl-9H-carbazole (I). Yield 85%, mp 68–70°C [18]. 1H NMR spectrum, δ, ppm: 1.30 t (3H, CH3, J = 6.9 Hz), 4.33–4.41 q (2H, CH2, J = 6.9 Hz), 7.12 t (2H, 2-H, 7-H, J = 7.2 Hz), 7.37 t (2H, 3-H, 6-H, J = 7.2 Hz), 8.06 d (2H, 4-H, 5-H, J = 7.2 Hz).

9-Alkyl-9H-carbazole-3-carbaldehydes III and IV (general procedure). Phosphoryl chloride, 3.7 ml (6.1 g, 0.04 mol), was added dropwise under stirring to a solution of 0.02 mol of N-alkylcarbazole I or II and 1.9 g (2 ml, 0.026 mol) of DMF in 40 ml of chlorobenzene. The mixture was stirred for 5 h at 65–70°C, cooled, poured into 200 ml of water, and extracted

Oxidation potential Ea, mV 1 Ea = 1004.7, Ea2 = 1339.7

Reduction potential Ec, mV 1 Ec = 1327.7, Ec2 = 1093, Ec3 = 878

IIa

Ea1 = 1272.5, Ea2 = 1339.7

Ec1 = 1068.6

VII

Ea1 = 1385, Ea2 = 1739.5

Ec1 = 1893, Ec2 = 1247.6, Ec3 = 961.2

VIII

Ea1 = 814.5, Ea2 = 1047.1

Ec1 = 1011.9, Ec2 = 785.7

IXa

Ea1 = 1407.9

Ec1 = 1235.2, Ec2 = 949.5

XI

Ea1 = 699.7, Ea2 = 1047.1

Ec1 = 610.8

XII

Ea1 = 818.2, Ea2 = 1230.1

Ec1 = 1344.0, Ec2 = 988.6

XIII

Ea1 = 1144.1, Ea2 = 1430.3

Ec = 1319.7

XIV

Ea1 = 1221.4, Ea2 = 1428.5, Ea3 = 1551.5

Ec2 = 1339.4

XV

Ea1 = 1093, Ea2 = 1356

Ec1 = 1389

XVI

Ea1 = 976.8, Ea2 = 1357.7

Ec1 = 1307.5

XVII

Ea1 = 1364

Ec1 = 1247

XVIIIa

Ea1 = 1064, Ea2 = 1317

Ec1 = 1181, Ec2 = 863.8

XIXa

Ea1 = 1387

Ec1 = 1670, Ec2 = 1056.4, Ec3 = 847

XXIa

Ea1 = 697.6

Ec1 = 597.8

Compound no. a I

9-Alkyl-9H-carbazoles I and II (general procedure). Carbazole, 16.7 g (0.1 mol), was dispersed in 300 ml of acetone, 40 ml of a 16 M solution of sodium hydroxide, a catalytic amount of benzyl(triethyl)ammonium chloride, and 0.2 mol of the corresponding alkyl bromide were added, and the mixture was heated for 12 h under reflux and cooled to room temperature. The organic layer was separated, the solvent was distilled off, and the solid residue was recrystallized from ethanol and dried in air.

9-Butyl-9H-carbazole (II). Yield 80%, mp 56– 58°C; published data [9]: mp 58–62°C. 1H NMR spectrum, δ, ppm: 0.85 t (3H, CH3, J = 7.5 Hz), 1.32 m (2H, CH2), 1.76 m (2H, CH2), 4.20 t (2H, CH2, J = 6.9 Hz), 7.14 t (2H, Harom, J = 7.2 Hz), 7.37 m (4H, Harom), 8.03 d (2H, Harom, J = 8.1 Hz).

533

a

Solvent MeCN–CH2Cl2, 1 : 1.

with methylene chloride (3 × 70 ml). The extracts were combined, washed with water and a solution of sodium hydrogen carbonate, and evaporated, and the viscous residue was washed with hexane and purified by chromatography on silica gel using hexane–ethyl acetate (9 : 1) as eluent. 9-Ethyl-9H-carbazole-3-carbaldehyde (III). Yield 73%, mp 86–88°C; published data [5]: mp 85–87°C. 1 H NMR spectrum, δ, ppm: 1.43 t (2H, CH 3 , J =


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SYUTKIN et al.

7.2 Hz), 4.31 q (3H, CH2, J = 7.2 Hz), 7.30 t (1H, 7-H, J = 8.1 Hz), 7.43 m (2H, 1-H, 8-H), 7.51 t (1H, 6-H, J = 8.4 Hz), 7.97 d (1H, 5-H, J = 8.4 Hz), 8.12 d (1H, 2-H, J = 8.4 Hz), 8.57 s (1H, 4-H), 10.06 s (1H, CHO). 9-Butyl-9H-carbazole-3-carbaldehyde (IV). Yield 55%, viscous substance. 1H NMR spectrum, δ, ppm: 0.88 t (3H, CH 3 , J = 7.2 Hz), 1.33 m (2H, CH 2 ), 1.77 m (2H, CH2), 4.18 t (2H, CH2, J = 7.2 Hz), 7.24 t (1H, 7-H, J = 8.1 Hz), 7.33 m (2H, 1-H, 8-H), 7.45 t (1H, 6-H, J = 8.1 Hz), 7.90 d (1H, 5-H, J = 8.1 Hz), 8.05 d (1H, 2-H, J = 8.1 Hz), 8.48 s (1H, 4-H), 10.00 s (1H, CHO). 3-Acetyl-9-alkyl-9H-carbazoles V and VI (general procedure). Tin(IV) chloride, 7 ml (15.6 g, 0.06 mol), was added to a solution of 0.03 mol of N-alkylcarbazole I or II in 60 ml of anhydrous methylene chloride, the mixture was stirred for 10 min, 2.3 ml (3.7 g, 0.03 mol) of acetyl bromide was added dropwise, and the mixture was stirred for 24 h at room temperature, poured into a mixture of ice with hydrochloric acid, and extracted with methylene chloride (3 × 70 ml). The extracts were combined, washed with water until neutral washings (pH 7), and evaporated, and the solid residue was purified by chromatography using methylene chloride–hexane (1 : 1) as eluent. 1-(9-Ethyl-9H-carbazol-3-yl)ethanone (V). Yield 80%, mp 109–111°C; published data [18]: mp 114– 115°C. 1H NMR spectrum, δ, ppm: 1.39 t (3H, CH3, J = 7.2 Hz), 2.68 s (3H, CH3), 4.32 q (2H, CH2, J = 7.2 Hz), 7.26 t (1H, 7-H, J = 7.2 Hz), 7.39 m (2H, 1-H, 8-H), 7.50 t (1H, 6-H, J = 7.2 Hz), 8.10 m (2H, 2-H, 5-H, J = 7.2 Hz), 8.70 s (1H, 4-H). 1-(9-Butyl-9H-carbazol-3-yl)ethanone (VI). Yield 75%, mp 52–56°C; published data [18]: mp 57–58°C. 1 H NMR spectrum, δ, ppm: 0.90 t (3H, CH 3 , J = 7.2 Hz), 1.36 m (2H, CH2), 1.80 m (2H, CH2), 2.67 s (3H, CH 3 ), 4.24 t (2H, CH 2 , J = 7.2 Hz), 7.25 t (1H, 7-H, J = 7.5 Hz), 7.35 m (2H, 1-H, 8-H), 7.47 t (1H, 6-H, J = 7.5 Hz), 8.09 m (2H, 2-H, 5-H), 8.69 s (1H, 4-H). 1(3)-Aryl-3(1)-(9-alkyl-9H-carbazol-3-yl)prop-2en-1-ones VII–XVIII (general procedure). A suspension of equimolar amounts (2 mmol) of the corresponding methyl ketone and aldehyde in 40 ml of anhydrous methanol was heated until it became homogeneous and was then cooled to room temperature, a solution of 3 g of potassium hydroxide in 10 ml of methanol was added under stirring, and the mixture was stirred for 24 h at room temperature or heated for 3 h under reflux (in the reaction with acetylferrocene).

The precipitate was filtered off, dried in air, and purified by column chromatography using methylene chloride as eluent. All products were yellow high-melting crystalline substances. 1-(9-Ethyl-9H-carbazol-3-yl)-3-(2-thienyl)prop2-en-1-one (VII). Yield 45%, decomposes above 220°C. 1H NMR spectrum, δ, ppm: 1.43 t (3H, CH3), 4.32–4.39 q (2H, CH2), 7.07 t (2H, thiophene, carbazole), 7.30 t (1H, carbazole), 7.34–7.42 m (4H, thiophene, carbazole), 7.49 t (1H, carbazole), 7.54 d (1H, CH=, J = 15.9 Hz), 8.00 d (1H, COCH=, J = 15.9 Hz), 8.16 d (2H, carbazole). Found, %: C 75.89; H 5.11; N 4.29. C21H17NOS. Calculated, %: C 76.10; H 5.17; N 4.23. 1,3-Bis(9-ethyl-9H-carbazol-3-yl)prop-2-en-1one (VIII). Yield 55%, mp 240°C. 1H NMR spectrum, δ, ppm: 1.45 m (6H, CH3), 4.40 q (4H, CH2), 7.28 t (2H, 7-H, 7′-H, J = 7.5 Hz), 7.36 d (1H each, CH=, J = 15.0 Hz), 7.42–7.52 m (5H, carbazole), 7.82 d (1H, COCH=, J = 15.0 Hz), 8.10–8.30 m (5H, carbazole), 8.43 s (1H, 4-H, HtCH=), 8.89 s (1H, 4′-H, HtC=O). Found, %: C 84.01; H 6.40. C31H26N2O3. Calculated, %: C 84.13; H 6.33. 3-(4-Bromophenyl)-1-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one (IX). Yield 57%, mp 128–131°C. 1 H NMR spectrum, δ, ppm: 1.47 t (3H, CH 3 , J = 7.2 Hz), 4.42 q (2H, CH 2 , J = 7.2 Hz), 7.04 d (1H, CH=, J = 15.9 Hz), 7.45–7.56 m (7H, Harom), 7.66 d (1H, COCH=, J = 15.9 Hz), 7.78 d (1H, carbazole), 8.12–8.24 m (2H, carbazole), 8.83 d (1H, carbazole). Mass spectrum, m/z (Irel, %): 406.1 (21), 404.05 (34), 403.3 (99) [M]+, 390.1 (28), 388 (30), 377 (17), 362 (16), 222.1 (37), 179.1 (28), 154.5 (43), 102 (17). C23H18BrNOS. M 404.30. 3-(9-Ethyl-9H-carbazol-3-yl)-1-ferrocenylprop2-en-1-one (XI). Yield 36%, mp 179°C. 1 H NMR spectrum, δ, ppm: 1.46 t (3H, CH3, J = 7.2 Hz), 4.23 s (5H, FeC5H5), 4.40 q (2H, CH2, J = 7.2 Hz), 4.58 s (2H, FeC5H4), 4.97 s (2H, FeC5H4), 7.19 d (1H, CH=, J = 15.9 Hz), 7.27 t (1H, carbazole), 7.43 d (1H, carbazole), 7.50 t (1H, carbazole), 7.78 d (1H, carbazole), 8.03 d (1H, COCH=, J = 15.9 Hz), 8.16 d (1H, carbazole), 8.36 s (1H, carbazole). Found, %: C 74.73; H 3.31. C27H23FeNO. Calculated, %: C 74.84; H 3.23. 3-(9-Ethyl-9H-carbazol-3-yl)-1-(2-thienyl)prop2-en-1-one (XII). Yield 45%, decomposes above 220°C. 1H NMR spectrum, δ, ppm: 1.44 t (3H, CH3, J = 7.2 Hz), 4.37 q (2H, CH2, J = 7.2 Hz), 7.17–7.30 m (3H, thiophene, carbazole), 7.41 d (1H, COCH=, J =



15.0 Hz), 7.42–7.45 m (3H, thiophene, carbazole), 7.65 d (1H, carbazole, J = 6.9 Hz), 7.78 d (1H, carbazole, J = 6.9 Hz), 7.91 d (1H, carbazole, J = 8.4 Hz), 8.03 d (1H, CH=, J = 15.0 Hz), 8.36 s (1H, carbazole). Found, %: C 75.97; H 4.01; S 9.73. C21H17NOS. Calculated, %: C 76.10; H 4.23; S 9.67. 1,3-Bis(9-butyl-9H-carbazol-3-yl)prop-2-en-1one (XIII). Yield 62%, mp 223–225°C. 1H NMR spectrum, δ, ppm: 0.95 m (6H, CH3), 1.37–1.44 m (4H, CH2), 1.87–1.91 m (4H, CH2), 4.28–4.37 m (4H, CH2), 7.17–7.39 m (3H, H arom), 7.40–7.54 m (5H, H arom), 7.76–7.86 m (2H, H arom ), 8.00 d (1H, COCH=, J = 15.9 Hz), 8.09–8.29 m (3H, Harom), 8.40 d (1H, CH=, J = 16.5 Hz), 8.89 s (1H, Harom). Found, %: C 84.19; H 5.78. C35H34N2O. Calculated, %: C 84.30; H 5.62. 1-(9-Butyl-9H-carbazol-3-yl)-3-(2-thienyl)prop2-en-1-one (XIV). Yield 74%, mp 110–112°C. 1 H NMR spectrum, δ, ppm: 0.94 t (3H, CH 3 , J = 7.5 Hz), 1.41 m (2H, CH2), 1.87 m (2H, CH2), 4.33 t (2H, CH2, J = 7.2 Hz), 7.09 t (1H, thiophene, J = 3.6 Hz), 7.29 t (1H, carbazole), 7.36–7.79 m (6H, thiophene, carbazole), 7.54 d (1H, CH=, J = 15.3 Hz), 8.00 d (1H, COCH=, J = 15.5 Hz), 8.02 d (2H, carbazole, J = 8.1 Hz), 8.8 s (1H, carbazole). Mass spectrum, m/z (Irel, %): 360.2 (26.3) [M]+, 359.2 (100), 331 (16), 317 (21), 316.1 (90), 288.1 (16), 179 (16). C23H21NOS. M 249.48. 3-(9-Butyl-9H-carbazol-3-yl)-1-(2-thienyl)prop2-en-1-one (XV). Yield 67%, mp 99–101°C. 1H NMR spectrum, δ, ppm: 0.95 t (3H, CH3, J = 7.2 Hz), 1.40 m (2H, CH2, J = 7.5 Hz), 1.88 m (2H, CH2), 4.32 t (2H, CH2, J = 7.0 Hz), 7.2 t (1H, thiophene, J = 3.6 Hz), 7.25–7.31 m (1H, carbazole), 7.42 d (2H, carbazole, J = 8.4 Hz), 7.47 d (1H, CH=, J = 15.6 Hz), 7.66 d (1H, thiophene, J = 4.8 Hz), 7.78 d (1H, carbazole, J = 8.4 Hz), 7.91 d (1H, thiophene, J = 4.2 Hz), 8.08 d (1H, COCH=, J = 15.6 Hz), 8.14 d (1H, carbazole, J = 7.5 Hz), 8.38 s (1H, carbazole). Found, %: C 76.75; H 5.53; N 4.01; S 8.84. C23H21NOS. Calculated, %: C 76.85; H 5.89; N 3.90; S 8.95. 1-(9-Butyl-9H-carbazol-3-yl)-3-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one (XVI). Yield 70%, mp 169–170°C. 1 H NMR spectrum, δ, ppm: 0.96 t (3H, CH3, J = 6.9 Hz), 1.36–1.49 m (5H, CH3, CH2), 1.86–1.94 m (2H, CH 2 ), 4.30–4.43 m (4H, NCH 2 ), 7.26–7.34 m (3H, carbazole), 7.45–7.54 m (6H, carbazole, CH=), 7.80–7.88 m (2H, carbazole), 8.13 d (1H, CH=, J = 15.6 Hz), 8.13–8.30 m (2H, carbazole), 8.44 s (1H, carbazole), 8.90 s (2H, carbazole). Found,

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%: C 84.11; H 6.32; N 6.0. C33H30N2O. Calculated, %: C 84.22; H 6.43; N 5.95. 3-(9-Butyl-9H-carbazol-3-yl)-1-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one (XVII). Yield 72%, mp 161–163°C. 1 H NMR spectrum, δ, ppm: 0.95 t (3H, CH3, J = 6.9 Hz), 1.37–1.49 m (5H, CH3, CH2), 1.82–1.92 m (2H, CH 2 ), 4.29–4.44 m (4H, NCH 2 ), 7.26–7.33 m (2H, carbazole), 7.44–7.54 m (6H, carbazole, CH=), 7.79–7.86 m (2H, carbazole), 8.13 d (1H, CH=, J = 15.6 Hz), 8.18–8.29 m (2H, carbazole), 8.42 s (1H, carbazole), 8.89 s (1H, carbazole). 3,3′-(1,4-Phenylene)bis[1-(9-ethyl-9H-carbazol3-yl)prop-2-en-1-one] (XVIII). Yield 72%, decomposition point 210°C. 1H NMR spectrum, δ, ppm: 1.48 t (6H, CH3, J = 6.9 Hz), 4.44 q (4H, CH2, J = 6.9 Hz), 7.27–7.34 m (4H, carbazole), 7.45–7.53 m (6H, carbazole), 7.78 s (4H, C6H4), 7.86 d (2H, carbazole), 8.20– 8.27 m (4H, carbazole), 8.87 s (2H, carbazole). Found, %: C 83.51; H 5.50; N 5.02. C40H32N2O2. Calculated, %: C 83.69; H 5.63; N 4.89. 4,6-Diarylpyrimidin-2-amines XIX–XXII (general procedure). A mixture of 3.7 mmol of the corresponding chalcone, 0.56 g (2.6 mmol) of guanidine sulfate (2 : 1 salt), 20 ml of ethanol, and 3 ml of 50% aqueous potassium hydroxide was heated for 1 h under reflux, 10 ml of hydrogen peroxide was added dropwise over a period of 30 min to the boiling mixture, the mixture was poured into cold water, and the precipitate was filtered off and purified by column chromatography using acetone–hexane (1 : 2) as eluent. 4,6-Bis(9-ethyl-9H-carbazol-3-yl)pyrimidin-2amine (XIX). Yield 30%, mp 161–163°C. 1H NMR spectrum, δ, ppm: 1.45 t (6H, CH3), 4.45 q (4H, CH2), 5.23 s (2H, NH2), 7.27–7.34 m (3H, carbazole, 5-H), 7.39–7.53 m (6H, carbazole), 8.11–8.17 m (4H, carbazole), 8.74 s (2H, carbazole). Found, %: C 79.69; H 5.52; N 14.60. C32H27N5. Calculated, %: C 79.81; H 5.65; N 14.54. 4-(4-Bromophenyl)-6-(9-ethyl-9H-carbazol-3-yl)pyrimidin-2-amine (XX). Yield 42%. 1H NMR spectrum, δ, ppm: 1.39 t (3H, CH3), 4.19–4.22 q (2H, CH2), 5.05 br.s (2H, NH 2 ), 7.50–7.53 m (6H, 5-H, C 6 H 4, carbazole), 7.68–7.71 m (5H, carbazole, C6H4). Found, %: C 64.95; H 4.18; N 12.80. C24H19BrN4. Calculated, %: C 65.02; H 4.32; N 12.64. 4-(9-Ethyl-9H-carbazol-3-yl)-6-ferrocenylpyrimidin-2-amine (XXI). Yield 40%. 1H NMR spectrum, δ, ppm: 1.46 t (3H, CH 3 ), 4.23 (5H, Fc), 4.38 m (2H, NCH2), 4.57 s (2H, Fc), 4.96 s (2H, Fc), 5.15 br.s (2H, NH2), 7.38–7.53 m (4H, carbazole, 5-H), 7.79 d (1H,


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carbazole, J = 8.02 Hz), 8.16 d (1H, carbazole, J = 7.2 Hz), 8.37 br.s (1H, carbazole), 8.62 br.s (1H, carbazole). Found, %: C 71.11; H 5.00; N 11.91. C28H24FeN4. Calculated, %: C 71.20; H 5.12; N 11.86. 4-(9-Ethyl-9H-carbazol-3-yl)-6-(2-thienyl)pyrimidin-2-amine (XXII). Yield 25%. 1H NMR spectrum, δ, ppm: 1.38 t (3H, CH 3 ), 4.41 q (2H, CH 2 ), 5.13 s (2H, NH2), 7.18–7.32 m (2H, thiophene, 5-H), 7.37– 7.52 m (2H, thiophene, carbazole), 7.83 d (1H, carbazole, J = 8.10 Hz), 8.11–8.21 m (2H, carbazole), 8.75 br.s (1H, carbazole), 8.83 d (1H, carbazole). Found, %: C 71.20; H 4.79; S 8.59. C22H18N4S. Calculated, %: C 71.32; H 4.90; S 8.66. This study was performed under financial support by the Russian Foundation for Basic Research (project no. 07-03-96 023-ural_a) and by the Ministry of Education and Science of the Russian Federation.

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