Thiazolidine-4-carboxylic acid

Phenylisocyanate added to a soln. of 620 mg. ethyl sjptro-cholestane-S -thiazoIidine-l -carboxylate, and allowed to stand overnight > 593 mg. N-phenylhydantoin of spiro-cholestane-3,2 -thiazolidine-4 -carboxylic acid. (S. Lieberman, P. Brazeau, and L. B. Hariton, Am. Soc. 70, 3094 (1948).)... 

Cysteine is first dissolved in distilled water which has been freed of oxygen by boiling. Formaldehyde of 30% (w/v) concentration is added while stirring and the temperature of the mixture rises, while the thiazolidine carboxylic acid begins crystallizing. The stirring is continued for 2 hours after which ethyl alcohol of 95% (w/v) concentration Is added to induce further crystallization. The mixture is left to stand for 24 hours at 4°C. The mixture is then filtered with retention of a crude product, which is purified by recrystallization from boiling distilled water. The crystals are then dried at about 40°C. The free acid is then converted to the sodium salt with NaOH. 

Kovacs-Hadady and Kiss [27] studied the chromatographic characteristics of thia-zolidinecarboxylic acid derivatives, formed by reaction of (i>) and (L)-penicillamine with various substituted benzaldehydes and heterocyclic aldehydes in order to evaluate the aldehydes as derivatizing agents for separation of the penicillamine enantiomers. The TLC method of Martens et al. [28] was used. Transformation to thiazolidine carboxylic acids with benzaldehyde and substituted benzaldehydes was not complete, so formaldehyde is still the preferred reagent for separation of the enantiomers. 

Isochem has set up a multipurpose electrochemical unit devoted to organic electrosynthesis. The unit located in Pithiviers (France) [115] is dimensioned for the production of 80 tons a year of cystein derivatives, such as cysteine base salts, carbocysteine, acetylcysteine, and thiazolidin carboxylic acids. 

Dimethyl-3,5-dimethyl-l//,3//-pyrrolo[l,2-r ][l,3]thiazole-6,7-dicarboxylate 399 (R = H) was prepared from cysteine 396 using the method developed of Padwa et al. <1989JOC644>. The thiazolidine carboxylic acid 397 (R = H), obtained by reaction of the cysteine with formaldehyde, was heated in the presence of acetic anhydride and DMAD to give the sulfide 399 by dipolar cycloaddition of the acetylene to the intermediate dipole 398 (Scheme 59) <2002J(P1)1795>. 

Aminothiazoline-4-carboxylic acid 2-lmino-4-thiazolidine-carboxylic acid... 

Similarly, 3-phenyl propionaldehyde gave rise to a 1 1.5 endo/exo mixture of adducts 110 (R = CH2CH2Ph), derived solely from reaction of the awfi-dipole. In an analogous fashion, thiazolidine carboxylic acid (111) also underwent awfi-dipole specific cycloaddition, with A-phenyl maleimide, after initial condensation with... 

Rommelsbacher, in following the concept of Holtz that mammalian alkaloids are formed from chemically reactive biogenic amines and amino acids by reaction with endogenously formed ketonic substrates under physiological conditions, has extended this idea to include indole-3-acetaldehyde. It was found that tryptamine, on incubation with pig brain and bovine brain, but not with liver tissue, formed the thiazolidine carboxylic acid 60 shown in Fig. 20 Ml). 

Resolution of Amino Acids. For the optical resolution of racemic threonine via replacing resolution, (S)-proline was utilized as an optically active cosolute although the structure of the imino acid is different from that of threonine. The same procedure was applied less sucessfully to the resolution of (R,S)-thiazolidine carboxylic acid. ... 

Maier (1973) studied the physical sorption of volatile aroma constituents by foods using IR spectroscopy. He observed that aliphatic aldehydes such as propanal (C.3), hexanal (C.6), acrolein (C.16) were also reacting chemically with some amino compounds, specially with cysteine (formation of thiazolidine carboxylic acids), with other amino acids, with glutathione and with urea. The bound aldehydes are nevertheless, in most cases, released by heating with water, especially during the percolation of the coffee beverage. 

K., Shih, J. C., Seif, L, and Sweedler, J. V., Serotonin catabolism and the formation and fate of 5-hydroxyindole thiazolidine carboxylic acid, J. Biol. Chem., 281, 13463, 2006. 

Cysteine with pyridoxal can also give a thiazolidine carboxylic acid (XXXXVI), (Heyl et al., 1948) ... 

Many antigenic determinants may derive from penicillins but most is known about the benzylpenicilloyl (BPO) determinant, a bifunctional structure comprising a nonpolar phenylacetamide and a polar thiazolidine carboxylic acid end (Levine 1963) (Fig. 4). 

Definition Lysine salt of thiazolidine carboxylic acid Empirical C10H20N3O4S Formula C6H14N2O2 C4H6NO2S Uses Surfactant in cosmetics... 

In the case of cysteine (5) the product obtained is contaminated by cystine and also by thiazolidine carboxylic acid (obtained by reaction of cysteine and formaldehyde, the latter arising from hydrolytic decomposition of acetamidomethanol, see section VI). However, the product could easily be purified by using ion exchange columns. On the other hand, anhydrous conditions should avoid the decomposition of the acetamidomethanol and indeed a reaction using hydrogen fluoride as a solvent results in quantitative yield of the pure product". 

Heterocyclic compounds. Thiazolidine-4-carboxylic acid and 5,6-dimethylthiazolidine-4-car-boxylic acid are formed by formaldehyde condensation from cysteine and penicillamine, respectively. The derivatization of penicillamine has been published (195). Table 14 and Fig. 15 present a summary of these results. The chromatographic characteristics of the thiazolidine carboxylic acids formed by the reaction of D,L-peniciIlamine with various substituted benzaldehydes and heterocyclic aldehydes have also been studied (177). 3-Carboxy-morpholine was separated by Gunther et al. (102). 

NPRO=N-nitrosoproline, NHPRO = N-nitroso-4-hydroxyproline, NHMTCA carboxylic acid, NTCA = N-nitroso-4-thiazolidine carboxylic acid, NMTCA = = N-nitroso-2-(hydroxymethyl)-4-thiazolidine N-nitroso-2-methyl-4-thiazolidine carboxylic acid. ... 

Synonyms Lysine, mono4-thiazolidinecarboxylate 1,3-Thiazolidine4-carboxylic acid Thiazolidine4-carboxylic acid Definition Lysine salt of thiazolidine carboxylic acid Empirical C4H2NO2S Properties M.w. 133.17 Uses Surfactant in cosmetics ManufUDistrib. AK Scientific MP Biomedicals Variati LysolecKhin... 

The simplest and most satisfactory method of preparing arylidene-enamino acid esters is the P-elimination from 2-aryl-4-thiazolidinecarbo-xylic acid esters (40) on treatment with silver carbonate 287A). Arylidene-enamino acid N-hydroxysuccinimide esters were prepared and combined with amino acid esters to yield Schiff bases of dehydro-dipeptides. This elimination reaction of thiazolidine carboxylic acid esters has been applied to prepare the extremely unstable benzyUdene dehydroalanine ester, although it was impossible to isolate it. Nevertheless its existence could be proved without a doubt when the reaction was carried out at 0° in trideuterioacetonitrile solution and was followed by NMR spectrometry. Within one half hour at room temperature the unstable substance started to decompose. 

FIGURE 3.5 Chromatograms on Chiralplate containing the following zones (1)L-5,5-dimethyl-4-thiazolidine carboxylic acid (L-3), (2) D,L-5,5-dimethyl-4-thiazolidine carboxylic acid (d,L-3), (3) D-5,5-dimethyl-4-thiazolidine carboxylic acid (d-3), (4) 3% L-3 in d-3, and (5) 3% d-3 in L-3. (Reprinted from the Macherey-Nagel Application Database. With permission.)... 

In his cephalosporin synthesis methyl levulinate was condensed with cysteine in acidic medium to give a bicyclic thiazolidine. One may rationalize the regioselective formation of this bicycle with the assumption that in the acidic reaction mixture the tMoI group is the only nucleophile present, which can add to the ketone. Intramolecular amide formation from the methyl ester and acid-catalyzed dehydration would then lead to the thiazolidine and y-lactam rings. The stereochemistry at the carboxylic acid a-... 

By virtue of their fused /3-lactam-thiazolidine ring structure, the penicillins behave as acylating agents of a reactivity comparable to carboxylic acid anhydrides (see Section 5.11.2.1). This reactivity is responsible for many of the properties of the penicillins, e.g. difficult isolation due to hydrolytic instability (B-49MI51102), antibacterial activity due to irreversible transpeptidase inhibition (Section 5.11.5.1), and antigen formation via reaction with protein molecules. 

Reactions between A -(l-chloroalkyl)pyridinium chlorides 33 and amino acids in organic solvents have a low synthetic value because of the low solubility of the amine partner. A special protocol has been designed and tested in order to circumvent this drawback. Soon after the preparation of the salt, an aqueous solution of the amino acid was introduced in the reaction medium and the two-phase system obtained was heated under reflux for several hours. However, this was not too successful because sulfur dioxide, evolved during the preparation of the salt, was converted into sulfite that acted as an 5-nucleophile. As a result, A -(l-sulfonatoalkyl)pyridinium betaines such as 53 were obtained (Section IV,B,3) (97BSB383). To avoid the formation of such betaines, the salts 33 were isolated and reacted with an aqueous solution of L-cysteine (80) to afford thiazolidine-4-carboxylic acids hydrochlorides 81 (60-80% yields). 

An example of 1,3-dipolar cycloaddition involving a thiazole dioxide derivative was described (99T(55)201). A-Benzoyl-(R)-thiazolidin-4-carboxylic acid 5,5-dioxide 120 was cyclized to the bicylic mesoionic thiazolo-oxazolium 5,5-dioxide with Ac O and reacted with the imine 121 in DMF... 

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