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KIYOSHI KOMINATO
1969 Volume 17 Issue 11 Pages
2193-2197
Published: November 25, 1969
Released on J-STAGE: March 31, 2008
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Since Schneider and Weltheim reported about the essential oils in garlic in 1892, many researchers have studied on its essential oils. Recently Stoll isolated odorless alliin from garlic and found this compound changed to odory allicin with the garlic enzyme. In this paper, isolation method of one kind of thioglycoside from garlic was reported. At first, garlic bulbs were treated with boiling water, crushed and extracted with methanol at a room temperature, and then thioglycoside was adsorbed on active carbon to exclude the concomitants. According to the color reactions and analyses, this compound was proved as R-CH : CH-CH
2-S-C
6H
8O
6·1/2Ca, in which R was a peptide containing a new amino acid, and carbohydrate part was calcium fructuronate. Its aglycon showed some sterilization effects for E. coli.
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KIYOSHI KOMINATO
1969 Volume 17 Issue 11 Pages
2198-2200
Published: November 25, 1969
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In the previous paper, scordinin A
1 was isolated from boiled garlic, and it was seemed as the biological active component in garlic. In this paper the constituents of scordinin A
1 were described from the hydrolysis products of scordinin A
1. By acid hydrolysis of scordinin A
1, fructuronic acid was detected, and by garlic enzyme allyl mercaptan was proved. And by hydrolysis with barium hydroxide, one kind of peptide, scormin, was isolated. From the above results, the author presumed that allyl thiofructuronic acid combined with scormin to form scordinin A
1, and on the chemical structure of scormin will be discussed in Part III in this series.
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IKUO ADACHI, HIDEO KANO
1969 Volume 17 Issue 11 Pages
2201-2208
Published: November 25, 1969
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Ring opening reactions with some bases were examined in the following quaternary salts : 2-ethyl-3, 4-diphenylisoxazolium chloroferrate (V), and 2, 4-dimethyl-3-phenyl-, 3, 4-diphenyl-2-methyl- and 2-methyl-3-phenylisoxazolium perchlorate (IXa, b and c). Treatments of V and IX with sodium alcoholate in alcohol gave the corresponding alkyl cinnamates (VIIa-e). By the use of aqueous sodium hydroxide, V and IXb gave the respective cinnamic anhydrides (Xa and b) contrary to the report of Kohler, et al., and IXa gave an unexpected product, 2, 5-diphenyl-1, 3, 4-trimethylpyrrole (XIa) along with usual ring cleaved products, XIIa and XIIIa. Reactions of IXa, b with several amines gave β-keto acid amides (XIIc-h), the ketones (XIIIa, b) and the pyrrole (XIa) (only from IXa), respectively. Reactions of IXa with Grignard reagents gave 5-substituted △
3-isoxazolines (XIVa, b). Similar 5-amino-△
3-isoxazolines (XVa-c) were obtained by cautious treatment of IXa, b with piperidine or morpholine. Solvolysis of X, XIV and XV were also investigated, and a tentative mechanism for the formation of the various products are presented.
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IKUO ADACHI
1969 Volume 17 Issue 11 Pages
2209-2216
Published: November 25, 1969
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Ring conversion reactions of the quaternary salts : 2, 4-dimethyl-3-phenyl-, 3, 4-diphenyl-2-methyl- and 2-methyl-3-phenylisoxazolium perchlorate (Ia, b and c) with some nucleophiles were investigated. Reactions of I with alkyl malonates in the presence of sodium alcoholates gave the corresponding 4-unsubstituted-2-pyridone-3-carboxylates (II) and their 4-hydroxy derivatives (III), along with 2, 5-diphenyl-1, 3, 4-trimethylpyrrole (IV) and alkyl cinnamates (V). Similar reactions of Ia with some active methylene compounds were also examined. Reactions of I with cyclic enamines gave 4-unsubstituted 1-methyl-2, 3-trimethylene or tetramethylenepyridinium perchlorates (XIII) besides β-kteo acid amides (XIV). Reactions of Ia with potassium cyanate and with phenylhydrazine in the presence of sodium hydroxide gave 3, 5-dimethyl-4-phenyluracil (XV) and 1, 5-diphenyl-3-hydroxy-4-methylpyrazole (XVI), respectively. On the contrary, the reaction of Ia with phenylhydrazine in the absence of sodium hydroxide resulted in the formation of 1, 5-diphenyl-4-methyl- and 1, 3-diphenyl-4-methylpyrazole (XVII and XVIII). A tentative mechanism of these ring conversion reactions of I are presented.
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TATSUO OZAWA, ISAO TOMITA, TAKAKO TOMITA
1969 Volume 17 Issue 11 Pages
2217-2222
Published: November 25, 1969
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The accumulation of acetoin in the culture medium of Saccharomyces carlsbergensis was specific with m-I deficiency. Its concentration in 48 hour culture medium reached to 8 μmoles/mg of dry cell and the ratio of acetoin production by the m-I deficient yeast to that by the normal yeast (m-I supplemented) was found to be 100-1000 in 48 hour cultivation in one of four media tested. Casein hydrolysate used as nitrogen source in the medium, changed this ratio greatly by their lots. pH during the cultivation changed slightly (between 4.5 and 5.0) and it gave no significant effects on acetoin accumulation. Addition of increased amount of ammonium sulfate to the medium gave an adverse effect on the growth of m-I deficient yeast and accelerated the acetoin accumulation. While the addition of cofactors for pyruvate oxidation such as lipoic acid, had no reducing effect for acetoin production, the addition of thiamine was critical for it in m-I deficient Saccharomyces carlsbergensis.
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KOTARO TAKAHASHI, MASARU OGURA, YOSHIHISA TANABE
1969 Volume 17 Issue 11 Pages
2223-2229
Published: November 25, 1969
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A triterpenoid C
30H
48O
5, mp 266-267°, was isolated from the roots of Rosa multiflora THUNB., and was proved to be identical with tormentic acid (2α, 18α-dihydroxyursolic acid). Plausible mass spectral fragmentations of the diacetate (II) were discussed.
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ZENICHI HORII, KOICHI MORIKAWA, ICHIYA NINOMIYA
1969 Volume 17 Issue 11 Pages
2230-2239
Published: November 25, 1969
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The lactim ether (XXII), prepared from 3-methoxy-2-piperidone (XXI) by the action of Meerwein reagent, condensed smoothly with benzyl cyanoacetate to give the Cope product (XXIII), which underwent debenzylation and decarboxylation, followed by sodium borohydride reduction and alcoholysis, yielding a mixture of ethyl cis- and trans-3-methoxy-2-piperidineacetates (XXIX). Cyclodehydration of XXIX with cyclohexanone afforded the vinylogous amides (XXX).
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BUNSUKE UMEZAWA, OSAMU HOSHINO, HIROSHI HARA, KEIKO OHYAMA, SATORU MIT ...
1969 Volume 17 Issue 11 Pages
2240-2244
Published: November 25, 1969
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Acid treatment (60% HClO
4) of veratrylamine N-tosylates (Va-d) as well as condensation of veratrole and formalin or of veratrylalcohol in the presence of strong acids was proved to give cyclotriveratrylene (III) mainly. On the other hand, the similar reaction of Va with various acids in organic solvents was found to afford both III and cyclotetraveratrylene (IV) in moderate yield.
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TETSUJI KAMETANI, MASUO KOIZUMI, KEIICHIRO FUKUMOTO
1969 Volume 17 Issue 11 Pages
2245-2249
Published: November 25, 1969
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Diazotization of 1-(2-amino-5-benzyloxy-4-methoxybenzyl)-1, 2, 3, 4-tetrahydro-6, 7-dimethoxy-2-methylisoquinoline (V), followed by thermal decomposition without metallic catalyst, afforded the O-benzylisosalutaridine (VIII) in 10% yield, which was debenzylated to give isosalutaridine (IV).
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TORIZO TAKAHASHI, YOSHIKI HAMADA, YOSHIO ITO
1969 Volume 17 Issue 11 Pages
2250-2255
Published: November 25, 1969
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Reaction of 2-anilinolepidine with 1.2 mole of nitric acid in acetic acid at room temperature afforded only a mononitrate (VIII). Dissolution of VIII into 98% sulfuric acid under ice chilling afforded 2-(o-nitroanilino) lepidine (I), 2-(p-nitroanilino) lepidine (III), and 2-(p-nitroanilino)-6-nitrolepidine (V). Reaction of VII with acetyl nitrate in dichloromethane at room temperature for 3 hr afforded I in 75% yield, while prolongation reaction time to 15 hr afforded 2-(2', 4'-dinitroanilino) lepidine (IV) in 95% yield. III was obtained by reaction of VII with a large excess of nitric acid. These reaction are optimal for the selective nitration of the anilino group of VII, in order to afford o-nitro (I), p-nitro (III), and o, p-dinitro (IV) derivertives.
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SABURO ISHIWATA, KEIICHI ITAKURA
1969 Volume 17 Issue 11 Pages
2256-2260
Published: November 25, 1969
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The Bischler-Napieralski reaction of the phenethylamides (VIa and VIb) was accelerated by the presence of an ethoxycarbamido group in the 3-position of the benzene ring and the ring-closure occured selectively at the position para to the ethoxycarbamido group to give the corresponding 3, 4-dihydroisoquinolines (VIIa and VIIb) in good yields.
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SABURO ISHIWATA, KEIICHI ITAKURA
1969 Volume 17 Issue 11 Pages
2261-2265
Published: November 25, 1969
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The Bischler-Napieralski cyclization of phenethylamide (VII), having an ethoxycarbamido group in the 3-position of the benzene ring was found to take place in the positions para and ortho to the ethoxycarbamido group, and the two isoquinoline derivatives could be separated in the stage of N-methyl-1, 2, 3, 4-tetrahydroisoquinolines (Xa and Xb) in 1 : 3.5 ratio (para to ortho). Deamination of the 8-amino compound (XIb) gave a mixture of 6, 7-dimethoxy derivative (XIb) and dl-nuciferin (XIIc), which were separated by chromatography on silica gel to give two components in 2 : 1 ratio.
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IKUTOSHI MATSUURA, KIYOSHI OKUI
1969 Volume 17 Issue 11 Pages
2266-2272
Published: November 25, 1969
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Improved syntheses of 1, 4-dihydroxypyrido [3, 4-d] pyridazine (II) and 1, 4-dichloropyrido [3, 4-d] pyridazine (I) were described. Reaction of I with alcohol and alkali gave 1, 4-dialkoxypyrido [3, 4-d] pyridazines (IIIa-c). Hydrolysis of I gave an isomeric mixture of 1-chloro-4-hydroxy- and 1-hydroxy-4-chloropyrido [3, 4-d] pyridazines (IV and V). Reaction of I with hydrazine hydrate afforded also an isomeric mixture of 1-chloro-4-hydrazino- and 1-hydrazino-4-chloropyrido [3, 4-d] pyridazines (VIII and IX). The structures of these compounds were determined by an alternative synthesis of V from known 1-hydroxy-4-aminopyrido [3, 4-d] pyridazine (VI) and by conversion of IX into V. Also described were the preparations of 1-hydroxypyrido [3, 4-d] pyridazine (VII) and isopropylidene derivatives (X and XI) of VIII and IX, and improved syntheses of 1, 4-dichlorophthalazine and ethyl 3-cyanoisonicotinate.
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YOSHIHISA OKAMOTO, TADAKAZU TSUJI, TAKEO UEDA
1969 Volume 17 Issue 11 Pages
2273-2278
Published: November 25, 1969
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The convenient synthesis of 2-substituted-6-amino-4, 5-dihydropyrimidine from the reaction of imidic ester with 3-aminopropionitrile was reported. Next, 2-phenyl- (V) and 2-(2-acylaminoethyl)-6-amino-4, 5-dihydropyrimidines were investigated to clarify their predominant form in the possible from the aspects of infrared spectra. Thus, it was found that V exists as the imino-form and 2-(2-acylaminoethyl)-6-amino-4, 5-dihydropyrimidines as the amino-form in the solid state. Further, it was described the synthesis of 3-acylaminopropionamidine possessing the heterocyclic ring for the purpose of potenciating the activity of benzamidopropionamidine which was studied previously.
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HIROSHI ISHIKAWA, YO MORI, SHINKICHI NIINOBE
1969 Volume 17 Issue 11 Pages
2279-2284
Published: November 25, 1969
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The effect of anti-inflammatory drugs on leucocyte migration and vascular permeability during acute inflammation was examined in lathyritic rats by carboxymethylcellulose pouch method. The above mentioned two unit reactions, especially leucocyte migration, in inflammation locus were promoted in lathyritic rats compared to normal rats. Inhibition pattern of protein exudation showed significant difference between normal and lathyritic groups in case of steroidal anti-inflammatory drugs. Forty percent inhibition in lathyritic rats was observed 3 hr after the injection of corticosteroids, while in normal rats there was no inhibition until 6 hr. There was no marked difference between these two groups in non-steroidal antiinflammatory drugs. The inhibitory effect of steroidal and non-steroidal anti-inflammatory drugs on leucocyte migration was almost the same as in the normal rats or slightly stimulated in lathyritic rats.
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KOSUKE MORIKAWA, MASAMICHI TSUBOI
1969 Volume 17 Issue 11 Pages
2285-2292
Published: November 25, 1969
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Ultraviolet absorbance versus temperature profile has been examined of seven helical nucleic acids in aqueous solutions with and without poly-L-ornithine. The hyperchromicity observed at the melting temperature of each nucleic acid is found to be lowered linearly as the amount of poly-L-ornithine added to the solution. This fact is taken as indicating that there is a stoichiometric complex of polyornithine plus nucleic acid formed. The ornithine/nucleotide mole ratio was determined to be 1/1 for the complexes of calf thymus DNA,
3) poly dAT, rice dwarf virus RNA, and poly rAU. The ratio was found to be 2/3 for the complexes of poly (A+U) and poly (A+2U), and 1/2 for the complex of poly (I+C).
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TOSHIAKI NAKASHIMA, IKUO SUZUKI
1969 Volume 17 Issue 11 Pages
2293-2298
Published: November 25, 1969
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8-Nitroquinoline (I) was contracted to 7-nitrooxindole (III) via 3-hydroxy-8-nitroquinoline (II) with hydrogen peroxide in acetic acid. 3-Hydroxyquinoline-8-carboxylic acid (XIV) and its ethyl ester (XV) were also contracted to oxindole-7-carboxylic acid (XVI) and its ethyl ester (XVII), respectively, in the same conditions. On the other hand, 3-hydroxyquinoline and 3-hydroxy-8-methylquinoline (XX) did not undergo contraction in the above conditions.
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AKIRA TAKAMIZAWA, KENTARO HIRAI, TERUYUKI ISHIBA
1969 Volume 17 Issue 11 Pages
2299-2305
Published: November 25, 1969
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The action of CS
2 on B
1-HCl in MeOH after treatment with Et
3N gave B
1-methyl-xanthogenate (II). This reaction was applied to potassium xanthogenate as a new B
1 precipitant. The reaction of II with primary amines gave thioureas, while the reaction with secondary amines yielded corresponding 2-methyl-4-amino-5-pyrimidinylmethylcarbodithioates by exchange with thiazole moiety of B
1. This substitution reaction was found to be caused by the reaction between B
1 and aminocarbodithioate. On the other hand, the reaction of CS
2 with B
1-Na salt followed by the action of alkyl halides afforded the S-dithioalkoxycarbonylthiamines readily.
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TAKESHI OISHI, MASAKO NAGAI, TAKESHI ONUMA, HITOSHI MORIYAMA, KOICHI T ...
1969 Volume 17 Issue 11 Pages
2306-2313
Published: November 25, 1969
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The reactions of the iminoether (VII) derived from α-piperidone with alkyl cyanoacetate, ethyl acetoacetate, and acetylacetone were investigated. The highly conjugated condensation products were then converted to the saturated compounds. Thus, isopelletierine (XVIII) was synthesized by the reduction of XIII, followed by reoxidation of the secondary alcohol (XVII) into the corresponding ketone. Then, condensation of the oxindole iminoethers with ethyl cyanoacetate was carried out and their reactivity was found to be considerably less than that of simple iminoethers.
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TAKESHI OISHI, MIWAKO OCHIAI, TSUNEKI NAKAYAMA, YOSHIO BAN
1969 Volume 17 Issue 11 Pages
2314-2318
Published: November 25, 1969
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Attempted condensation of dimethylacetamide diethylacetal (Ia) with ethyl phenylacetate (IV) was unsuccessful whereas the reaction of N, N-dimethylvinylamine (IIa) with IV afforded crotonic acid derivative (V) (type A reaction). On the other hand, intramolecular condensation between amide acetals with ester carbonyl (type B reaction) was found to proceed smoothly. Thus, the enamino ketone derivatives (Xa, b) were obtained from the amide acetals (IXa, b) by simply refluxing them in t-butanol.
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SADAO HAYASHI, TAICHIRO KOKENO
1969 Volume 17 Issue 11 Pages
2319-2329
Published: November 25, 1969
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Wolff-Kishner reduction under Huang Minlon's condition of 2-arylmethylene-3-oxo-steroids were investigated, and following results were obtained. 1. Reaction of 2-benzylidene-5α-androstan-3-one (I) gave 2α, 3α-phenylmethylene-5α-androstane (II) and 5α-androstano [3, 2-c] pyrazole (IV). 2. Reaction of 2-benzylideneandrost-4-en-3-one (XXII) gave 2α, 3α-phenylmethyleneandrost-4-ene (XXIII), 5β-androstano [3, 2-c] pyrazole (XXIV), IV and androst-4-eno [3, 2-c] pyrazole (XXV). 3. Reaction of 2-benzylideneandrost-4, 6-dien-3-one (XXVI) gave 2α, 3α-phenylmethyleneandrost-4, 6-diene (XXVII) and XXV. Stereochemistry of products and reasonable explanation for the reaction process were presented.
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MASANAO SHIMIZU, SHINICHI NAKAMURA, YOSHIYUKI TAKASE
1969 Volume 17 Issue 11 Pages
2330-2334
Published: November 25, 1969
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On the way of the study to improve the in vivo antibacterial activity of nitrofuran compounds, it was found that the some N-oxide derivatives of (5-nitro-2-furyl) vinyl heterocycles had the superior in vivo activity to the corresponding original compounds. To clarify whether such tendency was observed in general, thirteen (5-nitro-2-furyl) vinyl heterocycles and their N-oxide derivatives were co mpared on their oral protective effects in mice and additionally on the in vitro antibacterial activities and the plasma levels in rats. It was generally observed that the N-oxide derivatives were superior to the corresponding original compounds in the protective effects. Such superiority seemed to be partially attributed to the increase of the in vitro antibacterial activities and the plasma levels of the N-oxide derivatives.
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YOSHIRO KOBAYASHI, ITSUMARO KUMADAKI, SHIGERU TAGUCHI
1969 Volume 17 Issue 11 Pages
2335-2339
Published: November 25, 1969
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First, 2-, 3-, and 4-(trifluoromethyl) quinoline 1-oxides (IV, V, and VI) were synthesized. Next, their reactions with acetic anhydride and phosphoryl chloride and the Reissert reaction were carried out and compared with the reactions in the cases of pyridine series. The reactions of IV with acetic anhydride and phosphoryl chloride gave 4-substituted products, whereas in the cases of V and VI 2-substituted products were obtained. In the Reissert reaction of IV, the starting material was recovered ; in the cases of V and VI, 2-nitrile derivative was produced as well as a considerable amount of 2-hydroxy derivative as by-product. Then, the reaction of V with only potassium cyanide in methanol was carried out to obtain 3-(trifluoromethyl) cinchoninonitrile. The unique result as above was concluded to be due to the naphthoid structure of quinoline.
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SABURO MIZUTANI, YAEKO WAKURI, NAOMI YOSHIDA, TERUMI NAKAJIMA, ZENZO T ...
1969 Volume 17 Issue 11 Pages
2340-2348
Published: November 25, 1969
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4'-Hydrazino-2-stilbazole (4H2S) was discovered as a specific, selective and sensitive fluorometric reagent for α-oxo acids. Fluorescence characteristic of 4H2S-hydrazones of α-oxo acids were examined and a new fluorometric determination method of α-oxo acids was developed. By the application of this method, a simple and microdetermination procedure of total α-oxo acids in blood was established. This method was not interfered by biological materials, and the sensitivity was about 100-200 fold to that of the existing colorimetry.
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CHAUYANG CHEN, HARUHIKO YAMAMOTO, TAKAO KWAN
1969 Volume 17 Issue 11 Pages
2349-2352
Published: November 25, 1969
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Catalytic hydrogenation of calcium D-xylo-5-hexulosonate (5-keto-D-gluconate) has been investigated on transition metal catalysts with special interest in the selective formation of calcium L-idonate. The reaction completed usually within several hours under 20-100 kg/cm
2 hydrogen pressures at 80°. Initial rates on a Raney nickel catalyst were represented by dC/dt=k'P
H20.5 where C is the degree of conversion. Nickel, ruthenium and palladium gave rise to more L-idonate especially when prepared from their salts by treating with sodium borohydride. For example, 73% of the hydrogenated products was L-idonate on a "boron-modified-palladium"catalyst.
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TETSUJI KAMETANI, KAZUO KIGASAWA, MINEHARU HIIRAGI, HARUHIDE ISHIMARU
1969 Volume 17 Issue 11 Pages
2353-2357
Published: November 25, 1969
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RAM LAKHAN
1969 Volume 17 Issue 11 Pages
2357-2361
Published: November 25, 1969
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SATOSHI OMURA, AKIRA NAKAGAWA, KENJI SEKIKAWA, MASARU OTANI, TOJU HATA
1969 Volume 17 Issue 11 Pages
2361-2363
Published: November 25, 1969
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KENJI KUMAKI, SAKAE WADA, IKUO MORIGUCHI
1969 Volume 17 Issue 11 Pages
2364-2365
Published: November 25, 1969
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TOSHIO NAMBARA, TOSHIHIRO KUDO, HIROSHI HOSODA, KIKUKO MOTOJIMA, SHUJI ...
1969 Volume 17 Issue 11 Pages
2366-2370
Published: November 25, 1969
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HIROSHI MITSUHASHI, UKON NAGAI, TOHRU ENDO
1969 Volume 17 Issue 11 Pages
2370-2373
Published: November 25, 1969
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MINEO SANEYOSHI, KENJU TERASHIMA
1969 Volume 17 Issue 11 Pages
2373-2376
Published: November 25, 1969
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HIROYUKI SUDA, TOMIO TAKEUCHI, TOSHIHARU NAGATSU, MEIKI MATSUZAKI, IKU ...
1969 Volume 17 Issue 11 Pages
2377-2380
Published: November 25, 1969
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YUICHI KANAOKA, KAZUTAKA TANIZAWA, OSAMU YONEMITSU
1969 Volume 17 Issue 11 Pages
2381-2383
Published: November 25, 1969
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MASATAKA ICHIKAWA, HISASHI ICHIBAGASE
1969 Volume 17 Issue 11 Pages
2384-2388
Published: November 25, 1969
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YUZURU SHIMIZU, YOSHIMASA SATO, HIROSHI MITSUHASHI
1969 Volume 17 Issue 11 Pages
2391-2394
Published: November 25, 1969
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TOSHIO NAMBARA, MITSUTERU NUMAZAWA, SETSUKO AKIYAMA
1969 Volume 17 Issue 11 Pages
2394-2395
Published: November 25, 1969
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