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
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The raw materials used in this preparation method are difficult to obtain, and only

Method used

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  • 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

Example Embodiment

[0038] Example 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 using ethyl 2-(2,4-dimethylphenyl)-2-oxoacetate and methyl 4-iodobenzoate as raw materials -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) to the closed pressure tube 2 ) 4.49 mg (0.02 mmol), 2-(2,4-dimethylphenyl)-2-oxoacetate 41.2 mg (0.2 mmol), methyl 4-iodobenzoate 131.0 mg (0.5 mmol), 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 48 hours. The pass specification is F-254 TLC plate tracking, the reaction raw material no longer consumes less, the product no longer incre...

Example Embodiment

[0045] Example 2

[0046] Preparation of 9-hydroxyfluorene-9-carboxylic acid ester compound is 9-hydroxy-6,8-dimethyl-9H-fluorene-2,9-dicarboxylic acid diethyl ester:

[0047] Preparation of 9-hydroxy-6,8-dimethyl-9H-fluorene-2 ​​using ethyl 2-(2,4-dimethylphenyl)-2-oxoacetate and ethyl 4-iodobenzoate as raw materials ,Diethyl 9-dicarboxylate, 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 ethyl 2,4-dimethylbenzoate and 138.0mg (0.5mmol) of ethyl 4-iodobenzoate in the airtight pressure 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 pass specification is F-254 TLC plate tracking, the reaction raw material no longer consu...

Example Embodiment

[0052] Example 3

[0053] Preparation of 9-hydroxyfluorene-9-carboxylic acid ester compound is 9-hydroxy-1,3-dimethyl-5-nitro-9H-fluorene-9-carboxylic acid ethyl ester:

[0054] Preparation of 9-hydroxy-1,3-dimethyl-5-nitro-9H- with 2-(2,4-dimethylphenyl)-2-oxoacetate and o-nitroiodobenzene as raw materials The chemical reaction formula of fluorene-9-carboxylic acid ethyl ester is as follows:

[0055]

[0056] Specific steps are as follows:

[0057] Add 4.49mg (0.02mmol) of palladium acetate, 41.2mg (0.2mmol) of ethyl 2-(2,4-dimethylphenyl)-2-oxoacetate, and 124.5 of o-nitroiodobenzene into the airtight pressure tube. mg (0.5 mmol), 88.4 mg (0.4 mmol) of silver trifluoroacetate (AgTFA), 136.8 mg (1.2 mmol) of trifluoroacetic acid and 14.3 mg (0.08 mmol) of 2-fluoro-5-trifluoromethylaniline, 1.8 mL 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 F-254 TLC plate tracking, the rea...

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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

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Application Information

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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
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