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Tetra-substituted olefin and preparation method thereof

A tetra-substituted, alkene technology, applied in the preparation of carboxylate, chemical instruments and methods, preparation of organic compounds, etc., can solve the problems of poor stereoselectivity, harsh conditions, complicated steps for preparing raw materials, etc., and achieve mild conditions and post-treatment. Convenience, significant commercial value, and the effect of industrial application prospects

Inactive Publication Date: 2018-06-29
NANJING AGRICULTURAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Traditional methods for synthesizing tetrasubstituted olefins mainly include Horner-Wadsworth-Emmons reaction, Julia, Peterson, McMurry and Witting reactions, but this method has certain limitations, such as the preparation of raw materials is complicated and the conditions are relatively harsh, and the stereoselectivity is poor.

Method used

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  • Tetra-substituted olefin and preparation method thereof
  • Tetra-substituted olefin and preparation method thereof
  • Tetra-substituted olefin and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0032] The preparation method of raw material Ia: under nitrogen protection, at -78 ° C, add dry ether (45ml), n-hexane (26ml), n-butyllithium (60mmol, 27ml), add tetramethylethylenediamine (16.5mmol, 1.92g), added propyne bromide (30mmol, 3.56g) dropwise, and stirred for 20min to obtain a white solid. Dissolve diphenyl ketone (15 mmol, 2.73 g) in diethyl ether (15 ml), slowly add to the above solution, return to room temperature and stir for 2 h after the addition is complete. After the reaction was complete, it was extracted with ether, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and the obtained product was subjected to column chromatography (petroleum ether: ethyl acetate = 30:1). Purification obtained product (6.2mmol, 1.37g) was added in the dry bottle, and simultaneously added Pd (PPh 3 ) 2 Cl 2 (5mmol%, 175mg), CuI (5mmol%, 4 mg), iodobenzene (6.8mmol, 1.40g), dissolved in re-distilled triethylamine (20ml), and reacted at...

Embodiment 2

[0037] The preparation method of raw material Ib: under nitrogen protection, at -78°C, add dry diethyl ether (45ml), n-hexane (26ml), n-butyllithium (60mmol, 27ml), add tetramethylethylenediamine (16.5mmol, 1.92g), added propyne bromide (30mmol, 3.56g) dropwise, and stirred for 20min to obtain a white solid. Dissolve diphenyl ketone (15 mmol, 2.73 g) in diethyl ether (15 ml), slowly add to the above solution, return to room temperature and stir for 2 h after the addition is complete. After the reaction was complete, it was extracted with ether, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and the obtained product was subjected to column chromatography (petroleum ether: ethyl acetate = 30:1). Purification obtained product (6.2mmol, 1.37g) was added in the dry bottle, and simultaneously added Pd (PPh 3 ) 2 Cl 2 (5mmol%, 175mg), CuI (5mmol%, 4 mg), o-fluoroiodobenzene (6.8mmol, 1.5g), dissolved in re-distilled triethylamine (20ml), a...

Embodiment 3

[0042] Preparation method of raw material Ic: under nitrogen protection, at -78°C, add dry diethyl ether (45ml), n-hexane (26ml), n-butyllithium (60mmol, 27ml), add tetramethylethylenediamine (16.5mmol, 1.92g), added propyne bromide (30mmol, 3.56g) dropwise, and stirred for 20min to obtain a white solid. Dissolve diphenyl ketone (15 mmol, 2.73 g) in diethyl ether (15 ml), slowly add to the above solution, return to room temperature and stir for 2 h after the addition is complete. After the reaction was complete, it was extracted with ether, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and the obtained product was subjected to column chromatography (petroleum ether: ethyl acetate = 30:1). Purification obtained product (6.2mmol, 1.37g) was added in the dry bottle, and simultaneously added Pd (PPh 3 ) 2 Cl 2 (5mmol%, 175mg), CuI (5mmol%, 4 mg), m-fluoroiodobenzene (6.8mmol, 1.5g), dissolved in re-distilled triethylamine (20ml), and r...

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Abstract

The invention discloses tetra-substituted olefin and a preparation method thereof. The method takes a compound shown as a formula I and diethyl bromomalonate as raw materials, and the raw materials are illuminated by white light to react under the action of a photocatalyst and alkali; after reaction is finished, a compound shown as a formula II is obtained. The method has the advantages of moderate conditions, simplicity in operation, no strict requirements on equipment and high product yield; visible light is used for inducing the reaction; the raw materials are cheap and easy to obtain and asubstrate has a wide applicable range and can tolerate a lot of organic functional groups.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a tetrasubstituted olefin and a preparation method thereof. Background technique [0002] The structural units of tetrasubstituted alkenes are widely found in biologically active natural products and pharmaceuticals. Due to their unique structures, physical and electronic properties, and diverse reactivity of double bonds, the synthesis of tetrasubstituted alkenes has always attracted many chemical researchers. Research interests of experts, especially the regio- and stereoselective synthesis of multi-substituted alkenes is one of the research difficulties and hotspots in organic chemistry. The four-substituted olefin molecular skeleton widely exists in natural products, bioactive molecules and drug molecules, such as anticancer drugs Tamoxifen, Idoxifene (Idoxifene), Etacstil and natural products Vioxx, Nileprost, epi-Illudol and selective Estrogen receptor degrade...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/738C07C67/343
CPCC07C69/738
Inventor 朱映光周华婷彭琛孟菲顾晨
Owner NANJING AGRICULTURAL UNIVERSITY