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SHUNSAKU SHIOTANI, KEMMOTSU MITSUHASHI
1972 Volume 20 Issue 1 Pages
1-9
Published: January 25, 1972
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The mass spectra of some 1, 3-bridged 1, 2, 3, 4-tetrahydroisoquinoline derivatives were investigated and it was revealed that these compounds decompose to form completely aromatic evenelectron isoquinolinium ions as the major fragmentation processes by electron impact.
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SHOSHICHIRO KIMOTO, MASAO OKAMOTO, AKIKO WATANABE, TAKAKO BABA, ITSUO ...
1972 Volume 20 Issue 1 Pages
10-14
Published: January 25, 1972
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Two isomers of 4-hydroxy-2-methyl-
cis-decahydroisoquinoline were prepared and the conformations of these compounds were discussed by means of infrared spectroscopy.
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SEIGORO HAYASHI, MITSURU FURUKAWA, YOKO FUJINO, NOBUCHIKA ISHII, YOICH ...
1972 Volume 20 Issue 1 Pages
15-20
Published: January 25, 1972
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Several bisquarternary ammonium salts were synthesized and tested as to their antitumor activity. However, none of them exhibited any effective activity. Additionally, alkylation of nucleophiles with quarternary ammonium salts, dimethylaminomethyl
p-tolyl ether methiodide and ethylene bis (N, N-diethyl-N-methylammonium iodide), was examined. Dimethylaminomethyl
p-tolyl ether methiodide reacted successfully with nucleophiles, such as amine, thiol and alcohol, to give the expected compounds in which
p-tolyloxymethyl group was introduced to the nucleophilic compounds. On the other hand, ethylene his (N, N-diethyl-N-methylammonium iodide) reacted with thiophenol and diethyl malonate to give the methylated compounds, methyl phenyl sulfide and diethyl malonate respectively.
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TOSHITAKA KOGA, SUSUMU KAWASHIMA
1972 Volume 20 Issue 1 Pages
21-34
Published: January 25, 1972
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17β-Benzoyloxy-2α-hydroxy-5β-androstane (XIb), the key intermediate for the transannular cyclization reaction from 2C to 9C in the 5β-androstane system, was synthesized from testosterone (III) in six steps and in the overall yield of 17.6% via the intermediacy of 2α-hydroxy-4-en-3-oxo system (VII). The stereochemistry of the epoxidation of the 4-en-3-oao system (III) with alkaline hydrogen peroxide was established, the reaction favoring the formation of the 4β, 5-epoxide (IVb) to the formation of the 4α, 5-isomer (IVa) in the relative ratio of 5:1. Meanwhile, oxidation of XIb with Jones reagent afforded the 2-oxo-5β system (XIIIb) which exhibits negative Cotton effect curves with much weaker intensity compared with that of positive Cotton effect curves exhibited by the 2-oxo-5α system (XIIIa).
Treatment of XIb with lead tetraacetate in benzene afforded 17β-benzoyloxy-2α, 9α-epoxy-5β-androstane (XVII). The 17β-acetoxy analogue (XIX) of the 2α, 9α-epoxide (XVII) was converted to the 9α, 11α-epoxide system (XXII) via the 9 (11)-eno intermediate (XXI). Reductive cleavage of XXII with lithium-ethylamine afforded the 2α, 9α, -17β-trihydroxy-5β-androstane (XXIII) which gave 2α, 17β-diacetate (XXIV).
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MASARU NAKAMURA, KUNIHIDE MIHASHI, KEIKO EGAMI, TOSHIKO ARITA
1972 Volume 20 Issue 1 Pages
35-40
Published: January 25, 1972
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Two main coloring matters were isolated in crystalline forms in the color reaction of formaldehyde and diazotized sulfanilamide. Their structures were determined as 1, 3, 5-tri-(
p-sulfamo yr) phenylformazan and 1, 5-di-(
p-sulfamoyl) phenylformazan.
Similarly, two main coloring matters of the reaction of formaldehyde with diazotized
p-aminobenzoic acid were obtained as their methyl esters. They were identified as 1, 3, 5-tri-(
p-carbomethox y) phenylformazan and 1, 5-di-(
p-carbomethoxy) phenylformazan.
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HIDEAKI SHIRAI, TAMOTSU YASHIRO, TAIKI AOYAMA
1972 Volume 20 Issue 1 Pages
41-46
Published: January 25, 1972
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For the purpose of testing the biological activity, some galanthamine related compounds, spiro [4-hydroxycyclohexane-1, 4'-2', 3'-dihydro-6'-methoxy-1'-substituted-2'-methy1-1'
H-isoquinoline](IIIa, b, c) were synthesized by the application of the Bischler-Napieralski cyclization on the N-acyl compounds (VIIa, b, c).
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OSAMU IRINO, MITSURU TATEISHI, KAZUNAGA FUKAWA
1972 Volume 20 Issue 1 Pages
47-55
Published: January 25, 1972
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The metabolites of clofexamide (2-(
p-chlorophenoxy)-N-(2-diethylaminoethyl)-acetamide)(I) have been investigated in rat urine and feces. When rats were given a single 200mg/kg dose of clofexamide (I), thirteen metabolites were found in the urine and only unchanged clofexamide in the feces. Twelve metabolites were identified by their spectrometric data (infrared (IR), mass spectrum, ultraviolet (UV) and nuclear magnetic resonance (NMR) spectra) and by thin-layer chromatography (TLC). The following compounds were found to be present in the urine: unchanged clofexamide (I), 2-(
p-chlorophenoxy)-N-(2-diethylaminoethyl) acetarnide N-oxide (II), 2-(
p-chlorophenoxy)-N-(2-ethylaminoethyl) acetamide (III), 2-(
p-chlorophenoxy)-N-(2-aminoethyl) acetamide (IV), p-chlorophenoxyacetic acid (V),
p-chlorophenoxyaceturic acid (VI), 2-(4-chloro-3-hydroxyphenoxy)-N-(2-diethylaminoethyl) acetamide (VII), its glucuronide (VIII), 2-(4-chloro-2-hydroxyphenoxy)-N-(2-diethylaminoethyl) acetamide (IX), 2-(4-chloro-3-hydroxyphenoxy)-N-(2-ethylaminoethyl) acetamide (X), its glucuronide (XI) and 2-(4-chloro-2-hydroxyphenoxy)-N-(2-ethylaminoethyl) acetamide (XII).
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YOSUKE OHKURA, HIROSHI HAMADA, TSUTOMU MOMOSE
1972 Volume 20 Issue 1 Pages
56-59
Published: January 25, 1972
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A new colorimetric method is presented for the determination of serum isocitric dehydrogenase activity. This is based on the determination of 2-oxoglutaric acid formed in the enzyme reaction by means of the previously established selective color reaction of the acid. The method gives reliable results and is suitable to assay a large number of samples with a wide range of activity at the same time with 50μl of sample.
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HIKARU OZAWA, SHIGEO MURAI
1972 Volume 20 Issue 1 Pages
60-68
Published: January 25, 1972
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The analgesic, anti-inflammatory and antipyretic activities of six aminotroponoidcompounds were investigated.
Analgesic activities of 5-aminotropolone (I) and 2-aminotropone (II) are found to be equipotent to that of aminopyrine.
All the test compounds do not inhibit the development of the erythema induced by ultraviolet irradiation, but I and II show the strong inhibition (70-80%) of the enhancement of capillary permeability induced by acetic acid.
Compounds, I and II produce marked hypothermia in mice, rats, and guinea-pigs, and I and II show the antipyretic activities as same as aminopyrine.
The acute toxic symptoms of most of the test compounds are generally the extremities ataxia and the respiratory paralysis.
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AKITADA NAKAMURA, SHOZO KAMIYA
1972 Volume 20 Issue 1 Pages
69-75
Published: January 25, 1972
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The alkaline decomposition of 2, 3, 5, io-tetrahydro-lH-pyrazolo [1, 2-
b] phthalazin-s-one methiodide (VIIa), its methyl derivatives (VIIb-d), and 1, 2, 3, 4, 6, 11-hexahydropyridazo-[1, 2-
b] phthalazin-6-one methiodide (XIV) was examined. Compounds VIIa-d afforded 1-methyl-1, 3, 4, iob-tetrahydro-2H-pyrimido [2, 1-a] isoindol-6-ones (VI IIa-d), and XIV afforded 1-methyl-1, 2, 3, 4, 5, 11b-hexahydro-7H-1, 3-diazepino [2, 1-
a] isoindol-7-one (XV). In all cases the Stevens-type rearrangement involving lactam nitrogen migration from nitrogen to carbon occurred. Their configuration and conformation were discussed.
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SHIN-ICHIRO SAKAI, AKINORI KUBO, KIMIO KATSUURA, KYOKO MOCHINAGA, MAYU ...
1972 Volume 20 Issue 1 Pages
76-81
Published: January 25, 1972
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The action of selenium dioxide on several 2, 3-disubstituted indole derivatives was found to give the corresponding 2-acylindoles as shown in Table I. In the case of tricyclic mides, (VI and VII), this oxidation reaction resulted in the formation of a-vinylindoles and organoselenium compounds. On the basis of these products, the mechanism of the oxidation with selenium dioxide is discussed.
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TAKU NAGAO, SHINTARO NISHIO, HITOSHI KATO, KEIJIRO TAKAGI
1972 Volume 20 Issue 1 Pages
82-87
Published: January 25, 1972
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The effects of benzylidene chromanones and its related compounds on coronary and femoral blood flow were examined in anesthetized dogs. They exhibited vasodilating activity in both vascular beds, but less active than that of papaverine. Intravenous administration of 3-(4'-β-diethylaminoethoxy)-benzylidene chromanone HCl (CDY-902) caused an increase in coronary blood flow as well as a transient hypotension and persistent negative chronotropic action. No significant effect of CDY-902 on myocardial oxygen consumption of the dog
in situ was observed. On oxygen uptake of the rat heart slices CDY-902 elicited a decrease similar to papaverine. As the results were compared with those of papaverine, GTN and dipyridamole, CDY-902 appears to have a direct and nonselective effects on coronary vascular bed.
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MICHIO FUJIHARA, MITSUTAKA KAWAZU
1972 Volume 20 Issue 1 Pages
88-92
Published: January 25, 1972
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Treatment of 4-aminobenzofuran derivatives with hydrochloric acid led to the formation of 4-hydroxyindole derivatives in good yields, wheras alkaline hydrolysis of 4-acylaminobenzofurans gave 4-aminobenzofurans normally. Synthesis of pyrrolocoumarins and furoquinolones by thermal condensation of those above mentioned compounds with phenylmalonates are also described.
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SACHIKO KAWANISHI, SEIICHI SAKUMA, HIROKO OKINO, JUNZO SHOJI
1972 Volume 20 Issue 1 Pages
93-96
Published: January 25, 1972
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The chemical structures of two hydrolysis products of the crude glycoside fractiion of Chinese crude drug “Bei-Wujiapi (cortex of
Periploca sepium BGE.)” were studied. The one product is 4-O-(2-O-acetyl-β-D-digitalopyranosyl)-D-cymaropyranose and the other is methyl 4-O-(2-O-acetyl-β-D-digitalopyranosyl)-β-D-cymaropyranoside.
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KOICHI HIRAI, HIDEBUMI MATSUDA, YUKICHI KISHIDA
1972 Volume 20 Issue 1 Pages
97-101
Published: January 25, 1972
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2-Substituted thiazolidines (IIIa-g) were prepared by the reaction of 2-alkylthiothiazolines (II) and active methylene compounds. The tetra-substituted double bonds of IIIa-g were resistant to catalytic hydrogenation. N-Halogenation of IIIb was effected by t-butylhypochlorite or bromine in methanol-chloroform. BF
3-etherate treatment of IIIb in acetic anhydride gave three products, VI, VII and VIII. This new method of furoxane formation was also applicable to the conversion of ethyl nitroacetate to VI. The mechanisms of the formations of VI and VII are proposed briefly in Chart 4.
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MASATO ASAHINA, TSUTOMU YAMAHA, GINETTE SARRAZIN, KUNIKO WATANABE
1972 Volume 20 Issue 1 Pages
102-108
Published: January 25, 1972
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Continuous oral administration of sodium cyclamate (CHS-Na) to guinea pig caused the gradual increase of urinary excretion of cyclohexylamine (CHA) after a certain period. The amount of CHA excreted was not only different in individuals, but also dependent on each experiment. It was diminished when CHS-Na was administered orally with antibiotics or intraperitoneally. It was shown from the incubation experiments that apparent accumulation of CHA was observed by cecal contents or feces from the animal excreting CHA in urine by oral administration of CHS-Na, but not from that diminished the excretion by the above conditions. Any
in vitro study using animal tissues failed to detect the accumulation of CHA. Consequently it may be probable to assume the participation of duct microflora in the conversion of CHS-Na to CHA in guinea pig.
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TADASU TANAKA, TAKEO IWAKUMA, MICHIHIKO MIYAZAKI, MITSUYOSHI WAGATSUMA ...
1972 Volume 20 Issue 1 Pages
109-116
Published: January 25, 1972
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2, 3-Dihydro-4-hydroxy-1H-pyrrolo [2, 3-
b] quinolines (III) were prepared by reactions of 4-chloro-2, 3-dihydrofuro [3, 2-
c] quinolines (1) with ammonia or primary amines. 4-Chloro-2, 3-dihydro-1H-pyrrolo [2, 3-
b] quinolines (VIII) were also prepared by the same amination of 2, 4-dichloro-3-(β-chloroethyl)-quinolines (II) accompanied with various minor products.
The structures of these compounds were mainly confirmed by chemical methods.
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MAMORU KAMIYA, YUKIO AKAHORI
1972 Volume 20 Issue 1 Pages
117-121
Published: January 25, 1972
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The electronic spectrum and ionization potential of phenothiazi, ne were calculated parametrizing the angle of fold between the two lateral benzene planes on the basis of the Pariser-Parr-Pople SCF-MO-CI method, and the calculated results at the dihedral angles in a range of the values determined by other methods were found to be in good agreement with the observed spectral data. Also, the all valence-electronic structure, especially the hybridization state of the valence-atomic orbitals of the heteroatoms, was calculated using the extended Hiickel method in order to compare the electronic structures of the two possible spacial configurations with respect to the position of the proton attached to the nitrogen atom.
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TETSUO HIRAOKA, MASAFUMI YOSHIMOTO, YUKICHI KISHIDA
1972 Volume 20 Issue 1 Pages
122-132
Published: January 25, 1972
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A potential tetra-β A-ketide compound, 5, 5'-methylenebisisoxazole-3, 3'-dicarboxylate (IV) was prepared from 1, 4-pentadiyne (I) and carboethoxynitriloxide (II). The bisisoxazole (IV) was also synthesized by way of diethyl 5, 5'-methylene-bis (2-isoxazoline)-3, 3'-dicarboxylate (VII)(racemi) and (VIII)(meso). The methylene hydrogens of the compound (IV) was shown to have a nature of an active methylene group and to react with various electrophiles. The four position of the isoxazole ring of IV had also nucleophilic character, which was useful for obtaining a cyclohexane derivative. A possibility was presented that the compound (IV) could be an important starting material for a synthesis of poly β-diketone system.
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TETSUZO KATO, HIROSHI YAMANAKA, NOBUYA KATAGIRI, SHINICHI MASUDA
1972 Volume 20 Issue 1 Pages
133-141
Published: January 25, 1972
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The reaction of diketene with amino-methylpyridines (Ia-i) was investigated, and the products were identified by the mass spectroscopic study. The reaction of 2-(Ia) and 3-amino-methylpyridines (Ib, d, f, h) with diketene gave the pyridone derivatives (IIIa, b, d, f, h), but 4-amino-methylpyridines (Ic, e, g, i) afforded the pyrone derivatives (IVc, e, g, i). The mass spectrum of III showed the characteristic peaks at
m/e 243, 215, 187 and 175, and in the case of IV the strong peaks were observed at
m/e 151, 108, 67 and 43. Each fragmentation pathways were discussed.
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TETSUZO KATO, HIROSHI YAMANAKA, NOBUYA KATAGIRI, SHINICHI MASUDA
1972 Volume 20 Issue 1 Pages
142-146
Published: January 25, 1972
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Reaction of diketene with 2-aminopyridine (Ia), 2-amino-4-methylpyridine (Ib), and 2-amino-3-methylpyridine (Ic) gave 2-methyl-4H-pyrido [1, 2-
a] pyrimidin-4-one (Ma), 2, 8-dim.ethyl-4H-pyrido [1, 2-
a] pyrimidin-4-one (IIIb), and 2, 9-dimethyl-4H-pyrido [1, 2-
a]-pyrimidin-4-one (IIIc), respectively. Isomeric 2-one derivatives, such as 4-methyl-2H-pyrido [1, 2-
a] pyrimidin-2-one (IVa) and 4, 8-dimethyl-2H-pyrido [1, 2-
a] pyrimidin-2-me (IVb), were prepared by reaction of α-bromccrotonic acid with Ia and Ib, respectively. The differences were sufficiently great to permit mass, nuclear magnetic resonance, infrared and ultraviolet spectral data in a distinction of the structures between the 4-one (III) and 2-one derivatives (IV).
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ITIRO YOSIOKA, TSUTOMU NAKANISHI, HIROSHI YAMAUCHI, ISAO KITAGAWA
1972 Volume 20 Issue 1 Pages
147-156
Published: January 25, 1972
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Taking into the consideration of the established structures of two coexisting lichen triterpenoids, leucotylin (I) and zeorin (II), the re-investigation on the chemical correlation between leucotylin and ezorin has been undertaken. It has been elucidated that the authors' previous proposal on the structures of zeorin (II*), hopane (III*), and isohopane (XXI*) should be abandoned and the final conclusion on the stereostructure of zeorin (II) in addition to its correlation with leucotylin (I) has been presented. Furthermore, the structure of isoleucotylin (XXXVI), derivable from leucotylin along with leucotylidiene (XXXV) under the acid treatment, has been elucidated.
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KINZO NAGASAWA, NORIKO TANOURA
1972 Volume 20 Issue 1 Pages
157-162
Published: January 25, 1972
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Transformation of chitosan in conc. H
2SO
4 was investigated. Neither reaction temperature (0, 10, and 30°) nor time (1-10 hr) affected the degree of sulfation of chitosan, but it was markedly influenced by temperature of the ether used to separate sulfated products. It was proved that depolymerization of chitosan, which had been observed to be extremely stable to conc. H
2SO
4, was influenced by the remaining N-acetyl content in chitosan. As expected, chitosan was greatly depolymerized by treatment with hydrated conc. H
2SO
4 (80 and 90% of sulfuric acid by weight), and sulfated in a lesser extent than that of conc. H
2SO
4.
A hydrolysis constant,
K1 7.0×10
-2 min
-1, of the acid-labile sulfate in sulfated chitosan indicated a reliable formation of the N-sulfate bound to the amino group in sulfated chitosan.
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TAKUZO HISANO, MASATAKA ICHIKAWA
1972 Volume 20 Issue 1 Pages
163-166
Published: January 25, 1972
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Earlier, Meyer,
et al. examined the Niementowski reaction of s-phenyl-4 (3H)-quinazolinone and showed that 4 (3H)-quinazolinone is a strong enough base to form a salt, a carboxylate, when heated with a carboxylic acid, such as formic acid, phenylacetic acid, benzoic acid, salicylic acid, or anthranilic acid.
During the study on the Niementowski condensation of anthranilic acid with thiopicolinanilides, we also found that an anthranilate of 4 (3H)-quinazolinone is formed in the course of this reaction. In the present work, we would like to show that 4 (3H)-quinazolinone can act as a good proton acceptor and the frequency shift of hydrogen bonding, Δν(in cm
-1), with the change of the bonded counterpart, OH…B.
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MITSUJI YANAI, TOSHIO KINOSHITA, SHIGEKO TAKEDA, HIROSHI SADAKI
1972 Volume 20 Issue 1 Pages
166-170
Published: January 25, 1972
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TOSHIHIKO ARIYOSHI, EIGO TAKABATAKE
1972 Volume 20 Issue 1 Pages
170-174
Published: January 25, 1972
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HISASHI ICHIBAGASE, SHOJI KOJIMA, KAORU INOUE, AYAKA SUENAGA
1972 Volume 20 Issue 1 Pages
175-180
Published: January 25, 1972
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TOSHIHIKO ARIYOSHI, EIGO TAKABATAKE
1972 Volume 20 Issue 1 Pages
180-184
Published: January 25, 1972
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TADAKAZU TSUJI, YOSHIHISA OKAMOTO
1972 Volume 20 Issue 1 Pages
184-187
Published: January 25, 1972
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MEI-TAI WANG, KAZUHIRO IMAI, ZENZO TAMURA
1972 Volume 20 Issue 1 Pages
187-189
Published: January 25, 1972
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MICHIYUKI OGAWA, TAKEICHI SAKAGUCHI
1972 Volume 20 Issue 1 Pages
190-193
Published: January 25, 1972
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KIYOSHI ISONO, TSUNEMASA AZUMA
1972 Volume 20 Issue 1 Pages
193-196
Published: January 25, 1972
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AKIÉ IJIMA, HISAKO MIZUNO, KIYOSHI TAKAHASHI
1972 Volume 20 Issue 1 Pages
197-201
Published: January 25, 1972
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KOJI HAYASHI, ATSUKO NATORIGAWA, HIROSHI MITSUHASHI
1972 Volume 20 Issue 1 Pages
201-202
Published: January 25, 1972
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HIROSHI ISHII, TAKEHIKO TOZYO, MIHARU NAKAMURA, EBERHARD FUNKE
1972 Volume 20 Issue 1 Pages
203-205
Published: January 25, 1972
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S. M. DESHPANDE, A. K. SINGH
1972 Volume 20 Issue 1 Pages
206-208
Published: January 25, 1972
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MINORU SEKIYA, JIRO SUZUKI
1972 Volume 20 Issue 1 Pages
209-210
Published: January 25, 1972
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HIROSHI HIKINO, TAEKO TAKAHASHI, TSUNEMATSU TAKEMOTO
1972 Volume 20 Issue 1 Pages
210-212
Published: January 25, 1972
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MITIITI FUJITA, HIDEJI ITOKAWA, YUTAKA SASHIDA
1972 Volume 20 Issue 1 Pages
212-213
Published: January 25, 1972
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