Synthesis and characterization of o-fluorosulfinylaniline. A comparative vibrational study of fluorinated sulfinylaniline series

Jerez, Ana Laura Paez; Armiño, Diego J. Alonso de; Robles, Norma Lis

doi:10.1039/c5nj02252e

Cited by 8 publications

(3 citation statements)

References 28 publications

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“…As it was reported previously [2 , 34-37] N = S and S = O stretching modes are strongly coupled therefore, these vibrations may be better described as antisymmetric and symmetric stretching modes of the sulfinyl group. The series of compounds studied by our research group showed that for halogen monosubstituted sulfinylaniline derivatives (X = F [12][13][14] and Cl [15 , 16] ), the characteristic stretching modes of the NSO group change in a larger or smaller degree according to the position of the substituent in the aromatic ring. Not only frequency values modify according to the position of the substituent, but they also change in response to the electronic density in the aromatic ring itself.…”

Section: Vibrational Analysismentioning

confidence: 99%

“…Fluoro-substituted compounds were reported as relevant starting materials with great potential in the pharmaceutical industry [9][10][11] . Our recent studies regarding the conformational and vibrational properties of a series of fluorine [12][13][14] and chlorine [15 , 16] monosubstituted Nsulfinylanilines proved that the properties vary according to the position of the substituent in the aromatic ring and the prevalence of different electronic effects. These halogen atoms interact through mesomeric ( + M) and inductive (-I) effects with different extents.…”

Section: Introductionmentioning

confidence: 99%

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Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

Chemes

Lezama

Cutin

et al. 2021

Journal of Molecular Structure

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The presence of a perfluorinated functional group as a substituent of the aromatic ring in m -and otrifluoromethylsulfinylaniline may provide conformational and vibrational properties of interest for the synthesis of compounds of pharmacological relevance, as it was observed for other N-sulfinylaniline derivatives previously reported. The air sensitive and highly reactive compounds under study were prepared by the reaction of the corresponding aniline derivatives and thionyl chloride. The liquid samples were characterized by FT IR, Raman and NMR ( 1 H and 13 C) spectroscopies and GC/MS spectrometry. The experimental spectra indicate the presence of a single conformer of syn geometry ( syn of the C-N bond with respect to the S = O bond), in good agreement with results obtained by quantum chemical calculations derived from the Functional Density Theory. The stable conformation found as the global minimum of the potential energy surface was rationalized by considering intramolecular orbital interactions evinced by a Natural Bond Orbital (NBO) analysis and the quantum theory of Atoms In Molecules (AIM). Through this last approach, an intramolecular C-H O interaction meeting the characteristics of an anti -hydrogen bond was found.

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Section: Vibrational Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

Chemes

Lezama

Cutin

et al. 2021

Journal of Molecular Structure

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“…Our code, QUMVIA, uses analytic expressions for the VSCF integrals in a distributed Gaussian (DG) basis set…”

Section: Theorymentioning

confidence: 99%

A quartic force field coordinate substitution scheme using hyperbolic sine coordinates

Armiño

Bustamante

2017

Int J of Quantum Chemistry

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Quartic force fields (QFF) are currently the most cost-effective method for the approximation of potential energy surfaces for the calculation of anharmonic vibrational energies. It is known, although, that its performance can be less than satisfactory due to limitations related to slow convergence of the series. In this article, we present a coordinate substitution scheme using a combination of Morse and sinh coordinates, well adapted for its use with cartesian normal coordinates. We derive expressions for analytical integrals for use in VSCF and VCI calculations and show that the simultaneous substitution of symmetric and antisymmetric normal coordinates by Morse and sinh coordinates, respectively, significantly improves the vibrational transition frequencies for these modes in a well-balanced fashion. The accuracy of this substitution scheme is demonstrated by comparing one and two-dimensional sections of substituted and unsubstituted QFF with ab initio potential energy grids, as well as with vibrational energy calculations using as test cases two well-studied benchmark molecules: water and formaldehyde. We conclude that the coordinate substitution scheme presented constitutes a very attractive alternative to simple QFFs in the context of cartesian normal coordinates.quantum chemistry, quartic force fields, vibrational structure | I N T R O D U C T I O NThe calculation of accurate potential energy surfaces (PES) is certainly a crucial part of the computation of anharmonic vibrational energies and wavefunctions of molecular systems. Grid representations [1] of the PES are usually the most accurate option, although its high computational cost limits its application to very small systems, as the number of energy evaluations necessary for a complete grid rises exponentially with the number of normal modes. This limitation can be reduced somewhat by the use of N-mode coupling representations, [2][3][4] or more recently, adaptive sparse grid expansions. [5] Grids may be used directly, or converted into an analytical expression either by fitting [6] or interpolation [7] procedures. For example, very high accuracy have been obtained using reproducing kernel Hilbert space interpolation coupled to a grid representation for triatomic reactive systems. [8] Grid methods, even the most efficient examples of them, are still limited to small systems, so alternatives are needed for bigger molecules.Quartic force fields (QFF), this is, fourth order Taylor expansions of the potential with respect to the normal coordinates of the system, currently represent the best trade-off of accuracy and computational cost for the representation of molecular potential energy surfaces (PES) for anharmonic vibrational structure applications. The efficiency of the QFF scheme comes from the possibility of calculating the expansion coefficients by numerical differentiation of the potential, analytical gradients, or Hessians, if available. Moreover, recently Ramakrishnan and Rauhut presented an efficient scheme for computing QFFs from multimode exp...

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On the search of the influence of substituents in the structural and vibrational properties of p-substituted sulfinylanilines: Study of p-trifluoromethylsulfinylaniline

Chemes

Cutin

Alvarez

et al. 2018

Journal of Fluorine Chemistry

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Synthesis and characterization of o-fluorosulfinylaniline. A comparative vibrational study of fluorinated sulfinylaniline series

Cited by 8 publications

References 28 publications

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

A quartic force field coordinate substitution scheme using hyperbolic sine coordinates

On the search of the influence of substituents in the structural and vibrational properties of p-substituted sulfinylanilines: Study of p-trifluoromethylsulfinylaniline

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