Synthesis, crystal and molecular-electronic structure, and kinetic investigation of two new sterically hindered isomeric forms of the dimethyl[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride
| Autor: | L. Rublova, Bartosz Zarychta, Borys Mykhalichko, Volodymyr Olijnyk |
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| Rok vydání: | 2017 |
| Předmět: |
Steric effects
Substitution reaction 010405 organic chemistry Stereochemistry Hydrogen bond Organic Chemistry Triclinic crystal system 010402 general chemistry 01 natural sciences Kinetics of substitution reactions in aqueous solution 0104 chemical sciences Analytical Chemistry Inorganic Chemistry Crystallography chemistry.chemical_compound Quantum-chemical analysis chemistry X-ray crystal structure determination Intramolecular force Benzenesulfonyl chloride Structural isomer Molecule Ortho-effect Sterically hindered derivatives of aromatic sulfonic acids Spectroscopy |
| Zdroj: | Journal of Molecular Structure. 1137:1-8 |
| ISSN: | 0022-2860 |
| Popis: | Two new structural isomers – 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2) were synthesized by interaction of N-(2,4-dimethylphenyl)-N-methyl-benzenesulfonamide or N-(2,6-dimethylphenyl)-N-methylbenzenesulfonamide with chlorosulfonic acid. Both compounds have been structurally characterized by X-ray single crystal diffraction at 100 K. The crystals of 1 are triclinic: space group View the MathML source, a = 8.1542(2), b = 11.0728(3), c = 11.2680(3) Å, α = 116.557(3), β = 95.155(2), γ = 108.258(2)°, V = 831.97(4) Å3, Z = 2, R = 0.0251 for 2429 reflections; the crystals of 2 are monoclinic: space group P21/c, a = 11.7428(2), b = 11.3518(2), c = 12.5886(2) Å, β = 93.659(2)°, V = 1674.66(5) Å3, Z = 4, R = 0.0269 for 2622 reflections. The structure of both isomers is organized as molecular crystals. These sterically hindered organic molecules are cross-linked into framework by means of hydrogen bonds of Csingle bondH⋯O type (H⋯O distances are in range 2.27(2)–2.76(2) Å). The ab initio quantum-chemical calculations of an electronic structure of the isomeric molecules of 1 and 2 have been performed using the restricted Hartree-Fock method with a 6-31G* basis set. The calculated values of charge density concentrated on the electronegative atoms of the sterically hindered molecules are in good agreement with parameters of the intramolecular hydrogen bonds. The obtained data of the kinetic investigations of the substitution reactions in aqueous solution well correlate with stereo-chemical characteristics of the both molecules of the dimethyl[methyl(phenylsulfonyl)amino]-benzenesulfonyl chloride. |
| Databáze: | OpenAIRE |
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