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Synlett 2018; 29(14): 1861-1866
DOI: 10.1055/s-0037-1610201
letter
© Georg Thieme Verlag Stuttgart · New York

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 AffiliationsThis work was financially supported by the Russian Foundation for Basic Research (Grant 18-33-00528) and President of Russian Federation for Government support of Leading Scientific Schools (grant SS-5240.2018.3). The work was carried out in accordance with the approved plans of research works of the Institute of Petrochemistry and Catalysis of the Russian Academy of Sciences on the theme ‘Metal Complex Catalysis in the Synthesis of Hetero- and Metalloheterocycles’. State Registration No. AAAA-A17-117012610060-7 (2017-2019).
Further Information

Publication History

Received: 23 April 2018

Accepted after revision: 06 June 2018

Publication Date:
10 July 2018 (online)

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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610201.
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  • 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; Rf  = 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, Hа-6,13), 1.20–1.35 (m, 4 H, СH2, Hа-4,5,11,12), 1.40–1.60 (m, 8 H, CH2, Hb-5,12, Ha-7,14, H-2′,2′′), 1.80 (d, 2 J ba = 13.0 Hz, 2 H, СH2, Hb-6,13), 1.96 (d, 2 J ba = 14.0 Hz, 2 H, СH2, Hb-4,11), 2.07–2.15 (m, 2 H, CH2, Hb-7,14), 2.55 (br s, 2 H, CH, H-3b,10b), 2.62–2.70 (m, 6 H, CH2, Ha-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, Hа-1,8), 3.51 (d, 2 J ba = 9.6 Hz, 2 H, CH2, Hb-1,8), 3.91 (d, 2 J ba = 9.6 Hz, 2 H, CH2, Hb-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; Rf  = 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, Hа-5,6,12,13), 1.26–1.35 (m, 4 H, CH2, Hа-4,11, Hb-5,12), 1.46–1.54 (m, 2 H, СH2, Hа-7,14), 1.79 (d, 2 J ba = 11.6 Hz, 2 H, СH2, Hb-6,13), 1.99 (d, 2 J ba = 14.4 Hz, 2 H, СH2, Hb-4,11), 2.06–2.15 (m, 2 H, CH2, Hb-7,14), 2.54 (br s, 2 H, CH, H-3b,10b), 2.68 (d, 2 J ab = 9.6 Hz, 2 H, CH2, Ha-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, Hа-1,8), 3.67 (d, 2 J ba = 9.6 Hz, 2 H, CH2, Hb-1,8), 4.08 (d, 2 J ba = 9.6 Hz, 2 H, CH2, Hb-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; Rf  = 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, Hа-6,13), 1.22–1.36 (m, 8 H, СH2, Hа-4,5,11,12, H-3′,3′′), 1.43–1.57 (m, 8 H, CH2, Hа-7,14, Hb-5,12, H-2′,2′′), 1.76 (d, 2 J ba = 11.6 Hz, 2 H, СH2, Hb-6,13), 1.95 (d, 2 J ba = 14.4 Hz, 2 H, СH2, Hb-4,11), 2.06–2.15 (m, 2 H, CH2, Hb-7,14), 2.54 (br s, 2 H, CH, H-3b,10b), 2.62–2.73 (m, 6 H, CH2, Ha-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, Hа-1,8), 3.51 (d, 2 J ba = 9.6 Hz, 2 H, CH2, Hb-1,8), 3.90 (d, 2 J ba = 9.6 Hz, 2 H, CH2, Hb-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; Rf  = 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, Hа-6,13), 1.24–1.35 (m, 4 H, СH2, Hа-4,5,11,12), 1.48–1.62 (m, 4 H, CH2, Hа-7,14, Hb-5,12), 1.79 (d, 2 J ba = 14.4 Hz, 2 H, СH2, Hb-6,13), 1.98 (d, 2 J ba = 14.4 Hz, 2 H, СH2, Hb-4,11), 2.08–2.18 (m, 2 H, CH2, Hb-7,14), 2.49 (d, 2 J ab = 8.8 Hz, 2 H, CH2, Hа-3,10), 2.57 (br s, 2 H, CH, Ha-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, Hа-1,8), 3.77 (d, 2 J ba = 8.0 Hz, 2 H, CH2, Hb-1,8), 4.17 (d, 2 J ba = 8.0 Hz, 2 H, CH2, Hb-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.
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  • 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.
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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; Rf  = 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, Hа-6,13), 1.23–1.36 (m, 4 H, СH2, Hа-4,5,11,12), 1.48–1.62 (m, 4 H, CH2, Hа-7,14, Hb-5,12), 1.81 (d, 2 J ba = 12.0 Hz, 2 H, СH2, Hb-6,13), 2.00 (d, 2 J ba = 11.6 Hz, 2 H, СH2, Hb-4,11), 2.06–2.18 (m, 2 H, CH2, Hb-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, Hа-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, Hа-1,8), 3.63 (d, 2 J ba = 9.2 Hz, 2 H, CH2, Hb-1,8), 4.01 (d, 2 J ba = 9.2 Hz, 2 H, CH2, Hb-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; Rf  = 0.75 (MeOH). 1H NMR (500.17 MHz, CDCl3): δ = 1.12–1.19 (m, 2 H, СH2, Hа-6,13), 1.23–1.34 (m, 4 H, СH2, Hа-4,5,11,12), 1.37–1.51 (m, 6 H, CH2, Hb-5,12, Hа-2′,2′′,5′,5′′), 1.53–1.62 (m, 6 H, СH2, Hа-7,14, Hа-3′,3′′,4′,4′′), 1.67–1.74 (m, 4 H, СH2, Hb-3′,3′′,4′,4′′), 1.79 (d, 2 J ba = 10.0 Hz, 2 H, СH2, Hb-6,13), 1.85–1.91 (m, 4 H, CH2, Hb-2′,2′′,5′,5′′), 1.96 (d, 2 J ba = 11.6 Hz, 2 H, СH2, Hb-4,11), 2.06–2.15 (m, 2 H, CH2, Hb-7,14), 2.54 (br s, 2 H, CH, H-3b,10b), 2.60 (d, 2 J ab = 7.6 Hz, 2 H, CH2, Hа-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, Hа-1,8), 3.63 (d, 2 J ba = 7.6 Hz, 2 H, CH2, Hb-1,8), 4.03 (d, 2 J ba = 7.6 Hz, 2 H, CH2, Hb-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; Rf  = 0.73 (MeOH). 1H NMR (500.17 MHz, CDCl3): δ = 1.11–1.20 (m, 6 H, СH2, Hа-6,13, Hа-2′,2′′,6′,6′′), 1.23–1.33 (m, 10 H, СH2, Hа-4,5,11,12, Hа-3′,3′′,4′,4′′,5′,5′′), 1.42–1.49 (m, 2 H, CH2, Hb-5,12), 1.52–1.57 (m, 2 H, СH2, Hа-7,14), 1.62 (d, 2 J ba = 10.0 Hz, 2 H, СH2, Hb-6,13), 1.74–1.81 (m, 6 H, СH2, Hb-3′,3′′,4′,4′′,5′,5′′), 1.95–2.03 (m, 6 H, CH2, Hb-4,11, Hb-2′,2′′,6′,6′′), 2.06–2.14 (m, 2 H, СH2, Hb-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, Hа-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, Hа-1,8), 3.67 (d, 2 J ba = 7.6 Hz, 2 H, CH2, Hb-1,8), 4.09 (d, 2 J ba = 7.6 Hz, 2 H, CH2, Hb-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; Rf  = 0.73 (MeOH). 1H NMR (500.17 MHz, CDCl3): δ = 1.11–1.19 (m, 2 H, СH2, Hа-6,13), 1.23–1.33 (m, 4 H, СH2, Hа-4,5,11,12), 1.38–1.44 (m, 4 H, CH2, Hа-3′,3′′,6′,6′′), 1.46–1.58 (m, 16 H, СH2, Hа-7,14, Hb-5,12, Hа-2′,2′′,7′,7′′, H-4′,4′′,5′,5′′), 1.62–1.69 (m, 4 H, СH2, Hb-3′,3′′,6′,6′′), 1.78 (d, 2 J ba = 10.8 Hz, 2 H, СH2, Hb-6,13), 1.89–1.99 (m, 6 H, CH2, Hb-4,11, Hb-2′,2′′,7′,7′′), 2.06–2.15 (m, 2 H, СH2, Hb-7,14), 2.55 (br s, 2 H, CH, H-3b,10b), 2.63 (d, 2 J ab = 7.2 Hz, 2 H, CH2, Hа-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, Hа-1,8), 3.58 (d, 2 J ba = 7.6 Hz, 2 H, CH2, Hb-1,8), 3.98 (d, 2 J ba = 7.6 Hz, 2 H, CH2, Hb-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; Rf  = 0.75 (MeOH). 1H NMR (500.17 MHz, CDCl3): δ = 1.13–1.17 (2 H, СH2, Hа-6,13), 1.22–1.34 (m, 4 H, СH2, Hа-4,5,11,12), 1.43–1.64 (m, 24 H, CH2, Hb-5,12, Hа-7,14, Hа-2′,2′′,3′,3′′,7′,7′′,8′,8′′, H-4′,4′′,5′,5′′,6′,6′′), 1.68–1.89 (m, 10 H, СH2, Hb-6,13, Hb-2′,2′′,3′,3′′,7′,7′′,8′,8′′), 1.96 (d, 2 J ba = 13.6 Hz, 2 H, CH2, Hb-4,11), 2.06–2.15 (m, 2 H, СH2, Hb-7,14), 2.55 (br s, 2 H, CH, H-3b,10b), 2.61–2.71 (m, 2 H, CH2, Hа-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, Hа-1,8), 3.59 (d, 2 J ba = 8.8 Hz, 2 H, CH2, Hb-1,8), 3.99 (d, 2 J ba = 8.8 Hz, 2 H, CH2, Hb-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; Rf  = 0.77 (MeOH). 1H NMR (500.17 MHz, CDCl3): δ = 1.03–1.20 (m, 6 H, СH2, Hа-6,13, Hа-3′,3′′,7′,7′′), 1.22–1.38 (m, 6 H, СH2, Hа-4,5,11,12, Hа-5′,5′′), 1.40–1.59 (m, 14 H, CH2, Hа-7,14, Hb-5,12, Hb-3′,3′′,5′,5′′,7′,7′′, H-6′,6′′), 1.79 (d, 2 J ba = 10.0 Hz, 2 H, СH2, Hb-6,13), 1.98 (d, 2 J ba = 10.8 Hz, 2 H, CH2, Hb-4,11), 2.05–2.14 (m, 2 H, СH2, Hb-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, Hа-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, Hа-1,8), 3.66 (d, 2 J ba = 7.6 Hz, 2 H, CH2, Hb-1,8), 4.07 (t, 2 J ba = 8.6 Hz, 2 H, CH2, Hb-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.
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