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Synlett 2010(11): 1679-1681  
DOI: 10.1055/s-0029-1219957
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis and Structures of 1,10-Phenanthroline-Based Extended Triptycene Derivatives

Yi Jianga,b, Chuan-Feng Chen*a
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. of China
Fax: +86(10)62554449; e-Mail: cchen@iccas.ac.cn;
b Graduate School, Chinese Academy of Sciences, Beijing 100049, P. R. of China
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Publication History

Received 7 April 2010
Publication Date:
04 June 2010 (online)

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Abstract

A series of novel 1,10-phenanthroline-based extended triptycene derivatives were conveniently synthesized in good yields, and their structures were determined by ¹H NMR, ¹³C NMR, MALDI-TOF MS spectra, and elemental analysis.

Key words

triptycene - 1,10-phenanthroline - synthesis

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Preparation and Spectroscopic Data of 3d An ice-cold mixture of concentrated H2SO4 (10 mL) and HNO3 (5 mL) was added to 6d (438 mg, 1.5 mmol) and of KBr (1 g, 8.4 mmol). The mixture was reacted at r.t. for 8 h. The yellow solution was poured to over 500 mL of ice, neutralized carefully with NaOH until neutral to slightly acidic pH, and extracted with CHCl3 followed by drying with Na2SO4 and removal of solvent. The crude product was purified by silica gel column chromatography (eluant: PE-CH2Cl2 = 2:3) to afford 3d in 65% yield as white solid; mp 144-146 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 8.37 (d, J = 8.3 Hz, 2 H), 7.58 (d, J = 8.3 Hz, 2 H), 1.52 (s, 18 H). ¹³C NMR (75 MHz, CDCl3): δ = 179.3, 177.1, 152.3, 137.1, 125.8, 121.0, 39.1, 29.8. MS (EI): m/z = 322 [M+]. Anal. Calcd for C20H22N2O2: C, 74.51; H, 6.88; N, 8.69. Found: C, 74.34; H, 6.69; N, 8.57.

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Experimental Procedure and Characterizations for Representative Compound 2a
To a solution of compound 4 (284 mg, 1 mmol) in MeOH (50 mL) was added 3a (273 mg, 1.3 mmol). The solution was stirred under N2 overnight to give a yellow solution. The solvent was removed by rotary evaporation, and the red-orange residue was purified by silica gel column chromatog-raphy (eluant: MeOH-CH2Cl2 = 1:100) to give the product 2a in 67% yield as yellow solid; mp >300 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 9.45 (dd, J = 1.8, 6.3 Hz, 2 H), 9.17 (dd, J = 1.8, 2.7 Hz, 2 H), 8.19 (s, 2 H), 7.63-7.59 (m, 2 H), 7.55-7.51 (m, 4 H), 7.15-7.11 (m, 4 H), 5.74 (s, 2 H). ¹³C NMR (75 MHz, CDCl3): δ = 152.0, 147.7, 147.0, 143.6, 141.6, 140.0, 133.2, 127.3, 126.2, 124.2, 123.8, 122.8, 53.8. MS (MALDI-TOF): m/z = 459.2 [M + H]+, 481.1 [M + Na]+, 497.1 [M + K]+. Anal. Calcd for C32H18N4: C, 83.82; H, 3.96; N, 12.22. Found: C, 83.71; H, 4.13; N, 12.14.

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Experimental Procedure and Characterizations for Representative Compound 1c To a solution of compound 5 (344 mg, 1 mmol) in MeOH (50 mL) was added 3c (1.38 g, 4.3 mmol). The solution was stirred under N2 overnight to give a yellow solution. The solvent was removed by rotary evaporation, and the red-orange residue was purified by silica gel column chromatog-raphy (eluant: MeOH-CH2Cl2 = 1:50) to give the product 1c in 28% yield as yellow solid; mp >300 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 9.55 (d, J = 8.3 Hz, 6 H), 8.54 (s, 6 H), 7.69 (d, J = 8.3 Hz, 6 H), 6.36 (s, 2 H), 3.35-3.29 (m, 12 H), 1.90-1.89 (m, 12 H), 1.57-1.50 (m, 12 H), 1.02 (t, J = 7.3 Hz, 18 H). ¹³C NMR (75 MHz, CDCl3): δ = 165.9, 147.5, 143.5, 141.4, 140.8, 133.4, 124.9, 124.2, 123.0, 53.3, 39.0, 31.8, 22.9 14.1. MS (MALDI-TOF): m/z = 1203.6 [M + H]+. Anal. Calcd for C78H74N12 ˙H2O: C, 78.23; H, 6.40; N, 14.04. Found: C, 78.34; H, 6.23; N, 13.91.