Application of ionic iron (III) complex as catalyst in preparation of benzylamine compound

An ionic and compound technology, which is used in the preparation of amino compounds, organic compounds/hydrides/coordination complex catalysts, and organic compounds by condensation/addition reactions. It has a wide range of applications and is beneficial to large-scale industrial Synthetic applications, the effect of improving applicability

Active Publication Date: 2019-02-12
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, there are very few reports on oxidation reactions involving benzylic carbon-hydrogen bonds, and the published copper catalytic systems are only applicable to substrates containing benzylic secondary carbon-hydrogen bonds.
[0004] In the past ten years, iron-based catalysts have been rapidly developed due to their advantages of cheap and easy to obtain, low or non-toxic, and good biocompatibility. Literature Reports on Oxidation Reactions of Carbon-Hydrogen Bonds

Method used

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  • Application of ionic iron (III) complex as catalyst in preparation of benzylamine compound
  • Application of ionic iron (III) complex as catalyst in preparation of benzylamine compound
  • Application of ionic iron (III) complex as catalyst in preparation of benzylamine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment one: containing 1,3-di-tert-butylimidazolium cation (molecular formula is [( t BuNCHCHN t Bu)CH][FeBr 4 ]) Synthesis of ionic iron complexes

[0030] Add 1,3-di-tert-butylimidazolium bromide (0.26 g, 1.0 mmol) to a tetrahydrofuran solution of iron tribromide (0.27 g, 0.9 mmol), react at 60°C for 24 hours, and remove the solvent in vacuo , washed with hexane, drained, extracted with tetrahydrofuran, centrifuged to transfer the supernatant, added hexane to the supernatant for recrystallization, and reddish-brown crystals were precipitated at room temperature with a yield of 89%.

[0031] The product is subjected to elemental analysis, and the results are as follows:

[0032] Elemental analysis

[0033]

C：（%）

H：（%）

N：（%）

theoretical value

23.73

3.80

5.03

actual value

23.88

3.89

5.14

[0034] This complex [( t BuNCHCHN t Bu)CH][FeBr 4 ] exists in the form of ion pairs, where [FeBr 4 ] - Characterize...

Embodiment 2

[0038] Embodiment two: [( t BuNCHCHN t Bu)CH][FeBr 4 ] Catalyzed reaction of p-cyanoaniline with toluene

[0039] Add p-cyanoaniline (59 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (138 μl, 0.75 mmol) and toluene (7 ml) in turn in the reaction flask React at 120°C for 24 hours, cool to room temperature after the reaction, and purify the product by column chromatography (using a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:50 as the developing solvent), and the yield is 88%.

[0040] When the catalyst is ferric bromide (10mol%), the yield is only 8%; when the oxidant is tert-butyl hydroperoxide (1.5 times), the yield is only 22%.

[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): 7.38-7.28 (m, 7H), 6.58-6.55 (m, 2H), 4.73(s, 1H), 4.35 (s, 2H) ppm.

Embodiment 3

[0042] Embodiment three: [( t BuNCHCHN t Bu)CH][FeBr 4 ] Catalyzed reaction of p-cyanoaniline with p-tert-butyltoluene

[0043] Add p-cyanoaniline (59 mg, 0.5 mmol), catalyst (14 mg, 0.025 mmol), di-tert-butyl peroxide (138 μl, 0.75 mmol) and p-tert-butyltoluene to the reaction flask in sequence (7 ml) was reacted at 80°C for 60 hours, cooled to room temperature after the reaction, and the product was purified by column chromatography (using ethyl acetate / petroleum ether volume ratio of 1:50 mixed solvent as developing solvent), the yield 86%.

[0044] 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: 1H NMR (400 MHz, CDCl3, TMS): 7.45 (m, 4H), 7.32 (d, J = 7.9 Hz, 2H),6.69-6.60 (m, 2H), 4.65 (s, 1H), 4.39 (s, 2H), 1.38 (s, 9H) ppm.

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Abstract

The invention discloses the application of an ionic iron (III) complex as a catalyst in preparation of a benzylamine compound, that is, an ionic iron (III) complex having a formula of [(RNCHCHNR)CH][FeBr4] (R is tert-butyl) and containing 1,3-di-tert-butyl imidazolium cation is used as a catalyst, di-tert-butyl peroxide is used as an oxidizing agent, and a benzylamine compound is synthesized by oxidation reaction of a toluene/ethylbenzene compound with an aromatic amine. The application of an ionic iron (III) complex as a catalyst in preparation of a benzylamine compound has wide application range, and is applicable not only to a toluene compound containing a benzylic primary carbon-hydrogen bond but also to an ethylbenzene compound containing a benzyl secondary carbon-hydrogen bond. Thisis the first example of the preparation of a benzylamine compound by oxidation reaction of a toluene/ethylbenzene compound and an aromatic amine by an iron-based catalyst.

Description

technical field [0001] The invention belongs to the technical field of preparation of organic compounds, and in particular relates to the application of ionic iron (III) complexes as catalysts in the preparation of benzylamine compounds. Background technique [0002] As a key skeleton structure, benzylamine compounds widely exist in natural products, pesticides, polymers and drug molecules. The traditional synthesis of these compounds requires the use of prefunctionalized substrates, such as halogenated hydrocarbons, via Buchwald–Hartwig cross-coupling reactions (see: J. F. Hartwig, Acc. Chem. Res. , 2008, 41 , 1534). This method has disadvantages such as poor atom economy and the emission of halides that seriously pollute the environment. Therefore, the development of new methods for the synthesis of benzylamines has strong practical value. [0003] In recent years, the construction of carbon-nitrogen bonds through transition metal-catalyzed oxidation of carbon-hydrog...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/58C07D333/20C07C209/60C07C211/45C07C213/08C07C219/34C07C211/52B01J31/22
CPCB01J31/1815B01J2231/4277B01J2531/0213B01J2531/842C07C209/60C07C213/08C07C253/30C07D333/20C07C255/58C07C211/45C07C219/34C07C211/52
Inventor 孙宏枚李瑞鹏王丹
Owner SUZHOU UNIV
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