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Synlett 2017; 28(06): 669-672
DOI: 10.1055/s-0036-1588932
letter
© Georg Thieme Verlag Stuttgart · New York

New Method for the Synthesis of 1-Substituted (3a,6a)-Diaryl­glycolurils

Vladimir V. Baranov*
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation   eMail: Ase1313@mail.ru
b   Рeoples’ Friendship University of Russia, 6 Miklukho-Maklaya St., 117198 Moscow, Russian Federation
,
Maria M. Antonova
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation   eMail: Ase1313@mail.ru
,
Yulia V. Nelyubina*
c   A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St., 119991 Moscow, Russian Federation
,
Natalia G. Kolotyrkina
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation   eMail: Ase1313@mail.ru
,
Angelina N. Kravchenko
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation   eMail: Ase1313@mail.ru
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Publikationsverlauf

Received: 28. Oktober 2016

Accepted after revision: 17. Dezember 2016

Publikationsdatum:
10. Januar 2017 (online)

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Abstract

A new approach has been developed for the synthesis of 1-substituted 3а,6а-diarylglycolurils from an imidazolone, imidazo­oxazolone, imidazooxazinone, or imidazooxazepinone and urea in the presence of hydrochloric acid. The structure of 1-ethyl-3а,6а-diphenylglycoluril was confirmed by X-ray diffraction studies.

Key words

glycolurils - condensation - urea - imidazolones - polycycles

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588932.
  • Supporting Information
 

  • References and Notes

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  • 11 Tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-diones 1a–c and 1e–l; General Procedure A mixture of the appropriate substrate 7a–g, 8, 9a,b, or 10 (0.002 mol), urea (4a; 0.12 g, 0.002 mol), MeCN (15 mL), and 35.5% HCl (0.2 mL) was stirred at the reflux for 20 min (for 7a–g or 8), 25 min (for 9b), 50 min (for 10) or 8 h (for 9a). The mixture was cooled and the precipitate was filtered off and washed with CHCl3 (5 mL). 1-Methyl-3a,6a-diphenyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione (1a) White powder; yield: 0.443 g (72%); mp 308–310 °С (MeCN). 1H NMR (300 MHz, DMSO-d 6): δ = 2.53 (s, 3 H, Me), 6.88–6.98 (m, 2 H, Ph), 7.00–7.14 (m, 8 H, Ph), 7.86 (s, 1 H, NH), 7.97 (s, 1 H, NH), 8.16 (s, 1 H, NH). 13C NMR (75 MHz, DMSO-d 6): δ = 25.82 (Me), 79.86, 85.04 (C–C), 127.07, 127.16, 127.31, 127.77, 127.81, 127.98 [CH(Ph)], 135.45, 137.98 [C(Ph)], 159.48, 160.39 (C=O). HRMS (ESI-TOF): m/z [M + H]+ calcd for C17H16N4O2 + H: 309.1346; found: 309.1339. 1-Ethyl-3a,6a-diphenyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione (1b) White powder; yield: 0.470 g (73%); mp 307–309 °С (MeCN). 1H NMR (300 MHz, DMSO-d 6): δ = 1.04 (t, J = 7.0 Hz, 3 H, Me), 2.75–2.87 (m, 1 H, CH2), 3.13–3.25 (m, 1 H, CH2), 6.92–6.99 (m, 2 H, Ph), 7.00–7.14 (m, 8 H, Ph), 7.85 (s, 1 H, NH), 7.87 (s, 1 H, NH), 8.13 (s, 1 H, NH). 13C NMR (75 MHz, DMSO-d 6): δ = 14.60 (Me), 35.45 (CH2), 80.20, 85.48 (C–C), 127.11, 127.32, 127.34, 127.60, 127.86, 128.03 [CH(Ph)], 136.29, 138.05 [C(Ph)], 159.64, 160.37 (C=O). HRMS (ESI-TOF): m/z [M + H]+ calcd for C18H18N4O2 + H: 323.1503; found: 323.1500. 1-Benzyl-3a,6a-diphenyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione (1c) White powder; yield: 0.576 g (75%); mp 298–300 °С (MeCN). 1H NMR (300 MHz, DMSO-d 6): δ = 3.99 (d, J = 16.2 Hz, 1 H, CH2), 4.36 (d, J = 16.1 Hz, 1 H, CH2), 6.88–6.95 (m, 2 H, Ph), 6.97–7.03 (m, 3 H, Ph), 7.04–7.13 (m, 5 H, Ph), 7.14–7.33 (m, 5 H, Ph), 7.96 (s, 1 H, NH), 8.06 (s, 1 H, NH), 8.13 (s, 1 H, NH). 13C NMR (125 MHz, DMSO-d 6): δ = 44.22 (CH2), 80.57, 85.96 (C–C), 126.45, 127.13, 127.35, 127.46, 127.61, 127.96, 128.00, 128.09 [CH(Ph)], 135.71, 137.95, 139.09 [C(Ph)], 159.73, 160.40 (C=O). HRMS (ESI-TOF): m/z [M + H]+ calcd for C23H20N4O2 + H: 385.1659; found: 385.1657. 3a,6a-Diphenyl-1-propyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione (1e) White powder; yield: 0.470 g (70%); mp 305–307 °С (MeCN). 1H NMR (300 MHz, DMSO-d 6): δ = 0.77 (t, J = 7.3 Hz, 6 H, Me), 1.41–1.60 (m, 2 H, CH2), 2.58–2.68 (m, 1 H, CH2), 3.10–3.20 (m, 1 H, CH2), 6.92–6.99 (m, 2 H, Ph), 7.00–7.14 (m, 8 H, Ph), 7.84 (s, 2 H, NH), 8.07 (s, 1 H, NH). 13C NMR (75 MHz, DMSO-d 6): δ = 11.25 (Me), 21.91, 42.47 (CH2), 80.19, 85.45 (C–C), 127.07, 127.24, 127.31, 127.59, 127.82, 128.00 [CH(Ph)], 136.11, 138.06 [C(Ph)], 159.64, 160.33 (C=O). HRMS (ESI-TOF): m/z [M + H]+ calcd for C19H20N4O2 + H: 337.1659; found: 337.1658.
  • 12 CCDC 1511967 contains the supplementary crystallographic data for compound 1b. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.