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A kind of method of synthesizing cyanomethyl carboxylate

A technology for synthesizing cyanomethyl carboxylate and cyanomethyl carboxylate is applied in the preparation of carboxylic acid nitrile, chemical instruments and methods, preparation of organic compounds, etc., and can solve the problems of large amount of catalyst and insufficient atom economy. , to achieve the effect of single component, favorable for large-scale industrial synthesis application and good catalytic activity

Active Publication Date: 2019-05-17
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The existing reaction realizes direct esterification by decarboxylation of α-cyanoacetic acid, but this method is not atom-economical enough, and the amount of catalyst is also relatively large
So far, there are no literature reports involving the esterification of acetonitrile carbon-hydrogen bonds catalyzed by iron-based catalysts

Method used

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  • A kind of method of synthesizing cyanomethyl carboxylate
  • A kind of method of synthesizing cyanomethyl carboxylate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] 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

[0024] 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 vacuo, washed with hexane, drained, extracted with tetrahydrofuran, centrifuged to transfer the supernatant, added hexane to the supernatant for recrystallization, reddish-brown crystals were precipitated at room temperature, and the yield was 90% .

[0025] The chemical structural formula is as follows:

[0026]

[0027] Carry out elemental analysis to product, the result is as follows:

[0028] Elemental analysis

[0029]

C：（%）

H：（%）

N：（%）

theoretical value

23.64

4.15

5.01

actual value

23.88

4.31

5.34

[0030] This comp...

Embodiment 2

[0032] Embodiment two: [( t BuNCH 2 CH 2 N t Bu)CH][FeBr 4 ] Catalyzed esterification of benzoic acid with acetonitrile

[0033] Add benzoic acid (61.1 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232 microliters, 1.25 mmol) and acetonitrile (10 milliliters) successively in the reaction flask. React at 110°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 with a volume ratio of 1:20 as the developing solvent), and the yield is 80%.

[0034] Add benzoic acid (61.1 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (186 microliters, 1 mmol) and acetonitrile (10 milliliters) to the reaction flask successively. React at 110°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 with a volume ratio of 1:20 as the deve...

Embodiment 3

[0036] Embodiment three: [( t BuNCH 2 CH 2 N t Bu)CH][FeBr 4 ] Catalyzed esterification of 4-methoxybenzoic acid with acetonitrile

[0037] Add 4-methoxybenzoic acid (76.1 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232 μl, 1.25 mmol) and acetonitrile ( 10 ml), reacted at 100°C for 30 hours, cooled to room temperature after the reaction, and purified the product by column chromatography (using a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:5 as the developing solvent), the yield 85%.

[0038] Add 4-methoxybenzoic acid (76.1 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (278 μl, 1.5 mmol) and acetonitrile ( 10 ml), reacted at 100°C for 30 hours, cooled to room temperature after the reaction, and purified the product by column chromatography (using a mixed solvent of ethyl acetate / petroleum ether volume ratio of 1:5 as the developing solvent), the yield 84%.

[0039] Dissolve the product in CDCl 3 Medium (...

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Abstract

The invention discloses a method for synthesizing cyanomethyl carboxylate, which is [( t BuNCH 2 CH 2 N t Bu)CH][FeBr 4 ]’s ionic iron(III) complex containing 1,3-di-tert-butyl imidazolinium cation as a catalyst, using di-tert-butyl peroxide as an oxidant, to synthesize carboxylic acid by oxidative coupling reaction of carboxylic acid and acetonitrile Cyanomethyl esters. Carboxylic acid substrates suitable for use in the present invention relate to aliphatic carboxylic acids, aromatic carboxylic acids and heterocyclic carboxylic acids. This is the first example of preparing cyanomethyl carboxylate through the oxidative coupling reaction of carboxylic acid and acetonitrile realized by 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 cyanomethyl carboxylate. Background technique [0002] Cyanomethyl carboxylate exists in many natural products and drug molecules, and is also widely used in organic synthesis. Traditional methods for synthesizing such compounds require the use of pre-functionalized halides, such as chloroacetonitrile, etc. This method It is not atom-economical enough, and often needs to emit chemically polluted halides, so the development of a new method for the synthesis of cyanomethyl carboxylate has strong practical application value. [0003] In recent years, direct esterification of carbon-hydrogen bonds has gradually become a new method for the synthesis of carboxylic acid esters. Among them, it has been reported that the direct esterification reaction of the carbon-hydrogen bond at the ortho position of the oxygen atom, the ben...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C253/30C07C255/14B01J31/22
CPCB01J31/0284B01J31/1815B01J2231/49B01J2531/0213B01J2531/842C07C253/30C07C255/14
Inventor 孙宏枚
Owner SUZHOU UNIV
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