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Research On The Selective Reduction Properties Of Organolanthanide Hydride

Posted on:2004-04-18Degree:MasterType:Thesis
Country:ChinaCandidate:C B CheFull Text:PDF
GTID:2121360095957271Subject:Applied Chemistry
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According to the application of organolanthanide hydride and it is related compound and Claisen rearrangement. It is not reported that the selective reduction of organolanthanide hydride and the compound with many kinds of unsaturated function and the Claisen rearrangement of organolanthanide hydride. In this paper, we studied these reactions.Bis(indeny)rare-earth chloride was synthesised by trivalent rare-earth oxide and trivalent rare-earth chloride with indene as chelate agent. Bis(indeny)rare-earth hydride was synthesised by Bis(indeny) rare-earth chloride and exceeded sodium hydride in THF (tetrahydr-ofuran) solution. It is structure determined by IR, H NMR.The As-prepared Bis (indeny) rare-earth hydride reacted with unsaturated compound having carbonyl group, such as citronellaU dihydroc-arvone^ Methyl cinnamylate. It is turned out that carbonyl was selectively reducted by Bis(indeny)rare-earth hydride, the selectivity is 100%.We deduced that reactivity of unsaturated carbonyl compound was: Aldehyde>ketone>ester. At mordest condition, Bis (indeny)rare-earth hydride reacted with unsaturated carbonyl compound with allyl such as allyl-benzeneacetate, ally-butyrate, the enolated Claisen rearrangement was occurred. It was reduced in the basis of rearrangement.It could reduced the reaction tempreture of Claisen rearrangement.The enolate Claisen rearrangement can reduce a chiral carbon, aid-ehyde group that was reduced by reduction was also a potential chiral carbon. So, this reaction can open a new route for preparing chiral compound.
Keywords/Search Tags:indene, bis(indeny)rare-earth chloride, bis(indeny)rare-earth hydride, unsaturated carbonyl-compound, selective reduction, Claisen rearrangement
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