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Method for preparing low poly(thio)ether

A technology of oligoethers and aryl groups, which is applied in the fields of thioether preparation, ether preparation, organic chemistry, etc., can solve the problems of high economic cost and achieve the effect of cost reduction and high selectivity

Inactive Publication Date: 2011-02-09
SUZHOU UNIV
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AI Technical Summary

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

Method used

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Fe(acac) was sequentially loaded into a Schlenk test tube 3 (0.025mmol), CuI (0.025mmol), potassium carbonate (1.0mmol), and DMSO (2mL), the system was evacuated circularly and replaced with argon three times, and under gas protection, 1, 4-Diiodobenzene (0.5 mmol) and phenol (2.5 mmol). Then the system was sealed and heated in an oil bath at 140°C for about 24 hours. First, 4 mL of water was added to quench the reaction, and then extracted with ethyl acetate (4 mL×3). The organic phases were combined and dried with anhydrous sodium sulfate. Column chromatography (petroleum ether (60-90° C.) was used as the eluent) to obtain the coupled product 1,4-diphenoxybenzene (129.8 mg), with a yield of 99%. GC-MS showed that no monosubstituted product was detected in the system after the reaction. Its NMR data are: 1 H NMR (400MHz, CDCl 3 )(δ, ppm) 6.99-7.01(t, J=4Hz, 8H), 7.07-7.11(t, J=7.2Hz, 2H), 7.31-7.35(t, J=8.0Hz, 4H); 13 CNMR (300MHz, CDCl 3 ) (δ, ppm) 118.52, 120.7...

Embodiment 2

[0032] Fe(acac) was sequentially loaded into a Schlenk test tube 3 (0.025mmol), CuI (0.025mmol), potassium carbonate (1.0mmol), and DMSO (2mL), the system was evacuated circularly and replaced with argon three times, and under gas protection, 1, 3-Diiodobenzene (0.5 mmol) and phenol (2.5 mmol). Then the system was sealed and heated in an oil bath at 140°C for about 24 hours. First, 4 mL of water was added to quench the reaction, and then extracted with ethyl acetate (4 mL×3). The organic phases were combined and dried with anhydrous sodium sulfate. Column chromatography (petroleum ether (60-90° C.) was used as the eluent) was used to obtain the coupled product 1,3-diphenoxybenzene (123.3 mg), with a yield of 94%. Its NMR data are: 1 HNMR (400MHz, CDCl 3) (δ, ppm) 6.69-6.72 (m, 3H), 7.01-7.03 (d, J = 8.0Hz, 4H), 7.08-7.11 (t, J = 7.6Hz, 2H), 7.21-7.25 (t, J =8Hz, 1H), 7.30-7.34(t, J=8.0Hz, 4H); 13 C NMR (300MHz, CDCl 3 ) (δ, ppm) 110.99, 114.82, 120.83, 125.26, 131.46, 13...

Embodiment 3

[0034] Fe(acac) was sequentially loaded into a Schlenk test tube 3 (0.025mmol), CuI (0.025mmol), potassium carbonate (1.0mmol), and DMSO (2mL), the system was evacuated circularly and replaced with argon three times, and under gas protection, 1, 2-Diiodobenzene (0.5 mmol) and phenol (2.5 mmol). Then the system was sealed and heated in an oil bath at 140°C for about 24 hours. First, 4 mL of water was added to quench the reaction, and then extracted with ethyl acetate (4 mL×3). The organic phases were combined and dried with anhydrous sodium sulfate. Column chromatography (petroleum ether (60-90° C.) was used as the eluent) was used to obtain the coupled product 1,2-diphenoxybenzene (101.1 mg), with a yield of 77%. Its NMR data are: 1 HNMR (400MHz, CDCl 3 ) (δ, ppm) 6.88-6.90 (d, J = 8.0Hz, 4H), 7.00-7.04 (t, J = 7.6Hz, 2H), 7.04-7.11 (m, 4H), 7.23-7.25 (d, J =8.0Hz, 4H); 13 C NMR (300MHz, CDCl 3 ) (δ, ppm) 117.22, 121.20, 122.42, 124.33, 129.09, 147.33, 157.06; high-resol...

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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...

Claims

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Application Information

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IPC IPC(8): C07C43/29C07C319/14C07C323/09C07C321/30C07C41/01C07C43/275
Inventor 毛金成屈孝铭谢观雷李廷义
Owner SUZHOU UNIV
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