Tartaric acid derivatives extraction

Kmecz I, Simandi B, Szekely E, Fogassy E. Resolution of N-methylamphetamine enantiomers with tartaric acid derivatives by supercritical fluid extraction. Tetrahedron Asymmetry 2004 15(12) 1841-1845. 

The original commercial source of E was extraction from bovine adrenal glands (5). This was replaced by a synthetic route for E and NE (Eig. 1) similar to the original pubHshed route of synthesis (6). Eriedel-Crafts acylation of catechol [120-80-9] with chloroacetyl chloride yields chloroacetocatechol [99-40-1]. Displacement of the chlorine by methylamine yields the methylamine derivative, adrenalone [99-45-6] which on catalytic reduction yields (+)-epinephrine [329-65-7]. Substitution of ammonia for methylamine in the sequence yields the amino derivative noradrenalone [499-61-6] which on reduction yields (+)-norepinephrine [138-65-8]. The racemic compounds were resolved with (+)-tartaric acid to give the physiologically active (—)-enantiomers. The commercial synthesis of E and related compounds has been reviewed (27). The synthetic route for L-3,4-dihydroxyphenylalanine [59-92-7] (l-DOPA) has been described (28). 

Early examples of enantioselective extractions are the resolution of a-aminoalco-hol salts, such as norephedrine, with lipophilic anions (hexafluorophosphate ion) [184-186] by partition between aqueous and lipophilic phases containing esters of tartaric acid [184-188]. Alkyl derivatives of proline and hydroxyproline with cupric ions showed chiral discrimination abilities for the resolution of neutral amino acid enantiomers in n-butanol/water systems [121, 178, 189-192]. On the other hand, chiral crown ethers are classical selectors utilized for enantioseparations, due to their interesting recognition abilities [171, 178]. However, the large number of steps often required for their synthesis [182] and, consequently, their cost as well as their limited loadability makes them not very suitable for preparative purposes. Examples of ligand-exchange [193] or anion-exchange selectors [183] able to discriminate amino acid derivatives have also been described. 

Reaction with chelating agents. Such reactions have been used primarily for partial dealumination of Y zeolites. In 1968, Kerr (8,21) reported the preparation of aluminum-deficient Y zeolites by extraction of aluminum from the framework with EDTA. Using this method, up to about 50 percent of the aluminum atoms was removed from the zeolite in the form of a water soluble chelate, without any appreciable loss in zeolite crystallinity. Later work (22) has shown that about 80 percent of framework aluminum can be removed with EDTA, while the zeolite maintains about 60 to 70 percent of its initial crystallinity. Beaumont and Barthomeuf (23-25) used acetylacetone and several amino-acid-derived chelating agents for the extraction of aluminum from Y zeolites. Dealumination of Y zeolites with tartaric acid has also been reported (26). A mechanism for the removal of framework aluminum by EDTA has been proposed by Kerr (8). It involves the hydrolysis of Si-O-Al bonds, similar to the scheme in Figure 1A, followed by formation of a soluble chelate between cationic, non-framework aluminum and EDTA. 

One recent study showed that extraction of volatile substances from the wood dropped off sharply after 12 months of aging, though there was high variability between wines, highlighting the influence of such major oenological factors as the tartaric acid content and the potassium content and also the SO2 concentration in the wines, since SO2 can combine with certain furanic derivatives and phenolic aldehydes (Anci n et al. 2004 Ortega-Heras et al. 2007). 

A chemical reaction is carried out between the racemate and an optically active form (either laevo-or dextro-) of a substance capable of reacting with the racemate. This other optically active compound is usually derived from a natural source. To resolve the racemates of amines (or other bases) and alcohols, for example, use may be made of the naturally occurring d-tartaric acid (from wine tartar). The reaction with amines gives salts and esters are formed with alcohols. For the resolution of racemates of acids, use is frequently made of alkaloids such as quinine or stiychnine extracted from plants in which each of these alkaloids is present in an optically active form. The racemate mixture forms two diastereoisomers (compounds that are stereoisomers of each other, but are not enantiomers) of a derivative, with the optically active reagent used. If the... 

Abstract. Crown ethers derived from tartaric acid present a number of interesting features as receptor frameworks and offer a possibility of enhanced metal cation binding due to favorable electrostatic interactions. The synthesis of polycarboxylate crown ethers from tartaric acid is achieved by simple Williamson ether synthesis using thallous ethoxide or sodium hydride as base. Stability constants for the complexation of alkali metal and alkaline earth cations were determined by potentiometric titration. Complexation is dominated by electrostatic interactions but cooperative coordination of the cation by both the crown ether and a carboxylate group is essential to complex stability. Complexes are stable to pH 3 and the ligands can be used as simultaneous proton and metal ion buffers. The low extractibility of the complexes was applied in a membrane transport system which is a formal model of primary active transport. 

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