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小関 良宏
1969 年 17 巻 4 号 p.
633-638
発行日: 1969/04/25
公開日: 2008/03/31
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The cryoprotective action of glycerol on the strain L cells was studied. Glycerol, even when present only in the cell interior or only in the surrounding medium, apparently furnishes the cells cryoprotection to some extent, but glycerol in the cell interior seems to be more effective than in the medium. Its presence both in the cell interior and in the medium is a requisite for perfect protection against freezethawing injury.
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西村 民男, 田辺 信三, 徳 広茂, 河野 智行, 坂部 譲, 坂口 武一
1969 年 17 巻 4 号 p.
639-649
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
フリー
The structural limitation of positive compounds in the Voges-Proskauer Reaction was investigated with guanidines, ureas, thioureas, formamidine and formaldoxime, using the α-naphthol alkaline and diacetyl solution. Only guanidino derivatives showed positive reaction among compounds tested above. Strongly positive compounds were asym-1, 1-dialkylguanidines. Especially, 1, 1-dimethylguanidine, 1-methyl-1-phenylguanidine and 1, 1-pentamethyl-eneguanidine had the highest absorbance at 535 mμ. Creatine which was usually used in this reaction, showed second higher absorbance. Monosubstituted guanidine gave always moderately positive reaction, and unsubstituted one was weakly positive. sym-1, 3-Dialkylguanidines such as 1, 3-dimethylguanidine was negative, suggesting that a free amidino group [chemical formula] would be necessary for the positive V-P reaction. This is further supported by the fact that tri-, tetra- and pentamethylguanidine also gave negative reaction. 8-Hydroxyquinoline could be used in place of α-naphthol in this reaction. Conditions for color development, stability of colored solution and the effect of pH on the wave length of λ
max were studied.
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金井 貞, 市野 元信, 小嶋 孝司
1969 年 17 巻 4 号 p.
650-652
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
フリー
5, 6-Dihydroxy-5, 6-dihydro-2'-deoxyuridine (IIIa) and 5, 6-dihydroxy-5, 6-dihydrouridine (IIIb) were prepared via bromination of 2'-deoxyuridine (Ia) and uridine (Ib) respectively, followed by refluxing these unstable intermediates in the neutral conditions to replace the bromo group with the hydroxyl group. In the case of cytidine, however, the 5, 6-dihydroxy-5, 6-dihydro compound was not obtained by the same procedure as used for preparation of IIIa and IIIb from Ia and Ib.
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永田 耕一
1969 年 17 巻 4 号 p.
653-660
発行日: 1969/04/25
公開日: 2008/03/31
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Chemical reactivities of the metal complexes of thiohydroxamic acids was investigated. By alkylation or acylation, all the metal complexes except the nickel complex was dissociated to the corresponding metal ions and derivatives of thiohydroxamic acid. The nickel complex was benzoylated without undergoing the dissociation in chilled sodium hydroxide. Sodium or zinc salts or some derivatives of benzothiohydroxamic acid underwent the Lossen rearrangement, and the rearrangement products were isolated. However, the nickel complex did not give the rearrangement products in alkaline solution because of the stability of the chelated structure. From those results, it was confirmed that the hydroxyimino group of thiohydroxamic acid is in the syn configuration to the sulfur atom and that the transition metal complexes possess the five-membered chelate structure as shown in formular [chemical formula] (M=metal ion) in the solid state.
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永田 耕一
1969 年 17 巻 4 号 p.
661-668
発行日: 1969/04/25
公開日: 2008/03/31
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フリー
Several compounds possessing both mercapto and hydroxyimino groups, such as 2-mercaptoacetophenone oxime, 3-mercaptopropiophenone oxime and 5-nitro-2-mercapto-benzaldehyde oxime, were prepared, and their reactivities with metal ions were compared with those of the corresponding ketones or aldehyde and those of thiohydroxamic acids. It was found that these compounds did not show any sensitive color reactions with Fe
3+, Ti
4+, UO
2+2 and VO
2+ and did not form stable Fe
3+ and Cu
2+ complexes, differing from thiohydroxamic acids, and that the conversions of the compounds possessing both carbonyl and mercapto group to the corresponding oximes did not give any effect on the sensitivities and selectivities.
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水野 亘恭, 青木 大, 鎌田 皎
1969 年 17 巻 4 号 p.
669-676
発行日: 1969/04/25
公開日: 2008/03/31
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Relations between the properties of pyridoxine and pyridoxine 3, 4-diacylates and the changes of vehicles in percutaneous absorption were studied. a) Depilated skin : PIN is absorbed more rapidly than PIN-HCL. While, PIN showed a rapid change in blood level, PIN-DK, -DIK gave high blood level 24 hours after the application of the drugs. b) Normal skin : The normal skin cases for PIN, PIN-DK and -DIK showed the same blood level as depilated cases 8 or 24 hours after application of the drugs. The blood level of PIN did not decrease within 10 hours unlike the depilated skin.
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花木 昭, / 日野 亨, 赤星 三弥, SANYA AKABOSHI
1969 年 17 巻 4 号 p.
677-681
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
フリー
The effect of N-substituent on the stability in an aqueous solution of AET was studied. By the substitution, both the transguanylation and the cyclization were hindered. The reactive species of N-Et-AET, and probably of N'-Et-AET, for the transguanylation is the monoionic conjugate base. N'-Et-AET, being relatively stable in the presence of less than one equivalent alkali, may be dissociated through the two-steps ionization to the neutral conjugate base, which would be considered as one of the reactive species. The degree of the transformation of N-ethylated AET derivatives was as follows ; the transguanylation in the presence of 0.5 equivalent NaOH for 4 min at 15° : AET ; 0.95, N'-Et-AET ; 0.84, N'-Et-AET ; 0.27. the cyclization in 3 days at 30° : AET ; 0.95, N'-Et-AET ; 0.36, N'-Et-AET ; 0.29. The relationship between the transguanylation and the pH drop in the solution was discussed.
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佐藤 大助, 小林 節子, 森田 淳子
1969 年 17 巻 4 号 p.
682-689
発行日: 1969/04/25
公開日: 2008/03/31
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フリー
Treatment of gitoxin (I) with alkyl chloroformate in pyridine gave rise to alkoxycar-bonylation of hydroxyl groups in the order of 4'''-, 16- and 3'''-positions analogously to acetylation to afford gitoxin 4'''-mono-, 4''', 16-di-and 3''', 4''', 16-trialkoxycarbonates (II, III, IV), but the further esterification encountered with more difficulties than the acetylation. Gitoxin 3''', 4'''-cyclocarbonate (V) was also prepared and the interconversion between 3'''-mono-and 4'''-monomethoxycarbonates (VIIa, IIa) and V was investigated. Alkyl pyrocarbonates showed a less selectivity in alkoxycarbonylation of I than alkyl chloroformates, resulting in the formation of V, 16-alkoxy-and 3''', 4'''-cyclocarbonyl-16-alkoxycarbonates (IX, VIII) besides II, III and IV. IX was also formed by partial hydrolysis of III and VIII with dilute alkali.
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森 弘, 柴田 健雄, 常田 清, 沢井 政信
1969 年 17 巻 4 号 p.
690-698
発行日: 1969/04/25
公開日: 2008/03/31
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フリー
A novel synthetic method of preparation of the side chain of ecdysone, 22, 25-dihydroxycholestane side chain was developed. The sequence of this method was summarized as the procedures XI→XII→XIII→XIV→XVI→XVII (Chart 3)→XXV→XXVII→XXIX (Chart 5).
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岸川 虎比古, 及川 裕二, 滝谷 昭司
1969 年 17 巻 4 号 p.
699-702
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
フリー
Condensation of methyl (tri-O-acetyl-a-D-glucopyranosyl bromide) uronate with silver 2-pyridyl oxide in toluene gave methyl (2-pyridyl 2, 3, 4-tri-O-acetyl-β-D-glucopyranosid)-uronate (III). Removal of the protecting groups from III afforded the O-glucuronide of 2-hydroxy pyridine (V). The O→N rearrangement of the glucuronosyl residue in III was effected by refluxing the toluene solution of III in the presence of mercuric bromide. An attempt to hydrolyze V and VIII by the β-glucuronidase was made. It was found that whereas the O-glycoside (V) is hydrolysable by this enzyme, the N-glycoside (VIII) is completely inert to it. Acid-and alkali-catalyzed hydrolyses of V and VIII were also investigated.
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小林 邦夫, 本庄 美喜男
1969 年 17 巻 4 号 p.
703-708
発行日: 1969/04/25
公開日: 2008/03/31
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フリー
The reaction of chloroform with liq. ammonia in a sealed vessel at high temperatures furnished adenine, purine, and 8-aminopurine in 5, 7 and 1% yields, respectively. Similarly, the reaction between ethyl orthoformate and liq. ammonia yielded adenine (21%), purine (14%) and 8-aminopurine (3%), A possible mechanism has been proposed for the reaction, which involves a polymerization of formimidoyl derivative rather than an intermediary formation of aminomalononitrile.
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亀谷 哲治, 飯田 英夫, 菊地 豊彦, 水島 正勝, 福本 圭一郎
1969 年 17 巻 4 号 p.
709-713
発行日: 1969/04/25
公開日: 2008/03/31
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Dienone-phenol rearrangement of dienone (II) with concentrated sulfuric acid gave a cularine-type compound, 9-hydroxy-5, 6, 10-trimethoxy-1-methyl-1, 2, 3, 12, 12a-pentahydrobenzoxepino [2, 3, 4-i, j] isoquinoline (III), whose structure was assigned by spectroscopic method and its alternative synthesis of III from 1-(2-bromo-4-hydroxy-5-methoxybenzyl)-1, 2, 3, 4-tetrahydro-8-hydroxy-6, 7-dimethoxy-2-methylisoquinoline (XI). Moreover, this paper described the preparation of XI.
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中村 昭四郎, 丸本 靖子, 八巻 寛, 西村 敏男, 田中 信男, 浜田 雅, 石塚 雅章, 竹内 富雄, 梅沢 浜夫
1969 年 17 巻 4 号 p.
714-721
発行日: 1969/04/25
公開日: 2008/03/31
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フリー
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中井 昇, 長谷 純一
1969 年 17 巻 4 号 p.
722-728
発行日: 1969/04/25
公開日: 2008/03/31
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フリー
1. Four to six moles of sulfhydryl groups of yeast alcohol dehydrogenase were found to be high sensitivity for 5, 5'-dithiobis (2-nitrobenzoic acid) (DTNB). 2. There were two types of sulfhydryl groups in the active site of yeast alcohol dehydrogenase. Sulfhydryl groups of two of four active sites were easily modified by DTNB at 0°and the other were not. 3. Yeast alcohol dehydrogenase which was modified sulfhydryl groups of two of four active sites by DTNB, was fully restored in its enzyme activity by cysteine and was found to be the same conformation as the native enzyme. On the other hand, the enzyme which was modified more than two sulfhydryl groups in the active sites, was partially restored by cysteine, probably due to irreversibly conformational change. 4. DTNB competed with NAD for sulfhydryl group in the active site of yeast alcohol dehydrogenase.
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斎藤 保, 柴田 承二
1969 年 17 巻 4 号 p.
729-734
発行日: 1969/04/25
公開日: 2008/03/31
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From the root of licorice (Glycyrrhiza spp., Leguminosae) three new coumestan derivatives, named glycyrol, 5-O-methylglycyrol and isoglycyrol, have been isolated, whose structures have been established to be Ia, IIa and IIIa, respectively. Betulic acid was also obtained.
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奥田 拓男, 小西 邦弘
1969 年 17 巻 4 号 p.
735-737
発行日: 1969/04/25
公開日: 2008/03/31
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フリー
Coriose (D-altro-3-heptulose) (I) was synthesized by the lead tetraacetate oxidation of hydrolyzate of the mother liquor of 1, 3 : 5, 7-di-O-ethylidene-3-C-formyl-D-glycero-D-talo-heptitol-3 (1), 6-pyranose (IV) which was derived from 2, 4-O-ethylidene-D-erythrose (V) by the aldol condensation.
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関屋 実, 矢内原 千鶴子
1969 年 17 巻 4 号 p.
738-746
発行日: 1969/04/25
公開日: 2008/03/31
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It has been found that after heating with a reagent, given by 5HCO
2H·2N (C
2H
5)
3, several barbituric acid derivatives were methylated at the 5-position. The reaction was revealed to proceed through an intermediate, 5, 5'-methylidynebis (barbituric acid), which had been previously known as the usual reaction product obtained by heating with formic acid. The reaction course was found to involve an interesting aspect that the reagent carries out a saturation of the carbon-carbon double bond at the 5-position followed by a reductive fission of the bond.
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関屋 実, 矢内原 千鶴子, 鈴木 次郎
1969 年 17 巻 4 号 p.
747-751
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
フリー
By means of heating in triethylammonium formate given by 5HCO
2H·2N (C
2H
5)
3, hydrogenation of 5-methylidene bond attached to barbituric acids was effected in general. The method was found to be convenient for preparation of 5-arylmethylbarbituric acids and some other 5-alkylbarbituric acids with certain advantages : good yield of the products and selectivity at the double bond of 5-position.
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関屋 実, 矢内原 千鶴子, 鈴木 次郎
1969 年 17 巻 4 号 p.
752-755
発行日: 1969/04/25
公開日: 2008/03/31
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Investigation on the thermal TEAF reaction with 5-(3-indolylmethylene) barbituric acid is described in view of the courses of the product formations. With such a compound, not only the previously reported reduction of its methylidyne but also the succeeding reductive fission of the resulting methylene was revealed to occur in the reaction.
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井下田 浩, 土屋 隆, 中島 むつみ, 関屋 明子, 熊木 洋子, 中井 淑子, 野島 時世
1969 年 17 巻 4 号 p.
756-762
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
フリー
3-Hydroxypyridazine 1-oxide (I) and its methyl homologs (II), (III), and (IV) were submitted to electrophilic substitutions such as nitration and halogenation. Due to the additional polar effect of both N-oxide and hydroxyl groups, introduction of nitro group and halogen in 4-and/or 6-positions was successfully concluded. By heating with potassium hydrosulfide, nucleophilic substitution of the brominated compounds (XXXI and XXXVI) was also carried out, affording mercapto compounds (XXXII and XXXVII).
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井下田 浩, 土屋 隆, 中島 むつみ, 横川 秀晴
1969 年 17 巻 4 号 p.
763-769
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
フリー
NMR spectra of 3-hydroxypyridazine 1-oxides and their monomethylated derivatives were examined and structural propriety of their nitrated and halogenated products was confirmed by the analyses of the NMR spectra. Furthermore, in 3-hydroxypyridazine 1-oxides, predominance of enol form tautomer was proved by NMR data. The conclusion was also drawn by other spectral data (UV and IR).
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中村 秋枝, 前田 昌子, 木下 俊夫, 辻 章夫
1969 年 17 巻 4 号 p.
770-774
発行日: 1969/04/25
公開日: 2008/03/31
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It was found that glucosamine-HCl reacted with p-nitrobenzaldehyde in pyridinemethanol solution to yield Schiff base and gave a blue color by addition of tetraethylammonium hydroxide solution. This new color reaction is selective for 2-amino-2-deoxy sugars and α-amino carbonyl compounds, such as aminoacetaldehyde, δ-aminolevulinic acid and α-aminoacetophenone. The microdetection methods for 2-amino-2-deoxy sugars and their derivatives were proposed and the reaction mechanism was investigated.
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菊川 清見, 浮田 忠之進
1969 年 17 巻 4 号 p.
775-784
発行日: 1969/04/25
公開日: 2008/03/31
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2, 3'-Anhydro-1-(β-D-xylofuranosyl) uracil (IV) was allowed to react with sodium iodide in the presence of acetic acid. The major product isolated was proved to be 1-(5'-iodo-5'-deoxy-β-D-xylofuranosyl) uracil (V) whose structure was unambiguously established. The reaction of other halide ions on the anhydronucleoside (IV) furnished the same type of compounds, 1-(5'-chloro-5'-deoxy-β-D-xylofuranosyl) uracil (XVI) and 1-(5'-bromo-5'-deoxy-β-D-xylofuranosyl) uracil (XVII). By treatment of the compound (V) with silver acetate, 2, 3'-anhydro compound (IV) was recovered, and it was supposed that 2, 5'-anhydro-1-(β-D-xylofuranosyl) uracil (XII) initially produced was rearranged to the 2, 3'-anhydro compound (IV) by a nucleophilic attack of 3'-up hydroxyl function of XII at C
2 carbon of the uracil moiety.
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菊川 清見, 市野 元信, 浮田 忠之進
1969 年 17 巻 4 号 p.
785-797
発行日: 1969/04/25
公開日: 2008/03/31
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The reactions of methyl iodide with 2, 2'-anhydro-1-(β-D-arabinofuranosyl) uracil (I) and 2, 3'-anhydro-1-(β-D-xylofuranosyl) uracil (VIII) afforded the products (II and IX) containing methyl and iodo groups, respectively. The structure of the product (II) was firmly established to be N
3-methyl-2'-iodo-2'-deoxyuridine, and that of the product (IX) to be N
3-methyl-1-(5'-iodo-5'-deoxy-β-D-xylofuranosyl) uracil. The reaction mechanism to afford the compound (IX) from VIII was assumed to proceed via an initial intermediate, quaternary salt (XXI), and followed by the second intermediate of a quaternary 2, 5'-anhydro compound (XXIII), which was formed by an intramolecular attack by 5'-hydroxyl function at the C
2 carbon atom of the base moiety in XXI.
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菊川 清見, 市野 元信, 日馬 恒雄, 浮田 忠之進
1969 年 17 巻 4 号 p.
798-803
発行日: 1969/04/25
公開日: 2008/03/31
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1-(5'-Amino-5'-deoxy-β-D-xylofuranosyl) uracil (VIII) and N
3-methyl-1-(5'-amino-5'-deoxy-β-D-xylofuranosyl) uracil (IX) were synthesized by catalytic reduction of the respective 5'-azido nucleosides, which were obtained by nucleophilic attack of 1-(3, '5'-epoxy-β-D-xylofuranosyl) uracil (IV) or 1-(5'-halogeno-5'-deoxy-β-D-xylofuranosyl) uracils (II) and N
3-methyl-1-(3', 5'-epoxy-β-D-xylofuranosyl) uracil (V) or N
3-methyl-1-(5'-iodo-5'-deoxy-β-D-xylofuranosyl) uracil (III) by lithium azide in dimethylformamide. The structures of the products (VIII and XI) were firmly established.
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小石 真純, 福原 直子, 近藤 保
1969 年 17 巻 4 号 p.
804-809
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
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Polyphthalamide microcapsules were prepared by the interfacial polycondensation reactions between each of 1, 6-hexamethylenediamine and diethylenediamine and each of o-, m-, and p-phthaloyl dichlorides under various conditions. The size and size distribution of the microcapsules formed were determined and the factors affecting them were of studied. Favorable conditions were suggested to obtain the microcapsules of uniform size in a high yield.
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関屋 明子, 矢内原 千鶴子
1969 年 17 巻 4 号 p.
810-814
発行日: 1969/04/25
公開日: 2008/03/31
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亀谷 哲治, 佐藤 文夫
1969 年 17 巻 4 号 p.
814-818
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
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黒田 耕司, 橋詰 源蔵, 粂 蕗子
1969 年 17 巻 4 号 p.
818-821
発行日: 1969/04/25
公開日: 2008/03/31
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内藤 俊一, 水谷 光雄
1969 年 17 巻 4 号 p.
822-826
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
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池川 昭子, 金庭 延慶
1969 年 17 巻 4 号 p.
827-834
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
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中川 国夫, 尾上 弘, 南 恭二
1969 年 17 巻 4 号 p.
835-837
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
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後藤 茂, 都築 脩三, 井口 定男
1969 年 17 巻 4 号 p.
837-840
発行日: 1969/04/25
公開日: 2008/03/31
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内山 充, 渋谷 正興
1969 年 17 巻 4 号 p.
841-843
発行日: 1969/04/25
公開日: 2008/03/31
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小倉 治夫, 伊藤 常男, 岡本 孝, 大村 智
1969 年 17 巻 4 号 p.
844-846
発行日: 1969/04/25
公開日: 2008/03/31
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堀井 善一, 森川 浩一, 二宮 一弥
1969 年 17 巻 4 号 p.
846-848
発行日: 1969/04/25
公開日: 2008/03/31
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星 明夫, 官沢 文彦, 榑谷 和男
1969 年 17 巻 4 号 p.
848-850
発行日: 1969/04/25
公開日: 2008/03/31
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ヒキノ ヒロシ, 伊藤 邦雄, 竹本 常松
1969 年 17 巻 4 号 p.
854-855
発行日: 1969/04/25
公開日: 2008/03/31
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吉岡 一郎, 木村 孟淳
1969 年 17 巻 4 号 p.
856-857
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
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百瀬 勉, 大倉 洋甫, 小橋 一弥
1969 年 17 巻 4 号 p.
858-859
発行日: 1969/04/25
公開日: 2008/03/31
ジャーナル
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