Partial resolution of amino acids by column chromatography on a polystyrene resin containing an optically active copper(II) complex

Snyder, Richard V.; Angelici, Robert J.; Meck, R.

doi:10.1021/ja00763a017

Cited by 83 publications

(13 citation statements)

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“…From the obtained results in both the present and previous study8, it is possible to consider that the selectivity between the two isomers obtained using the ion-pair extraction procedure is caused mainly by the following two reasons: (1) In an aqueous solution the cations of the cinchona alkaloids exist as aquo-ions having slightly different solvation energies. When these aquo-ions are extracted into organic phases, the extractability of the aquo-ions must be influenced in accordance with the small differences in their solvation energies in both phases.…”

Section: Resultssupporting

confidence: 54%

Solvent Extraction of a Chiral Ion-Pair between Some Cinchona Alkaloids and Acid Derivatives of Camphor

Tsurubou

1991

ANAL. SCI.

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Two pairs of cinchona alkaloids, quinine/quinidine and cinchonine/cinchonidine, were extracted by ion-pair formation with some anions of camphor derivatives. The extraction behaviors are examined, and the differences between the two isomers compared. These alkaloids were extracted into chloroform and 1,2-dichloroethane in the pH range 4 -7 as a 1:1 ion-pair with chiral anions. The relationship between the distribution ratio of the ion-pair and pH is discussed. In the pH range between the pKa, and pKa2 values of cinchona alkaloids, the extraction constants were determined, and the differences caused by the effect of substituents of cinchona alkaloids and counter ions were examined. The solvent effect were also studied. KeywordsStereoselectivity, cinchona alkaloid, camphor derivative , chiral ion-pair Several investigations regarding the optical resolution of isomers have been reported which used gas and liquid chromatographic methods.l-4 However, very little is known about the interaction between the solid phase and the solute in the mobile phase, since attention has been focused on the preparation of chiral solid phases that can bind the various enantiomeric forms with different strength.5-' There have also been a few reports regarding stereoselectivity in liquid-liquid extraction, although it is one of the simplest separation procedures in analytical chemistry. One of the main reasons may be that the effect of a steric hindrance between optical isomers seems very unlikely to appear as a difference in the distribution ratios.In a previous papers the author discussed the diastereomeric separation of ion-pair extraction between some cinchona alkaloids (two pairs of cinchona alkaloids, the quinine/ quinidine and cinchonine/ cinchonidine) and some chiral organic acids, such as Nacetyl amino acids. The extraction constants of the ion-pair with quinidine was always greater than that of quinine in each organic acid so far examined. Similarly, the extraction constants with cinchonine were greater than that of the cinchonidine almost examined. These differences in the extraction constant ratio (from 1.3 to 2.5) have been obtained. Also, in a previous study, it was confirmed that the differences of the log D values obtained by ion-pair extraction between cinchona alkaloids, such as quinine and quinidine, and the achiral counter anion of perchlorate were hardly observed. Consequently, in order to achieve a more effective diastereomeric separation of optical isomers by ion-pair extraction, it seems to be necessary the employ some chiral counter anions.In the present study two pairs of cinchona alkaloids, the quinine/ quinidine and cinchonine/ cinchonidine, were extracted with some acid derivatives of camphor in order to examine the effect of a substituent. The effect of the (+) and (-) forms of cinchona alkaloids and counter anions were also studied. Experimental Apparatus and reagentsA Hitachi Model 556 double-beam spectrophotometer used was equipped with a cell holder coupled with a Komatsu-Yamato Model CTR-220 thermostat...

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Section: Resultssupporting

confidence: 54%

Solvent Extraction of a Chiral Ion-Pair between Some Cinchona Alkaloids and Acid Derivatives of Camphor

Tsurubou

1991

ANAL. SCI.

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“…Studies of the use of optically active supports such as starch, wool, lactose, and cellulose (10)(11)(12)(13)(14)(15)(16)(17) and, more recently, synthetic resin matrices (18)(19)(20)(21)(22)(23)(24)(25)(26) have yielded several successful resolution methods. Still, selection of the appropriate matrix required for resolution of a given pair of optical isomers is difficult and usually empirical.…”

Section: Discussionmentioning

confidence: 99%

Resolution of DL-Tryptophan by Affinity Chromatography on Bovine-Serum Albumin-Agarose Columns

Stewart

Doherty

1973

Proc. Natl. Acad. Sci. U.S.A.

125

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Bovine-serum albumin, known to have antipodal specificity in the binding of tryptophan, was selected as the affinity chromatographic matrix for the attempted chromatographic resolution of DL-tryptophan. Complete resolution was accomplished when DL-tryptophan was chromatographed on bovine-serum albuminsuccinoylaminoethyl-Sepharose.Resolution of optical isomers by conventional methods is frequently laborious and incomplete. The mechanical and chemical methods are empirical in nature, and in practice choosing the appropriate resolving agents and physical means of separation can be difficult. Resolutions based on highly specific biological properties have been limited to enzyme reactions, and these reactions always resulted in chemical modification of one of the isomers. Differential binding of some optical isomers by a few serum proteins has been reported. Examples include binding of DI-tryptophan to bovine-serum albumin (1) and dl-aldosterone to corticosteroid-binding globulin (2). It would seem that this property of steroselective binding of optical isomers by proteins could be used for resolution of some optical isomers. We have begun studies to investigate this possibility and report here the resolution of DL-tryptophan on affinity columns of bovine-serum albumin-succinoylaminoethyl-agarose. (5), in which dipeptides are formed by reaction of the tryptophan with -glutamic acid N-carboxyanhydride, the -glutamyl-D-tryptophan is separated from the L-glutamyl-L-tryptophan by ion-exchange chromatography, and each diastereomer is quantitated. LTryptophan content was determined by the method of Guilbault and Hieserman (6) with -amino-acid oxidase, and an Aminco fluoromicrophotometer with a CS 7-60 primary filter and a 47B, 2A combination secondary filter.The substituted agarose supports were prepared according to Cuatrecasas (7) with cyanogen bromide. The extent of coupling was determined from amino-acid analyses of hydrolysates of the support material, and coupling efficiencies of 5-6% were normally obtained. Chromatographic columns were packed with either bovine-serum albumin linked directly to the agarose beads (bovine-serum albumin-agarose), bovineserum albumin linked to the agarose beads by an ethylenediamine-succinic acid leash (bovine-serum albumin-succinoylaminoethyl-agarose), or defatted bovine-serum albumin linked to the agarose beads by the same leash (defatted bovine-serum albumin-succinoylaminoethyl-agarose). Control columns were packed with agarose or leashed agarose (no bovine-serum albumin) as appropriate. RESULTSPreliminary experiments in which bovine-serum albuminagarose columns were used for chromatography of DLtryptophan indicated that there was some resolution of the DI,-tryptophan on these columns. However, these columns did not give reproducible results, due to the fact that the column material seemed to be altered during regeneration. In contrast, chromatography of DL-tryptophan on either of the two leashed column materials was reproducible, and hence these column materials were used in...

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“…Their results show that partial resolution of several amino acids is possible on such a sorbent. 8 In this paper, we report the preparation and the chemical properties of asymmetric sorbents similar to those prepared by Davankov and Vesa. The aim of this work was to elucidate the effect of certain parameters on the exchange capacities of the two series of asymmetric sorbents obtained from copper ions complexation of a-amino acids linked to chloromethylated or chlorosulfonated polystyrene:…”

Section: Introductionmentioning

confidence: 92%

“…In the first step, chloromethylated polystyrene was treated with dimethyl sulfide in a waterisopropanol mixture following a preparation of sulfonium derivatives outlined by Snyder et a1. 8 The conversion rate is shown in Figure 2. It is apparent that more than 80% of chloromethyl groups have reacted after 24 hr.…”

Section: Attachment Of A-amino Acid To Chloromethylated Polystyrenementioning

confidence: 99%

Synthesis of copper(II) complexes of asymmetric resins prepared by attachment of α-amino acids to crosslinked polystyrene

Petit¹,

Jozefonvicz²

1977

J. Appl. Polym. Sci.

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SynopsisIn order to use ligand exchange resins for chromatographic resolution of racemic compounds, two series of asymmetric sorbents were prepared by attachment of various optically active a-amino acids onto crosslinked polystyrene. Chloromethylated and chlorosulfonated styrene-divinylbenzene copolymers were prepared and then treated with a-amino acids. Results show that reaction of aamino acids with polystyrene could be carried to a substitution of 15% to 40% of the aromatic rings depending on many parameters. Stable copper(I1) complexes of the asymmetric resins were prepared. Potentiometric methods were adapted to the case of insoluble materials such as resins. These methods indicate that bis-chelate complexes are formed.

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Partial resolution of amino acids by column chromatography on a polystyrene resin containing an optically active copper(II) complex

Cited by 83 publications

References 0 publications

Solvent Extraction of a Chiral Ion-Pair between Some Cinchona Alkaloids and Acid Derivatives of Camphor

Solvent Extraction of a Chiral Ion-Pair between Some Cinchona Alkaloids and Acid Derivatives of Camphor

Resolution of DL-Tryptophan by Affinity Chromatography on Bovine-Serum Albumin-Agarose Columns

Synthesis of copper(II) complexes of asymmetric resins prepared by attachment of α-amino acids to crosslinked polystyrene

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