CN1203040C - Method for synthesizing diaryl ether by using amino acid as additive - Google Patents
Method for synthesizing diaryl ether by using amino acid as additive Download PDFInfo
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- CN1203040C CN1203040C CN 03129451 CN03129451A CN1203040C CN 1203040 C CN1203040 C CN 1203040C CN 03129451 CN03129451 CN 03129451 CN 03129451 A CN03129451 A CN 03129451A CN 1203040 C CN1203040 C CN 1203040C
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Abstract
The present invention provides a reaction method which takes an amino acid as an additive, and a Cu salt is taken as a catalyst so as to make a synthesis reaction of diaryl ether carry out under a mild condition. The amino acid can be monosubstituted (or bisubstituted)-on-nitrogen alpha-amino acid or beta-amino acid. The used catalyst and a ligand in the present invention have low price, easy acquisition, stabilization in the air, mild reaction condition, high yield and easy product separation, and the present invention has a high application prospect.
Description
Technical field
The present invention relates to use amino acid as additive, mantoquita is as carrying out Liv Ullmann diaryl ether synthetic method under the condition of facilitating agent.Realized synthesizing by this method to a series of diaryl ether compounds.
Background technology
Liv Ullmann diaryl ether building-up reactions (Ullmann, F.ber Dtsch.Chem.Ges.1904,37,853.) is academic and industrial for a long time developing history (Lindley, J.Tetrahedron 1984,40,1433) arranged all.But because reaction requires to carry out under hot conditions, and needs a large amount of Tong Shijis, reason such as productive rate is lower makes the application of this reaction be subjected to very big restriction.Use palladium to facilitate agent ((a) Torraca, K.E. in recent years; Huang, X.; Parrish, C.A.; Buchwald, S.L.J.Am.Chem.Soc.2002,123,10770; (b) Aranyos, A.; Old, D.W.; Kiyomori, A.; Wolfe, J.P.; Sadighi, J.P.; Buchwald, S.L.J.Am.Chem.Soc.1999,121,4369; (c) Mann.G.; Incarvito, C.; Rheigold, A.L.; Hartwig, J.F.; J.Am.Chem.Soc.1999,121,3224), the condition that this reaction is carried out has had very big improvement.But, use palladium to facilitate agent and still exist a lot of restrictions, be difficult to reaction such as the substrate that much contains some functional groups, and palladium reagent is relatively more expensive.Thereby in the past few years, be catalyzer with Cu, some comparatively gentle methods of reacting by the interpolation part have obtained very big development.(Gujadhur, R.K.; Bates.C.G., Venkataraman, D., Org.Lett.2001,3,4315.), (Marcoux, J.-F.; Doye, S.; Buchwald, S.L.J.Am.Chem.Soc.1997,119,10539) by adding suitable part, use the Cu salt of catalytic amount, can reduce the reflection temperature greatly, synthesizing under comparatively gentle condition of diaryl ether carried out.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of reaction method: use amino acid as additive, Cu salt makes the building-up reactions of diaryl ether be able to carry out under condition as mild as a dove as catalyzer.
Involved reaction can adopt following reaction expression to represent among the present invention
Wherein X-is iodine or bromine, and R represents 2-, 3-, and the substituting group of 4-position, or represent two on the aromatic ring to replace or multi-substituent.Can be H, EtO-, NO
2-,-CN ,-COR
1(R
1Be H, C
1-C
6Alkyl, aryl etc.) ,-COOH ,-COOR
2(R
2Side C
1-C
6Alkyl), halogen (fluorine, chlorine, bromine), C
1-C
6Alkyl, C
1-C
6Alkoxyl group, aryl or-NR
3R
4(R
3, R
4Be H, C
1-C
6Alkyl or benzyl etc.).R also represents the aromatic ring of benzo, as naphthalene nucleus.Described aryl is recommended as phenyl, (substituting group is C to substituted-phenyl
1-C
6Alkyl, C
1-C
6Alkoxyl groups etc.), naphthyl or five arrives seven-membered ring heteroaryl for example pyridine, pyrroles, imidazoles, furans, thiophene etc.
R ' represents the 2-on the phenol ring, 3-, and one of 4-position replaces, two replacement or multi-substituents.Can be C
1-C
6Straight or branched alkyl, C
1-C
6Alkoxy or halogen (fluorine, chlorine, bromine) etc.
The part that uses among the present invention can be replacement or a dibasic a-amino acid or a beta-amino acids on the nitrogen, and the substituting group on the described nitrogen is recommended as C
1-C
6Alkyl or benzyl etc. are such as proline(Pro), n-formyl sarcolysine base glycine, nitrogen benzyl glycine, nitrogen benzyl-Beta-alanine, nitrogen, nitrogen-N-methylsarcosine, nitrogen, nitrogen-dibenzyl glycine or nitrogen, nitrogen dibenzyl-Beta-alanine etc.
The mantoquita that uses among the present invention can be monovalence copper or cupric salt, as CuI, CuBr, CuCl, CuCN, CuSO
4, CuCl
2Or Cu (OAc)
2Deng.
In the reaction of the present invention, employed catalyzer mantoquita consumption is recommended as 1%mol to 20%mol (with respect to aryl halide), the part that uses and the mol ratio of Cu salt are recommended as 1: 1 to 10: 1, and the mol ratio of employed phenolic compound and halogenated aromatic compound is recommended as 1.0: 1 to 2: 1.
The temperature that reaction is carried out is recommended as 40～110 ℃, further is recommended as 75～95 ℃, especially is recommended as 90 ℃.The reaction times recommendation is 1～72 hour, further is recommended as 8～30 hours.
In the reaction of the present invention, employed alkali can be K
2CO
3, Cs
2CO
3, CsF, K
3PO
4, NaOH or KOH etc.Employed solvent can be DMSO (dimethyl sulfoxide (DMSO)), DMF (N, dinethylformamide), DMA (N,N-dimethylacetamide), Dioxane (dioxane), CH
3Alcoholic solvent such as CN, I-PrOH, toluene or glycol dimethyl ether, ether solvents such as diethylene glycol dimethyl ether.
Employed catalyzer and part low price are easy to get among the present invention, and be stable in the air, with the reacting phase ratio of reporting in the document of the same type, the temperature of reaction reduces about 30 ℃, reaction conditions gentleness very, and the productive rate height, product is easily separated, and good application prospects is arranged.
Embodiment
To help to understand the present invention by following examples of implementation, but not limit content of the present invention.
Embodiment 1
The preparation of 4-methoxyphenyl phenylate
In a reaction tubes, add 468mg to the methoxy iodobenzene (MW=234.04,2.0mmol), add then 282mg phenol (MW=94.11,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mg N; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 22h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 350mg product, productive rate 87%.
1H?NMR(CDCl
3，300MHz)δ3.80(s，3H)，6.87-7.00(m，7H)，7.29(m，1H)；MS?m/z?200(M
+)，185，169，129，123，95，77，63，51，50，41.
Embodiment 2
3,5-3,5-dimethylphenyl phenylate
In a reaction tubes, add 464mg 3,5-dimethyl iodobenzene (MW=232.01,2.0mmol), add then 282mg phenol (MW=94.11,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mg N; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 16h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 383mg product, productive rate 97%.
1H?NMR(CDCl
3，300MHz)δ2.28(s，6H)，6.64(s，2H)，6.73(s，1H)，7.01(m，3H)，7.32(m，2H)；MS?m/z?198(M
+)，183，169，155，129，115，105，98，91，77，65，51，41.
Embodiment 3
The preparation of m-nitro base phenylate
In a reaction tubes, add nitro iodobenzene between 498mg (MW=249.01,2.0mmol), add then 282mg phenol (MW=94.11,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mgN; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 16h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 3422mg product, productive rate 98%.
1H?NMR(CDCl
3，300MHz)δ7.07(m，2H)，7.22(m，1H)，7.32(m，，1H)，7.40-7.53(m，3H)，7.80(t，J＝2.1Hz，1H)；MS?m/z?215(M
+)，198，168，141，128，115，102，92，77，63，51.
Embodiment 4
The preparation of guaiacyl phenylate
In a reaction tubes, add the adjacent methoxy iodobenzene of 468mg (MW=234.04,2.0mmol), add then 282mg phenol (MW=94.11,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 84mg N; N-N-methylsarcosine (MW=139.58; 0.6mmol), 21mg CuI (MW=190.446,0.2mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 24h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 221mg product, productive rate 56%.
1H?NMR(CDCl
3，300MHz)δ3.84(s，3H)，6.95(m，6H)，7.30(t，J＝8.1Hz，2H)；MS?m/z?200(M
+)，185，169，129，123，95，77，63，51，50，41.
Embodiment 5
The preparation of 3-aminomethyl phenyl-4 '-p-methoxy-phenyl ether
In a reaction tubes, add 468mg to the methoxy iodobenzene (MW=234.04,2.0mmol), add then the 324mg m-methyl phenol (MW=108,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mg N; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 22h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 389mg product, productive rate 91%.
1H?NMR(CDCl
3，300MHz)δ2.32(s，3H)，3.81(s，3H)，6.73(d，J＝8.4Hz，2H)，6.87(m，3H)，6.98(m，2H)，7.21(t，J＝7.8Hz，1H)；MS?m/z?214(M
+)，199，171，143，128，91，77，65，51，41.
Embodiment 6
The preparation of 3-fluorophenyl-4 '-tert-butyl-phenyl ether
In a reaction tubes, add fluorine iodobenzene between 444mg (MW=222,2.0mmol), add then the 450mg p-tert-butylphenol (MW=150,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mg N; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 22h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 405mg product, productive rate 83%.
1H?NMR(CDCl
3，300MHz)δ1.35(s，9H)，6.80(m，3H)，6.98(m，2H)，7.28(m，1H)，7.38(m，2H)；MS?m/z?244(M
+)，229，201，118，117，100，91，77，65，51；Anal.Calcd.for?C
16H
17FO?requiered?C：78.66，H：7.01，found?C：78.81，H：7.17.
Embodiment 7
2-methoxyphenyl-3 ', the preparation of 5 '-3,5-dimethylphenyl ether
In a reaction tubes, add 464mg 3,5-dimethyl iodobenzene (MW=232.01,2.0mmol), add then 372mg phenol (MW=124,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mg N; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 16h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 381mg product, productive rate 84%
1H?NMR(CDCl
3，300MHz)δ2.27(s，6H)，3.85(s，3H)，6.58(s，2H)，6.69(s，1H)，6.96(m，3H)，7.11(m，1H)；MS?m/z?228(M
+)，213，198，195，182，169，119，113，105，95，91，79，77，65，57，43.Anal.Calcd.for?C
15H
16O
2?requiered?C：78.92，H：7.06，found?C：78.74，H：7.41.
Embodiment 8
1-[4-(2-naphthyloxy)-phenyl] ethyl ketone
In a reaction tubes, add 492mg 4-ethanoyl iodobenzene (MW=246.05,2.0mmol), add then the 432mg beta naphthal (MW=144,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mg N; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 16h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 425mg product, productive rate 82%
1H?NMR(CDCl
3，300MHz)δ2.61(s，3H)，7.06(m，2H)，7.26(m，1H)，7.47(m，3H)，7.78(m，1H)，7.89(m，2H)，7,96(m，2H)；MS?m/z?262(M
+)，247，218，189，127，115，101，95，83，77，63，51，43；Anal.Calcd.for?C
18H
14O
2?requires?C：82.42，H：5.38，found?C：82.47，H：5.58.
Embodiment 9
2, the preparation of 4-3,5-dimethylphenyl-4 '-cyano group phenylate
In a reaction tubes, adding 458mg 4-cyano group iodobenzene (MW=229.02 2.0mmol), adds 366mg 2 then, and the 4-xylenol (MW=122,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 21mg N; N-N-methylsarcosine (MW=139.58; 0.15mmol), 8mg CuI (MW=190.446,0.04mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 16h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 418mg product, productive rate 94%
1H?NMR(CDCl
3，300MHz)δ2.11(s，3H)，2.34(s，3H)，6.87(m，3H)，7.02(m，1H)，7.09(s，1H)，7.56(m，2H)；MS?m/z?223(M
+)，208，190，180，167，153，140，127，121，105，97，79，77，65，51，41；Anal.Calcd.for?C
15H
13NO?requires?C：80.69，H：5.87，N：6.27，found?C：80.52，H：5.79，N：.6.15.
Embodiment 10
The preparation of tolyloxy biphenyl between 4-
In a reaction tubes, add 466mg 4-bromo biphenyl (MW=23311,2.0mmol), add then sylvan between 324mg (MW=108,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 84mg N; N-N-methylsarcosine (MW=139.58; 0.6mmol), 39mg CuI (MW=190.446,0.2mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 24h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 466mg product, productive rate 90%
1H?NMR(CDCl
3，300MHz)δ2.35(s，3H)，6.88(m，2H)，6.93(d，J＝7.5Hz，1H)，7.06(m，2H)，7.23(m，1H)，7.35(m，1H)，7.43(m，2H)，7.58(m，4H)；MS?m/z260(M
+)，241，231，217，202，191，178，169，152，141，127，115，102，91，77，65，51.
Embodiment 11
The benzoic preparation of 3-(4-methoxyphenyl)
In a reaction tubes, add the 402mg m-bromobenzoic acid (MW=201.02,2.0mmol), add then the 372mg p methoxy phenol (MW=124,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 84mg N; the N-N-methylsarcosine (MW=139.58,0.6mmol), 39mg CuI (MW=190.446; 0.2mmol); 4ml Dioxane under nitrogen protection, reacts 24h as solvent in 90 ℃ of oil baths; cooling; add 5 ml waters, use the dilute hydrochloric acid acidifying, at every turn with 10 milliliters of ethyl acetate extractions; repeat four times; extraction liquid is washed with saturated common salt, behind the anhydrous sodium sulfate drying, filters; the filtrate decompression distillation; cross silicagel column and separate (leacheate sherwood oil: ethyl acetate=3: 1), obtain the 435mg product, productive rate 90%
1H?NMR(CDCl
3，300MHz)δ3.84(s，3H)，6.92(m，2H)，7.03(m，2H)，7.22(m，1H)，7.42(m，1H)，7.64(m，1H)，7.80(m，1H)；MS?m/z?244(M
+)，229，212，199，183，173，157，129，123，92，76，65，51，41，Anal.Calcd.for?C
14H
12O
4?requires?C：68.85，H：4.95，found?C：68.82，H：4.83.
Embodiment 12
The preparation of two (4-methoxyphenyl) ether
In a reaction tubes, add 374mg to the methoxyl group bromobenzene (MW=187,2.0mmol), add then the 372mg p methoxy phenol (MW=124,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 84mg N; N-N-methylsarcosine (MW=139.58; 0.6mmol), 39mg CuI (MW=190.446,0.2mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 24h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 400mg product, productive rate 87%
1H?NMR(CDCl
3，300MHz)δ3.79(s，6H)，6.83(d，J＝9.3Hz，4H)，6.91(d，J＝9.3Hz，4H)；MS?m/z?230(M
+)，215，200，187，172，155，144，123，115，107，95，92，77，64，53，41.
Embodiment 13
The preparation of 4-methoxyphenyl 4 '-chlorobenzene ether
In a reaction tubes, add 374mg to the methoxyl group bromobenzene (MW=187,2.0mmol), add then the 386mg para-chlorophenol (MW=128.56,3mmol), 1.3g Cs
2CO
3(MW=325.82,4mmol), 84mg N; N-N-methylsarcosine (MW=139.58; 0.6mmol), 39mg CuI (MW=190.446,0.2mmol); 4ml Dioxane is as solvent; under nitrogen protection, in 90 ℃ of oil baths, react 24h, cooling; add 5 ml waters; with 10 milliliters of ethyl acetate extractions, repeat four times, extraction liquid is washed with saturated common salt at every turn; behind the anhydrous sodium sulfate drying; filter, the filtrate decompression distillation is crossed silicagel column and is separated (leacheate sherwood oil: ethyl acetate=30: 1); obtain the 366mg product, productive rate 78%
1H?NMR(CDCl
3，300MHz)δ3.80(s，3H)，6.89(m，4H)，6.95(m，2H)，7.23(d，J＝9.0Hz，2H)；MS?m/z?236，234，219，191，184，171，163，156，139，128，123，111，99，92，85，75，63，57，50，41.
Claims (8)
1. the synthetic method of a diaryl ether is characterized in that using amino acid as additive, and Cu salt is expressed as follows with reaction expression as catalyzer:
Wherein X-is iodine or bromine,
R represents 2-, and single replacement, two of 3-or 4-position replaces or multi-substituents, and substituting group is H, EtO-, NO
2-,-CN ,-COR
1,-COOH ,-COOR
2, halogen, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, aryl or-NR
3R
4R wherein
1Be H, C
1-C
6Alkyl or aryl, R
2Be C
1-C
6Alkyl, R
3, R
4Be H, C
1-C
6Alkyl or benzyl;
R or represent the aromatic ring of benzo;
On behalf of the replacement of one on the phenol ring, two, R ' replace or multi-substituents, and substituting group is C
1-C
6Straight or branched alkyl, C
1-C
6Alkoxy or halogen,
Described part is replacement or a dibasic a-amino acid or a beta-amino acids on the nitrogen.
2. the synthetic method of diaryl ether as claimed in claim 1, it is characterized in that on the described nitrogen that one replaces or dibasic a-amino acid or beta-amino acids are proline(Pro), n-formyl sarcolysine base glycine, nitrogen benzyl glycine, nitrogen benzyl-Beta-alanine, nitrogen, nitrogen-N-methylsarcosine, nitrogen, nitrogen-dibenzyl glycine or nitrogen, nitrogen dibenzyl-Beta-alanine.
3. the synthetic method of diaryl ether as claimed in claim 1 is characterized in that described mantoquita is CuI, CuBr, CuCl, CuCN, CuSO
4, CuCl
2Or Cu (OAc)
2
4. the synthetic method of diaryl ether as claimed in claim 1, it is characterized in that described catalyzer mantoquita consumption is that 1%mol is to 20%mol with respect to aryl halide, the part that uses and the mol ratio of Cu salt are 1: 1 to 10: 1, and the mol ratio of employed phenolic compound and halogenated aromatic compound is 1.0: 1 to 2: 1.
5. the synthetic method of diaryl ether as claimed in claim 1, it is characterized in that reacting the temperature of carrying out is 40～110 ℃.
6. the synthetic method of diaryl ether as claimed in claim 1, it is characterized in that reacting the temperature of carrying out is 75～95 ℃.
7. the synthetic method of diaryl ether as claimed in claim 1 is characterized in that described alkali is K
2CO
3, Cs
2CO
3, CsF, K
3PO
4, NaOH or KOH.
8. the synthetic method of diaryl ether as claimed in claim 1 is characterized in that described solvent is dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, dioxane, CH
3CN, alcohol, toluene or ether solvent.
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| WO2008082510A1 (en) * | 2006-12-21 | 2008-07-10 | E.I. Du Pont De Nemours And Company | Process for the synthesis of ethers of aromatic acids |
| CN102059145B (en) * | 2010-09-16 | 2012-07-11 | 中国科学技术大学 | Catalyst, method for synthesizing (S)-octopamine and method for synthesizing (S)-N-trans-feruloyloctopamine |
| CN102030655B (en) * | 2010-10-21 | 2013-03-27 | 上虞颖泰精细化工有限公司 | Synthesis method of diphenyl ether derivate, combined production method of oxyfluorfen and acifluorfen and synthesis method of oxyfluorfen |
| CN111925325B (en) * | 2020-02-17 | 2021-12-17 | 浙江大学 | Synthetic method of diaryl ether compound |
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2003
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