In dehydration of 1, 1-diphenylcyclopentane-tetrone dihydrate (1) and in dehydrogenation of 1, 2-dihydroxy-4, 4-diphenylcyclopentene-3, 5-dione (4), the formation of 1, 1-diphenylcyclopentane-tetrone (3) was detected. The compound 3 reacted with stilbene at its two adjacent carbonyl groups to give the 1, 4-cycloaddition products, 5 and 6. Dehydrating ability of 3 towards acenaphthene is comparable to that of ο-chloranil, and its redoxpotential was assumed to be 0.7-0.87 V.

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Autoxidative cleavage of N-p-tolyl-D-glucosylamine (I) in ethanol solution containing p-toluidine yielded three pigments, X₁, X₃, and X₃, which were isolated together with other decomposition products. These pigments were identified with 2, 3-dideoxo-2, 3-di(p-tolylimino)-5-methylindoline (X₁) (reddish brown), 5, 5'-dimethylindirubin (X₂)(violet), and 3-deoxo-3-(p-tolylimino)-5, 5'-dimethylindirubin (X₃) (violet). These pigments were formed from the C₁ -C₂ fragment of the sugar and p-toluidine, and their structure was identified by synthesis from 5-methylisatin (X) by a different route. Free radical signal was detected in the electron spin resonance spectrum of the rection mixture of I and p-toluidine, and the signal was retained during the browning reaction which required a large amount of oxygen at the initial stage of the reaction. These results indicate that a free radicald formation was involved in this amino-carbonyl reaction and, therefore, the pigments obtained here were formed from C₁-C₂ fragments produced by the radical reaction between the sugar and the amine.

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Determination of iodine in organic iodine compound and in the see-weed "Wakame"(Undaria pinnatifida) by non-dispersive fluorescence X-ray analysis was carried out, employing ²⁴¹Am (100 mCi) source. A detector of 13/(4)"φ×1" NaI(Tl) scintillation crystal and a 400-channel pulse height analyzer were employed for the X-ray spectrum measurement. The analysis can be made within 10 minutes with the standard deviation of less than 1% for samples containing more than 0.1% iodine. In the case of Wakame, iodine is concentrated by ashing and can be determined up to 80 ppm. The results obtained by this method show 2-3% greater values than those by a conventional pharmacopoeial method. The present method is simple, has good reproducibility, and seems to be well applicable to the analysis of pharmaceutical preparations.

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Photochemical reaction of the mixture of 3-(p-toluenesulfonyl)-1, 2-dihydro-3H-pyrazino[3, 2, 1-kl]phenoxazine (I) and 4-benzenesulfonyl-1, 2, 3, 4-tetrahydro[1, 4]diazepino[3, 2, 1-kl]phenoxazine (VII) in benzene gave 1, 2-dihydro-3H-pyrazino[3, 2, 1-kl]phenoxazine (III), 1, 2, 3, 4-tetrahydro[1, 4]diazepino[3, 2, 1-kl]phenoxazine (IV), 6-(p-toluenesulfonyl)-1, 2-dihydro-3H-pyrazino[3, 2, 1-kl]phenoxazine (V), and 7-benzenesulfonyl-1, 2, 3, 4-tetrahydro-[1, 4]diazepino[3, 2, 1-kl]phenoxazine (XI), but 6-benzenesulfonyl-1, 2-dihydro-3H-pyrazino-[3, 2, 1-kl]phenoxazine (XIII) and 7-(p-toluenesulfonyl)-1, 2, 3, 4-tetrahydro[1, 4]diazepino-[3, 2, 1-kl]phenoxazine (VI), compounds formed by intermolecular rearrangement of the substituent, were not obtained. Therefore, it was concluded that the formation mechanism of V and XI progressed by the solvent cage reaction.

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Relation of the chemical structure and toxicity to radioprotective activities was examined with various compounds having cysteamine as the fundamental skeleton. Radioprotective effect showed no marked change by substitution of SH group with SSO₂H group or its conversion to S-S type by bimolecular condensation. It was also found that the effect was retained even when the NH₂ group was substituted with other group(s), or by the formation of a 5-membered or 6-membered cyclic structure.

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Four glucosides were isolated from the fruits of Cornus officinalis SIEB. et ZUCC.(Cornaceae). Three of them were identified with morroniside (VII), loganin (IV), and sweroside. The other one was a new iridoid glucoside, 7-ο-methylmorroniside (VI), (tetraacetate (I), mp 103-105°) which seemed to be an artifact formed during the extraction process.

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As one of studies on active principles of tar, antifungal constituents in charred egg yolk or in egg tar were examined. Four active principles, (I), (II), (III), and (IV), were isolated by a suitable combination of counter-current distribution and column chromatography.(I) mp 195°, C₁₁H₈N₂, (II), mp 232°, C₁₂H₁₀N₂, (III), mp 217° (picrate), C₁₆H₁₈N₂ (m/e238), and (IV), mp 236-238° (picrate), C₁₆H₁₈N₂ (m/e 238), were found to be identica1 with norharman, harman, 1-isopentyl-β-carboline, and 1-(1-methyl-butyl)-β-carboline, respectively.

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As one of studies on active principles of tar, antihistamic and antifungal constituents in dry-distillation tar of non-fat soybean were examined. Four active principles (I), mp 195°, C₁₁H₈N₂, (II), mp 232°, C₁₂H₁₀N₂, (III), mp 248-250° (picrate), and (IV), mp 218-220° (picrate) were isolated by a suitable combination of column chromatography and were identified with norharman, harman, benzo[f]quinoline, and phenanthridine, respectively.

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Two lignan glucosides have been isolated from the leaves of Symplocos lucida. Their structures were established as (-)-pinoresinol-β-D-glucoside and (-)-pinoresinol monomethyl ether-β-D-glucoside, respectively.

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4, 4'-Biphenyldisulfonate of N-methyl-N, N-bis (3-methylsulfonyloxypropyl) amine (838-D) and p-to1uenesulfonate of bis (3-methylsulfonyloxypropyl) amine (864-T) were effective on several experimental tumors of ascites or solid form in mice and rats. Especially, 864-T showed a marked effect at a dose of 10 mg/kg or above, against tumors such as AH 66 and AH 7974 less sensitive to most alkylating agents ever known. The compounds decreased number of leucocyte in the peripheral blood and also weight of the spleen at a dose of 10 or 50 mg/kg, but these toxic signs appeared more severely in rats than in mice. In general the toxic manifestation of 864-T was milder than 838-D.

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Treatment of 3, 6-dimethylpyridazine 1, 2-dioxide (I) with nitric acid in sulfuric acid at room temperature gave 4-nitro-3, 6-dimethylpyridazine 1, 2-dioxide (II) as yellow needles in a good yield. Heating of I with sulfuric and nitric acids at 70° gave 4-nitro-3, 6-dimethylpyridazine 1-oxide (IV), 4-nitro-3, 6-dimethylpyridazine 2-oxide (V), and 3, 6-dimethylpyridazine 1-oxide (III) with the formation of II. On the other hand, nitration of I with benzoyl nitrate in chloroform afforded II in a very poor yield. I was highly resistant to other electrophilic reactions, such as bromination, sulfonation, and Mannich reaction. Condensation of I and benzaldehyde, with sodium methoxide as a catalyst, resulted in the formation of 3, 6-distyrylpyridazine 1, 2-dioxide (VII).

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Physicochemical properties of proteinases (Ficin A, B, C and D) from the latex of Ficus carica var. HORAISHI were examined. They resembled in sedimentation constant, partial specific volume, specific rotation, extinction coefficient and intrinsic viscosity, but differed in isolectric point. Each of these enzymes appeared to consist of a single polypeptide chain with amino terminal leucine. They differed in amino acid composition, particularly in the content of lysine, threonine, valine and leucine, and Ficin B and C contained one buried sulfhydryl group. Finger prints of Ficin A, B, C and D were much differed. It is concluded that Ficin A, B, C and D have similar physical properties.

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The phase-separation in the ternary system of solvent-1, nonsolvent-2, and polymer-3 was studied and the volume fraction of each component in the dilute phase (v₁', v₂', v₃') and in the concentrated phase (v₁", v₂", v₃") were calculated accordins to Flory's theoretical equations. The values at the plaint point, (v₁)_pl, (v₂)_pl, (v₃)_pl, were also calculated according to Scott's equations. In this treatment it was assumed that P₁=P₂=1, P₃=P«1 for the polymerization degree P=100, 250, 500, 1000, 2500, 5000, 10000, ∞, and A=X₁₃/P₁=X₃₁/P₃, -0.4, 0, 0.4, B=X₁₃/P₁=X₂₁/P₂, -2, -1, 0, 1, C=X₂₃/P₂=X₃₂/P₃, 0.75, 2, 5 for the interaction parameters. From these calculations, theoretical solubility limit equation was obtained of various polymerization degree and various interaction parameters ;(v₂)_ppt=f(P)-g(P)log(v₃)_ppt.and f(P)=k₁+g(P)logk₂. The linear relation between g(P) and logarithm P satisfied the equation g(P)=k₃P^-0.532.

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4-Methylquinoline, when treated with chlorine in carbon tetrachloride, undergoes addition reaction to give 5, 6, 7, 8, 8-pentachloro-5, 6, 7, 8-tetrahydro-4-methylquinoline. Similarly, 2-chloro-4-methylquinoline and 4-chloro-2-methylquinoline undergo addition reaction to give 2, 5, 6, 7, 8-pentachloro-5, 6, 7, 8-tetrahydro-4-methylquinoline and 4, 5, 6, 7, 8, 8-hexachloro-5, 6, 7, 8-tetrahydro-2-methylquinoline, respectively. On the other hand, similar chlorination of 2-ethoxy-4-methylquinoline gives 6, 8-dichloro-2-ethoxy-4-methylquinoline and 3, 6-dichloro-4-methylcarbostyril. Ch1orination of 2-chloroquinoline gives 2, 5, 6, 7, 8-pentachloro-5, 6, 7, 8-tetrahydroquinoline but that of 4-chloroquinoline or quinoline gives mainly 3, 4, 6, 8-tetrachloroquinoline.

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A newly precoated plate for thin-layer chromatography (TLC) has been prepared, which is made from a mixture of Kieselguhr and fused glass powder. Because this sintered plate contains no organic binders such as starch, polyvinyl alcohol, polyethylene, etc., it is not charred under any drastic conditions, i.e. by heating after spraying corrosive reagents such as sulfuric acid, chromic acid mixture, trichloroacetic acid, antimony trichloride, etc. Thin-layer chromatographic separation of various organic compounds such as azo dyes, sugars, higher fatty acids, and polychlorinated biphenyls (PCB) was examined by using this new plate, and it was found that this plate gave good reproducibility of separation as reliable as the home-made plates prepared from the commercial Keiselguhr. This plate is mechanically stable, heat-stable, and acid-resistant. Moreover, it can be repeatedly used by soaking the chromatogram into cleaning solutions.

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The non-phenolic tertiary alkaloids from Corydalis incisa PERS., in each vegetative and reproductive phases, were investigated. Three new natural alkaloids, l-tetrahydrocorysamine, acetylcorynoline, and acetylisocorynoline, and five unknown alka1oids, TN-4, -5, -12, -21, and -23 were isolated from this plant, in addition to isocorynoline, corynoline, corycavine, and protopine. Yield of these alkaloids (Table I), indicates that variation in the content of alkaloids is attributed to the growing stage.

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In order to examine the reactivity of ring carbon at 4-position towards nucleophilic reagents, reaction of 4-methoxyquinazoline (III), 2-methyl-2-(4-quinalinyl) propiophenone (IV), and α-phenyl-4-quinalineacetonitrile (V) with various nucleophilic reagents was carried out. The reaction of III with phenylacetonitrile, ethyl cyanoacetate, and malononitrile in methanol, in the presence of a methoxide ion, respectively afforded the corresponding V, methyl α-cyano-4-quinazolineacetate (VI), and 4-quinazolinemalononitrile (VII). The reaction of IV with methoxide ion, aniline, butylamine, piperidine, and hydrazine respectively afforded the corresponding III, 4-anilino- (X), 4-butylamino- (XI), 4-piperidino- (XII), and 4-hydrazino-quinazoline (XIII). In the reaction of IV with acetone and acetophenone, in the presence of sodium amide, β-diketones corresponding to 4-isopropylquinazoline (XV) were produced as 1-phenyl-1, 3-butanedione (XVI) and 1, 3-diphenyl-1, 3-propanedione (XVII). The reaction of V with methoxide ion, aniline, butylamine, and piperidine respectively afforded III, X, XI, and XII.

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Catalytic effect of some metal cyano complexes on the Sandmeyer reaction was examined by determination of benzonitrile using gas-liquid chromatography. The catalytic action of copper- and nickel-cyano complex was effective but the other metal-cyano complexes, such as those of silver, gold, cadmium, cobalt, chromium, iron, manganese, mercury, palladium, platinum, and zinc were weak or negligible. A difference in catalytic action between copper- and nickelcyano complex was seen in the effect of reaction conditions. Good yield of benzonitrile was obtained with the former by all pH ranges in the solution, but with the latter, only in alkaline solution. The Sandmeyer reaction did not run quantitatively and some kind of by-products were obtained. As the main by-product, phenol was detected and determined when the reaction was run in acidic solution. In neutral and alkaline solution, two other acidic products were found. They were separated by alumina column chromatography and recrystallized from methanol-water mixture to yellow microplates, mp 151°, and reddish brown needles, mp 134°. The former was identified as p-hydroxyazobenzene and the latter as 2, 4-bisphenylazophenol.

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Effect of thiol and disulfide compounds on thiol-disulfide transhydrogenase (TDTH), glutathione reductase (GR), and glucose-6-phosphate dehydrogenase (G6PD) were studied in normal and alloxan-diabetic rats. 1. In both in vitro and in vivo experiments, GR activity in the pancreas, liver, and kidney of normal and alloxan diabetic (AD) rats was inhibited by glutathione (GSH), 2-mercaptopropionylglycine (MPG), and cysteine, while there was no significant difference in the GR activity between rats receiving the oxidized form of these three compounds and the control. 2. GSH-oxidized MPG-TH activity and GSH-cystine-TH activity in vitro and in vivo were examined and neither MPG nor cysteine was found to produce a significant difference in the TDTH activity. 3. G6PD activity in vivo was increased in the early period after GSH and MPG administration. The oxidized form of these compounds decreased G6PD activity. The results of these experiments showed that thiol compounds had effect on GR activity and indirectly increased glucokinase (GK) activity. Oxidized GSH had no effect on these three enzymes for GK assay, but acted directly GK enzyme and decreased GK activity. It is of great interest that thiol compounds have a stronger effect on the enzymes in AD rats than in normal rats.

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Absorption, distribution, metabolism, and excretion of 2-mercaptopropionylglycine (MPG) were studied by giving 50 mg/kg of ³⁵S-labeled MPG to rats. The results are sammarized as follows : 1) MPG was readily absorbed from the gastrointestinal tract and reached the highest blood level shortly after administration. (15-30 min). MPG was rapidly excreted. Four hours after administration, 73% of the dose given intraperitoneally and 48% of the dose given orally were excreted in the urine. 2) In earlier period after administration (15-30 min), considerable accumulation of MPG was observed in the kidney, pancreas, adrenal, liver, etc. MPG remaining in these organs was less than 1 μg/g 24 hr after administration. 3) Distribution in blood was such that 30 minutes after intraperitoneal injection, about 70% of MPG was found in red cells. On the other hand, more than 60% of radioactivity was observed in the fraction of blood protein. Examination of subcellular distribution of MPG in the liver revealed maximum localization in mitochondria. 4) As for metabolites in urine, 6 spots were detected on thin-layer chromatogram. The main metabolites were 3 including MPG, its disulfide, and thiolactic acid. The other three were unidentified.

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1) Accumulation of cadmium and its effect on various organs of the rat was discussed. 2) During the first week of daily intraperitoneal administration of cadmium chloride, body weight of rats decreased and then it increased in spite of repeated injection. 3) Most of cadmium given by intraperitoneal administration accumulated in the liver and kidney, but not in the brain. 4) After intraperitoneal administration of cadmium chloride, non-protein-bound sulfhydryl content decreased in the liver, while protein-bound sulfhydryl content increased in the kidney. 5) Changes in the fatty acid composition by cadmium administration were not observed in various organs of the rat.

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The neutral volatile oil of the flower stalk of Petasites japonicus was separated by silica gel column chromatography and then by gas chromatography. Isopentanol, 3-hexen-1-ol, 1-nonen-3-ol, l-linalool, and veratrole were identified as the minor constituents. The volatile oils of the flower stalk collected from various places in Japan and oils extracted from various organs of the plant were examined (Table I). Large quantities of 1-nonene and angelic acid were found in any parts of the plant. The oil obtained from flower stalks consisted mainly of 1-undecene, 1-tridecene, 3-acetoxy-1-nonene, β-elemene, and β-bisabolene, and the oil from the leaves consisted mainly of 1-tridedene, β-caryophyllene, and alcohols.

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