First Synthesis of 2,9-Disubstituted cis-2,3a,7b,9,10a,14b-
Hexaazaperhydrodibenzotetracenes

Elena B. Rakhimova; Victor Yu. Kirsanov; Ekaterina S. Mescheryakova; Leonard M. Khalilov; Askhat G. Ibragimov; Usein M. Dzhemilev

doi:10.1055/s-0037-1610201

Synlett, Table of Contents

Synlett 2018; 29(14): 1861-1866
DOI: 10.1055/s-0037-1610201

letter

First Synthesis of 2,9-Disubstituted cis-2,3a,7b,9,10a,14b- Hexaazaperhydrodibenzotetracenes

Elena B. Rakhimova*

Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russian Federation Email: rakhimovaelena@mail.ru

,

Victor Yu. Kirsanov

Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russian Federation Email: rakhimovaelena@mail.ru

,

Ekaterina S. Mescheryakova

Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russian Federation Email: rakhimovaelena@mail.ru

,

Leonard M. Khalilov

Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russian Federation Email: rakhimovaelena@mail.ru

,

Askhat G. Ibragimov

Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russian Federation Email: rakhimovaelena@mail.ru

,

Usein M. Dzhemilev

Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russian Federation Email: rakhimovaelena@mail.ru

› Author Affiliations

Abstract

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Abstract

The first synthesis of 2,9-disubstituted cis-2,3а,7b,9,10a,14b-hexaazaperhydrodibenzotetracenes has been accomplished through intermolecular heterocyclization of N,N-bis(methoxymethyl)alkylamines with cis-1,6,7,12-tetraazaperhydrotetracene in the presence of SmCl₃·6H₂O catalyst or by recyclization of 1,3,5-tricycloalkyl-1,3,5-triazinanes with cis-1,6,7,12-tetraazaperhydrotetracene in the presence of NiCl₂·6H₂O catalyst. The structures were established by 1D (¹H, and ¹³C) and 2D (HSQC, HMBC, COSY, NOESY) NMR spectroscopy, MALDI TOF/TOF mass spectrometry, and X-ray diffraction analyses.

Key words

polycycles - catalysis - heterocyclization - tetraazaperhydrotetracenes - hexaazaperhydrodibenzotetracenes

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References

References and Notes
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16 (3bS*,7aR*,10bS*,14aR*)-2,9-Dialkylperhydro-1H,8H-2,3a,7b, 9,10a,14b-hexaazadibenzo[fg,op]tetracenes 2–5; General Procedure A round-bottom flask equipped with a magnetic stirrer bar was charged with MeOH (5 mL), SmCl₃∙6 H₂O (0.018 g, 0.05 mmol), and the appropriate N,N-di(methoxymethyl)alkylamine (2.00 mmol), prepared in situ by the reported procedure (see Ref. 6), and the mixture was stirred at r.t. for 30 min. Next, cis-1,6,7,12-tetraazaperhydrotetracene (1; 1.00 mmol) in MeOH (5 mL), prepared in situ by the reaction of (±)-cis-cyclohexane-1,2-diamine (0.23 g, 2.00 mmol) with 40 wt% aq glyoxal (0.14 g, 1.00 mmol), was added and the resultant mixture was stirred at 20 °C for 3 h. The mixture was then concentrated, and the residue was purified by column chromatography (silica gel, MeOH). Compounds 2–5 were obtained as colorless crystals (recrystallized from MeOH). The final products 2–5 were identified by spectroscopic methods. (3bS*,7aR*,10bS*,14aR*)-2,9-Dipropylperhydro-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (2) Colorless crystals; yield: 0.31 g (74%); mp 181–183 °C; R_f = 0.74 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 0.92 (t, ³ J = 7.2 Hz, 6 H, CH₃, H-3′,3′′), 1.14–1.18 (m, 2 H, СH₂, H_а-6,13), 1.20–1.35 (m, 4 H, СH₂, H_а-4,5,11,12), 1.40–1.60 (m, 8 H, CH₂, H_b-5,12, H_a-7,14, H-2′,2′′), 1.80 (d, ² J _ba = 13.0 Hz, 2 H, СH₂, H_b-6,13), 1.96 (d, ² J _ba = 14.0 Hz, 2 H, СH₂, H_b-4,11), 2.07–2.15 (m, 2 H, CH₂, H_b-7,14), 2.55 (br s, 2 H, CH, H-3b,10b), 2.62–2.70 (m, 6 H, CH₂, H_a-3,10, H-1′,1′′; 2 H, СH, H-7а,14а), 3.04 (br s, 2 H, CH, H-14с,14d), 3.41 (d, ² J _ab = 9.6 Hz, 2 H, CH₂, H_а-1,8), 3.51 (d, ² J _ba = 9.6 Hz, 2 H, CH₂, H_b-1,8), 3.91 (d, ² J _ba = 9.6 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 12.0 (C-3′,3′′), 19.5 (С-7,14), 19.8 (C-5,12), 21.2 (C-2′,2′′), 25.6 (C-6,13), 28.0 (C-4,11), 54.1 (C-1′,1′′), 57.6 (C-3b,10b), 59.5 (C-7a,14a), 69.8 (C-3,10), 70.38 (C-1,8), 77.9 (C-14c,14d). MALDI TOF/TOF, m/z (I _оtн, %): 415 [M – H]⁺ (100). Anal. Calcd for C₂₄H₄₄N₆: С, 69.18; H, 10.65; N, 20.17. Found: С, 69.05; H, 10.60; N, 20.11. (3bS*,7aR*,10bS*,14aR*)-2,9-Diisopropylperhydro-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (3) Colorless crystals; yield: 0.30 g (72%); mp 180–182 °C; R_f = 0.71 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 1.10 and 1.12 (d, ³ J = 6.8 Hz, 12 H, CH₃, H-2′,2′′,3′,3′′), 1.15–1.23 (m, 4 H, СH₂, H_а-5,6,12,13), 1.26–1.35 (m, 4 H, CH₂, H_а-4,11, H_b-5,12), 1.46–1.54 (m, 2 H, СH₂, H_а-7,14), 1.79 (d, ² J _ba = 11.6 Hz, 2 H, СH₂, H_b-6,13), 1.99 (d, ² J _ba = 14.4 Hz, 2 H, СH₂, H_b-4,11), 2.06–2.15 (m, 2 H, CH₂, H_b-7,14), 2.54 (br s, 2 H, CH, H-3b,10b), 2.68 (d, ² J _ab = 9.6 Hz, 2 H, CH₂, H_a-3,10; 2 H, СH, H-7а,14а), 3.02 (br s, 2 H, CH, H-14с,14d), 3.20–3.26 (m, 2 H, CH, H-1′,1′′), 3.40 (d, 2 H, ² J _ab = 9.6 Hz, CH₂, H_а-1,8), 3.67 (d, ² J _ba = 9.6 Hz, 2 H, CH₂, H_b-1,8), 4.08 (d, ² J _ba = 9.6 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 19.6 (С-7,14), 20.0 (C-5,12), 20.6 and 20.9 (C-2′,2′′,3′,3′′), 25.6 (C-6,13), 28.0 (C-4,11), 48.8 (C-1′,1′′), 57.9 (C-3b,10b), 59.7 (C-7a,14a), 67.2 (C-3,10), 67.7 (C-1,8), 78.0 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 455 [M + K]⁺ (30), 439 [M + Na]⁺ (30), 415 [M – H]⁺ (100). Anal. Calcd for C₂₄H₄₄N₆: С, 69.18; H, 10.65; N, 20.17. Found: С, 69.07; H, 10.59; N, 20.10. (3bS*,7aR*,10bS*,14aR*)-2,9-Dibutylperhydro-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (4) Colorless crystals; yield: 0.35 g (78%); mp 184–186 °C; R_f = 0.71 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 0.92 (t, ² J = 7.2 Hz, 6 H, CH₃, H-4′,4′′), 1.13–1.17 (m, 2 H, СH₂, H_а-6,13), 1.22–1.36 (m, 8 H, СH₂, H_а-4,5,11,12, H-3′,3′′), 1.43–1.57 (m, 8 H, CH₂, H_а-7,14, H_b-5,12, H-2′,2′′), 1.76 (d, ² J _ba = 11.6 Hz, 2 H, СH₂, H_b-6,13), 1.95 (d, ² J _ba = 14.4 Hz, 2 H, СH₂, H_b-4,11), 2.06–2.15 (m, 2 H, CH₂, H_b-7,14), 2.54 (br s, 2 H, CH, H-3b,10b), 2.62–2.73 (m, 6 H, CH₂, H_a-3,10, H-1′,1′′; 2 H, СH, H-7а,14а), 3.03 (br s, 2 H, CH, H-14с,14d), 3.40 (d, ² J _ab = 9.6 Hz, 2 H, CH₂, H_а-1,8), 3.51 (d, ² J _ba = 9.6 Hz, 2 H, CH₂, H_b-1,8), 3.90 (d, ² J _ba = 9.6 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 14.1 (C-4′,4′′), 19.5 (С-7,14), 19.8 (C-5,12), 20.7 (C-3′,3′′), 25.6 (C-6,13), 28.0 (C-4,11), 30.2 (C-2′,2′′), 51.9 (C-1′,1′′), 57.6 (C-3b,10b), 59.5 (C-7a,14a), 69.7 (C-3,10), 70.4 (C-1,8), 77.9 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 443 [M – H]⁺ (100). Anal. Calcd for C₂₆H₄₈N₆: С, 70.22; H, 10.88; N, 18.90. Found: С, 70.13; H, 10.82; N, 18.81. (3bS*,7aR*,10bS*,14aR*)-2,9-Di-tert-butylperhydro-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (5) Colorless crystals; yield: 0.33 g (75%); mp 186–188 °C; R_f = 0.72 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 1.18 (br s, 18 H, CH₃, H-2′,2′′,3′,3′′,4′,4′′; 2 H, СH₂, H_а-6,13), 1.24–1.35 (m, 4 H, СH₂, H_а-4,5,11,12), 1.48–1.62 (m, 4 H, CH₂, H_а-7,14, H_b-5,12), 1.79 (d, ² J _ba = 14.4 Hz, 2 H, СH₂, H_b-6,13), 1.98 (d, ² J _ba = 14.4 Hz, 2 H, СH₂, H_b-4,11), 2.08–2.18 (m, 2 H, CH₂, H_b-7,14), 2.49 (d, ² J _ab = 8.8 Hz, 2 H, CH₂, H_а-3,10), 2.57 (br s, 2 H, CH, H_a-3b,10b), 2.74 (d, ³ J = 11.6 Hz, 2 H, CH, H-7а,14а), 2.99 (br s, 2 H, CH, H-14с,14d), 3.25 (d, ² J _ab = 8.8 Hz, 2 H, CH₂, H_а-1,8), 3.77 (d, ² J _ba = 8.0 Hz, 2 H, CH₂, H_b-1,8), 4.17 (d, ² J _ba = 8.0 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 19.8 (С-7,14), 19.9 (C-5,12), 25.6 (C-6,13), 27.3 (C-2′,2′′,3′,3′′,4′,4′′), 28.2 (C-4,11), 53.1 (C-1′,1′′), 58.4 (C-3b,10b), 60.1 (C-7a,14a), 65.6 (C-3,10), 65.8 (C-1,8), 77.9 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 443 [M – H]⁺ (100). Anal. Calcd for C₂₆H₄₈N₆: С, 70.22; H, 10.88; N, 18.90. Found: С, 70.10; H, 10.81; N, 18.82.
17 Sheldrick GM. Acta Crystallogr., Sect. A 2008; 64: 112
18 Macrae CF. Edgington PR. McCabe P. Pidcock E. Shields GP. Taylor R. Towler M. van de Streek J. J. Appl. Crystallogr. 2006; 39: 453
19 Single crystals of 2 were grown from MeOH and studied on an XCalibur Eos. All crystallographic calculations were conducted using SHELX (see Ref. 17). The crystal structure was generated by using Mercury (see Ref. 18). Crystal data for 2. C₂₄H₄₄N₆, M = 416.65, orthorhombic, P _bca (no. 61), a = 7.2116 (6) Å, b = 17.582 (2) Å, c = 18.9304 (17) Å, V = 2400.3 (4) Å³, T = 293 (2) K, D _calcd = 1.153 mg/m³, Z = 4; reflections collected = 5246, independent reflections = 2127 (R _int = 0.0212), final R indexes [I > 2σ(I)]: R ₁ = 0.0706, wR ₂ = 0.1803; R indexes (all data): R ₁ = 0.1141, wR ₂= 0.2163, GOF = 1.045. CCDC 1833412 contains the supplementary crystallographic data for compound 2. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
20 Oda S. Sam B. Krische MJ. Angew. Chem. Int. Ed. 2015; 54: 8525
21 Lian X. Lin L. Fu K. Ma B. Liu X. Feng X. Chem. Sci. 2017; 8: 1238
22 Gong J. Li S.-W. Qurban S. Kang Q. Eur. J. Org. Chem. 2017; 3584
23 Ji D. Sun J. Org. Lett. 2018; 20: 2745
24 Zhu C. Xu G. Sun J. Angew. Chem. Int. Ed. 2016; 55: 11867
25 Peng S. Cao S. Sun J. Org. Lett. 2017; 19: 524
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28 (3bR ^*,7aS ^*,10bS ^*,14aR ^*)-2,9-Dicycloalkyl-1H,8H-2,3a,7b,9, 10a,14b-hexaazadibenzo[fg,op]tetracene 6–11; General Procedure A round-bottomed flask equipped with a magnetic stirrer bar was charged with MeOH (5 mL), NiCl₂·6 H₂O (0.012 g, 0.05 mmol), and the appropriate 1,3,5-tricycloalkyl-1,3,5-triazinane (2.00 mmol), prepared in situ by the reported procedure (see Ref. 7), and the mixture was stirred at r.t. for 30 min. cis-1,6,7,12-Tetraazaperhydrotetracene (1; 1.00 mmol) in MeOH (5 mL), prepared in situ by the reaction of (±)-cis-cyclohexane-1,2-diamine (0.23 g, 2.00 mmol) with 40 wt% aq glyoxal (0.14 g, 1.00 mmol) was added, and the mixture was stirred at 20 °C for 3 h, then concentrated. The residue was separated by column chromatography (silica gel, MeOH). The white precipitate was collected by filtration and washed twice with MeOH (5 mL). Compounds 6–11 were obtained as white powdery crystals (6 was recrystallized from MeOH; 7–11 were recrystallized from CHCl₃). The final products 6–11 were identified by spectroscopic methods. (3bR ^*,7aS ^*,10bS ^*,14aR ^*)-2,9-Dicyclopropyl-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (6) White powdery crystals; yield: 0.31 g (75%); mp 243–245 °C; R_f = 0.73 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 0.45–0.55 (m, 8 H, CH₂, H-2′,2′′,3′,3′′), 1.16–1.20 (2 H, СH₂, H_а-6,13), 1.23–1.36 (m, 4 H, СH₂, H_а-4,5,11,12), 1.48–1.62 (m, 4 H, CH₂, H_а-7,14, H_b-5,12), 1.81 (d, ² J _ba = 12.0 Hz, 2 H, СH₂, H_b-6,13), 2.00 (d, ² J _ba = 11.6 Hz, 2 H, СH₂, H_b-4,11), 2.06–2.18 (m, 2 H, CH₂, H_b-7,14), 2.28–2.35 (m, 2 H, CH, H-1′,1′′), 2.58 (br s, 2 H, CH, H-3b,10b), 2.66 (d, ² J _ab = 8.8 Hz, 2 H, CH₂, H_а-3,10), 2.74 (d, ³ J = 11.6 Hz, 2 H, CH, H-7а,14а), 3.08 (br s, 2 H, CH, H-14с,14d), 3.41 (d, ² J _ab = 9.2 Hz, 2 H, CH₂, H_а-1,8), 3.63 (d, ² J _ba = 9.2 Hz, 2 H, CH₂, H_b-1,8), 4.01 (d, ² J _ba = 9.2 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 5.9 and 6.2 (C-2′,2′′,3′,3′′), 19.6 (С-7,14), 19.7 (C-5,12), 25.6 (C-6,13), 28.1 (C-4,11), 32.9 (C-1′,1′′), 57.8 (C-3b,10b), 59.6 (C-7a,14a), 70.4 (C-3,10), 70.5 (C-1,8), 77.8 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 411 [M – H]⁺ (100). Anal. Calcd for C₂₄H₄₀N₆: С, 69.86; H, 9.77; N, 20.37. Found: С, 69.73; H, 9.71; N, 20.28. (3bR ^*,7aS ^*,10bS ^*,14aR ^*)-2,9-Dicyclopentyl-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (7) White powdery crystals; yield: 0.37 g (79%); mp 246–248 °C; R_f = 0.75 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 1.12–1.19 (m, 2 H, СH₂, H_а-6,13), 1.23–1.34 (m, 4 H, СH₂, H_а-4,5,11,12), 1.37–1.51 (m, 6 H, CH₂, H_b-5,12, H_а-2′,2′′,5′,5′′), 1.53–1.62 (m, 6 H, СH₂, H_а-7,14, H_а-3′,3′′,4′,4′′), 1.67–1.74 (m, 4 H, СH₂, H_b-3′,3′′,4′,4′′), 1.79 (d, ² J _ba = 10.0 Hz, 2 H, СH₂, H_b-6,13), 1.85–1.91 (m, 4 H, CH₂, H_b-2′,2′′,5′,5′′), 1.96 (d, ² J _ba = 11.6 Hz, 2 H, СH₂, H_b-4,11), 2.06–2.15 (m, 2 H, CH₂, H_b-7,14), 2.54 (br s, 2 H, CH, H-3b,10b), 2.60 (d, ² J _ab = 7.6 Hz, 2 H, CH₂, H_а-3,10), 2.67 (d, ³ J = 9.6 Hz, 2 H, CH, H-7а,14а), 3.03 (br s, 2 H, CH, H-14с,14d), 3.21–3.28 (m, 2 H, СH, H-1′,1′′), 3.33 (d, ² J _ab = 7.6 Hz, 2 H, CH₂, H_а-1,8), 3.63 (d, ² J _ba = 7.6 Hz, 2 H, CH₂, H_b-1,8), 4.03 (d, ² J _ba = 7.6 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 19.6 (С-7,14), 19.9 (C-5,12), 24.1 and 24.2 (C-3′,3′′,4′,4′′) 25.6 (C-6,13), 28.0 (C-4,11), 31.1 and 31.2 (C-2′,2′′,5′,5′′), 57.8 (C-3b,10b), 59.7 (C-7a,14a), 60.1 (C-1′,1′′) 69.3 (C-3,10), 69.7 (C-1,8), 77.8 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 507 [M + K]⁺ (100), 491 [M + Na]⁺ (50), 467 [M – H]⁺ (50). Anal. Calcd for C₂₈H₄₈N₆: С, 71.75; H, 10.32; N, 17.93. Found: С, 71.67; H, 10.27; N, 17.85. (3bR ^*,7aS ^*,10bS ^*,14aR ^*)-2,9-Dicyclohexyl-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (8) White powdery crystals; yield: 0.40 g (81%); mp 239–241 °C; R_f = 0.73 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 1.11–1.20 (m, 6 H, СH₂, H_а-6,13, H_а-2′,2′′,6′,6′′), 1.23–1.33 (m, 10 H, СH₂, H_а-4,5,11,12, H_а-3′,3′′,4′,4′′,5′,5′′), 1.42–1.49 (m, 2 H, CH₂, H_b-5,12), 1.52–1.57 (m, 2 H, СH₂, H_а-7,14), 1.62 (d, ² J _ba = 10.0 Hz, 2 H, СH₂, H_b-6,13), 1.74–1.81 (m, 6 H, СH₂, H_b-3′,3′′,4′,4′′,5′,5′′), 1.95–2.03 (m, 6 H, CH₂, H_b-4,11, H_b-2′,2′′,6′,6′′), 2.06–2.14 (m, 2 H, СH₂, H_b-7,14), 2.51 (br s, 2 H, CH, H-3b,10b), 2.63–2.67 (m, 2 H, CH, H-7а,14а), 2.68 (d, ² J _ab = 7.6 Hz, 2 H, CH₂, H_а-3,10), 2.79–2.85 (m, 2 H, СH, H-1′,1′′), 3.01 (br s, 2 H, CH, H-14с,14d), 3.41 (d, ² J _ab = 7.6 Hz, 2 H, CH₂, H_а-1,8), 3.67 (d, ² J _ba = 7.6 Hz, 2 H, CH₂, H_b-1,8), 4.09 (d, ² J _ba = 7.6 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 19.6 (С-7,14), 20.0 (C-5,12), 25.5 (C-4′,4′′) 25.6 (C-3′,3′′,5′,5′′), 26.1 (С-6,13), 28.0 (C-4,11), 30.4 and 30.8 (C-2′,2′′,6′,6′′), 57.4 (C-1′,1′′), 57.8 (C-3b,10b), 59.7 (C-7a,14a), 67.0 (C-3,10), 67.3 (C-1,8), 78.1 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 495 [M – H]⁺ (100). Anal. Calcd for C₃₀H₅₂N₆: С, 72.53; H, 10.55; N, 16.92. Found: С, 72.41; H, 10.49; N, 16.82. (3bR ^*,7aS ^*,10bS ^*,14aR ^*)-2,9-Dicycloheptyl-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (9) White powdery crystals; yield: 0.42 g (80%); mp 216–218 °C; R_f = 0.73 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 1.11–1.19 (m, 2 H, СH₂, H_а-6,13), 1.23–1.33 (m, 4 H, СH₂, H_а-4,5,11,12), 1.38–1.44 (m, 4 H, CH₂, H_а-3′,3′′,6′,6′′), 1.46–1.58 (m, 16 H, СH₂, H_а-7,14, H_b-5,12, H_а-2′,2′′,7′,7′′, H-4′,4′′,5′,5′′), 1.62–1.69 (m, 4 H, СH₂, H_b-3′,3′′,6′,6′′), 1.78 (d, ² J _ba = 10.8 Hz, 2 H, СH₂, H_b-6,13), 1.89–1.99 (m, 6 H, CH₂, H_b-4,11, H_b-2′,2′′,7′,7′′), 2.06–2.15 (m, 2 H, СH₂, H_b-7,14), 2.55 (br s, 2 H, CH, H-3b,10b), 2.63 (d, ² J _ab = 7.2 Hz, 2 H, CH₂, H_а-3,10), 2.66–2.70 (m, 2 H, CH, H-7а,14а), 2.92–2.98 (m, 2 H, СH, H-1′,1′′), 2.99 (br s, 2 H, CH, H-14с,14d), 3.39 (d, ² J _ab = 7.2 Hz, 2 H, CH₂, H_а-1,8), 3.58 (d, ² J _ba = 7.6 Hz, 2 H, CH₂, H_b-1,8), 3.98 (d, ² J _ba = 7.6 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 19.9 (С-7,14), 19.7 (C-5,12), 25.1 and 25.1 (C-3′,3′′,6′,6′′), 25.6 (С-6,13), 28.1 (C-4,11), 28.2 and 28.5 (C-4′,4′′,5′,5′′), 31.0 and 31.4 (C-2′,2′′,7′,7′′), 57.9 (C-3b,10b), 59.8 (C-7a,14a), 60.3 (C-1′,1′′), 67.4 (C-3,10), 67.7 (C-1,8), 78.0 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 563 [M + K]⁺ (40) , 547 [M + Na]⁺ (30), 523 [M – H]⁺ (100). Anal. Calcd for C₃₂H₅₆N₆: С, 73.23; H, 10.76; N, 16.01. Found: С, 73.11; H, 10.69; N, 15.97. (3bR ^*,7aS ^*,10bS ^*,14aR ^*)-2,9-Dicyclooctyl-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (10) White powdery crystals; yield: 0.45 g (82%); mp 222–224 °C; R_f = 0.75 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 1.13–1.17 (2 H, СH₂, H_а-6,13), 1.22–1.34 (m, 4 H, СH₂, H_а-4,5,11,12), 1.43–1.64 (m, 24 H, CH₂, H_b-5,12, H_а-7,14, H_а-2′,2′′,3′,3′′,7′,7′′,8′,8′′, H-4′,4′′,5′,5′′,6′,6′′), 1.68–1.89 (m, 10 H, СH₂, H_b-6,13, H_b-2′,2′′,3′,3′′,7′,7′′,8′,8′′), 1.96 (d, ² J _ba = 13.6 Hz, 2 H, CH₂, H_b-4,11), 2.06–2.15 (m, 2 H, СH₂, H_b-7,14), 2.55 (br s, 2 H, CH, H-3b,10b), 2.61–2.71 (m, 2 H, CH₂, H_а-3,10, 2 H, CH, H-7а,14а), 2.99 (br s, 4 H, CH, H-14с,14d, H-1′,1′′), 3.37 (d, ² J _ab = 9.2 Hz, 2 H, CH₂, H_а-1,8), 3.59 (d, ² J _ba = 8.8 Hz, 2 H, CH₂, H_b-1,8), 3.99 (d, ² J _ba = 8.8 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 19.8 (С-7,14), 20.0 (C-5,12), 24.6 and 25.0 (C-3′,3′′,7′,7′′), 25.6 (С-6,13), 26.3 (C-5′,5′′), 27.0 and 27.2 (C-4′,4′′,6′,6′′), 28.1 (C-4,11), 29.3 and 29.9 (C-2′,2′′,8′,8′′), 58.0 (C-3b,10b), 58.4 (C-1′,1′′), 59.8 (C-7a,14a), 67.4 (C-3,10), 67.8 (C-1,8), 78.1 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 591 [M + K]⁺ (40), 575 [M + Na]⁺ (40), 551 [M – H]⁺ (100). Anal. Calcd for C₃₄H₆₀N₆: С, 73.86; H, 10.94; N, 15.20. Found: С, 73.71; H, 10.88; N, 15.13. (3bR ^*,7aS ^*,10bS ^*,14aR ^*)-2,9-Dibicyclo[2.2.1]hept-2-yl-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (11) White powdery crystals; yield: 0.40 g (77%); mp 271–273 °C; R_f = 0.77 (MeOH). ¹H NMR (500.17 MHz, CDCl₃): δ = 1.03–1.20 (m, 6 H, СH₂, H_а-6,13, H_а-3′,3′′,7′,7′′), 1.22–1.38 (m, 6 H, СH₂, H_а-4,5,11,12, H_а-5′,5′′), 1.40–1.59 (m, 14 H, CH₂, H_а-7,14, H_b-5,12, H_b-3′,3′′,5′,5′′,7′,7′′, H-6′,6′′), 1.79 (d, ² J _ba = 10.0 Hz, 2 H, СH₂, H_b-6,13), 1.98 (d, ² J _ba = 10.8 Hz, 2 H, CH₂, H_b-4,11), 2.05–2.14 (m, 2 H, СH₂, H_b-7,14), 2.24 (br s, 2 H, CH, H-4′,4′′), 2.32 (br s, 2 H, CH, H-2′,2′′), 2.45 (t, ² J _ab = 7.6 Hz, 2 H, СH₂, H_а-3,10), 2.54 (br s, 2 H, СH, H-3b,10b), 2.64–2.69 (m, 2 H, CH, H-7а,14а), 2.70–2.74 and 2.75–2.79 (m, 2 H, СH, H-1′,1′′), 3.02 (br s, 2 H, CH, H-14с,14d), 3.14 and 3.23 (d, ² J _ab = 7.6 Hz, 2 H, CH₂, H_а-1,8), 3.66 (d, ² J _ba = 7.6 Hz, 2 H, CH₂, H_b-1,8), 4.07 (t, ² J _ba = 8.6 Hz, 2 H, CH₂, H_b-3,10). ¹³C NMR (125.78 MHz, CDCl₃): δ = 19.6 (С-7,14), 19.8 and 19.9 (C-5,12), 25.6 and 25.7 (С-6,13), 27.8 and 27.9 (6′,6′′), 28.1 and 28.2 (C-4,11), 28.3 and 28.5 (C-7′,7′′), 35.0 and 35.3 (C-3′,3′′), 36.2 and 36.3 (C-4′,4′′), 37.6 (C-5′,5′′), 38.1 and 38.2 (C-2′,2′′) 57.7 and 57.9 (C-3b,10b), 59.8 and 59.9 (C-7a,14a), 62.4 and 62.6 (C-1′,1′′), 68.2 and 68.4 (C-3,10), 68.5 and 68.7 (C-1,8), 77.7 and 77.8 (C-14c,14d). MALDI TOF/TOF: m/z (%) = 559 [M + K]⁺ (15), 543 [M + Na]⁺ (10), 519 [M – H]⁺ (100). Anal. Calcd for C₃₂H₅₂N₆: С, 73.80; H, 10.06; N, 16.14. Found: С, 73.67; H, 10.01; N, 16.05.
29 Khalilov LM. Spivak AYu. Vasil’eva EV. Fatykhov AA. Prokhorova NA. Tolstikov GA. Chem. Nat. Compd. 1991; 27: 318 Khim. Prir. Soedin. 1991, 3, 368
30 Khalilov LM. Panasenko AA. Muslukhov RR. Tolstikov GA. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1988; 37: 1569 Izv. Akad. Nauk SSSR Ser. Khim. 1988, 1760
31 Mokrov GV. Likhosherstov AM. Lezina VP. Gudasheva TA. Bushmarinov IS. Antipin MYu. Russ. Chem. Bull. 2010; 59: 1254 ; Izv. Akad. Nauk, Ser. Khim. 2010, 1228
32 Krohn K. Cludius-Brandt S. Synthesis 2010; 1344
33 Kukushkin YuN. Reactivity of Coordination Compounds 1987; 288 ; (in Russian)

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