In continuation of work on new types of non-narcotic analgesics, various 3-sub-stituted 6, 6-dimethyl (or 6-phenyl)-1, 2, 3, 4, 5, 6-hexahydro-3-benzazocines, were synthesized by a simple modification of the morphine molecule, via the Friedel-Crafts type cyclization of 4-N-phenethylamino-2-methyl-2-butanols or N-(3-methyl-2-butenyl- or cinnamyl)-phenethylamines. Cyclization of N-substituted N-bis (3-methyl-2-butenyl) amines gave 1-substituted 4, 4-dimethyl-3-(1-methylvinyl) piperidines. The analgesic activity of tested compounds indicated that 8, 9-dimethoxy-3, 6, 6-trimethyl-1, 2, 3, 4, 5, 6-hexahydro-3-benzazocine had the most potent activity.

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Several 4-morpholinyl esters of N-Boc- or N-Z-amino acids gave corresponding amino acid 4-morpholinyl esters under acidic deprotecting condition (HCl or HBr) generally employed in peptide synthesis. In addition, it was found that the 4-morpholinyl ester bond can be cleaved readily by catalytic reduction.

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In order to examine the structure and stability relationship of secondary amine of aminoalkylesters, derivatives of [(C₆H₅)(m-CH₃O-C₆H₄) CHCOOCH₂CH₂NHR³] were synthesized, changing R³ to CH₃ (I), C₂H₅ (II), n-C₃H₇ (III), iso-C₃H₇ (IV), n-C₄H₉ (V) and CH₂C₆H₅ (VII). With the use of a protonated amine ester as a reaction species, catalytic constants of hydrogen ion (k_H) and hydroxyl ion (k_OH) were determined. The substituent effect on k_H and k_OH was explained with Taft Es values, and the case in which an unprotonated amine ester was taken as being hydrolyzed spontaneously was discussed briefly.

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In order to examine the structure and stability relationship of tertiary amine of aminoalkylesters, derivatives of [(C₆H₅)(m-CH₃O-C₆H₄) CHCOOCH₂CH₂R³] were synthesized, changing R³ to N (CH₃)₂ (I), N (C₂H₅)₂ (II), N (n-C₃H₇)₂ (III), N (iso-C₃H₇)₂ (IV), N (n-C₄H₉)₂ (V), [chemical formula] (VI) and [chemical formula] (VII). By the use of a protonated amine ester as a reaction species, catalytic constants of hydrogen ion (k_H) and hydroxyl ion (k_OH) were determined. The substituents in tertiary amine ester were less effective, either for k_H or k_OH than in secondary amine ester. Although the reactivity of diethylamino esters decreased in the order of secondary amine>tertiary amine≈quaternary ammonium salt for k_H, or secondary amine>tertiary amine>>quaternary ammonium salt for k_OH, the ratios of (k_H)_sec/(k_H)_ter and (k_OH)_sec/(k_OH)_ter (sec and ter denoting secondary and tertiary, respectively) decreased when the ester reactivity decreased.

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Eye-lens capsule has one layer of epithelium inside its anterior part and this lens epithelium is said to play an important role in active transport. Therefore, the membrane potential and the membrane permeability coefficient of the epithelium-capsule were compared with those of the capsule whose epithelium was taken off in distilled water. Measurement of membrane potential of the capsule and the epithelium-capsule showed that the capsule is a positively charged membrane and that the epithelium-capsule is a negatively charged membrane, and that charge density of the latter is four or five times larger than that of the former in the absolute value. It was also found that the reduced permeability coefficient of the epithelium-capsule is considerably smaller than that of the capsule, although the permeability coefficient is about the same value for both membranes with and without the epithelium at sufficiently high electrolyte concentration.

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The reactions of heterocyclic ketenethioacetal derivatives, containing a quaternary nitrogen as an electron-attracting group, with nucleophilic reagents (amines and active methylenes) gave the corresponding substituted compounds. By the application of these reactions, fulvalene (IIIb), imidazoline (Va₁, VIa₁, Vb, Vc, Vd₂), and oxazoline (Va₂, VIa₂, Vd₂) derivatives were obtained.

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Chalcone (I) or 4-nitrochalcone (II) reacted with phenylsulfenyl chloride in acetic acid to give 1-chloro-1-phenyl-2-phenylthio-3-phenyl-3-propanone (III) or 1-p-nitro-phenyl-1-chloro-2-phenylthio-3-phenyl-3-propanone (IV) as an adduct. However, the reaction of 5'-methyl-2'-methylthiochalcones (VII to XIII) or 5'-chloro-2'-methylthio-chalcones (XIV to XVIII) with arylsulfenyl chloride did not afford such an adduct. In this reaction, 5-methyl- or 5-chloro-thioaurones (XIX to XXX) were formed from these chalcones (VII to XVIII) by a five-membered ring closure with demethylation of their methylthio groups. This reaction is available as an one step method for synthesis of thioaurones from 2'-methylthiochalcones.

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Preparation of porous sintered plates of metal oxide is described. Magnesium silicate, magnesium oxide, titanium dioxide, or zinc oxide was used as adsorbent, and soda-lime glass as a binder. A mixture of one part of adsorbent and three to four parts of finely powdered soda-lime glass was suspended in organic solvents, and the slurry was spread on soda-lime glass plate and air-dried. The thin-layer was heated in an electric furnace at 400-700°for several minutes to yield an adsorbent-fused glass layer. Stability of the porous metal oxide adsorbents against a high temperature was found from the fact that no sintering of the adsorbents occurred as evidenced by scanning electron microscopy and X-ray diffraction, and thermogravimetric differential thermal analysis and thermogravimetric differential scanning colorimetry to a higher temperature failed to show thermal mass change or transition under the welding condition, except titanium dioxide which showed the crystal thermal change of crystal form from anatase to rutile form. These porous sintered plates of metal oxides were used for the thin -layer chromatographic separation of organic compounds and very satisfactory results were obtained by the use of magnesium silicate sintered plate for sugars and cardiac glycosides, titanium dioxide sintered plate for pesticides, and magnesium oxide sintered plate for sterols and steroidal sapogenins.

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A new flavonoid was isolated from the root of Epimedium grandiflorum MORR.(Berberidaceae) and named epimedoside A. The structure of epimedoside A was determined as 8-isopentenylkaempferol rhamnosyl-7-glucoside on the basis of chemical and spectroscopic evidences.

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Two new flavonoids were isolated from the root of Epimedium grandiflorum MORR.(Berberidaceae) and were named epimedoside B and epimedoside C. Their structures were established from their chemical and spectroscopic evidences as 8-isopentenylkaempferol 4'-rhamnoside and 8-isopentenylkaempferol 7-glucoside, respectively. De-O-methyl-β-anhydroicaritin was also isolated from this root.

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β-(3, 5-Dioxo-1, 2, 4-oxadiazolidin-2-yl)-L-alanine (Ia) was proposed for quisqualic acid (I), an acidic amino acid isolated from Quisqualis Fructus on the basis of chemical and physiochemical properties, and confirmed by synthesis. A new hydroxyureido derivative, 2-amino-3-(1-hydroxyureido) propionic acid (II), was obtained by an alkaline treatment of I. 2-Amino-3-(3-hydroxyureido) propionic acid (IIb) and isoquisqualic acid, [β-(3, 5-dioxo-1, 2, 4-oxadiazolidin-4-yl) alanine](Ib) were also synthesized.

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In order to examine the fluorescence characteristics and biological activities, synthesis of 3-aminoisocarbostyril derivatives was carried out. Reaction of (2-cyanomethyl)-benzoic acids (Ia and Ib) with aniline, benzylamine, and cyclohexylamine in chloro-benzene gave the corresponding 3-substituted aminoisocarbostyrils (IIa-e) in a good yield. Replacement of the amino group in 3-position took place by the reaction of 3-aminoisocarbostyrils (III, IV, VI, and IX) with primary amines (methylamine, ethyl-amine, cyclohexylamine, benzylamine, and aniline), while 2-amino-3-hydrazinoisocarbostyril (XIII) was obtained by their reaction with hydrazine hydrate.

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Incorporation of propionate into the propionamide of aureothricin (I) has been demonstrated as a result of a comparison of ¹³C-NMR spectra of I in natural abundance level and enriched, which was obtained by feeding sodium propionate [3-¹³C] to the culture of Streptomyces luteoreticuli.

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Essential oils of the young trees of Metasequoia glyptostroboides Hu et Cheng were examined. The yield of oils from shoots was 0.08-0.09%, and the oils contained l-α-pinene as high as 80.3-86.1%. The branchlet oil was obtained in the yeild of 0.002%, and contained 22.7% of β-pinene, 11.8% of α-terpinyl acetate, and 5.3% of α-calacorene, together with 7.0% of 1-octen-3-yl acetate and 6.0% of 1-octen-3-ol. The yield of trunk oil was 0.009%, and the main constituents determined were calamenene and α-cadinol, and others have not yet been identified.

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The silkworm larvae at the 5th instar excreted 0.66-0.77% of combined glycine in their feces (I) between 1st and 8th day, whereas a large amount of combined glycine was detected in the feces (II) of matured (matured) silkworm (green feces and rid feces contained 3.28% and 13, 04%, respectively, of combined glycine). Glycine was easily liberated by hydrolysis from I but with difficulty from II. Ratios of glycine-N to total-N in I, green feces, red feces, and mulberry leaves were 6.28%, 11.89%, 15.86%, and 6.80%, respectively. These results suggest that glycine in I may be liberated from indigested proteins of mulberry leaves and that in II from uric acid or some purine derivatives, which liberate glycine under drastic hydrolysis conditions.

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The conversion of N-acetyl-N-(o-aminobenzenesulfonyl)-o-toluidine (I') into N-acetamidobenzenesulfonyl-o-toluidine (II') was investigated in acidic solution (H₀-2-pH 4). The reaction passes through the intermediate 2-o-tolyl-3-methyl-1, 2, 4-benzothiadiazine 1, 1-dioxide (III) and the intermediate is especially accumulated in H₀<-1 solution. Then, III can easily be synthesized from I' in 8N HCl solution at 50°.

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The alkaloidal components of the leaves of three kinds of Erythrina plants (Leguminosae), Erythrina poeppigiana (Walp) O.F. COOK (E.umbrosa BELLO), Erythrina glauca WILLD., and Erythrina variegata L.collected in the Singapore Botanical Garden, were examined. As a result of this examination, five Erythrina alkaloids, erysotrine (IX), 11-hydroxy-erysotrine (XV), erythraline (IV), erythrinine (XVI), and erysodine (I), a benzyltetrahydroisoquinoline alkaloid, N-nororientaline (XVII), and an alkaloid of dibenz [d, f]-azonine-type, erybidine (XVIII), were respectively isolated and characterized.

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