Synthetic method of 1, 1-2 fluorine - 1, 3 - acetylene compounds

A synthesis method and compound technology, which are applied in the field of synthesis of 1,1-difluoro-1,3-enyne compounds, can solve problems such as low practicability, achieve good universality, high efficiency, stable and easy-to-obtain raw materials Effect

Active Publication Date: 2015-08-19
PEKING UNIV
View PDF1 Cites 3 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the practicability of these methods is low. Firstly, the synthesis of coupling blocks with difluoroolefins itself is a big problem, requiring relatively harsh conditions

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
  • Synthetic method of 1, 1-2 fluorine - 1, 3 - acetylene compounds
  • Synthetic method of 1, 1-2 fluorine - 1, 3 - acetylene compounds
  • Synthetic method of 1, 1-2 fluorine - 1, 3 - acetylene compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] 2,4-Diphenyl 1,1-difluoro-1-en-3-yne

[0049]Take a 10mL Schlenk tube, put it into a magnet stopper, put a rubber stopper on it, heat and dry it, and cool it under nitrogen, then add 68mg (0.2mmol ), lithium tert-butoxide 32mg (0.4mmol), cuprous iodide 8mg (0.04mmol), appropriate amount of additives, nitrogen pumping, then add 3mL 1,4-dioxane, add phenylacetylene 20mg (0.2 mmol). React at a certain temperature on an electromagnetic heating stirrer for about 2 hours. After the reaction, use a 10mL sand core column filled with 3cm high silica gel to filter and elute with an appropriate amount of petroleum ether. The resulting filtrate is removed from the reaction solvent by a rotary evaporator and purified by column chromatography to obtain 2,4-diphenyl 1,1-difluoro-1-en-3-yne, its structure is shown in the following formula:

[0050]

[0051] Taking this reaction as an example, under the condition that other conditions remain unchanged, by adjusting the type or rea...

Embodiment 2

[0057] 2-(4’-fluorophenyl)-4-phenyl 1,1-difluoro-1-en-3-yne

[0058] Take a 10mL Schlenk tube, put it into a magnetic sub-plug and put a rubber stopper on it, heat it to dry, cool it under nitrogen, then add 1,1,1-trifluoromethyl-2-(4'-fluorophenyl)ketone and p-toluenesulfonate Acylhydrazone 72mg (0.2mmol), lithium tert-butoxide 32mg (0.4mmol), cuprous iodide 8mg (0.04mmol), tetrabutylammonium chloride 11mg (0.04mmol), lithium trifluoromethanesulfonate 31mg (0.2mmol ), nitrogen pumped for ventilation, then 3mL of 1,4-dioxane was added, and 20mg (0.2mmol) of phenylacetylene was added under stirring. React on a 60° C. electromagnetic heating stirrer for about 2 hours. After the reaction, use a 10mL sand core column filled with 3cm high silica gel to filter and elute with an appropriate amount of petroleum ether. The resulting filtrate is removed from the reaction solvent using a rotary evaporator, and purified by column chromatography to obtain 2-(4'-fluoro Phenyl)-4-phenyl 1,...

Embodiment 3

[0062] 2-(4’-Chlorophenyl)-4-phenyl 1,1-difluoro-1-en-3-yne

[0063] Take a 10mL Schlenk tube, put it into a magnet stopper and put a rubber stopper on it, heat and dry, cool under nitrogen, then add 1,1,1-trifluoromethyl-2-(4'-chlorophenyl)ketone and p-toluenesulfonate Acylhydrazone 75mg (0.2mmol), lithium tert-butoxide 32mg (0.4mmol), cuprous iodide 8mg (0.04mmol), tetrabutylammonium chloride 11mg (0.04mmol), lithium trifluoromethanesulfonate 31mg (0.2mmol ), nitrogen pumped for ventilation, then 3mL of 1,4-dioxane was added, and 20mg (0.2mmol) of phenylacetylene was added under stirring. React on a 60° C. electromagnetic heating stirrer for about 2 hours. After the reaction is over, use a 10mL sand core column with 3cm high silica gel to filter and elute with an appropriate amount of petroleum ether. The resulting filtrate is removed from the reaction solvent using a rotary evaporator, and purified by column chromatography to obtain 2-(4'-chloro Phenyl)-4-phenyl 1,1-diflu...

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 synthetic method of 1, 1-2 fluorine - 1, 3 - acetylene compounds. The synthetic method enable tosylhydrazones and acetylene compounds of Alpha, alpha, alpha, 3 methyl ketone to react in organic solvent. 1, 1-2 fluorine - 1, 3 - acetylene compounds is obtained through the catalysis of cuprous CuX and the existing of soda and annexing agent. The synthetic method of 1, 1-2 fluorine - 1, 3 - acetylene compounds preferentially uses copper iodide which is cheap and stable as catalyst, and the operation is relatively convenient and easy. Also the copper iodide has good tolerance and universality to functional groups. The invention has the advantages that the raw materials are easy to obtain, the reaction cost is relative low, and the reaction time is relative short. The invention is suitable for the preparation of 1, 1-2 fluorine - 1, 3 - acetylene compounds.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a synthesis method of 1,1-difluoro-1,3-enyne compound. Background technique [0002] Due to its special chemical properties, fluorine atoms play an important role in the fields of material science, life science, and pharmaceuticals. Therefore, how to efficiently introduce fluorine-containing functional groups has become an important research direction for synthetic chemists. Among them, 1,1-difluoro-1,3-enyne compound is a special kind of enyne compound, which has a good application prospect. The traditional methods for synthesizing this kind of compounds are mainly: 1) using the building block containing difluoroalkene and alkyne for coupling synthesis, 2) using Wittig reaction. However, the practicability of these methods is low. Firstly, the synthesis of coupling blocks with difluoroolefins is a big problem, requiring relatively harsh conditions, and there is a big problem in...

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): C07C17/26C07C22/08C07C25/24C07C43/225C07C41/30C07C205/11C07C201/12C07D333/12C07C211/52C07C209/68C07C69/78C07C67/343C07D213/26C07F7/12
Inventor 王剑波张志坤周奇于位之李天骄吴国骄张艳
Owner PEKING 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