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Method for synthesizing benzoyl methylene malonic ester compound

A technology of benzoylmethylene malonate and synthesis method, which is applied to the preparation of organic compounds, chemical instruments and methods, and preparation of carboxylate, can solve the problems of difficult synthesis and industrial application limitations, and achieve Easy operation, low cost, cheap and easy-to-obtain catalyst

Active Publication Date: 2017-01-25
ZHEJIANG UNIV OF TECH
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Problems solved by technology

There is only one example of the synthetic method of benzoylmalonate compounds that can still be retrieved at present, and the target product is synthesized with 2-phenyl-3-nitro-1-1-diesteryl cyclopropane as raw material, but This method is very difficult to synthesize raw materials, and has great restrictions on the industrial application of benzoylmalonate compounds (see Thangavel Selvi et al. J.Org.Chem.2014,79,3653-3658)

Method used

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  • Method for synthesizing benzoyl methylene malonic ester compound
  • Method for synthesizing benzoyl methylene malonic ester compound
  • Method for synthesizing benzoyl methylene malonic ester compound

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Experimental program
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Effect test

Embodiment 1

[0030]

[0031] With 52.4mg (0.2mmol) 2-phenyl-1,1-dicarboxycyclopropane, 1.63mg (0.01mmol) FeCl 3 , 141.7mg (0.4mmol) Selectfluor, was added to a 10mL round bottom flask, and then 4mL of acetonitrile was added as a solvent. Then, magnetically stir at 80° C. for 12 h. Then, 1g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. : 1) as eluent, collect the eluent that contains product, and eluent evaporates solvent and obtains product pure product benzoylmethylenemalonate ethyl ester. The material was a yellow liquid in 79% yield.

[0032] Characterization data: 1 H NMR (CDCl 3 , 400MHz): δ7.96(d, J=8.5Hz, 2H), 7.84(s, 1H), 7.64-7.61(m, 1H), 7.54-7.49(m, 2H), 4.37-4.27(m, 4H ), 1.35(t, J=7.0Hz, 3H), 1.26(t, J=7.0Hz, 3H); 13 CNMR (100MHz, CDCl 3 ): δ189.3, 164.5, 162.9, 136.6, 136.2, 135.3, 134.2, 129.0, 128.9, 62.5, 62.0, 14.1, 13.7.

Embodiment 2

[0034]

[0035] 55.2 mg (0.2 mmol) of 2-(4-methylphenyl)-1,1-dicarboethoxycyclopropane, 3.25 mg (0.02 mmol) of FeCl 3 , 141.7mg (0.4mmol) Selectfluor, was added to a 10mL round bottom flask, and then 4mL of acetonitrile was added as a solvent. Then, magnetic stirring was performed at 70° C. for 16 h. Then, 1g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. : 1) as eluent, collect the eluent containing product, the eluent evaporates solvent to obtain product pure product ethyl 4-methylbenzoylmethylenemalonate. The material was a yellow liquid, 73% yield.

[0036] Characterization data: 1 H NMR (CDCl 3 , 400MHz): δ7.87-7.83(m, 3H), 7.30(d, J=8.0Hz, 2H), 4.37-4.25(m, 4H), 2.43(s, 3H), 1.35(t, J=7.2 Hz, 3H), 1.26(t, J=7.0Hz, 3H); 13 C NMR (100MHz, CDCl 3 ): δ188.8, 164.6, 163.1, 145.5, 136.2, 135.6, 133.7, 129.7, 129.0, 62.4, 61.9, 21.8, 14.0, 13.8.

Embodiment 3

[0038]

[0039] 67.2mg (0.2mmol) of 2-(3,4-dimethoxyphenyl)-1,1-diethylcarboxycyclopropane, 1.63mg (0.01mmol) of FeCl 3 , 70.8mg (0.2mmol) Selectfluor, was added to a 10mL round bottom flask, and then 3mL of acetonitrile was added as a solvent. Then, magnetic stirring was performed at 90° C. for 12 h. Then, 1g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. : 1) As an eluent, collect the eluent containing the product, and the eluent is evaporated to remove the solvent to obtain the pure product 3,4-dimethoxybenzoylmethylenemalonate ethyl ester. The material was a yellow liquid, 57% yield.

[0040] Characterization data: 1 H NMR (CDCl 3 , 400MHz): δ7.85(s, 1H), 7.61(d, J=10.4Hz, 1H), 7.55(s, 1H), 6.93(d, J=8.4Hz, 1H), 4.37-4.29(m, 4H), 3.98(s, 3H), 3.94(s, 3H), 1.37(t, J=7.2Hz, 3H), 1.28(t, J=7.0Hz, 3H); 13 C NMR (100MHz, CDCl3): δ187.4, 164.8, 163.1, 154.5, 149.7, ...

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Abstract

The invention discloses a method for synthesizing a benzoyl methylene malonic ester compound of a formula II as shown in the description. The method comprises the following steps: by taking a diester cyclopropane compound of a formula I as shown in the description as a raw material, under the action of an iron catalyst, by taking Selectfluor as an oxidant, in the presence of an acetonitrile solvent, performing stirring reaction for 8-16 hours at 70-90 DEG C, and after the reaction is completed, performing aftertreatment on a reaction liquid to obtain the benzoyl methylene malonic ester compound of the formula II as shown in the description. The method disclosed by the invention has the advantages that the raw materials are low in price and easily accessible, the process is simple, the operation is simple and convenient, environmental friendliness is achieved, the yield is high, and the functional group universality is good.

Description

[0001] (1) Technical field [0002] The invention belongs to the technical field of organic compound synthesis, and in particular relates to a synthesis method of benzoylmethylene malonate compounds. [0003] (2) Background technology [0004] Methylene malonate is an important organic raw material containing a variety of active groups. Due to its various active groups, it is widely used in the fields of medicine, pesticides, dyes and other fields. Among them, diethyl ethoxymethylene malonate is an important intermediate for the preparation of heterocyclic compounds. It can be used as a raw material to synthesize pyrazole, pyrimidine, isoxazole, quinoline and other substances, and has good application value; 1-1 methylene malonate is a new type of surfactant copolymer benzylidene malonate is a UV absorber. In a word, the synthesis of methylene malonate compounds has great research value. [0005] Benzoylmalonate compounds also have important research significance because of t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/313C07C69/738
CPCC07C67/313C07C69/738
Inventor 刘运奎汪衡张剑
Owner ZHEJIANG UNIV OF TECH
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