From alpha-carbamoyl-alpha-cyanooxiranes to 3-halogenopyruvamides.

The crystal structures of the first stable alpha-diol from the alpha-halogenopyruvamide series, 3-chloro-2, 2-dihydroxy-3-phenylpropanamide, C(9)H(10)ClNO(3), and three products [3-(4-chlorophenyl)-2-cyano-2,3-epoxypropanamide, C(10)H(7)ClN(2)O(2), 3-bromo-2-cyano-2-hydroxy-3-p-tolylpropanamide, C(11)H(11)BrN(2)O(2), 3-bromo-2-oxo-3-p-tolylpropanamide, C(10)H(10)BrNO(2)] obtained during the systematic synthesis of alpha-halogenopyruvamides are reported. The crystal structures are dominated by hydrogen bonds involving an amide group. The stability of the geminal diol could be ascribed to hydrogen bonds which involve both hydroxyl groups.

Studies on 2-benzyloxy-4H-3,1-benzoxazin-4-ones as serine protease inhibitors.

The class of 3,1-benzoxazin-4-ones includes potent inhibitors of various serine proteases. Structural investigation on three 2-benzyloxy-4H-3,1-benzoxazin-4-ones (1-3) are described with respect to their reactivity to alkaline hydrolysis. The 13C NMR data of 2-benzyloxy-5-methyl-4H-3,1-benzoxazin-4-one 3 are discussed. This peri substituted compound was subjected to a crystal structure analysis. The heterocyclic skeleton together with the carbonyl oxygen and the methyl carbon is planar, and only small angle distortions occurred. The inhibition of neutrophil serine proteases by 1-3 is reported. The different reactivity of the 5-methyl derivative 3 towards serine proteases is mainly influenced by specific interactions within the active sites. Thus, 3 was found to rapidly acylate human leukocyte proteinase 3 and exhibited a Ki value of 1.8 nM.

Powder Structure Solutions of the Compounds Potassium Phenoxide-Phenol: C(6)H(5)OK.xC(6)H(5)OH (x = 2, 3).

We report the ab initio structure solutions of two solvent containing potassium phenoxides by high-resolution powder X-ray diffraction. Both compounds are of interest for the classification of the mechanism of Kolbe-Schmitt type reactions. C(6)H(5)OK.2C(6)H(5)OH crystallizes in space group Abm2, Z = 4, with unit cell parameters a = 10.12458(4) Å, b = 21.2413(1) Å, c = 7.89784(3) Å. C(6)H(5)OK.3C(6)H(5)OH crystallizes in space group Pbca, Z = 8, with unit cell parameters a = 22.7713(1) Å, b = 25.4479(2) Å, c = 7.75549(4) Å. Both compounds show polymeric zigzag chains [K([6])O(2)([2])O([1])pi(phenyl)([1])] aligned along the c-axis. The coordination of the potassium ions is similar for both compounds. They lie at the center of distorted octahedra of five oxygen atoms and one phenyl ring, which donates its pi electrons. The distortion decreases as the number of free phenol increases.

Novel Alkali-Metal Coordination in Phenoxides: Powder Diffraction Results on C(6)H(5)OM (M = Li, Na, K, Rb, Cs).

We report the ab initio structure solutions of C(6)H(5)OM (M = K, Rb, Cs) by high-resolution powder X-ray diffraction. The compounds, which are of interest for reactions of the Kolbe-Schmitt type, are isostructural. The crystal structures are orthorhombic, space group Pna2(1), Z = 12, with lattice parameters (a, b, c in Å) 14.1003(1), 17.9121(1), and 7.16475(1) for the K compound, 14.4166(2), 18.2028(2), and 7.4009(1) for the Rb compound, and 14.8448(2), 18.5070(2), and 7.6306(1) for the Cs compound. They have a chain structure [M([6])] along the crystallographic c axis. This is a very unusual arrangement in which two different alkali-metal coordination spheres are observed: a distorted octahedron and a 3-fold oxygen coordination. In the latter, the 3-fold-coordinated unsaturated alkali metals additionally show weak interactions with phenyl rings. We also give powder patterns for the compounds with M = Li, Na. The former crystallizes in the monoclinic space group P2(1)/a with lattice parameters a = 22.594 Å, b = 4.7459 Å, c= 10.053 Å, and beta = 97.82 degrees with Z = 8, but no structure solution was possible. The powder pattern for the Na phenolate is in agreement with the earlier single-crystal structure.

Peer assessment of social reputation in community samples of disruptive and nondisruptive children: utility of the revised class play method.

Examined the psychometric properties of the Revised Class Play (RCP), a peer assessment measure of social reputation, in epidemiological samples of disruptive (n = 220) and nondisruptive (n = 104) children in Grades 2 through 5. Principal components analyses yielded a four-factor solution that was similar for disruptive and nondisruptive children and to previous research with this instrument. Discriminative function analyses demonstrated that the four RCP dimensions were each successful in predicting group membership, with the leadership and social etiquette dimensions best able to differentiate disruptive and nondisruptive groups. Regression modeling showed that the variance accounted for by the four RCP dimensions was large and varied for specific dimensions based on the criterion variable chosen. The advantages of the RCP as a devise for tracking social competence and peer reputation in high-risk disruptive children are discussed.