Dynamic Structure of Organic Compounds in Solution According to NMR Data and Quantum Mechanical Calculations. V. Substituted Benzalanilines

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Abstract

We investigated the dynamic structure of benzalaniline derivatives, in which an important factor is the inhibited internal rotation of benzene rings. The parameters of conformational processes of this type are characterized based on NMR spectroscopy data and quantum mechanical calculations. In these compounds, nitrogen atoms play a key role. It has been shown that important information is provided by NMR parameters with the direct participation of nitrogen, which become available in experiments with 15N-enriched compounds. Important new information about the conformation of molecules of this class can be provided by the spin-spin interaction constants involving 15N nuclei. A series of [15N]enriched benzalaniline derivatives with substituents in the ortho position of the benzene ring distant from the nitrogen was studied. It has been shown that substituents can act as both a stabilizing (R = F, OH, OCH3) and a destabilizing factor (R = CH3). The influence of medium acidity on these conformational equilibria was studied. This type of structural motif can be used to design pH-induced molecular switches. According to our estimates, the molecular switching energy of [15N]-2-fluorobenzalaniline is ~7 kcal/mol, which is one of the highest values for molecular switches of this type.

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About the authors

V. V. Stanishevsky

Lomonosov Moscow State University

Email: vchertkov@hotmail.com
ORCID iD: 0009-0004-5955-8233
Russian Federation, 1, Leninskie Gory, Moscow, 119991

A. K. Shestakova

State Scientific Research Institute of Chemistry and Technology of Organoelement Compounds

Author for correspondence.
Email: vchertkov@hotmail.com
ORCID iD: 0000-0002-2252-6914
Russian Federation, 38, Enthusiastov Hwy, Moscow, 105118

V. A. Chertkov

Lomonosov Moscow State University

Email: vchertkov@hotmail.com
ORCID iD: 0000-0001-8699-5894
Russian Federation, 1, Leninskie Gory, Moscow, 119991

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Supplementary files

Supplementary Files
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2. Scheme 1. Numbering of atoms in benzylidenaniline derivatives 1-5 and 1a-5a

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3. Scheme 2. Synthesis of substituted [15N]benzylidenanilines 1-5

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4. Fig. 1. Fragments of 13C NMR spectra of compound 3 (top, signals C-7, C-6 and C-1, left to right) and its nitrogen-unenriched analogue (bottom, signals C-7, C-6 and C-1, left to right)

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5. Fig. 2. PPE cross section of benzylidenaniline 1 and its protonated form 1a as a function of dihedral angle φ

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6. Fig. 3. PPE cross section of benzylidenaniline 2 and its protonated form 2a as a function of dihedral angle φ

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7. Fig. 4. PPE cross section of benzylidenaniline 3 and its protonated form 3a as a function of dihedral angle φ

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8. Fig. 5. Conformational transition during protonation of compound 3

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9. Fig. 6. Fragment of the 1H NMR spectrum of the protonated form of compound 3, the proton signal of the quaternised nitrogen atom is shown (CD3CN, 303 K, ‘Bruker AV-600’)

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10. Fig. 7. Conformational transition during protonation of compound 4

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11. Fig. 8. PPE cross section of substituted benzylideneaniline 5 and its protonated form 5a as a function of dihedral angle φ

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12. Fig. 9. Conformational transition during protonation of compound 5

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13. Fig. 10. Comparison of the experimental and calculated nJCN CCCVs

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