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Method for preparing allylamine compounds

An allylamine and compound technology, applied in the field of preparation of organic compounds, can solve problems such as narrow application range of substrates, and achieve the effects of clear catalyst structure, wide application range and easy air

Active Publication Date: 2018-04-20
东营悦来湖园区运营管理有限公司
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  • Claims
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Problems solved by technology

[0003] In recent years, the direct amination reaction of carbon-hydrogen bonds to construct carbon-nitrogen bonds has become a new method for the synthesis of amine compounds, which avoids the use of halogenated hydrocarbons and has better atom economy and environmental friendliness. properties, the catalysts used in the prior art are β -Diimino copper (I) complexes, tetrabutylammonium iodide, but these methods have certain limitations, mainly because the scope of application of the substrate is narrow, only suitable for aromatics containing electron-withdrawing groups amines, and for aromatic amines containing electron-donating groups, it is impossible to carry out
[0004] In the past ten years, iron-based catalysts have been rapidly developed due to their advantages such as cheap and easy to obtain, low or non-toxic, and good biocompatibility, but so far, no iron-based catalysts have been used in aromatic amines and Application Report of Oxidative Coupling Reaction of Allyl Hydrocarbons to Synthesis of Allylamines

Method used

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  • Method for preparing allylamine compounds

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Experimental program
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Effect test

Embodiment 1

[0028] Embodiment one: containing 1,3-di-tert-butyl imidazolinium cation (molecular formula is [( t BuNCH 2 CH 2 N t Bu)CH][FeBr 4 ]) Synthesis of ionic iron complexes

[0029] Add 1,3-di-tert-butylimidazolinium chloride (0.22 g, 1.0 mmol) and NaBr (0.15 g, 1.5 mmol) sequentially to a solution of ferric tribromide (0.29 g, 1.0 mmol) in THF , reacted at 60 ° C for 24 hours, removed the solvent in vacuum, washed with hexane, drained, extracted with tetrahydrofuran, transferred the supernatant by centrifugation, added hexane to the supernatant for recrystallization, and precipitated reddish-brown crystals at room temperature with a yield of 90 %.

[0030] Carry out elemental analysis to product, the result is as follows:

[0031] Elemental analysis

[0032]

C：（%）

H：（%）

N：（%）

theoretical value

23.64

4.15

5.01

actual value

23.88

4.31

5.34

[0033] This complex [( t BuNCH 2 CH 2 N t Bu)CH][FeBr 4 ] exists in the for...

Embodiment 2

[0037] Embodiment two: [( t BuNCH 2 CH 2 N t Bu)CH][FeBr 4 ] catalyzed oxidative coupling reaction of aniline with cyclohexene

[0038] Add aniline (46 μl, 0.5 mmol), catalyst (14 mg, 0.025 mmol), di-tert-butyl peroxide (138 μl, 0.75 mmol) and cyclohexene (2 ml) to the reaction flask in sequence , ethyl acetate (0.5 ml) was reacted at 130°C for 24 hours, cooled to room temperature after the reaction, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:50 as the developing solvent ), with a yield of 95%.

[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): 7.10-7.06 (m, 2H), 6.61-6.57 (m, 1H), 6.54-6.51 (m, 2H), 5.77-5.74 (m, 1H), 5.68-5.65 (m, 1H), 3.90 (s, 1H), 3.51 (s, 1H), 1.95-1.93 (m, 2H), 1.84-1.79 (m, 1H), 1.67-1.52 (m, 3H).

Embodiment 3

[0040] Embodiment three: [( t BuNCH 2 CH 2 N t Bu)CH][FeBr 4] catalyzed oxidative coupling reaction of p-methylaniline with cyclohexene

[0041] In the reaction flask, add p-methylaniline (54 mg, 0.5 mmol), catalyst (14 mg, 0.025 mmol), di-tert-butyl peroxide (138 microliters, 0.75 mmol), cyclohexene (2 ml), ethyl acetate (0.5 ml) was reacted at 120°C for 28 hours, cooled to room temperature after the reaction, and the product was purified by column chromatography, (with a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:20 For developing agent), the yield was 83%.

[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, CDCl 3 , TMS): 6.89 (d, J = 8.1 Hz, 2H), 6.46 (d, J = 8.4Hz, 2H), 5.76-5.72 (m, 1H), 5.69-5.64 (m, 1H), 3.87 (s, 1H), 3.26 (s, 1H),2.15 (s, 3H), 1.94-1.92 ( m, 2H), 1.81-1.78 (m, 1H), 1.66-1.50 (m, 3H).

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Abstract

The invention discloses a method for preparing allylamine compounds. The allylamine compounds are synthesized by taking an ionic iron (III) complex which has a molecular formula of [(RNCH2CH2NR)CH][FeBr4] (R is tert-butyl) and contains 1,3-di-tert-butyl imidazoline cation as a catalyst, taking di-tert-butyl peroxide as an oxidant and carrying out oxidative coupling reaction on amine compounds andallyl hydrocarbon compounds. The method disclosed by the invention has wide application range, can be used for aromatic amine containing an electron-withdrawing group, is effective for aromatic aminecontaining an electron-donating group, and is a first case of preparing the allylamine compounds through the oxidative coupling reaction of the amine compounds and the allyl hydrocarbon compounds, which is realized 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 a preparation method of allylamine compounds. Background technique [0002] As a key skeleton structure, allylamine 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 halohydrocarbons, via Buchwald–Hartwig cross-coupling reactions (see: J. F. Hartwig, Acc. Chem. Res. , 2008, 41, 1534). This method requires the discharge of halides that seriously pollute the environment, and has many steps and poor atom economy. Therefore, the development of more environmentally friendly and efficient synthetic methods has strong practical application value. [0003] In recent years, the direct amination reaction of carbon-hydrogen bonds to construct carbon-nitrogen bonds has become a new method for the synthesis of amine...

Claims

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Application Information

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IPC IPC(8): C07C209/02C07C211/45C07C211/52C07C253/30C07C255/58C07C221/00C07C225/22B01J31/22
CPCC07C209/02B01J31/0284B01J31/16C07C2601/16C07C211/48
Inventor 孙宏枚周巧云
Owner 东营悦来湖园区运营管理有限公司
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