A new development in the chemistry of arenes activated toward S(N)Ar reactions by the cyclopentadienyliron (FeCp+) moiety is presented in this work. A class of diiron complexes of diphenoxybenzenes was prepared in a highly efficient and very mild fashion. Dihydroxyaromatic compounds served as dinucleophiles, allowing for the formation of the diiron complexes. This could be achieved in either a one or two step procedure. A wide variety of dinucleophiles were incorporated into this study, as well as a number of FeCp+ activated arenes. It is shown that these reactions are not inhibited by bulky substituents on either the dinucleophiles or activated arenes. The diiron complexes themselves could also undergo S(N)Ar reactions, provided that the complexed arenes contained a chlorine substituent. This allowed for the functionalization of the complexes with species that could not be introduced directly in their syntheses. The carbon nucleophiles generated from ethyl cyanoacetate or (phenylsulfonyl)acetonitrile could be attached to the complexed ethers in this manner. The FeCp+ moieties were removed easily by photolytic demetalation which allowed for the recovery of a wide range of functionalized diphenoxybenzenes. This methodology is advantageous over all those previously reported and should be a practical route to the synthesis of aromatic ethers.
Ligand-free highly effective iron/copper co-catalyzed formation of dimeric aryl ethers or sulfides
作者:Xiaoming Qu、Tingyi Li、Yan Zhu、Peng Sun、Hailong Yang、Jincheng Mao
DOI:10.1039/c1ob05155e
日期:——
Highly selective coupling of diiodoarenes with phenols or phenthiols can be performed by using a low-cost, benign character and readily available Fe/Cu catalytic system in the absence of ligands. It is noteworthy that the desired dimeric aryl ethers or sulfides could be obtained in high yields by coupling between diiodoarenes and phenols, or diphenols with aryl iodides.
Anisotropic melt polyesters with improved glass transition temperature
申请人:E.I. DU PONT DE NEMOURS AND COMPANY
公开号:EP0262900A2
公开(公告)日:1988-04-06
Novel melt-spinnable anisotropic-melt-forming polyesters from certain disubstituted hydroquinones and terephthalic acid have high glass transition temperatures.
Cross-linkable thermotropic liquid crystalline aromatic polyesters comprising at least one unit derived from an aromatic diol substituted with at least one allyl group, in combination with units derived from dioxyaryl and dicarboxyaryl monomers.
Selective displacement of aryl fluorides with hydroquinone: synthesis of 4-phenoxyphenols
作者:Benjamin F. Marcune、Michael C. Hillier、Jean-François Marcoux、Guy R. Humphrey
DOI:10.1016/j.tetlet.2005.09.025
日期:2005.11
The selective displacement of a variety of aryl fluorides with hydroquinone has been achieved to give substituted 4-phenoxyphenols 3. In some cases the addition of 18-crown-6 resulted in a significant rate enhancement, and the reactions could be carried out at lower temperature. One of these derivatives, 3a (X = Cl) was converted to 2-propyl-4-(4-chlorophenoxy)phenol 2a, a precursor to the PPAR gamma receptor agonist 1. (c) 2005 Elsevier Ltd. All rights reserved.
BINÄRE LEGIERUNGEN AUF BASIS VON POLYETHERAMIDEN UND CYCLOOLEFINPOLYMEREN