Abstract
In this chapter, we highlight the power of vibrational spectroscopy as central technique to investigate the structure and reactivity of two relevant families of nitrogen-containing heterocyclic molecules: hydantoins and mercaptoimidazoles . Infrared spectroscopy is used in connection with the matrix isolation technique to investigate the structures of the isolated molecules and their photochemistry , while both infrared and Raman spectroscopies , supplemented by thermodynamics, microscopy, and diffraction techniques, are used to investigate neat condensed phases of the compounds and transitions between these phases. The experimental studies are supported by extensive computational studies, which include several approaches for detailed analysis of the electron density.
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References
Whittle E, Dows DA, Pimentel GC (1954) Matrix isolation method for the experimental study of unstable species. J Chem Phys 22:1943–1944
Norman I, Porter G (1954) Trapped atoms and radicals in a glass ‘cage’. Nature 174:508–509
Holler TP, Ruan F, Spaltenstein A, Hopkins PB (1989) Total synthesis of marine mercaptohistidines: ovothiols A, B, and C. J Org Chem 54:4570–4575
Hand CE, Honek JF (2005) Biological chemistry of naturally occurring thiols of microbial and marine origin. J Nat Prod 68:293–308
Zoete V, Vezin H, Bailly F, Vergoten G, Catteau J-P, Bernier J-L (2000) 4-mercaptoimidazoles derived from the naturally occurring antioxidant ovothiols 2. Computational and experimental approach of the radical scavenging mechanism. Free Rad Res 32:525–533
Crépin A, Wattier N, Petit S, Bischoff L, Fruit C, Marsais F (2009) Aminoacid-derived mercaptoimidazoles. Org Biomol Chem 7:128–134
Nagasaka A, Hidaka H (1976) Effect of antithyroid agents 6-propyl-2-thiouracil and l-methyl-2-mercaptoimidazole on human thyroid iodide peroxidase. J Clin Endocrinol Metab 43:152–158
Heath H, Toennies G (1958) The preparation and properties of ergothioneine disulphide. Biochem J 68:204–210
Phan H, Lekin K, Winter SM, Oakley RT, Shatruk M (2013) Photoinduced solid state conversion of a radical σ-dimer to a π-radical pair. J Am Chem Soc 135:15674–15677
Matsuzaki H, Fujita W, Awaga K, Okamoto H (2003) Photoinduced phase transition in an organic radical crystal with room-temperature optical and magnetic bistability. Phys Rev Lett 91:017403
Brás EM, Fausto R (2018) An insight into methimazole phototautomerism: Central role of the thiyl radical and effect of benzo substitution. J Mol Struct. https://doi.org/10.1016/j.molstruc.2018.02.013 (in press)
Brás EM, Fausto R (2018) Controlled light-driven switching in 2-thiobenzimidazole. J Photoch Photobio A 357:185–192
Arunan E, Desiraju GR, Klein RA, Sadlej J, Scheiner S, Alkorta I, Clary DC, Crabtree RH, Dannenberg JJ, Hobza P, Kjaergaard HG, Legon AC, Mennucci B, Nesbitt DJ (2011) Definition of the hydrogen bond. Pure Appl Chem 83:1637–1641
Lodochnikova OA, Bodrov AV, Saifina AF, Nikitina LE, Litvinov IA (2013) A new polymorph of methimazole: Single crystal and powder X-ray diffraction study. J Struct Chem 54:140–147
Khan H, Badshah A, Shaheen F, Giek C, Qureshi RA (2008) 1-methyl-1H-benzimidazole-2(3H)-thione. Acta Cryst E 64:o1141
Form GR, Raper ES, Downie TC (1976) The crystal and molecular structure of 2-mereaptobenzimidazole. Acta Cryst B 32:345–348
Block SS (2003) Disinfection, sterilization and preservation, 4th edn. Lea & Febiger Inc., Philadelphia, USA
Kumar CSA, Kavitha CV, Vinaya K, Prasad SBB, Thimmegowda NR, Chandrappa S, Raghavan SC, Rangappa KS (2009) Synthesis and in vitro cytotoxic evaluation of novel diazaspiro bicyclo hydantoin derivatives in human leukemia cells: a SAR study. Invest New Drugs 27:327–337
Kavitha CV, Nambiar M, Kumar CSA, Choudhary B, Muniyappa K, Rangappa KS, Raghavan SC (2009) Novel derivatives of spirohydantoin induce growth inhibition followed by apoptosis in leukemia cells. Biochem Pharmacol 77:348–363
Sarges R, Schnur RC, Belletire JL, Peterson MJ (1988) Spiro hydantoin aldose reductase inhibitors. J Med Chem 31:230–243
Yang K, Tang Y, Iczkowski KA (2010) Phenyl-methylene hydantoins alter CD44-specific ligand binding of benign and malignant prostate cells and suppress CD44 isoform expression. Am J Transl Res 2:88–94
Park HS, Choi HJ, Shin HS, Lee SK, Park MS (2007) Synthesis and characterization of novel hydantoins as potential COX-2 inhibitors: 1,5-Diarylhydantoins. Bull Korean Chem Soc 28:751–757
Comber RN, Reynolds RC, Friedrich JD, Manguikian RA, Buckheit RW, Truss JW, Shannon WM, Secrist JA (1992) 5,5-disubstituted hydantoins: syntheses and anti-HIV activity. J Med Chem 35:3567–3572
Cruz-Cabeza AJ, Schwalbe CH (2012) Observed and predicted hydrogen bond motifs in crystal structures of hydantoins, dihydrouracils and uracils. New J Chem 36:1347–1354
Faris WM, Safi ZS (2014) Theoretical investigation of tautomerism stability of hydantoin in the gas phase and in the solution. Orient J Chem 30:1045–1054
Ildiz GO, Nunes CM, Fausto R (2013) Matrix isolation infrared spectra and photochemistry of hydantoin. J Phys Chem A 117:726–734
Ildiz GO, Boz I, Unsalan O (2012) FTIR spectroscopic and quantum chemical studies on hydantoin. Opt Spectrosc 112:665–670
Nogueira BA, Ildiz GO, Canotilho J, Eusébio MES, Fausto R (2014) Molecular structure, infrared spectra, photochemistry, and thermal properties of 1-methylhydantoin. J Phys Chem A 118:5994–6008
Nogueira BA, Ildiz GO, Henriques MSC, Paixão JA, Fausto R (2017) Structural and spectroscopic characterization of the second polymorph of 1-methylhydantoin. J Mol Struct 1148:111–118
Nogueira BA, Ildiz GO, Canotilho J, Eusébio MES, Henriques MSC, Paixão JA, Fausto R (2017) 5-methylhydantoin: from isolated molecules in a low-temperature argon matrix to solid state polymorphs characterization. J Phys Chem A 121:5267–5279
Rosado MTS, Lopes Jesus AJ, Reva ID, Fausto R, Redinha JS (2009) Conformational cooling dynamics in matrix-isolated 1,3-butanediol. J Phys Chem A 113:7499–7507
Reva ID, Lopes Jesus AJ, Rosado MTS, Fausto R, Eusébio ME, Redinha JS (2006) Stepwise conformational cooling towards a single isomeric state in the four internal rotors system 1,2-butanediol. Phys Chem Chem Phys 8:5339–5349
Reva I, Nowak MJ, Lapinski L, Fausto R (2015) Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers. Phys Chem Chem Phys 17:4888–4898
Rostkowska H, Lapinski L, Khvorostov A, Nowak MJ (2003) Photochemical double-proton-transfer reactions in 2,6-dithiopurine. A matrix isolation study. J Phys Chem A 107:804–809
Chmura B, Rode MF, Sobolewski AJ, Lapinski L, Nowak MJ (2008) A computational study on the mechanism of intramolecular oxo–hydroxy phototautomerism driven by repulsive πσ* state. J Phys Chem A 112:13655–13661
Bazargani MF, Talavat L, Naderi S, Khavasi HR (2011) 2-[(1H-Imidazol-2-yl)disulfanyl]-1H-imidazole. Acta Cryst E 67:o2585
Steed KM, Steed JW (2015) Packing problems: high Z′ -crystal structures and their relationship to cocrystals, inclusion compounds, and polymorphism. Chem Rev 115:2895–2933
Rozenberg MS (1996) IR spectra and hydrogen bond energies of crystalline acid salts of carboxylic acids. Spectrochim Acta A 52:1559–1563
Rozenberg MS, Shoham G, Reva I, Fausto R (2004) Low temperature FTIR spectroscopy and hydrogen bonding in cytosine polycrystals. Spectrochim Acta A 60:463–470
Acknowledgements
This investigation has been performed within the Project PTDC/QEQ-QFI/3284/2014–POCI-01-0145-FEDER-016617, funded by the Portuguese “Fundação para a Ciência e a Tecnologia” (FCT) and FEDER/COMPETE 2020-EU. The Coimbra Chemistry Centre (CQC) is supported by FCT, through the project UI0313/QUI/2013, also cofunded by FEDER/COMPETE 2020-EU. E.M.B. and B.A.N. thank FCT for the grant CCMAR/BI/0013/2017, within Project PTDC/MAR-BIO/4132/2014, and the Ph.D. grant SFRH/BD/129852/2017, respectively. R.F. and G.O.I. acknowledge the financial support through the project MATIS–Materiais e Tecnologias Industriais Sustentáveis (FCT and CENTRO-01-0145-FEDER-000014).
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Fausto, R., Ildiz, G.O., Brás, E.M., Nogueira, B.A. (2019). Hydantoins and Mercaptoimidazoles: Vibrational Spectroscopy as a Probe of Structure and Reactivity in Different Environments, from the Isolated Molecule to Polymorphs. In: Koleżyński, A., Król, M. (eds) Molecular Spectroscopy—Experiment and Theory. Challenges and Advances in Computational Chemistry and Physics, vol 26. Springer, Cham. https://doi.org/10.1007/978-3-030-01355-4_7
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