A kind of preparation method of β, γ-unsaturated ester compound

An ester compound, unsaturated technology, applied in the beta field, can solve the problems of long reaction time, unsuitable for industrial production and application, etc., and achieves the effects of low price, mild reaction conditions and high yield

Active Publication Date: 2019-06-18
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

This reaction is carried out under the condition of visible light, needs to use expensive photocatalyst terpyridyl ruthenium chloride, and the catalytic system also needs to be carried out under the condition of alkali and various organic additives, and the reaction time is too long, so it is not suitable for industrial production application ( See prior art document 2: Visible-LightPhotocatalytic Radical Alkenylation ofα-Carbonyl Alkyl Bromides and Benzyl Bromides, Chem.Eur.J.2013, 19, 5120-5126)

Method used

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  • A kind of preparation method of β, γ-unsaturated ester compound
  • A kind of preparation method of β, γ-unsaturated ester compound
  • A kind of preparation method of β, γ-unsaturated ester compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Into a dry 10 mL schlenk bottle were added 72.0 mg (0.4 mmol) of 1,1-diphenylethylene, 99.6 mg (0.6 mmol) of methyl 2-bromopropionate, 9.3 mg (0.04 mmol) of silver oxide, and tert-butyl peroxide. Alcohol 72.0 mg (0.8 mmol), triethylamine 80.8 mg (0.8 mmol), N,N-dimethylacetamide (2 mL), and the reaction flask was stirred at 80° C. under argon atmosphere for 24 h. After the completion of the reaction, the reaction solution was washed with saturated brine, extracted with ethyl acetate (3×10 mL), the organic phase was collected, and dried over anhydrous magnesium sulfate. The organic solvent was removed by rotary evaporation, and the residue was separated by silica gel column chromatography (petroleum ether / ethyl acetate) to obtain the target product (methyl 2-methyl-4,4-diphenylbut-3-enoate), yellow Oily liquid, 92% yield. 1 H NMR (400MHz, CDCl 3 ) δ: 7.40-7.32(m, 3H), 7.25-7.19(m, 7H), 6.12(d, J=10.4Hz, 1H), 3.67(s, 3H), 3.32-3.28(m, 1H), 1.27 (d, J=6.8Hz, 3H); 13 C ...

Embodiment 2

[0027] Into a dry 10 mL schlenk bottle were added 72.0 mg (0.4 mmol) of 1,1-diphenylethylene, 99.6 mg (0.6 mmol) of methyl 2-bromopropionate, 11 mg (0.04 mmol) of silver carbonate, and tert-butanol peroxide. 72.0 mg (0.8 mmol), 80.8 mg (0.8 mmol) of triethylamine, N,N-dimethylacetamide (2 mL), and the reaction flask was stirred at 80° C. under an argon atmosphere for 24 h. After the completion of the reaction, the reaction solution was washed with saturated brine, extracted with ethyl acetate (3×10 mL), the organic phase was collected, and dried over anhydrous magnesium sulfate. The organic solvent was removed by rotary evaporation, and the residue was separated by silica gel column chromatography (petroleum ether / ethyl acetate) to obtain the target product (methyl 2-methyl-4,4-diphenylbut-3-enoate) as the product rate 85%.

Embodiment 3

[0029] According to the method of Example 1, the difference is that 117 mg (0.8 mmol) of DTBP is added to replace the butanol in the peroxidation step to obtain the target product in a yield of 15%.

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Abstract

The invention discloses a preparation method of beta, gamma-unsaturated ester. A structural formula of the beta, gamma-unsaturated ester is shown in the description. The preparation method of the beta, gamma-unsaturated ester comprises the following steps: adding 1,1-diphenylethlene and 2-bromopropionate into a reaction system containing a silver catalyst, an oxidant, alkali and a solvent for reacting.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of a β, γ-unsaturated ester compound. Background technique [0002] β, γ-Unsaturated esters are an important class of organic synthesis intermediates. In recent years, chemists have been working on new methods for the synthesis of β, γ-unsaturated esters. [0003] In 2012, Lei Aiwen et al. reported a Heck-Type alkenylation reaction of α-carbonyl alkyl bromide catalyzed by nickel (see Equation 1). The reaction needs to be carried out under the conditions of tetrakistriphenylphosphine nickel as the catalyst, dppp as the ligand and potassium phosphate as the base. It has good substrate adaptability and yield, and a series of β, γ-unsaturated esters are synthesized. (See Prior Art Document 1: Nickel-Catalyzed Heck-Type Alkenylation of Secondary and Tertiary a-Carbonyl Alkyl Bromides, Angew. Chem. Int. Ed. 2012, 51, 3638-3641). [0004] [0005] ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/343C07C69/618
CPCC07C67/343C07C69/618
Inventor 黄会燕魏文廷朱文明应炜炜赵船丽杨晨光陈卫东
Owner NINGBO UNIV
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