Physicochemical studies of organic compounds: long range inractions and conformational analysis of organofluorine compounds.

• Grant number: 11/01170-1
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: August 01, 2011
• End date: June 30, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Roberto Rittner Neto
• Grantee: Rodrigo Antonio Cormanich
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil

Abstract

The present PhD thesis reports physicochemical studies of several organic compounds. In particular, it was studied the conformational preferences and the intramolecular interactions of dipeptide models, as the Ac-Gly-NHMe and its fluorinated and N-methyl derivatives CF3-C(O)-Gly-NHMe and Ac-Gly-N(Me)2. Furthermore, the present work studies the physicochemistry of intra- and intermoecular long range interactions in several fluorinated organic compounds, as non-usual C-H‡‡‡p hydrogen bonds with the solvent and CF‡‡‡FC interactions. It was also studied the conformational isomerism of 2-fluoroethanol, 3-fluoropropanol and 4-fluorobutanol and evaluated the importance of CF‡‡‡HO hydrogen bonding formation for its conformational isomerism. Experimental data from 1H and 19F NMR and infrared spectroscopies in several solventes and X-ray diffraction of crystalline structures were used. Some fluorinated compounds are not commercial, which were synthesised and characterised. Moreover, in order to compare and elucidate the experimental results, theoretical chemistry methods were used in several levels, by using DFT functionals with and without dispersion corrections and ab initio methods. In particular, NBO analysis was used to evaluate the contribution of stereoelectronic effects. Long-range interactions were studied by theoretical chemistry topological methods, as the QTAIM, NCI, ELF and DORI. Theoretical calculations of spin-spin coupling constants and frequencies for the isolated structure of these compounds and in solvent, by considering the IEF-PCM implicit solvent model, were also carried out. The results obtained by the experimental and theoretical methods were compared, which provided descriptions of the results that any of them alone could accomplish.

Scientific publications

(13)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

CORMANICH, RODRIGO A.; RITTNER, ROBERTO; O'HAGAN, DAVID; BUEHL, MICHAEL. Inter- and Intramolecular CF center dot center dot center dot C=O Interactions on Aliphatic and Cyclohexane Carbonyl Derivatives. Journal of Computational Chemistry, v. 37, n. 1, SI, p. 25-33, JAN 5 2016. (11/01170-1, 14/25903-6)

CORMANICH, RODRIGO A.; BUEHL, MICHAEL; RITTNER, ROBERTO. Understanding the conformational behaviour of Ac-Ala-NHMe in different media. A joint NMR and DFT study. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 13, n. 35, p. 9206-9213, 2015. (11/01170-1, 14/25903-6)

SILLA, JOSUE M.; CORMANICH, RODRIGO A.; RITTNER, ROBERTO; FREITAS, MATHEUS P.. Does intramolecular hydrogen bond play a key role in the stereochemistry of alpha- and beta-D-glucose?. Carbohydrate Research, v. 396, p. 9-13, SEP 19 2014. (11/01170-1, 12/03933-5)

SILLA, JOSUE M.; FREITAS, MATHEUS P.; CORMANICH, RODRIGO A.; RITTNER, ROBERTO. The Reverse Fluorine Perlin-like Effect and Related Stereoelectronic Interactions. Journal of Organic Chemistry, v. 79, n. 13, p. 6385-6388, JUL 4 2014. (11/01170-1, 12/03933-5)

CORMANICH, R. A.; RITTNER, R.; FREITAS, M. P.; BUEHL, M.. The seeming lack of CF center dot center dot center dot HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solution. Physical Chemistry Chemical Physics, v. 16, n. 36, p. 19212-19217, 2014. (11/01170-1, 12/03933-5)

CORMANICH, R. A.; RITTNER, R.; BUEHL, M.. Conformational preferences of Ac-Gly-NHMe in solution. RSC ADVANCES, v. 5, n. 17, p. 13052-13060, 2015. (11/01170-1, 12/03933-5)

CORMANICH, RODRIGO A.; RITTNER, ROBERTO; O'HAGAN, DAVID; BUEHL, MICHAEL. Inter- and Intramolecular CF center dot center dot center dot C=O Interactions on Aliphatic and Cyclohexane Carbonyl Derivatives. Journal of Computational Chemistry, v. 37, n. 1, p. 9-pg., 2016-01-05. (14/25903-6, 11/01170-1)

CORMANICH, RODRIGO A.; KEDDIE, NEIL S.; RITTNER, ROBERTO; O'HAGAN, DAVID; BUEHL, MICHAEL. Particularly strong C-H center dot center dot center dot pi interactions between benzene and all-cis 1,2,3,4,5,6-hexafluorocyclohexane. Physical Chemistry Chemical Physics, v. 17, n. 44, p. 29475-29478, 2015. (11/01170-1, 14/25903-6)

CORMANICH, RODRIGO A.; RITTNER, ROBERTO; O'HAGAN, DAVID; BUEHL, MICHAEL. Analysis of CF center dot center dot center dot FC Interactions on Cyclohexane and Naphthalene Frameworks. Journal of Physical Chemistry A, v. 118, n. 36, p. 7901-7910, SEP 11 2014. (11/01170-1)

SILLA, JOSUE M.; DUARTE, CLAUDIMAR J.; CORMANICH, RODRIGO A.; RITTNER, ROBERTO; FREITAS, MATHEUS P.. Conformational analysis of 2,2-difluoroethylamine hydrochloride: double gauche effect. Beilstein Journal of Organic Chemistry, v. 10, p. 877-882, APR 16 2014. (11/01170-1, 12/03933-5, 11/11098-6)

CORMANICH, RODRIGO A.; DURIE, ALASTAIR; BJORNSSON, RAGNAR; RITTNER, ROBERTO; O'HAGAN, DAVID; BUEHL, MICHAEL. Density Functional Study of Interactions between Fluorinated Cyclohexanes and Arenes. Helvetica Chimica Acta, v. 97, n. 6, p. 797-807, JUN 2014. (11/01170-1, 12/03933-5)

CORMANICH, RODRIGO A.; DUCATI, LUCAS C.; TORMENA, CLAUDIO F.; RITTNER, ROBERTO. Phenylalanine and tyrosine methyl ester intramolecular interactions and conformational analysis by H-1 NMR and infrared spectroscopies and theoretical calculations. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 123, p. 482-489, APR 5 2014. (11/01170-1, 12/03933-5)

DUARTE, CLAUDIMAR J.; CORMANICH, RODRIGO A.; DUCATI, LUCAS C.; RITTNER, ROBERTO. H-1 NMR and theoretical studies on the conformational equilibrium of tryptophan methyl ester. Journal of Molecular Structure, v. 1050, p. 174-179, OCT 24 2013. (11/01170-1, 12/03933-5, 11/11098-6)

Academic Publications

(References retrieved automatically from State of São Paulo Research Institutions)

CORMANICH, Rodrigo Antonio. Physicochemical studies of organic molecules: long range interactions and conformational analysis of organofluorine compounds. 2015. Doctoral Thesis - Universidade Estadual de Campinas (UNICAMP). Instituto de Química Campinas, SP.