Determination of the structures of benzotriazole(H2O)1,2 clusters by IR–UV spectroscopy and ab initio theory

Schmitt, Michaël; Plützer, Ch.; Kleinermanns, Karl

doi:10.1039/b104889a

Cited by 8 publications

(7 citation statements)

References 21 publications

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“…1,2,4-Triazole exists only as the 1 H -tautomer; however, Elguero and co-workers found examples of 3(5)-substituted 1,2,4-triazoles, to wit, the halogeno derivatives, which prefer the 4 H -tautomer . In other cases of C-substituted triazoles, tautomeric equilibria are also very complex. 5d, Benzotriazole, for example, exists in the gas phase at 0 K as the 2 H -tautomer, but with increasing temperature its population decreases in favor of the 1 H -tautomer, which is the form exclusively observed in the solid state and in solution. 24d, …”

Section: 2 Heteroaromatics With An Endo Hn(ch) N N Moietymentioning

confidence: 99%

Tautomeric Equilibria in Relation to Pi-Electron Delocalization

Raczyńska¹,

Kosinska²,

and³

et al. 2005

Chem. Rev.

314

267

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Section: 2 Heteroaromatics With An Endo Hn(ch) N N Moietymentioning

confidence: 99%

Tautomeric Equilibria in Relation to Pi-Electron Delocalization

Raczyńska¹,

Kosinska²,

and³

et al. 2005

Chem. Rev.

314

267

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“…It is also evident in several experiments that in the gas phase both tautomers may coexist 11–14. However, in solution it is clear that the 1H tautomer is indeed more stable, in particular in the case of polar solvents 13, 15, 17–20. This is likely to be an immediate consequence of the fact that the dipole moment of the 1H form is considerably larger 13 (by a factor close to 10) than the 2H.…”

Section: Introductionmentioning

confidence: 96%

“…1). The relative stability of the 1H and 2H tautomers have been studied both theoretically and experimentally by several groups 11–20. There are recent experimental 17 indications that in the gas phase the 1H is more stable than the 2H by only ca.…”

Section: Introductionmentioning

confidence: 99%

Electronic polarization of 1H‐benzotriazole in water: Ground and first excited‐state dipole moments

Ludwig

Coutinho

Borin

et al. 2003

Int J of Quantum Chemistry

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Sequential Monte Carlo and quantum mechanical calculations of the electronic polarization of the ground and first vertical excited states of 1H-benzotriazole in water are made. Using statistically uncorrelated configurations and CASSCF ab initio calculations the increase in the ground and excited state dipole moments of 1H-benzotriazole from gas phase to aqueous environment are obtained as 2.89 Ϯ 0.10 and 2.75 Ϯ 0.11 D, leading to total moments of 6.89 Ϯ 0.10 and 6.40 Ϯ 0.11 D, respectively. Structures are sampled using the statistical correlation interval obtained from the autocorrelation function of the energy and statistical convergence of the calculated dipole moments is shown. These water-polarized dipole moments of 1H-benzotriazole are used to obtain the solvatochromic shift of the first absorption transition. The resulting theoretical blue shift of 570 cm Ϫ1 for the strong and characteristic 3 * transition is in good agreement with the inferred experimental value of ϳ700 cm Ϫ1 . The use of the gas-phase values of the dipole moments are useful for the qualitative understanding of the shift but the polarization of the solvent is required to achieve quantitative agreement.

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“…Although both base structures demonstrated decreased rates of uptake with the addition of the 1-amino group, the effect was especially pronounced on the benzotriazole base structure, with nearly complete removal at 48 h for BT compared to no significant removal for 1A-BT. This difference is likely due to the availability of a reactive bonding site on the 2 position carbon in 1A-BZ, allowing for some transporter interaction even if the 1 position reactive heterocyclic ring nitrogen is occupied by an amino group. , In contrast, in 1A-BT no such bonding site is available in the triazole ring (even accounting for 1H/2H resonance) when an amino group is present.…”

Section: Resultsmentioning

confidence: 99%

Functional Group Properties and Position Drive Differences in Xenobiotic Plant Uptake Rates, but Metabolism Shares a Similar Pathway

Muerdter,

Powers,

Webb

et al. 2023

Environ. Sci. Technol. Lett.

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Plant uptake of xenobiotic compounds is crucial for phytoremediation (including green stormwater infrastructure) and exposure potential during crop irrigation with recycled water. Experimentally determining the plant uptake for every relevant chemical is impractical; therefore, illuminating the role of specific functional groups on the uptake of trace organic contaminants is needed to enhance predictive power. We used benzimidazole derivatives to probe the impact of functional group electrostatic properties and position on plant uptake and metabolism using the hydroponic model plant Arabidopsis thaliana. The greatest plant uptake rates occurred with an electron-withdrawing functional group at the 2 position; however, uptake was still observed with an electron-donating group. An electron-donating group at the 1 position significantly slowed uptake for both benzimidazole- and benzotriazole-based molecules used in this study, indicating possible steric effects. For unsubstituted benzimidazole and benzotriazole structures, the additional heterocyclic nitrogen in benzotriazole increased plant uptake rates compared to benzimidazole. Analysis of quantitative structure–activity relationship parameters for the studied compounds implicates energy-related molecular descriptors as uptake drivers. Despite significantly varied uptake rates, compounds with different functional groups yielded shared metabolites, including an impact on endogenous glutathione production. Although the topic is complex and influenced by multiple factors in the field, this study provides insights into the impact of functional groups on plant uptake, with implications for environmental fate and consumer exposure.

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Determination of the structures of benzotriazole(H2O)1,2 clusters by IR–UV spectroscopy and ab initio theory

Cited by 8 publications

References 21 publications

Tautomeric Equilibria in Relation to Pi-Electron Delocalization

Tautomeric Equilibria in Relation to Pi-Electron Delocalization

Electronic polarization of 1H‐benzotriazole in water: Ground and first excited‐state dipole moments

Functional Group Properties and Position Drive Differences in Xenobiotic Plant Uptake Rates, but Metabolism Shares a Similar Pathway

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