The hydrogen bond acidity and other descriptors for oximes

Abraham, Michael H.; Gil-Lostes, Javier; Cometto‐Muñiz, J. Enrique; Cain, William S.; Poole, Colin F.; Atapattu, Sanka N.; Abraham, Raymond J.; Leonard, Paul

doi:10.1039/b811688a

Cited by 21 publications

(15 citation statements)

References 25 publications

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“…We have also examined the effect of volatile solutes on nasal pungency thresholds (NPT), eye irritation thresholds (EIT) and odor detection thresholds (ODT) in humans, and have obtained equations based on eqn 3 for log(1/NPT), 121 log(1/EIT) 122 and log (1/ODT). 121 Coefficients for the most up-to-date data 123 are given in Table 6.…”

Section: Discussionmentioning

confidence: 99%

“…The closeness of methanol as a model solvent for inhalation anesthesia has already been noticed. 124 However, NMF is a much more reasonable model for processes in which the main step is transfer from the gas phase to a receptor site/area that probably consists of proteins, as is likely the case for nasal pungency 121 and eye irritation 122. In fact, various studies have shown that many chemicals produce chemical sensory irritation (i.e., chemesthesis) via activation of proteins from various subfamilies of transient receptor potential (TRP) ion channels 125–129…”

Section: Discussionmentioning

confidence: 99%

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Partition of compounds from water and from air into amides

2009

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Literature data on partitioning of compounds from the gas phase to a number of amides and from water to the amides has been collected and analyzed through the Abraham solvation equations. The resulting equations are statistically good enough to be used for the prediction of further partition coefficients, and allow deductions to be made about the chemical properties of the amides, as solvents. For example, tertiary amides have no hydrogen bond property at all, secondary amides are rather weak hydrogen bond acids, and primary amides are stronger hydrogen bond acids than are alcohols as solvents. Equations for partitioning from the gas phase to amide solvents can also be used to test if the amides are possible models for a number of biological phases and biological processes. It is shown that no organic solvent is a suitable model for phases such as blood, brain, muscle, liver, heart or kidney, but that a number of rather non-polar solvents are models for fat. N-methylformamide is shown to be the best (and excellent) model for eye irritation and nasal pungency in humans, suggesting that the receptor site in these processes is protein-like.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Partition of compounds from water and from air into amides

2009

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“…Most appear to be adequate for modeling the available data, but this may well be a result of the experimental noise in most datasets. There are many approaches to calculating descriptors; some calculate as many different descriptors as possible [50,51], whereas the more traditional approach is to use descriptors whose meaning and relationship to the target property are clear [52]. Given the danger of adding chance correlations with additional descriptors [53], keeping the number of candidate descriptors as low as possible seems reasonable.…”

Section: Sar Modelingmentioning

confidence: 99%

Predictive Modeling of Molecular Properties: Can We Go beyond Interpretation?

Clark

2011

Modeling of Molecular Properties

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Truly predictive modeling is a rarity in chemistry and biology. This is true for both explicit calculational techniques (quantum chemistry, force fields) and for implicit methods such as quantitative structure-property relationship (QSPR) models and other interpolation techniques. It is true that, for sufficiently small molecules for which a single-determinant Hartree-Fock wavefunction provides a good description, CCSD(T) [1, 2] calculations using an adequate basis set produce gas-phase results that usually rival or better experimental accuracy. This is very positive but of limited use in the impure, finite-temperature condensed-phase world in which many important processes take place. The automobile industry is used to a situation in which the results of crash simulations agree very closely with experimental crash testsso much so that the latter no longer form part of the design process. The fields of chemistry and biology, however, are a very long way from this idyllic situation. This is perhaps surprising, because the physics behind the processes and the systems considered is believed to be well known, such that their accurate modeling should be possible. This aim of this chapter is to analyze the current situation, to identify weaknesses and opportunities in chemical and life-science modeling, and maybe even to suggest some improvements in what can be done. The first stage, however, is to consider the nature of both models and modeling. Models and ModelingModels are exactly that. Unlike CCSDT, they are not an accurate and defined truncation of a physically exact theory, but are rather a simplified representation of a complex object that is intended to behave like the object itself. Behave is a key concept here. It is well known to the multiscale community [3] that a coarse-grain version of a more complex force field can only reproduce a limited set of the Modeling of Molecular Properties, First Edition. Edited by Peter Comba.

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“…A direct consequence of this proposal is that the effects produced by protonation and by HB should be related. Since the protonation effect (Δδ in ppm) for trimethylphosphine (TMPO) (Me 3 P) is much larger than for trimethylamine (Me 3 N), 60.5 vs 13.8 ppm, we wondered whether 31 P chemical shifts of phosphine can be used as probes for the HBA of XH (a Brønsted acid) . Note that the overall range of chemical shifts for both nuclei is similar, about 1500 ppm…”

Section: Introductionmentioning

confidence: 99%

Is it possible to use the ³¹P chemical shifts of phosphines to measure hydrogen bond acidities (HBA)? A comparative study with the use of the ¹⁵N chemical shifts of amines for measuring HBA

Alkorta

Elguero

2017

J of Physical Organic Chem

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The geometries, energies, and nuclear magnetic resonance (NMR) chemical shifts of 3 bases (trimethylphosphine, trimethylamine, and trimethylphosphine oxide), their 3 protonated cations, and 15 hydrogen-bonded complexes (corresponding to the HF, HNC, HCN, HCCH, H 2 O, and CH 3 OH Brønsted acids) have been calculated at the B3LYP/6-311++G(d,p) level. The determination of hydrogen bond acidities by NMR is classically performed using the 31 P chemical shifts Me 3 PO. This method is more reliable than the use of the 15 N NMR chemical shifts of Me 3 N. This work shows that the 31 P NMR chemical shifts of Me 3 P cannot be used. The raison of the difference between Me 3 P on one hand and Me 3 PO and Me 3 N on the other will be discussed.

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The hydrogen bond acidity and other descriptors for oximes

Abstract: The solvation descriptors for cyclohexanone oxime and acetone oxime have been obtained from measurements on water-solvent partitions, and gas-liquid

Cited by 21 publications

References 25 publications

Partition of compounds from water and from air into amides

Partition of compounds from water and from air into amides

Predictive Modeling of Molecular Properties: Can We Go beyond Interpretation?

Is it possible to use the ³¹P chemical shifts of phosphines to measure hydrogen bond acidities (HBA)? A comparative study with the use of the ¹⁵N chemical shifts of amines for measuring HBA

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The hydrogen bond acidity and other descriptors for oximes

Abstract: The solvation descriptors for cyclohexanone oxime and acetone oxime have been obtained from measurements on water-solvent partitions, and gas-liquid

Cited by 21 publications

References 25 publications

Partition of compounds from water and from air into amides

Partition of compounds from water and from air into amides

Predictive Modeling of Molecular Properties: Can We Go beyond Interpretation?

Is it possible to use the 31P chemical shifts of phosphines to measure hydrogen bond acidities (HBA)? A comparative study with the use of the 15N chemical shifts of amines for measuring HBA

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Product

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Is it possible to use the ³¹P chemical shifts of phosphines to measure hydrogen bond acidities (HBA)? A comparative study with the use of the ¹⁵N chemical shifts of amines for measuring HBA