CN109053463B - Method for converting diaryl ether into N-cyclohexyl aniline compound - Google Patents
Method for converting diaryl ether into N-cyclohexyl aniline compound Download PDFInfo
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Abstract
The invention discloses a method for converting diaryl ether into N-cyclohexyl aniline compounds, namely, under the action of a catalyst, the diaryl ether compounds react with ammonia water and a reducing agent to form medicine or natural product skeleton N-cyclohexyl aniline and derivatives thereof with important physiological activity. The invention has the advantages of simple and easily obtained raw materials, high conversion rate, important product and good yield, and has wide application prospect in the degradation and deep development and utilization of lignin and polyphenyl ether plastics.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for converting diaryl ether into an N-cyclohexyl aniline compound.
Background
Wood is a renewable resource that is most widely distributed in nature. Lignin is mainly present between the cellulose fibers of wood, and is present in woody plants up to 25%, the second most abundant organic matter in the world (cellulose is the first), which is a very important renewable resource. The lignin structure fragment is shown in figure 1. It is a biopolymer with a three-dimensional network structure formed by connecting oxo-phenylpropanol structural units with each other through ether bonds and carbon-carbon bonds. The most important chain connection is three ether bonds (shown as figure 1) of beta-O-4, alpha-O-4, 4-O-5 and partial carbon-carbon bonds, and the aryl ether bonds can be converted into high-value fine chemicals by cracking, so how to effectively break the three ether bonds becomes a key point for lignin degradation, and the method has important significance for converting high-molecular polymer lignin into high-value-added small-molecular organic compounds and performing biorefinery on the high-molecular polymer lignin.
In addition, Polyphenylene Oxide (PPO) is one of five general industrial plastics in the world, and the structure of the PPO mainly contains diaryl ether skeleton. The waste polyphenyl ether plastics after being used contain a large amount of diaryl ether bonds, so that the polyphenyl ether plastics are difficult to degrade and accumulate for a long time to form white pollution which pollutes the environment. Therefore, how to effectively break the ether bond becomes a key point for degrading the polyphenyl ether plastic, and has important significance for converting the degradation and recycling of the polyphenyl ether plastic into high value-added small molecular organic compounds and biorefining thereof.
Currently, the lignin degradation research mainly uses diphenyl ether, phenyl benzyl ether and phenyl phenethyl ether as corresponding model substrates of three ether bonds of 4-O-5, alpha-O-4 and beta-O-4 (as shown in figure 2). The bond energies of carbon-oxygen bonds corresponding to the three model substrates are different greatly, and the bond energy of the carbon-oxygen bond of the phenyl benzyl ether is 218 kJ.mol-1The bond energy of the carbon-oxygen bond of phenyl phenethyl ether is 289 kJ.mol-1The bond energy of the carbon-oxygen bond of the diphenyl ether is 314 kJ.mol-1. It can be seen from the bond energy data that the most difficult cleavage of the three carbon-oxygen bonds is diphenyl ether. Due to the higher diphenyl ether linkage energy, usually CArHydrogenolysis of the-O bond requires high temperature(s) (II)>250 ℃ and a greater hydrogen pressure of (c) ((>30bar) over a heterogeneous catalyst. These conditions result in poor chemical selectivity for the hydrogenolysis hydrogenation, wasting hydrogen and resulting in low yields of aromatic products. Until 2011, the Hartwig group did not break through the carbon-oxygen bond cleavage of diphenyl ether, degrading diphenyl ether to phenol and benzene (Science,2011,332,439; j.am.chem. soc.,2012,134,20226), and then other groups also successfully degraded diphenyl ether to phenol and benzene (angew.chem., int.ed.,2013,52, 12674; angew.chem., int.ed.,2016,55, 1474; catal.commu.2014, 52, 36; ind.eng.chem.res.2014,53,2633; j.org.chem.2014,79,10189; catal.2016, 1766, 201555), followed by other groups degrading diphenyl ether to cyclohexanol (j.am.chem.soc.,2012,134, 20768), cyclohexane (chemcatc chem, 4, chem.64; cata.17632; 201mS. 6,7611, 20111, 201mS.31, cyclohexanol (com. chem.r.t., 1995, 389, 29, nat. 73, 2018, cyclohexanol (com. j.am.chem.chem.r., chem.r., chest., 31, chest., 389), nat, 1988, nat 2, cz, com.r.t., cz. As can be seen from the results of the above studies, the main task of the present invention is to degrade diphenyl ether into the simplest fractionsOrganic compounds (benzene, phenol, cyclohexane, cyclohexanol, cyclohexanone, dicyclohexyl ether, etc.) are industrially relatively low in value. From the perspective of social sustainable development and green chemistry, how to effectively convert diphenyl ether into a compound with high added value (such as a nitrogen-containing compound) in one step has good economic value and significance. The nitrogen-containing compound is a basic skeleton of a large group of natural product alkaloids with important biological activity, and accounts for more than 90 percent of all medicaments.
Another patent application (201810093386.3) filed by the Applicant discloses a synthetic process for converting diaryl ethers of model compounds of lignin 4-O-5 into nitrogen-containing compounds, the reaction being as follows:
disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a method for converting diaryl ethers into N-cyclohexylanilines.
The invention is realized by adopting the following specific technical scheme:
a method for converting a diaryl ether to an N-cyclohexyl aniline, comprising:
under the action of a catalyst, diaryl ether, ammonia water and a reducing agent are mixed and reacted to obtain an N-cyclohexyl aniline compound,
the structural formula of the diaryl ether is as follows:
the structural formula of the N-cyclohexyl aniline compound is as follows:
wherein Ar is a benzene ring or a substituted benzene ring, Ar' is a benzene ring, a substituted benzene ring, a naphthalene ring or a substituted naphthalene ring, and R is hydrogen or C1-C12 alkyl or aryl substituted group;
the substituted benzene ring is a benzene ring with at least one C1-C12 alkyl, aryl, alkoxy, aryloxy, halogen, ester group, hydroxyl and/or acyl substituent group;
the substituted naphthalene ring is a naphthalene ring with at least one C1-C12 alkyl, aryl, alkoxy, aryloxy, halogen, ester group, hydroxyl and/or acyl substituent group.
In the present invention, Ar and Ar' may be the same or different.
In the present invention, the aryl group includes, but is not limited to, phenyl group, 2-methylphenyl group, 3-methylphenyl group, p-methylphenyl group, halophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, p-methoxyphenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, p-carboxyphenyl group, phenol group, benzophenone group, naphthyl group, furan group, thiophene group, pyrrole group, tetrahydrofuran group, benzofuran group, 2, 3-dihydrobenzofuran group, biphenyl group, etc.; the alkoxy group includes, but is not limited to, methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, isopentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-undecyloxy, n-dodecyloxy, and the like; the aryloxy group includes, but is not limited to, phenoxy, benzyloxy, 2-methylphenoxy, 3-methylphenoxy, p-methylphenoxy, halophenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, p-methoxyphenoxy, 2-carboxyphenoxy, 3-carboxyphenoxy, p-carboxyphenoxy, naphthoxy, etc.; the ester group is-COOR', -ONO2or-OCOR ', R' includes but is not limited to C1-C12 alkyl; the acyl group is-COR ", and R" includes but is not limited to C1-C12 alkyl, amino and the like.
In the present invention, the alkyl group having C1-C12 includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, n-undecyl, n-dodecyl and the like; the halogen includes fluorine, chlorine, bromine, iodine.
In the invention, the catalyst is an iron group element or a platinum group element existing in a simple substance or compound form: metallic palladium, metallic ruthenium, metallic rhodium, metallic platinum, metallic nickel, metallic iron, bis (cyclooctadiene) nickel, nickel chloride, nickel acetate, palladium chloride, palladium acetate, bis (triphenylphosphine) palladium chloride, ferric chloride, ferrous chloride, rhodium chloride, ruthenium chloride, platinum chloride, palladium hydroxide, etc. The above catalyst may also be supported on a carrier such as carbon, silica, aluminum trioxide, molecular sieve, etc., such as palladium/carbon, palladium hydroxide/carbon, palladium/silica, rhodium/carbon, ruthenium/carbon, platinum/carbon. Preferably, the catalyst is palladium hydroxide on carbon. Wherein the amount of the catalyst is 10-30 mol% of the diaryl ether. Preferably, the catalyst is used in an amount of 20 mol% of the diaryl ether.
In the present invention, the reducing agent is: potassium formate, lithium formate, cesium formate, ammonium formate, sodium hydride, lithium aluminum hydride, sodium borohydride, calcium hydride. Preferably, the reducing agent is sodium borohydride. Wherein the amount of the reducing agent is 0.5 to 3 times equivalent of the diaryl ether. Preferably, the reducing agent is used in an amount of 1 equivalent to the diaryl ether.
In the present invention, the following solvents can be selected for the reaction: toluene, 1, 4-dioxane, fluorobenzene, dimethyl sulfoxide, water, o-xylene, m-xylene and p-xylene, and preferably, the solvent is m-xylene. The solvent is used in an amount such that the concentration of the diaryl ether is in the range of 0.005 to 1mmol/mL, and preferably, the solvent is used in an amount such that the concentration of the diaryl ether is 0.2 mmol/mL.
In the invention, the reaction temperature is 140-160 ℃, and preferably 150 ℃.
In the present invention, the reaction time is 12 to 36 hours, and preferably, the reaction temperature is 24 hours.
In the present invention, the reaction is performed under the protection of an inert gas, preferably, the inert gas is argon.
In the present invention, the amount of aqueous ammonia is kept in excess relative to the diaryl ether in order to increase the conversion of the diaryl ether.
In contrast to another patent application (201810093386.3) by the applicant, the applicant has unexpectedly found that diaryl ethers can be converted into more value-added N-cyclohexylanilines by reacting the diaryl ether with aqueous ammonia.
Drawings
FIG. 1 is a lignin structural fragment;
FIG. 2 shows model substrates for three ether linkages, 4-O-5, α -O-4, β -O-4.
Detailed Description
The following is a detailed description of the embodiments of the present invention with reference to specific examples. The following are only some specific examples of the present invention. It is obvious that the invention is not limited to the following examples of embodiment, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
The starting materials used in the present invention may be commercially available or synthesized using methods known in the art.
Example 1
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding diphenyl ether (0.2mmol) and ammonia water (1mmol) solution dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase to give a filtrate with a benzene yield of 82%. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 a. Product 3a (yield: 83%):1H NMR(CDCl3,400MHz)δ:7.17(t,J＝8, 2H),6.67(t,J＝8Hz,1H),6.60(d,J＝8Hz,2H),3.25(tt,J＝10.0,3.7Hz,1H),2.09-2.04(m, 2H),1.79-1.75(m,2H),1.69-1.65(m,1H),1.43-1.27(m,2H),1.18-1.12(m,3H)；13C NMR (CDCl3,100MHz)δ:147.3,129.2,116.8,113.1,51.6,33.4,25.9,25.0.
example 2
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of m-xylyl ether (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase to give 85% toluene yield. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 b. Product 3b (yield: 79%): cis-isomer1H NMR(400MHz,CDCl3) δ:7.08(dd,J＝8,7.2Hz,1H),6.51(d,J＝8Hz,1H),6.43(d,J＝8Hz,2H),3.74-3.67(m,1H), 2.29(s,3H),1.75-1.54(m,7H),1.38-1.27(m,1H),1.09-1.04(m,1H),0.94(d,J＝6.5Hz, 3H).13C NMR(100MHz,CDCl3)δ:147.3,139.0,129.1,117.6,113.7,110.0,47.4,38.8,34.0, 30.4,27.1,21.8,21.7,20.6.
trans-isomer 1H NMR(400MHz,CDCl3)δ:7.10-7.05(m,1H),6.52(d,J＝8Hz,1H),6.44(s, 2H),3.26(tt,J＝12,3.8Hz,1H),2.29(s,3H),2.13-2.10(m,2H),1.84-1.78(m,1H),1.73-1.69 (m,1H),1.58-1.46(m,1H),1.42-1.33(m,1H),1.04-0.96(m,1H),0.95(d,J＝8Hz,3H), 0.90-0.70(m,2H).13C NMR(100MHz,CDCl3)δ:147.4,139.0,129.1,117.8,113.9,110.2, 52.0,42.5,34.6,33.4,32.0,25.0,22.5,21.7.
Example 3
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of p-xylyl ether (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase to give a toluene yield of 88%. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 c. Product 3c (yield: 82%): cis-isomer1H NMR(400MHz,CDCl3) δ:6.98(d,J＝8.0Hz,2H),6.54(d,J＝8.0Hz,2H),3.53(quint,J＝4.5Hz,1H),2.24(s,3H), 1.77-1.73(m,2H),1.67-1.53(m,5H),1.27-1.23(m,2H),0.94(d,J＝8Hz,3H).13C NMR(100 MHz,CDCl3)δ:145.0,129.7,125.9,113.3,48.3,30.9,29.7,29.2,21.4,20.4.
trans-isomer 1H NMR(400MHz,CDCl3)δ:7.00(d,J＝8Hz,2H),6.54(d,J＝8.5Hz,2H), 3.19-3.09(m,1H),2.24(s,3H),2.13-2.10(m,2H),1.77-1.75(m,2H),1.44-1.41(m,1H), 1.16-1.03(m,4H),0.93(d,J＝8Hz,3H).13C NMR(100MHz,CDCl3)δ:145.1,129.7,126.1, 113.5,52.4,34.1,33.5,32.3,22.3,20.3.
Example 4
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), the reaction tube was evacuated, argon gas was introduced, the replacement was repeated three times, and p-diethylphenyl ether (0.2 m) dissolved in m-xylene was introduced under an argon atmospheremol) and ammonia water (1mmol) solution are slowly added into a reaction tube by a syringe, and the reaction tube is placed in an oil bath at 150 ℃ to be heated and stirred for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite, the filtrate was tested in the vapour phase for 80% ethylbenzene yield. The filtrate was concentrated and separated using an activated thin layer chromatography plate (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 d. Product 3d (yield: 69%): cis-isomer1H NMR(400MHz, CDCl3)δ:7.01(d,J＝8Hz,2H),6.57(d,J＝8.6Hz,2H),3.56-3.54(m,1H),2.53(q,J＝8Hz, 2H),1.73-1.59(m,6H),1.38-1.29(m,5H),1.20(t,J＝8Hz,3H),0.90(t,J＝8Hz,3H).13C NMR(100MHz,CDCl3)δ:145.3,132.5,128.5,113.2,48.6,37.8,29.4,28.3,27.9,27.4,16.0, 11.7.
trans-isomer 1H NMR(400MHz,CDCl3)δ:7.00(d,J＝8Hz,2H),6.56(d,J＝8.6Hz,2H), 3.20-3.13(m,1H),2.53(q,J＝8Hz,2H),2.16-2.12(m,2H),1.84-1.81(m,2H),1.26-1.15(m, 8H),1.08-0.99(m,2H),0.90(t,J＝8Hz,3H).13C NMR(100MHz,CDCl3)δ:145.4,132.7, 128.5,113.3,52.7,39.0,33.6,31.7,29.6,27.9,16.0,11.7.
Example 5
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of p-dipropyl phenyl ether (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in a 150 ℃ oil bath for heating and stirring for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase to give 83% propylbenzene yield. Concentrating the filtrate, and layering with activated thin layerThe final product 3e was obtained after separation on chromatography plates (eluent: n-hexane/ethyl acetate 30/1). Product 3e (yield: 71%): cis-isomer1H NMR(400MHz, CDCl3)δ:6.98(d,J＝8Hz,2H),6.55(d,J＝8Hz,2H),3.55-3.52(m,1H),2.7(t,J＝8.6Hz, 2H),1.77-1.51(m,8H),1.38-1.19(m,7H),0.90(m,6H).13C NMR(100MHz,CDCl3)δ:145.4, 131.2,129.2,113.2,52.7,39.4,37.2,37.0,33.7,32.1,25.0,20.2,14.5,14.0.
trans-isomer 1H NMR(400MHz,CDCl3)δ:6.98(d,J＝8Hz,2H),6.54(d,J＝8.6Hz,2H), 3.19-3.12(m,1H),2.47(t,J＝8Hz,2H),2.14-2.11(m,2H),1.82-1.79(m,2H),1.61-1.58(m, 2H),1.36-1.17(m,5H),1.11-1.03(m,4H),0.90-0.88(m,6H).13C NMR(100MHz,CDCl3)δ: 145.3,131.0,129.2,113.1,48.7,37.2(2C),35.7,29.4,27.8,25.0,20.2,14.4,13.9.
Example 6
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(2-fold equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of bis (4-fluorophenyl) ether (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 36 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase to give a filtrate benzene yield of 62%. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 a. Product 3a (yield: 48%):1H NMR(CDCl3,400MHz)δ:7.17(t, J＝8,2H),6.67(t,J＝8Hz,1H),6.60(d,J＝8Hz,2H),3.25(tt,J＝10.0,3.7Hz,1H), 2.09-2.04(m,2H),1.79-1.75(m,2H),1.69-1.65(m,1H),1.43-1.27(m,2H),1.18-1.12(m,3H)；13C NMR(CDCl3,100MHz)δ:147.3,129.2,116.8,113.1,51.6,33.4,25.9,25.0.
example 7
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of bis (4-methoxydiphenyl) ether (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 36 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase to give 58% methoxybenzene yield from the filtrate. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 a. Product 3a (yield: 42%):1H NMR(CDCl3,400 MHz)δ:7.17(t,J＝8,2H),6.67(t,J＝8Hz,1H),6.60(d,J＝8Hz,2H),3.25(tt,J＝10.0,3.7 Hz,1H),2.09-2.04(m,2H),1.79-1.75(m,2H),1.69-1.65(m,1H),1.43-1.27(m,2H), 1.18-1.12(m,3H)；13C NMR(CDCl3,100MHz)δ:147.3,129.2,116.8,113.1,51.6,33.4,25.9, 25.0.
example 8
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 3-methyl diphenyl ether (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in a 150 ℃ oil bath for heating and stirring for reaction. 24The reaction was stopped after hours, the reaction tube was taken out of the oil bath, cooled naturally to room temperature, diluted with ethyl acetate, and the reaction was filtered through celite, and the yield of benzene in the filtrate was 65% by gas phase detection. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 b. Product 3b (yield: 74%): cis-isomer1H NMR(400MHz,CDCl3) δ:7.08(dd,J＝8,7.2Hz,1H),6.51(d,J＝8Hz,1H),6.43(d,J＝8Hz,2H),3.74-3.67(m,1H), 2.29(s,3H),1.75-1.54(m,7H),1.38-1.27(m,1H),1.09-1.04(m,1H),0.94(d,J＝6.5Hz, 3H).13C NMR(100MHz,CDCl3)δ:147.3,139.0,129.1,117.6,113.7,110.0,47.4,38.8,34.0, 30.4,27.1,21.8,21.7,20.6.
trans-isomer 1H NMR(400MHz,CDCl3)δ:7.10-7.05(m,1H),6.52(d,J＝8Hz,1H),6.44(s, 2H),3.26(tt,J＝12,3.8Hz,1H),2.29(s,3H),2.13-2.10(m,2H),1.84-1.78(m,1H),1.73-1.69 (m,1H),1.58-1.46(m,1H),1.42-1.33(m,1H),1.04-0.96(m,1H),0.95(d,J＝8Hz,3H), 0.90-0.70(m,2H).13C NMR(100MHz,CDCl3)δ:147.4,139.0,129.1,117.8,113.9,110.2, 52.0,42.5,34.6,33.4,32.0,25.0,22.5,21.7.
Example 9
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 4-methyl diphenyl ether (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in a 150 ℃ oil bath for heating and stirring for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a 73% yield of benzene from the filtrate by gas phase detection. Concentrating the filtrate, and purifying with activated thin layer chromatography plate (eluent: n-hexane/ethyl acetate)30/1) to yield the final product 3 c. Product 3c (yield: 82%): cis-isomer1H NMR(400MHz,CDCl3) δ:6.98(d,J＝8.0Hz,2H),6.54(d,J＝8.0Hz,2H),3.53(quint,J＝4.5Hz,1H),2.24(s,3H), 1.77-1.73(m,2H),1.67-1.53(m,5H),1.27-1.23(m,2H),0.94(d,J＝8Hz,3H).13C NMR(100 MHz,CDCl3)δ:145.0,129.7,125.9,113.3,48.3,30.9,29.7,29.2,21.4,20.4.
trans-isomer 1H NMR(400MHz,CDCl3)δ:7.00(d,J＝8Hz,2H),6.54(d,J＝8.5Hz,2H), 3.19-3.09(m,1H),2.24(s,3H),2.13-2.10(m,2H),1.77-1.75(m,2H),1.44-1.41(m,1H), 1.16-1.03(m,4H),0.93(d,J＝8Hz,3H).13C NMR(100MHz,CDCl3)δ:145.1,129.7,126.1, 113.5,52.4,34.1,33.5,32.3,22.3,20.3.
Example 10
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 4-phenoxybiphenyl (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in a 150 ℃ oil bath for heating and stirring for reaction. After 24 hours the reaction was stopped, the reaction tube was taken out of the oil bath, cooled naturally to room temperature, diluted with ethyl acetate and the reaction was filtered through celite. The filtrate was concentrated and separated on activated tlc plate (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3a, biphenyl (11%) and cyclohexylbenzene (82%). Product 3a (yield: 76%):1H NMR(CDCl3,400MHz)δ:7.17 (t,J＝8,2H),6.67(t,J＝8Hz,1H),6.60(d,J＝8Hz,2H),3.25(tt,J＝10.0,3.7Hz,1H), 2.09-2.04(m,2H),1.79-1.75(m,2H),1.69-1.65(m,1H),1.43-1.27(m,2H),1.18-1.12(m,3H)；13C NMR(CDCl3,100MHz)δ:147.3,129.2,116.8,113.1,51.6,33.4,25.9,25.0.
example 11
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 2-phenoxynaphthalene (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in a 150 ℃ oil bath for heating and stirring for reaction. After 24 hours the reaction was stopped, the reaction tube was taken out of the oil bath, cooled naturally to room temperature, diluted with ethyl acetate and the reaction was filtered through celite. The filtrate was concentrated and separated using activated tlc plates (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3a, naphthalene (17%) and 1,2,3, 4-tetrahydronaphthalene (74%). Product 3a (yield: 73%):1H NMR(CDCl3,400MHz)δ:7.17 (t,J＝8,2H),6.67(t,J＝8Hz,1H),6.60(d,J＝8Hz,2H),3.25(tt,J＝10.0,3.7Hz,1H), 2.09-2.04(m,2H),1.79-1.75(m,2H),1.69-1.65(m,1H),1.43-1.27(m,2H),1.18-1.12(m,3H)；13C NMR(CDCl3,100MHz)δ:147.3,129.2,116.8,113.1,51.6,33.4,25.9,25.0.
example 12
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 2-p-tolyloxynaphthalene (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 24 hours the reaction was stopped, the reaction tube was taken out of the oil bath, cooled to room temperature naturally, diluted with ethyl acetate and thenThe reaction solution was filtered through celite. The filtrate was concentrated and separated using activated tlc plates (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3a, naphthalene (14%) and 1,2,3, 4-tetrahydronaphthalene (76%). Product 3c (yield: 77%): cis-isomer1H NMR(400MHz, CDCl3)δ:6.98(d,J＝8.0Hz,2H),6.54(d,J＝8.0Hz,2H),3.53(quint,J＝4.5Hz,1H),2.24 (s,3H),1.77-1.73(m,2H),1.67-1.53(m,5H),1.27-1.23(m,2H),0.94(d,J＝8Hz,3H).13C NMR(100MHz,CDCl3)δ:145.0,129.7,125.9,113.3,48.3,30.9,29.7,29.2,21.4,20.4.
trans-isomer 1H NMR(400MHz,CDCl3)δ:7.00(d,J＝8Hz,2H),6.54(d,J＝8.5Hz,2H), 3.19-3.09(m,1H),2.24(s,3H),2.13-2.10(m,2H),1.77-1.75(m,2H),1.44-1.41(m,1H), 1.16-1.03(m,4H),0.93(d,J＝8Hz,3H).13C NMR(100MHz,CDCl3)δ:145.1,129.7,126.1, 113.5,52.4,34.1,33.5,32.3,22.3,20.3.
Example 13
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(1 equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 4-p-tolyloxy biphenyl (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 24 hours the reaction was stopped, the reaction tube was taken out of the oil bath, cooled naturally to room temperature, diluted with ethyl acetate and the reaction was filtered through celite. The filtrate was concentrated and separated on activated tlc plate (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3a, biphenyl (11%) and cyclohexylbenzene (81%). Product 3c (yield: 82%): cis-isomer1H NMR(400MHz,CDCl3) δ:6.98(d,J＝8.0Hz,2H),6.54(d,J＝8.0Hz,2H),3.53(quint,J＝4.5Hz,1H),2.24(s,3H), 1.77-1.73(m,2H),1.67-1.53(m,5H),1.27-1.23(m,2H),0.94(d,J＝8Hz,3H).13C NMR(100 MHz,CDCl3)δ:145.0,129.7,125.9,113.3,48.3,30.9,29.7,29.2,21.4,20.4.
trans-isomer 1H NMR(400MHz,CDCl3)δ:7.00(d,J＝8Hz,2H),6.54(d,J＝8.5Hz,2H), 3.19-3.09(m,1H),2.24(s,3H),2.13-2.10(m,2H),1.77-1.75(m,2H),1.44-1.41(m,1H), 1.16-1.03(m,4H),0.93(d,J＝8Hz,3H).13C NMR(100MHz,CDCl3)δ:145.1,129.7,126.1, 113.5,52.4,34.1,33.5,32.3,22.3,20.3.
Example 14
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(2 times equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 1, 4-diphenoxybenzene (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase with 84% benzene yield. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 a. Product 3a (yield: 123%):1H NMR(CDCl3,400MHz)δ:7.17 (t,J＝8,2H),6.67(t,J＝8Hz,1H),6.60(d,J＝8Hz,2H),3.25(tt,J＝10.0,3.7Hz,1H), 2.09-2.04(m,2H),1.79-1.75(m,2H),1.69-1.65(m,1H),1.43-1.27(m,2H),1.18-1.12(m,3H)；13C NMR(CDCl3,100MHz)δ:147.3,129.2,116.8,113.1,51.6,33.4,25.9,25.0.
example 15
A moderate stirrer was placed in a dry reaction tube (20 ml) and palladium hydroxide/carbon (20 mol%), NaBH was added4(2 times equivalent), then vacuumizing the reaction tube, filling argon, repeatedly replacing for three times, slowly adding a solution of 1, 3-diphenoxybenzene (0.2mmol) and ammonia water (1mmol) dissolved in m-xylene into the reaction tube by using a syringe under the argon atmosphere, and placing the reaction tube in an oil bath at 150 ℃ for heating and stirring for reaction. After 24 hours the reaction was stopped and the tube was removed from the oil bath, allowed to cool to room temperature, diluted with ethyl acetate and the reaction was filtered through celite in a gas phase to give a filtrate with a benzene yield of 82%. The filtrate was concentrated and separated by activated thin layer chromatography (eluent: n-hexane/ethyl acetate 30/1) to give the final product 3 a. Product 3a (yield: 112%):1H NMR(CDCl3,400MHz)δ:7.17 (t,J＝8,2H),6.67(t,J＝8Hz,1H),6.60(d,J＝8Hz,2H),3.25(tt,J＝10.0,3.7Hz,1H), 2.09-2.04(m,2H),1.79-1.75(m,2H),1.69-1.65(m,1H),1.43-1.27(m,2H),1.18-1.12(m,3H)；13C NMR(CDCl3,100MHz)δ:147.3,129.2,116.8,113.1,51.6,33.4,25.9,25.0。
Claims (14)
1. a method for converting a diaryl ether to an N-cyclohexyl aniline, comprising:
under the action of a catalyst, diaryl ether, ammonia water and a reducing agent are mixed and reacted to obtain an N-cyclohexyl aniline compound,
the structural formula of the diaryl ether is as follows:
，
the structural formula of the N-cyclohexyl aniline compound is as follows:
，
wherein Ar is a benzene ring or a substituted benzene ring, Ar' is a benzene ring, a substituted benzene ring or a naphthalene ring, and R is hydrogen or C1-C12 alkyl;
the substituted benzene ring is a benzene ring with a C1-C12 alkyl, aryl, alkoxy, aryloxy or halogen substituted group;
the aryl is phenyl, 2-methylphenyl, 3-methylphenyl, p-methylphenyl, halogenated phenyl, 2-methoxyphenyl, 3-methoxyphenyl, p-methoxyphenyl, 2-carboxyphenyl, 3-carboxyphenyl, p-carboxyphenyl or phenol group; the alkoxy is methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-undecyloxy, n-dodecyloxy; the aryloxy is phenoxy, 2-methylphenoxy, 3-methylphenoxy, p-methylphenoxy, halogenated phenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, p-methoxyphenoxy, 2-carboxyphenoxy, 3-carboxyphenoxy, p-carboxyphenoxy;
the catalyst is metal palladium, metal ruthenium, metal rhodium, metal platinum, metal nickel, bis (cyclooctadiene) nickel, nickel chloride, nickel acetate, palladium chloride, palladium acetate, bis (triphenylphosphine) palladium chloride, rhodium chloride, ruthenium chloride, platinum chloride and palladium hydroxide;
the reducing agent is potassium formate, lithium formate, cesium formate, ammonium formate, sodium hydride, lithium aluminum hydride, sodium borohydride and/or calcium hydride.
2. The method of claim 1, wherein the alkyl group of C1-C12 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, n-undecyl, n-dodecyl; the halogen is fluorine, chlorine, bromine or iodine.
3. The method of claim 1, wherein the catalyst is palladium hydroxide.
4. The process of claim 1 wherein the catalyst is present in an amount of from 10 to 30 mole percent based on the diaryl ether.
5. The process of claim 4 wherein the catalyst is present in an amount of 20 mole percent of the diaryl ether.
6. The method of claim 1, wherein the reducing agent is sodium borohydride.
7. The method of claim 1, wherein the reducing agent is used in an amount of 0.5 to 3 times equivalent to the diaryl ether.
8. The method of claim 7, wherein the reducing agent is used in an amount of 1 equivalent to the diaryl ether.
9. The method as claimed in claim 1, wherein the reaction temperature is 140-160 ℃.
10. The method of claim 9, wherein the temperature of the reaction is 150 degrees celsius.
11. The method of claim 9, wherein the reaction time is 12 to 36 hours.
12. The method of claim 11, wherein the reaction time is 24 hours.
13. The method of claim 1, wherein the reaction is carried out under the protection of an inert gas.
14. The method of claim 13, wherein the inert gas is argon.
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