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Polysubstituted 1,4-diene compound and preparation method thereof

A technology of compound and diene, which is applied in the field of multi-substitution, can solve the problems of poor tolerance of coupling products to substrate groups, delay of synthesis efficiency, inability to achieve high functionalization of diene skeleton, etc., and achieve high yield High, easy to obtain raw materials, good economical effect

Inactive Publication Date: 2019-09-27
NANJING UNIV OF TECH
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0003] The traditional method of synthesizing 1,4-diene compounds is mainly to obtain 1,4-diene compounds through cross-coupling of allyl compounds and alkenes or alkyne compounds under transition metal catalyzed conditions, but these methods are mostly It is used to synthesize internal 1,4-diene compounds, but it is powerless for the synthesis of terminal 1,4-diene compounds; moreover, using this method, the coupling products obtained are less tolerant to substrate groups , it is impossible to achieve a high degree of functionalization of the diene skeleton, and usually, the allyl compounds used are allyl compounds containing easier leaving groups obtained through conversion of allyl alcohol, which greatly delays the synthetic efficiency

Method used

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  • Polysubstituted 1,4-diene compound and preparation method thereof
  • Polysubstituted 1,4-diene compound and preparation method thereof
  • Polysubstituted 1,4-diene compound and preparation method thereof

Examples

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Embodiment 1

[0034] The synthesis of embodiment 11-phenylprop-2-en-1-alcohol

[0035] (1) Dissolve benzaldehyde in THF at -10°C, slowly add vinylmagnesium bromide Grignard reagent dropwise, stir at -10°C for 15 minutes, then continue stirring at room temperature for 4 to 8 hours to obtain a reaction mixture ; Wherein, the mol ratio of described benzaldehyde and vinylmagnesium bromide is 1:(1~2);

[0036] (2) Quenching the reaction with saturated ammonium chloride solution, extracting the reaction mixture, drying, and distilling off the solvent under reduced pressure, the residue was purified by silica gel chromatography with petroleum ether and ethyl acetate (PE / EA) to obtain a colorless Liquid 1-phenylprop-2-en-1-ol.

Embodiment 2

[0037] Synthesis of Example 21-phenyl-2-(triphenyl-λ5-phosphoryl)ethane-1-one

[0038] (1) Under reflux conditions, dissolve 2-bromoacetophenone and triphenylphosphine in THF, then continue to stir at reflux temperature for 6 to 12 hours to obtain a reaction mixture; wherein, the 2-bromoacetophenone The molar ratio with triphenylphosphine is 1:(1~1.5);

[0039] (2) Filter the above reaction mixture, wash the filter cake with ethyl acetate (EA), dissolve the filter cake with dichloromethane (DCM), add saturated sodium hydroxide solution, stir at room temperature for 30-60min, and use saturated Sodium chloride was separated into layers, the reaction mixture was extracted, dried, and the solvent was distilled off under reduced pressure to obtain 1-phenyl-2-(triphenyl-λ5-phosphoryl)ethan-1-one as a pale yellow solid.

Embodiment 3

[0041] (1) In a 10mL Shrek tube, under argon atmosphere, add 1-phenylprop-2-en-1-ol (0.36mmol), 2-(triphenyl-1,5-phosphorous) Ethyl acetate (0.3 mmol), barium bis(trifluoromethylsulfonyl)imide (5 mol%), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride dichloromethane The complex (3mol%) was stirred and reacted at 100°C in dimethyl sulfoxide (2mL), and the reaction equation was:

[0042]

[0043] (2) After the reaction was carried out for 48 hours, an aqueous formaldehyde solution (37%, 0.5 mL) was added to the reaction mixture, and the reaction was continued at room temperature for 12 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and saturated brine. After drying, the ethyl acetate was distilled off under reduced pressure, and petroleum ether and ethyl acetate (PE / EA=9: 1) The residue was purified to obtain yellow liquid (E)-2-methylene-5-phenylpent-4-enoic acid ethyl ester with a yield of 90%. Wherein, the proton...

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Abstract

The invention discloses a polysubstituted 1,4-diene compound and a preparation method thereof. The method comprises the following steps: adding an allyl alcohol raw material, phosphorus ylide with stable carbonyl / ester, barium bis(trifluoromethylsulfonyl)imide, and a 1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex into a reaction solvent in sequence, and performing a catalytic reaction for 46-50 h under argon atmosphere, the temperature of 98-102 DEG C and a stirring state; adding aldehyde into a reaction system, continuing to react for 11-13 h under room temperature, extracting for removing the reaction solvent in reaction liquid, and purifying to obtain the polysubstituted 1,4-diene compound. The method disclosed by the invention is wide in application range of substrates; a reaction by-product is only water; the method is environmentally friendly, simple in operation, non-toxic and harmless, easily-available in raw materials and high in yield, and has excellent economical efficiency; moreover, the polysubstituted 1,4-diene compound obtained by the method is an excellent chemical synthesis reagent and plays an important role in synthetic chemistry and drug synthesis.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a multi-substituted 1,4 diene compound and a preparation method thereof. Background technique [0002] 1,4-Diene compounds play an important role in organic synthesis. Due to their unique chemical, biological, and pharmaceutical activities, they are important structures in natural products and drug molecules, and are widely used in chemical synthesis and pharmaceutical science. It has unique anti-leukemic, antibiotic and anti-cancer properties. For example, vicenilactam, ripostatin, jerangolid and many fatty acid molecules contain this structure. [0003] The traditional method of synthesizing 1,4-diene compounds is mainly to obtain 1,4-diene compounds through cross-coupling of allyl compounds and alkenes or alkyne compounds under transition metal catalyzed conditions, but these methods are mostly It is used to synthesize internal 1,4-diene compou...

Claims

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Application Information

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IPC IPC(8): C07C69/618C07C67/343C07C45/71C07C49/563C07C49/796C07C49/813C07D213/55C07F7/08
CPCC07C69/618C07C49/563C07C49/796C07C49/813C07D213/55C07F7/081C07F7/083C07C2601/02C07B2200/09
Inventor 解沛忠付伟山罗德平
Owner NANJING UNIV OF TECH
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