CN112694375B - Application of iron (III) complex containing 1,3-di-tert-butylimidazole cation in synthesis of aryl benzyl ether compounds - Google Patents
Application of iron (III) complex containing 1,3-di-tert-butylimidazole cation in synthesis of aryl benzyl ether compounds Download PDFInfo
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Abstract
The invention discloses an application of an iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds, and particularly relates to synthesis of corresponding aryl benzyl ether compounds through oxidative coupling reaction of phenolic compounds and toluene compounds by taking di-tert-butyl peroxide as an oxidant. The invention realizes the oxidative coupling of the phenolic compound and the toluene compound by taking the iron (III) complex as the catalyst for the first time. This is the first example of a phenolic compound with the benzylic C (sp) 3 ) The oxidative coupling reaction of the-H bond provides a new method for synthesizing aryl benzyl ether compounds. Compared with the existing synthesis method, the method avoids using toxic and polluting halogenated hydrocarbon and strong alkali, has better atom economy, and accords with the development concept of green synthetic chemistry.
Description
Technical Field
The invention belongs to the technical field of preparation of organic compounds, and particularly relates to an application of an iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds.
Background
The aryl benzyl ether is widely existed in medical molecules as an important structural fragment, is also an important organic synthesis intermediate, and can be used for synthesizing medicines, dyes, spices and the like. The traditional method for preparing such compounds is the Williamson synthesis, which requires the use of toxic and polluting halogenated hydrocarbons and strong bases. Therefore, the development of a new method with atom economy and green environmental friendliness for synthesizing the compound has strong practical application value. Examples of drug molecules containing aryl benzyl ether structural fragments are as follows:
in recent decades, transition metal catalyzed carbon-hydrogen (C-H) bond functionalization reactions have become a new approach to the construction of carbon-carbon (C-C) and carbon-hetero (C-X) bonds, which avoids the pre-synthesis and use of halogenated hydrocarbons and thus is very atom economical and environmentally friendly. In recent years, oxidative coupling reactions involving carboxylic acids have been used to construct C (sp) 3 ) the-O bond has been studied greatly, and provides a new method for synthesizing carboxylic ester compounds. However, involving an oxidative coupling reaction involving less acidic phenolic compounds to construct C (sp) 3 ) Reports of-O bonds are rare. In 2012, the Reddy group used copper acetate as a catalyst and tert-butyl peroxide as an oxidant, and realized the C (sp) ortho-position between a phenolic compound and an oxygen atom 3 -H) oxidative coupling of bonds (see: kumar, G.S., pieber, B., reddy, K.R., kappa, C.O., a,Chem. Eur. J. 2012, 18, 6124). In 2013, the Patel group tried oxidative coupling reaction of phenolic compounds and toluene compounds with copper acetate hydrate as catalyst and tert-butyl peroxide as oxidant, and the expected target product was aryl benzyl ether compound, but the final product was phenolic ester compound, which is caused by unstable and rapid oxidation of the intermediate aryl benzyl ether compound into phenolic ester compound (see: saroj, K. R.; srimanta G.; arghya, B.; anupal, G.; nilufa, K.; patel, B. K.),Org. Lett. 2013, 15, 4106）。
iron, one of the most abundant metals on earth, hasCheap and easily available, good biocompatibility and the like. At present, phenolic compounds and C (sp) related to iron-based catalysts 3 ) The oxidative coupling reaction of-H bond is only one example. 2014, wu Yongchang as Fe 2 (CO) 9 Is used as a catalyst, tert-butyl peroxide is used as an oxidant, and the ortho-position C (sp) of the phenolic compound and the oxygen atom is realized 3 -H) oxidative coupling of bonds (see: barve, B, D, wu, Y, C, koriek, M, cheng, Y, wang, J, chang, F, R.Org. Lett. 2014, 16, 1912）。
So far, no literature report on constructing aryl benzyl ether compounds by catalyzing oxidative coupling reaction of phenolic compounds and toluene compounds by using iron catalysts is found.
Disclosure of Invention
The invention aims to provide a new method for synthesizing aryl benzyl ether compounds, namely, aryl benzyl ether compounds with molecular formula [ () t BuNCH=CHN t Bu)CH][FeBr 4 ]The corresponding aryl benzyl ether compound is synthesized by taking the 1,3-di-tert-butyl imidazole cation-containing iron (III) complex as a catalyst and di-tert-butyl peroxide as an oxidant through the oxidative coupling reaction of a phenol compound and a toluene compound. [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Is a simple and easily obtained iron (III) complex with definite structure and air stability.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the application of the iron (III) complex containing 1,3-di-tert-butyl imidazole cation in synthesizing aryl benzyl ether compounds; the method for synthesizing the aryl benzyl ether compound comprises the steps of taking a phenol compound and a toluene compound as raw materials, and reacting in the presence of a catalyst and an organic oxidant to obtain the aryl benzyl ether compound;
the chemical structural formula of the catalyst is as follows:
in the invention, the chemical structural formula of the toluene compound is as follows:
r is hydrogen, methoxy or halogen;
R 2 hydrogen and methyl.
The phenolic compound is a compound with hydroxyl connected on an aromatic ring or a heteroaromatic ring, such as phenol, substituted phenol, hydroxypyridine, hydroxyquinoline and hydroxybenzothiazole; the chemical structural formula of the phenol and the substituted phenol is as follows:
R 1 the substituent is alkyl, nitro, trifluoromethyl, acetoxy, halogen or acetyl, and the alkyl is methyl or tert-butyl. Such as 4-nitrophenol, 4-trifluoromethylphenol, 4-acetoxyphenol, 2,6-dichlorophenol, 2-acetylphenol, phenol, 4-methylphenol, 4-tert-butylphenol.
In the technical scheme, a toluene compound is used as a reaction substrate and a solvent, and the molar ratio of a catalyst to a phenol compound to an organic oxidant is (0.05-0.10) to 1 to (0.5-1.5); preferably 0.10: 1: 1.5.
In the technical scheme, the reaction temperature is 90-140 ℃ and the reaction time is 15-40 hours; the reaction temperature is preferably 110 to 130 ℃ and the reaction time is preferably 20 to 30 hours.
In the technical scheme, after the reaction is finished, the reaction product is cooled to room temperature, the product is purified through column chromatography, and a mixed solvent of ethyl acetate and petroleum ether in a volume ratio is used as a developing solvent to obtain the aryl benzyl ether compound.
In the above technical solution, the organic oxidant is an organic peroxide, such as di-tert-butyl peroxide.
The reaction process of the present invention can be represented as follows:
due to the application of the technical scheme, the invention has the following advantages:
1. the invention realizes the oxidative coupling of the phenolic compound and the toluene compound by taking the iron (III) complex as the catalyst for the first time. This is the first example of a phenolic compound with the benzylic C (sp) 3 ) The oxidative coupling reaction of the-H bond provides a new method for synthesizing aryl benzyl ether compounds. Compared with the existing synthesis method, the method avoids using toxic and polluting halogenated hydrocarbon and strong alkali, has better atom economy, and accords with the development concept of green synthetic chemistry.
2. The iron catalyst adopted by the invention has the advantages of simple synthesis, definite structure and stable air, shows good catalytic activity and is beneficial to large-scale industrial synthesis application.
Detailed Description
All the raw materials of the invention are commercial products, and the specific preparation method and the test method are the conventional techniques in the field. The invention is further described below with reference to the following examples:
the first embodiment is as follows: containing 1,3-di-tert-butyl imidazole cation (molecular formula [ (II) [) t BuNCH=CHN t Bu)CH][FeBr 4 ]) Synthesis of iron (III) complexes of
1,3-Di-tert-butylimidazolium bromide (0.26 g, 1.0 mmol) was added to a solution of iron tribromide (0.27 g, 0.9 mmol) in tetrahydrofuran 60 g oC The reaction is carried out for 24 hours, the solvent is pumped out in vacuum, hexane is washed, the solvent is pumped out, tetrahydrofuran is used for extraction, the clear solution is centrifuged and transferred, hexane is added into the clear solution for recrystallization, and reddish brown solid powder is separated out at room temperature, and the yield is 91%.
The chemical structural formula is as follows:
elemental analysis of the product resulted in the following:
iron complexes are not characterized as being nuclear magnetic due to their paramagnetic properties.
Complex [ () ( t BuNCH=CHN t Bu)CH][FeBr 4 ]In the form of ion pairs, in which [ FeBr ] 4 ] - It was characterized by Raman spectroscopy and was found to be 204 cm -1 Characteristic peaks are observed, and are consistent with the reports in the literature (Melissa, S.; eric, R. S.; eric, V. P.; freeman, R. G.), Inorg. Chem., 2001, 40, 2298）。
cationic moiety of the complex [ ((iii)) t BuNCH=CHN t Bu)CH] + The molecular ion peak is observed at 181.1699 and theoretically at 181.1699, and the peak is observed to be consistent with the theory.
The obtained compound was confirmed to be the objective compound.
The second embodiment: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-nitrophenol with toluene
4-Nitrophenol (69.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 mL) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 10 as a developing agent) to obtain the yield of 89%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): 8.29 - 8.17 (m, 2H), 7.48 - 7.37 (m, 5H), 7.08 -7.00 (m, 2H), 5.19 (s, 2H)。
the product is p-nitrophenyl benzyl ether:
replacing the iron catalyst with 20 mol% copper powder, and obtaining no target product (trace) under the same other conditions; the iron catalyst was replaced with 60 mol% copper powder, and di-t-butyl peroxide was increased to 1.0 mmol, but the other conditions were unchanged, and the target product (trace) was not obtained.
Example three: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-trifluoromethylphenol with toluene
4-Trifluoromethylphenol (81.05 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 mL) were added sequentially to the flask at 130 deg.F o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (with petroleum ether as a developing agent) with the yield of 86%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): 7.53 (d, J = 8.7 Hz, 2H), 7.45 - 7.30 (m, 5H), 7.01 (d, J = 8.7 Hz, 2H), 5.08 (s, 2H).
example four: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-acetoxyphenol with toluene
4-Acetoxyphenol (76.07 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 mL) were added to the flask in succession at 130. Mu.l oC The reaction is carried out for 24 hours, the reaction is cooled to room temperature after the reaction is finished, and the product is purified by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 10 as a developing solvent), and the yield is 82%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), closed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 , TMS): 8.03 - 7.97 (m, 2H), 7.45 - 7.33 (m, 5H), 7.00 (dd, J = 8.5, 1.3 Hz, 2H), 5.12 (s, 2H), 3.89 (d, J = 0.9 Hz, 3H).
example five: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling reaction of 2,6-dichlorophenol and toluene
2,6-dichlorophenol (81.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 ml) were added sequentially to the reaction flask at 130 f oC The reaction is carried out for 24 hours, the reaction is cooled to room temperature after the reaction is finished, and the product is purified by column chromatography (by taking petroleum ether as a developing agent) with the yield of 81 percent.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): 7.65-7.59 (m, 2H), 7.48-7.32 (m, 5H), 7.07-7.00 (m, 1H), 5.09 (s, 2H).
example six: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 2-acetylphenol with toluene
2-Acetylphenol (60.0. Mu.l, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 ml) were added sequentially to the reaction flask at 130. Mu.l oC And (3) reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 5 as a developing agent) to obtain the yield of 80%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), closed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 , TMS): 7.73 (dd, J = 7.8, 1.9 Hz, 1H), 7.40 - 7.22 (m, 6H), 6.95 - 6.87 (m, 2H), 5.02 (s, 2H), 2.53 (s, 3H).
example seven: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of phenol with tolueneShould be taken
To the flask were added phenol (44.0. Mu.l, 0.5 mmol), catalyst (22 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 ml) in that order at 130. Mu.l oC The reaction is carried out for 24 hours, the reaction is cooled to room temperature after the reaction is finished, and the product is purified by column chromatography (by taking petroleum ether as a developing agent) with the yield of 80 percent.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): 7.44 - 7.24 (m, 7H), 6.99 - 6.91 (m, 3H), 5.03 (s, 2H)。
the iron catalyst was replaced with 20 mol% Cu (OAc) 2 Otherwise, the target product (trace) was not obtained.
Example eight: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-methylphenol with toluene
4-Methylphenol (54.07 mg, 0.5 mmol), catalyst (22 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 ml) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 10 as a developing agent) to obtain the yield of 79 percent.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): 7.64 - 7.45 (m, 5H), 7.29 - 7.24 (m, 2H), 7.10 - 7.04 (m, 2H), 5.18 (s, 2H), 2.47 (s, 3H).
example nine: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-tert-butylphenol with toluene
4-tert-butylphenol (75.1 mg, 0.5 mmol), catalyst (22 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol) were added sequentially to the flaskMol), toluene (4.5 ml), at 130 o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (with petroleum ether as a developing agent) to obtain the yield of 75%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): δ 7.47 - 7.32 (m, 7H), 6.97 - 6.93 (m, 2H), 5.07 (s, 2H), 1.33 (s, 9H).
example ten: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 2-hydroxypyridine with toluene
2-Hydroxypyridine (47.6 mg, 0.5 mmol), catalyst (42 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 ml) were added sequentially to the reaction flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (with petroleum ether as a developing agent) to obtain the yield of 78%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): 7.35 - 7.26 (m, 6H), 6.63 - 6.57 (m, 1H), 6.12 (td, J = 6.7, 1.4 Hz, 1H), 5.13 (s, 2H).
example eleven: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 8-hydroxyquinoline with toluene
8-Hydroxyquinoline (72.6 mg, 0.5 mmol), catalyst (42 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 mL) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (with petroleum ether as a developing agent) to obtain the yield of 75%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), closed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 , TMS): 8.77 (dd, J = 4.2, 1.6 Hz, 1H), 8.12 (d, J= 1.6 Hz, 1H), 7.41 - 7.27 (m, 8H), 7.23 - 7.18 (m, 1H), 4.26 (s, 2H).
the iron catalyst was replaced with 20 mol% copper powder, and di-t-butyl peroxide was increased to 1.0 mmol, but the other conditions were unchanged, and the target product (trace) was not obtained.
Example twelve: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 2-hydroxybenzothiazoles with toluene
2-hydroxybenzothiazole (75.6 mg, 0.5 mmol), catalyst (42 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 mL) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 30 as a developing agent) to obtain the yield of 68%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 , TMS): δ 7.42 (dd, J = 7.7, 1.3 Hz, 1H), 7.35 - 7.18 (m, 6H), 7.15 - 7.10 (m, 1H), 6.95 (dd, J = 8.0, 1.2 Hz, 1H), 5.15 (s, 2H).
example thirteen: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-nitrophenol with ethylbenzene
4-Nitrophenol (69.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), toluene (4.5 mL) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 50 as a developing agent) to obtain the yield of 79 percent.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 ): δ 8.10 - 8.03 (m, 2H), 7.36 - 7.23 (m, 5H), 6.93 - 6.86 (m, 2H), 5.39 (q, J = 6.5 Hz, 1H), 1.67 (d, J = 6.4 Hz, 3H).
example fourteen: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling reaction of 4-nitrophenol and p-methoxytoluene
4-Nitrophenol (69.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), p-methoxytoluene (4.5 ml) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 20 as a developing agent) to obtain the yield of 96%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), closed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 ): δ 8.19 (d, J = 9.3 Hz, 2H), 7.35 (d, J = 8.7 Hz, 2H), 6.97 (dd, J = 31.0, 9.0 Hz, 4H), 5.08 (s, 2H), 3.82 (s, 3H).
example fifteen: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-nitrophenol with 3-fluorotoluene
4-Nitrophenol (69.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), 3-fluorotoluene (4.5 mL) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether of 1: 20 as a developing agent) to obtain the yield of 90%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 ): δ 8.26 - 8.15 (m, 2H), 7.41 - 7.34 (m, 1H), 7.17 (dd, J = 20.2, 8.5 Hz, 2H), 7.08 - 6.99 (m, 3H), 5.16 (s, 2H).
example sixteen: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-nitrophenol with 2-fluorotoluene
4-Nitrophenol (69.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), 2-fluorotoluene (4.5 mL) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 20 as a developing agent) to obtain the yield of 93 percent.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), closed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 ): δ 8.26 - 8.15 (m, 2H), 7.41 - 7.34 (m, 1H), 7.17 (dd, J = 20.2, 8.5 Hz, 2H), 7.08 - 6.99 (m, 3H), 5.16 (s, 2H).
example seventeen: [ ( t BuNCH=CHN t Bu)CH][FeBr 4 ]Catalyzed oxidative coupling of 4-nitrophenol with 4-bromotoluene
4-Nitrophenol (69.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140. Mu.l, 0.75 mmol), 4-bromotoluene (4.5 mL) were added sequentially to the flask at 130 deg.C o And C, reacting for 24 hours, cooling to room temperature after the reaction is finished, and purifying the product by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 50 as a developing agent) to obtain the yield of 91%.
The product was dissolved in CDCl 3 Medium (about 0.4 mL), sealed, characterized at room temperature on a Unity Inova-400 NMR apparatus: 1 H NMR (400 MHz, CDCl 3 ): δ8.21 - 8.10 (m, 2H), 7.46 (dd, J = 9.3, 2.5 Hz, 2H), 7.23 (d, J = 8.1 Hz, 2H), 7.00 - 6.89 (m, 2H), 5.03 (s, 2H).
the invention synthesizes the aryl benzyl ether compound by the oxidative coupling reaction of the phenolic compound and the toluene compound under the catalysis of the iron catalyst for the first time, has strong application prospect, and can provide a new method with atom economy and environmental friendliness for the synthesis of the compounds.
Claims (2)
1. The application of the iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesizing aryl benzyl ether compounds is characterized in that a phenol compound and a toluene compound are used as raw materials, the iron (III) complex containing 1,3-di-tert-butyl imidazole cations is used as a catalyst, and the reaction is carried out in the presence of an organic oxidant to obtain the aryl benzyl ether compounds;
the chemical structural formula of the iron (III) complex containing 1,3-di-tert-butylimidazole cation is as follows:
the chemical structural formula of the toluene compound is as follows:
r is hydrogen, methoxy, halogen; r 2 Hydrogen and methyl;
the phenolic compound is phenol, substituted phenol, hydroxypyridine, hydroxyquinoline or hydroxybenzothiazole; the substituted phenol is 4-nitrophenol, 4-trifluoromethylphenol, 4-acetoxyphenol, 2,6-dichlorophenol and 2-acetylphenol;
the reaction temperature is 90-140 ℃ and the reaction time is 15-40 hours; the mol ratio of the catalyst, the phenolic compound and the organic oxidant is (0.05-0.10) to 1 to (0.5-1.5);
the organic oxidant is di-tert-butyl peroxide.
2. The application of the iron (III) complex containing 1,3-di-tert-butylimidazole cations in synthesizing aryl benzyl ether compounds as claimed in claim 1, wherein the reaction is cooled to room temperature after the reaction is finished, and the product is purified by column chromatography to obtain the aryl benzyl ether compounds.
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| CN109320434A (en) * | 2018-10-22 | 2019-02-12 | 苏州大学 | Ionic iron (III) complex is preparing the application in benzyl aminated compounds as catalyst |
| WO2020087233A1 (en) * | 2018-10-29 | 2020-05-07 | 南通纺织丝绸产业技术研究院 | Application of ionic iron (iii) complex as catalyst in preparation of benzylamine compound |
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| CN109320434A (en) * | 2018-10-22 | 2019-02-12 | 苏州大学 | Ionic iron (III) complex is preparing the application in benzyl aminated compounds as catalyst |
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