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

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

References and Notes

• 1 Bartlett PD. Ryan MJ. Cohen SG. J. Am. Chem. Soc.  1942,  64:  2649 
• 2a Iwamura H. Mislow K. Acc. Chem. Res.  1988,  21:  175 
• 2b Kelly TR. Bowyer MC. Bhaskar KV. Bebbington D. Garcia A. Lang F. Kim MH. Jette MP. J. Am. Chem. Soc.  1994,  116:  3657 
• 2c Kelly TR. Silva RA. Silva HD. Jasmin S. Zhao Y. J. Am. Chem. Soc.  2000,  122:  6935 
• 2d Godinez CE. Zepeda G. Garcia-Garibay MA. J. Am. Chem. Soc.  2002,  124:  4701 
• 3a Long TM. Swager TM. J. Am. Chem. Soc.  2002,  124:  3826 
• 3b Chong JH. Ardakani SJ. Smith KJ. ManLachlan MJ. Eur. Chem. J.  2009,  15:  11824 
• 4 Marc Veen E. Postma PM. Jonkman HT. Spek AL. Feringa BL. Chem. Commun.  1999,  1709 
• 5 Hart H. Bashir-Hashemi A. Luo J. Meador MA. Tetrahedron  1986,  42:  1641 
• 6 Chong JH. MacLachlan MJ. J. Org. Chem.  2007,  72:  8683 
• 7 Hilton CL. Jamison CR. Zane HK. King BT.
  J. Org. Chem.  2009,  74:  405 
• 8 Long TM. Swager TM. Adv. Mater.  2001,  13:  601 
• 9a Zhu X.-Z. Chen C.-F. J. Am. Chem. Soc.  2005,  127:  13158 
• 9b Zong Q.-S. Chen C.-F. Org. Lett.  2006,  8:  211 
• 9c Han T. Chen C.-F. Org. Lett.  2006,  8:  1069 
• 9d Cao J. Jiang Y. Zhao J.-M. Chen C.-F. Chem. Commun.  2009,  1987 
• 9e Cao J. Lu H.-Y. You X.-J. Zheng Q.-Y. Chen C.-F. Org. Lett.  2009,  11:  4446 
• 9f Jiang Y. Cao J. Zhao J.-M. Xiang J.-F. Chen C.-F. J. Org. Chem.  2010,  75:  1767 
• 10a Roelfs G. Feringa BL. Angew. Chem. Int. Ed.  2005,  44:  3230 
• 10b Frey J. Tock C. Collin J.-P. Heitz V. Sauvage J.-P. J. Am. Chem. Soc.  2008,  130:  4592 
• 11 Paw W. Eisenberg R. Inorg. Chem.  1997,  36:  2287 
• 12a Ishi-i T. Yaguma K. Kuwahara R. Taguri Y. Mataka S. Org. Lett.  2006,  8:  585 
• 12b Dietrich-Buchecker CO. Marnot PA. Sauvage J.-P. Tetrahedron Lett.  1982,  50:  5291 
• 14 Chong JH. MacLachlan MJ. Inorg. Chem.  2006,  45:  1442 

13

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.

15

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.

16

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.