A gem-difluoropolycyclic compound and its preparation method

A technology of polycyclic compounds and gem-difluoro compounds, applied in the field of gem-difluoro polycyclic compounds and their preparation, can solve the problems of large restrictions, small quantities, and limited applications, and achieve the effects of increasing acidity, low cost, and high reaction efficiency

Inactive Publication Date: 2017-10-13
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] As early as the last century, scientists realized the synthesis of aryl difluorides by using aryl iodides and difluorozinc reagents. This method needs to use an excessive amount of metal copper, and has relatively large restrictions. Various metal organic reagents are used as the starting point. Raw materials, the source of raw materials is relatively limited, which also limits the application of this method in the synthesis of functionalized difluoropolycyclic compounds; Mild and practical, but this type of method only undergoes one reaction to generate aryl gem-difluoro compounds, and the number of rings in the product is small, so the method cannot be used to synthesize gem-difluoro polycyclic compounds

Method used

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  • A gem-difluoropolycyclic compound and its preparation method
  • A gem-difluoropolycyclic compound and its preparation method
  • A gem-difluoropolycyclic compound and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Example 1 Synthesis of 3,3-difluoro-1,9-diphenylcyclopentaquinoline

[0047] Using phenylacetylene as a reaction alkyne to obtain chlorodifluoromethylalkynimine c, add 1 part of c to a Schlenk bottle, add 2 parts of styrene, 2 parts of potassium carbonate, and 0.01 part of triple Pyridine ruthenium chloride, 0.5 parts of triethylamine and appropriate amount of acetonitrile, after stirring for 12 hours under visible light, the reaction solution is concentrated, and the mixed solvent of petroleum ether / ethyl acetate=20:1 is used as the eluent for column chromatography purification. 3,3-difluoro-1,9-diphenylcyclopentaquinoline was obtained with a yield of 84%, and its structure is shown below:

[0048]

[0049] The NMR data of the compound are as follows:

[0050] 1 H NMR (400 MHz, CDCl3) δ 8.36 (d, J = 8.5 Hz, 1H), 7.75 (ddd, J = 8.4, 6.7, 1.4 Hz, 1H), 7.57 (dd, J = 8.5, 0.9 Hz, 1H) , 7.50 – 7.40 (m, 2H),7.30 (tt, J = 7.5, 1.2 Hz, 1H), 7.27 – 7.23 (m, 1H), 7.08 – 6....

Embodiment 2

[0051] Example 2 Synthesis of 3,3-difluoro-1-(4-methyl)phenyl-9-phenylcyclopentaquinoline

[0052] Using phenylacetylene as a reaction alkyne to obtain chlorodifluoromethylalkynimine c, add 1 part of c to a Schlenk bottle, add 5 parts of 4-methylstyrene and 4 parts of potassium carbonate under a nitrogen atmosphere, 0.01 part of Eosin Y and appropriate amount of acetonitrile, stirred under 1W LED light for 8 hours, then concentrated the reaction solution, and purified by column chromatography with petroleum ether / ethyl acetate=20:1 mixed solvent as eluent to obtain 3,3 -Difluoro-1-(4-methyl)phenyl-9-phenylcyclopentaquinoline, the yield is 87%, and its structure is shown below:

[0053]

[0054] The NMR data of the compound are as follows:

[0055] 1 H NMR (400 MHz, CDCl 3 ) δ 8.39 (d, J = 8.5 Hz, 1H), 7.78 (ddd, J =8.4, 6.7, 1.4 Hz, 1H), 7.60 (dd, J = 8.5, 0.9 Hz, 1H), 7.53 – 7.43 (m,2H),7.34 (tt, J = 7.5, 1.2 Hz, 1H), 7.30 – 7.25 (m, 1H), 7.10 (td, J = 7.6, 0....

Embodiment 3

[0056] Example 3 Synthesis of 3,3-difluoro-1-(4-methoxy)phenyl-9-phenylcyclopentaquinoline

[0057] Use phenylacetylene as the reaction alkyne to obtain chlorodifluoromethylalkynimine c, add 1 part of c to the Schlenk bottle, add 3 parts of 4-methoxystyrene and 3 parts of sodium carbonate under nitrogen atmosphere , 0.005 parts of Rose Bengal and 0.005 parts of triethylamine and acetonitrile solvent, after stirring for 4 hours under 1W LED light, the reaction solution was concentrated, petroleum ether / ethyl acetate=20:1 mixed solvent as eluent column layer Analysis and purification can obtain 3,3-difluoro-1-(4-methoxy)phenyl-9-phenylcyclopentaquinoline with a yield of 87%, and its structure is as follows:

[0058]

[0059] The NMR data of the compound are as follows:

[0060] 1 H NMR (400 MHz, CDCl 3 ) δ 8.36 (d, J = 8.5 Hz, 1H), 7.76 (ddd, J =8.4, 6.7, 1.5 Hz, 1H), 7.56 (dd, J = 8.4, 0.9 Hz, 1H), 7.51 – 7.45 (m, 1H),7.38 (t, J = 7.5 Hz, 1H), 7.29 – 7.24 (m, 1H),...

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Abstract

The present invention relates to a gem-difluoro polycyclic compound preparation method, the preparation method specifically includes the following steps: a halo-difluoromethyl alkynyl imine compound is reacted with an olefin for 6 ~ 24h under basic conditions in the presence of a photosensitizer as a catalyst by visible light irradiation at the reaction temperature of 0 ~ 50 DEG C, the halo-difluoromethyl alkynyl imine compound has the general formula shown in the specification, the substituted olefin has the general formula shown in the specification; wherein R1 ~ R6 is any group, R2 is a substituent at any positions on the benzene ring, the number of R2 substituents is 1 to 4, when the number of the R2 substituents is multiple, the R2 substituents same or different, and the ortho positions of benzene ring amino cannot simultaneously be substituted by the R2.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a gem-difluoropolycyclic compound and a preparation method thereof. Background technique [0002] The introduction of fluorine atoms into organic molecules can often improve the fat solubility and electronegativity of compounds. So far, 20% of organic drug molecules and 30% of agricultural organic matter contain fluorine atoms. The small atomic radius, strong electronegativity, high C-F bond energy and special induced resonance characteristics of fluorine atoms endow fluorine-containing compounds with good physical and biological properties. [0003] As early as the last century, scientists realized the synthesis of aryl difluorides by using aryl iodides and difluorozinc reagents. This method needs to use an excessive amount of metal copper, and has relatively large restrictions. Various metal organic reagents are used as the starting point. Raw materials, the source ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D221/16C07D401/04C07D491/052C07D221/18C07D409/04
CPCC07D221/16C07D221/18C07D401/04C07D409/04C07D491/052
Inventor 周磊谢洋肖铁波
Owner SUN YAT SEN UNIV
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