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Preparation method of all-position replacement fluorene compounds obtained through halogen adjustment and control

A kind of fluorene compound, halogen technology

Active Publication Date: 2015-12-30
NANJING UNIV OF POSTS & TELECOMM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this reaction requires the use of o-methylarylboronic acid as a substrate, which limits the applicability of the substrate to some extent.

Method used

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  • Preparation method of all-position replacement fluorene compounds obtained through halogen adjustment and control
  • Preparation method of all-position replacement fluorene compounds obtained through halogen adjustment and control
  • Preparation method of all-position replacement fluorene compounds obtained through halogen adjustment and control

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Example 1: Under nitrogen protection, add phenylboronic acid (0.45mmol, 54.9mg) and palladium acetate (0.009mmol, 0.28mg) in a Schlenk reaction tube, in the glove box, add potassium phosphate (1.8mmol, 382.0mg) , tricyclohexylphosphine (0.018mmol, 5.0mg), lithium chloride (0.45mmol, 19.1mg), Molecular sieves (200 mg). Add o-bromobenzyl bromide (0.3mmol, 75mg) and pivalic acid (0.24mmol, 24.5mg) to the system successively under a nitrogen atmosphere, then add 5ml of tetrahydrofuran, stir for 5 minutes, and place the reaction React in a pot at 120°C for 12 hours. After the reaction was over, 3 milliliters of saturated ammonium chloride solution was added to the system to quench the reaction, and 15 milliliters of ethyl acetate was added for extraction three times. The organic phases were combined, dried over anhydrous sodium sulfate, and separated by column chromatography to obtain the product with a yield of 85%. %. Such as figure 2 , 3 shown.

[0054] In embodim...

Embodiment 11

[0058] Example 11: Under nitrogen protection, add phenylboronic acid (0.33mmol, 40.2mg) in a Schlenk reaction tube, palladium acetate (0.009mmol, 0.28mg), in the glove box, add potassium carbonate (1.8mmol, 248.8mg) , Tricyclohexylphosphine (0.018 mmol, 5.0 mg). Add o-chlorobenzyl bromide (0.3mmol, 61.7mg) and pivalic acid (0.3mmol, 30.6mg) to the system successively under a nitrogen atmosphere, then add 2ml of tetrahydrofuran, stir for 5 minutes, and react Placed in a pot at 130°C for 12 hours. After the reaction was over, 3 milliliters of saturated ammonium chloride solution was added to the system to quench the reaction, and 15 milliliters of ethyl acetate was added for extraction three times. The organic phases were combined, dried over anhydrous sodium sulfate, and separated by column chromatography to obtain the product with a yield of 62 %. Such as Figure 22 , 23 shown.

Embodiment 12-18

[0059] Example 12-18: Under nitrogen protection, arylboronic acid (0.33mmol), palladium acetate (0.009mmol, 0.28mg) was added in a Schlenk reaction tube, and potassium carbonate (1.8mmol, 248.8mg) was added in the glove box , Tricyclohexylphosphine (0.018 mmol, 5.0 mg). Add o-chlorobenzyl bromide (0.3mmol, 61.7mg) and pivalic acid (0.3mmol, 30.6mg) to the system successively under a nitrogen atmosphere, then add 2ml of tetrahydrofuran, stir for 5 minutes, and react Placed in a pot at 130°C for 12 hours. After the reaction was completed, 3 ml of saturated ammonium chloride solution was added to the system to quench the reaction, and 15 ml of ethyl acetate was added three times for extraction. The organic phases were combined, dried over anhydrous sodium sulfate, and separated by column chromatography to obtain the product. Such as Figure 24 to figure Figure 37 shown.

[0060] Table 2: Reaction of o-chlorobenzyl bromide with arylboronic acids.

[0061]

[0062] The pro...

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Abstract

The invention relates to a preparation method of all-position replacement fluorene compounds obtained through halogen adjustment, control and synthesis. The method comprises the steps that at the temperature of 120-130 DEG C, halogen benzyl bromide reacts with arylboronic acid for 12 hours in a tetrahydrofuran solution under the atmosphere of inorganic base, additives and nitrogen where palladium acetate / tricyclohexylphosphine serves as a catalytic system, and a series of fluorene compounds are obtained. According to both methods, simple, economical and easily-obtained raw materials serve as the base materials, synthesis of the all-position replacement fluorene compounds is achieved through a palladium catalytic cascade reaction, and the compounds have a great application prospect in medicine synthesis midbodies and organic optoelectronic material science.

Description

technical field [0001] The invention belongs to the field of preparation methods of various position-substituted fluorene compounds. Background technique [0002] Fluorene compounds widely exist in nature and natural products, and are key intermediates in the synthesis of many biomedical molecules. A series of fluorene-based material molecules with variable structures can be obtained by functionalizing the 9-position and 2,7-position. In the past forty years, with the development of organic semiconductor materials, fluorene-based material molecules have become the most important structural framework in the field of organic optoelectronic materials due to their special optoelectronic properties, and are widely used in organic / polymer light-emitting diodes (OLEDs) , organic solar cell (OPV), organic field effect transistor (OFET) and other fields. Since fluorene is a commercial industrial product extracted from tar, it is relatively easy to obtain, and changes in the structu...

Claims

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Application Information

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IPC IPC(8): C07C13/567C07C13/547C07C1/32C07C43/21C07C41/30C07C25/22C07C22/04C07C17/263C07D333/78
Inventor 宋娟孙威李亚丽
Owner NANJING UNIV OF POSTS & TELECOMM
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