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A kind of copper catalyzed method for synthesizing β-keto ester

A ketoester, copper-catalyzed technology, applied in the field of synthetic chemistry, can solve the problems of unstable diketene, harsh reaction conditions, complex products, etc., and achieve the effects of good substrate universality, mild reaction conditions, and wide substrate range.

Active Publication Date: 2022-05-31
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, the Claisen ester condensation method is in the presence of a strong base such as sodium alkoxide, a nucleophilic addition reaction occurs between an ester that removes α-H and the carbonyl of another molecule of ester, and then removes an alkoxy group to generate a β-keto acid Esters, due to the existence of cross-condensation, make the product complex and the yield is low; diketene alcoholization method uses diketene and corresponding alcohols as raw materials to prepare β-ketoesters, and the diketene used is unstable at room temperature and difficult to store; Michael synthesized The method needs to treat ethyl acetate with n-butyllithium at -78°C and then react with the corresponding acid chloride. The reaction conditions are harsh and the reagents are expensive.

Method used

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  • A kind of copper catalyzed method for synthesizing β-keto ester
  • A kind of copper catalyzed method for synthesizing β-keto ester
  • A kind of copper catalyzed method for synthesizing β-keto ester

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023]

[0024] Into the reaction tube were sequentially added ethyl benzoyl acetate (1.0 mmol), benzyl chloride (1.0 mmol), catalyst CuI (0.05 mmol), K 2 CO 3 (0.06 mmol), then 2 mL of solvent toluene was added, and the reaction was carried out at 60° C. for 12 hours. After the reaction, the reaction solution was concentrated, and the corresponding product was obtained by column chromatography, and the isolated yield was 87%. 1 H NMR (400MHz, CDCl 3 )δ: 1.21(t, J=7.5Hz, 3H), 2.73(dd, J=5.0, 17.0Hz, 1H), 3.38(q, J=10.0Hz, 1H), 4.11(q, J=7.5Hz, 2H), 5.11(q, J=5.0Hz, 1H), 7.21~7.25(m, 1H), 7.17(d, J=4.5Hz, 4H), 7.38~7.41(m, 2H), 7.49(tt, J =1.5,7.5Hz,1H),7.98~8.00(m,2H).

Embodiment 2

[0026]

[0027] Into the reaction tube were sequentially added ethyl benzoyl acetate (1.0 mmol), 4-methylbenzyl chloride (1.2 mmol), catalyst CuI (0.05 mmol), Cs 2 CO 3 (0.08 mmol), then 2 mL of solvent toluene was added, and the reaction was carried out at 80° C. for 16 hours. After the reaction, the reaction solution was concentrated, and the corresponding product was obtained by column chromatography, and the isolated yield was 89%. 1 H NMR (400MHz, CDCl 3 )δ: 1.21(t, J=7.0Hz, 3H), 2.29(s, 3H), 2.71(dd, J=5.0, 17.0Hz, 1H), 3.36(dd, J=10.0, 17.0Hz, 1H), 4.11(q,J=7.0Hz,2H),5.07(q,J=5.0,10.0Hz,1H),7.10(d,J=8.0Hz,2H),7.19(d,J=8.0Hz,2H), 7.39 (t, J=7.5Hz, 2H), 7.39 (t, J=7.5Hz, 1H), 7.98 (d, J=7.0Hz, 2H).

Embodiment 3

[0029]

[0030] Into the reaction tube were sequentially added ethyl benzoyl acetate (1.0 mmol), 4-cyanobenzyl bromide (1.2 mmol), catalyst cuprous iodide CuI (0.05 mmol), Cs 2 CO 3 (0.10 mmol), then 2 mL of solvent toluene was added, and the reaction was carried out at 90° C. for 18 hours. After the reaction was completed, the reaction solution was concentrated, and the corresponding product was obtained by column chromatography. The isolated yield was 93%. 1 H NMR (400MHz, CDCl 3 )δ: 1.21 (t, J=7.1Hz, 3H), 2.74 (dd, J=5.5, 17.0Hz, 1H), 3.70 (dd, J=9.3, 17.0Hz, 1H), 4.11 (q, J=7.2 Hz,2H),5.18(dd,J=5.5,9.3Hz,1H),7.42~7.46(m,4H),7.54(t,J=7.4Hz,1H),7.60~7.61(m,2H),7.94 ~7.96 (m, 2H).

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Abstract

The invention relates to a copper-catalyzed method for synthesizing β-ketoester. The method comprises: dissolving ethyl acyl acetate and halogenated hydrocarbon in an organic solvent, adding a copper catalyst and alkali, and reacting at 60-90°C After 12-18 hours, the β-keto ester was obtained through separation and purification. Compared with the prior art, the synthesis process of the present invention is simple and green, has excellent selectivity and higher yield, and has a wide range of substrates, and has wide application value in the fields of biology and medicinal chemical industry.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and relates to a copper-catalyzed method for synthesizing beta-ketoester. Background technique [0002] β-ketoesters are important and widely used intermediates in organic synthesis. They are widely used in the synthesis of heterocycles and ketones, and play an important role in agriculture, pharmacy, dyeing industry and supramolecular self-assembly research. The typical synthetic studies of β-ketoesters include Claisen ester condensation method, diketene alcoholation method and Michael synthesis method. Among them, in the Claisen ester condensation method, in the presence of a strong base such as sodium alkoxide, one molecule of the ester from which α-H has been removed undergoes a nucleophilic addition reaction with the carbonyl group of another molecule of ester, and then the alkoxy group is removed to form a β-keto acid. Esters, due to the existence of cross-condensation, make th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/343C07C69/738C07C253/30C07C255/57C07C227/10C07C229/42
CPCC07C67/343C07C253/30C07C227/10C07C69/738C07C255/57C07C229/42Y02P20/584
Inventor 姚子健靳永旭樊晓楠云雪静高永红邓维
Owner SHANGHAI INST OF TECH
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