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Method of preparing benzylamine compound

The technology of a compound and benzylamine is applied in the field of preparation of organic compounds, and achieves the effect of wide application range, being conducive to large-scale industrial synthesis application and improving applicability

Active Publication Date: 2019-01-18
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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  • Method of preparing benzylamine compound
  • Method of preparing benzylamine compound
  • Method of preparing benzylamine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment one: containing 1,3-di-tert-butylimidazolium cation (molecular formula is [( t BuNCHCHN t Bu)CH][FeBr 4 ]) Synthesis of ionic iron complexes

[0028] 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%.

[0029] The product is subjected to elemental analysis, and the results are as follows:

[0030] Elemental analysis

[0031]

C：（%）

H：（%）

N：（%）

theoretical value

23.73

3.80

5.03

actual value

23.88

3.89

5.14

[0032] This complex [( t BuNCHCHN t Bu)CH][FeBr 4 ] exists in the form of ion pairs, where [FeBr 4 ] - Characterize...

Embodiment 2

[0036] Embodiment two: [( t BuNCHCHN t Bu)CH][FeBr 4 ] Catalyzed reaction of p-cyanoaniline with toluene

[0037] 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%.

[0038] 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%.

[0039] 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

[0040] Embodiment three: [( t BuNCHCHN t Bu)CH][FeBr 4 ] Catalyzed reaction of p-cyanoaniline with p-tert-butyltoluene

[0041] 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 in the reaction flask in sequence (7 milliliters) 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%.

[0042] 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, 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 a method of preparing a benzylamine compound. The method comprises the following steps of by taking 1,3-di-tert-butylimidazolin cation contained ionic iron (III) complex with amolecular formula being [(RNCHCHNR)CH][FeBr4] (wherein R is a tertiary butyl group) as a catalyst and di-tert-butyl peroxide as an oxidizing agent, and performing oxidizing reaction on a methylbenzene / ethylbenzene compound and arylamine to synthesize the benzylamine compound. The method is wide in application range, is suitable for a methylbenzene compound containing benzyl-position primary carbon-hydrogen bonds and also suitable for an ethylbenzene compound containing benzyl-position secondary carbon-hydrogen bonds. The method is a first case that preparation of the benzylamine compound through oxidizing reaction of the methylbenzene / ethylbenzene compound and the arylamine is realized with an iron catalyst.

Description

technical field [0001] The invention belongs to the technical field of preparation of organic compounds, and in particular relates to a preparation method 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-hydrogen bonds has become a new method for the synthesis of ami...

Claims

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Application Information

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IPC IPC(8): C07C209/02C07C211/52C07C211/48C07C253/30C07C255/58C07C231/12C07C233/07C07D333/20B01J31/22
CPCB01J31/1815C07C209/02C07C211/48C07C211/52C07C231/12C07C233/07C07C253/30C07C255/58C07D333/20
Inventor 孙宏枚王丹李瑞鹏
Owner SUZHOU UNIV
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