Chiral recognition by the S,S and R,R enantiomers of dimethyldioxopyridino-18-crown-6 as measured by temperature-dependent proton NMR spectroscopy in CD2Cl2, titration calorimetry in methanol at 25.degree., and selective crystallization

Bradshaw, Jerald S.; Jones, Brian A.; Davidson, Richard B.; Christensen, James J.; Lamb, John D.; Izatt, Reed M.; Morin, Frederick G.; Grant, David M.

doi:10.1021/jo00138a043

Cited by 21 publications

(9 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In addition to peaks for the molecular ions and a series corresponding to cleavage of ethyleneoxy units, all specta exhibited a base peak of 121 mass units. The mass spectra of [8][9][10] showed strong similarities to those of 6 and 7 described previously in detail. 15 The structures of all new macrocycles were consistent with their IR and NMR spectra, molecular weight determinations, and combustion analyses.…”

Section: Resultssupporting

confidence: 70%

“…Specific details are given for each compound. 3,6,9,3.1]octadeca-l-(18),14,16-triene-2,13-dithione (1). Compound 20 (6.95 g, 30.6 mmol) and 4.65 g (31 mmol) of triethylene glycol were used in method B with NaOCH3 as the catalyst.…”

Section: General Procedures For the Preparation Of Macrocyclicmentioning

confidence: 99%

“…Found: C, 50.68; H, 5.56; mol wt 375. 3,6,9,12,15,18,3.1 Jheptacosal( 27),23,25-triene-2,22-dithione (4). Compound 20 (10.0 g, 44 mmol) and hexaethylene glycol (12.4 g, 44 mmol) were used in method A with CsOCH3 as the catalyst.…”

Section: General Procedures For the Preparation Of Macrocyclicmentioning

confidence: 99%

“…The free ligand was obtained in an overall 69% yield. 3,6,9,octadeca-l-(18),14,16-triene (6). Compound 1 (250 mg, 0.80 mmol) was dissolved in 10 mL of dry tetrahydrofuran (THF).…”

Section: General Procedures For the Preparation Of Macrocyclicmentioning

confidence: 99%

See 3 more Smart Citations

Preparation of macrocyclic polyether-thiono diester and -thiono tetraester ligands containing either the pyridine subcyclic unit or the oxalyl moiety, their complexes, and their reductive desulfurization to crown ethers

Jones¹,

Bradshaw²,

Brown³

et al. 1983

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

The preparation of seven new macrocyclic polyether-thiono diesters and one new macrocyclic polyether-thiono tetraester is reported. The new macrocyclic compounds containing a pyridine subcyclic unit formed complexes with metal and alkylammonium salts. Complex formation by some of these ligands was shown by variabletemperature NMR spectroscopy and by cation transport through a CHC13 membrane. All of the thiono compounds were reductively desulfurized to form the corresponding crown ethers.A variety of macrocyclic polyether-diester compounds (the diester crowns) have been prepared via an alkoxidecatalyzed transesterification procedure.1,2 This method gives higher yields and cleaner products for a majority of systems than the traditional synthetic procedure using diacid chlorides and glycols. Our work on the desulfurization of thiono esters1 23 coupled with their known ability to undergo transesterification with alkoxide catalysts4 prompted us to investigate thiono diesters as macrocycle precursors.We now report the preparation of new thiono diester (and tetraester in the case of 13) crowns containing pyridine and oxalate units (1-5, 11-13 Chart I). The pyridine-containing crowns are good complexing agents for alkali metal and primary alkylammonium cations.5 6'7 Many of the new thiono-substituted pyridino ligands formed stable complexes with a variety of salts. Macrocycle 5 is the dithiono analogue of the chiral dimethyl dioxo compound8 which exhibited high enantiomeric selectivity when complexed with the enantiomers of chiral amine salts as shown by variable-temperature NMR spectroscopy, titration calorimetry, and selective crystallization.9 Not only are these new thiono-substituted crowns interesting for their chemical properties but they also are precursors to the etheral crowns when treated with Raney nickel. Each thiono crown prepared here was subjected to the Raney nickel reductive desulfurization procedure3,10 to give the series of macrocyclic polyether pyridino crowns 6-10 and crowns 14 and 15. The pyridino crowns are expected f Contribution No. 304 from the Institute for Thermochemical Studies.

show abstract

Section: Resultssupporting

confidence: 70%

Section: General Procedures For the Preparation Of Macrocyclicmentioning

confidence: 99%

Section: General Procedures For the Preparation Of Macrocyclicmentioning

confidence: 99%

“…The free ligand was obtained in an overall 69% yield. 3,6,9,octadeca-l-(18),14,16-triene (6). Compound 1 (250 mg, 0.80 mmol) was dissolved in 10 mL of dry tetrahydrofuran (THF).…”

Section: General Procedures For the Preparation Of Macrocyclicmentioning

confidence: 99%

See 2 more Smart Citations

Preparation of macrocyclic polyether-thiono diester and -thiono tetraester ligands containing either the pyridine subcyclic unit or the oxalyl moiety, their complexes, and their reductive desulfurization to crown ethers

Jones¹,

Bradshaw²,

Brown³

et al. 1983

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…In general, the complexation is controlled by the size, structural shape, and hydrophobic properties of the guests. The detection and characterization of these complexes have been explored through calorimetric, 27,28 X-ray diffraction, 29,30 NMR, 31–33 computational studies, 34 and ESI-MS. 35 Among these analytical methods, NMR is one of the most useful methods due to its easy application and the detailed structural information on the nature of the complex that can be obtained. NMR is widely used in host—guest chemistry because it can readily distinguish encapsulation and surface or peripheral binding of the substrate to the host.…”

Section: Introductionmentioning

confidence: 99%

Complexation of Microcystins and Nodularin by Cyclodextrins in Aqueous Solution, a Potential Removal Strategy

Chen

Dionysiou

Ο'Shea

2011

Environ. Sci. Technol.

View full text Add to dashboard Cite

Cyanotoxins are potent toxic compounds produced by cyanobacteria during algal blooms, which threaten drinking water supplies. These compounds can poison and kill animals and humans. The host—guest interactions of α-, β-, and γ-cyclodextrins (CD) with problematic cyanotoxins, including microcystins (MCs) and nodularin (NOD), were investigated to demonstrate the potential application of CDs for the removal of these toxins from drinking water or applications related to their separation or purification. MCs and NOD have a hydrophobic Adda chain, which contains diene and benzene functional groups. The complexation of these cyanotoxins with CDs was monitored by nuclear magnetic resonance (NMR). The 1H NMR spectra for MCs are unchanged upon addition of α-CD (smallest host). However, addition of larger hosts, β-CD and γ-CD, leads to significant changes in chemical shifts of the benzene and diene resonances on the 3-amino-9-methoxy-2,6,8-trimethal-10-phenyldeca-4,6-dienoic acid (Adda) chain of MCs and NOD. Solution pH, natural organic matter, and salinity do not appreciably influence the host—guest complexation under our experimental conditions. The experimental binding constants for MCs and NOD with γ-CD are relatively strong, ranging from 1155 to 507 M−1. The observed changes in chemical shifts for specific protons and competitive binding experiments demonstrate a 1:1 inclusion complex between γ-CD and MCs or NOD, with the Adda chains threading through the CD ring, resulting in an inclusion complex. Our results suggest that CD-type substrates are useful hosts for the complexation of MCs and NOD. CDs can be readily attached to a number of polymeric or solid supports and their functionality tailored to strengthen specific host—guest interactions. With further development of such materials, CD host—guest chemistry may find direct application in the removal and/or separation science of these compounds.

show abstract

Macrocyclic Pyridines

Newkome¹,

Gupta²,

Sauer³

1985

Chemistry of Heterocyclic Compounds: A Series of Monographs

View full text Add to dashboard Cite

Chiral recognition by the S,S and R,R enantiomers of dimethyldioxopyridino-18-crown-6 as measured by temperature-dependent proton NMR spectroscopy in CD2Cl2, titration calorimetry in methanol at 25.degree., and selective crystallization

Cited by 21 publications

References 3 publications

Preparation of macrocyclic polyether-thiono diester and -thiono tetraester ligands containing either the pyridine subcyclic unit or the oxalyl moiety, their complexes, and their reductive desulfurization to crown ethers

Preparation of macrocyclic polyether-thiono diester and -thiono tetraester ligands containing either the pyridine subcyclic unit or the oxalyl moiety, their complexes, and their reductive desulfurization to crown ethers

Complexation of Microcystins and Nodularin by Cyclodextrins in Aqueous Solution, a Potential Removal Strategy

Macrocyclic Pyridines

Contact Info

Product

Resources

About