Pub Date : 2002-01-01DOI: 10.1246/NIKKASHI.2002.467
Naoki Morinaga, M. Uchigashima, M. Rahim, K. Onishi, Kazufumi Takahashi, Y. Kosugi
The carboxylation of m-aminophenol with potassium hydrogencarbonate in aqueous solutions has been studied kinetically. The formation of 4-hydroxyanthranilic acid (4HAA) has been found for the first time in the carboxylation of m-aminophenol which gives only p-aminosalicylic acid (pAS) in the usual Kolbe-Schmitt reaction. Since 4HAA was easily decarboxylated, the product was removed from the reaction mixture after the carboxylation for 1 h at 60 °C. This method was repeated three times and 4HAA was obtained as a major product in 30.2% yield.
{"title":"The Kolbe-Schmitt Reaction in Aqueous Solutions.","authors":"Naoki Morinaga, M. Uchigashima, M. Rahim, K. Onishi, Kazufumi Takahashi, Y. Kosugi","doi":"10.1246/NIKKASHI.2002.467","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.467","url":null,"abstract":"The carboxylation of m-aminophenol with potassium hydrogencarbonate in aqueous solutions has been studied kinetically. The formation of 4-hydroxyanthranilic acid (4HAA) has been found for the first time in the carboxylation of m-aminophenol which gives only p-aminosalicylic acid (pAS) in the usual Kolbe-Schmitt reaction. Since 4HAA was easily decarboxylated, the product was removed from the reaction mixture after the carboxylation for 1 h at 60 °C. This method was repeated three times and 4HAA was obtained as a major product in 30.2% yield.","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":"86115899","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":"Electrochemical Reduction of Nickel(II) Hydroxide Deposited on Carbon Powder and Application to a New Activation Method for Hydrogen Storage Alloy Negative Electrodes.","authors":"S. Morishita, Y. Isogai, K. Itoh, S. Towata, K. Abe","doi":"10.1246/NIKKASHI.2002.129","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.129","url":null,"abstract":"水酸化ニッケル(II)の析出したカーボン粉末[Ni(OH)2/C]をカソード分極後，X線回折，磁気測定ならびにTEM観察を行った．カーボン粉末の表面に析出した水酸化ニッケル(II)の1.4%以上が電気化学的に還元されて金属ニッケル微粒子を生成した．生成したニッケル微粒子が充放電反応の活性点として作用するため，Ni(OH)2/Cの添加によって水素吸蔵合金負極の初期活性化が促進された．","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":"82208934","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.2002.475
Seiji Tanaka, K. Kawasaki, Mariko Hirao, K. Kishikawa, S. Kohmoto, Makoto Yamamoto*
Previously we reported regioselective formation of dianions derived from liner nitroalkanes in the presence of n-BuLi and HMPA. The formation of nitroalkane dianions either α,α- or α,β-dianions depended on the order of addition of reagents. However, the usage of a carcinogen suspected compound like HMPA is undesirable. Therefore we re-investigated the new combination of bases and aprotic dipolar solvents other than HMPA. After exploration of a variety of their combination, it was found that the combination of LDA and DMPU resulted in the formation of α,β-dianion with the best regioselectivity; the ratio of α- to β-adduct was 1 to 14 in the reaction of nitroethane with benzaldehyde.
{"title":"Regioselective Aldol Addition Reaction of Nitroalkane Dianions.","authors":"Seiji Tanaka, K. Kawasaki, Mariko Hirao, K. Kishikawa, S. Kohmoto, Makoto Yamamoto*","doi":"10.1246/NIKKASHI.2002.475","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.475","url":null,"abstract":"Previously we reported regioselective formation of dianions derived from liner nitroalkanes in the presence of n-BuLi and HMPA. The formation of nitroalkane dianions either α,α- or α,β-dianions depended on the order of addition of reagents. However, the usage of a carcinogen suspected compound like HMPA is undesirable. Therefore we re-investigated the new combination of bases and aprotic dipolar solvents other than HMPA. After exploration of a variety of their combination, it was found that the combination of LDA and DMPU resulted in the formation of α,β-dianion with the best regioselectivity; the ratio of α- to β-adduct was 1 to 14 in the reaction of nitroethane with benzaldehyde.","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":"89754767","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.2002.359
K. Ogawa, C. Shimasaki, T. Yoshimura, S. Ono, I. Yamazaki
{"title":"Synthesis of Cross-Linked Starch with Acrylic Acid","authors":"K. Ogawa, C. Shimasaki, T. Yoshimura, S. Ono, I. Yamazaki","doi":"10.1246/NIKKASHI.2002.359","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.359","url":null,"abstract":"","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":"77607680","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.2002.471
Seiji Tanaka, Mikinao Ito, K. Kishikawa, S. Kohmoto, Makoto Yamamoto*
A mild and convenient method for generation of nitrile oxide is established by iodosylbenzene oxidation of aldehyde oximes. Aldehyde oximes were converted to furoxans in almost quantitative yields via dimerization of corresponding nitrile oxides upon oxidation. When the oxidation was carried out in the presence of alkene and alkyne dipolarophiles, isoxazolines or isoxazoles were obtained in good yields.
{"title":"A Convenient Method of Generation of Nitrile Oxides by Iodosylbenzene and Its Reaction.","authors":"Seiji Tanaka, Mikinao Ito, K. Kishikawa, S. Kohmoto, Makoto Yamamoto*","doi":"10.1246/NIKKASHI.2002.471","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.471","url":null,"abstract":"A mild and convenient method for generation of nitrile oxide is established by iodosylbenzene oxidation of aldehyde oximes. Aldehyde oximes were converted to furoxans in almost quantitative yields via dimerization of corresponding nitrile oxides upon oxidation. When the oxidation was carried out in the presence of alkene and alkyne dipolarophiles, isoxazolines or isoxazoles were obtained in good yields.","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":"85946470","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 Sulfate Ion on Crystal Structure and Activity for Methane Oxidation of Iron Oxide Prepared from Goethite.","authors":"Masanao Orihara, Suminori Tanaka, Sigeo Kawakami, K. Nakagawa, Masahiro Kato, S. Sugiyama, T. Moriga, I. Nakabayashi","doi":"10.1246/NIKKASHI.2002.11","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.11","url":null,"abstract":"ゲータイト(α-FeO(OH))を前駆物質として合成した酸化鉄を用いてメタン酸化活性試験を行った．ゲータイトは水酸化ナトリウム水溶液と硫酸鉄水溶液を混合した懸濁液の空気酸化により調製され，その熱分解により酸化鉄を得た．酸化鉄によるメタン酸化活性は硫酸イオンの存在で抑制されることがわかった．そこで，ゲータイトを硫酸に浸漬してその表面に硫酸イオン(SO42−)を存在させ，残存した硫酸イオンがゲータイトから調製された酸化鉄の結晶構造とメタン酸化活性に及ぼす影響について詳しく検討した．その結果，硫酸イオンは250 °C付近で起こるゲータイトからヘマタイト(α-Fe2O3)への相転移温度を約30 °C高温側へシフトさせることが明らかになった．また，この硫酸イオンは鉄原子に電子を供与して鉄の酸化力を減少させ，300 °Cから500 °Cの温度範囲においてメタン酸化活性を低下させ，かつメタンの部分酸化を引き起こす．さらに硫酸イオンによって，相転移して生成したヘマタイト中に多くの格子欠陥が存在し，(113l)(l : 0，1，2)面に代表される鉄原子の並びに関係する特定の面以外，すなわち酸素が関与する原子配列を乱すことがわかった．硫酸処理されたゲータイトから得られたヘマタイトを触媒として，550 °C以上でメタン酸化活性試験を行ったところ，硫酸処理なしのゲータイトから得られたヘマタイトよりも高活性であった．550 °C以上の温度においてヘマタイト表面の硫酸イオンは脱離するが，硫酸イオンによってもたらされたヘマタイトの格子欠陥は残り，この格子欠陥が高活性の要因であると考えられる．","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":"88614918","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 .ALPHA.-Lithium Aluminate Fiber and Its Stability in Molten Carbonate Salt.","authors":"K. Takizawa, A. Hagiwara","doi":"10.1246/NIKKASHI.2002.97","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.97","url":null,"abstract":"溶融炭酸塩形燃料電池(MCFC)では，電解質保持板の補強材料としてアルミナ(Al2O3)繊維が用いられているが，経時的に腐食劣化することが知られている．電解質保持板構成材料であるアルミン酸リチウム(LiAlO2)については，長期運転でも劣化が少ないとされるα相が注目されている．そこで補強材についてもα-アルミン酸リチウムを適用することを試みた．出発物質としてγ相のアルミナ繊維を用いて炭酸リチウムとの反応を検討した結果，600–650 °Cの温度で二酸化炭素雰囲気下において繊維形状を保った良好なα-アルミン酸リチウム繊維を合成することができた．さらにこの繊維の溶融炭酸塩中における耐食性をアルミナ繊維と比較検討した．電解質保持板を模擬したα-アルミン酸リチウム粉末と繊維の混合物は，溶融炭酸塩中でもアルミナ繊維と同等の耐食性を示した．また結晶構造はα相を維持していた．これらの結果から，長期耐久性に優れた“α-アルミン酸リチウム電解質保持板”への可能性を示すことができた．","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":"88749386","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":"Incorporation with Possible Regular Arrangement of Silver Ion in Interlayer Region of Mg/Al Layered Double Hydroxide with Interlayer Thiosulfate Ion.","authors":"E. Kanezaki, Kazuki Maeda","doi":"10.1246/NIKKASHI.2002.393","DOIUrl":"https://doi.org/10.1246/NIKKASHI.2002.393","url":null,"abstract":"あらかじめ，チオ硫酸イオンを層間に取り込んだMg/Al-LDH前駆物質を合成し，そののち前駆物質とAg+イオンとを水溶液中で反応させることにより層間にAg+イオンを取り込んだ層状複水酸化物(Ag+-LDH)を合成した．Ag+-LDHのFT-IRスペクトルの解析から，層間のAg+イオンはチオ硫酸イオンの末端硫黄原子が2個配位した直線型構造を持つことがわかった．この固体の示差熱曲線中には，前駆物質と類似した熱変化が観測されたが，幾つかのピークではAg+イオンの取り込みによりピーク温度がシフトした．また，それぞれの固体の組成式をよく支持する熱重量曲線が得られた．Ag+-LDHの粉末X線回折図には，取り込んだAg+イオン量の増加とともに，(002)回折線強度が相対的に増加した．これは，層間に取り込まれたAg+イオンが，層に平行に規則的に並んだ格子面を持つ新たな結晶格子を形成したためと考えた．","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":"76559896","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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