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Beta-halogenated enamine acid ester compound and preparation method thereof

A technology of haloenaminoate esters and compounds, which is applied in the field of β-haloenaminoate ester compounds and its preparation, can solve the problems of insufficient active groups and functional application limitations, and achieve simple reaction conditions and high Synthetic availability, effects of good substrate suitability

Active Publication Date: 2020-07-17
JIANGSU UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although there are related methods to prepare enaminoate compounds, the preparation reaction usually requires the presence of expensive transition metal catalysts or at least two or more multi-step reactions to obtain the target product, and there are not enough active groups, so the functional application is limited. limit

Method used

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  • Beta-halogenated enamine acid ester compound and preparation method thereof
  • Beta-halogenated enamine acid ester compound and preparation method thereof
  • Beta-halogenated enamine acid ester compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Synthesis of β-bromoeninoate compound ethyl(Z)-2-bromo-3-(dipropylamino)acrylate

[0026]

[0027] A polytetrafluoroethylene magnet was placed in a dry 15 mL pressure-resistant tube, and then DMF (1 mL), ethyl propiolate (51 μL, 0.5 mmol) and di-n-propylamine (103 μL, 0.75 mmol) were sequentially added. After the reaction mixture was stirred at room temperature for 10 min, DABCO (112.12 mg, 1 mmol) and NBS (177.98 mg, 1 mmol) were added thereto. The reaction mixture was stirred at room temperature for 2 h, then quenched with 15 mL of saturated brine; then extracted with ethyl acetate (10 mL×3 times), the organic phases were combined, and dried over anhydrous sodium sulfate; Go out ethyl acetate, obtain crude product; This crude product is purified with neutral alumina chromatographic column, with V 石油醚 :V 乙酸乙酯 =10:1 as the developer, the pure product was obtained as light yellow oil with a yield of 81%.

[0028] Identification data of the product of thi...

Embodiment 2

[0030] Example 2: Synthesis of β-bromoeninoate compound ethyl(Z)-2-bromo-3-morpholinoacrylate

[0031]

[0032] A polytetrafluoroethylene magnet was placed in a dry 15 mL pressure-resistant tube, and then DMF (1 mL), ethyl propiolate (51 μL, 0.5 mmol) and morpholine (66 μL, 0.75 mmol) were sequentially added. After the reaction mixture was stirred at room temperature for 10 min, DABCO (112.12 mg, 1 mmol) and NBS (177.98 mg, 1 mmol) were added to the solution. The reaction mixture was stirred at 50° C. for 4 h, then quenched with 15 mL of saturated brine; then extracted with ethyl acetate (10 mL×3 times), and the organic phases were combined and dried over anhydrous sodium sulfate. Ethyl acetate was spun off using a rotary evaporator to obtain the crude product. This crude product is purified with neutral alumina chromatographic column, with V 石油醚 :V 乙酸乙酯 =4:1 was used as the developer, and the pure product was obtained as a white solid with a yield of 68%.

[0033] Iden...

Embodiment 3

[0035] Example 3: Synthesis of β-bromoenidinate compound ethyl(Z)-2-bromo-3-(pyrrolidin-1-yl)acrylate

[0036]

[0037]A polytetrafluoroethylene magnet was placed in a dry 15 mL pressure-resistant tube, and then DMF (1 mL), ethyl propiolate (51 μL, 0.5 mmol) and tetrahydropyrrole (66 μL, 0.75 mmol) were sequentially added. After the reaction mixture was stirred and reacted in an ice-water bath for 10 min, DABCO (112.12 mg, 1 mmol) and NBS (177.98 mg, 1 mmol) were further added thereto. The reaction mixture was stirred at 0° C. for 0.5 h, then quenched with 15 mL of saturated brine; then extracted with ethyl acetate (10 mL×3 times), and the organic phases were combined and dried over anhydrous sodium sulfate. Ethyl acetate was spun off using a rotary evaporator to obtain the crude product. This crude product is purified with neutral alumina chromatographic column, with V 石油醚 :V 乙酸乙酯 =10:1 as developing solvent, the pure product was obtained as pale yellow oil with a yield...

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PUM

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Abstract

The invention discloses a beta-halogenated enamine acid ester compound and a preparation method thereof. The structure of the beta-halogenated enamine acid ester compound is shown as a formula I whichis described in the specification. In the formula I, R1 and R2 are selected from alkyl groups, morpholine, pyrrole, benzyl groups and hydrogen; X is Br or Cl; and EWG is an electron withdrawing group. The preparation method comprises the following steps: sequentially mixing dimethylformamide, an alkyne-terminated compound and secondary amine or derivatives thereof, carrying out stirring, mixing and sufficient reacting, adding triethylene diamine and N-halogenated imide, carrying out stirring and sufficient reacting at 0-50 DEG C, performing quenching with saturated edible salt water, and allowing a quenched product to pass through a column for purification so as to obtain the beta-halogenated enamine acid ester compound. According to the method, the enamine acid ester compound with high activity is prepared by utilizing metal catalysis-free multi-component reactions, operation is simple and convenient, assembly efficiency is high, automation can be easily realized, and the used raw materials are cheap and easy to obtain; and the method has the advantages of simple, mild and green reaction conditions and good substrate applicability, and can realize high yield in virtue of most amino compounds (especially the secondary amine).

Description

technical field [0001] The invention belongs to the technical field of synthesis of pharmaceutical intermediates, and relates to a β-halogenated enaminoate compound and a preparation method thereof. Background technique [0002] Enamine compounds are an important class of synthetic intermediates in organic synthesis. Their biggest structural feature has multiple functional groups, and the structure contains two electron-deficient centers C 1 and C 3 , an electron-rich center C 2 The lone pair of electrons with the amino nitrogen atom, so this type of compound can react with both electrophiles and nucleophiles. In addition, its structure contains a double bond, so theoretically all reactions applicable to double bonds, such as radical addition, olefin metathesis, cycloaddition, epoxidation, hydrogenation, Michael addition, Sonogashira and Suzuki coupling etc., also apply to enamines. [0003] As the key structural unit of many bioactive molecules, enamines often appear in...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/04C07B39/00C07C227/08C07C227/16C07C229/30C07D295/145C07C315/04C07C317/28C07C221/00C07C225/16
CPCC07B43/04C07B39/00C07C227/08C07C227/16C07D295/145C07C315/04C07C221/00C07C229/30C07C317/28C07C225/16
Inventor 陈孝云袁书侠汤耀南孙晨阳陈妍陈凯伟陈光朱宝成
Owner JIANGSU UNIV OF SCI & TECH
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