Enantiomeric recognition of organic ammonium salts by chiral crown ethers based on the pyridino-18-crown-6 structure

Journal Article · Fri Jan 27 00:00:00 EST 1984 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00176a026· OSTI ID:6139381

Davidson, R B; Bradshaw, J S; Jones, B A; Dalley, N K; Christensen, J J; Izatt, R M

Enantiomeric recognition by several chiral dimethyl-substituted macrocycles of the pyridino-18-crown-6 type for chiral organic ammonium salts has been studied by titration calorimetry in CH/sub 3/OH, temperature-dependent /sup 1/H NMR spectroscopy in CD/sub 2/CL/sub 2/, and selective crystallization. Results from the three procedures are consistent in demonstrating either host-guest recognition or nonrecognition in the systems investigated. Futhermore, enaniomeric recognition by one chiral host for a pair of chiral guests is correlated with X-ray crystallographic data for the same system. The chiral dimethyl-substituted ligands used in the study include three dimethyl diester pyridino-18-crown-6 ligands, dimethyl thiono diester pyridino-18-crown-6, and dimethyl-pyridino-18-crown-6 ligands. All of these ligands exhibited chiral recognition. Dimethylpyridino-18-crown-6 in complexation with (R)- and (S)-(..cap alpha..-(1-naphthyl)ethyl)ammonium perchlorate exhibited the largest ratio of ..delta..G/sub c/+ yet observed by the /sup 1/H NMR technique. A diphenyl-substituted diester pyridino-18-crown-6 where the phenyl substituents are in less rigid portion of the macrocycle failed to show chiral recognition.

• OSTI ID: 6139381
• Journal Information: J. Org. Chem.; (United States), Vol. 49:2
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
POLYETHYLENE GLYCOLS
TITRATION
ACTIVATION ENERGY
CALORIMETRY
CHEMICAL REACTION KINETICS
CHLOROFORM
CORRELATIONS
CRYSTAL STRUCTURE
ENANTIOMORPHS
ESTERS
EXPERIMENTAL DATA
LIGANDS
METHANOL
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC SOLVENTS
ORGANIC SULFUR COMPOUNDS
PERCHLORATES
PYRIDINES
THERMODYNAMIC PROPERTIES
X-RAY DIFFRACTION
ALCOHOLS
AZINES
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE COMPOUNDS
COHERENT SCATTERING
DATA
DIFFRACTION
ENERGY
GLYCOLS
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
POLYMERS
REACTION KINETICS
SCATTERING
SOLVENTS
SPECTRA
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)