Gas chromatographic enantiomer separation of agrochemicals using modified cyclodextrins

König, Wilfried Α.; Icheln, Detlef; Runge, Torsten M.; Pfaffenberger, Bernd; Ludwig, Peter; Hühnerfuß, Heinrich

doi:10.1002/jhrc.1240140804

Cited by 106 publications

(73 citation statements)

References 23 publications

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“…17,18 In essential oils, this analysis possesses a great importance in the control of quality of these oils, where they supply important information about its authenticity detecting the presence of possible synthetic adulterants. 19 So far, no reports are available about the enantiomeric composition of volatile oils from propolis.…”

Section: Introductionmentioning

confidence: 99%

Chiral Analysis of Monoterpenes in Volatile Oils From Propolis

Simionatto

Facco

Morel

et al. 2012

J. Chil. Chem. Soc.

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The essential oils obtained by hydrodistillation from samples of propolis manufactured in three regions of Rio Grande do Sul State at Brazil, were analyzed through CG, CG-MS and chiral phase gas chromatography (CPGC). These analyses display the presence of samples with elevated essential oil purport, when compared with plants. The yields obtained were until 3.8%. The samples exhibited similar composition, with predominance of the monoterpenes a-pinene (57-63%), b-pinene (12.5-30.8%) and limonene (1.5-11.2%). In chiral analysis of these constituents were observed modifications in the enantiomeric excess of isomers of a-pinene and limonene in relation with source location of the sample, already in the chiral analysis of b-pinene were detected only elevated excess of the enantiomer with the (-) configuration. The antimicrobial activity of the crude essential oil was assayed against five bacteria. The best result was obtained against Staphylococcus aureus.

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Section: Introductionmentioning

confidence: 99%

Chiral Analysis of Monoterpenes in Volatile Oils From Propolis

Simionatto

Facco

Morel

et al. 2012

J. Chil. Chem. Soc.

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“…The capillary is then filled with a 0.2% solution of the cyclodextrine derivative and OV 1701 (1:1; m m -1 ) according to the procedure described previously. 2 …”

Section: Column Preparationmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11] Various chiral mono and sesquiterpenes common to essential oils and other economically important products could be resolved on columns coated with per-O-alkylated/acylated cyclodextrins. [11][12][13][14][15][16] The number of cyclodextrin derivatives that is prepared and evaluated for enantioselective gas chromatography is still declining in recent years.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Chromatographic Evaluation of the new phase heptakis (3-O-pentafluoropropionyl-2,6-di-O-pentyl)-β-cyclodextrin

Mallmann¹,

Ethur²,

Silva³

et al. 2010

J. Braz. Chem. Soc.

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Neste trabalho uma nova fase estacionária quiral, heptaquis (3-O-pentafluoropropionil-2,6-di-O-pentil)-b-ciclodextrina, foi sintetizada e avaliada frente uma grande variedade de compostos voláteis quirais. O novo derivado de ciclodextrina foi usado para a separação de componentes de óleos essenciais, como hidrocarbonetos, cetonas, aldeídos, álcoois de cadeia longa, compostos halogenados e compostos contendo nitrogênio e enxofre.In this work, a new chiral stationary phase heptakis (3-O-pentafluoropropionyl-2,6-di-Opentyl)-b-cyclodextrin was synthesized and evaluated with a wide variety of volatile chiral compounds. As a result, the new cyclodextrin derivative can be applied to the separation of chiral components of essential oils, as hydrocarbons, ketones, aldehydes, alcohols and of various classes of synthetic chiral compounds, as long chain alcohols, halocarbons, nitrogen and sulfur containing compounds. Keywords: enantioselective gas chromatography, heptakis (3-O-pentafluoropropionyl-2,6-di-O-pentyl)-b-cyclodextrin, pentafluoropropionyl group IntroductionCyclodextrins (CDs) derivatives, especially those of a-, b-and g-cyclodextrins, are used widely as chiral stationary phases (CSPs) in gas chromatography (GC) as an efficient method for enantioseparation of a wide variety of volatile compounds of different functionality. [1][2][3][4][5][6][7][8][9][10][11] Various chiral mono and sesquiterpenes common to essential oils and other economically important products could be resolved on columns coated with per-O-alkylated/acylated cyclodextrins. [11][12][13][14][15][16] The number of cyclodextrin derivatives that is prepared and evaluated for enantioselective gas chromatography is still declining in recent years. The most important chiral stationary phases know to data, as octakis (3-O-butyryl-2,6-di-O-pentyl)-g-cyclodextrin (Lipodex E) 17 , heptakis (3-O-pentyl-2,6-di-O-methyl)-bcyclodextrin 18 and octakis (3-O-methyl-2,6-di-O-pentyl)-gcyclodextrin 12 , were obtained in the late 80's and 90's. In this work we describe the preparation and the enantioseparation ability of heptakis (3-O-pentafluoropropionyl-2,6-di-O-pentyl)-b-cyclodextrin derivative with pentyl groups at the 2 and 6 positions and the pentafluoropropionyl group in the 3 position of their glucose unit. The pentafluoropropionyl group is used as hydroxyl group protection in oligomannoside synthesis, 19 but not used yet as derivatizing agent in CDs. The enantioselectivity of the new phase was evaluated with a number of natural chiral components of essential oils as hydrocarbons, alcohols, ketones and lactones, and determination of enantiomeric composition in asymmetric synthesis. The enantiomers of (+/-)-a-pinene, (+/-)-limonene, alcohols as (+/-)-menthol, (+/-)-neo-menthol, (+/-) borneol, (and its acetyl and/or O-trifluoroacetyl derivatives), ketones as (+/-)-carvone, (+/-)-camphor and (+/-)-a-ionone could be resolved. In addition, chiral secondary and tertiary long chain alcohols, halocarbons, nitrogen and sulfur containing compounds may also be resolved....

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“…1,2 On CD CSPs, the enantiomers of a wide variety of structurally diverse racemates have been resolved. A number of chiral recognition mechanisms have been established depending on the particular chiral guest and cyclodextrin derivative under investigation.…”

Section: Introductionmentioning

confidence: 99%

“…A number of chiral recognition mechanisms have been established depending on the particular chiral guest and cyclodextrin derivative under investigation. [1][2][3][4] However, a reasonable model is still lacking to explain GC enantiomer separation on cyclodextrin based CSPs.…”

Section: Introductionmentioning

confidence: 99%

Enantiomer Separation of Mandelates and Their Analogs on Cyclodextrin Derivative Chiral Stationary Phases by Capillary Gc

et al. 2001

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Mandelic acid and α-methoxymandelic acid were purchased from TCI (Japan). 3-Phenyllactates were prepared according to the literature method.14 Ethyl 2-hydroxy-4-phenylbutyrate is the product of asymmetric hydrogenation of ethyl pyruvate on cinchonidine-modified Pt/Al2O3 catalyst, 7 supplied by the State Key Laboratory of Catalysis (China). All other reagents were commercially available.All the α-hydroxycarboxylic acids were esterified with methanol or ethanol and 98% sulfuric acid, according to a previously published procedure. 14 Instruments and proceduresChromatographic separations were performed with a modified GC-1121 capillary gas chromatograph (Shanghai Analytical Instrument Factory, China) equipped with a flame-ionization detector. Both the injector and detector temperatures were maintained at 250˚C. With H2 as the carrier gas, all the separations were performed isothermally with a split ratio of 1:100.Chiral columns were prepared as described earlier. 13 Briefly, fused silica capillary tubes (30 m × 0.25 mm i.d.) deactivated using PEG-20M were coated statically with mixture solutions of the CD derivatives and polysiloxane diluents dissolved in CH2Cl2, and then conditioned at 190˚C for over 4 h. Enantiomer separation of mandelates and their analogs, which are important intermediates in asymmetric synthetic and pharmaceutical chemistry, was investigated by capillary gas chromatography using different cyclodextrin derivative chiral stationary phases (CD CSPs). The used cyclodextrin derivatives included permethylated β-CD (PMBCD),, respectively. Among all the CSPs used, PMBCD and DNTBCD exhibited the broadest and best enantioselectivity for all the racemates investigated. Some thermodynamic parameters were evaluated and an enthalpy-entropy compensation effect was observed in enantiomer separation processes of mandelates and their analogs. Based on thermodynamic data and molecular mechanics calculations, the chiral recognition mechanism of mandelate derivatives on CD CSPs is discussed.

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Gas chromatographic enantiomer separation of agrochemicals using modified cyclodextrins

Cited by 106 publications

References 23 publications

Chiral Analysis of Monoterpenes in Volatile Oils From Propolis

Chiral Analysis of Monoterpenes in Volatile Oils From Propolis

Synthesis and Chromatographic Evaluation of the new phase heptakis (3-O-pentafluoropropionyl-2,6-di-O-pentyl)-β-cyclodextrin

Enantiomer Separation of Mandelates and Their Analogs on Cyclodextrin Derivative Chiral Stationary Phases by Capillary Gc

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