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RESEARCH ARTICLE
Contents Vol 59(1)

Synthesis of Azobenzenophanes with a Large Molecular Cavity

Perumal Rajakumar A B , Beeran Senthilkumar A and Kannupal Srinivasan A
+ Author Affiliations
- Author Affiliations

A Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600025, Tamil Nadu, India.

B Corresponding author. Email: perumalrajkumar2003@yahoo.co.in

Australian Journal of Chemistry 59(1) 75-77 https://doi.org/10.1071/CH05254
Submitted: 26 September 2005  Accepted: 29 December 2005   Published: 31 January 2006

Abstract

The design and synthesis of four large-cavity azobenzenophanes, capable of forming photochemically controllable complexes with organic guest molecules, are described. These azobenzenophanes, possessing m-terphenyl, aromatic carbonyl, and chiral BINOL spacers, were synthesized from the corresponding bisphenols and dibromides using simple O-alkylation methodology. A preliminary photochemical study was carried out on the aromatic carbonyl spacer containing azobenzenophane, and the isosbestic points for the cis–trans isomerization process appeared at 319 and 419 nm.


Acknowledgments

The authors thank CSIR, India, for financial assistance; SAIF, IIT Madras for NMR spectra; and RSIC, Lucknow, for FAB-MS spectra.


References


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[2]   (a) S. Shinkai, T. Minami, Y. Kusano, O. Manabe, J. Am. Chem. Soc. 1983, 105,  1851.
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* Cyclophane 1: Yield 19%. Mp 248°C. νmax/cm−1 1724 (C=O). δH (300 MHz, CDCl3) 7.89 (d, J 8.8, 8H), 7.51–7.24 (m, 22H), 7.10 (d, J 8.8, 8H), 5.19 (s, 8H), 3.39 (s, 6H). δC (75 MHz, CDCl3 + [D6]DMSO) 174.4, 151.7, 144.5, 140.6, 137.3, 134.3, 133.7, 132.7, 131.3, 129.1, 127.3, 119.8, 74.6, 56.6. m/z (FAB-MS) 1052 (M+). (Found: C 77.4, H 5.0, N 5.3. C68H52N4O8 requires C 77.6, H 5.0, N 5.3%).

† Cyclophane 2: Yield 15%. Mp 263°C. νmax/cm−1 1654 (C=O). δH (500 MHz, CDCl3) 7.68 (d, J 8.6, 8H), 7.42 (s, 8H), 7.40 (d, J 8.0, 8H), 7.23 (d, J 8.0, 8H), 6.87 (d, J 8.6, 8H), 5.37 (s, 8H). δC (125 MHz, CDCl3) 196.1, 159.1, 147.8, 140.5, 137.2, 130.2, 129.3, 129.1, 123.8, 120.6, 72.8. m/z (FAB-MS) 1048 (M+). (Found: C 77.9, H 4.5, N 5.2. C68H48N4O8 requires C 77.9, H 4.6, N 5.3%).

‡ Cyclophane 3: Yield 16%. Mp 234°C. δH (400 MHz, CDCl3) 7.96 (d, J 8.3, 8H), 7.66–7.53 (m, 22H), 7.07 (d, J 8.3, 8H), 5.21 (s, 8H), 2.46 (s, 6H). δC (100 MHz, CDCl3) 153.6, 146.5, 141.2, 136.2, 134.7, 133.6, 128.3, 127.9, 126.0, 123.1, 115.1, 69.9, 22.7. m/z (FAB-MS) 964 (M+). (Found: C 82.4, H 5.4, N 5.8. C66H52N4O4 requires C 82.1, H 5.4, N 5.8%).

Cyclophane 4: Yield 23%. [α]D25 −17.1 (c 1.0, CHCl3). Mp 182°C. δH (500 MHz, CDCl3) 7.94–7.89 (m, 12H), 7.37–7.34 (m, 16H), 7.28–7.20 (m, 4H), 7.02–7.00 (m, 8H), 5.20 (d, J 13.2, 4H), 5.08 (d, J 13.2, 4H). δC (125 MHz, CDCl3) 153.7, 140.2, 134.2, 129.5, 129.3, 128.0, 127.3, 126.7, 126.5, 125.3, 123.7, 122.6, 120.3, 115.4, 70.2. m/z (FAB-MS) 984 (M+). (Found: C 82.8, H 4.8, N 5.6. C68H48N4O4 requires C 82.9, H 4.9, N 5.7%).