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

Preparing method by using unactivated olefin hydrogen trifluoride methylation and application thereof

A technology of methylphenoxy and methoxyphenoxy, which is applied in the field of compound synthesis, can solve the problems of high catalyst consumption, expensive, limited applicability, etc., and achieve wide applicability, high conversion number, and mild reaction conditions Effect

Active Publication Date: 2017-06-27
HUBEI ENG UNIV
View PDF0 Cites 10 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Hydrotrifluoromethylation of unsaturated olefins is a direct and efficient method for the synthesis of trifluoromethyl-substituted organic compounds, but there are few reports on the use of unactivated olefins as substrates
Moreover, in the few synthetic methods that have been reported, there are also many shortcomings, such as higher catalyst dosage, expensive trifluoromethylation reagents, etc., which limit the applicability of this type of reaction.

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
  • Preparing method by using unactivated olefin hydrogen trifluoride methylation and application thereof
  • Preparing method by using unactivated olefin hydrogen trifluoride methylation and application thereof
  • Preparing method by using unactivated olefin hydrogen trifluoride methylation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Preparation of Compound II-1:

[0036]

[0037] A. Add unactivated olefin I-1 (R 1 = phenoxy, R 2 =hydrogen, n=4) (44.1mg, 0.25mmol), sodium trifluoromethanesulfinate (78.0mg, 0.50mmol) and photocatalyst Ir[dF(CF 3 )ppy] 2 (dtbpy)PF 6(2mol%, 5.6mg); The ratio of the amount of substance of the sodium trifluoromethanesulfinate and I-1 is 2.0; The photocatalyst Ir[dF(CF 3 )ppy] 2 (dtbpy)PF 6 The amount used is 2.0% of the amount of substance in I-1;

[0038] B, after vacuumizing and changing argon, add solvent (methanol) 3mL; Described solvent is methyl alcohol; The ratio of the milliliter number of described solvent methanol and the amount of substance of I-1 is 12.0;

[0039] C. Irradiate the Schlenk tube with a fluorescent lamp, stir and react; the wavelength range of the fluorescent lamp is visible light, and the power is 36W; the reaction temperature is room temperature (20-25°C, the same below), and the reaction time is 24 hours;

[0040] D. After the reac...

Embodiment 2

[0045] Preparation of compound II-2:

[0046]

[0047] Add unactivated olefin I-2 (R 1 = p-methylphenoxy, R 2 =hydrogen, n=4) (47.6mg, 0.25mmol), sodium trifluoromethylsulfinate (78.0mg, 0.50mmol) and Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (5.6 mg, 0.005 mmol). After evacuating and changing the argon gas, add 3 mL of solvent (methanol), irradiate the Schlenk tube with a fluorescent lamp, and stir to carry out the reaction. The wavelength range of the fluorescent lamp is visible light, the power is 36W, the reaction temperature is room temperature, and the reaction time is 24 hours. After the reaction, add water to the system to quench the reaction, extract with ethyl acetate (3×10mL), separate the organic phase, and use anhydrous Na 2 SO 4 Dry, filter and remove solvent by rotary evaporation. The residue was subjected to column chromatography with pure petroleum ether, separated and purified to obtain the target product II-253mg, and the yield was 82%.

[0048] 1 H NMR (...

Embodiment 3

[0052] Preparation of Compound II-3:

[0053]

[0054] Add unactivated olefin I-3 (R 1 = p-methoxyphenoxy, R 2 =hydrogen, n=4) (51.6mg, 0.25mmol), sodium trifluoromethylsulfinate (78.0mg, 0.50mmol) and Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 (5.6 mg, 0.005 mmol). After evacuating and changing the argon gas, add 3 mL of solvent (methanol), irradiate the Schlenk tube with a fluorescent lamp, and stir to carry out the reaction. The wavelength range of the fluorescent lamp is visible light, the power is 36W, the reaction temperature is room temperature, and the reaction time is 24 hours. After the reaction, add water to the system to quench the reaction, extract with ethyl acetate (3×10mL), separate the organic phase, and use anhydrous Na 2 SO 4 Dry, filter and remove solvent by rotary evaporation. The residue was subjected to column chromatography with pure petroleum ether, separated and purified to obtain the target product II-356mg, and the yield was 82%.

[0055] 1 H NMR...

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 preparing method by using unactivated olefin hydrogen trifluoride methylation and application thereof. The method comprises the following steps: A, adding unactivated olefin I, sodium trifluoromethanesulfonate and a photocatalystIr[dF(CF3)ppy]2(dtbpy)PF6 into a Schlenk tube; B, vacuumizing, replacing argon, adding methyl alcohol; C, irradiating the Schlenk tube with a fluorescent lamp, and stirring to react; and D, after reaction is finished, adding water into the system to perform a quenching reaction, extracting with ethyl acetate, separating an organic phase, drying, filtering, performing rotary evaporation to remove a solvent, chromatographing the residue through an ethyl acetate / petroleum ether mixed solvent to obtain a target product II, wherein the proportion of the ethyl acetate / petroleum ether mixed solvent is selected according to different polarities of the product, and silica gel is adopted as a solid phase in column chromatography. The method applied to medicinal molecule synthesis is feasible, is simple and convenient to operate, and is used for implementing an unactivated olefin hydrogen trifluoride methylation reaction to prepare a series of trifluoromethyl-containing target compounds by selecting low-price trifluoromethyl reagent under a mild condition.

Description

technical field [0001] The invention relates to the field of compound synthesis, more specifically to a preparation method for hydrotrifluoromethylation of unactivated olefins, and also relates to the application of the preparation method for hydrotrifluoromethylation of unactivated olefins in the synthesis of drug molecules. Background technique [0002] Trifluoromethyl (CF 3 ) strong electron-withdrawing properties and the stability of the C-F bond, the polarity, dipole moment, lipophilicity and metabolic stability of the organic compound containing trifluoromethyl group in the structure will be significantly changed, so this type of compound is called It is widely used in the fields of medicine, pesticide and new functional materials. For example, the herbicide Trifluralin, the depression drug Prozac, and the type 2 diabetes drug Januvia all contain trifluoromethyl. [0003] In the synthesis of trifluoromethyl-substituted organic compounds, the hydrotrifluoromethylation...

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
Patent Type & Authority Applications(China)
IPC IPC(8): C07C43/225C07C41/30C07C47/575C07C45/69C07C49/84C07C321/28C07C319/20C07C69/78C07C67/293C07D209/48C07C317/14C07C315/04C07C67/347C07C233/07C07C231/12C07C49/813C07J1/00C07B39/00C07C22/08C07C17/272
CPCC07B39/00C07C17/272C07C22/08C07C41/30C07C43/225C07C45/69C07C47/575C07C49/813C07C49/84C07C67/293C07C67/347C07C69/78C07C231/12C07C233/07C07C315/04C07C317/14C07C319/20C07C321/28C07D209/48C07J1/00
Inventor 朱磊汪连生李博解付伯桥李伟
Owner HUBEI ENG 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