Prediction of chromatographic parameters for some anilines by molecular connectivity

Summary The possible relation existing between R_F values obtained by thin-layer chromatography for a group of anilines with connectivity indices proposed by Kier and Hall has been studied. Using multivariable regression the corresponding connectivity functions, selected for their respective correlation coefficients, standard deviations, Snedecor’s F and Student’s t were obtained. Regression analysis of the connectivity functions gives a correct prediction of the experimental elution sequence for this group of substances on silica gel stationary phases and various mobile phases of different polarity. The corresponding random and stability studies of the different prediction models selected were carried out, showing good stability and null randomness in all cases.     

Calculation of chromatographic properties of barbiturates by molecular topology

Summary A study has been made of the relationship between the R_F values obtained by thin layer chromatography for a group of barbiturates and the connectivity indices proposed by Kier and Hall. By using multivariable regression we obtained the corresponding connectivity functions, which were selected on the basis of their respective statistics parameters. The regression analysis of the connectivity functions shows a correct prediction of the experimental elution sequence for this group of molecules on silicagel with two mobile phases of different polarity. The corresponding random and stability studies of the different prediction models selected were carried out, demonstrating good stability and null randomness in all cases. The results also demonstrated that different structural features determine the R_F values in TLC of barbiturates.     

Optimization of chromatographic systems for the high-performance thin-layer chromatography of flavonoids

Summary To characterize the retention and selectivity of separations of 23 flavonoids (aglycones and glycosides) relationships betweenR _F and modifier concentration were determined for silica and diol adsorbents (with mixtures of ethyl acetate and methanol as mobile phases), for cyanopropyl silica (with mixtures of ethyl acetate and dichloromethane as mobile phases), for aminopropyl silica (with mixtures of ethyl acetate, methanol and water as mobile phases) and for octadecyl silica (with mixtures of methanol and water as mobile phases). Owing to large polarity differences between aglycones and glycosides, these groups of compounds cannot be separated other than by use of reversed-phase systems, for which the selectivity is lower. It follows from correlation plots ofR _F1 againstR _F2 that for some pairs of adsorbents (e. g. silica and diol) selectivity differences are small; for others the points in the plot are widely dispersed, indicating selectivity differences. The chemometric database obtained can be used to choose optimum chromatographic systems for the separation of given sets of flavonoids and for planning gradient elution programs for separation of flavonoid aglycones and glycosides in a single TLC experiment.     

Control of the synthesis of some biologically active substances by thin-layer chromatography

Summary The aim of this investigation was the synthesis of -aryl propionic acids which might be expected to have antiinflammatory activity. The total synthesis of -(4-benzoylphenyl)--methyl propionic acid was monitored by thin-layer chromatography. The adsorption of the compounds of interest was found to be dependent upon the polarity of the eluting solvents. The observed retentions were mathematicaly analysed, and the system that showed the best separation of reactants evaluated. A least squares method was used to determine the best geometric curve expressing the relationship between values for R_f and eluent composition.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Thin-layer chromatographic separation of some closely related olefinic benzo- and naphtofurans

Summary A method is reported for the separation of 16 closely related 2-(1, 2-diphenylvinyl)-3-phenylbenzofuran and 2-(1, 2-diphenylvinyl)-1-phenylnaphtho[2,1-b] furan derivatives on thin-layers of silica gel-G.     

Relationship between molecular connectivity indices of barbiturates and chromatographic parameters

Summary 166 data sets of different chromatographic parameters for barbiturates taken from the literature were correlated with the first order valence connectivity indices. The most significant correlations were found for HPLC. The correlations depend on the structure of the substituents and the substitution mode of the barbituric acid ring.Preliminary results of this work have been published at the Annual Meeting of the Polish Chemical Society, in Krakow, September 17–20, 1980.     

A convenient method for the Ru(0)-catalyzed regioselective deuteration of N-alkyl-substituted anilines

A highly effective and operationally practical method for the regioselective deuteration of N-alkyl-substituted anilines employing Ru₃(CO)₁₂ (?1 mol %) as catalyst and D₂O as deuterium source was described. A variety of N-alkyl-substituted anilines were efficiently deuterated (up to 98%) at the ortho and/or para position with respect to the nitrogen at neutral conditions. Under the present conditions, deuterated anilines can be easily obtained with simple extraction and evaporation. Substituents with aromatic methoxy groups would not influence the selectivity compared to previous method.     

A semicrystalline inorganic ion-exchanger for thin-layer chromatographic separation of phenolic compounds

Summary The thin-layer chromatographic behaviour of 28 phenolic compounds was studied on semicrystalline stannic tungstate layers using various solvent systems of which formic acid and n-butanol-formic acid were found to be the most useful for the separation of these compounds. Dimethyl sulphoxide was found to act as a self detector for a number of phenols. An interesting feature of the study of phenols using stannic tungstate is the novel separation of different isomeric compounds. A number of binary, ternary and quarternary separations of bioanalytical and immunophysiological importance have been achieved.     

Thin-layer chromatographic separation and identification of some anions on copper sulphate impregnated silica gel layers

Summary Thin-layer chromatographic behaviour of thirteen anions on plain silica gel and silica gel impregnated with copper sulphate solution has been investigated in aqueous-organic solvents containing acetone, some of which have achieved reliable and reproducible separations. The effect of copper sulphate concentration on the mobility of anions has been examined. The results obtained on plain silica gel have been compared with those obtained on copper sulphate impregnated layers. The impregnated layers dramatically change the selectivity and permit separations not possible on untreated silica. Aqueous sodium chloride-acetone (9∶1) and ammonium hydroxide-acetone (9∶1) were the most effective solvent systems for differential migration of anions. Better results in terms of clarity of detection and compactness of spots were found with HCOOH-acetone as compared to HCl-acetone. The effect of anion loading on R_F values has been investigated and identification limits on impregnated layers determined.     

Analysis and chromatographic separation of some steroid hormones on NH2 layers

Summary The previously described analytical method for carbohydrates, catecholamines, uric acid, creatine and creatinine using thin-layer chromatography on aminomodified HPTLC plates and subsequent thermal activation of the chromatogram zones is expanded to include several steroid hormones. Specifically, they are the pharmacologically relevant compounds cortisone and hydrocortisone, estradiol and estradiol benzoate, estriol, estrone, methyltestosterone, testosterone and testosterone propionate, prednisolone, pregnandiol and triol, progesterone and Reichstein's S.     

Critical evaluation of experimental conditions influencing the surface-enhanced Raman spectroscopic (SERS) detection of substances separated by layer liquid chromatographic techniques

Summary Surface-enhanced Raman spectra (SERS) ofp-dimethylaminobenzylidenerhodanine have been recorded on silica gel 60 F₂₅₄ and Si60 F₂₅₄ Raman TLC plates. Spectra were enhanced by use of a silver sol prepared according to the modified Lee-Meisel procedure. The standard deviations of the intensities and the band ratios for the seven most intense peaks were calculated for 30 parallel measurements. Although the Raman plate gives more reproducible results, several experimental difficulties are encountered in the development of chromatograms. SERS detection of ascorbigen and 1′-methylascorbigen was performed after chromatography on silica gel 60 F₂₅₄ TLC and HPTLC plates and on Si60 F₂₅₄ Raman TLC plates. Traditional development was used for the silica gel 60 F₂₅₄ TLC plates and Si60 F₂₅₄ Raman plates, and the personal OPLC technique for the silica gel 60 F₂₅₄ HPTLC plates. It was found that the SERS spectrum gave information about the indole ring only. Because bonding of the analyte to the stationary phase results in a change in molecular conformation-in contrast with the behaviour of rhodanine-the type of the plateused and the development procedure employed can significantly influence the quality of the SERS spectrum. Presented at Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary September 1–3, 1999     

Quasi-column chromatography of barbituric acid derivatives II. Separation on Non-polar adsorbents using binary water-organic solvent mixtures as the mobile phase

Summary Twenty barbituric acid derivatives having four different types of substitution were separated in TLC-S chambers. Using non-polar adsorbents (silanized silica gel or silica gel coated with paraffin oil) and binary water-organic solvent mixtures as the mobile phase. Linear relationships between R_M and the concentration of the organic solvent were observed for the majority of the investigated compounds. The non-polar absorbents ensure a better separation than untreated silica gel especially for the therapeutically useful C₅ disubstituted barbiturates. The results can be used for the optimization of the systems for the chromatography of barbiturates. The R_f values were correlated with the number of carbon atoms of the substitutions, molecular connectivity and a parameter associated with the molecular volume. The best correlations were obtained for this last parameter.     

An improved HPTLC method for the rapid identification and quantification of sulfonamides

Summary R_f values of twenty therapeutic sulfonamides have been estimated in seven solvent systems. Based on these data a simple identification scheme was developed demanding only three solvent systems for complete separation.Quantification of corresponding fluorescamine derivatives at nanogram level was performed by the use of an TLC-scanner configured online with a microcomputer. Mathematical treatment of standard curves using the computer program Curve Fitter are discussed. Validity and reproducibility of results are compared with data obtained by HPLC and show good correlation.     

Cross-dehydrogenative coupling strategy for phosphonation and cyanation of secondary N-alkyl anilines by employing 2,3-dichloro-5,6-dicyanobenzoquinone

The cross-dehydrogenative coupling strategy for metal-free phosphonation and cyanation of secondary N-alkyl anilines has been developed firstly under mild reaction conditions. Based on detailed optimization of reaction conditions, the substrate generality of N-alkyl anilines and various hydrogen phosphonates has been investigated, and a series of versatile α-aminophosphonates and α-aminonitriles were therefore furnished in good to excellent yields. A plausible collective reaction mechanism through dehydrogenation to imine formation, then to respective α-aminophosphonates and α-aminonitriles was proposed.     

Retention parameters of some isomeric 2-benzoylbenzoic acids in reversed-phase ion-pair high performance thin-layer and column chromatography

Summary The 2-benzoylbenzoic acid series was investigated by reversed-phase, high-performance, thin-layer and column chromatography using various alkylammonium salts and di(2-ethylhexyl)orthophosphoric acid as polar associating reagents. The effects of the individual substituents on retention were quantified by log k and R_M values. The compounds investigated differing in molecular structure (hydrophilic and hydrophobic substituents) commonly occurring groups in drugs and biologically active substances provide information on molecular interaction in these ion-pair systems. The combined effects on retention of organic modifier and ion-pair reagent concentration were investigated.     

Use of a Graphical Method to Predict the Retention Times of Selected Flavonoids in HPLC from Thin-Layer Chromatographic Data

Similarities and differences between the retention characteristics of octadecylsilica wettable with water used in TLC and RP-18 used in HPLC have been elucidated by use of the linear relationships between log k and R_M. The stationary phases compared were investigated with the same mobile phases—binary mixtures of methanol and water, acetonitrile and water, and tetrahydrofuran and water. For these adsorbents of the same type but differing in specific surface area the correlation line was shifted by log (_systemI/_systemII). High values of the correlation coefficients obtained over the whole range of mobile phase organic modifier concentration examined indicated that the TLC systems could be used to predict HPLC conditions for flavonoid separation.     

Relationship between the lipophilicity and specific hydrophobic surface area of some pesticides by RP-HPLC and HPTLC

Summary Using methanol-water mixtures as the mobile phases, the retention behaviors of thirty-seven pesticides were determined in RP-HPLC and RP-HPTLC. Regular retention behavior was observed for all the investigated pesticides: theirR _m and logk values decreasing linearly with increasing concentration of methanol in the mobile phase. The lipophilicity and specific hydrophobic surface area values for each compound were obtained and they have a good linear relationship. Although the chemical structures of these pesticides were different, factor analysis proved that the lipophilicity and specific hydrophobic surface area of these compounds have much in common, and the insecticides, fungicides and herbicides could not be distinguished from each other according to their lipophilicity parameters obtained from chromatography method.