5-Oxo-5H-[1]benzopyrano[2,3-b]pyridine-3-carboxylic acids 23 and their tetrazole analogues 24 were synthesized from 4-oxo-4H-1-benzopyran-3-carbonitriles 3 or 2-amino-4-oxo-4H-1-benzopyran-3-carboxaldehydes 4. When administered intravenously, they exhibited antiallergic activity in a reaginic PCA test in rats. In the carboxylic acid series, the activity was influenced by the substituents at the 2-position and increased substantially in the following order: Me, OMe less than NH2 less than OH, H less than NHOMe. On the other hand, in the tetrazole series, 2-unsubstituted derivatives showed the highest activity. Regardless of the kinds of substituents at positions 2 and 3, compounds bearing an alkyl group, especially an isopropyl group at the 7-position, were superior in activity to the corresponding unsubstituted compounds. Among these alkyl derivatives, 3-carboxylic acid derivatives, i.e., 23c (7-ethyl), 23g (2-amino-7-isopropyl), 23r [2-(methoxyamino)-7-isopropyl], and a 3-tetrazole derivative 24c (7-isopropyl), were 41-184 times as potent as disodium cromoglycate. They also exhibited remarkable activity when administered orally; clinical studies on 23g (AA-673) are in progress.
NH 4 F is demonstrated to be a promising mineralizer for the acidic ammonothermal crystal growth of GaN. In comparison with other acidic mineralizers such as NH 4 Cl, NH 4 Br, and NH 4 I, NH 4 F behaves distinctively different. First, NH 4 F affords a negative temperature gradient for crystal growth of GaN in supercritical NH 3 at a temperature range from 550 to 650 °C. Second, it enables GaN crystal growth in polar (c plane), semipolar, and nonpolar directions (a plane and m plane). Third, NH 4 F remarkably increases both the growth rate and quality of the GaN crystal. With the aid of NH 4 F, self-nucleation of GaN and bulk growth of hexagonal GaN crystals from the self-nucleated seed have been realized.
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