A Synthesis of Novel Perinaphthenones from Acetylenic Esters and Acenaphthoquinone–Malononitrile Adduct in the Presence of Triphenylphosphine

Abstract

A facile protocol involving Tebby zwitterions (PPh₃-acetylenic esters) and the Knoevenagel condensation product of acenaphthylene-1,2-dione with malononitrile or ethyl cyanoacetate for the selective synthesis of a new series of perinaphthenone derivatives is described. Triphenylphosphine plays a catalytic role in these transformations. The structure of a typical product was confirmed by X-ray crystallography. The merits of this method include high yields of products, good atom economy, and a metal-free catalyst.

Key words

perinaphthenones - acenaphthylenedione - alkynoate esters - triphenylphosphine - malononitrile

• References and Notes

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• 14 1H-Phenalen-1-one Derivatives 4a–j; General Procedure A mixture of PPh₃ (0.026 g, 0.1 mmol) and CH₂Cl₂ (5 mL) at 0 °C was added dropwise over 10 min to a stirred solution of the appropriate Knoevenagel adduct 1 or 2 (1 mmol) and acetylenic ester 3 (1 mmol) in CH₂Cl₂ (5 mL). The mixture was then allowed to warm to r.t. and stirred for 12 h. The solvent was removed under reduced pressure, and the residue was purified by column chromatography [silica gel, hexane–EtOAc (2:1)]. Dimethyl 2-Cyano-3-(2-cyano-1-oxo-1H-phenalen-3-yl)but-2-enedioate (4a) Yellow solid; yield: 0.31 g (84%); mp 185–190 °C. IR (KBr): 3057, 2952, 2194 (CN), 1728 (C=O), 1654 (C=O), 1571, 1437 (C=C_Ar), 1255, 1008, 778 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 3.94 (s, 3 H, MeO), 4.02 (s, 3 H, MeO), 7.77 (t, ³ J = 7.5 Hz, 1 H Ar-H), 7.92 (t, ³ J = 7.5 Hz, 1 H Ar-H), 8.13 (d, ³ J = 7.5 Hz, 1 H, Ar-H), 8.26 (d, ³ J = 8.0 Hz, 1 H Ar-H), 8.30 (d, ³ J = 8.0 Hz, 1 H Ar-H), 8.78 (d, ³ J = 7.5 Hz, 1 H Ar-H). ¹³C NMR (125 MHz, CDCl₃): δ = 53.9 (2 × MeO), 111.1 (CN), 111.8 (CN), 112.3 (C), 113.0 (C), 122.5 (C), 126.7 (CH), 126.8 (C), 127.9 (CH), 131.2 (C), 131.9 (C), 132.5 (CH), 133.6 (CH), 136.3 (CH), 136.7 (CH), 150.5 (C), 153.1 (C), 158.6 (C=O), 162.1 (C=O), 177.7 (C=O). EI-MS: m/z (%) = 372 (M⁺, 82), 313 (53), 299 (48), 272 (51), 255 (100), 226 (50), 200 (32). Anal. Calcd for C₂₁H₁₂N₂O₅ (372.34): C, 67.74; H, 3.25; N, 7.52. Found: C, 67.95; H, 3.32; N, 7.61. Dimethyl 2-Cyano-3-[2-(ethoxycarbonyl)-1-oxo-1H-phenalen-3-yl]but-2-enedioate (4f) Yellow solid; yield: 0.36 g (86%); mp 180–185 °C. IR (KBr): 3055, 2988, 2214 (CN), 1727 (C=O), 1625 (C=O), 1588, 1370 (C=C_Ar), 1269, 780 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 1.25 (t, ³ J = 7.0 Hz, 3 H Me), 3.28 (s, 3 H, MeO), 3.52 (s, 3 H, MeO), 4.48 (q, ³ J = 7.0 Hz, 2 H, CH₂O), 7.73 (t, ³ J = 7.5 Hz, 1 H Ar-H), 7.88 (t, ³ J = 7.5 Hz, 1 H Ar-H), 8.10 (d, ³ J = 8.0 Hz, 1 H, Ar-H), 8.31 (d, ³ J = 8.0 Hz, 1 H Ar-H), 8.33 (d, ³ J = 8.0 Hz, 1 H Ar-H), 8.64 (d, ³ J = 7.5 Hz, 1 H Ar-H). ¹³C NMR (125 MHz, CDCl₃): δ = 13.8 (Me), 52.0, 52.7 (2 × MeO), 64.6 (CH₂O), 114.6 (CN), 122.9 (C), 126.1 (CH), 126.5 (CH), 127.1 (C), 127.6 (C), 128.4 (C), 128.5 (CH), 128.7 (CH), 129.2 (C), 131.3 (C), 131.9 (CH), 133.6 (CH), 149.1 (C), 150.7 (C), 158.3 (C=O), 161.8 (C=O), 162.3 (C=O), 187.2 (C=O). EI-MS: m/z (%) = 419 (M⁺, 91), 360 (62), 345 (53), 318 (52), 301 (100), 275 (42), 246 (25), 202 (34). Anal. Calcd for C₂₃H₁₇NO₇ (419.10): C, 65.87; H, 4.09; N, 3.34. Found: C, 65.99; H, 4.16; N, 3.41.
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