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AKIRA MIZUTANI, TOYOHIRO KITAMURA, NAOKI YAMADA, HITOSHI INABA, YUKIO ...
1974 Volume 22 Issue 9 Pages
1955-1962
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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The main hypocalcemic protein from bovine parotid gland was purified by chromatography on DEAE-cellulose, gel chromatography on Sepharose 6B, preparative polyacrylamide gel electrophoresis, and second gel chromatography on Sepharose 6B, resulting in a single substance by analytical disc electrophoresis, gel chromatography, and isoelectric focusing. This purified protein lowered the serum calcium concentration by 10.83±1.01% in a dose of 0.008mg/kg in rabbits. Amino acid analysis of this protein revealed its relatively acidic nature. Its molecular weight was found to be 48000 by sodium dodecyl sulfate-polyacrylamide gel electrophoresis.
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TADAMASA DATE, KEIICHI AOE, KEISHI KOTERA, KIMIO UMINO
1974 Volume 22 Issue 9 Pages
1963-1967
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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In order to confirm the proposed structure and to elucidate stereochemistry of pentenomycins, an X-ray crystal structure analysis of monobromopentenomycin triacetate (C
12H
13O
7Br) (I) has been carried out. The crystals of (I) are orthorhombic with space group P2
12
12
1 and the unit cell dimensions are a
0=9.588 (2), b
0=21.445 (7) and c
0=6.983 (1) Å ; Z=4. the absolute configuration was determined by the use of the anomalous dispersion effect of the bromine atom for Cu Kα radiation. From the analytical data, (I) was confirmed to be 4, 5-diacetoxy-5-acetoxymethyl (4 : S, 5 : S)-2-bromo-cyclopent-2-en-1-one.
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KOUICHIRO UMEMOTO
1974 Volume 22 Issue 9 Pages
1968-1974
Published: September 25, 1974
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A series of experiments was carried out to prove the possibility that the morphological character of crystalline inorganic components in a plant might become a valuable index in elucidating the kinship of plants, and detailed examinations were made on the crystalline pattern of calcium oxalate present in the leaves of sweet potato plants (Ipomoea batatas LAM. var. edulis MAKINO) grown in vastly different conditions ; presence and absence of light (natural light and darkness). It was thereby found that the crystalline pattern was identical in two samples, indicating that the morphological character of crystalline inorganic components formed in a plant is independent of its photochemical reaction system. These results, together with results obtained from my past studies, indicate that "the morphological character of crystalline inorganic components present in a plant is one of the important characters inherent in and is a specific character reflecting the properties of the protoplasmic character and a genetic character."
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CHIAKI MORIWAKI, KEIKO YAMAGUCHI, HIROSHI MORIYA
1974 Volume 22 Issue 9 Pages
1975-1980
Published: September 25, 1974
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The perfusion of the mesenteric vascular system with Krebs-Ringer solution was carried out on the rats, and the vasodilator and BAEE-esterolytic activities in the perfusate were determined after the intestinal administration of hog pancreatic kallikrein. The recoveries of both kallikrein activities agreed well with each other and with that of
131Imacromolecules in the case of a combined administration of
131I-kallikrein. The transmission of kallikrein through the intestine seemed to reach its maximum within 30 min after the administration and it diminished rapidly thereafter. The mesenteric perfusate formed a few precipitin bands against the anti-kallikrein rabbit serum on the double immunodiffusion, and one of them was also positive in the activity-staining utilizing BAEE-esterolytic activity. These results suggest that the pancreatic kallikrein is transmitted from the intestine to the vascular system, maintaining its enzymic properties and its immunoreactivity and that about 1% of the given kallikrein seems to be absorbed into the mesenteric vein under this experimental condition.
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HISASHI ISHII, YASUOKI MURAKAMI, HARUKI TAKEDA, TOKUO FURUSE
1974 Volume 22 Issue 9 Pages
1981-1989
Published: September 25, 1974
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Fischer indolization of ethyl pyruvate 5-chloro-2-methoxyphenylhydrazone (6) with anhydrous zinc chloride gave ethyl 4-amino-6-chloroindole-2-carboxylate (12) as a main product, with three other expected in doles, (7), (8) and (5). Cyclization of ethyl pyruvate 2-methoxyphenylhydrazone (1) with p-toluenesulfonic acid in the presence of diethyl malonate afforded ethyl 4-(ethoxycarbonylacetamido)-indole-2-carboxylate (28) and diethyl 4-(ethoxycarbonylacetamido)-3, 6'-biindole-2, 2'-dicarboxylate (30) with five other indole derivatives, (11), (10), (26), (27), and (32). The pathway leading to such a 4-aminoindole product in the abnormal Fischer indolization of a 2-methoxyphenylhydrazone derivative is discussed.
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MITSURU FURUKAWA, TAKESHI YUKI, SEIGORO HAYASHI
1974 Volume 22 Issue 9 Pages
1990-1995
Published: September 25, 1974
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The reactions of arylcarbonylethylthiosulfates (I) with hydrazines and hydroxylamines were investigated. The compound I reacted with phenylhydrazine to give 1-phenyl-3-aryl-2-pyrazolines (II). The reaction of I with hydrazine, however, gave 1-β-arylcarbonylethyl-3-aryl-2-pyrazolines (III). On the other hand, in the reaction of I with N, N-dimethylhydrazine, demethylation occurred to afford 1-methyl-3-aryl-2-pyrazolines (IV). In the reaction of I with hydroxylamine, 3-aryl-2-isoxazolines (V) and β, β'-hydroxylamino-bis-propiophenones (VI) were obtained under refluxing conditions and at room temperature, respectively. Moreover, the reaction of I with phenylhydroxylamine gave N-arylcarbonylethylhydroxylamines (VIII).
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YOSHISHIGE SATO, MARI SAKUMA, MAKIKO KIMURA, FUMIE NAKAZATO, KAZUAKI N ...
1974 Volume 22 Issue 9 Pages
1996-2003
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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The distribution of tritium-labeled Penfluridol (
3H-TLP-607), a potent and longacting neuroleptics, was studied in mice and rats by the whole body autoradiographic technique. In mice after intravenous administration the highest concentration of radioactivity was found in the lung, heart muscle, skeletal muscle, kidney and moderate in the central nervous system. In the brain the radioactivity in the cortices of the cerebrum and the cerebellum was higher than in the white matter, and a fair amount of radioactivity was observed also in the hippocampus. In the case of oral administration the highest radioactivity in various organs was observed 2 to 8 hours after the administration. In these periods the highest concentration was found in the lung, kidney and spleen, next to these in the thyroid and blood, and moderate in the central nervous system and sexual organs. In pregnant mice after oral administration,
3H-TLP-607 and its radioactive metabolites passed through the placenta into the fetuses, but the concentration in the fetuses was lower than in the mother. In rats the distribution pattern after oral administration was similar to that in mice ; highest in the lung, kidney, spleen and moderate in the central nervous system. The distribution in the rat brain also resembled that in the mouse brain, but the uptake into the hippocampus was observed more remarkably. In female rats high radioactivity was found in the ovary, low in the mammary gland in earlier periods, and vice versa 16 hours later.
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MIKIO HORI, TADASHI KATAOKA, HIROSHI SHIMIZU, MICHIHIRO MIYAGAKI
1974 Volume 22 Issue 9 Pages
2004-2013
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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In order to elucidate the mechanism of the ligand-exchange reaction between sulfonium salt and organolithium, the reactions of organolithiums with 10-substituted 9, 9-dimethylthioxanthenium salts and dibenzothiophenium salts having a bulky group at 5-position have been carried out to get the results, as shown in Tables I and II. It has been proposed that the SN2 type mechanism is valid for the ligand exchange in the reactions described above.
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MIKIO HORI, TADASHI KATAOKA, HIROSHI SHIMIZU, MICHIHIRO MIYAGAKI, MASA ...
1974 Volume 22 Issue 9 Pages
2014-2019
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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5-Substituted 10, 11-dihydrodibenzo [b, f] thiepinium salts were synthesized in order to elucidate the mechanism of reactions between acyclic triarylsulfonium salts and organolithiums. The reaction of aryllithiums with 5-substituted 10, 11-dihydrodibenzo [b, f] thiepinium salts has been investigated to get the results, as shown in Table I. The mechanisms for the formation of all products of the runs in Table I have been clearly explained as shown in Chart 3.
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MIKIO HORI, TADASHI KATAOKA, HIROSHI SHIMIZU, MICHIHIRO MIYAGAKI
1974 Volume 22 Issue 9 Pages
2020-2029
Published: September 25, 1974
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In order to compare the mechanisms of reactions of sulfonium salts with organolithiums and Grignard reagents, the reactions between 5-substituted dibenzothiophenium salts and methyllithium, methylmagnesium halides, and phenylmagnesium halides have been investigated to get a large difference as shown in Tables I and II, respectively. The reactions of 5-substituted dibenzothiophenium salts with methyllithium gave ring-opening products (I) as main products in Table I, whereas the reactions of those with methylmagnesium iodide gave no I or only little. Instead, these reactions gave ringopening products (III) as main products in Table II. The mechanisms of the formation of the products of the runs in Table I and II have been explained as shown in Chart 2 and Chart 4, respectively.
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MIKIO HORI, TADASHI KATAOKA, HIROSHI SHIMIZU, MICHIHIRO MIYAGAKI, TAKA ...
1974 Volume 22 Issue 9 Pages
2030-2041
Published: September 25, 1974
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The reactions of 5-substituted dibenzothiophenium salts, having one or two substituents, with sodium alkoxides and benzenethiolate have been studied in the protic solvents. The results in Table I showed that the 5-substituted dibenzothiophenium salts with alkoxide ions mostly proceed via aromatic bimolecular nucleophilic substitution and ligand exchange as shown in Chart 7. It has been also found that the reactions of 5-substituted dibenzothiophenium salts with benzenethiolate ion support the validity of the mechanism proceed by the aromatic bimolecular nucleophilic substitution as shown in Table II.
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KENICHIRO MINEGISHI, TSUTOMU YAMAHA
1974 Volume 22 Issue 9 Pages
2042-2047
Published: September 25, 1974
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Absorption, excretion, and distribution of Guinea Green B were investigated in rats. This color was hardly absorbed when given orally ; only 2.28% of the dose of the color was recovered in the bile after 24hr. The cumulative recovery of biliary excretion amounted to 86.5% at 4hr and 96.5% at 24hr after intravenous injection. The color was not metabolized except the formation of the leuco form in the large intestine. In the case of intravenous injection, the color disappeared rapidly from various tissues except in the liver and kidney.
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ISAMU MURAKOSHI, FUMIO IKEGAMI, FUMIO KATO, KAZUO TOMITA, SHOJI KAMIMU ...
1974 Volume 22 Issue 9 Pages
2048-2050
Published: September 25, 1974
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Crude extracts prepared from Citrullus, Pisum and Leucaena seedlings catalyze the glucosylation of 3-hydroxy-5-methylisoxazole (I) by uridine-5'-diphosphoglucose to yield 3-β-D-glucopyranosyloxy-5-methylisoxazole (II). The enzyme (s) from Citrullus also catalyzed the synthesis of 2-β-D-glucopyranosyl-5-methylisoxazolin-3-one (III), although at a very slow rate. The optimum pH of the reaction was 7.5. Some other properties of the enzyme (s) are also described. Extracts of Citrullus also catalyzed the hydrolysis of II into I and D-glucose. The optimum pH for this reaction was 5.5. An analogous reaction for the hydrolysis of III could not be demonstrated.
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TAKUZO HISANO, MASATAKA ICHIKAWA
1974 Volume 22 Issue 9 Pages
2051-2057
Published: September 25, 1974
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In order to clarify in more detail the cyclization mechanism of thioanilides to benzothiazoles under the modified Willgerodt-Kindler reaction condition, quinaldine (I) was heated with meta-substituted anilines (II) or meta-substituted nitrobenzenes (III) in the presence of sulfur. Further, in order to examine on solvent effects through these processes, dimethylformamide (DMF) was employed. Although the yields of these reactions were different, the reactions also gave similarly thioanilides and one of the two possible benzothiazoles. The latter was proved to have the structure of 5-substituted 2-(2-quinolyl) benzothiazoles (V) by independent synthesis. On the other hand, the expected two isomeric benzothiazoles (V and VI) were obtained from the oxidaitve cyclization of thioanilides (IV) by the modified Jacobson reaction. Moreover, the thioanilides obtained from I or 2-picoline were found to react with the corresponding II in the presence of sulfur in DMF at 160-170°to give the selective cyclization product, respectively.
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TOSHIO MIYAZAKI, YASUTA NAOI
1974 Volume 22 Issue 9 Pages
2058-2063
Published: September 25, 1974
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Main water-soluble polysaccharide, PS-1, [α]
25D+166° (c=1, H
2O), from the cell wall of Cladosporium herbarum is a glucan. Results of periodate oxidation, Smith degradation, and methylation studies showed that the glucan consists of linear structure possessing a few branches. It contains (1→3) and (1→4) D-glucopyranosyl-linkages. Result of proton magnetic resonance studies showed the glycosidic linkage in the glucan to be α-configuration.
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SHO INOUE, AKIO OGINO, MASAHIRO KISE, MASAHIKO KITANO, SUMIE TSUCHIYA, ...
1974 Volume 22 Issue 9 Pages
2064-2068
Published: September 25, 1974
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The 1-octanol-water partition coefficient, P, of a number of substituted aminouracil derivatives was determined. The log P values were found to be composed additively from π values, (the increments in log P), attributable to each substituent at various positions. The π values of substituents are position specific and are governed by their hydrophobicity as well as by their electronic effect on the ring system.
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TETSUO OZAWA, YOICHI IITAKA, MASAAKI HIROBE, TOSHIHIKO OKAMOTO
1974 Volume 22 Issue 9 Pages
2069-2074
Published: September 25, 1974
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The structure of the bromoacetylated dimer-A (BADA) benzene solvate ; C
30H
26O
2N
6Br
2·C
6H
6 has been determined by X-ray diffraction method in order to elucidate the dimer-A structure ; (C
13H
12N
3)
2 obtained by the reaction of acridine with hydroxylamine-O-sulfonic acid (NH
2OSO
3H, HAS). The crystals ; BADA·C
6H
6 are triclinic with space group P
1-and the unit-cell dimensions are a=9.167, b=10.618, c=10.379Å, α=99.60, β=119.61, γ=95.21°. One formula unit is contained in the cell. The crystal structure was solved by the heavy-atom method and refined by the block-matrix least-squares method including anisotropic thermal parameters. The final R value for 1106 non-zero observed structure factors was 0.07. BADA was found to be a benzalazine derivative, 2, 2'-(2-bromoacetylaminoanilino)-benzalazine. On the basis of the result obtained by the present determination and the comparison of ultraviolet and nuclear magnetic resonance spectra, the structure of dimer-A has been established.
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HIROSHI IWASE
1974 Volume 22 Issue 9 Pages
2075-2080
Published: September 25, 1974
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The structural effect of the amino acids on the resolution of enantiomers and the relative retention times were studied by gas chromatography on OV-1 and polyethylene glycol adipate as the stationary phases. Relation between the separation factors and structure of racemic amino acids was discussed. It was concluded that the separation factors of racemic amino acids depend on the relative size of the substituents on the asymmetric carbon and the position of amino group.
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NOBORU SHIMAHARA, NOBUYUKI NAKAJIMA, HIROSHI HIRANO
1974 Volume 22 Issue 9 Pages
2081-2085
Published: September 25, 1974
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Thiamine monochloride (Ia) was found to easily decompose in methanol solution to produce a crystalline compound X (II), which is believed to be derived from the pyrimidine part of thiamine, and 5-(2-hydroxyethyl)-3-methylthiazole (III). The ratio and rate of this decomposition are affected by the kind of alcohol, its dilution rate, reaction temperature, the acidity and basicity of the solution and concentration of Ia. Decomposition of Ia in methanol in the presence of pyridine gave N-[2-methyl-4-aminopyrimidyl-(5)]-methylpyridinium chloride (V) and III.
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NOBORU SHIMAHARA, HIROYUKI ASAKAWA, YUTAKA KAWAMATSU, HIROSHI HIRANO
1974 Volume 22 Issue 9 Pages
2086-2090
Published: September 25, 1974
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Thiamine mononitrate (Ib) was easily decomposed in methanol solution to produce crystalline compound (X') and 5-(2-hydroxyethyl)-4-methylthiazole (III). The structure of this compound (X') was presumed to be pentamethi (1, 4-dihydro-4-imino-2-methyl)-pyrimidinylen-1, 5-amer nitrate (IIc) from spectral and chemical data, and this was confirmed by the synthesis of 9-amino-2, 7, 10-trimethyl-5H-dipyrimido [1, 6-α : 4', 5'-d] pyrimidine derived from IIc. Compound (X), which was produced by the decomposition of thiamine monochloride (Ia) in methanol, is the hydrochloride of a base in IIc. IIc in aqueous solution reacted with acidic sodium sulfite to give 4-amino-2-methylpyrimidinyl-5-methanesulfonic acid (IX), and with III to give Ib.
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HIROSHI TOMISAWA, REIKO FUJITA, HIROSHI HONGO, HIDEKI KATO
1974 Volume 22 Issue 9 Pages
2091-2096
Published: September 25, 1974
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The Friedel-Crafts reaction of 1-methyl-2 (1H)-pyridone (I), 1-methyl-2 (1H)-quinolone (II), and 2-methyl-1 (2H)-isoquinolone (III) with benzoyl chloride was successfully carried out. I gave products identified as 5-benzoyl-1-methyl-2 (1H)-pyridone (IV), 3-benzoyl-1-methyl-2 (1H)-pyridone (V), and 3, 5-dibenzoyl-1-methyl-2 (1H)-pyridone (VI). II gave 3-benzoyl-1-methyl-2 (1H)-quinolone (VII) and 6-benzoyl-1-methyl-2 (1H)-quinolone (VIII), and III gave 4-benzoyl-2-methyl-1 (2H)-isoquinolone (IX) and 5-benzoyl-2-methyl-1 (2H)-isoquinolone (X).
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YOSHIRO KOBAYASHI, ITSUMARO KUMADAKI, HARUO SATO, YASUO SEKINE, TERUO ...
1974 Volume 22 Issue 9 Pages
2097-2100
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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Application of N-oxidation using sodium tungstate as a catalyst was attempted with diazines and diazanaphthalenes, some of which are labile to peracids, and found to be especially useful. N-Oxides of quinazoline and pyrimidine were obtained from the bases by this method. Pyrazine and quinoxaline were oxidized stepwise to the dioxides through monooxides.
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CHIKARA KANEKO, AKIKO SUGIMOTO, SACHIKO YAMADA, MASAYUKI ISHIKAWA, SAT ...
1974 Volume 22 Issue 9 Pages
2101-2107
Published: September 25, 1974
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The procedure used for the preparation of 1α-hydroxycholesterol from cholesta-1, 4-dien-3-one was applied to 17, 17-ethylenedioxyandrosta-1, 4-dien-3-one and 20, 20-ethylenedioxypregna-1, 4-dien-3-one. The successful results described in this paper serve to provide a basis for evaluation of wide scope of this procedure for the introduction of a hydroxyl group at 1α-position of 3-oxygenated steroid derivatives. The procedure consists of three steps starting from 3-keto-△
1, 4-steroids available readily from 3-oxygenated steroids : 1) deconjugation to 3-keto-△
1, 5-steroids, 2) reduction with metalhydride to 3β-hydroxy-△
1, 5-steroids, and 3) hydroboration to 1α, 3β-dihydroxy-△
5-steroids. This paper also includes definite identification of the final and intermediate compounds in the procedure and interpretation of their mass and nuclear magnetic resonance spectroscopic behaviors.
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KAZUO ITO, HITOSHI TANAKA
1974 Volume 22 Issue 9 Pages
2108-2112
Published: September 25, 1974
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Irradiation of methanolic solution of amide (VIII) by a 100 W high pressure mercury lamp in the presence of sodium hydroxide afforded a mixture of three phenolic irradiation products, whose structures were proved to be IX, X and XI respectively on the basis of chemical and spectral studies. Among these photocyclization products, X was reducted with sodium borohydride and boron trifluoride to provide the amine (XIII), which was converted with formalin and sodium borohydride to erybidine (I).
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KIMIO UMINO, TOTARO YAMAGUCHI, YUKIO ITO
1974 Volume 22 Issue 9 Pages
2113-2117
Published: September 25, 1974
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Eleven acyl and alkyliden derivatives of pentenomycin I (I) were synthesized for obtaining an improved antibiotic. All derivatives synthesized showed same order of or improved antimicrobial activity than the natural antibiotic. Among these derivatives, 2-bromo-4, 5, 6-triacetylpentenomycin I (XIV) showed strongest antimicrobial activity.
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TAKASHI MATSUI, MITSUO NAGANO, JUNZO TOBITSUKA, KOZO OYAMADA
1974 Volume 22 Issue 9 Pages
2118-2122
Published: September 25, 1974
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Reactions of ethoxycarbonyl isothiocyanate (2a) with heterocyclic amines whose PKa values range from 2.95 to 9.17 were examined. Regardless of the base strengths, the heterocyclic amines except 4-aminopyridine afforded the addition products in a good yield in the nucleophilic reactions with 2a. 4-Aminopyridine (14) which afforded no addition product with 2a yielded ethyl N-(4-pyridyl) carbamate (16). Probably the nucleophilic substitution of 14 occurs at the ring nitrogen atom and the pyridinium salt (15) formed in the initial stage of the reaction rearranged intermolecularly and resulted in the formation of 16.
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TAKASHI MATSUI, MITSUO NAGANO
1974 Volume 22 Issue 9 Pages
2123-2130
Published: September 25, 1974
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Ambident reactivities of alkoxycarbonyl isothiocyanates (2) with heterocyclic amines were discussed from the concept of charge and frontier controlled interactions which is a qualitative interpretation of the hard and soft acids and bases (HSAB) principle. The calculated charge densities indicate hard nucleophiles have the tendency to attack on the carbonyl carbon atom and soft nucleophiles on the isothiocyanato moiety of 2. To clarify the difference in basic behavior of heterocyclic amines, correlations existing in the ionization data of pyridinium and thiazolium ions were analyzed using the dual substituent parameters of F (field) and R (resonance). It seems likely that the F effect results mostly from charge controlled interactions and the R effect from electron transfer interactions between the nearly degenerate overlapping orbitals. It was suggested that the magnitude of the F and R factors of the regression equations can be an indication of the charge and frontier controlled interactions between the two interacting molecules and the F effect may have an important role in determining the pathway of approach in the initial stage of the reactions.
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ISOO ITO, SHINICHI NAGAI
1974 Volume 22 Issue 9 Pages
2131-2135
Published: September 25, 1974
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Treatment of methyl 4-benzyl-5-oxo-1-phenyl-3-pyrazoline-3-acetate (7a) with dimethyl sulfate followed by hydrolysis of the resulting methyl 4-benzyl-2-methyl-5-oxo-1-phenyl-3-pyrazoline-3-acetate (9) afforded 4-benzyl-2-methyl-5-oxo-1-phenyl-3-pyrazoline-3-acetic acid (12). 1-Methyl-2-phenyl-3, 9-dioxo-1, 2, 3, 4, 9, 10-hexahydrobenzo [4, 5]-cyclohepta [1, 2-c] pyrazole (2) was prepared by cyclization of 12 with polyphosphoric acid. The synthesis of 1-methyl-2-phenyl-3, 4-dioxo-1, 2, 3, 4, 9, 10-hexahydrobenzo [4, 5] cyclohepta-[1, 2-c] pyrazole (3) which is structurally related to 2 was also carried out starting from 4-bromo-3-bromomethyl-2-methyl-1-phenyl-3-pyrazolin-5-one (15).
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KOZO OKADA, YOTARO KUROSAWA, MINORU HIRAMOTO
1974 Volume 22 Issue 9 Pages
2136-2141
Published: September 25, 1974
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The method of solid phase synthesis was applied to the preparation of isariin (Ia), a β-hydroxydodecanoic acid-containing cyclodepsipeptide metabolite of Isaria cretacea, and its isomer (Ib). The open-chain depsipeptide, H-Val-D-Leu-Ala-Val-DL-Hyd-Gly-OH, was synthesized by coupling successively BOC-Val-DL-Hyd-OH, alanine, and Z-Val-D-Leu-OH to resin-bound glycine using dicyclohexylcarbodiimide (DCC) or DCC+hydroxysuccinimide (HOSu) as coupling agent. After cleavage from the resin the depsipeptide was cyclized by means of DCC+HOSu. The cyclization product was successfully resolved, after chromatographic purification on Dowex 50×4 and Sephadex LH-20 column, by preparative thin-layer chromatography on silica gel to afford Ia and Ib in moderate yields.
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AKITADA NAKAMURA, SHOZO KAMIYA
1974 Volume 22 Issue 9 Pages
2142-2146
Published: September 25, 1974
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When heated with potassium t-butoxide (t-BuOK), 4-methyl-2, 3, 5, 10-tetrahydro-1H-pyrazolo [1, 2-b] phthalazinium iodide (I) gave 2-(3-methylaminopropyl) isoindole (IV), while 5-methyl-1, 4, 6, 11-tetrahydropyridazino [1, 2-b] phthalazinium iodide (VII) gave 1-(2-methylaminomethylbenzyl) pyrrole (X) on heating with t-BuOK and also with sodium methoxide (CH
3ONa). Analogously, 13-methyl-5-oxo-5, 7, 12, 14-tetrahydrophthalazino-[2, 3-b] phthalazinium iodide (XII) reacted with CH
3ONa to give 13-methyl-5, 7, 12, 13a-tetrahydro-13H-isoindolo [2, 3-b] [2, 4] benzodiazepin-5-one (XIII) and-7-one (XIV). These reactions were interpreted to proceed by the initial abstraction of α-benzyl or α-allyl proton.
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CHIKARA KANEKO, SUMIE HAYASHI, YOSHIRO KOBAYASHI
1974 Volume 22 Issue 9 Pages
2147-2154
Published: September 25, 1974
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Photolysis of a series of 2-(trifluoromethyl) quinoline 1-oxides (1a-d) in various solvent is reported. In contrast to the large solvent effects upon the product distribution as found in the photolysis of quinoline 1-oxide and its 2-alkylated derivatives, the photolysis of these four N-oxides shows no such solvent effects and results in the formation of the corresponding 3, 1-benzoxazepines (IIa-d), irrespective of the kinds of solvents used for irradiation. Similarly, the photolysis of 1-(trifluoromethyl) isoquinoline 2-oxide (IV) is also found to give the corresponding 1, 3-benzoxazepine (V) as a sole rearrangement product. A mechanistic rationalization of these photo-rearrangement reactions is presented.
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TADASHI WATABE, KAZUKO AKAMATSU
1974 Volume 22 Issue 9 Pages
2155-2158
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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Hydrolysis of oxides of n-1-olefins, heptene, octene, decene, dodecene, tetradecene, and hexadecene, by hepatic microsomal epoxide hydrolase and their inhibitory effects on the hydrolase activity have been described. Enzymatic reaction rates were the highest in heptene oxide, high in tetradecene and hexadecene oxides, and the lowest in decene oxide. The decene oxide inhibited enzymatic hydrolysis of safrole oxide most significantly ; much more significant than octene oxide that is recognized as a potent inhibitor. A curve representing relationship between alkyl side chain length of the n-1-olefin oxides and their enzymatic reaction rates showed a reciprocal pattern to that for their inhibitory effects on the hydrolase activity.
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TETSUJI KAMETANI, TAMIKO TAKAHASHI, MASAHIRO KAJIWARA, YOSHIRO HIRAI, ...
1974 Volume 22 Issue 9 Pages
2159-2163
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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Naphthoquinone (14) reacted with the o-quinodimethanes, which were generated from the benzocyclobutenes (9, 10 and 11), o-xylyl dibromide (12) and N-aminodihydroisoindole (13), to give the naphthacene-5, 12-quinones (15, 16, 17 and 18), respectively.
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TOSHIO KAWASAKI, TETSUYA KOMORI, KAZUMOTO MIYAHARA, TOSHIHIRO NOHARA, ...
1974 Volume 22 Issue 9 Pages
2164-2175
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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Two compounds, positive (red) to the Ehrlich reagent and predominant in the methanol extracts of the fresh rhizomes of Dioscorea gracillima MIQ., were isolated. Their structures were established as 26-O-β-D-glucopyranosyl 22-methoxyfurost-5-ene-3β, 26-diol 3-O-β-chacotrioside (I), mp 187-191°(decomp.), [α]
D-95.6°, and its 22-hydroxy analog (I'), mp 190-196°(decomp.), [α]
D-79.8°, the furostanol bisglycosides corresponding to 25D-spirost-5-en-3β-ol (diosgenin) 3-O-β-chacotrioside (dioscin) (III), the major component of the stored materials. I is regarded as an artifact formed from I', and I'and I are named proto-dioscin and methyl proto-dioscin, respectively. Smilax-saponin B, which had been assigned a structure, diosgenin hexaglycoside, was identical with I and the structure is revised. Among the Ehrlich positive compounds in the methanol extracts of the fresh rhizomes of D. septemloba THUNB., the major, mp 249-251°(decomp.), [α]
D-76.9°, was isolated and characterized as the analog (II) of I, chacotriose being replaced by gracillimtriose, corresponding to gracillin (IV). One of the minor components was identified with the 22-hydroxy compound (II') of II, mp 235-238°(decomp.), [α]D-57.8°. II'and II are named proto-gracillin and methyl proto-gracillin, respectively. Kikuba-saponin, which had been assigned the structure, IV monoglucoside, was identical with II and the structure is revised.
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TOSHIO NAMBARA, MASAKI TAKAHASHI, YUKIKO TSUCHIDA, MITSUTERU NUMAZAWA
1974 Volume 22 Issue 9 Pages
2176-2180
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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Three new hapten-carrier conjugates were prepared from the 6α-, 6β-, and 7α-hydroxyestradiol monohemisuccinates by coupling with bovine serum albumin employing the mixed anhydride technique. The specificity of antiestradiol antisera elicited in the rabbit by immunization with each of these antigens was assessed by testing the crossreaction with the closely related steroids. The results indicated that highly specific antisera to estradiol would be produced by antigen whose steroidal moiety is coupled to a protein through the 6α, 6β or 7α position remote from the inherent functional groups.
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KENJI SUZUKI, YUSUKE SASAKI
1974 Volume 22 Issue 9 Pages
2181-2187
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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Synthesis of five glycine analogs of H-Arg-Phe-Ser-Trp-Gly-Ala-Glu-Gly-Gln-Arg-OH, in which amino acid residues at positions 3, 6 and 7 are replaced by glycine, is reported. Correlation of structure and activity of the encephalitogenic decapeptide fragment is discussed on the basis of the activity in guinea pigs and circular dichroism spectra of the synthetic glycine analogs.
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YUSUKE SASAKI
1974 Volume 22 Issue 9 Pages
2188-2191
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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TAKASHI ABIKO
1974 Volume 22 Issue 9 Pages
2191-2196
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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NAOTAKA YAMAOKA, TAICHI USUI, HIROSHI SUGIYAMA, SHUICHI SETO
1974 Volume 22 Issue 9 Pages
2196-2200
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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TAKUO OKUDA, SETSUO SAITO, KYOKO WATANABE, CHIYOKO HIEDA
1974 Volume 22 Issue 9 Pages
2202-2204
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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YUICHI KANAOKA, YASUMARU HATANAKA
1974 Volume 22 Issue 9 Pages
2205-2206
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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KUOHSIUNG LEE, TOSHIRO IBUKA, RONGYANG WU
1974 Volume 22 Issue 9 Pages
2206-2208
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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HIROSHI NAKAMURA, ZENZO TAMURA
1974 Volume 22 Issue 9 Pages
2208-2210
Published: September 25, 1974
Released on J-STAGE: March 31, 2008
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