Pd(0)-catalyzed polyaddition of bifunctional vinyloxiranes with phenol derivatives: The synthesis of polymers containing an allyl aryl ether moiety in the main chain

摘要

The palladium(0)-catalyzed polyaddition of bifunctional vinyloxiranes [1,4-bis(2-vinylepoxyethyl)benzene (1a) and 1,4-bis(1-methyl-2-vinylepoxyethyl)benzene (1b)] with oxygen nucleophiles such as hydroquinone and bisphenol A gave new unsaturated polyethers containing an allyl aryl ether moiety and pendant hydroxy groups. The polyaddition with la was largely affected by the phosphine ligands employed and the reaction temperature. The polyaddition with hydroquinone and bisphenol A was conducted at room temperature for 24 h in tetrahydrofuran in the presence of PPh3 and gave the desired polyethers in good yields, the number-average molecular weights (M.) of which were 5700 and 7700, respectively. 1,2-Bis(diphenylphosphino)ethane (dppe) was not effective in the polyaddition with la. The polyaddition of 1b with hydroquinone and bisphenol A gave the corresponding polyethers despite the kinds of ligands employed (PPh3 and dppe), contrary to the polyaddition with 1a. The polyaddition of 1b with 4,4'-biphenol was also carried out in the presence of Pd-2(dba)(3) . CHCl3/dppe as a catalyst (where dba is dibenzylideneacetone) and afforded the expected polyether with a high M-n value (M-n = 24,900). In addition, vinyloxirane 1b could reacted with racemic 1,1'-bi-2-naphthol to give the corresponding polyether in a good yield. (C) 2002 Wiley Periodicals, Inc. [References: 10]