Tartaric Acid Utilization

Among the many species and strains of LAB, only Lactobacillus brevis (heterofermenter) and Lactobacillus plantarum (homofermenter) have been identified as being able to utilize L(+)-tartaric acid (Krumperman and Vaughn, 1966). As described by Radler and Yannissis (1972), L. brevis converts tartaric first to oxaloacetic acid. Subsequently, a portion of the intermediate is decarboxylated, yielding acetic acid and CO2 the remainder is reduced and dehydrated to succinic acid see Fig. 1-12A. By comparison, L. plantarum decarboxylates oxaloacetic acid to pyruvic acid, which is subsequently reduced to lactic acid as well as decarboxylated to acetic acid (Radler and Yannissis, 1972) see Fig. 1-13. 

Reduction of fructose (or fructose-6-phosphate) by heterofermentative lac-tobacilli yields mannitol. In the process, NADH is reoxidized. Reoxidation of the coenzyme permits the bacteria to produce acetate from acetyl-phosphate (rather than regenerate oxidized coenzyme by reduction to ethanol) and, thus, produce an additional ATP. 

Mannitol salt formation is also used as a laboratory diagnostic test for the separation of homofermenters (which do not reduce fructose in formation of mannitol) from heterofermenters, which utilize the pathway described above. From the winemaker s perspective, the importance of mannitol formation, by itself, is uncertain except to increase the potential for acetic acid production. Sponholz (1993) reports that it is associated with bacterially mediated deterioration in high-pH sweet wines. He concludes that the best technique for the prevention is acidulation, whereby the pH is lowered to the point ( 3.5) at which the likelihood of growth of most spoilage lactics is precluded. 

In low-acid wines, the growth of pediococci may result in formation of extracellular dextrins. Referred to as ropiness, the defect is detected as increased viscosity and oiliness. Ropiness usually begins in the bottom of cooperage and eventually envelopes the container. Although generally associated with the activity of Pediococcus sp. in high-pH, low-acid sweet wines, Leuconostoc sp. have also been implicated (Mayer, 1974). 

Red wines are reported to be found to suffer from this defect more frequently than whites. This most likely is the result of the inherent bitter 

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T. Lowitz Decolorization of tartaric acid utilizing charcoal 1776-1778... 

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. 

The retrosynthetic analysis presented in Scheme 6 (for 1, 2, and 16-19) focuses on these symmetry elements, and leads to the design of a strategy that utilizes the readily available enantiomers of xylose and tartaric acid as starting materials and/or chiral auxiliaries to secure optically active materials.14 Thus by following the indicated disconnections in Scheme 6, the initially generated key intermediates 16-19 can be traced to epoxide 23 (16,19 =>23),... 

Simultaneous determination of both cations and anions in acid rain has been achieved using a portable conductimetric ion-exclusion cation-exchange chromatographic analyzer.14 This system utilized the poly(meth-ylmethacrylate)-based weak acid cation exchange resin TSK-Gel OA-PAK-A, (Tosoh , Tokyo, Japan) with an eluent of tartaric acid-methanol-water. All of the desired species, 3 anions and 5 cations, were separated in less than 30 minutes detection limits were on the order of 10 ppb. Simultaneous determination of nitrate, phosphate, and ammonium ions in wastewater has been reported utilizing isocratic IEC followed by sequential flow injection analysis.9 The ammonium cations were detected by colorimetry, while the anions were measured by conductivity. These determinations could be done with a single injection and the run time was under 9 minutes. 

Biosyntheses of hexuronic acids and L-ascorbic acid in plants and animals are closely related. Hexuronic acids, L-ascorbic acid, and L-tartaric acid (a possible precursor of dihydroxyfumaric acid) commonly occur together in plants. If a rat is given chloretone (an antispasmodic), both L-ascorbic acid and D-glucuronic acid are excreted in increased quantity.244 Unlike humans, rats can synthesize their own vitamin C, and are therefore independent of outside sources. Here, D-glucose and D-galactose can be utilized, but not D-mannose. 

Dipolar cycloaddition reactions are of main interest in nitrile oxide chemistry. Recently, reviews and chapters in monographs appeared, which are devoted to individual aspects of these reactions. First of all, problems of asymmetric reactions of nitrile oxides (130, 131), including particular aspects, such as asymmetric metal-catalyzed 1,3-dipolar cycloaddition reactions (132, 133), development of new asymmetric reactions utilizing tartaric acid esters as chiral auxiliaries (134), and stereoselective intramolecular 1,3-dipolar cycloadditions (135) should be mentioned. Other problems considered are polymer-supported 1,3-dipolar cycloaddition reactions, important, in particular, for combinatorial chemistry... 

More recently, Szdntay and co-workers (232) succeeded in performing the enantioselective total synthesis of both natural and unnatural antipodes of yohimbine and -yohimbine. Utilizing second-order asymmetric induction, either the levorotatory or dextrorotatory antipode of key tetracyclic intermediate 400 could be obtained by the use of (—)- or (+)-tartaric acid, respectively. 

Lumyong S etal.. Endophytes fromThailand Isolation and screening for tartaric acid and ohgosaccharide production, BiotechnolSust Util Biol Res Tropics 12 394— 403, 1998. 

Isoflavone derivatives along with nonvolatile components in soy sauce were also analyzed by gradient reversed-phase HPLC. This HPLC profile of soy sauce was further utilized by a pattern recognition program to understand the quality differences of soy sauces (132), and three isoflavone derivatives (esters of tartaric acid with daidzein, genistein, and 8-hydroxygenistein) were found to contribute significantly to the differentiation in fermented soy sauce. Fermented... 

In other diethylzinc studies, a neural network modelling approach has been used to predict the utility of new enantioselective catalysts,222 norephedrine-derived ligands with three stereogenic centres catalyse enantioselective addition to aldehydes and to chalcones,223 and a chiral sulfonamide ligand based on tartaric acid gives good ees in addition to both aldehydes and ketones.224... 

The complex of tartaric acid and antimony (emetic) was described three centuries ago. Nevertheless, the structure of this compound has been elucidated these last fifteen years by X-ray diffraction ( 1 ). In fact, emetic presents a binuclear cyclic structure. Many authors mentioned similar complex with transition metals (vanadium (2), chromium (3)) or metalloids (arsenic (4), bismuth (5)). Emetic with phosphorus was not mentioned. Nevertheless, tartaric acid or alkyl tartrates has been utilized in phosphorus chemistry tartaric acid reacts with trialkyl phosphites giving heterocyclic phosphites (6). Starting from alkyl tartrates, we prepared spirophosphoranes with a P-H bond and sixco-ordinated compounds (7). With unprotected tartaric acid, many possibilities appear condensation as a diol, as a di(oc-hydro-xyacid), or even as a 8-hydroxyacid. 

In addition to the use of malo-lactic fermentation in red wines, it also has been tried in V. vinifera cultivar Chardonnay. In the experiments known to the author, the use of the malo-lactic fermentation in Chardonnay has not proved successful from a sensory point of view. In general, the rise in pH was too great and the buffering capacity of the wine too great to permit adequate adjustment with tartaric acid. However, this work is continuing in conjunction with a number of variations in the local viticultural practices to produce Chardonnay of a lower total acidity. In addition to the use of malo-lactic fermentation for the reduction of the acidity, considerable work has been done in Washington on the use of acid reduction with calcium. Both calcium carbonate and the double salt precipitation, as described by Steele (23, 24), have been utilized. Some very significant successes have been achieved, particularly with the double salt method. 

A wide variety of substituted y-butyrolactones can be prepared directly from olefins and aliphatic carboxylic acids by treatment with manganic acetate. This procedure is illustrated in the preparation of 7-( -OCTYL)-y-BUTYROLACTONE. Methods for the synthesis of chiral molecules are presently the target of intensive investigation. One such general method developed recently is the employment of certain chiral solvents as auxiliary agents in asymmetric synthesis. The preparation of (S.SM+H, 4-BIS(DIMETHYLAMINO)-2,3-DIMETHOXY-BUTANE FROM TARTARIC ACID DIETHYL ESTER provides a detailed procedure for the production of this useful chiral media an example of its utility in the synthesis of (+)-(/ )-l-PHENYL-l-PEN-TANOL from benzaldehyde and butyllithium is provided. 

Oxyacids, like citric or tartaric acids, and polyols, like saccharose are also used, mainly as masking agents, in qualitative analysis. The action of some specific reagents, like oc-a -bipyridyl for iron(II) and dimethylglyoxime for nickel(II), is also based on the formation of chelate complexes. In quantitative analysis the formation of chelates is frequently utilized (complexometric titrations). ... 

Preparative Methods racemic a-methylbenzylamine has been resolved utilizing chiral acids such as tartaric acid and (S)-(—)-carbamalactic acid, among others. Several stereospecific syntheses have been reported. ... 

Conversion of L-ascorbic acid to tartaric acid in the grape was limited to certain stages of development (Tables I and II). Leaves detached from the tip of the vine or the position opposite the flower cluster prior to anthesis (or at anthesis) readily utilized ascorbic acid for tartaric acid... 

Inomata, K., Ukaji, Y. Development of new asymmetric reactions utilizing tartaric acid ester as a chiral auxiliary design of an efficient chiral dinucleating system. Rev. on Heteroa. Chem. 1998, 18, 119-140. 

Utilization of the single hydrogen bond between pyridine and benzoic acids in SLCP s has been a source of inspiration for other groups in the development of main-chain supramolecular polymers based on diacids and dipyridines.53-56 Supramolecular rod-coil polymers have been developed by assembly of 4,4 -bipyridines and telechelic polypropylene oxide with benzoic acid end-groups, which show highly ordered liquid crystalline phases.57 The use of tartaric acid derivatives in combination with bipyridine units resulted in the formation of hydrogen-bonded, chiral main-chain LCP s, as has been shown by circular dichroism measurements, optical microscopy, and X-ray data.58,59... 

New asymmetric reactions utilizing tartaric acid esters as chiral auxiliaries (formation of N- and A,0-heteroeyeles by nucleophilic addition of iminoderivatives or 1,3-dipolar cycloaddition of nitrile oxides and nitrones) 03SL1075. 

Hoffmann-LaRoche has developed a process that utilizes R,R-tartaric acid/ NaBr modified Raney nickel catalyst in the asymmetric hydrogenation of 60 to give 61 in 100% yield and 90-92% ee (6-100-kg scale) for the synthesis of the intermediate of tetrahydrolipstatin (62), a pancreatic lipase inhibitor (Scheme 22) [5]. 

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