12-, 15-, and 18-Membered-ring nitrogen-pivot lariat ethers: syntheses, properties, and sodium and ammonium cation binding properties

Schultz, Rose Ann; White, Brandyn; Dishong, Dennis M.; Arnold, Kristin A.; Gokel, George W.

doi:10.1021/ja00309a039

Cited by 203 publications

(82 citation statements)

References 4 publications

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“…[3,[17][18][19][20] A stronger binding of sodium ions by N-substituted aza-15-crown-5 ethers is reported if six oxygen atoms beside the nitrogen atom are present for binding. [21,22] This is in agreement with our findings in the solid state. Two solvent molecules (ethanol) were incorporated into the complex to increase the coordination number of the sodium ion.…”

Section: Resultssupporting

confidence: 93%

New Fluorescent Calix Crown Ethers, Part II: Synthesis and Complex Formation in Solution and the Solid State

Stoll¹,

Brodbeck²,

Wiegmann³

et al. 2008

Eur J Org Chem

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New luminescent 1-aza-15-crown-5 ethers bearing a coumarin unit were synthesised leading to the cavitand-based calix crown ether 9. The solid-state structures of crown ethers 5 and 6 and the solid-state structures of the sodium and potassium iodide complexes of crown ether 5 are presented. The association constants for the complex formation with alkali metal ions in methanol were determined. Only weak complexes were formed (K Na = 286 M -1 , K K = 392 M -1 ). The aza-15-crown-5 ether was attached by a methylene unit to a cavitand to give the new fluorescent calix crown ether 9. The association constants for the sodium and potassium complexes in methanol were investigated as well, and an en-

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Section: Resultssupporting

confidence: 93%

New Fluorescent Calix Crown Ethers, Part II: Synthesis and Complex Formation in Solution and the Solid State

Stoll¹,

Brodbeck²,

Wiegmann³

et al. 2008

Eur J Org Chem

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“…Moreover, the synthesized spacer-chromoionophores provide even better binding properties than the unsubstituted parent aza-crowns. The alkyl side-arm seems to favor the complexation ability as previously reported by other authors for non-chromogenic lariat aza-crown ethers [12][13][14]. In that case, the relationship between crown cavity size and cation diameter becomes clear because aza-15-crown-5 derivatives 19a-c provide with Na + about ten times larger constants than with K + .…”

Section: Discussionsupporting

confidence: 75%

Spacer-chromoionophores - polymethine dye substituted aza-crown ethers with increased complexation ability

Boila‐Göckel¹,

Junék

1999

J. prakt. Chem.

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Chromoionophores are crown ether derivatives, which contain a chromophoric group [1][2][3]. These functional dyes are of a great interest for analytical applications [4,5], especially in medical diagnostics and therapy. A great number of chromo-and also fluoroionophores, starting from aldehydes of N-phenyl-aza-15-crown-5 or N-phenyl-aza-18-crown-6 are described in the literature [6 -11]. Substitution of the aminic H-atom in aza-crowns leads to nitrogen-pivot lariat crowns, and it was shown that alkyl groups increase the binding strength of the metal complexes [12 -14]. The present paper deals with the synthesis of deeply colored polymethine crown ether derivatives and the influence of the electron acceptor properties of the side chain on the complexation, depending upon conjugation of the chromophore with the nitrogen of the aza-crowns. Abstract. Aromatic aldehyde derivatives of N-phenyl-aza-15-crown-5 2, N-phenyl-aza-18-crown-6 8, and benzo-15-crown-5 10 are condensed with malononitrile and 2-amino-1,1,3-tricyano-1-propene to give light yellow to orange colored crown ether derivatives 4, 5a, 9a, 11, and 12. 5a and 9a were acylated with ethyl chloroformate to give the magenta colored dyes 5b and 9b, respectively. By condensation of N-(4-nitrosophenyl)-aza-15-crown-5 3 with 2-amino-1,1,3-tricyano-1-propene the magenta dye 6a is obtained. Acylation of 6a with ethyl chloroformiate leads to the deep blue colored dye 6b. In these derivatives the nitrogen or oxygen atoms of the crown ethers are part of the chro-mophoric system and binding properties are affected. Further chromophoric derivatives of aza-crown ethers are stu-died in which these are separated from the chromophoric moiety by a spacer. N-(ω-chloroalkyl)-N-alkylanilines 14a -c were attached to aza-15-crown-5 13a and aza-18-crown-6 13b to yield the spacer crown ether derivatives 15a -c and 16a -c, respectively. The formylated spacer crown ether derivatives 17a -c and 18b were condensed with 2-amino-1,1,3-tricyano-1-propene to give the orange spacer-chromoionophores 19a -c and 20. In these crown ether derivatives the extended conjugation is interrupted by the spacer and good binding properties are obtained. The complex formation constants of the crown ether derivatives with Na + and K + are determined using 1 H NMR spectroscopy. dimeric malononitrile (2-amino-1,1,3-tricyanopropene), respectively, is a Knoevenagel condensation which occurs under mild conditions using piperidine as catalyst. The yellow colored chromoionophores 4 and 5a, showing UV/Vis absorption maxima at about λ max = 430 nm, are obtained with a quite good yield.13-(4-Nitrosophenyl)-1,4,7,10-tetraoxa-13-azacyclopentadecane 3 was as well prepared according to Dix and Vögtle [6]. With the dimeric malononitrile it afforded with good yield the magenta colored dye 6a (λ max = 524 nm, CH 3 CN).N-Phenyl-aza-18-crown-6 7 was synthesized according to Dix und Vögtle [6], and the corresponding aldehyde 8 similarly to the crown ether aldehyde 2 prepared by Vilsmeier formylation. Formation of side produc...

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“…39 High selectivity over Na + is shown and, 3 also shows little fluorescence sensitivity to pH (from 6.8 to 7.8). The complexes formed with K + are weak (with Kd = 29 mM) but sufficient for monitoring intracellular situations (see below).…”

Section: Mementioning

confidence: 97%

Information gathering and processing with fluorescent molecules

Daly

Ling

Silva

2014

Front. Chem. Sci. Eng.

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12-, 15-, and 18-Membered-ring nitrogen-pivot lariat ethers: syntheses, properties, and sodium and ammonium cation binding properties

Cited by 203 publications

References 4 publications

New Fluorescent Calix Crown Ethers, Part II: Synthesis and Complex Formation in Solution and the Solid State

New Fluorescent Calix Crown Ethers, Part II: Synthesis and Complex Formation in Solution and the Solid State

Spacer-chromoionophores - polymethine dye substituted aza-crown ethers with increased complexation ability

Information gathering and processing with fluorescent molecules

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