Bulletin of the Institute for Chemical Research, Kyoto University最新文献

{"title":"Studies on Lactone Formation in Vapor Phase. (I) : Synthesis of γ-Butyrolactone","authors":"S. Oka","doi":"10.1246/BCSJ.34.12","DOIUrl":"https://doi.org/10.1246/BCSJ.34.12","url":null,"abstract":"Vapor phase catalytic dehydrogenation of 1,4-butanediol to γ-butyrolactone with reduced copper supported on various carriers was studied. It was found that copper supported on zinc oxide or magnesium oxide was a superior catalyst. In the case of a catalyst consisting of 20% copper and 80% zinc oxide, the yield and space time yield of γ-butyrolactone were 95% and 0.28 at 230∼240°C, respectively.","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"126 1","pages":"220-220"},"PeriodicalIF":0.0,"publicationDate":"1963-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83012431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Infrared Absorption Spectra of Some Monovalent Metal Salts of Fatty Acids","authors":"R. Gotoh, T. Takenaka","doi":"10.1246/NIKKASHI1948.84.5_392","DOIUrl":"https://doi.org/10.1246/NIKKASHI1948.84.5_392","url":null,"abstract":"酢酸からステアリン酸の問の4種の酸のリチウム塩と10種の酸のナトリウム塩,カリウム塩,および銀塩をつくり,4000～440cm-1における吸収スペクトルを固体状態で測定した。銀塩を除く3種の金属塩については水溶液でもスペクトルの測定を行なっ・た。固休では,アルキル基に関する吸収は主として炭素鎖の長さにより,COO一イオンに関する吸収は主として金属塩の種類によって変化する。これらの吸収の変化のようすがCOOおよび金属イオンの影響や,結晶内での分子の配列状態の変化などと関連して検討された。水溶液においてはスペクトルは塩の種類に関係なく,C恥基の縦ゆれ(またはひねり)振動や横ゆれ振動による吸収は固体状態にくらべて非常に幅広くなる。この事実は,水溶液でCnH2n+1COOイオンが金属イオンの影響を受けない状態にあり,しかも炭素鎖中のCH2基はC-C軸のまわりで自由に回転していることを示すものと思われる。","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"31 1","pages":"219-219"},"PeriodicalIF":0.0,"publicationDate":"1963-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83245853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of Adjacent Group on the Rocking Frequencies of Methyl Group","authors":"T. Takenaka, R. Gotoh","doi":"10.1246/NIKKASHI1948.83.9_997","DOIUrl":"https://doi.org/10.1246/NIKKASHI1948.83.9_997","url":null,"abstract":"(CH3),nXHm-n型メチル化合物とその重水素化物のCH3およびCD3横ゆれ振動数,γcH3,および7cD2,を周期律表のIV族から～VII族までのX原子について検討した。ここにmはX原子の原子価,πは1から勉までの整数である。これらの振動数変化は原子価角HCXに関する力の定数の相違によるものと考えられ,この振動が他の振動と混合しているとみられる場合を除いて,それぞれrcx3=582log(κx/rcx2)+1045, γcd3=416log(xx/γcH2)+778であらわされる。ここにxxはX原子の電気陰性度,γcxはC-X結合の原子間隔である。上記二つの式の間の関係はメチル基の重水素化にともなう運動エネルギー行列の変化を考慮して理論的に説明される。上式ならびに竹申がさきに示した対称変角振動数についての関係式が,CH3NO2やCH3CCI3など上記以外のメチル化合物についても成立すると考えて,それらの分子について観測された振動数からメチル基と直接結合する原子団の電気陰性度を求め,結果を種々の方法によって得られた文献値と比較した。","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"70 1","pages":"405-405"},"PeriodicalIF":0.0,"publicationDate":"1963-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76214706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New Addition Reactions. (IV) : The Addition of Schiff Bases to Diketene","authors":"R. Oda, S. Takashima, M. Okano","doi":"10.1246/BCSJ.35.1843","DOIUrl":"https://doi.org/10.1246/BCSJ.35.1843","url":null,"abstract":"S (2) In the decarboxylation of 3-aryl-2-oxazolidinones, the electronic effect of the substituent on the benzene ring indicates that the fission of the N-C bond of the urethane group in the 2-oxazolidinone ring is rate-determining. (3) The initial rate of the aliphatic amine-catalyzed decarboxylation of 3-aryl-2-oxazolidinones is of the pseudo-first-order; it also depends on the concentration and structure of the amine. A mechanism has been proposed which involves a nucleophilic attack of amine on the carbonyl-carbon atom. An amine having an hydroxyl or amino group on the ,B-carbon shows a large rate-acceleration; this suggests the simultaneous electrophilic participation by the active hydrogen of these groups. (4) The initial rate of the decarboxylation of 2-oxazolidinone itself, catalyzed by aliphatic amine, is of the second-order in oxazolidinone and of the first-order in amine. From this a concerted mechanism has been inferred, in which the amine acts as a nucleophile and the other oxazolidinone acts as an electrophile. New Addition Reactions. (IV) The Addition of Schiff Bases to Diketene Ryohei ODA, Shunichi TAKASHIMA and Masaya OKANO BUetin of the Chemical Society of Japan, 35, 1843 (1962) Treatment of diketene with N-benzylidene-t-butylamine afforded a cyclic adduct, adduct, 1-t-butyl-6-phenyl-2,4-piperidinedione, in an excellent yield. Simlar reactions with N-methylene-t-butylamine and N-methylenecyclohexylamine also gave the corresponding piperidinediones, but the yields were very low. New Addition Reactions. (V) Dimerization of Diketene Ryohei ODA, Shunichi TAKASHIMA and Masaya OKANO Bulletin of the Chemical Socity of Japan,:\"'36, 476 (1963) When diketene was treated with 5-10mo1. 96 of aluminum tribromide in ethylene dichloride at 10-20° C for about thirty hours, a mixture of two dimers, 2,6-dimethyl-'}'-pyrone-3-carboxylic acid and dehydroacetic acid (ratio 4 : 7), was obtained in ca. 6096 yield without any formation of a polymeric by-product. This result is contrast to other Lewis acid-catalyzed reactions (d. Makromol. Chem., 39, 243 (1960) ; 43, 149 (1961)).","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"71 1","pages":"223-223"},"PeriodicalIF":0.0,"publicationDate":"1962-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74367903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New Addition Reactions. (II) : Addition of Aliphatic Epoxides to Schiff Bases","authors":"R. Oda, M. Okano, Shohei Tokiura, Akira Miyasu","doi":"10.1246/BCSJ.35.1216","DOIUrl":"https://doi.org/10.1246/BCSJ.35.1216","url":null,"abstract":"S New Addition Reactions. (H) Addition of Aliphatic Epoxides to Schiff Bases Ryohei ODA, Masaya OKANO, Shohei TOKIURA, and Akira MIYASU Bulletin of the Chemical Society of japan, 35, 1216 (1962) By the stannic chloride-catalyzed addition of aliphatic epoxides to Schiff bases, various oxazolidines have been obtained. For expample, the reaction of propylene oxide with N-t-butylazomethine and benzalaniline afforded 3-t-butyl-5-methyloxazolidine and 5-methyl-2,3-diphenyloxazolidine in 2496 and 3096 yieeds, respectively. The use of boron trifluoride as a catalyst resulted in a lower yield of the desired adduct. New Addition Reactions. (HI) Addition of Aliphatic Epoxides to Nitriles Ryohei ODA, Masaya OKANO, Shohei TOKIURA, and Fujio MISUMI Bulletin of the Chemical Society of japan, 35, 1219 (1962) Upon treatment of aliphatic epoxides with aliphatic or aromatic nitriles in cold concentrated sulfuric acid, the formation of the cyclic adducts, 2,4and/or 2,5-disubstituted 2-oxazolines, has been observed in low yields (below 2096). The reaction of caetonitrile with propylene oxide gave a mixture of 2,4and 2,5dimethyl-2-oxazoline (70: 30), while the reaction with epichlorohydrin afforded only 4(or 5-) chloromethyl-2-methyl-2-oxazoline. Partial Asymmetric Synthesis in the Conjugate Addition of a Grignard Reagent to an a, .a-Unsaturated Ester Yuzo INOUYE and H. M. W ALBORSKY journal of Organic Chemistry, 27, 2706 (1962) In the series of our asymmetric synthesis studies, a successful asymmetric synthesis in a Diels-Alder condensation has recently been reported (H. M. Walborsky, L. Barash and T. C. Davis, j. Org. Chem., 26, 4778 (1961» and the resemblance in mechanism suggested the possibility of asymmetric synthesis in the conjugate addition of a Grignard reagent to an a, ,B-unsaturated ester. The addition of phenylmagnesium bromide to (-)-menthyl crotonate resulted (406 )","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"60 1","pages":"406-406"},"PeriodicalIF":0.0,"publicationDate":"1962-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77662151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Relationships between Thermal Expapansion and Packing of Partrticles of Refractory Clay Bodies","authors":"S. Nagasaki, A. Watanabe, K. Yoshizaki, K. Umeya","doi":"10.2109/jcersj1950.69.790_323","DOIUrl":"https://doi.org/10.2109/jcersj1950.69.790_323","url":null,"abstract":"Thermal expansion at temperatures up to 1000°C was determined for pressed powders of fire clays, stony substances, and their mixtures. The thermal expansion curves obtained for their mixtures did not agree with those calculated from those of their components by assuming the additive relationship. A mechanism which explains this result was described.","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"104 1","pages":"413-413"},"PeriodicalIF":0.0,"publicationDate":"1962-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79189585","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Some Considerations on the Measuring Method of the Thixotropic Properties of Some Clay Slips","authors":"K. Umeya","doi":"10.2472/jsms1952.10.328","DOIUrl":"https://doi.org/10.2472/jsms1952.10.328","url":null,"abstract":"S the amount of platinum, 0.0196, was too small to have an effect on tan 0, and also the cardinal component of base glass, such as MgO, ALO\" and SiO \"behaved themselves rather indifferent. On the contrary, LLO showed a strong influence, and the decrease of Li\"O content seemed to be especially fovourable for the formation of /:l-spodumen and consequently the lowering of tan o. ( 3 ) Effect of additional components. The glasses of the base composition, Li20 4, MgO 15, AbO\" 15, and Si02 62 by weight, and added by a small amount of any of the components, Na20, K\"O, BeO, CaO, SrO, ZnO, CdO or PbO were melted and reheated at above 950°C. Among such second components PbO was the most effective, giving tano of 3-4)< 10--1 at 1 Mc at room temperaure with the addition of PbO: 0.045 mols to 104g of the base glass. Some Considerations on the Measuring Method of the Thixotropic Properties of Some Clay Slips Kaoru UMEYA Zairyo Shilwn (Journal of the Japan Society for Testing Materials), 10, 328 (1961) Two measuring methods are mainly used to obtain the thixotropic properties of clay slips. One of these is the method to measure the thixotropic properties by the stress decay, and the other is the hysteresis loop method. The author has already reported the results obtained through the stress decay method, and here in this paper, the results gained from the hysteresis loop method are reported. The results obtained by this method indicate that ( 1) the hysteresis area, that is, thixotropic behavior, of the caly slips, decreases exponentially with the increase of the water content, (2) the hysteresis area, also, decreases exponentially with the increase of the amount of deflocculant quantity. The thixotropic levels are decided by the method of the stress decay, and the degrees of thixotropic behavior may be obtained by the hysteresis loops, and yet no distinct relation has been found so far between the thixotropic levels and degrees of thixotropy. In this paper, we obtain the conversing constant between the two quantities experimentally, and the conversing constant are decided using several clay slips.","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"12 1","pages":"412-412"},"PeriodicalIF":0.0,"publicationDate":"1962-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74408368","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polymerization of Alkylene Oxides","authors":"J. Furukawa, T. Saegusa, T. Tsuruta","doi":"10.1627/jpi1959.3.39","DOIUrl":"https://doi.org/10.1627/jpi1959.3.39","url":null,"abstract":"A review of catalysts for the high polymerization of alkylene oxides was given, from which it was deduced that a metal-oxygen bond was an essential element of active species in most cases.Then, two catalytic systems which were found in our laboratory were discussed. First, the active species of the system of diethylzinc and water was mentioned, and the reaction mechanism was suggested. The second system consists of an organometallic compound and an acidic oxide such as alumina or silica-alumina. These systems induce anionic polymerization of alkylene oxide and it can be assumed that adsorption of monomer on metal of the metal-oxygen bond plays an influential role both in activation of monomer and in controlling the stereoregularity.","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"8 1","pages":"414-414"},"PeriodicalIF":0.0,"publicationDate":"1962-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85511638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Inductive Effect of Substituents on the Symmetrical Methyl Deformation Frequencies of Aliphatic Hydrocarbons","authors":"T. Takenaka","doi":"10.1246/NIKKASHI1948.82.10_1309","DOIUrl":"https://doi.org/10.1246/NIKKASHI1948.82.10_1309","url":null,"abstract":"脂肪族炭化水素のメチル基におよぼす置換基の影響を検討するため, CH3(CH2)n-1XHm-1 型分子の CH3 対称変角振動数δCH3を周期律表の 4 族から 7 族までの X 原子(mはその原子極)につき, n を 1 から 5 まで変えて測定した。n=1 なる CH3XHm-1 型分子の振動数と X 原子の電気陰性度χX の対数との間には, X 原子の属する周期律表の各周期および族ごとに,それぞれ直線関係が成立する。この振動数変化は変角振動に関する力の定数の相違によるものと考えられ,この振動数と C-X 結合の伸縮に対する力の定数との関係を考慮することによりなる関係式で整理される。ここにγcx は C-X 結合の原子間隔である。この関係式は CH3XHm-1型分子ばかりでなく,(CH3)2XHm-2,… 一一(CH8)辮Xなる一連の分子についても偏差士工%以内で成立する。(CH3)2CH3(CH2)n-1XHm-1型分子の(n≧2)の n 増加にともなう振動数変化は,上式をこれらの分子に適用し,メチル基とt直接結合する炭素原子の電気陰性度が置換基の誘起効果によって変化することを考慮してよく説明できる。","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"0 1","pages":"407-407"},"PeriodicalIF":0.0,"publicationDate":"1961-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89038706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Separation and Spectrophotometric Determination of Uranium by the Extraction of the Dibenzoylmethane Chelate with Butyl Acetate","authors":"T. Shigematsu, M. Tabushi","doi":"10.1246/nikkashi1948.81.2_265","DOIUrl":"https://doi.org/10.1246/nikkashi1948.81.2_265","url":null,"abstract":"ウランのジベンゾイルメタン塩を pH6～7の溶液から酢酸ブチルで抽出し酢酸ブチル層の 400mμ 付近の吸収を利用してウランを光度定量した。抽出の際, EDTA-Ca を隠蔽剤として使用することにより, 多くの金属との融合が可能になり, この方法を核分裂生成物とウランとの分離に適用して除染係数 104－105 で核分裂生成物の放射能と分離できた。","PeriodicalId":9502,"journal":{"name":"Bulletin of the Institute for Chemical Research, Kyoto University","volume":"63 1","pages":"261-261"},"PeriodicalIF":0.0,"publicationDate":"1961-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78258428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}