Study on Synthesis and Properties of Functional Material Poly [Sila (N-Substituted) Imine]
功能材料聚[硅拉(N-取代)亚胺]的合成及性能研究
基本信息
- 批准号:01430017
- 负责人:
- 金额:$ 16.64万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for General Scientific Research (A)
- 财政年份:1989
- 资助国家:日本
- 起止时间:1989 至 1990
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
Palladium-catalyzed insertion reactions of isocyanides into silicon-silicon linkage of oligosilanes have been studied. A variety of disilanes reacted with aliphatic and aromatic isocyanides in the presence of palladium (O) tetrakis (triphenylphosphine) complex or palladium (II) acetate to give the corresponding bis (silyl) N-substituted imines in moderate yields. Oligosilanes were reacted with an excess of 2, 6-disubstituted aryl isocyanide in the presence of palladium (II) acetate, resulting in regular insertion of the isocyanide into each silicon-silicon linkage giving poly (silaimine) derivatives. The palladium catalyzed regular insertion was successfully achieved with up to hexasilane. Partial insertion of the isocyanide into oligosilanes was also achieved selectively by use of the limiting amount of isocyanide. New skeletal rearrangement of tetrasilanes was found in the palladium catalyzed reaction of tetrasilanes with one molar equivalent of 2, 6-disubstituted phenyl isocyanide to afford 2, 4-disila-3, 3-bis (silyl)-1-azacyclobutane derivatives, which was properly reconstituted from four fragments of tetrasilane and two fragments of isocyanide. Noteworthy is that the skeletal rearrangement was assisted by tert-alkyl isocyanide ligand on palladium catalyst.
研究了钯催化的异氰化物插入低聚硅烷的硅-硅键中的反应。在钯 (O) 四(三苯基膦)络合物或乙酸钯 (II) 存在下,各种乙硅烷与脂肪族和芳香族异氰化物反应,以中等产率得到相应的双(甲硅烷基)N-取代亚胺。在乙酸钯 (II) 存在下,低聚硅烷与过量的 2, 6-二取代芳基异氰化物反应,导致异氰化物规则插入每个硅-硅键中,得到聚(硅胺)衍生物。钯催化的规则插入已成功实现,用量高达六硅烷。通过使用有限量的异氰化物,还可以选择性地将异氰化物部分插入低聚硅烷中。在四硅烷与一摩尔当量的 2, 6-二取代苯基异氰化物的钯催化反应中发现了新的四硅烷骨架重排,得到 2, 4-二硅基-3, 3-双(甲硅烷基)-1-氮杂环丁烷衍生物,该衍生物由四个四硅烷片段和两个四硅烷片段正确重构。 异氰化物。值得注意的是,骨架重排是由钯催化剂上的叔烷基异氰化物配体辅助的。
项目成果
期刊论文数量(7)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Y.ITO: "NーSubstituted Organo(silyliminomethyl)stannanes:Synthetic Equivalent to Organosilylcarbonyl Anion and Carbonyl Dianion" J.Am.Chem.Soc.109. 7888-7890 (1987)
Y.ITO:“N-取代的有机(甲硅烷基亚氨基甲基)锡烷:有机甲硅烷基羰基阴离子和羰基二价阴离子的合成等效物”J.Am.Chem.Soc.109(1987)。
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Y.ITO: "Novel Skeletal Rearrangement Reaction of Tetrasilanes with Aryl Isocyanides" J.Chem.Soc.,Chem.Commun.1494-1495 (1989)
Y.ITO:“四硅烷与芳基异氰化物的新颖骨架重排反应”J.Chem.Soc.,Chem.Commun.1494-1495 (1989)
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M.MURAKAMI: "Conjugate Addition of NーSubstituted Organo(silyliminomethyl)copper(I)to α,βーUnsaturated Carbonyl Compounds" Tetrahedron Lett.29. 355-358 (1988)
M.MURAKAMI:“N-取代的有机(甲硅烷基亚氨基甲基)铜(I)与α,β-不饱和羰基化合物的共轭加成”Tetrahedron Lett.29 (1988)。
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Y.ITO: "Palladium / tertーAlkyl Isocyanide as a Highly Efficient Catalytic System for Interーand Intramolecular Bisーsilylation of Carbonーcarbon Triple Bond" J.Org.Chem.(1991)
Y.ITO:“钯/叔烷基异氰化物作为碳-碳三键分子间和分子内双硅烷化的高效催化体系”J.Org.Chem.(1991)
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M. MURAKAMI: "Conjugate Addition of N-Substituted Organo (silyliminomethyl) copper (I) to alpha, beta-Unsaturated Carbonyl Compounds" Tetrahedron Lett.Vo1.29. 355-358 (1988)
M. MURAKAMI:“N-取代的有机(甲硅烷基亚氨基甲基)铜 (I) 与 α,β-不饱和羰基化合物的共轭加成”四面体 Lett.Vo1.29。
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ITO Yoshihiko其他文献
ITO Yoshihiko的其他文献
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{{ truncateString('ITO Yoshihiko', 18)}}的其他基金
Asymmetric Synthesis of Usseful Natural Products by Means of Organosilicon Compounds
利用有机硅化合物不对称合成有用的天然产物
- 批准号:
07454164 - 财政年份:1995
- 资助金额:
$ 16.64万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Preparation of Optically Active Helical Polymer Materials for Separation of Optically Active Compounds
用于光学活性化合物分离的光学活性螺旋聚合物材料的制备
- 批准号:
06555279 - 财政年份:1994
- 资助金额:
$ 16.64万 - 项目类别:
Grant-in-Aid for Developmental Scientific Research (B)
Oligomerizations of o-Diisocyanobenzenes by Organometallic Compounds - Synthesis of Functional Nitrogen-Containing Aromatic Polymers
有机金属化合物低聚邻二异氰苯-功能性含氮芳香族聚合物的合成
- 批准号:
63850177 - 财政年份:1988
- 资助金额:
$ 16.64万 - 项目类别:
Grant-in-Aid for Developmental Scientific Research
Synthesis of Biologically Active Natural Products on the Basis of Silafunctional Compounds
基于硅功能化合物的生物活性天然产物的合成
- 批准号:
61470093 - 财政年份:1986
- 资助金额:
$ 16.64万 - 项目类别:
Grant-in-Aid for General Scientific Research (B)