Method for preparing low poly(thio)ether

Abstract

The invention belongs to the field of catalytic coupling reaction of low poly(thio)ether, and in particular relates to a method for preparing the low poly(sulfur)ether. In the method, low polyether or low polythioether is prepared from an aryl-containing (sulfur)phenolic compound and aryl halides serving as reaction substrates by performing C-O or C-S bonding and coupling reaction under the catalysis of a catalyst, wherein a halogen atom in the aryl halides is chloride, bromine or iodine; the aryl-containing (sulfur)phenolic compound is aryl-containing unary (sulfur)phenol or aryl-containing binary (sulfur)phenol; moreover, when the aryl-containing (sulfur)phenolic compound is the aryl-containing binary (sulfur)phenol, the aryl halides are single-halogenated aromatics; when the aryl-containing (sulfur)phenolic compound is the aryl-containing unary (sulfur)phenol, the aryl halides are two-halogenated aromatics; and the catalyst is an iron / copper composite catalyst. The method avoids the use of a noble metal palladium catalyst, avoids the use of a ligand, and simultaneously enlarges the range of suitable substrates.

Description

technical field [0001] The invention belongs to the field of catalytic coupling synthesis of oligomeric (sulfide) ethers, in particular to a method for preparing oligomeric ethers or oligomeric sulfides by catalytic coupling using a palladium-free and ligand-free iron / copper mixed catalyst system . Background technique [0002] Polyphenylene ether or polysulfide, as a class of useful polymer materials, has received widespread attention in the past decade regarding its effective synthesis. Oligomerized oxygen- or sulfur-containing molecules are also a very useful class of synthetic building blocks and functional materials. [0003] In the prior art, the method for synthesizing oligomeric ether or oligomeric thioether has following several kinds: [0004] (1) The most direct synthesis method is carried out through the coupling reaction of C-O(S) bonding in the presence of a palladium catalyst; and this reaction was first realized at high temperature using an equivalent amoun...

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Problems solved by technology

[0005] (2) Until 2002, the Buchwald research group of the Massachusetts Institute of Technology in the United States first reported that a catalytic amount of cuprous iodide (10mol%) supplemented with 2-formic acid pyridine (20mol%) as a ligand can make the reaction in a relatively mild conditions (110°C); but this catalytic system is only suitable for aryl iodides (see: Maiti, D.; Buchwald, S.L.J.Org.Chem.2010, 75, 1791-1794)

[0006] (3) In 2007, the Bolm research group of RWTH Aachen University in Germany found that ferric chloride (10mol%) / 2,2,6,6-tetramethyl-3,5-heptanedione (20mol%) can be The reaction was catalyzed at 135°C to obtain relatively good results, but this system is also only applicable to aryl iodides (see: O.Bistri, A.Correa, C.Bolm, Angew.Chem.Int.Ed.2008, 47 , 586)

[0007] Above-mentioned technical scheme (2) and (3) also all need the participation of ligand, make the economic cost of reaction very high