Synthesis of Monomers for Oxygen Enrichment Membrane

富氧膜单体的合成

• 批准号: 06555280
• 负责人: CHATANI Naoto
• 金额: $ 0.64万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06555280/
• 关键词: Vinylsilane; Vinylgermane; Allylsilane; Oxygen Enrichment Membrane; ケイ素

1. The reaction of terminal acetylenes with Me_3SiI (1) and dialkylzinc reagents in the presence of Pd (PPh_3)_4 gave vinylsilanes. In all cases the trimethylsilyl group adds to the terminal carbon of the acetylenes and the alkyl group is introduced at the internal carbon. Both aromatic and aliphatic terminal acetylenes undergo the coupling reaction with high regio-and stereoselectivities.2. The reaction of stirene with allyltrimethylsilane (2) in the presence of RuHCl (CO) (PPh_3)_3 as a catalyst resulted in dehydrogenative silylation to afford (E) -1-phenyl-2- (trimethylsilyl) ethylene in 66% yield. The reactions of 4-chloro- and 4-methoxy-stirenes, and 2-vinylnaphthalene with 2 provide the corresponding (E) -beta-substituted vinylsilanes in 49-76% yields.3. The reaction of trimethylgermyl cyanide (Me_3GeCN,3) with terminal aromatic acetylenes in the presence of PdCl_2 results in the addition of 3 to the carbon-carbon triple bonds with high regioselectivity leading to beta-cyano vinylgermanes in high yields. The stereoselectivity depends on the electronic nature of the substituents on the aromatic ring. The reaction of terminal aliphatic acetylenes also afford the adduct with high regio- and stereoselectivity.

1.在Pd（PPh_3）_4存在下，端炔与Me_3SiI（1）和二烷基锌试剂反应，生成乙烯基硅烷。在所有情况下，三甲基甲硅烷基加到乙炔的末端碳上，烷基引入到内部碳上。芳族和脂肪族末端炔类都能进行高区域和立体选择性的偶联反应.在RuHCl（CO）（PPh_3）_3催化下，苯乙烯与烯丙基三甲基硅烷（2）反应，进行双硅烷化反应，得到（E）-1-苯基-2-（三甲基硅基）乙烯，产率66%。4-氯-和4-甲氧基-苯乙烯和2-乙烯基萘与2的反应以49-76%的产率提供相应的（E）-β-取代的乙烯基硅烷。在PdCl_2存在下，三甲基锗腈（Me_3GeCN，3）与末端芳炔反应，以较高的区域选择性在碳-碳三键上加成3，高产率地得到β-氰基乙烯基锗烷。立体选择性取决于芳环上取代基的电子性质。末端脂肪炔的反应也提供了高的区域和立体选择性的加合物。

项目成果

N.Chatani: "Pd-Catalyzed Coupling Reaction of Acetylense,Iodo Trirotly-silane,and Organozinc Reagents for the Steroselective Synthesis of Vinylsilanes" The Journal of Organic Chemistry. 60. 1834-1840 (1995)

N.Chatani：“用于乙烯基硅烷立体选择性合成的乙酰基、碘三旋硅烷和有机锌试剂的钯催化偶联反应”有机化学杂志。

N.Chatani: "Preparation of Vinylgermanes and a Germole by the Pd-Catalyzed Reactions of MezGeCN with Acetylenes" Journal of Organometallic Chemistry. 473. 335-342 (1994)

N.Chatani：“通过 MezGeCN 与乙炔的 Pd 催化反应制备乙烯基锗烷和 Germole”《有机金属化学杂志》。

Naoto Chatani: "Preparation of Vinylgermanes and a Germole by the Pd-Catalyzed Reactions of Me_3GeCN with Acetylenes" J.Organomet.Chem.473. 335-342 (1994)

Naoto Chatani：“通过 Me_3GeCN 与乙炔的 Pd 催化反应制备乙烯基锗烷和 Germole”J.Organomet.Chem.473。

Naoto Chatani: "Pd-Catalyzed Coupling of Acetylenes, Me_3SiI,and Organozinc Reagents as a Synthetic Method of Stereoselective Vinylsilanes" J.Org.Chem.60. 1834-1840 (1995)

Naoto Chatani：“乙炔、Me_3SiI 和有机锌试剂的钯催化偶联作为立体选择性乙烯基硅烷的合成方法”J.Org.Chem.60。

Naoto Chatani et al: "Pd-Catalyzed Coupling Reaction of Acetylenes,Iodotrimethylsilane,and Organozinc Reagents for the Stereoselective Syhtheses of Vinylsilanac" The Journal of Organic Chemistvy. 60. 1834-1840 (1995)

Naoto Chatani 等人：“用于乙烯基硅烷立体选择性合成的乙炔、碘三甲基硅烷和有机锌试剂的钯催化偶联反应”有机化学杂志。