Of tartar

CsHsO. Colourless, crystalline solid m.p. 115 C. Prepared by the dry distillation of tartaric acid or by reduction of itaconic or cilra-conic acids. Forms an anhydride when heated to 200"C. 

Tartaric acid is noteworthy for a) the excellent way in which the majority of its salts Crystallise, and h) the frequent occurrence of salts having mixed cations. Examples of the latter are sodium potassium tartrate (or Rochelle salt), C4H40 NaK, used for the preparation of Fehling s solution (p. 525), sodium ammonium tartrate, C4H OaNaNH4, used by Pasteur for his early optical resolution experiments, and potassium antimonyl tartrate (or Tartar Emetic), C4H404K(Sb0). The latter is prepared by boiling a solution of potassium hydrogen tartrate (or cream of tartar ) with antimony trioxide,... 

Tartar emetic, as its name indicates, can be used medicinally to cause vomiting. For the preparation of tartar emetic intended for medicinal use, pure antimony trioxide, free (in particular) from traces of arsenic, must of course be employed. 

Sulphuric add test. Warm 0 5 g. of tartaric acid or a tartrate with i ml. of cone. H2SO4. Heavy charring takes place, CO and SOj being evolved. 

Fenton s reagent. To a solution of tartaric acid or a tartrate add 1 drop of freshly prepared ferrous sulphate solution, i drop of hydrogen peroxide solution and then excess of NaOH solution an intense violet coloration is produced, due to the ferric salt of dihydroxyfumaric acid, HOOC C(OH) C(OH)COOH. 

Pyruvic acid is conveniently prepared by the distillation of tartaric acid with a dehydrating agent, such as potassium bisulphate ... 

The separation of a racemic mixture into its enantiomeric components is termed resolution The first resolution that of tartaric acid was carried out by Louis Pasteur m 1848 Tartaric acid IS a byproduct of wine making and is almost always found as its dextrorotatory 2R 3R stereoisomer shown here m a perspective drawing and m a Fischer projection... 

Occasionally an optically inactive sample of tartaric acid was obtained Pasteur noticed that the sodium ammonium salt of optically inactive tartaric acid was a mixture of two mirror image crystal forms With microscope and tweezers Pasteur carefully sep arated the two He found that one kind of crystal (m aqueous solution) was dextrorota tory whereas the mirror image crystals rotated the plane of polarized light an equal amount but were levorotatory... 

Although Pasteur was unable to provide a structural explanation—that had to wait for van t Hoff and Le Bel a quarter of a century later—he correctly deduced that the enantiomeric quality of the crystals was the result of enantiomeric molecules The rare form of tartanc acid was optically inactive because it contained equal amounts of (+) tartaric acid and (—) tartaric acid It had earlier been called racemic acid (from Latin racemus meaning a bunch of grapes ) a name that subsequently gave rise to our pres ent term for an equal mixture of enantiomers... 

Could the unusual optically inactive form of tartaric acid stud... 

Multiple Chiral Centers. The number of stereoisomers increases rapidly with an increase in the number of chiral centers in a molecule. A molecule possessing two chiral atoms should have four optical isomers, that is, four structures consisting of two pairs of enantiomers. However, if a compound has two chiral centers but both centers have the same four substituents attached, the total number of isomers is three rather than four. One isomer of such a compound is not chiral because it is identical with its mirror image it has an internal mirror plane. This is an example of a diaster-eomer. The achiral structure is denoted as a meso compound. Diastereomers have different physical and chemical properties from the optically active enantiomers. Recognition of a plane of symmetry is usually the easiest way to detect a meso compound. The stereoisomers of tartaric acid are examples of compounds with multiple chiral centers (see Fig. 1.14), and one of its isomers is a meso compound. 

Stake s reagent dissolve 30 g of ferrous sulfate and 20 g of tartaric acid in water and dilute to 1 liter. When required for use, add strong ammonia until the precipitate first formed is dissolved. 

Tartaric acid [526-83-0] (2,3-dihydroxybutanedioic acid, 2,3-dihydroxysuccinic acid), C H O, is a dihydroxy dicarboxyhc acid with two chiral centers. It exists as the dextro- and levorotatory acid the meso form (which is inactive owing to internal compensation), and the racemic mixture (which is commonly known as racemic acid). The commercial product in the United States is the natural, dextrorotatory form, (R-R, R )-tartaric acid (L(+)-tartaric acid) [87-69-4]. This enantiomer occurs in grapes as its acid potassium salt (cream of tartar). In the fermentation of wine (qv), this salt forms deposits in the vats free crystallized tartaric acid was first obtained from such fermentation residues by Scheele in 1769. 

Chemical Properties. The notation used by Chemical Abstracts to reflect the configuration of tartaric acid is as follows (R-R, R )-tartaric acid [S7-69A-] (4) (S-R, R )-tartaric acid [147-71-7] (5) and y j O-tartaric acid [147-73-9] (6). Racemic acid is an equimolar mixture of the two optically active enantiomers and, hence, like the meso acid, is optically inactive. 

For the production of tartar emetic (antimony potassium tartrate [28300-74-5]), potassium bitartrate [868-14 ] and antimony oxide, Sb202, are added simultaneously to water in a stainless-steel reactor. The reaction mixture is diluted, filtered, and collected in jacketed granulators where crystallization takes place after cooling. Centrihiging, washing, and drying complete the process. 

Economic Aspects. The estimated total worldwide market for tartaric acid is 58,000 t and potassium bitartrate (acid basis) is 20,000 t. The majority of tartaric acid consumption, represented by beverage, food, and pharmaceutical appHcations, is shown in Table 10. Potassium bitartrate (cream of tartar) is primarily used in baking powders and mixes. 

In the United States, prices for tartaric acid have ranged from 1.10 to 6.61/kg since the early 1970s with Httie consistency. The 1993 Hst price of tartaric acid in the United States was 6.50/kg fob plant packaged in 100-lb (45.5-kg) bags (39). Much of the fluctuation is a result of the availabihty of raw materials for production. 

Wine Making. Wine making is one of the principal areas of tartaric acid use. There is a relationship between the size of the grape crop and its tartaric acid content when grapes are pressed. In poor harvest years, the tartaric acid content is low in good harvest years, the tartaric acid content is high. Thus, in poor harvest years, tartaric acid often is added to correct acid deficiencies in wine. 

Cream of tartar is used in baiting powder and in prepared baiting mixes (see Bakery processes and leavening agents). Its limited solubihty at low temperatures inhibits the reaction with bicarbonate until baiting temperature is reached, thus releasing a significant portion of the carbon dioxide at the optimum time. 

Oxidation. Maleic and fumaric acids are oxidized in aqueous solution by ozone [10028-15-6] (qv) (85). Products of the reaction include glyoxyhc acid [298-12-4], oxalic acid [144-62-7], and formic acid [64-18-6], Catalytic oxidation of aqueous maleic acid occurs with hydrogen peroxide [7722-84-1] in the presence of sodium tungstate(VI) [13472-45-2] (86) and sodium molybdate(VI) [7631-95-0] (87). Both catalyst systems avoid formation of tartaric acid [133-37-9] and produce i j -epoxysuccinic acid [16533-72-5] at pH values above 5. The reaction of maleic anhydride and hydrogen peroxide in an inert solvent (methylene chloride [75-09-2]) gives permaleic acid [4565-24-6], HOOC—CH=CH—CO H (88) which is useful in Baeyer-ViUiger reactions. Both maleate and fumarate [142-42-7] are hydroxylated to tartaric acid using an osmium tetroxide [20816-12-0]/io 2LX.e [15454-31 -6] catalyst system (89). 

In the days of alchemy and the phlogiston theory, no system of nomenclature that would be considered logical ia the 1990s was possible. Names were not based on composition, but on historical association, eg, Glauber s salt for sodium sulfate decahydrate and Epsom salt for magnesium sulfate physical characteristics, eg, spirit of wiae for ethanol, oil of vitriol for sulfuric acid, butter of antimony for antimony trichloride, Hver of sulfur for potassium sulfide, and cream of tartar for potassium hydrogen tartrate or physiological behavior, eg, caustic soda for sodium hydroxide. Some of these common or trivial names persist, especially ia the nonchemical Hterature. Such names were a necessity at the time they were iatroduced because the concept of molecular stmcture had not been developed, and even elemental composition was incomplete or iadeterminate for many substances. 

Similar to the hydrolysis of malonates and glutarates, conversion of mesoderivatives of tartaric acid can be accompHshed with Candida glindracea hpase (CCL) and porcine Hver esterase in very good yield (23). Hydrolysis of (3) with esterase gives (+)-(4) with an ee 90.5% in >90% yield. Hydrolysis with hpase results in the formation of ( —)-(4) ee 92.5%, >90% yield). 

The united filtrate is evaporated on the steam bath until the volume amounts to 200 cc., at which point crystals should have already begun to separate from the hot solution. After standing at room temperature for twenty-four hours or longer, the crystals are filtered by suction as free from mother liquor as possible and recrystallized from an equal weight of distilled water (Note 5). The filtrate from this recrystallization is evaporated on the steam bath and the second crop of /-tartaric acid filtered and recrystallized as before. The -yield is 65-75 (32-5-35-5 per cent of the theoretical amount). 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Since chirality is a property of a molecule as a whole, the specific juxtaposition of two or more stereogenic centers in a molecule may result in an achiral molecule. For example, there are three stereoisomers of tartaric acid (2,3-dihydroxybutanedioic acid). Two of these are chiral and optically active but the third is not. 

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