One-pot reactions of bicyclic zinc enolate generated from Ni-catalyzed reductive cyclization to furnish octahydro-4,7-ethanobenzofuran-9-one derivatives

The one-pot reactions of catalytically generated bicyclic zinc enolate with various electrophiles are reported. The zinc enolate as a key intermediate is efficiently delivered from Ni-catalyzed reductive cyclization of alkynyl cyclohexadienone. Employing aldehydes, imine, nitroalkene, and α,β-unsaturated carbonyl compounds as electrophiles, this new class of one-pot reactions gave multi-functionalized cis-hydrobenzofurans and octahydro-4,7-ethanobenzofuran-9-one derivatives in moderate to good yields.     

Dilute solutions of poly(vinyl alcohol) derived from vinyl trifluoroacetate

The dilute-solution behavior of poly(vinyl alcohol) (PVA_VTFA), derived from vinyl trifluoroacetate, in water-dimethylsulfoxide (DMSO) mixtures was investigated. With solvent mixtures ranging from 10 to 20 vol % DMSO, the relation between the reduced viscosity η_sp/C and the polymer concentration C was linear for polymer concentrations above 0.2 g/dL, whereas in solutions in mixed solvents of other compositions the dependence was linear for polymer concentrations above 0.1 g/dL. The relation between the intrinsic viscosity [η] obtained for aqueous solutions of PVA_VTFA and the molecular weight M estimated from viscosity measurements in solutions of poly(vinyl acetate) (PVA_VTFA), obtained by acetylation of PVA_VTFA, was given by [η] = 7.34 × 10^?4 M^0.63. The value of [η] was greatest for the solvent mixture with 10 vol % DMSO and smallest for about 50 vol % DMSO, and Huggins constants k were smallest and greatest for these two cases, respectively. The turbidity of the solutions of low-molecular-weight PVA_VTFA, was higher than that of high-molecular-weight PVA_VTFA up to 30 vol % DMSO, and the reverse relation held for 40-70 vol % DMSO.     

Studies on antiallergy agents. III. Synthesis of 2-anilino-1,6-dihydro-6-oxo-5-pyrimidinecarboxylic acids and related compounds

A series of 2-anilino-1,6-dihydro-6-oxo-5-pyrimidinecarboxylic acids with various substituents was synthesized and evaluated in the rat passive cutaneous anaphylaxis test for antiallergic activity. High activity by intraperitoneal and oral administrations was observed for the 3-trifluoromethyl and 2-alkoxyanilino derivatives (64, 79, 81, 82 and 85). Structure-activity relationships are discussed.     

Abnormal uterine cavity: differential diagnosis with MR imaging

The objective of the study was to assess the usefulness of magnetic resonance (MR) imaging in distinguishing malignant from benign conditions in patients with an abnormal uterine cavity. Fifty-four patients that were suspected of having abnormal uterine cavities were retrospectively evaluated by using MR imaging. The diagnosis of an abnormal uterine cavity included a thickened endometrium, and/or a endometrial mass, and/or a submucosal mass. Threshold values to classify the uterine cavity as abnormal on sagittal T₂-weighted images were >10 mm for premenopausal women and >5 mm for postmenopausal women. Malignancy was diagnosed when lesions invaded the myometrial/junctional zone, and/or lesion enhancement was lower than that of the adjacent myometrium. The results found that histology confirmed 18 malignant and 37 benign lesions. Twelve of 15 endometrial carcinomas and 3 malignant mixed mesodermal tumors (MMMT) were correctly characterized as malignant on enhanced T₁-weighted images; whereas 6 of 15 endometrial carcinomas and 3 MMMT were correctly characterized on T₂-weighted images. Thirty-four of 37 benign cases were correctly characterized as not malignant on enhanced T₁-weighted images. One of 14 submucosal leiomyomas, one endometrial stromal metaplasia, and one of ten pathologically normal endometria were misdiagnosed on enhanced T₁-weighted images but were correctly diagnosed on T₂-weighted images. The overall sensitivity, specificity, and accuracy for distinguishing malignant from benign central uterine masses were 83%, 92%, and 89% for enhanced T₁-weighted image, and 50%, 97%, and 82% for T₂-weighted image, respectively. We came to the conclusion that in diagnosing patients with abnormal uterine cavity, MR imaging may help differentiate malignant from benign disorders.