The self-assembly of 3-[4‘-(diethylboryl)phenyl]pyridine (3) and 3-[3‘-(diethylboryl)phenyl]pyridine
(4) was investigated by 1H and 11B NMR spectroscopies and vapor pressure osmometry. It can be
seen that in solution 3 affords an equilibrium mixture of oligomers including a cyclic trimer as a
major component via intermolecular boron−nitrogen coordination bonds, which is supported by
temperature-, concentration-, and solvent-dependent behaviors of 3. In contrast, 4 seems to afford
a mixture of oligomers including a cyclic dimer in solution. Judging from the low coalescence
temperature in variable-temperature NMR in toluene-d
8 and easy scrambling with the corresponding
3-[(diethylboryl)pheny]-5-methoxypyridines at ambient temperature, it is concluded that the
intermolecular boron−nitrogen coordination bonds made by 3 or 4 are weaker than those formed
by 3-(diethylboryl)pyridine (1) or 2-(diethylboryl)-5-methylpyridine (2). Poor thermal stability was
supported by electrospray mass spectrometry and structural analyses utilizing a semi-empirical
molecular orbital calculation AM1. It is noted that in the assembly of 4 there is a tendency to
maintain high tetrahedral character at the boron atom in the complex at the expense of strain
energy. Thus, these features of 3 and 4 in solution are in marked contrast to those of 1 and 2.
We investigated 61 patients (38 boys and 23 girls) under 18 years of age with obsessive-compulsive symptoms seen in the Department of Psychiatry, Nagoya University Hospital, from 1982 until 1986. In this period, a total of 1293 patients under 18 years of age visited the clinic. The percentage of patients with obsessive-compulsive symptoms was 5%. The earliest onset of symptoms was at age 3 years, and the average age of onset was 11.6 years. We found no particular tendency in terms of the number of siblings and the birth order of the patients. Obsessive traits were the fundamental personality traits of patients. Moreover, according to the other characteristics of personality, the patients were subdivided into schizothymic, viscous temperament, and cyclothymic. Parents of the patients were more apt than usual to have obsessive-compulsive personalities. Psychiatric disturbances and occupations were also investigated. Incidents related to school situations commonly triggered obsessive-compulsive symptoms. The most frequently noted obsessive thought was dirt phobia, and the most common compulsive behavior was washing. School refusal and violence at home were especially common as associated symptoms of obsessive-compulsive symptoms. We also describe the treatment regimen and the outcomes of the patients.
A facile method for the synthesis of 1- and 2-pyridylazulenes, and of 1,3-dipyridylazulenes, is described. Color and spectral changes of these pyridylazulenes upon the addition of either acid or metal ions were investigated in detail. The color changed from blue to red upon the addition of trifluoroacetic acid or soft metal ions, depending on the substitution patterns of the pyridyl group on the azulene skeleton. The structures of the protonated or coordinated products were examined on the basis of the spectral data. It was found that the protonation or coordination of metal ions occurred on the nitrogen atom of the pyridine ring, but not on the carbon atom of azulene ring. The transition intervals of several pyridylazulenes for use as pH indicators were also determined.
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