Synlett 2017; 28(12): 1427-1431
DOI: 10.1055/s-0036-1588771
letter
© Georg Thieme Verlag Stuttgart · New York

Homoconjugated and Spiro Push–Pull Systems: Cycloadditions of Naphtho- and Anthradiquinones with Electron-Rich Alkynes

Cagatay Dengiz, Timothy M. Swager*
  • Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA   Email: tswager@mit.edu
Further Information

Publication History

Received: 31 January 2017

Accepted after revision: 08 March 2017

Publication Date:
11 April 2017 (eFirst)

Abstract

We report the synthesis and characterization of three new classes of push–pull chromophores using [2+2]-cycloaddition reactions of electron-rich alkynes and electron-poor alkenes. Previous investigations have focused on the reactions of cyano-substituted electron acceptors. This study demonstrates that cyano-free electron acceptors, naphtho- and anthradiquinones, can also be used to access extended push–pull systems. The effects of the structural changes on the spectroscopic and electronic properties were investigated by UV/vis spectroscopy. Structures were confirmed by X-ray and NMR analysis in solution.

Supporting Information

 
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  • 16 General Procedure for the Synthesis of Homoconjugated and Spiro Push–Pull Systems Diquinone (1 equiv) was added under Ar to a solution of electron-rich alkyne (1 equiv) in DCE (5 mL). The mixture was stirred at 25 °C for 3 h and the solvent removed under reduced pressure. The residue was purified by FCC (SiO2, CHCl3) to give homoconjugated and spirocyclic products. Compound 3a: Naphthazarin (1, 100 mg, 0.532 mmol) was added under Ar to a solution of electron-rich alkyne 2a (77 mg, 0.532 mmol) in DCE (5 mL). The mixture was stirred at 25 °C for 3 h and the solvent removed under reduced pressure. The residue was purified by flash column chromatography (FCC; SiO2, CHCl3) to give homoconjugated chromophore 3a (62 mg, 35%) as a dark-orange solid. Rf = 0.13 (SiO2; CHCl3); mp 215–218 °C. 1H NMR (400 MHz, CDCl3, 298 K): δ = 2.99 (s, 6 H), 6.43 (s, 1 H), 6.65 (quasi d, J = 9.0 Hz, 2 H), 6.80 (s, 4 H), 7.63 (quasi d, J = 9.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3, 298 K): δ = 189.0, 187.6, 151.5, 150.7, 140.3, 139.7, 128.4, 123.7, 117.3, 111.6, 68.7, 64.6, 40.2 ppm. UV/vis (CH2Cl2): λmax (ε) = 453 (2400), 323 nm (21800 M–1 cm–1). ESI-HRMS: m/z calcd for C20H15NO4 +: 334.1074; found: 334.1076 [M + H]+. Compounds 5a and 6a: Quinizarin (4, 50 mg, 0.210 mmol) was added under Ar to a solution of electron-rich alkyne 2a (31 mg, 0.210 mmol) in DCE (5 mL). The mixture was stirred at 25 °C for 3 h and the solvent removed under reduced pressure. The residue was purified by FCC (SiO2, CHCl3) to give homoconjugated chromophore 5a (31 mg, 39%) and 6a (4 mg, 5%) as a dark-orange solids. Compound 5a: Rf = 0.13 (SiO2; CHCl3); mp 125–130 °C. 1H NMR (400 MHz, CDCl3, 298 K): δ = 2.99 (s, 6 H), 6.53 (s, 1 H), 6.66 (quasi d, J = 8.9 Hz, 2 H), 6.83 (s, 2 H), 7.67 (quasi d, J = 8.9 Hz, 2 H), 7.73–7.80 (m, 2 H), 8.03–8.12 ppm (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3, 298 K): δ = 189.9, 188.5, 188.4, 187.3, 151.4, 150.9, 140.7, 139.9, 135.04, 134.96, 134.7, 134.2, 128.41, 128.39, 128.1, 124.2, 117.7, 111.6, 69.5, 65.5, 40.2 ppm. UV/vis (CH2Cl2): λmax (ε) = 411 (3400), 318 nm (22200 M–1 cm–1). ESI-HRMS: m/z calcd for C24H17NO4 +: 384.1230; found: 384.1220 [M + H]+. Compound 6a: Rf = 0.26 (SiO2; CHCl3); mp 144–147 °C. 1H NMR (400 MHz, CDCl3, 298 K): δ = 3.00 (s, 6 H), 5.79 (d, J = 10.0 Hz, 1 H), 6.17 (s, 1 H), 6.68 (quasi d, J = 9.0 Hz, 2 H), 7.50 (quasi d, J = 9.0 Hz, 2 H), 7.53 (d, J = 10.0 Hz, 1 H), 7.93 (dd, J = 5.7, 3.1 Hz, 2 H), 8.13 (dd, J = 5.7, 3.1 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3, 298 K): δ = 193.3 (2 C=O) 159.9, 150.8, 147.5, 144.4, 136.2, 134.7, 126.9, 126.0, 125.1, 118.6, 117.6, 112.2, 103.0, 73.2, 40.4 ppm. UV/vis (CH2Cl2): λmax (ε) = 480 (12500), 323 nm (14300 M–1 cm–1). ESI-HRMS: m/z calcd for C24H17NO4 +: 384.1230; found: 384.1227 [M + H]+.