Pub Date : 2002-02-10DOI: 10.1246/NIKKASHI.2002.239
睦司 酒井, 政史 出口, 浩司 東
Under nitrogen atmosphere diethyl maleate was hydrogenated to give diethyl succinate in a high yield with metallic nickel/Zn/H2O/EtOH catalyst system in the presence of a large amount of zinc powder and water. Metallic nickel was an active species for the hydrogenation and zinc powder and water were reagents to produce hydrogen. Benzylideneaniline was hydrogenated to give N-phenylbenzylamine in a moderate yield under the reaction conditions and it was appreciably hydrolyzed to afford aniline and benzaldehyde at the same time.
{"title":"金属ニッケル/亜鉛/水/エタノール触媒系による不飽和エステルの水素化反応","authors":"睦司 酒井, 政史 出口, 浩司 東","doi":"10.1246/NIKKASHI.2002.239","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.239","url":null,"abstract":"Under nitrogen atmosphere diethyl maleate was hydrogenated to give diethyl succinate in a high yield with metallic nickel/Zn/H2O/EtOH catalyst system in the presence of a large amount of zinc powder and water. Metallic nickel was an active species for the hydrogenation and zinc powder and water were reagents to produce hydrogen. Benzylideneaniline was hydrogenated to give N-phenylbenzylamine in a moderate yield under the reaction conditions and it was appreciably hydrolyzed to afford aniline and benzaldehyde at the same time.","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80866036","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}
Pub Date : 2002-01-10DOI: 10.1246/NIKKASHI.2002.103
H. Kusama, K. Okabe, H. Arakawa
Hydrogenation reaction of CO2 over Rh/FSM-16 and Rh/SiO2 catalysts prepared by impregnation method was carried out. The Rh/FSM-16 catalyst showed higher CO2 conversion and turnover frequency than Rh/SiO2 one. The main product was CO over SiO2 supported catalyst, but it was CH4 over FSM-16 supported one irrespective of reaction temperature. From the results of TEM and H2 chemisorption, the mean particle size of Rh for Rh/FSM-16 was smaller than that for Rh/SiO2. The ratio of chemisorbed CO to chemisorbed H was smaller for Rh/FSM-16 catalyst than Rh/SiO2 one. It was suggested that this finding reflected the difference in product selectivity of CO2 hydrogenation between FSM-16 and SiO2 supported Rh catalysts.
{"title":"Hydrogenation Reaction of CO_2 by Using FSM-16 and SiO_2 Supported Rh Catalysts","authors":"H. Kusama, K. Okabe, H. Arakawa","doi":"10.1246/NIKKASHI.2002.103","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.103","url":null,"abstract":"Hydrogenation reaction of CO2 over Rh/FSM-16 and Rh/SiO2 catalysts prepared by impregnation method was carried out. The Rh/FSM-16 catalyst showed higher CO2 conversion and turnover frequency than Rh/SiO2 one. The main product was CO over SiO2 supported catalyst, but it was CH4 over FSM-16 supported one irrespective of reaction temperature. From the results of TEM and H2 chemisorption, the mean particle size of Rh for Rh/FSM-16 was smaller than that for Rh/SiO2. The ratio of chemisorbed CO to chemisorbed H was smaller for Rh/FSM-16 catalyst than Rh/SiO2 one. It was suggested that this finding reflected the difference in product selectivity of CO2 hydrogenation between FSM-16 and SiO2 supported Rh catalysts.","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88449433","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}
Pub Date : 2002-01-10DOI: 10.1246/NIKKASHI.2002.107
仁 草間, 裕則 荒川
CO2 hydrogenation was carried out over alkali metals such as Li, Na and K promoted silica-supported Rh–Co catalysts (Rh–Co–M/SiO2). Na additive was most effective of the three alkali metals for ethanol formation over 5 wt% Rh–Co(1 : 1)/SiO2. The added amount of Na influenced product selectivity as well as CO2 conversion. The highest ethanol selectivity was obtained over 5 wt% Rh–Co–Na (1 : 1 : 0.5)/SiO2 catalyst. The mechanism of promotion effect of Na added amount was investigated by means of in situ FT-IR observation during reaction. The variation of Na added amount changed the ratio of Rh2–(CO)3 and bridged type adsorbed CO species to linear type one. This finding suggested that the amount of Na affected on the hydrogenation ability of Rh–Co/SiO2 catalysts, leading to the difference in CO2 hydrogenation activity.
{"title":"シリカ担持ロジウム‐コバルト‐アルカリ金属触媒を用いた二酸化炭素の水素化反応","authors":"仁 草間, 裕則 荒川","doi":"10.1246/NIKKASHI.2002.107","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.107","url":null,"abstract":"CO2 hydrogenation was carried out over alkali metals such as Li, Na and K promoted silica-supported Rh–Co catalysts (Rh–Co–M/SiO2). Na additive was most effective of the three alkali metals for ethanol formation over 5 wt% Rh–Co(1 : 1)/SiO2. The added amount of Na influenced product selectivity as well as CO2 conversion. The highest ethanol selectivity was obtained over 5 wt% Rh–Co–Na (1 : 1 : 0.5)/SiO2 catalyst. The mechanism of promotion effect of Na added amount was investigated by means of in situ FT-IR observation during reaction. The variation of Na added amount changed the ratio of Rh2–(CO)3 and bridged type adsorbed CO species to linear type one. This finding suggested that the amount of Na affected on the hydrogenation ability of Rh–Co/SiO2 catalysts, leading to the difference in CO2 hydrogenation activity.","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80292758","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":"Porous Carbon Powders Prepared from Spherical Phenolic Resin Powder by Thermal Plasma Carbonization and Their Electrochemical Properties.","authors":"S. Maruyama, M. Kurihara, T. Ishigaki, Kenji Watanabe, T. Takizawa, Y. Moriyoshi","doi":"10.1246/NIKKASHI.2002.27","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.27","url":null,"abstract":"平均粒径約25 μmの球状フェノール樹脂粒子を高周波熱プラズマ中に供給して，加熱 · 分解することにより炭素粉末を合成した．熱プラズマ処理により得られた炭素粉末粒子は，多孔質で，表面が黒鉛化され内部は非晶質構造を示す傾斜構造を持つ粒子で，通常の低温熱処理あるいは高温黒鉛化では得られないものであった．このプラズマ合成炭素粉末をリチウム二次電池の負極材として用いるときの，リチウムイオンの挿入脱離反応を検討した結果，傾斜構造を裏付ける挙動，すなわち黒鉛化を示す挙動と非晶質構造に由来する挙動が確認できた．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84538321","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":"Synthesis of Aromatic Polyester Having Oligosaccharide in the Main Chain.","authors":"K. Hatanaka, R. Shiraishi, K. Katsuraya, K. Okuyama","doi":"10.1246/NIKKASHI.2002.53","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.53","url":null,"abstract":"D-ラクトースのC-6位とC-6′位にある第一級ヒドロキシ基を選択的にトリチル基で保護し，第二級ヒドロキシ基を有する他の位置にはアセチル基を導入した．脱トリチル化の反応では，アシル転移が起こり，C-6位とC-4′位にフリーの水酸基を有するアセチル化ラクトースを合成した．得られた1,2,3,2′,3′,6′-ヘキサ-O-アセチル-D-ラクトースと二塩化テレフタロイルを反応させることにより，オリゴ糖鎖を有するポリエステルを合成した．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73528827","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}
Pub Date : 2002-01-01DOI: 10.1246/NIKKASHI.2002.481
H. Shimofuruya, Asami Fujii, I. Suzuki, Yoshihiko Kunieda
Antioxidative effects of Taheebo extract, obtained from the bulk of Tabebuia avellanedae Lorents and Griseb, were examined by two assay methods for radical scavenging activity on DPPH and inhibitory effect on linoleic acid peroxidation. In the case of the DPPH method, Taheebo showed the electron donating ability to DPPH and its ability corresponded to that of trolox in the present experimantal condition. On the other hand, in the autoxidation of liloleic acid, Taheebo extract showed the most inhibitory effect in teas tested (green tea and oolong tea.). These results suggested that Taheebo extract was a desirable antioxidant.
{"title":"Antioxidative Effect of Taheebo Extract.","authors":"H. Shimofuruya, Asami Fujii, I. Suzuki, Yoshihiko Kunieda","doi":"10.1246/NIKKASHI.2002.481","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.481","url":null,"abstract":"Antioxidative effects of Taheebo extract, obtained from the bulk of Tabebuia avellanedae Lorents and Griseb, were examined by two assay methods for radical scavenging activity on DPPH and inhibitory effect on linoleic acid peroxidation. In the case of the DPPH method, Taheebo showed the electron donating ability to DPPH and its ability corresponded to that of trolox in the present experimantal condition. On the other hand, in the autoxidation of liloleic acid, Taheebo extract showed the most inhibitory effect in teas tested (green tea and oolong tea.). These results suggested that Taheebo extract was a desirable antioxidant.","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75790651","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":"Characterization of Electrode Materials during Degradation Process of Li-ion Batteries.","authors":"Noboru Sato, Koichi Hirao, Eiji Hayashi, Gen Katagiri","doi":"10.1246/NIKKASHI.2002.189","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.189","url":null,"abstract":"正極にLiMn2O4を，負極にグラファイトを用いたリチウムイオン電池は，エネルギー密度と出力密度が大きい点で自動車用駆動源として期待されている．しかし，自動車用途では低温から高温までの広い範囲で電池が使用されるため，特に高温領域におけるサイクル劣化が問題になる．45 °Cの温度条件下でサイクル劣化を起こしたリチウムイオン電池に対して，正負極の劣化状態について解析した． 正極の構造変化についてESRとNMRを用いて解析したところ，スピネル型LiMn2O4は，ヤーン · テラー効果により正方晶Li2Mn2O4に変化したことが確認された．スピネル型LiMn2O4に比べて正方晶Li2Mn2O4ではリチウムの拡散が遅くなることから，この結晶の転移が容量低下と内部抵抗の上昇の一因となっているものと考えられた． また負極表面では，サイクル劣化により新たな皮膜が形成されていることがXPS測定により確認できた．この皮膜には電解質であるLiPF6の分解成分が含まれていたために，皮膜が厚くなることが電池の内部抵抗上昇の一因になっているものと考察された．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73137796","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":"Effects of Various Ions on the Synthesis of Strontium Phosphates Obtained by Homogeneous Precipitation Method.","authors":"Chiharu Kato, K. Fujita, Keizo Matsuda","doi":"10.1246/NIKKASHI.2002.321","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.321","url":null,"abstract":"尿素の加水分解を利用した均一沈殿法によるストロンチウムの各種リン酸塩の合成における反応条件について詳しく調べた．その結果，反応溶液のpH変化や加熱時間のほかに，Sr2+イオン濃度やCl−イオン濃度も各種リン酸塩の生成過程やSr–Ap(ストロンチウムアパタイト)の組成に影響を及ぼした．均一沈殿法によるSr–Apの合成では，初期生成物としてα-SrHPO4が生成し，(i)α-SrHPO4からSr3(PO4)2を経てSr–Apになる場合と，(ii)α-SrHPO4からβ-SrHPO4を経てSr–Apになる場合の二系統の生成過程がある．初期生成物であるα-SrHPO4はpH 6.2付近では，反応溶液のSr2+イオン濃度が低いとSr3(PO4)2に，Sr2+イオン濃度が高いとβ-SrHPO4に変化し，pH 7.2付近では反応溶液のSr2+イオン濃度にかかわらずβ-SrHPO4に変化した．中間生成物であるSr3(PO4)2やβ-SrHPO4は反応溶液のSr2+イオン濃度やCl−イオン濃度が高いほど短時間でSr–Apに変化した．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73853793","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":"Alkylation of Diphenyl Oxide with Long Chain Olefins Using Smectite Clay Catalysts.","authors":"Hitoshi Asakura, H. Tomioka","doi":"10.1246/NIKKASHI.2002.37","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.37","url":null,"abstract":"各種スメクタイト粘土触媒を長鎖オレフィンによるジフェニルオキシドの液相アルキル化反応に用い，触媒物性(細孔等)と反応生成物の関係を考察した．酸処理により生成するメソ細孔を持つものはかさ高い基質の反応に高い活性を示し，AlCl3に代替しうる．一方，カードハウス構造を持つサポナイトはY-型ゼオライトと似た反応組成を与えた．また，シート構造を持つモンモリロナイトは，高温処理ではシート収縮により活性を失うが，120 °C程度の乾燥条件下では酸処理品に準じた活性を示した．生成物のかさ高さと細孔径との間には相関が認められ，大きいものほどポリアルキル体，およびo-体の比率が高くなった．側鎖アルキル異性体分布はp-体においては広くなるが，これは置換基の立体障害と一部オレフィンの異性化のためと考えられる．一次元細孔を持つモルデナイトは，直線形状を持つ生成物に対して選択性を示した．粘土系触媒は生成物組成の面からミクロ細孔系触媒と均一系触媒の中間に位置づけられた．","PeriodicalId":19311,"journal":{"name":"Nippon Kagaku Kaishi","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88661778","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}
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