Application of iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds

A technology of di-tert-butyl imidazolium and aryl benzyl ether, which is applied in the field of preparation of organic compounds to achieve good catalytic activity, clear structure, and good atom economy

Active Publication Date: 2021-04-23
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2013, the Patel research group used copper acetate hydrate as a catalyst and tert-butanol peroxide as an oxidant to try the oxidative coupling reaction of phenolic compounds and toluene compounds. The expected target product is aryl benzyl ether compounds , but the final product is a phenolic ester compound, the reason is that the intermediate aryl benzyl ether compound is unstable and rapidly oxidized to a phenolic ester compound (see: Saroj, K. R.; Srimanta G.; Arghya, B.; Anupal, G.; Nilufa, K.; Patel, B. K., Org. Lett.2013, 15,4106)
[0006] So far, there is no literature report on the construction of aryl benzyl ether compounds through the oxidative coupling reaction of phenolic compounds and toluene compounds catalyzed by iron-based catalysts

Method used

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  • Application of iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds
  • Application of iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds
  • Application of iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment one: containing 1,3-di-tert-butylimidazolium cation (molecular formula is [( t BuNCH=CHN t Bu)CH][FeBr 4 ]) synthesis of iron(III) complexes

[0030] 1,3-Di-tert-butyl imidazolium bromide (0.26 g, 1.0 mmol) was added to a THF solution of ferric tribromide (0.27 g, 0.9 mmol), 60 oC The reaction was carried out under vacuum for 24 hours, the solvent was removed in vacuo, washed with hexane, drained, extracted with tetrahydrofuran, and the supernatant liquid was transferred by centrifugation. Hexane was added to the supernatant liquid for recrystallization, and a reddish-brown solid powder was precipitated at room temperature, with a yield of 91%.

[0031] The chemical structural formula is as follows:

[0032]

[0033] Carry out elemental analysis to product, the result is as follows:

[0034]

[0035] Since the iron complex is paramagnetic, it was not characterized by NMR.

[0036] Complex [( t BuNCH=CHN t Bu)CH][FeBr 4 ] exists in the form of io...

Embodiment 2

[0039] Embodiment two: [( t BuNCH=CHN t Bu)CH][FeBr 4 ] catalyzed oxidative coupling reaction of 4-nitrophenol with toluene

[0040] Add 4-nitrophenol (69.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140 μl, 0.75 mmol), toluene (4.5 ml ), at 130 oC for 24 hours, after the reaction was cooled to room temperature, the product was purified by column chromatography (with a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:10 as the developing solvent), and the yield was 89%.

[0041] Dissolve the product in CDCl 3 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 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).

[0042] The product is p-nitrophenylbenzyl ether:

[0043]

[0044] The above-mentioned iron catalyst was replaced with 20 mol% copper powder, and other conditions were unchanged, and the target ...

Embodiment 3

[0045] Embodiment three: [( t BuNCH=CHN t Bu)CH][FeBr 4 ] catalyzed oxidative coupling reaction of 4-trifluoromethylphenol with toluene

[0046] Add 4-trifluoromethylphenol (81.05 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (140 microliters, 0.75 mmol) and toluene ( 4.5 ml) at 130 o The reaction was carried out at C for 24 hours, cooled to room temperature after the reaction, and the product was purified by column chromatography (petroleum ether was used as developing agent), and the yield was 86%.

[0047] Dissolve the product in CDCl 3 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 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).

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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 a method for synthesizing corresponding aryl benzyl ether compounds by taking di-tert-butyl peroxide as an oxidizing agent and carrying out oxidative coupling reaction on phenolic compounds and toluene compounds. According to the method, the iron (III) complex is used as the catalyst for the first time, and oxidative coupling of the phenolic compound and the toluene compound is realized. The method is the first oxidative coupling reaction of phenolic compounds and benzyl C(sp3)-H bonds, and a new method is provided for synthesizing aryl benzyl ether compounds. Compared with an existing synthesis method, the method provided by the invention avoids using toxic and polluting halogenated hydrocarbon and strong base, has better atom economy, and conforms to the development concept of green synthetic chemistry.

Description

technical field [0001] The invention belongs to the technical field of preparation of organic compounds, and in particular relates to the application of iron (III) complexes containing 1,3-di-tert-butylimidazolium cations in the synthesis of aryl benzyl ether compounds. Background technique [0002] As an important structural fragment, aryl benzyl ether widely exists in pharmaceutical molecules, and is also an important class of organic synthesis intermediates, which can be used in the synthesis of medicines, dyes, spices, etc. The traditional preparation method of such compounds is the Williamson synthesis method, which requires the use of toxic and polluting halogenated hydrocarbons and strong bases. Therefore, it is of great practical value to develop new methods with atom economy and green environmental friendliness to synthesize such compounds. Examples of drug molecules containing aryl benzyl ether structural fragments are as follows: [0003] [0004] In the past...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/04C07C41/01C07C43/174C07C43/205C07C45/64C07C49/84C07C67/29C07C69/157C07C201/12C07C205/37C07D215/26C07D277/68B01J31/22
CPCC07B41/04C07C201/12C07C67/29C07C41/01C07C45/64C07D215/26C07D277/68B01J31/1815B01J2531/842B01J2231/4288C07C205/37C07C69/157C07C43/1742C07C49/84C07C43/205
Inventor 孙宏枚宋艳玲
Owner SUZHOU UNIV
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