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  1. C0700 総合理学研究所
  2. 03 紀要論文
  3. 01 Science Journal of Kanagawa University
  4. 0290 29巻

反応のタイプと発見のエピソードで学ぶ有機金属化学(5)

http://hdl.handle.net/10487/00015650
http://hdl.handle.net/10487/00015650
8cdff2e8-6b49-4c6c-af26-ef51fa3392cb
名前 / ファイル ライセンス アクション
20 20 反応のタイプと発見のエピソードで学ぶ有機金属化学(5) (1.1 MB)
Item type 紀要論文 / Departmental Bulletin Paper(1)
公開日 2019-06-07
タイトル
タイトル 反応のタイプと発見のエピソードで学ぶ有機金属化学(5)
言語 ja
タイトル
タイトル Organometallic Chemistry Based on Reaction Types and Anecdotes of Discoveries (5)
言語 en
言語
言語 jpn
キーワード
言語 en
主題Scheme Other
主題 transition metal comounds
キーワード
言語 en
主題Scheme Other
主題 metal alkylss
キーワード
言語 en
主題Scheme Other
主題 polymerization
キーワード
言語 en
主題Scheme Other
主題 metathesi
資源タイプ
資源タイプ識別子 http://purl.org/coar/resource_type/c_6501
資源タイプ departmental bulletin paper
著者 加部, 義夫

× 加部, 義夫

ja 加部, 義夫

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内容記述タイプ Abstract
内容記述 Organic compounds containing carbon-metal bonds are called organometallic compounds. Such compounds have been known and studied since the 19 century and have been widely used for synthetic transformation in modern organic chemistry. Their many educational benefits could result in the use of reaction types and discoveries in undergraduate and graduate classes in organic and organometallic chemistry. The repeating growth reaction of alkylaluminum with ethylene was discovered by Ziegler. An anomalous result was obtained on one occasion. Instead of converting ethylene into a mixture of ethylene oligomer, its dimer, i.e., 1-butene, was almost the only product. The promoter for this unexpected reaction was eventually found to be a trace of nickel salts, which was accidentally mixed into the reaction due to the use of an uncleaned metal autoclave after a hydrogenation experiment (Nickel effect). Since nickel salt could have such a marked influence on the course of ethylene with alkylaluminium, curiosity was aroused about the influence of transition metal salts. Ziegler and his group finally found that salt of Ti markedly accelerated the growth reaction, leading to the deposition of polyethylene. Natta found sterically controlled polypropylene with R3Al/TiCl3 instead of R3Al/TiCl4. Furthermore, he also found the polymerization of cyclic olefins with R3Al/ MoCl6 or WCl6, but he misunderstood the reaction mechanism. Subsequent chemists disclosed the correct reaction mechanism : olefin metathesis of a carbene intermediate. A similar mechanism is applied as a Ziegler-Natta polymerization alternative to the insertion mechanism of transition alkylmetals. This Ziegler-Natta catalysts (R3Al-TiCl3/TiCl4) open the reaction types of transmetalation between typical elements/metals and transition metals, which develops into a modern Ni-and Pd-catalyzed cross-coupling reaction. The Ziegler-Natta catalyst reaction of butadiene and acetylene produced rubber as well as conduction polymer.
言語 en
内容記述
内容記述タイプ Other
内容記述 教育論文
言語 ja
書誌情報 en : Science Journal of Kanagawa University

巻 29, p. 113-119, 発行日 2018-06-30
ISSN
収録物識別子タイプ PISSN
収録物識別子 1880-0483
書誌レコードID
収録物識別子タイプ NCID
収録物識別子 AA12068302
著者版フラグ
出版タイプ VoR
出版タイプResource http://purl.org/coar/version/c_970fb48d4fbd8a85
その他の言語のタイトル
その他のタイトル Organometallic Chemistry Based on Reaction Types and Anecdotes of Discoveries (5)
出版者
出版者 神奈川大学総合理学研究所
言語 ja
出版者
出版者 Research Institute for Integrated Science, Kanagawa University
言語 en
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