阅读说明：本技术 含1,3-二叔丁基咪唑阳离子的铁（iii）配合物在合成芳基苄基醚类化合物中的应用 (Application of iron (III) complex containing 1, 3-di-tert-butylimidazole cation in synthesis of aryl benzyl ether compounds ) 是由 孙宏枚 宋艳玲 于 2021-01-22 设计创作，主要内容包括：本发明公开了含1,3-二叔丁基咪唑阳离子的铁(III)配合物在合成芳基苄基醚类化合物中的应用,具体以过氧化二叔丁基为氧化剂,通过酚类化合物与甲苯类化合物的氧化偶联反应来合成相应的芳基苄基醚类化合物。本发明首次以铁(III)配合物为催化剂,实现了酚类化合物与甲苯类化合物的氧化偶联。这是首例酚类化合物与苄位C(sp～3)-H键的氧化偶联反应,为合成芳基苄基醚类化合物提供了一种新方法。相对于现有合成方法,本发明避免使用有毒和污染性的卤代烃以及强碱,具有更好的原子经济性,符合绿色合成化学的发展理念。(The invention discloses 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 using 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.)

1. The application of the iron (III) complex containing 1, 3-di-tert-butyl imidazole cation in synthesizing aryl benzyl ether compounds; the chemical structural formula of the 1, 3-di-tert-butyl imidazole cation-containing iron (III) complex is as follows:

。

2. the application of the iron (III) complex containing 1, 3-di-tert-butylimidazolium cations in synthesizing aryl benzyl ether compounds according to claim 1, which 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-butylimidazolium cations is used as a catalyst, and the aryl benzyl ether compounds are obtained by reaction in the presence of an organic oxidant.

3. The use of the iron (III) complex containing 1, 3-di-tert-butylimidazolium cation according to claim 2 for the synthesis of aryl benzyl ether compounds, wherein the reaction temperature is 90-140 ℃ and the reaction time is 15-40 hours.

4. The application of the iron (III) complex containing 1, 3-di-tert-butylimidazole cations in synthesizing aryl benzyl ether compounds according to claim 2, wherein the molar ratio of the catalyst to the phenolic compound to the organic oxidant is (0.05-0.10) to 1 to (0.5-1.5).

5. The application of the iron (III) complex containing 1, 3-di-tert-butylimidazole cations in synthesizing aryl benzyl ether compounds according to claim 2, 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.

6. The use of the iron (III) complex containing 1, 3-di-tert-butylimidazolium cation according to claim 2 for the synthesis of aryl benzyl ether compounds, wherein the toluene compounds have the following chemical formula:

r is hydrogen, methoxy, halogen; r²Hydrogen and methyl.

7. The application of the 1, 3-di-tert-butylimidazolium cation iron (III) -containing complex in synthesizing aryl benzyl ether compounds according to claim 2, wherein the phenolic compound is phenol, substituted phenol, hydroxypyridine, hydroxyquinoline or hydroxybenzothiazole.

8. The use of the iron (III) complex containing 1, 3-di-tert-butylimidazolium cation according to claim 7 for the synthesis of arylbenzyl ether compounds, wherein the substituted phenol has the following chemical formula:

R¹is nitro, trifluoromethyl, acetoxy, halogen or acetyl.

9. The use of the iron (III) complex containing 1, 3-di-tert-butylimidazolium cation according to claim 8 for the synthesis of aryl benzyl ether compounds, wherein the substituted phenol is 4-nitrophenol, 4-trifluoromethylphenol, 4-acetoxyphenol, 2, 6-dichlorophenol, 2-acetylphenol.

10. The use of the iron (III) complex containing 1, 3-di-tert-butylimidazolium cation according to claim 2 for the synthesis of aryl benzyl ether compounds, wherein the organic oxidant is an organic peroxide.

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-butylimidazolium 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 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, relate toConstruction of C (sp) by oxidative coupling reaction involving less acidic phenolic compounds³) 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 first realized that phenolic compounds were ortho-positioned to the oxygen atom by C (sp)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 is one of the most abundant metals on the earth, and has the advantages of low price, easy obtainment, good biocompatibility and the like. At present, phenolic compounds and C (sp) related to iron-based catalysts³) The oxidative coupling reaction of-H bond is only one example. Wu Yongchang subject group in 2014 with Fe₂(CO)₉Is 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 realized³-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 [ ()^tBuNCH=CHN^tBu)CH][FeBr₄]The iron (III) complex containing 1, 3-di-tert-butyl imidazole cation is used as a catalyst, di-tert-butyl peroxide is used as an oxidant, and the catalyst is prepared by reacting a phenolic compound withThe corresponding aryl benzyl ether compound is synthesized by the oxidative coupling reaction of the toluene compound. [(^tBuNCH=CHN^tBu)CH][FeBr₄]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, halogen;

R²hydrogen 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:

R¹the 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-Methyl phenol, 4-tert-butyl phenol.

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 110-130 ℃ and the reaction time is 20-30 hours.

In the technical scheme, after the reaction is finished, the reaction product is cooled to room temperature, the product is purified by column chromatography, and the aryl benzyl ether compound is obtained by taking a mixed solvent of ethyl acetate and petroleum ether in volume ratio as a developing agent.

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 [ () (^tBuNCH=CHN^tBu)CH][FeBr₄]) 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% ^oCThe 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 [ () (^tBuNCH=CHN^tBu)CH][FeBr₄]In the form of ion pairs, in which [ FeBr ]₄]^-It was characterized by Raman spectroscopy and was found to be at 204 cm^-1Characteristic 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))^tBuNCH=CHN^tBu)CH]⁺The molecular ion peak is observed at 181.1699, theoretically 181.1699, and is consistent with theory.

The obtained compound was confirmed to be the objective compound.

Example two: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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.C^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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 ^oCThe 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]Catalyzed oxidative coupling of 2, 6-dichlorophenol with 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. mu.l ^oCThe 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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 ^oCAnd (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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]Catalyzed oxidative coupling of phenol with toluene

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) were added sequentially to the reaction flask at 130. mu.l ^oCThe 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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)₂Otherwise, the target product (trace) was not obtained.

Example eight: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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 were added to the flask in this order(4.5 ml) at 130^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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-t-butyl peroxide (140. mu.l, 0.75 mmol), toluene (4.5 ml) were added sequentially to the flask at 130 deg.C^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, TMS): δ 7.47 - 7.32 (m, 7H), 6.97 - 6.93 (m, 2H), 5.07 (s, 2H), 1.33 (s, 9H).

example ten: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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 reaction flask at 130 deg.C^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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 reaction flask at 130. mu.l^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃, 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃): 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃): 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]Catalytic 4-nitro groupOxidative coupling reaction of phenol and 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^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃): 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃): 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: [(^tBuNCH=CHN^tBu)CH][FeBr₄]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.M, M) were added to the flask in that orderL, 0.75 mmol), 4-bromotoluene (4.5 ml) at 130^oAnd 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 CDCl₃Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:¹H NMR (400 MHz, CDCl₃): 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.