CN111138259A - Method for preparing diaryl ether compound - Google Patents
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- CN111138259A CN111138259A CN201911335728.9A CN201911335728A CN111138259A CN 111138259 A CN111138259 A CN 111138259A CN 201911335728 A CN201911335728 A CN 201911335728A CN 111138259 A CN111138259 A CN 111138259A
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Abstract
The present invention relates to a process for preparing a diaryl ether compound, comprising the steps of: dispersing aromatic heterocyclic borate compounds, nitrobenzene compounds, copper catalysts, alkaline compounds and additives in an organic solvent, heating and stirring until the reaction is finished, extracting the reaction liquid by the organic solvent, separating and purifying to obtain diaryl ether compounds. Compared with the prior art, the beneficial effects of the technical scheme are that: the diaryl ether compound can be efficiently prepared under the catalysis of divalent copper with stable property and low price; the reaction is carried out in the air under the condition of heating without additional protection of inert gas, and the environment is friendly; expensive catalysis and ligand are not needed in the reaction, the selectivity of the reaction is high, the tolerance of the functional group of the substrate is good, the whole reaction process is simple and easy to implement, and the method is a brand new synthesis method of diaryl ether compounds.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for synthesizing diaryl ether compounds.
Background
Diaryl ether and derivatives thereof are important basic structures in natural products and pharmaceutical intermediates, and are widely applied in the fields of natural products, pharmaceutical chemistry, polymer science and the like, such as anticancer drugs Combretastatin A-4, cytomycin Riccardin C and ACE inhibitor (-) -K-13.
In the prior art, Ullmann coupling (Ullmann) reactions, i.e. coupling of aryl halides and phenols, are one of the main methods for the synthesis of diaryl ethers and their derivatives [ Cai, q.; zuo, b.; ma, d.angelw.chem., int.ed.,2006,45,1276 ]. However, the traditional ullmann coupling reaction conditions are harsh, and the monovalent copper with the chemical equivalent is usually used as a catalyst, so that the side reaction is more, the economic benefit is lower, and the environmental pollution is larger.
Recently, methods for preparing diaryl ethers from nitroaromatic compounds have been proposed, such as Wuhuayue, which utilizes noble metal rhodium to catalyze the coupling of arylboronic acid and nitroaromatic to obtain a target product [ ZHEN, X.W.; ding, j.c.; chen, j.x.; gao, w.x.; liu, m.c.; wu, h.y.org.lett.2011,13,1726. ]; wuyangjie et al reported a method for palladium-catalyzed coupling of nitroarenes and phenols [ Wang, h.l.; yu, a.j.; cao, a.j.; chang, j.b.; wu, y.j.appl.organomet.chem.2013,27,611. ]; sarkate et al reported a method for the microwave catalyzed coupling synthesis of diaryl ethers from nitroarenes and phenols [ Sarkate, a.p.; bahekar, s.s.synlett,2013,24,1513.
Although the coupling reaction using nitroaromatic as raw material has been developed, the method still has some limitations, and needs to be carried out under the protection of nitrogen, needs to use expensive transition metal catalyst and ligand, has long reaction time, harsh reaction conditions, and needs to improve the product yield and produce more by-products.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provide a method for synthesizing diaryl ether compound with high selectivity and high yield.
A process for preparing a diaryl ether compound comprising the steps of:
dispersing an aromatic heterocyclic borate compound with a structure I, a nitrobenzene compound with a structure II, a copper catalyst, an additive and an alkaline compound in an organic solvent, heating, stirring, separating and purifying to obtain a diaryl ether compound with a structure III.
Compared with the prior art, the beneficial effects of the technical scheme are that: the reaction is carried out in the air under the condition of heating, no additional protection of inert gas is needed, the environment is friendly, and the condition is mild; expensive catalyst and ligand are not needed, the reaction selectivity is high, the functional group tolerance of the substrate is good, the whole reaction process is simple and easy to implement, few by-products are generated, the yield is high, and the method is a brand-new synthesis method of diaryl ether compounds.
Further, a substituent R1Is one of hydrogen, alkoxy, halogen, C1-C8 alkyl and phenyl.
Further, a substituent R2Is one of aldehyde group and cyano group.
Further, the molar ratio of the aromatic heterocyclic borate compound with the structure I to the nitrobenzene compound with the structure II, the copper catalyst, the additive, the alkaline compound and the organic solvent is as follows: 1: (1-3): (0.05-0.2): (1-2): (1-3): (100-150). The reaction can be carried out more thoroughly, and the difficulty of subsequent separation and purification is reduced.
Further, in the reaction process of heating and stirring, the reaction temperature is 80-100 ℃. The reaction rate is accelerated while side reactions are reduced.
Further, the heating and stirring time is 16-24 hours. The reaction is fully carried out.
Further, the copper catalyst is one or a mixture of any more of copper acetate, copper oxide, copper bromide, copper trifluoromethanesulfonate, copper acetylacetonate, copper sulfate, copper fluoride and copper chloride. Cheap bivalent copper is used as a catalyst, so that the cost is reduced.
Further, the alkaline compound is one or a mixture of any more of cesium carbonate, potassium hydroxide and potassium carbonate.
Further, the additive is one or a mixture of any more of potassium hydrogen persulfate complex salt, potassium persulfate and hydrogen peroxide.
Further, the organic solvent is one or a mixture of any more of dimethyl sulfoxide and N-methyl pyrrolidone A.
Drawings
FIG. 1 shows the product obtained in example 11H NMR (nuclear magnetic resonance) spectrum;
FIG. 2 shows the product obtained in example 113A C NMR spectrum;
FIG. 3 shows the product obtained in example 21H NMR spectrum;
FIG. 4 shows the product obtained in example 213A C NMR spectrum;
FIG. 5 shows the product obtained in example 31H NMR spectrum;
FIG. 6 shows the product obtained in example 313A C NMR spectrum;
FIG. 7 shows the product obtained in example 41H NMR spectrum;
FIG. 8 shows the product obtained in example 413A C NMR spectrum;
FIG. 9 shows the results of example 51H NMR spectrum;
FIG. 10 shows the results of example 513A C NMR spectrum;
FIG. 11 shows the results of example 61H NMR spectrum;
FIG. 12 shows the results obtained in example 613A C NMR spectrum;
FIG. 13 shows the product obtained in example 71H NMR spectrum;
FIG. 14 shows the results of example 713A C NMR spectrum;
FIG. 15 shows the results of example 81H NMR spectrum;
FIG. 16 shows the results of example 813C NMR spectrum.
Detailed Description
The invention particularly uses aromatic heterocyclic borate compounds and nitrobenzene compounds as reactants, and the aromatic heterocyclic borate compounds and the nitrobenzene compounds are heated and stirred to react in an organic solvent in the presence of a copper catalyst, an additive and a basic compound, and after the reaction is finished, the organic solvent is extracted, separated and purified to obtain diaryl ether compounds. The reaction formula is as follows:
in the formula, a compound I is an aromatic heterocyclic borate compound, a compound II is a nitrobenzene compound, and Cat.Cu represents a copper catalyst; base represents a basic compound; additive represents an additive; solvent means organic solvent.
The specific reaction steps are as follows:
s1, adding the aromatic heterocyclic borate compound I, the nitrobenzene compound II, the copper catalyst, the additive, the alkaline compound and the organic solvent into a reaction bottle;
s2, heating and stirring at the reaction temperature of 80-100 ℃ to react for 16-24 hours;
s3, after the reaction in the step S2 is finished, adding water into the reaction flask for quenching reaction;
s4: extracting the reaction liquid obtained in the step S3 by using an organic extractant;
s5: combining the organic layers obtained in step S4 and drying them;
s6: and (4) evaporating the dried organic layer obtained in the step S6 to dryness under reduced pressure, and separating and purifying to obtain the diaryl ether compound.
Wherein the optimal range of the molar ratio of the aromatic heterocyclic borate compound I, the nitrobenzene compound II, the copper catalyst, the additive, the alkaline compound and the organic solvent is 1: (1-3): (0.05-0.2): (1-2): (1-3): (100-150).
Wherein, the substituent R1Is hydrogenOne of alkoxy, halogen, C1-C8 alkyl and phenyl; wherein the C1-C8 alkyl is more preferably methyl and the alkoxy is preferably methoxy.
Wherein, the substituent R2Is one of aldehyde group and cyano group.
The copper catalyst is copper acetate (Cu (OAc)2) Copper oxide (CuO), copper bromide (CuBr)2) Copper trifluoromethanesulfonate (Cu (OTf)2) Copper acetylacetonate (Cu (acac)2) Copper sulfate (CuSO)4) Copper fluoride (CuF)2) Copper chloride (CuCl)2) One or a mixture of any more of them; most preferably, the catalyst is copper acetate (Cu (OAc)2)。
The alkaline compound is cesium carbonate (Cs)2CO3) Potassium hydroxide (KOH), potassium carbonate (K)2CO3) One or a mixture of any more of them; most preferably, the basic compound is cesium carbonate (Cs)2CO3)。
The additive is potassium hydrogen persulfate complex salt (Oxone) and potassium persulfate (K)2S2O8) Hydrogen peroxide (H)2O2) One or a mixture of any more of them; most preferably, the additive is potassium bisulfate complex salt (Oxone).
The organic solvent is one or a mixture of any more of dimethyl sulfoxide (DMSO) and N-methyl pyrrolidone (NMP); most preferably, the organic solvent is dimethyl sulfoxide (DMSO).
The organic extractant is any one of ethyl acetate, dichloromethane and diethyl ether, and most preferably, the organic solvent is ethyl acetate.
The present invention will be further described with reference to the accompanying drawings and examples.
Example 1
The synthetic route of the invention is as follows:
at room temperatureAdding an aromatic heterocyclic borate compound 1a, a p-nitrobenzaldehyde compound 2a and a catalyst Cu (OAc) into a reaction bottle2The additive Oxone and the alkali Cs2CO3And a reaction solvent DMSO. Wherein the molar ratio of the 1a to the 2a compounds is 1:2, 1a and the catalyst Cu (OAc)2In a molar ratio of 1:0.05 (or 1:0.1 or 1:0.2), 1a to the additive Oxone in a molar ratio of 1:1, 1a to the alkali Cs2CO3The molar ratio of 1:2.5, 1a and the organic solvent in the reaction is about 1:150, and the mixture is stirred and heated to 100 ℃ under the condition of air, and the reaction is carried out for 24 hours. After the reaction is finished, water is added to quench the reaction, then the crude product is extracted by ethyl acetate, organic layers are combined, and anhydrous Na is added2SO4Drying, evaporating to dryness under reduced pressure, separating and purifying to obtain the corresponding product 3a with a yield of 92% (1a: Cu (OAc))2Either 1:0.05) or 94% (1a: Cu (OAc)2Either 1:0.1) or 95% (1a: Cu (OAc)2＝1:0.2)。
The structure of the product obtained in example 1 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature control, and the result proves that the substance is the product of the structural formula 3 a.
Of the resulting product1H NMR and13c NMR spectrum is shown in figures 1 and 2, and the data of the product 3a are as follows:
1H NMR(500MHz,CDCl3)δ9.95(s,1H),7.88(d,J＝7.7Hz,2H),7.44(t,J＝7.3Hz,2H),7.29-7.24(m,1H),7.11(t,J＝8.4Hz,4H).
13C NMR(126MHz,CDCl3)δ190.9,163.3,155.2,132.1,131.4,130.3,125.1,120.5,117.7.
example 2
The synthetic route of the invention is as follows:
adding aromatic heterocyclic borate compound 1b, p-nitrobenzaldehyde compound 2a, CuO powder as catalyst, and Oxone or K as additive into a reaction flask at room temperature2S2O8Or H2O2And a basic compound Cs2CO3And a reaction solvent DMSO. Wherein the molar ratio of the 1b to the 2a compounds is 1:2, the molar ratio of the 1b to the CuO powder as the catalyst is 1:0.05, and the molar ratio of the 1b to the additive Oxone or K2S2O8Or H2O2The molar ratio of 1:1, 1b to alkali Cs2CO3The molar ratio is 1:2.5, 1b and the organic solvent of the reaction are mixed in a molar ratio of about 1:150, heated to 80 ℃ under air with stirring, and reacted for 16 hours. After the reaction is finished, water is added to quench the reaction, the crude product is extracted by ethyl acetate, organic layers are combined, and anhydrous Na is added2SO4Drying, evaporating to dryness under reduced pressure, separating and purifying to obtain the corresponding product 3b with a yield of 86% (Oxone) or 77% (K)2S2O8) Or 74% (H)2O2)。
The structure of the product obtained in example 2 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature control, and the result proves that the substance is the product of the structural formula 3 b.
Of the resulting product1H NMR and13c NMR spectrum is shown in FIGS. 3 and 4, and data of the product 3 b:
1H NMR(500MHz,CDCl3)δ9.92(s,1H),7.86–7.84(m,2H),7.70–7.69(m,2H),7.06(d,J＝8.6Hz,2H),6.85–6.84(m,2H).
13C NMR(126MHz,CDCl3)δ190.8,162.7,154.5,133.3,132.1,131.8,122.2,117.9,117.8.
example 3
The synthetic route of the invention is as follows:
at room temperature, adding the aromatic heterocyclic borate compound 1c, the p-nitrobenzaldehyde compound 2a and a catalyst CuBr into a reaction bottle2An additive Oxone and a basic compound Cs2CO3And a reaction solvent DMSO. Wherein, the molar ratio of 1c to 2a isIs 1:2, 1c and catalyst CuBr2The molar ratio of 1:0.05, the molar ratio of 1c to the additive Oxone is 1:1 (or 1:1.5 or 1:2), 1c is to the alkali Cs2CO3The molar ratio of 1:2.5, 1c to the reaction organic solvent was about 1:150, and the mixture was heated to 90 ℃ under air with stirring for 20 hours. After the reaction is finished, water is added to quench the reaction, the crude product is extracted by ethyl acetate, organic layers are combined, and anhydrous Na is added2SO4Drying, evaporation to dryness under reduced pressure, isolation and purification gave the corresponding product 3c in 85% (1c: Oxone ═ 1: 1) or 87% (1c: Oxone ═ 1: 1.5) or 80% (1c: Oxone ═ 1:2) yield.
The structure of the product obtained in example 3 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature control, and the result proves that the substance is the product of the structural formula 3 c.
Of the resulting product1H NMR and13the C NMR spectrum is shown in FIGS. 5 and 6, and the data of the product 3C:
1H NMR(500MHz,CDCl3)δ9.92(s,1H),7.84(d,J＝8.6Hz,2H),7.29(t,J＝7.8Hz,1H),7.04(t,J＝7.1Hz,3H),6.90–6.88(m,2H),2.37(s,3H).
13C NMR(126MHz,CDCl3)δ190.9,163.5,155.2,140.6,132.1,131.3,130.0,125.9,121.2,117.7,117.6,21.5.
example 4
The synthetic route of the invention is as follows:
at room temperature, the aromatic heterocyclic borate compound 1d, the p-nitrobenzaldehyde compound 2a and the catalyst Cu (OTf) are added into a reaction bottle2An additive Oxone and a basic compound Cs2CO3Or KOH or K2CO3And a reaction solvent DMSO. Wherein the molar ratio of the 1d to the 2a compound is 1:2, the 1d and the catalyst Cu (OTf)2In a molar ratio of 1:0.05, 1d to the additive Oxone in a molar ratio of 1:1, 1d to the alkali Cs2CO3Or KOH or K2CO3Is 1:2.5, the molar ratio of 1d to the reaction organic solvent is about 1:150, and the mixture is heated to 80 ℃ under air stirring and reacted for 22 hours. After the reaction is finished, water is added to quench the reaction, the crude product is extracted by ethyl acetate, organic layers are combined, and anhydrous Na is added2SO4Drying, evaporating to dryness under reduced pressure, separating and purifying to obtain corresponding product 3d with yield of 81% (Cs)2CO3) Or 70% (KOH) or 73% (K)2CO3)。
The structure of the product obtained in example 4 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature control, and the result proves that the substance is the product of the 3d structural formula.
Of the resulting product1H NMR and13c NMR spectrum is shown in FIGS. 7 and 8, and data of the product 3 d:
1H NMR(500MHz,CDCl3)δ9.91(s,1H),7.84–7.82(m,2H),7.21(d,J＝8.1Hz,2H),7.04–7.02(m,2H),6.99–6.97(m,2H),2.37(s,3H).
13C NMR(126MHz,CDCl3)δ190.9,163.8,152.8,134.9,132.1,131.2,130.8,120.6,117.4,21.0.
example 5
The synthetic route of the invention is as follows:
at room temperature, the aromatic heterocyclic borate compound 1e, the p-nitrobenzaldehyde compound 2a and the catalyst Cu (acac) are added into a reaction bottle2An additive Oxone and a basic compound Cs2CO3And a reaction solvent DMSO. Wherein, the mol ratio of the 1e to the 2a compound is 1:2, the 1e and the catalyst Cu (acac)2The molar ratio of 1:0.05, the molar ratio of 1e to the additive Oxone is 1:0.5, the molar ratio of 1e to the alkali Cs is2CO3The molar ratio of 1:2.5 (or 1:1 or 1:3), the molar ratio of 1e to the reaction organic solvent is about 1:150, and the mixture is stirred and heated to 100 ℃ under air conditions for 24 hours of reaction.
After the reaction is finished, water is added to quench the reaction, the crude product is extracted by ethyl acetate, organic layers are combined, and anhydrous Na is added2SO4Drying, evaporating to dryness under reduced pressure, separating and purifying to obtain corresponding product 3e with yield of 85% (1e: Cs)2CO31: 2.5) or 70% (1e: Cs)2CO31: 1) or 79% (1e: Cs)2CO3＝1：3)。
The structure of the product obtained in example 5 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature control, and the result proves that the substance is a product with a 3e structural formula.
Of the resulting product1H NMR and13c NMR spectrum is shown in FIGS. 9 and 10, and data of the product 3 e:
1H NMR(500MHz,CDCl3)δ9.88(s,1H),7.81–7.79(m,2H),7.03–6.98(m,4H),6.93–6.91(m,2H),3.81(s,3H).
13C NMR(126MHz,CDCl3)δ190.8,164.2,157.0,148.2,132.0,130.9,121.9,116.8,115.2,55.7.
example 6
The synthetic route of the invention is as follows:
at room temperature, adding the aromatic heterocyclic borate compound 1f, the p-nitrobenzaldehyde compound 2a and a catalyst CuSO into a reaction bottle4An additive Oxone and a basic compound Cs2CO3And a reaction solvent DMSO or NMP. Wherein the molar ratio of the 1f to the 2a compound is 1:2, and the 1f and the catalyst CuSO4The molar ratio of 1 to 0.05, the molar ratio of 1f to the additive Oxone is 1 to 1, the molar ratio of 1f to the alkali Cs is2CO3Molar ratio 1:2.5, 1f to reaction organic solvent about 1:150, heating to 100 ℃ under air condition with stirring, and reacting for 20 hours.
After the reaction, water was added to quench the reaction, the crude product was extracted with ethyl acetate, and the organic layers were combinedAnhydrous Na2SO4Drying, evaporation to dryness under reduced pressure, separation and purification gave the corresponding product 3f in 89% (DMSO) or 71% (NMP) yield.
The structure of the product obtained in example 6 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature control, and the result proves that the substance is a product with a 3f structural formula.
Of the resulting product1H NMR and13c NMR spectra are shown in FIGS. 11 and 12, and data of the product 3 f:
1H NMR(500MHz,CDCl3)δ9.94(s,1H),7.89–7.86(m,2H),7.65–7.59(m,4H),7.47(t,J＝7.7Hz,2H),7.39-7.36(m,1H),7.18–7.11(m,4H).
13C NMR(126MHz,CDCl3)δ190.9,163.3,154.7,140.3,138.2,132.1,131.5,129.0,128.9,127.53,127.1,120.8,117.8.
example 7
The synthetic route of the invention is as follows:
adding the aromatic heterocyclic borate compound 1a, the o-nitrobenzaldehyde compound 2b and a catalyst CuF into a reaction bottle at room temperature2An additive Oxone and a basic compound Cs2CO3And a reaction solvent DMSO. Wherein the molar ratio of 1a to 2b is 1:2, and 1a is mixed with a catalyst CuF2The molar ratio of 1:0.05, the molar ratio of 1a to the additive Oxone is 1:1, the molar ratio of 1a to the alkali Cs is2CO3The molar ratio of 1:2.5, 1a and the organic solvent of the reaction is about 1:100 (or about 1:150), and the mixture is heated to 100 ℃ under air condition with stirring and reacted for 24 hours.
After the reaction is finished, water is added to quench the reaction, the crude product is extracted by diethyl ether, organic layers are combined, and anhydrous Na is added2SO4Drying, evaporation to dryness under reduced pressure, separation and purification gave 3g of the corresponding product in 82% (1a: DMSO ≈ 1:100) or 86% (1a: DMSO ≈ 1: 150).
The structure of the product obtained in example 7 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature controls and confirmed that the material was 3g of the product of formula.
Of the resulting product1H NMR and13c NMR spectrum is shown in FIGS. 13 and 14, and data of 3g of the product:
1H NMR(500MHz,CDCl3)δ10.53(s,1H),7.94(dd,J＝7.8,1.8Hz,1H),7.53-7.49(m,1H),7.42–7.37(m,2H),7.20–7.17(m,2H),7.08–7.06(m,2H),6.91-6.89(m,1H).
13C NMR(126MHz,CDCl3)δ189.5,160.1,156.5,135.9,130.2,128.6,127.0,124.5,123.5,119.5,118.6.
example 8
The synthetic route of the invention is as follows:
at room temperature, the aromatic heterocyclic borate compound 1a, the p-nitrile benzaldehyde 2c and the catalyst CuCl are added into a reaction bottle2An additive Oxone and a basic compound Cs2CO3And a reaction solvent DMSO. Wherein the molar ratio of the 1a to the 2c compounds is 1:2 (or 1:1 or 1:3), and the 1a and the catalyst CuCl2The molar ratio of 1:0.05, the molar ratio of 1a to the additive Oxone is 1:1, the molar ratio of 1a to the alkali Cs is2CO3The molar ratio of 1:2.5, 1a and the organic solvent in the reaction is about 1:150, and the mixture is stirred and heated to 100 ℃ under the condition of air, and the reaction is carried out for 24 hours.
After the reaction is finished, water is added to quench the reaction, the crude product is extracted by dichloromethane, organic layers are combined, and anhydrous Na is added2SO4Drying, evaporation to dryness under reduced pressure and isolation purification gave the corresponding product 3h in 77% (1a:2c ═ 1:2) or 62% (1a:2c ═ 1: 1) or 74% (1a:2c ═ 1:3) yield.
The structure of the product obtained in example 8 was analyzed and the results were compared to those obtained in Chang et al [ Peng, D.; yu, a.; wang, h.; wu, y.; chang, J.tetrahedron 2013,69,6884-6889 ] reported literature control, and the result proves that the substance is the product of the 3h structural formula.
Of the resulting product1H NMR and13c NMR spectrum is shown in FIGS. 15 and 16, and data of the product 3 h:
1H NMR(500MHz,CDCl3)δ7.60(d,J＝8.7Hz,2H),7.42(t,J＝7.9Hz,2H),7.23(t,J＝7.4Hz,1H),7.07(d,J＝8.3Hz,2H),7.00(d,J＝8.7Hz,2H).
13C NMR(126MHz,CDCl3)δ161.8,154.9,134.3,130.4,125.3,120.5,119.0,118.0,105.9.
Claims (10)
1. a process for preparing a diaryl ether compound, comprising the steps of:
dispersing an aromatic heterocyclic borate compound with a structure I, a nitrobenzene compound with a structure II, a copper catalyst, an additive and an alkaline compound in an organic solvent, heating, stirring, separating and purifying to obtain a diaryl ether compound with a structure III.
2. The process according to claim 1 for preparing a diaryl ether compound, wherein: substituent R1Is one of hydrogen, alkoxy, halogen, C1-C8 alkyl and phenyl.
3. The process according to claim 1 for preparing a diaryl ether compound, wherein: substituent R2Is one of aldehyde group and cyano group.
4. The process according to claim 1 for preparing a diaryl ether compound, wherein: the molar ratio of the aromatic heterocyclic borate compound with the structure I to the nitrobenzene compound with the structure II, the copper catalyst, the additive, the alkaline compound and the organic solvent is as follows: 1: (1-3): (0.05-0.2): (1-2): (1-3): (100-150).
5. The process according to claim 4, wherein: in the reaction process of heating and stirring, the reaction temperature is 80-100 ℃.
6. The process according to claim 5, wherein: the heating and stirring time is 16-24 hours.
7. The process according to claim 1 for preparing a diaryl ether compound, wherein: the copper catalyst is one or a mixture of any more of copper acetate, copper oxide, copper bromide, copper trifluoromethanesulfonate, copper acetylacetonate, copper sulfate, copper fluoride and copper chloride.
8. The process according to claim 1 for preparing a diaryl ether compound, wherein: the alkaline compound is one or a mixture of any more of cesium carbonate, potassium hydroxide and potassium carbonate.
9. The process according to claim 1 for preparing a diaryl ether compound, wherein: the additive is one or a mixture of any more of potassium hydrogen persulfate composite salt, potassium persulfate and hydrogen peroxide.
10. The process according to claim 1 for preparing a diaryl ether compound, wherein: the organic solvent is one or a mixture of any more of dimethyl sulfoxide and N-methyl pyrrolidone A.
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| JPH0971549A (en) * | 1995-09-06 | 1997-03-18 | Nitto Kasei Co Ltd | Production of diaryl ether compound |
| CN102531856A (en) * | 2011-12-22 | 2012-07-04 | 温州大学 | Method for synthesizing asymmetric diaryl ether derivative |
| CN107573215A (en) * | 2017-09-15 | 2018-01-12 | 温州大学 | A kind of synthetic method of diarylcarbinols class compound |
| CN111116542A (en) * | 2019-12-30 | 2020-05-08 | 浙江工业大学 | Synthetic method of benzoxas compound |
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| JPH0971549A (en) * | 1995-09-06 | 1997-03-18 | Nitto Kasei Co Ltd | Production of diaryl ether compound |
| CN102531856A (en) * | 2011-12-22 | 2012-07-04 | 温州大学 | Method for synthesizing asymmetric diaryl ether derivative |
| CN107573215A (en) * | 2017-09-15 | 2018-01-12 | 温州大学 | A kind of synthetic method of diarylcarbinols class compound |
| CN111116542A (en) * | 2019-12-30 | 2020-05-08 | 浙江工业大学 | Synthetic method of benzoxas compound |
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| JILEI ZHANG等: ""Ligand-free copper-catalyzed coupling of nitroarenes with arylboronic acids"", 《GREEN CHEMISTRY》, vol. 14, 27 February 2012 (2012-02-27), pages 912 - 916 * |
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