Investigation of Enantiomer Bonding on a Chiral Stationary Phase by FT-Raman Spectrometry

Horvath, Elisabeth; Kocsis, László; Frost, Raymond; Hren, B.; Lp, Szabó

doi:10.1021/ac9712411

Cited by 11 publications

(8 citation statements)

References 15 publications

(24 reference statements)

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“…25 It is also known that longer aliphatic chains perturb hydrogen binding of analyte to the amide group involved in the primary recognition of enantiomers. 26,27 In conclusion, we have shown that efficient brush-type CSPs can be prepared by functionalization of the persub-stituted benzene derivative 1. In particular, those containing chiral, -basic (R)-NEA unit connected via a glycinetype spacer group can resolve a wide range of -acidic racemic compounds.…”

Section: Resultsmentioning

confidence: 75%

New chiral stationary phases based on (R)-1-naphthylethylamine bound to 2,4,5,6-tetrachloro-1,3-dicyanobenzene

1999

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Chiral functionalization of 2,4,5,6‐tetrachloro‐1,3‐dicyanobenzene (1) by regioselective nucleophilic substitution of one or two chlorine atoms by optically pure (R)‐(+)‐1‐naphthylethylamine (NEA), or by a glycine unit as a spacer to (R)‐NEA, enables the preparation of brush‐type chiral selectors (2, 3, 9, 13). By the introduction of the 3‐aminopropyltriethoxysilyl (APTES) group, reactive intermediates 4a/b, 5, 10a/b, and 14a/b are obtained (a/b indicate a mixture of regioisomers with APTES in 6‐ and 2‐position). Binding of these to silica gel afforded four novel chiral stationary phases (CSPs) 6, 7, 15, and 16. HPLC columns containing CSPs with (R)‐NEA directly linked to polysubstituted aromatic ring (6, 7) are not very effective in resolution of most of the 23 racemic analytes, whereas the columns with distant π‐basic subunits (15, 16) exhibited higher resolving efficacy, in particular towards the isopropyl esters of racemic N‐3,5‐dinitrobenzoyl‐α‐amino acids. Effective resolution of test racemates reveals the importance of the presence of the hydrogen bond donor amido group and the distance between the persubstituted benzene ring in 1 and the π‐basic naphthalene ring of (R)‐NEA. Chirality 11:722–730, 1999. © 1999 Wiley‐Liss, Inc.

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Section: Resultsmentioning

confidence: 75%

New chiral stationary phases based on (R)-1-naphthylethylamine bound to 2,4,5,6-tetrachloro-1,3-dicyanobenzene

1999

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“…According to the literature data, the conclusion about the mechanism is mostly based on general deliberations, sometimes computer methods, 14 but rarely on using the NMR spectroscopy which requires a previous synthesis of CSPÕs analogues, 15 and recently on the using of IR and Raman spectroscopy of solid phases. 16,17 The latter is not completely pursuant to reality since, during the chromatography, chiral recognition evolves around the surface of solid carriers, not in the liquid phase. Therefore as the method, which could gather the most data about real interactions, we chose NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

The enantiomeric recognition of dihydropyrimidonic compounds by chiral selectors derived from 4- or 2-chloro-3,5-dinitrobenzoic acid

Gazić¹,

Kontrec²,

Lesac³

et al. 2005

Tetrahedron: Asymmetry

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“…The chiral recognition mechanisms that separate chiral solutes having p-donor groups have been investigated by HPLC (Pirkle and Welch, 1984;Wainer and Alembik, 1986;, NMR spectrometry (Pirkle and Pochapsky, 1987), X-ray crystallography , Raman spectrometry (Horvóth et al, 1998) and computational studies (Lipkowitz et al, 1988;Topiol et al, 1988). The aim of these studies has been to clarify the interactions required for forming diastereomeric complexes that achieve complete enantiomeric separations.…”

Section: Introductionmentioning

confidence: 99%

A study of chiral recognition for NBD‐derivatives on a Pirkle‐type chiral stationary phase

Kato¹,

Fukushima²,

Shimba³

et al. 2001

Biomedical Chromatography

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A chiral stationary phase (CSP 1) derived from an (S)-N-3,5-dinitrobenzoyl-1-naphthylglycine showed excellent enantiomeric separation for amino acid derivatives with a fluorogenic reagent, 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), in high-performance liquid chromatography (HPLC). We compared elution profiles (separation factor and elution order) of NBD-amino acids and their analogs on HPLC, to determine the diastereomeric complex between the chiral moiety of CSP 1 and NBD-amino acid, which is responsible for the chiral recognition. (1)H-NMR studies of a mixture of model compound of CSP 1 and NBD-Ala suggest that the diastereomeric complex is composed of two hydrogen bonding sites at the amino proton and oxygen atom, and a pi-pi interaction by the benzofurazan structure (2,1,3-benzoxadiazole) of NBD-amino acid. Furthermore CSP 1 was able to separate esters, amides and alpha-methyl amino acids derivatized with NBD-F.

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Investigation of Enantiomer Bonding on a Chiral Stationary Phase by FT-Raman Spectrometry

Cited by 11 publications

References 15 publications

New chiral stationary phases based on (R)-1-naphthylethylamine bound to 2,4,5,6-tetrachloro-1,3-dicyanobenzene

New chiral stationary phases based on (R)-1-naphthylethylamine bound to 2,4,5,6-tetrachloro-1,3-dicyanobenzene

The enantiomeric recognition of dihydropyrimidonic compounds by chiral selectors derived from 4- or 2-chloro-3,5-dinitrobenzoic acid

A study of chiral recognition for NBD‐derivatives on a Pirkle‐type chiral stationary phase

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