Synthesis and Photochemical Transformations of a few Olefin appended Dibenzobarrelenes

Ambily Mary Jacob, Gisha George

Abstract


Several olefin appended dibenzobarrelenes and bisdibenzobarrelenes were synthesized by Diels-Alder reaction between 9-alkenylanthracenes and dimethyl acetylenedicarboxylate (DMAD) under carefully controlled conditions. Efficient intramolecular quenching of barrelene triplet was observed in the case of a few of the resultant dibenzobarrlenes.

Keywords


Diels-Alder reaction, dibenzobarrelenes, dibenzosemibullvqlenes, dibenzocyclootatetraenes, di-π-methane rearrangement.

Full Text:

PDF

References


Zimmerman HE. Rearrangements in Ground and Excited States. de Mayo P (Ed.). Academic Press: New York, 1980; 3: 131.

Scheffer JR, Yang J. CRC Handbook of Organic Photochemistry and Photobiology. Horspool WM, Sea, PS (Ed.). CRC Press, Boca Raton, FL, USA, 1995: 204.

Hixon SS, Mariano PS, Zimmerman HE. Di-.pi.-methane and oxa-di-.pi.-methane rearrangements. Chem Rev 1973; 73: 531.

Cristol SJ, Kaufman RL, Opitz SM et al. Photochemical transformations. 33. Some studies of the photorearrangements of dibenzobarrelenes. A novel excitation-transfer relay mechanism. J Am Chem Soc 1983; 105: 3226.

Chen J, Scheffer JR, Trotter J. Differences In Photochemical Reactivity Of 9,10-Ethenoanthracene Derivatives In Liquid And Crystalline Media. Tetrahedron 1992; 48: 3251.

Zimmerman HE, Sulzbach HM, Tollefson MB. Experimental and theoretical Exploration of the Detailed Mechanism of the Rearrangement of Barrelenes to Semibullvalenes – Diradical Intermediates and Transition-states. J Am Chem Soc 1993; 115: 6548.

Sajimon MC, Ramaiah D, Ajayakumar S et al. Substituent Effects on Regioselectivity in the Photorearrangement of a Few Naphthobarrelenes1. Tetrahedron 2000; 56: 5421.

Kumar CV, Murty BARC, Lahiri S, et al. Photochemical transformations and laser flash photolysis studies of dibenzobarrelenes containing 1,2-dibenzoylalkene moieties. J Org Chem 1984; 49: 4923.

Prathapan S, Asok K, Cyr DR et al. Phototransformations of bridgehead-substituted dibenzobarrelenes. Steady-state and laser flash photolysis studies. J Org Chem 1987; 52: 5512.

Murty BARC, Prathapan S, Kumar CV. Steady-state and laser flash photolysis studies of bridgehead-substituted dibenzobarrelenes. J Org Chem 1985; 50: 2533.

Kumar SA,Rajesh CS, Das S et al. Photorearrangements of bridgehead-disubstituted dibenzobarrelene esters and lactones. J Photochem Photobiol A 1995; 86: 177.

Kumar SA,Ramaiah D, Eldho NV et al. Phototransformations of Bridgehead–Substituted Dibenzobarrelenes. Steady State and Laser Flash Photolysis Studies of 9–benzoyl and 9–(a–hydroxybenzyl)–Substituted Dibenzobarrelenes. J Photochem Photobiol A 1997; 103: 69.

Sajimon MC, Ramaiah D, Muneer M et al. Steady State Photolysis of Bridgehead Disubstituted Dibenzobarrelenes and Interesting Thermal Isomerization of Their Photoproducts. J Photochem Photobiol A 2000; 136: 209.

Jacob AM, Prathapan S. Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes. Ph. D Thesis, CUSAT, 2008. Available from: http://dyuthi.cusat.ac.in/purl/3008.

Fox T, Roesch N, Cortes J et al. On the electronic structure of barrelene-based rigid organic donor-acceptor systems. A comparison of INDO/S-CI calculations with absorption and fluorescence emission spectra. Chem Phys 1993; 175: 357.


Refbacks

  • There are currently no refbacks.