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Synthesis method of benzoyl methylene malonate derivatives

A technology for the synthesis of benzoylmethylene malonate and its synthesis method, which is applied to the preparation of carboxylic acid esters, chemical instruments and methods, and the preparation of organic compounds. The effect of simplicity, cost reduction and simple process

Active Publication Date: 2017-01-11
ZHEJIANG UNIV OF TECH
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AI Technical Summary

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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  • Synthesis method of benzoyl methylene malonate derivatives
  • Synthesis method of benzoyl methylene malonate derivatives
  • Synthesis method of benzoyl methylene malonate derivatives

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030]

[0031] With 52.4mg (0.2mmol) 2-phenyl-1,1-dicarboxycyclopropane, 1.94mg (0.01mmol) AgBF 4 , 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, 83% 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] 55.2mg (0.2mmol) of 2-(4-methylphenyl)-1,1-diethoxycyclopropane, 3.88mg (0.02mmol) of AgBF 4 , 141.7mg (0.4mmol) Selectfluor, was added to a 10mL round bottom flask, and then 4mL of acetonitrile was added as a solvent. Next, magnetically stir at 70° C. for 20 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 the product, and the eluent evaporates the solvent to obtain product pure product ethyl 4-methylbenzoylmethylenemalonate. The material was a yellow liquid, 77% 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-dicarboxycyclopropane, 1.94mg (0.01mmol) of AgBF 4 , 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 110° 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 and the yield was 67%.

[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,...

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Abstract

The invention discloses a synthesis method of benzoyl methylene malonate derivatives as shown in a formula II. Diester-based cyclopropane compound shown in the formula I is used as a raw material, under the action of a silver catalyst, Selectfluor is taken as an oxidizing agent, and in an acetonitrile solvent, the reaction materials are stirred at 70-110 DEG C and allowed to react for 8-24 hours, and after the reaction, the reaction solution is subjected to post-treatment to prepare the benzoyl methylene malonate derivatives shown in the formula II. The synthesis method disclosed by the invention has the advantages of cheap and easily available raw materials, simple process, simplicity and convenience in operation, and being environment-friendly, high in yield, good in functional group universality and the like.

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 derivatives. [0003] (2) Background technology [0004] Methylene malonate is an important organic raw material containing a variety of active groups. Because it contains a variety of active groups, it can be used in the synthesis of raw materials in various fields, and is widely used in 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] Benzoylma...

Claims

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Application Information

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