Chemical and spectroscopic studies have shown that cimigol (I), a triterpene alcohol occurring as itself and as an aglycone in the roots of Cimicifuga acerina (SIEB.et ZUCC.) C.TANAKA, C.simplex WORMSK and C.japonica SPRENGEL, is a stereoisomer at C₁₅ and C₂₄ configuration to cimigenol (II), which is found to be a major constituent in several species of this genus.

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Several ο-nitrophenylsulfenyl amino acid 4-morpholinyl esters, newly prepared, were converted to amino acid 4-morpholinyl esters, which were coupled with carbobenzoxy amino acid by dicyclohexylcarbodiimide method to give Z-dipeptide 4-morpholinyl esters. In addition, two tetrapeptide derivatives were synthesized by using the 4-morpholinyl esters.

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Pyrolysis of 2, 2, 2-tri (aryl and alkyl) ethyl S-methyl xanthates (RCH₂OCSSCH₃) afforded olefins accompanying 1, 2-shift of the aryl group. To elucidate this reaction mechanism, kinetic studies were made. The first-order rate constants for pyrolysis of xanthates in a variety of solvents were determined. Judging from the solvent effect estimated on the basis of E_T-value, the solvent effect on the reaction rate of VIII (R=CH₃-(C₆H₅)₂C) and IX (R=C₆H₅(CH₃)₂C) appears too small to attribute the reaction mechanism to the one via an ion pair which has been already proposed. However, in the case of V (R=(C₆H₅)₃C), the solvent effect, Hammatt parameter, ρ=+1.35, and also kinetic isotope effect, k_H/k_D=1.21, indicate that the reaction may have an ionic character.

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Two types of products, 8-acetonyl-2, 3-methylenedioxy-9, 10-dimethoxy-13-oxido-5, 6-dihydrobenz [α] acridizinium (IV) and 2-acetyl-3-hydroxy-4, 5-dimethoxyindenone-1 (V), in addition to II and III, were isolated from the oxidation of acetoneberberine (I) with KMnO₄. They were characterized from spectroscopic data and chemical transformations. Refluxing of TV with 10% HCl did not remove the acetonyl group. Reduction of IV with NaBH₄ afforded 8-(2-hydroxypropyl)-13-hydroxytetrahydroberberine (VIII) and 8-(2-hydroxypropyl)-13-oxidoberberinium (IX), while reduction with zinc dust in aqueous acetic acid led to the concurrent elimination of the acetony1 group to form tetrahydroberberine (X) and 13-β-hydroxytetrahydroberberine (dl-ophiocarpine) (XI).

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Some kinds of amides can be obtained in a good yield by a liquid-phase ammonoxidation of aldehydes in ether at -20° to -25° with nickel peroxide. Benzylic and allylic alcohols were also effectively converted into the corresponding amides in a similar way. The reaction proceeds by hydrogen abstraction from the intermediate, α-amino-alcohol, which is in equilibrium with aldehyde and ammonia. Nickel peroxide is considered to be the only effective oxidant in this reaction. The substituent effect on the reaction rates of benzaldehyde derivatives was examined and it was found that the reaction rate decreased in the order of m-nitrobenzaldehyde, benzaldehyde, and p-methoxybenzaldehyde, which was attributed to the increasing equilibrium concentration of the corresponding α-amino-alcohol, and the rate of hydrogen abstraction from α-amino-alcohols was hardely affected by substituents.

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The reaction of vitamin K₃ (I) with some thiol compounds was studied by polarography in 80% ethanol containing acetate buffer and sodium perchlorate. In the absence of' oxygen in solution, thiol compounds react with I to form naphthohydroquinones having a thioether linkage as the result of the addition of SH group at 3-position of naphthoquinone ring in I. The reaction products changed to quinone-thioether compounds by air oxidation with the formation of hydrogen peroxide. The reaction mechanisms were confirmed by e1ectrochemica1 and spectrophotometric measurements of I in the presence of various thiol compounds. The effect of pH on the reaction rate was examined by following the change in the diffusion current of I with time at various pH's. In the case of the I-cysteine (IIg) reaction system, the polarograms were somewhat complicated compared with those obtained with other thiol compounds. These experimental results suggested that the subsequent reaction must be taken into account after the formation of hydroquinone-thioether compound between I and IIg.

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The antiulcerogenic and anti-inflammatory activities of saponin have been examined by oral administration in rats. Saponins for "Tochinoki" (Aesculus turbinata Br.), "Saikachi" (Gleditschia japonica MIQ.), and "Mi" (Madhuca longifolia L.) were active in both tests and the potency of anti-inflammatory activity of these saponins was about one-fifth that of phenylbutazone. On the other hand, deacylated derivative of saponin and sapogenol were generally found much less reactive.

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Hexahydro-2-methylpyrimidine was prepared in a good yield and selectively by gas phase reaction of trimethylenediamine with ethylene glycol. The reaction was carried out over 10 kinds of silica-alumina catalysts within the temperature range of 220-440°. They were Neobead (I), 5% K₂O-Neobead (II), 6.8% Cr₂O₃-Neobead (III), synthetic zeo1ite (IV), 5% K₂O-synthetic zeolite (V), natural zeolite (Clinoptilolite, Itaya, Yamagata) (VI), 5% SiO₂+95% Al₂O₃ (VII), 30% SiO₂+70% Al₂O₃ (VIII), 50% SiO₂+50% Al₂O₃ (IX), and 70% SiO₂+30% Al₂O₃ (X). Yield and selectivity of a series of zeolites were higher than that of Neobeads. The yield and selectivity were higher in case of catalysts VII, VIII, IX, and X when SiO₂ content was larger. Among all these catalysts, VI gave the best yield of hexahydro-2-methylpyrimidine, which was 65% under the condition of molar ratio of 1 : 3, for feed rate of materials of 1 ml/min, weight of packed catalyst of 30g, and reaction temperature of 315°.

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Kessoglycol 2-acetyl-8-acylates (III-1 to -17), kessoglycol 8-acylates (VI-1 to-5), and kessoglycol 2, 8-diacylates (V-1 to -5) were prepared in order to examine their sedative effect in mice comparing with that of kessoglycol 2, 8-diacetate (I), to prolong the sleeping time induced by sodium hexobarbitate administered orally. III-1 to III-17 were found to be less effective, but V-3 and VI-3 were equal or more effective than I. The structure-activity relationship of these compounds was not established as yet.

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Kessoglycol and kessoglycol derivatives, such as kessoglycol 2-monoacetate, kessoglycol 8-monoacetate, kessan-2-hydroxy-8-one, kessan-2-acetoxy-8-one, and kessoglycol diacetate (active control substance) were tested for the prolongation effect on sleeping time after sodium hexobarbitate administration in mice. Kessoglycol 8-monoacetate was found to be more potent than kessoglycol diacetate in this test. In addition, some pharma-cological action of kessoglycol 8-monoacetate was examined. Its effect on spontaneous motor activity, as judged by an open-field test, and anti-electroshock convulant action were not found in mice. Hypothermic action was evidently observed by oral administration of 200mg/kg in mice. Aggressiveness response by electrostimulation was inhibited by a single administration of 100mg/kg but not by 200mg/kg of kessoglyco1 diacetate. It may be concluded from these finding, that kessoglycol 8-monoacetate has a sedative action and is more potent than kessoglycol diacetate.

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In order to clarify the geometric structures of luteoreticulin and its degradation product, 2, 4-dimethyl-5-(p-nitrophenyl)-2, 4-pentadienoic acid, various model compounds were synthesized and their nuclear magnetic resonance (NMR) spectra were compared. The structures of the pentadienoicacid derivative and luteoreticulin were assumed from their NMR data as 2, 4-dimethyl-5-(p-nitrophenyl)-2-trans-4-trans-pentadienoic acid II and I.

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In order to examine whether a nitro group in the furan ring of 3, 4-diphenylfuran derivatives is required for their antibacterial activity, 5-nitro-3, 4-bis (4-substituted phenyl)-2-furaldehydes (IV and XII) and their derivatives were synthesized, 5-Nitro-3, 4-diphenyl-2-furaldehyde (IV) was synthesized from 3, 4-diphenyl-2-furaldehyde (I), via 3, 4-diphenyl-2-(1, 3-dioxolan-2-yl) furan (VII), acetine intermediate, 5-nitro-3, 4-diphenyl-2-(1, 3-dioxo1an-2-yl)-2-acetoxy-2, 5-dihydrofuran (VIII), and 5-nitro-3, 4-diphenyl-2-(1, 3-dioxolan-2-yl) furan (IX). Similarly, 5-nitro-3, 4-bis (4-methoxyphenyl)-2-furaldehyde (XII) was synthesized but its acetine intermediate could not be isolated. Antibacterial tests of these compounds showed them to be practically ineffective.

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D-Glucaric acid, a β-glucuronidase inhibitor, in various mammalian urine was determined by using both chemical and enzymic methods. The different results obtained from two methods and the high recovery of added D-glucaric acid Obtained from enzymic method suggested the presence of a strong inhibitor of β-glucuronidase other than D-glucaric acid in guinea-pig urine. It was a non-dialyzable inhibitor of β-glucuronidase. Sodium chloride was added to guinea-pig urine dialyzed to 0.58M to precipitate Tamm-Horsfall mucoprotein. After centrifugation at 7970×g, a non-dialyzable β-glucuronidase inhibitor was isolated and extensively purified from the spernatant by Sephadex G-50 chromatography, by treatment with pronase-P, trypsin, and papain in order to remove the contamination of denatured proteins, and by preparative paper electrophoresis. The purified inhibitor of β-glucuronidase was judged homogeneous by polyacrylamide gel electrophoresis and Sephadex G-100 chromatography.

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Properties of non-dialyzable β-glucuronidase inhibitor isolated from guinea-pig urine were examined by using the calf liver β-glucuronidase (ketodie). It was a heat stable inhibitor of β-glucuronidase. Kinetic studies indicated that the substance functions as a non-competitive inhibitor and it was a relatively specific inhibitor for β-glucuronidase. The inhibitory activity of purified inhibitor on β-glucuronidase was stronger than those of acid mucopolysaccharides. chondroitin sulfate A, B, and C, heparin, and hyaluronic acid. Electrophoretic pattern of the purified inhibitor was completely different from those of the latter substances.

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Polysaccharide mixture xylan and g1ucomannan were prepared from the waste water of the steeping alkali solution of wood pulp in a better yield and in higher purity than by the conventional methods. Concentrated waste water, adjusted to 7.5-10% sodium hydroxide concentration, produced a flocculent precipitate by the addition qf excess methanol. This precipitate had a good filtrability to be recovered on Buchner funnel. Graded hydrolysis of this precipitate with hydrochloric acid in methanol gave ash-free polysaccharide mixture, mainly composed of D-xylose, D-mannose, and D-glucose, and free from L-arabinose. Xylan was recovered from water dispersion of polysaccharide mixture as a precipitate. Glucomannan in the supernatant was recovered by fractional precipitation with methanol.

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4, 5-Dialkoxy-2-nitrobenzaldehydes (IXa to IXd) were condensed with anilines (Xa to Xd), followed by immediate treatment with triethyl phosphite, to afford 5, 6-dialkoxy-2-aryl-2-H-indazoles (VIa to VIl) in a fair yield. Nuclear magnetic resonance and infrared spectra of the indazoles were discussed.

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Various 1, 3-substituted 6-cyanouracils (IIIa-g, IVa-g) were prepared by the reaction of the corresponding 5-bromouracils (Ia-g, IIa-g) and sodium cyanide in dimethyl formamide or 50% aqueous ethiol. In this reaction, treatment of 1, 3-disubstituted 5-bromouracils (IIa-g) with sodium cyanide in 50% aqueous ethanol, afforded 1, 3-disubstitued 6-carbamoyluracils (Va-g). Antibacterial activity of these compounds in vitro was tested.

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