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Sterically encumbered 2,6-dibenzhydryl-4-methylphenyl derived ligand systems: synthesis and structures

Abstract

 Bulky 2,6-dibenzhydryl-4-methylaniline, I undergoes diazotization upon treatment with \(\hbox {H}_{2}\hbox {SO}_{4}/\hbox {NaNO}_{2}\), which upon further reaction with KI affords 1-iodo-2,6-dibenzhydryl-4-methylbenzene, 1. Reaction of I with one equivalent of acetylacetone in ethanol under reflux condition affords mono-Schiff base, 4-(2,6-dibenzhydryl-4-methylphenylamino)pent-3-ene-2-one, 2. Similarly, I reacts with half equivalent of 2-hydroxy-5-methylisophthalaldehyde or one-third equivalent of 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde in ethanol under reflux condition to afford bis-Schiff base, 2,6-bis(((2,6-dibenzhydryl-4-methylphenyl)imino)methyl)-4-methylphenol, 3 and tris-Schiff base, 2,4,6-tris(((2,6-dibenzhydryl-4-methylphenyl)amino)methylene)cyclohexane-1,3,5-trione, 4, respectively. Further, I upon reaction with triflic acid affords (2,6-dibenzhydryl-4-methylphenyl)ammonium triflate, 5 whereas upon reaction with HBr and HCl affords co-crystals I \(\cdot \)HBr, 6 and I \(\cdot \)HCl, 7. All the new products were isolated in moderate to good yield and characterized by spectroscopic (IR, ESI-mass, NMR, UV-Vis) and microanalytical (CHN) techniques, in addition to a single crystal X-ray diffraction study for 1, 2 and 4-7.

Graphical Abstract

JCSC-D-17-00649 Synopsis A bulky amine was employed to synthesise various compounds containing 2,6-dibenzhydrylphenyl group. These compounds include a bulky iodo-derivative, one mono-, one bis- and one tris-Schiff base, one triflate salt of the bulky amine and two co-crystals of the bulky amine with HBr or HCl.

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Acknowledgements

R. M. is grateful to SERB, New Delhi for a J. C. Bose Fellowship (SB/S2/JCB-85/2014) through which this research work was carried out. P. S. thanks IIT Bombay for a Post-doctoral Fellowship. IIT Bombay is greatly acknowledged for providing analytical and instrumental facilities.

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Correspondence to Ramaswamy Murugavel.

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Saxena, P., Murugavel, R. Sterically encumbered 2,6-dibenzhydryl-4-methylphenyl derived ligand systems: synthesis and structures. J Chem Sci 129, 1499–1512 (2017). https://doi.org/10.1007/s12039-017-1353-8

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Keywords

  • Sterically encumbered ligands
  • bulky aryl groups
  • Schiff bases
  • acid-base adducts
  • co-crystals