A Novel Isocyanide-Based Three-Component Condensation Reaction: Synthesis of Fully Substituted Imino- and Spiroiminocyclopentenes

Ahmad Shaabani; Ali Hossein Rezayan; Abbas Rahmati; Afshin Sarvary

doi:10.1055/s-2007-980364

LETTER

A Novel Isocyanide-Based Three-Component Condensation Reaction: Synthesis of Fully Substituted Imino- and Spiroiminocyclopentenes

Ahmad Shaabani*, Ali Hossein Rezayan, Abbas Rahmati, Afshin Sarvary
Department of Chemistry, Shahid Beheshti University, P.O. Box 19396-4716, Tehran, Iran
Fax: +98(21)22431663; e-Mail: a-shaabani@cc.sbu.ac.ir;

Abstract

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Abstract

The zwitterion formed from alkyl or aryl isocyanides and dialkyl acetylenedicarboxylate added to electron-deficient tetracyanoethylene or 7,7,8,8-tetracyanoquinodimethane to form fully substituted imino- or spiroiminocyclopentenes in excellent yields without using catalyst.

Key words

isocyanides - tetracyanoethylene - 7,7,8,8-tetracyanoquinodimethane - iminocyclopentene - spiroiminocyclopentene

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References

References and Notes

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Typical Procedure for the Preparation of Dimethyl 5-( tert -Butylimino)-3,3,4,4-tetracyanocyclopent-1-ene-1,2-dicarboxylate ( 4a) To a magnetically stirred solution of tetracyanoethylene (0.128 g, 1.0 mmol) and dimethylacetylenedicarboxylate (0.140 g, 1.0 mmol) in CH₂Cl₂ (15 mL) was added dropwise a mixture of tert-butyl isocyanide (0.83 g, 1 mmol) in CH₂Cl₂ (2 mL) at -10 °C over 10 min. The mixture was allowed to warm to r.t. and was stirred for 15 h. After completion of the reaction, the solvent was removed under vacuum and the residue was crystallized from CH₂Cl₂- n-hexane (1:2) to yield 0.353 g of 4a as a cream powder (100%); mp 161-162 °C. IR (KBr): ν_max = 2256, 2207, 1739 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.56 [s, 9 H, (CH₃)₃C], 3.96 (s, 3 H, OCH₃), 4.06 (s, 3 H, OCH₃). ¹³C NMR (75 MHz, CDCl₃): δ = 23.20 [C(CN)₂], 30.16 [(CH₃)₃C], 46.77 [C(CN)₂], 53.93 (OCH₃), 54.69 (OCH₃), 62.22 (CN=), 108.05 (CN), 108.75 (CN), 133.29, 139.53, 145.60 (3 signals for olefinic carbons), 158.29 (C=O), 160.26 (C=O). MS: m/z (%) = 353 (20) [MH⁺], 338 (25), 298 (25), 57 (100), 41 (75). Anal. Calcd for C₁₇H₁₅N₅O₄: C, 57.79; H, 4.28; N, 19.82. Found: C, 57.89; H, 4.90; N, 19.93.
Typical Procedure for the Preparation of Dimethyl 5-(2,6-Dimethylphenylimino)-4,4-dicyano-3-spiro-2-(cyclohexa-2,5-dienylidene)malononitrilecyclopent-1-ene-1,2-dicarboxylate ( 8a) To a magnetically stirred solution of 7,7,8,8-tetracyanoquinodimethane (0.204 g, 1.0 mmol) and dimethylacetylenedicarboxylate (0.140 g, 1.0 mmol) in CH₂Cl₂ (15 mL) was added dropwise a mixture of 2,6-dimethylphenylisocyanide (0.131 g, 1 mmol) in CH₂Cl₂ (2 mL) at -10 °C over 10 min. The mixture was allowed to warm to r.t. and was stirred for 24 h. After completion of the reaction, the solvent was removed under vacuum and the residue was crystallized from CH₂Cl₂-n-hexane (1:2) to yield 0.429 g of 8a as a brown powder (90%); mp 178 °C (dec.). IR (KBr): ν_max = 2227, 1747, 1731 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.96 (s, 6 H, 2 CH₃-Ar), 3.25 (s, 3 H, OCH₃), 4.01 (s, 3 H, OCH₃), 6.84-7.39 (m, 7 H). ¹³C NMR (75 MHz, CDCl₃): δ = 17.75 (2 CH₃-Ar), 53.27, 54.39, 60.54 [3 signals for 2 OCH₃ and C(CN)₂], 85.06 (C spiro), 109.78 (CN), 111.31 (CN), 125.60, 127.27, 127.87, 131.21, 136.59, 138.56, 139.65, 144.98, 146.64, 152.03, 153.47, 159.03 (C=O), 160.23 (C=O). MS: m/z (%) = 477 (30) [M⁺], 419 (35), 401 (30), 105 (40), 77 (100), 59 (50), 41 (20). Anal. Calcd for C₂₇H₁₉N₅O₄: C, 67.92; H, 4.01; N, 14.67. Found: C, 67.46; H, 3.87; N, 15.40.