Process for the preparation of aromatic alkenyl compounds

A technology of aromatic alkenes and compounds, applied in the preparation of sulfides, organic chemistry, etc., can solve the problems of high catalyst consumption, poor reaction selectivity, high reaction temperature, etc., and achieve the effect of good reactivity

Active Publication Date: 2020-12-01
WUYI UNIV
View PDF5 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Many classic coupling reactions are more and more widely used, but they still have disadvantages that cannot be ignored: this type of reaction needs to pre-functionalize the substrate in advance to make electrophiles such as halides or halide-like compounds and hydrophilic reagents. Nuclear reagents, etc.
The common problems of the above synthesis tec

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Process for the preparation of aromatic alkenyl compounds
  • Process for the preparation of aromatic alkenyl compounds
  • Process for the preparation of aromatic alkenyl compounds

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0060] The present invention also provides a kind of preparation method of thioether:

[0061] Step A: Under air atmosphere at room temperature, add benzyl bromide (10.0mmol), thiophenol (10.0mmol) and K2CO3 (1.52g, 11.0mmol) in DMF (10.00mL) to a 50mL flask, and keep the mixture at This temperature continues to stir reaction 4h;

[0062] Step B: 15 mL of water was added to the reaction mixture, while ethyl acetate (25 mL) was added and stirred for 5 min, the upper layer was washed with brine three times, and dried over anhydrous sodium sulfate;

[0063] Step C: Evaporate the solvent under reduced pressure, and subject the residue to silica gel column chromatography to obtain thioether.

[0064] It should be pointed out that the substances used in the specific embodiments of the present invention can be purchased from the market. As long as the structural formula is the same, they can be applied to the preparation method of the present invention. Since no improvement is invol...

Embodiment 1

[0066]

[0067] Under an air atmosphere at 80°C, 0.4 mmol of thioether with the structural formula AA, 0.8 mmol of ethyl acrylate, [Cp*IrCl 2 ] 2 0.006mmol, AgBF 4 0.024mmol and Cu(OAc) 2 0.48mmol of the mixture was added to 2mL of hexafluoroisopropanol and stirred for 12h. The reaction mixture was cooled to room temperature and filtered through diatomaceous earth. The solvent was evaporated under reduced pressure, and the residue was subjected to silica gel column chromatography (ethyl acetate / petroleum ether =1:10, v / v), to obtain colorless liquid (E)-3-(3-methyl-2-((p-tolylthio)methyl)phenyl) ethyl acrylate, the compound is mono Alkenylated product, 85% yield. 1 H NMR (400MHz, CDCl 3 , TMS) δ7.94 (d, J = 16.0Hz, 1H), 7.36 (dd, J1 = 6.8Hz, J2 = 7.6Hz, 1H), 7.29-7.26 (m, 2H), 7.21-7.15 (m, 2H ), 7.07(d, J=8.0Hz, 2H), 6.22(d, J=15.6Hz, 1H), 4.25(q, J=7.2Hz, 2H), 4.15(s, 2H), 2.41(s, 3H ), 2.32(s, 3H), 1.33(t, J=7.2Hz, 3H). 13 C NMR (100MHz, CDCl 3 )δ 166.7, 142.1...

Embodiment 2

[0069]

[0070] Under an air atmosphere at 80°C, 0.4 mmol of thioether, 0.8 mmol of ethyl acrylate, [Cp*IrCl 2 ] 2 0.006mmol, AgBF 4 0.024mmol and Cu(OAc) 2 0.48mmol of the mixture was added to 2mL of hexafluoroisopropanol and stirred for 12h. The reaction mixture was cooled to room temperature and filtered through diatomaceous earth. The solvent was evaporated under reduced pressure, and the residue was subjected to silica gel column chromatography (ethyl acetate / petroleum ether =1:15, v / v), to obtain colorless liquid (E)-3-(5-chloro-2-((p-tolylthio)methyl)phenyl) ethyl acrylate, the compound is monoene The ylated product was obtained with a yield of 58%. 1 H NMR (400MHz, CDCl 3,TMS)δ7.86(d,J=16Hz,1H),7.49(d,1H),7.21-7.19(m,3H),7.09-7.04(q,3H),6.29(d,J=15.6Hz, 1H), 4.26(q, J=6.8Hz, 2H), 4.06(s, 2H), 2.31(s, 3H), 1.34(t, J=6.8Hz, 3H). 13 CNMR (100MHz, CDCl 3 )δ 166.3, 139.9, 137.7, 135.3, 135.2, 133.4, 132.6, 131.9, 130.7, 129.7, 129.6, 126.5, 121.1, 60.6, 37.5, 2...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention discloses a preparation method of an aromatic alkenyl compound. The aromatic alkenyl compound comprises thioether and a carbon-carbon double bond substrate, wherein the ratio of the amount of substance of the thioether and the carbon-carbon double bond substrate is 1:(2 to 4); the compound further comprises [Cp*IrCl2]2 and Cu(OAc)2, wherein the ratio of the amount of substance of the[Cp*IrCl2]2 and the thioether is (0.005 to 0.05):1, and the ratio of the amount of substance of the Cu(OAc)2 and the thioether is (1.2 to 2.4):1; the thioether, the carbon-carbon double bond substrate, the [Cp*IrCl2]2 and the Cu(OAc)2 are mixed, and are stirred in solvent for 12 h, and the reaction temperature is 60 to 90 DEG C. The preparation method disclosed by the invention has the advantagesthat the time consumption of a reaction is short; the selectable range of the thioether and the carbon-carbon double bond substrate is wide; the reaction does not need to be performed under oxygen-free and high-pressure conditions; the reaction conditions are mild; the catalyst consumption is less; the method is applied to industrial production; the production cost is saved; the production cycleis shortened; good economy is realized; the controlled synthesis of target products is realized; the controllability is high.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of an aromatic alkenyl compound. Background technique [0002] Traditional transition metal-catalyzed cross-coupling reactions provide an efficient method for the synthesis of carbon-carbon and carbon-heterobond bonds. Many classic coupling reactions are more and more widely used, but they still have disadvantages that cannot be ignored: this type of reaction needs to pre-functionalize the substrate in advance to make electrophiles such as halides or halide-like compounds and hydrophilic reagents. Nuclear reagents, etc. The steps of the reaction are increased and the atom economy is reduced. Therefore, whether the functional group of the carbon-hydrogen bond can be directly realized, so that the substrate can directly participate in the reaction, will greatly improve the efficiency. [0003] Due to the step and atom economy, the most commonly used strategy...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
IPC IPC(8): C07C319/20C07C323/56
CPCC07C319/20C07C323/56
Inventor 李辰王东辉陈娴
Owner WUYI UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap