A Novel Method for the Synthesis of Furo-imidazo[3.3.3]propellanes from Thiocarbonohydrazides

Abstract

Novel furo-imidazo[3.3.3]propellanes are synthesized via reactions of thiocarbonohydrazides with (1,3-dioxo-2,3-dihydro-1H-inden-2-ylidene)propanedinitrile in tetrahydrofuran. A rationale for these conversions involving nucleophilic addition on the dicyanomethylene carbon atom is presented. The structures of these unexpected products are confirmed by using IR, NMR, mass spectrometry and single-crystal X-ray diffraction.

Key words

donor–acceptor interactions - thiocarbonohydrazides - (1,3-dioxo-2,3-dihydro-1H-indene-2-ylidene)propanedinitrile - furo-imidazo[3.3.3]propellanes

• References and Notes

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• 25 Furo-imidazo[3.3.3]propellanes 5; General Procedure To a solution of 4 (1.0 mmol) in dry THF (15 mL) was added thiocarbonohydrazide 1a–d (1.0 mmol) in dry THF (15 mL) and the mixture stirred over 30 min. The orange color of the solution quickly became reddish-brown, and the mixture was allowed to stand for 3 h at r.t. during which time a fine colorless crystalline product separated. The precipitate was filtered off, washed with THF, dried and recrystallized from MeCN–DMF for 5a and from MeCN for 5b–d to give pure product 5a–d. 1-[2,9-Diamino-3-cyano-4-oxo-10-thioxo-4H-3a,8b-(epiminomethanoimino)indeno[1,2-b]furan-11-yl]-3-ethylthiourea (5a) Yield: 0.361 mg (90%); colorless crystals; mp 256–258 °C (MeCN–DMF). IR (KBr): 3339–3190 (NH), 2201 (CN), 1723 (CO), 1590 (ArC=C), 1354, 996 (C=S, C–N), 1093 (C–O–C) cm^–1. ¹H NMR (300 MHz, DMSO-d ₆): δ = 1.10–1.15 (t, J = 7.5 Hz, 3 H, CH₃), 3.58–3.60 (q, J = 7.5 Hz, 2 H, CH₂), 4.97 (br s, 2 H, NNH₂), 7.53–7.55 (m, 1 H, ArCH), 7.69–7.84 (m, 2 H, ArCH), 7.87–8.01 (m, 1 H, ArCH), 8.57 (s, 1 H, NHEt), 9.51 (br s, 2 H, NH₂), 10.13 (s, 1 H, ³NH). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 13.97 (CH₃), 38.63 (CH₂), 50.97 (furan C3), 78.28 (furan C4), 102.44 (furan C5), 116.65 (CN), 125.08, 126.42, 132.32, 134.48 (ArCH), 136.89, 141.64 (ArC), 168.54 (furan C2), 180.37, 181.28 (C=S), 190.32 (indeno CO). MS (EI): m/z (%) = 401 (100) [M]⁺, 375 (33), 358 (60), 335 (20), 210 (50), 77 (45), 66 (18), 56 (76). Anal. Calcd for C₁₆H₁₅N₇O₂S₂: C, 47.87; H, 3.77; N, 24.42; S, 15.97. Found: C, 47.80; H, 3.85; N, 24.53; S, 15.85. 1-Allyl-3-[2,9-diamino-3-cyano-4-oxo-10-thioxo-4H-3a,8b-(epiminomethanoimino)indeno[1,2-b]furan-11-yl]thiourea (5b) Yield: 0.380 mg (92%); colorless crystals; mp 260–262 °C (MeCN). IR (KBr): 3353–3156 (NH), 2207 (CN), 1733 (CO), 1590 (ArC=C), 1375, 1002 (C=S, C–N), 1090 (C–O–C) cm^–1. ¹H NMR (300 MHz, DMSO-d ₆): δ = 4.80–4.85 (m, 2 H, allyl CH₂N), 4.97 (br s, 2 H, NNH₂), 5.25–5.31 (m, 2 H, allyl CH₂), 5.86–5.93 (m, 1 H, allyl CH=), 7.53–7.55 (m, 1 H, ArCH), 7.69–7.82 (m, 1 H, ArCH), 7.84–7.86 (m, 1 H, ArCH), 7.92–8.03 (m, 1 H, ArCH), 8.95 (s, 1 H, NH allyl), 9.69 (br s, 2 H, NH₂), 10.26 (s, 1 H, ³NH). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 45.71 (allyl CH₂N), 51.00 (furan C3), 78.25 (furan C4), 102.32 (furan C5), 115.17 (allyl CH₂=), 116.50 (CN), 124.90, 126.25, 132.09, 134.22 (ArCH), 136.69, 141.50 (ArC), 137.01 (allyl CH=), 168.35 (furan C2), 180.06, 181.04 (C=S), 190.39 (indeno CO). MS (EI): m/z (%) = 413 (30) [M]⁺, 397 (40), 387 (60), 358 (80), 203 (25), 115 (20), 77 (100), 66 (18), 56 (76). Anal. Calcd for C₁₇H₁₅N₇O₂S₂: C, 49.38; H, 3.66; N, 23.71; S, 15.51. Found: C, 49.24; H, 3.73; N, 23.62; S, 15.64. 1-Benzyl-3-[2,9-diamino-3-cyano-4-oxo-10-thioxo-4H-3a,8b-(epiminomethanoimino)indeno[1,2-b]furan-11-yl]thiourea (5c) Yield: 0.402 mg (87%); colorless crystals; mp 284–286 °C (MeCN). IR (KBr): 3336–3195 (NH), 2205 (CN), 1728 (CO), 1590 (ArC=C), 1384, 999 (C=S, C–N), 1097 (C–O–C) cm^–1. ¹H NMR (300 MHz, DMSO-d ₆): δ = 4.43 (s, 2 H, CH₂Ph), 4.97 (br s, 2H, NNH₂), 7.14–7.32 (m, 2 H, ArCH), 7.38–7.40 (m, 2 H, ArCH), 7.55–7.57 (m, 2 H, ArCH), 7.73–7.85 (m, 1 H, ArCH), 7.95–8.01 (m, 2 H, ArCH), 9.27 (s, 1 H, NH benzyl), 9.75 (br s, 2 H, NH₂), 10.35 (s, 1 H, ³NH). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 46.71 (CH₂Ph), 51.20 (furan C3), 78.44 (furan C4), 102.46 (furan C5), 116.26 (CN), 125.11, 126.52, 126.74, 127.84, 132.33, 134.47 (ArCH), 136.29, 138.28, 141.77 (ArC), 168.68 (furan C2), 180.77, 182.01 (C=S), 190.28 (indeno CO). MS (EI): m/z (%) = 463 (15) [M]⁺, 437 (65), 397 (40), 358 (35), 253 (25), 105 (22), 91 (50), 77 (100), 66 (18). Anal. Calcd for C₂₁H₁₇N₇O₂S₂: C, 54.41; H, 3.70; N, 21.15; S, 13.83. Found: C, 54.26; H, 3.65; N, 21.29; S, 13.70. 1-[2,9-Diamino-3-cyano-4-oxo-10-thioxo-4H-3a,8b-(epiminomethanoimino)indeno[1,2-b]furan-11-yl]-3-phenylthiourea (5d) Yield: 0.382 mg (85%); colorless crystals; mp 275–277 °C (MeCN). IR (KBr): 3341–3165 (NH), 2201 (CN), 1727 (CO), 1592 (ArC=C), 1386, 998 (C=S, C–N), 1098 (C–O–C) cm^–1. ¹H NMR (300 MHz, DMSO-d ₆): δ = 4.99 (br s, 2 H, NNH₂), 7.16–7.20 (m, 1 H, ArCH), 7.32–7.38 (m, 2 H, ArCH), 7.56–7.68 (m, 2 H, ArCH), 7.76–7.84 (m, 2 H, ArCH), 7.88–8.02 (m, 2 H, ArCH), 9.41 (s, 1 H, NH phenyl), 9.92 (br s, 2 H, NH₂), 10.59 (s, 1 H, ³NH). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 51.32 (furan C3), 78.28 (furan C4), 102.62 (furan C5), 116.10 (CN), 124.12, 124.86, 125.56, 126.16, 127.80, 132.38, 135.55 (ArCH), 136.96, 138.98, 141.68 (ArC), 168.74 (furan C2), 180.61, 180.98 (C=S), 190.20 (indeno CO). MS (EI): m/z (%) = 449 (10) [M]⁺, 423 (30), 383 (55), 358 (70), 314 (62), 239 (20), 135 (45), 77 (100), 66 (18). Anal. Calcd for C₂₀H₁₅N₇O₂S₂: C, 53.44; H, 3.36; N, 21.81; S, 14.27. Found: C, 53.56; H, 3.43; N, 21.89; S, 14.42.
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