Structural and vibrational study of the Ci(1) conformation of 18-crown-6.
Optimized geometry, vibrational frequencies and IR absorption intensities were calculated for the Ci(1) conformation of 18c6. Optimized geometry was compared with the experimental geometry and that of the Ci(2) conformation of 18c6. The Ci(1) conformation is more planer than the Ci(2) conformation of 18c6, which provides an explanation that free 18c6 in the crystal phase has a Ci(1) conformation. Vibrational frequencies were scaled using an unvaried one-scale-factor scaling of 0.928. Calculated vibrational frequencies were compared with the experimental vibrational frequencies. The root-mean-square deviation of the difference between the calculated and experimental frequencies was only 15 cm(-1). This excellent agreement between the calculated and experimental frequencies is an indication of the proper assignment of the fundamental vibrational frequencies of the Ci(1) conformation of 18c6.
Enhanced rates of dihydropyridine to pyridinium hydrogen transfer in complexes of an active macrocyclic receptor molecule
The complexes formed by the dihydropyridine-bearing macrocyclic receptor molecule (I) with the pyridinium substrates (S1) and (S2) display enhanced rates of internal H-transfer which may be inhibited by addition of other complexable cations.
Synthesis of 2,4-dideoxy-.beta.-D-erythro-hexopyranosyl nucleosides
The synthesis of 1-(2,4-dideoxy-β-D-erythro-hexopyranosyl)thymine (12) 1 was accomplished using two different synthetic routes. It was obtained starting either from 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose or from tri-O-acetyl-D-glucal. The other modified nucleosides, with either a cytosine, guanine, or adenine moiety, were synthesized using the second reaction scheme. Deoxygenation reactions were accomplished with the (2,4-dichlorophenoxy)thiocarbonyl derivatives generated in situ