Chromatographic behaviour of diastereomers : III. Thin-Layer chromatographic behaviour of diastereomeric 4-substituted 6,7-dialkoxy-3-aryl-tetrahydroisoquinolines and -isochromans

doi:10.1016/S0021-9673(00)93772-5

Journal of Chromatography A

Volume 132, Issue 1, 1 February 1977, Pages 73-82

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Abstract

Twenty three pairs of diastereomeric tetrahydroisoquinolines (X = N) and isochromans (X = O) of the type

where Y = CO₂Me or CH₂OH have been separated by thin-layer chromatography on silica gel using solvent systems with and without secondary solvent effects. For the N-alkyltetrahydroisoquinolines and for isochromans having Y = CO₂Me, the relation R_F(trans) >R_F(cis) has been established, whereas for the remaining compounds R_F(cis) >R_F(trans). In terms of Snyder's theory, this difference in behaviour can be attributed to two-point adsorption in the first case and to one-point adsorption in the second case, via definite conformations.

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Additivity of retention of diastereoisomeric and enantiomeric arylphthalides, aryl(arylene)phthalides and aryldiphthalides of dyadic and triadic composition
2020, Journal of Chromatography A
Citation Excerpt :
As can be seen from Fig. 3, the meso isomers are characterized by shorter chromatographic retention times and they always elute first, whereas racemic isomers elute second. By analogy with published data on the adsorption for dimeric compounds of other classes [33-43], the difference in the chromatographic behavior of diastereoisomers of diaryldiphthalides can be explained by the difference in the mode of their adsorption, which, in turn, is determined by the configuration and preferred conformation of these compounds. When studying by liquid chromatographic techniques [34-36], TLC [37-41] and GLC [42,43] the effects of steric and stereo-electronic factors on the separation of a wide range of diastereoisomeric pairs of compounds of various classes (amides, esters, acids), it was found that in most cases, racemic diastereomers elute later than the meso‑isomers [37-39].
For the first time, four series of new phthalide-containing heteroaromatic compounds were separated by reverse phase HPLC: O_YO, O_YS, S_YS; O_YO_YO, O_YO_YS, S_YO_YS; S_YS_YS, S_YS_YO, O_YS_YO; O_YYO, O_YYS, S_YYS, (where O – diphenyloxide, S – diphenylsulfide, Y – phthalide group). A fundamental difference was established in the chromatographic behavior of diaryl(arylene)diphthalides, built on the principle of “head-to-tail”, and diaryldiphthalides with a structure of “head-to-head”. The meso and chiral diastereoisomers of the former were eluted by one peak, while the latter existed in solution in the forms of stable cis (racemic form) and trans (meso form) rotamers with different retention times. It was shown that to calculate the retention times of related diarylphthalides, diaryl(arylene)phthalides, diastereoisomeric and enantiomeric diaryldiphthalides of an asymmetric structure, the half-sum rule can be applied according to which: t_R(A-X-B)≈[(t_R(A-X-A)+t_R(B-X-B)]/2. For diaryl(arylene)diphthalides of a triadic structure, a modified additive scheme for calculating retention times is proposed, including multiplication and division operations: t_R(A-A-A) = t_R(A-A-B) × t_R(A-B-B)/t_R(B-B-B).
The rotameric (R*,S*)- and (R*,R*)-biaryl-3,3′-diphthalides of polyphenylene series
2019, Tetrahedron
Citation Excerpt :
This conclusion was made on the basis of HPLC data, according to which the meso-isomers are characterized by smaller retention times and always eluted first, and chiral diphthalides eluted second (Fig. 5). By analogy with literature data on adsorption of diastereoisomers of other classes [28–38], differences in chromatographic behavior of the diastereomeric diphthalides can be explained by a different mechanism of their adsorption, which in its turn is determined by configurational structure and preferred conformation of these compounds. It is considered, that compounds adsorbed on an adsorbent's surface posses the same conformation as in a solution [28–30].
A wide range of diastereomeric pairs of biaryl-3,3′-diphthalides with aromatic (heteroaromatic) substituents of polyphenylene series (including halogen substituted) was synthesized. All of them were separated and characterized by the methods of X-ray analysis, HPLC, IR-, 1H and 13C NMR spectroscopy. It was determined that solubility, tendency to adsorption and related to it retention times, chemical shifts of equivalent hydrogen and carbon atoms of biaryl-3,3′-diphthalides diastereoisomers are determined firstly by the stereo-electronic effects of two adjacent strongly polar phthalide groups. It was shown that both in crystalline phase and in solution all the diphthalides, regardless of the chemical structure of their substituents, are existing as stable rotamers with cis or synperiplanar (chiral forms) and trans or antiperiplanar (meso-forms) conformation.
Chromatographic behaviour of diastereoisomers. XIII. Adsorptivity of esters of Z- and E-2,3-diphenylpropenoic acids and similar compounds on silica in terms of the Snyder theory
1997, Journal of Chromatography A
Thin-layer chromatography (TLC) of eight Z and E esters of the type C₆H₅CH=C(C₆H₅)CO₂R was studied using 20 computer-selected mobile-phases on the basis of the Snyder theory, the mobile phases having strength, ε, equal to 0.165 or 0.250 and different values of localization, m and polarity, P′. The available values of ε enabled the calculation of the energy of adsorption of all groups i participating in the solute structures under selected conditions. The ester group proved to be the only absorbing group. This, in combination with the configuration of the diastereosomers, explained their adsorptivity including the relative retention E>Z found in all cases studied. The approach was applied to data found by Cooper for eight similar diastereoisomers. The tuning effect of P′ on ε and adsorptivity is discussed, both being of importance in the selection of mobile phases for liquid-solid chromatography (LSC), including preparative separations. The application of the Snyder theory to the diastereoisomers studied in this series of papers is summarised.
Chromatographic behaviour of diastereoisomers XII. Effects of alumina on separations of esters of maleic and fumaric acids
1994, Journal of Chromatography A
The thin-layer chromatographic separations on three different aluminas of twenty diastereoisomeric 1,2-disubstituted ethenes, ROOCCH CHCOOR, were studied with 24 mobile phases having strength, ε, in the range 0.210–0.250 and a wide variety of solvent selectivity effects. The relative retention of the diastereoisomers was always Z >E independently of the type of the alumina and the increase in the selectivity of the mobile phases and the effective volume of the group R as a result of an expected site chelation via the two ester groups in Z isomers only. A comparison shows that the separations of these diastereoisomers are similar with both alumina and silica using a given mobile phase. However, the overall separation obtained on any alumina is better than that found for silica.
Chromatographic behaviour of diastereoisomers. IX. Application of a microcomputer program to the thin-layer chromatographic separation of some diastereoisomers on silica
1988, Journal of Chromatography A
The thin-layer chromatographic separation of four diastereoisomeric amino esters and isochromans on silica was studied using 21 mobile phases composed of two to six solvents and selected by means of a microcomputer program. The mobile phases had a constant strength ε of 0.354. The experimental R_F values were in the range 0.12–0.82, showing the applicability of the microcomputer program based on Snyder's displacement model to the choice of suitable mobile phases. The variation of the latter does not affect the relative retention of each diastereoisomeric pair but affects its relative separation as predicted by theory and shown for binary mobile phases in other studies in this series.
Chromatographic behavior of diastereoisomers. VIII. Solvent selectivity effects in separations on silica
1986, Journal of Chromatography A
Solvent strength values and solvent selectivity effects have been studied for twenty diastereoisomers compounds (ten threo and erythro pairs) as a function of mobile phase composition, in thin-layer chromatography on silica. Forty-six different mobile phases were studied, composed of twelve different solvents, and comprising almost 500 k′ values. These data are compared with predictions from a previous model and found to give generally good agreement between experiment and theory. The general importance of solvent—solute localization in determining changes in band-spacing (α-values) was confirmed.

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Journal of Chromatography A

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Cited by (15)

Additivity of retention of diastereoisomeric and enantiomeric arylphthalides, aryl(arylene)phthalides and aryldiphthalides of dyadic and triadic composition

The rotameric (R,S)- and (R,R)-biaryl-3,3′-diphthalides of polyphenylene series

Chromatographic behaviour of diastereoisomers. XIII. Adsorptivity of esters of Z- and E-2,3-diphenylpropenoic acids and similar compounds on silica in terms of the Snyder theory

Chromatographic behaviour of diastereoisomers XII. Effects of alumina on separations of esters of maleic and fumaric acids

Chromatographic behaviour of diastereoisomers. IX. Application of a microcomputer program to the thin-layer chromatographic separation of some diastereoisomers on silica

Chromatographic behavior of diastereoisomers. VIII. Solvent selectivity effects in separations on silica