Studies on amphiprotic compounds. 3. Hydrogen-bonding basicity of oxygen and sulfur compounds

Abboud, José‐Luis M.; Roussel, Christian; Gentric, Emilie; Sraidi, Khadija; Lauransan, Jacques; Guiheneuf, Georges; Kamlet, Mortimer J.; Taft, Robert W.

doi:10.1021/jo00242a039

Cited by 37 publications

(21 citation statements)

References 8 publications

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“…O-H..0 versus O-H..S hydrogen bonding, can be answered as follows: for the intra-molecular hydrogen bonds of 2-hydroxy-(thio)benzoyl compounds considered in this study the AgoH frequency shifts and hence the spectroscopically determined strengths of the O-H..S bonds are similar to, or even larger than those of the corresponding O-H..O bonds, which agrees with the predictions of the model calculations [-8] and with the results of some few previous literature studies [9][10][11][12]. No attempts will be made in the present paper for an interpretation of the experimental findings, neither for the determined hydrogen bond sequences, nor for the observed similarities and differences between oxygen and sulfur proton acceptors.…”

Section: Discussionsupporting

confidence: 89%

“…Some few IR studies on intra-molecular O-H..S bonds available on the literature [9][10][11][12] seem to confirm these predictions and the differences between oxygen and sulfur proton acceptors have been qualitatively interpreted to result from the larger lone pair extension of sulfur and from an increased covalent character of the H..S bond [6,13].…”

Section: Introductionmentioning

confidence: 95%

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Hydrogen bonding in 2-hydroxybenzoyl and 2-hydroxythiobenzoyl compounds: Spectroscopic characterization and spectroscopic bond strength sequences

Steinwender

Mikenda

1994

Monatsh Chem

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Section: Discussionsupporting

confidence: 89%

Section: Introductionmentioning

confidence: 95%

Hydrogen bonding in 2-hydroxybenzoyl and 2-hydroxythiobenzoyl compounds: Spectroscopic characterization and spectroscopic bond strength sequences

Steinwender

Mikenda

1994

Monatsh Chem

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“…In this section, each of these potential hydrogen-bonding interactions was tested by replacing the oxygen with sulfur. As sulfur is a weaker hydrogen-bond acceptor than oxygen ( [37][38][39][40][41][42] and references therein), thio substitution would be expected to diminish the catalytic advantage provided by a hydrogen bond from the 2′-OH.…”

Section: Hydrogen-bond Donation From the 2′ ′-Oh Of U(-1)?mentioning

confidence: 99%

The role of the cleavage site 2′-hydroxyl in the Tetrahymena group I ribozyme reaction

Yoshida

Shan

Herschlag

et al. 2000

Chemistry & Biology

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“…It was important to check this independence of hydrogen bonding effect since we have already quantified the difference in hydrogen bonding ability of thiazolinone and thiazolinethione compounds. 21 It is worth noting that the contribution to lipophilicity when hydrogen is substituted by a methyl on the heterocycle or on the aryl ring is the same since the coefficients associated to X , and X3 are almost equal. (Fig.…”

Section: Lipophilicity Resultsmentioning

confidence: 99%

Effects of alkyl substituents on chiral separation of N‐arylthiazolin‐2‐(thi)‐one atropisomers on tris (p‐methylbenzoyl)cellulose beads and cellulose triacetate: Lipophilicity aspects

Roussel

Popescu

1994

Chirality

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ABSTRAC7The determination of lipophilicity of the title compounds allowed treatment of the data for chiral separation (capacity factors) on CTA and CTPB accordmg to these parameters. A linear correlation between In k'(+) and log k'w was found on both CTA and CTPB, as far as the substituents are situated in the plane of the aryl ring or the heterocycle. This correlation with a nonchiral descriptor allows treatment of capacity factors for (-)-enantiomers as deviations from the lipophilicity line or derived parallels. It results in a clear description of the molecular area affecting enantioselectivity. Application to larger alkyl derivatives shows that the effect of the substituent should be treated on a basis of attractive effect in the case of CTA and on the basis of attractive and repulsive effects for CTPB. KEY WORDS: chiral HPLC, experimental design, quantitative substituent effects, recognition mechanism Chiral recognition mechanisms in cooperative CSPs such as cellulose derivatives provide a fascinating field of research'" since the discriminating sites are not clearly identified in contrast to the molecular CSPs in which the chiral selector is well defined."6 As a consequence, the methodologies to address chiral discrimination in cooperative phases will be different than those applied in the case of a well-defined molecular selector. Stereoselectivity for a given couple of antipodes results from the energy difference between diastereomeric solute-CSP complexes whereas capacity factors k' are related to the energy of interaction of each enantiomer with the CSP. In cooperative CSP one approach might be to develop a series of molecules which are structurally related and which differ by appropriate substitutions around the same framework. If one can linearize the effect of the substitution pattern for each enantiomer of the same configuration, the enantioselectivity will be simply the difference between these two linearisations for a given set of substituents. Such a linearisation might be performed using the PLS approach,7 however, it seems clear that chiral descriptors as well as nonchiral descriptors are needed.The lipophilicity parameter is one of the nonchiral descriptors generally used in studies of quantitative structure-activity relationship.' To obtain a relationship between chiral retention of enantiomers and their lipophilic interaction within a chiral phase, we have determined the capacity factors on cellulose triacetate CTA and trisu-methylbenzoy1)cellulose beads CTPB chiral stationary phases and the lipophilicity parameters for a series of N-aryl substituted heterocyclic atropisomers (the general structure is given in Fig. 1 1-8 are related by a factorial design approach which allows the quantification of the effects of structural parameters X,, X,, X, on the chiral retention on CTA,' CTPB,l" and on the lipophilicity parameter. In this paper we attempt to relate the capacity factor of the enantiomers of compounds 1-8 with their lipophilicity parameter and to extend the approach to chiral separation...

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Studies on amphiprotic compounds. 3. Hydrogen-bonding basicity of oxygen and sulfur compounds

Cited by 37 publications

References 8 publications

Hydrogen bonding in 2-hydroxybenzoyl and 2-hydroxythiobenzoyl compounds: Spectroscopic characterization and spectroscopic bond strength sequences

Hydrogen bonding in 2-hydroxybenzoyl and 2-hydroxythiobenzoyl compounds: Spectroscopic characterization and spectroscopic bond strength sequences

The role of the cleavage site 2′-hydroxyl in the Tetrahymena group I ribozyme reaction

Effects of alkyl substituents on chiral separation of N‐arylthiazolin‐2‐(thi)‐one atropisomers on tris (p‐methylbenzoyl)cellulose beads and cellulose triacetate: Lipophilicity aspects

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