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

Simple preparation method of 9-hydroxyfluorene-9-carboxylate compound

A technology of ester compound and hydroxyfluorene, applied in the field of organic synthesis, can solve problems such as difficulty in obtaining raw materials, and achieve the effects of less reaction by-products, alleviating the pressure on the environment, and less waste discharge

Active Publication Date: 2020-09-29
WUHAN UNIV OF TECH
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The raw materials used in this preparation method are difficult to obtain, and only 11-hydroxyl-6-phenyl-11H-benzo[a]fluorene-11-carboxylate compounds can be obtained

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
  • Simple preparation method of 9-hydroxyfluorene-9-carboxylate compound
  • Simple preparation method of 9-hydroxyfluorene-9-carboxylate compound
  • Simple preparation method of 9-hydroxyfluorene-9-carboxylate compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Preparation of 9-ethyl-2-methyl-9-hydroxy-6,8-dimethyl-9H-fluorene-2,9-dicarboxylate:

[0040] Preparation of 9-ethyl-2-methyl-9-hydroxy-6,8 from ethyl 2-(2,4-dimethylphenyl)-2-oxoacetate and methyl 4-iodobenzoate -Dimethyl-9H-fluorene-2,9-dicarboxylate, the chemical reaction formula is as follows:

[0041]

[0042] Specific steps are as follows:

[0043] Add palladium acetate (Pd(OAc) 2 ) 4.49mg (0.02mmol), ethyl 2-(2,4-dimethylphenyl)-2-oxoacetate 41.2mg (0.2mmol), methyl 4-iodobenzoate 131.0mg (0.5mmol), Silver trifluoroacetate (AgTFA) 88.4mg (0.4mmol), trifluoroacetic acid (TFA) 136.8mg (1.2mmol) and 2-fluoro-5-trifluoromethylaniline 14.3mg (0.08mmol), 1.8mL hexafluoroiso Propanol, 0.2mL anhydrous acetic acid, put the reaction solution in a heater at 100°C and stir for 48h, the passing specification is The thin-layer chromatographic plate of F-254 is tracked, and the reaction raw material is no longer consumed and reduced, and the product is no longer increas...

Embodiment 2

[0046] Preparation of 9-hydroxyfluorene-9-carboxylate compound as 9-hydroxy-6,8-dimethyl-9H-fluorene-2,9-dicarboxylate diethyl ester:

[0047] Preparation of 9-hydroxy-6,8-dimethyl-9H-fluorene-2 ​​from ethyl 2-(2,4-dimethylphenyl)-2-oxoacetate and ethyl 4-iodobenzoate , 9- diethyl carboxylate, the chemical reaction formula is as follows:

[0048]

[0049] Specific steps are as follows:

[0050] Add 4.49mg (0.02mmol) of palladium acetate, 41.2mg (0.2mmol) of formyl ethyl 2,4-dimethylbenzoate, and 138.0mg (0.5mmol) of ethyl 4-iodobenzoate into a sealed pressure-resistant tube. ), silver trifluoroacetate (AgTFA) 88.4mg (0.4mmol), trifluoroacetic acid 136.8mg (1.2mmol) and 2-fluoro-5-trifluoromethylaniline 14.3mg (0.08mmol), 1.8mL hexafluoroisopropyl Alcohol, 0.2mL of anhydrous acetic acid, put the reaction solution in a heater at 100°C and stir for 48 hours, the passing specification is The thin-layer chromatographic plate of F-254 is tracked, and the reaction raw material...

Embodiment 3

[0053] Preparation of 9-hydroxyfluorene-9-carboxylate compound as ethyl 9-hydroxy-1,3-dimethyl-5-nitro-9H-fluorene-9-carboxylate:

[0054] Preparation of 9-hydroxy-1,3-dimethyl-5-nitro-9H- from 2-(2,4-dimethylphenyl)-2-oxoethyl acetate and o-nitroiodobenzene Ethyl fluorene-9-carboxylate, the chemical reaction formula is as follows:

[0055]

[0056] Specific steps are as follows:

[0057] Add 4.49 mg (0.02 mmol) of palladium acetate, 41.2 mg (0.2 mmol) of ethyl 2-(2,4-dimethylphenyl)-2-oxoacetate, and 124.5 mg of o-nitroiodobenzene into a sealed pressure-resistant tube. mg (0.5mmol), silver trifluoroacetate (AgTFA) 88.4mg (0.4mmol), trifluoroacetic acid 136.8mg (1.2mmol) and 2-fluoro-5-trifluoromethylaniline 14.3mg (0.08mmol), 1.8mL Hexafluoroisopropanol, 0.2mL of anhydrous acetic acid, put the reaction solution in a heater at 100°C and stir for 48 hours, the passing specification is The thin-layer chromatographic plate of F-254 is tracked, and the reaction raw material...

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 relates to a simple preparation method of a 9-hydroxyfluorene-9-carboxylate compound. The method comprises the following step: with a benzoyl formate compound I and an iodobenzene compound II as raw materials, under the catalysis of Pd(OAc)2 and trifluoroacetic acid, carrying out a cyclization reaction by using silver trifluoroacetate as an oxidant and 2-fluoro-5-trifluoromethylaniline as a ligand to obtain the 9-hydroxyfluorene-9-carboxylate compound. Compared with an existing method, the method of the invention has the advantages that reaction raw materials are easy to synthesize through a classical reaction; 2, the reaction is simple and convenient, operation is easy, a target product can be obtained in one step, few reaction byproducts are produced, little waste is discharged, the product is directly purified by using column chromatography, strong acid or strong base is not needed for aftertreatment, pressure on the environment is greatly reduced, purification effectis good, and yield can reach 60-90%; and 3, reaction expansibility is strong, a novel method for synthesizing the 9-hydroxyfluorene-9-carboxylate compound is provided, and the compound which is not synthesized before can be synthesized.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a simple preparation method of 9-hydroxyfluorene-9-carboxylate compounds. Background technique [0002] Fluorene structures are found in many pharmaceuticals and are especially prevalent in agrochemicals and bioactive compounds. In addition, they are also widely used in the preparation of luminescent complexes, dyes and optoelectronic materials. For example, 9-hydroxyfluorene derivatives were recently proposed as precursors for the preparation of new promising fluorene-derived compounds for use as wakefulness enhancers in place of the drug modafinil. [0003] Most of the 9-hydroxyfluorene-9-carboxylate compounds have important biological activities due to their unique chemical structures. The currently reported preparation method is through AgNTf 2 Catalyzed, in dichloroethane solvent from diphenylacetylene and 3-(2-formyl phenyl) methyl propiolate reactio...

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): C07C67/343C07C67/56C07C69/94C07C201/12C07C201/16C07C205/55
CPCC07C67/343C07C67/56C07C201/12C07C201/16C07C2603/18C07C69/94C07C205/55
Inventor 张方林吴永迪
Owner WUHAN UNIV OF TECH
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