Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Beta-all carbon quaternary carbon-alpha-fluoroalkyl ketone compound and synthesis method and application thereof

A technology of fluoroalkyl ketones and synthetic methods, which is applied in the fields of carbon-based compound preparation, organic chemical methods, chemical instruments and methods, etc.

Inactive Publication Date: 2019-10-25
EAST CHINA NORMAL UNIV
View PDF0 Cites 5 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] So far, there have been many reports on the addition of fluorinated nucleophiles to highly active electrophiles, but due to the inertness of alkenes, there have been no reports on the addition of fluorinated nucleophiles to simple alkenes to synthesize β-all carbon quaternary Carbon-α-fluoroalkyl ketones

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
  • Beta-all carbon quaternary carbon-alpha-fluoroalkyl ketone compound and synthesis method and application thereof
  • Beta-all carbon quaternary carbon-alpha-fluoroalkyl ketone compound and synthesis method and application thereof
  • Beta-all carbon quaternary carbon-alpha-fluoroalkyl ketone compound and synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0085] Synthesis of β-all-carbon quaternary carbon-α-fluoroalkyl ketone Ⅲ-1:

[0086]

[0087] Add 3.6 mg perchloric acid (70% wt), distilled water (2.5 mL), olefin I-1 (33.1 mg, 0.25 mmol), and phenyl-substituted difluoroenol silyl ether II-1 to a 5.0 mL reaction flask in sequence (570mg, 2.5mmol), the reaction solution was stirred at 50°C for 15h. TLC detects that the raw materials have basically reacted, and the reaction is stopped. The reaction solution was extracted with ethyl acetate for 3 times, dried over anhydrous sodium sulfate, transferred to a 50mL round bottom flask, added about 1.0g of crude silica gel, spin-dried, followed by column chromatography and eluent (petroleum ether), to obtain product III- 1 is 66.3mg of colorless liquid, the yield is 92%. 1 H NMR (400MHz, CDCl 3 ):δ7.56-7.54(m,2H),7.45-7.41(m,1H),7.36-7.34(m,2H),7.26-7.17(m,5H),2.46-2.37(m,1H),1.99 -1.90(m,1H),1.60(s,3H),0.75(t,J=7.2Hz,3H); 13 C NMR (100MHz, CDCl 3 ): δ191.28(t, J=30.3Hz), 13...

Embodiment 2

[0089] Synthesis of β-all-carbon quaternary carbon-α-fluoroalkyl ketone Ⅲ-2:

[0090]

[0091] Add trifluoromethanesulfonic acid (3.8mg, 0.025mmol), olefin I-2 (37.6mg, 0.25mmol), phenyl-substituted difluoroenolsilyl ether II-1 (85.5, 0.375 mmol), tetrahydrofuran (2.5 mL); the reaction solution was stirred at room temperature for 5 h. TLC detects that the raw material has basically reacted completely, and the reaction is stopped. The reaction solution was transferred to a 50mL round-bottomed flask, and the solvent was drained under the oil pump, followed by direct column chromatography and eluent (DCM / petroleum ether=1 / 20) to obtain 63.6 mg of product III-2 as a colorless liquid, Yield 83%. 1 H NMR (400MHz, CDCl 3 ):δ7.64-7.62(m,2H),7.49-7.46(m,1H),7.33-7.26(m,4H),6.93-6.89(m,2H),2.40-2.31(m,1H),1.98 -1.89(m,1H),1.58(s,3H),0.73(t,J=1.9Hz,3H); 13 C NMR (100MHz, CDCl 3 ): δ190.93(t, J=30.2Hz), 161.88(d, J=245.3Hz), 134.22(t, J=1.9Hz), 133.98(dd, J=4.8, 4.5Hz), 133.40, 1...

Embodiment 3

[0093] Synthesis of β-all-carbon quaternary carbon-α-fluoroalkyl ketone Ⅲ-3:

[0094]

[0095] In the 5.0mL reaction flask, add H 2 SO 4 (5mg, 0.05mmol), olefin I-3 (41.7mg, 0.25mmol), phenyl-substituted difluoroenol silyl ether II-1 (285.4mg, 1.25mmol), toluene (2.5mL); After stirring at 30°C for 20h. TLC detects that the raw material has basically reacted completely, and the reaction is stopped. Transfer the reaction solution to a 50mL round-bottomed flask, drain the solvent under the oil pump, perform direct column chromatography, eluent (dichloromethane / petroleum ether=1 / 20), and obtain product III-3 as a colorless liquid 68.4 mg, yield 85%. 1 H NMR (400MHz, CDCl 3 ):δ7.67-7.65(m,2H),7.49-7.46(m,1H),7.31-7.24(m,4H),7.20-7.18(m,2H),2.38-2.29(m,1H),1.97 -1.88(m,1H),1.56(s,3H),0.72(t,J=7.6Hz,3H); 13 C NMR (100MHz, CDCl 3 ): δ190.60(t, J=30.3Hz), 136.91(t, J=2.4Hz), 134.11(t, J=2.1Hz), 133.46, 133.22, 130.18, 129.77(t, J=4.1Hz), 128.16, 128.11, 120.58(t, J=260.2Hz)...

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 beta-all carbon quaternary carbon-alpha-fluoroalkyl ketone compound and a synthesis method and application thereof. The compound has the structure shown in the following equation, has potential biological activity and pharmacodynamic activity, provides a strong technical support for development of new drugs, and has high practical value; and the synthesis method starts from olefin and the nucleophile agent fluoroenol silane, and efficiently synthesizes the beta-all carbon quaternary carbon-alpha-fluoroalkyl ketone compound in one step through a simple addition reaction. The beta-all carbon quaternary carbon-alpha-fluoroalkyl ketone compound and the synthesis method and application thereof have the characteristics that raw materials are cheap and readily available;the reaction condition is mild and operation is simple; and the application range of substrates is wide, and the higher yield can be obtained.

Description

technical field [0001] The invention belongs to the technical field of organic compounds, and relates to β-all-carbon quaternary carbon-α-fluoroalkyl ketone compounds and a method for synthesizing the compounds starting from fluoroenol silicon ethers and simple olefins. Background technique [0002] Fluorine is located in the main group VII of the second period of the periodic table, and is the most electronegative element with a small atomic radius. Many research results have shown that the introduction of fluorine atoms or fluorine-containing groups into organic compounds can improve the physical and chemical properties of the corresponding compounds, as well as increase the bioavailability, lipophilicity, binding affinity, and metabolic stability of bioactive molecules. properties and membrane permeability. Therefore, the selective introduction of fluorine atoms or fluorine-containing groups into known drugs or bioactive molecules is an important means for drug modificat...

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): C07C45/00C07C49/813C07C67/00C07C69/712C07C49/84C07D333/22C07C49/733C07H15/203C07H1/00
CPCC07C45/00C07C49/813C07C67/00C07C69/712C07C49/84C07D333/22C07C49/733C07H15/203C07H1/00C07B2200/07C07C2601/14C07C2602/08C07C2602/10C07C2602/12
Inventor 周剑胡小思余金生
Owner EAST CHINA NORMAL UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com