Palladium-catalyzed formation and reactions of iodo- and bromosiloxane intermediates

Journal of Organometallic Chemistry 697 巻 1 号 51-56 頁 2012 発行
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タイトル ( eng )
Palladium-catalyzed formation and reactions of iodo- and bromosiloxane intermediates
作成者
Lu Zhou
Mizumo Tomonobu
収録物名
Journal of Organometallic Chemistry
697
1
開始ページ 51
終了ページ 56
抄録
Polysiloxanes are useful materials because of their functionality, such as high thermal stability, electrical resistance, and hydrophobicity. In this regard, we studied palladium-catalyzed formation of iodo-and bromopolysiloxanes from two types of hydrosiloxanes, alpha,omega-dihydropoly(dimethylsiloxane) (1) and cyclotetra(hydromethylsiloxane) (2), and their reactions. Treatment of 1 with mixtures of cyclic ethers or lactones and MeI or allylBr in the presence of a catalytic amount of PdCl2 gave the corresponding alpha,omega-bis(haloalkoxy and haloalkanoyloxy) poly(dimethylsiloxane)s in good yields, via iodo-and bromopoly(dimethylsiloxane) intermediates. Transformation of the iodobutoxy-terminal units in the resulting poly(dimethylsiloxane) into aminoalkoxy groups was examined. The formation of alpha,omega-diiodo- and dibromopoly(dimethylsiloxane)s from 1 was confirmed by spectrometric analysis as well as by quenching experiments with ethanol. A reaction of alpha,omega-dibromopoly(dimethylsiloxane) with 2,5-dilithiothiophene gave a polydimethylsiloxane-thiophene alternating polymer. Similar palladiumcatalyzed reactions of 2 with THF/MeI, THF/allylBr, and delta-valerolactone/allylBr afforded cyclo(halobutoxy- and bromobutanoyloxymethylsiloxane) s in moderate yields. This would provide a new strategy for the introduction of various substituents to the terminal positions of linear polysiloxane and to the cyclosiloxane core.
著者キーワード
Polysiloxane
Boromosilane
Iodosilane
Palladium catalyst
Cyclic ether
Lactone
NDC分類
化学 [ 430 ]
言語
英語
資源タイプ 学術雑誌論文
出版者
Elsevier Science SA
発行日 2012
権利情報
(c) 2012 Elsevier B.V. All rights reserved.
出版タイプ Author’s Original(十分な品質であるとして、著者から正式な査読に提出される版)
アクセス権 オープンアクセス
収録物識別子
[ISSN] 0022-328X
[DOI] 10.1016/j.jorganchem.2011.10.012
[NCID] AA00704122
[DOI] http://dx.doi.org/10.1016/j.jorganchem.2011.10.012