Synthesis of Crown Ethers from (+)-Tartaric Acid : Improved Procedures

Anantanarayan, Ashok; Carmicheal, V. A.; Dutton, Philip J.; Fyles, Thomas M.; Pitre, M. J.

doi:10.1080/00397918608057199

Cited by 11 publications

(5 citation statements)

References 6 publications

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“…Partial hydrogenolysis of the dibenzyl ether gave a mixture from which the desired 5 could be isolated by a solvent extraction sequence. A survey of other bases and reaction conditions eventually revealed that the use of one equivalent of sodium hydride with 4, followed by excess benzyl bromide, produced 5 cleanly without loss of chiral integrity (22,24). The subsequent coupling of 5 with the tetrahydropyranyl ether of 2-bromoethanol, followed by hydrolysis of the Thp ether 6 gave the alcohol 7 as anticipated (23).…”

Section: Synthesis Of Ligandsmentioning

confidence: 99%

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Synthesis and metal ion complexation behavior of polycarboxylate 18-crown-6 ethers derived from tartaric acid

Dutton¹,

Fyles²,

McDermid³

1988

Can. J. Chem.

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. Can. J. Chem. 66, 1097 (1988). The metal ion complexation behavior of four 18-crown-6 ethers derived from (+)-and meso-tartaric acid is examined. Preparations of a meso-crown ether diacid and of a crown ether hexacid from three units of (+)-tartaric acid are described. Acidity constants and stability constants for complexation of metal cations in aqueous solution were determined by potentiometric titration. The complexes are substantially stabilized by favourable electrostatic interactions and are of similar stability to complexes of cryptands and EDTA. The complexation behavior of the series can be rationalized in terms of electrostatic interactions, direct coordination of the cations by at least one carboxylate from the crown ether periphery, and rigidification of the ligands as the anionic charge increases. Distributions of charge influence the relative stability of isomeric complexes. Highly charged polycarboxylate crown ethers are effective, but relatively unselective, cation complexing agents for a range of cations. The complexes are stable to pH 3 and the ligands can be used as simultaneous pH and metal ion buffers. The underlying theme in the complexation chemistry of 18C6 prefer an ideal D3d symmetry (1 8). Thus, both RR1 8C6A2 macrocycles, is the control of complex formation by control of and 18C6A4 are incapable of symmetrically interacting with a ligand structure through synthesis ( l , 2 ) . From this perspective, bound cation, either by direct contact or by indirect coulombic crown ethers derived from (+)-tartaric acid possess a number of attraction without some distortions of the macrocycle from appealing features as frameworks for the construction of specific complexing agents. Firstly, the carboxyl groups provide an easy synthetic entry to a wide range of derivatives (3-7). Secondly, the tartaric acid units show a strong conformational preference for an anti disposition of the carboxylates and other carboxylate derived groups (8-12). This limits overall conformational flexibility (8,11,12) and leads to well-defined conformations in which the carboxylate derived groups lie axial to the plane of the macrocycle (8-12). Lateral interactions between substituent groups and bound substrates are thus favored (3,4,13,14). Finally, the presence of charged groups on the macrocyclic periphery leads to markedly enhanced cation complexation relative to uncharged ligands of similar structure (3,8,12). This is primarily a result of a favorable electrostatic interaction between the anionic ligand and the complexed cation (5,8).Additional effects may be important. The carboxylates could act as additional ligating sites in a fashion similar to the neutral donor arms of lariat ethers (15,16). Evidence from infrared and nuclear magnetic resonance spectroscopy (12), from electron spin resonance spectroscopy (1 I), and from analysis of stability constant data (12,17) suggests that direct and cooperative carboxylate-cation interactions occur, especially with small cations in solvents of moderate polarity. Such contac...

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Section: Synthesis Of Ligandsmentioning

confidence: 99%

“…The syntheses of RR18C6A2 and 18C6A4 have been reported (8,21,22); the syntheses of RS18C6A2 and 18C6A6 follow directly from previous methods (Fig. 2).…”

Section: Synthesis Of Ligandsmentioning

confidence: 99%

Synthesis and metal ion complexation behavior of polycarboxylate 18-crown-6 ethers derived from tartaric acid

Dutton¹,

Fyles²,

McDermid³

1988

Can. J. Chem.

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“…31) and 1-{[5-(1,2-dithiolan-3-yl)pentanoyl]oxy}-2,5-pyrrolidinedione, 32 were of commercially available purity, and used without further purication. 31) and 1-{[5-(1,2-dithiolan-3-yl)pentanoyl]oxy}-2,5-pyrrolidinedione, 32 were of commercially available purity, and used without further purication.…”

Section: Methodsmentioning

confidence: 99%

“…All chemicals for the preparation of optically active crown ether-modied tips, except for 2 (ref. 31) and 1-{[5-(1,2-dithiolan-3-yl)pentanoyl]oxy}-2,5-pyrrolidinedione, 32 were of commercially available purity, and used without further purication. Also, 3 was obtained from cysteine methyl ester chloride salt by anion exchange.…”

Section: Methodsmentioning

confidence: 99%

Single-molecule force spectroscopic study on chiral recognition of cysteine derivatives immobilized on a gold substrate by using AFM tips chemically modified with optically active crown ethers

et al. 2014

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The chiral recognition of cysteine derivatives immobilized on a gold substrate using atomic force microscopy (AFM) tips chemically modified with optically active crown ethers was quantitatively investigated with single-molecule force spectroscopy (SMFS). Interestingly, the chiral recognition ability of the optically active crown ether-modified tip was entirely opposite to that of its optical isomermodified tip. The difference of rupture forces for the chiral recognition was determined to be about 40 pN under our experimental conditions. ; Tel: +81 73 457 8254 † Electronic supplementary information (ESI) available: Preparation of crown ether-unmodied tip, representative force-extension curve except for the stretching of a single chain, representative force-extension curves for the other combinations of tips and substrates, force-extension curve using (R,R,R,R)-1-modied tip and (S)-3-modied substrate in the presence of KSCN, force-extension curve using crown ether-unmodied tip and (S)-3-modied substrate, and typical force-extension curve badly tting with WLC model plot. See

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“…The the ligand structure. Nowhere is this more evident than in the meso-diacid crown ether was an ineffective cation-complexing numerous macrocycles derived from R,R-(+)-tartaric acid (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16). The tartaric acid units exhibit a strong preference for an anti disposition, resulting in well-defined conformations in solution (4,(6)(7)(8)13) and in the solid state (17)(18)(19).…”

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confidence: 99%

Polycarboxylate crown ethers from meso-tartaric acid

Fronczek¹,

Gandour²,

Fyles³

et al. 1991

Can. J. Chem.

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The synthesis of crown ethers derived from meso-tartaric acid was investigated. The sodium salt of the bis(dimethy1amide) of meso-tartaric acid reacted with diethylene glycol ditosylate to give a mixture of 18-crown-6 tetraamide and 27-crown-9 hexaamide crown ethers. ' The 2R,3S,1 IS, 12R 18-crown-6 isomer crystallized in triclinic space group P1 (a = 7.557(2), b = 8.866(2), c = 10.4133(13) A, a = 94.13(2). P = 95.86(2), y = 99.26(2)", R = 0.040 for 2090 observed of 3129 unique reflections). The structures of the remaining products were then assigned from the NMR spectra. The solution conformations of the amide crown ethers were examined by NMR, and provide a rationale for the product distribution obtained. One of the 18-crown-6 isomers and a mixture of the two 27-crown-9 isomers were hydrolyzed to the respective crown ether carboxylic acids, and the stability constants for complexation of cations were determined by potentiometric titration. The meso tetra-and hexacarboxylates are remarkably nonselective and inefficient cation complexing agents, compared to related crown ethers from R,R-(+)-tartaric acid, due to the unfavorable conformational control exerted by the tartaro units.Key words: crown ether synthesis, complexation, crown ether conformation, meso-tartaric acid, crystal structure. On a rCalisC des synthkses d'Cthers couronnes dCrivCs de l'acide miso-tartrique. On a fait rCagir le sel de sodium du bis-dimkthylamide de l'acide mbo-tartrique avec le ditosylate du diCthylkneglyco1 et on a obtenu un mClange des Cthers 18-couronne-6 tCtr_amide et 27-courone-9 hexamide. L'isomkre 2R,3S,l lS,12R de 1'Cther 18-couronne-6 cristallise dans le grouped'espace P1 (a = 7,557(2), b = 8,866(2) et c = 10,4133(13) A, a = 94,13(2), P = 95,86(2) et y = 99,26(2)'; R = 0,040 pour 2090 observCes k partir de 3129 rCflexions uniques). On a attribuC les autres structures sur la base de leurs spectres RMN. En se basant sur la RMN, on a examink les conformations en solution de l'amide des Cthers couronnes et on a ainsi obtenu une explication pour la distribution des produits. On a hydrolysC un des isomkres de 1'Cther 18-couronne-6 ainsi qu'un melange de deux isomtres de 1'Cther 27-couronne-9 et on a ainsi obtenu les acides correspondants; faisant appel A un titrage potentiomCtrique, on a dCtermin6 leurs constantes de stabilitC pour la complexation de cations. ComparCs aux composts correspondants issus de I'acide R,R-(+)-tartrique, les tttra-et hexa-carboxylates m6so sont des agents complexants de cations remarquablement inefficaces et non-stlectifs; cet propriCtC est le rksultat d'un contr6le conformationnel non favorable exercC par les unites tartriques.

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Synthesis of Crown Ethers from (+)-Tartaric Acid : Improved Procedures

Cited by 11 publications

References 6 publications

Synthesis and metal ion complexation behavior of polycarboxylate 18-crown-6 ethers derived from tartaric acid

Synthesis and metal ion complexation behavior of polycarboxylate 18-crown-6 ethers derived from tartaric acid

Single-molecule force spectroscopic study on chiral recognition of cysteine derivatives immobilized on a gold substrate by using AFM tips chemically modified with optically active crown ethers

Polycarboxylate crown ethers from meso-tartaric acid

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