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Complexing properties of 3′,5′‐disubstituted‐4′‐hydroxybenzyl armed monoaza‐12‐crown‐4 and armed monoaza‐15‐crown‐5 ethers and crystal structures of the alkali metal ion complexes
Author(s) -
Habata Yoichi,
Akabori Sadatoshi,
Zhang Xian Xin,
Izatt Reed M.,
Bradshaw Jerald S.
Publication year - 2001
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570380614
Subject(s) - chemistry , alkali metal , lithium (medication) , potassium , metal , caesium , mannich reaction , crystal structure , crown ether , medicinal chemistry , inorganic chemistry , polymer chemistry , organic chemistry , ion , catalysis , medicine , endocrinology
A series of monoaza‐15‐crown‐5 ethers (2b‐2h) having 4′‐hydroxy‐3′,5′‐disubstituted benzyl groups have been prepared by the Mannich reaction of 2,6‐disubstituted phenols with the corresponding N ‐methoxymethylmonoaza‐crown ethers. Competitive transport through a chloroform membrane by 12‐crown‐4 derivatives (lithium, potassium and cesium) and 15‐crown‐5 derivatives (sodium, potassium and cesium) were measured under basic‐source phase and acidic‐receiving phase conditions. All ligands transported size‐matched alkali‐metal cations. Ligands 1h and 2h with two fluorine atoms in the side arm gave higher metal ion transport rates than those of dimethyl‐ (1a and 2a), diisopropyl‐ (1b and 2b), and butylmethyl‐ (1d and 2d) derivatives. X‐ray crystal structures of six alkali metal complexes with monoaza‐12‐crown‐4‐derivatives ( 1b‐LiSCN, 1b‐KSCN, 1c‐NaSCN, 1d‐LiSCN, 1f‐RbSCN and 1h‐LiSCN ) and three alkali metal complexes with 15‐crown‐5 derivatives ( 2b‐KSCN, 2c‐KSCN , and 2e‐KSCN ) along with crystal structures of some new ligands (1b, 1c, 1d, 1f, and 2c) are also reported. These X‐ray analyses indicate that the crystal structures of the alkali metal ion complexes of these new armed‐crown ethers changed depending on the substituents at the 3′‐ and 5′‐positions of the appended hydroxybenzyl arms.