P -tartaric

Iuliana E. Deprez, B. P. Tartar, Andre L. Versatile Acylation of V-Nucleo-philes Using a New Polymer-Supported 1 -Hydroxybenzotriazole Derivative, Pop, J. Org. Chem. 1997, 62, 2594. 

The submitters used u.s.p. tartaric acid. The checkers used the Eastman Kodak Company acid, m.p. 169-171°. 

De Weille JR, Schweitz H, Macs P, Tartar A, Lazdunski M (1991) Proc Natl Acad Sci USA 88 2437... 

The designation chiral pool was introduced to denote an available source of enan-tiomerically pure natural products. These include the (S)-amino acids as well as (S)-lactic acid, (S)-malic acid, (P,P)-tartaric acid, and p-D-glucose. How the knowledge of their chirality can be utilized for asymmetric syntheses is demonstrated by the chiral auxiliaries (S)- and (J )-l-amino-2-(methoxymethyl)pyrrolidine developed by Enders and abbreviated as SAMP (15) and RAMP [237]. They are conveniently synthesized from (S)-or (R)-proline [238]. 

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. 

CHjCOCOOH. A colourless liquid with an odour resembling that of ethanoic acid, m.p. 13 C, b.p. 65 C/lOmm. It is an intermediate in the breakdown of sugars to alcohol by yeast. Prepared by distilling tartaric acid with potassium hydrogen sulphate. Tends 10 polymerize to a solid (m.p. 92 C). Oxidized to oxalic acid or ethanoic acid. Reduced to ( + )-Iactic acid. 

Racemic acid, ( )-tartaric acid, is a compound of the two active forms. M.p. 273 C (with IHjO), m.p. 205°C (anhydrous). Less soluble in water than (-t-)-tartaric acid. Formed, together with mesotartaric acid, by boiling (4-)-tartaric acid with 30% NaOH solution, or by oxidation of fumaric acid. Potassium hydrogen racemate is very insoluble. 

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,... 

Acetophenone similarly gives an oxime, CHjCCgHjlCtNOH, of m.p. 59° owing to its lower m.p. and its greater solubility in most liquids, it is not as suitable as the phenylhydrazone for characterising the ketone. Its chief use is for the preparation of 1-phenyl-ethylamine, CHjCCgHslCHNHj, which can be readily obtained by the reduction of the oxime or by the Leuckart reaction (p. 223), and which can then be resolved by d-tartaric acid and /-malic acid into optically active forms. The optically active amine is frequently used in turn for the resolution of racemic acids. 

The purified commercial di-n-butyl d-tartrate, m.p. 22°, may be used. It may be prepared by using the procedure described under i o-propyl lactate (Section 111,102). Place a mixture of 75 g. of d-tartaric acid, 10 g. of Zeo-Karb 225/H, 110 g. (136 ml.) of redistilled n-butyl alcohol and 150 ml. of sodium-dried benzene in a 1-litre three-necked flask equipped with a mercury-sealed stirrer, a double surface condenser and an automatic water separator (see Fig. Ill, 126,1). Reflux the mixture with stirring for 10 hours about 21 ml. of water collect in the water separator. FUter off the ion-exchange resin at the pump and wash it with two 30-40 ml. portions of hot benzene. Wash the combined filtrate and washings with two 75 ml. portions of saturated sodium bicarbonate solution, followed by lOu ml. of water, and dry over anhydrous magnesium sulphate. Remove the benzene by distillation under reduced pressure (water pump) and finally distil the residue. Collect the di-n-butyl d-tartrate at 150°/1 5 mm. The yield is 90 g. 

Several structures of the transition state have been proposed (I. D. Williams, 1984 K. A. Jorgensen, 1987 E.J. Corey, 1990 C S. Takano, 1991). They are compatible with most data, such as the observed stereoselectivity, NMR measuiements (M.O. Finn, 1983), and X-ray structures of titanium complexes with tartaric acid derivatives (I.D. Williams, 1984). The models, e. g., Jorgensen s and Corey s, are, however, not compatible with each other. One may predict that there is no single dominant Sharpless transition state (as has been found in the similar case of the Wittig reaction see p. 29f.). 

Tartar emetic was the subject of controversy for many years, and a variety of iacorrect stmctures were proposed. In 1966, x-ray crystallography showed that tartar emetic contains two antimony(III) atoms bridged by two tetranegative D-tartrate residues acting as double bidentate ligands to form dipotassium bis[D-p.-(2,3-dihydroxybutanedioato)]diantimonate [28300-74-5] (41). 

By a modified Bischler-Napieralsky reaction, 6 -nitrophenylaceto-jS-3 4-methylenedioxyphenylethylamide, resulting from the condensation of -3 4-methylenedioxyphenylethylamine with 2-nitrophenylacetyl chloride, was converted into 6 nitro-l-benzyl-6 7-methylenedioxy-3 4-dihydroisoquinoline. The methiodide of the latter was reduced with zinc and hydrochloric acid to 6 -amino-l-benzyl-2-methyl-6 7-methylenedioxy-1 2 3 4-tetrahydro/soquinoline dihydrochloride, which by the Pschorr ring-closure reaction, produced dZ-roemerine (IV, p. 317), m.p. 85-7°. By treatment in succession with d- and Z-tartaric acids, the dZ-base was resolved into Z- and tZ-forms. Synthetic Z-roemerine is dimorphic, m.p. 85-7° and 102°, and has [aju — 79-9° (EtOH), these constants being in good agreement with those of the natural base. 

The dl-pukateine methyl ether obtained in small yield in the analogous synthesis was isolated as the hydriodide and resolved by the successive use of d- and 1-tartaric acids into the 1-base, m.p. 136°, [a]ff° — 252° (EtOH), identical with the methyl ether of pukateine, and the d-base, m.p. 136°, [a] " -f 256-4° (EtOH). 

Hoshino and Kobayashi (1933) have also described the resolution of di-eserethole by crystallising the mixed d-hydrogen tartrates from alcohol, when d-eserethole d-hydrogen tartrate [m.p. 173-4°, [a]D ° + 113° (HgO) ] separated first. The base recovered from the mother liquors yielded with 1-tartaric acid, l-ha.se i-hydrogen tartrate (m.p. 173-4°, [ajj, — 113°). The active picrates had m.p. 133-6° and the di-picrate m.p. 132°. 

Add calcium chloride and stir with a glass rod. A crystalline precipitate of calcium tartrate, C.,H40(,Cad-4H20, is formed u hich dissolves in acetic acid and caustic alkalis. Repeat the fniegoing test, but add a few drojts of acetic acid before the calcium chloride. There is no precipitate. Calcium sulphate also gives no precipitate with tartaric acid or neutial tartrates, ( compare reactions for OKalic acid, p. 100). 

Tile tartaric acid is finely powdered and mi.Ked with half the above quantity (80 c.c.) of absolute alcohol. The mixture is heated on the water-bath with upright condenser until dissolved. The flask is immersed in cold water, and the well-cooled solution saturated with dry hydrochloric acid gas (prepared in the usual way by dropping cone, sulphuric acid into cone, hydiochloric acid, see Fig. 65, p. 93). After standing for an... 

The ( (inversion of active tartaric acid into the inactive forms is known. s nwe mi Million, Aw< according to Winther is effected by the uiU uhangc ol the gi-oujis round each asymmetric carbon atom successively so that p.art of the active acid is fiisl con-wiled into luesotiut.nit acid, uliidi then passes into the laevo ariety,... 

Sodium (and potassium) tetrathionate, M2S4O5, can be made by oxidation of thiosulfate by I2 (p. 714) and the free acid liberated (in aqueous solution) by addition of the stoichiometric amount of tartaric acid. 

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