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Synthesis of esterifiable fluorene diborate

A synthesis method and the technology of dialkyl diboronic esters are applied in the field of new method synthesis of dialkyl diboronic esterified fluorene monomers, which can solve the problems of unsuccessful synthesis of diboronic esters, increased difficulty of experiments, and problems in experiments. Harsh conditions and other problems, to achieve the effect of great practical value, simple post-processing, and short reaction time

Active Publication Date: 2009-05-13
溧阳常大技术转移中心有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Synthesizing dialkyl diboronic esterified fluorene with this method, although obtained good effect under the condition of not using any catalyst, there are some shortcomings as follows: (1) the reaction needs to be carried out in multiple steps
(2) The experimental conditions are relatively harsh
Such a low temperature is generally achieved with a dry ice and acetone bath or liquid nitrogen, which increases the difficulty of the experiment during the experiment
(3) The risk of the experiment is high
This is mainly for the dehydration treatment of the solvent tetrahydrofuran (THF) used in the experiment. The process is to put sodium metal into the flask containing the corresponding solvent THF, and then heat it. In the process, it will Produces hydrogen gas which may cause an explosion hazard if not handled properly
(4) The reaction takes a long time, generally more than 24 hours
(5) The operation is complicated and the requirements for the laboratory are high
However, there is no report of any successful synthesis of diboronic acid esters of halogenated aromatics or halogenated heterocyclic aromatics by this method

Method used

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  • Synthesis of esterifiable fluorene diborate
  • Synthesis of esterifiable fluorene diborate
  • Synthesis of esterifiable fluorene diborate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Reactant 2,7-dibromo-9,9-dioctylfluorene and catalyst PdCl 2 The molar ratio of (dppf) is: 1:6%

[0026] Catalyst PdCl 2 The molar ratio of (dppf) to DABCO is: 1:16

[0027] Add 2mmol 2,7-dibromo-9,9-dioctylfluorene, 4.4mmol double pinacol borate 12%mmolPdCl in a 100ml four-necked flask equipped with a thermometer and a magnetic stirrer 2 (dppf), 192% mmol DABCO, 12 mmol potassium acetate and 10 ml toluene, vacuumize and feed nitrogen, and continuously stir and react for 4 h under the condition of heating in an oil bath at 80°C. The organic layer was separated, the aqueous layer was extracted several times with toluene, the organic layers were combined, and the organic layer was washed several times with water, then dried with anhydrous magnesium sulfate, and then passed through a column (silica gel as the solid phase, toluene as the mobile phase), and the Evaporate the solvent to dryness with an evaporator to obtain a crude product as a pale yellow solid, and finall...

Embodiment 2

[0029] Reactant 2,7-dibromo-9,9-dioctylfluorene and catalyst PdCl 2 The molar ratio of (dppf) is: 1:6%

[0030] Catalyst PdCl 2 The molar ratio of (dppf) to DABCO is: 1:20

[0031] Add 2mmol 2,7-dibromo-9,9-dioctylfluorene, 4.4mmol double pinacol borate 12%mmolPdCl in a 100ml four-necked flask equipped with a thermometer and a magnetic stirrer 2 (dppf), 240% mmol DABCO, 12 mmol potassium acetate and 10 ml toluene were vacuumed and nitrogen gas was introduced, and the reaction was continuously stirred for 4 h under the condition of heating in an oil bath at 80°C. The organic layer was separated, the aqueous layer was extracted several times with toluene, the organic layers were combined, and the organic layer was washed several times with water, then dried with anhydrous magnesium sulfate, and then passed through a column (silica gel as the solid phase, toluene as the mobile phase), and the Evaporate the solvent to dryness with an evaporator to obtain a crude product as a pa...

Embodiment 3

[0033] Reactant 2,7-dibromo-9,9-dioctylfluorene and catalyst PdCl 2 The molar ratio of (dppf) is: 1:4%

[0034] Catalyst PdCl 2 The molar ratio of (dppf) to DABCO is: 1:4

[0035]Add 2mmol 2,7-dibromo-9,9-dioctylfluorene, 4.4mmol double pinacol borate 8%mmolPdCl to a 100ml four-necked flask equipped with a thermometer and a magnetic stirrer 2 (dppf), 32% mmol DABCO, 12 mmol potassium acetate and 10 ml toluene, vacuumize and blow in nitrogen, and continuously stir and react for 6 h under the condition of heating in an oil bath at 80°C. The organic layer was separated, the aqueous layer was extracted several times with toluene, the organic layers were combined, and the organic layer was washed several times with water, then dried with anhydrous magnesium sulfate, and then passed through a column (silica gel as the solid phase, toluene as the mobile phase), and the Evaporate the solvent to dryness with an evaporator to obtain a crude product as a pale yellow solid, and finally...

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Abstract

The invention relates to a novel synthesis method for dialkyl diboronic acid esterification fluorene. The combination of palladium catalysts such as PdCl2 (dppf) and amine substances containing nitrogen ligands such as triethylenediamine (DABCO) or formamine (methenamine) and so on is taken as a catalytic system of the reaction, and methylbenzene is taken as a solvent to be continuously heated and stirred to react for certain hours under the protection of nitrogen atmosphere to successfully realize the boric acid esterification of dibromodialkylfluorene and realize the transformation of a synthesis process of the boric acid esterification of the dibromodialkylfluorene. Compared with the prior butyl lithium method, the method has the advantages that: (1) reaction conditions are easier to obtain, and the reaction operation is simple; (2) the experimental operation has high safety; (3) the reaction time is greatly reduced; and (4) the obtained product has high yield. The method also has the advantages that the method has an advanced process route, reasonable industrial conditions, simple and safe experimental operation, higher product yield, and larger practical value, and is a more ideal synthesis route.

Description

technical field [0001] The invention relates to the field of synthesizing polymer semiconductor materials such as polyfluorene and its copolymer, and mainly relates to a new method for synthesizing an important monomer dialkyl diboronate fluorene in polyfluorene-based polymer semiconductor materials. Background technique [0002] The current synthesis of dialkyl diboronic esterified fluorene mainly adopts the butyllithium route (references: [1] Sun Wenbin et al. New Chemical Materials [J]. 2007, 35 (8): 28. [2 ] Tang et al. Polymer [J]. 2007, 48: 4412-4418.), its yield is generally on the middle level (see Figure 2 for the synthetic route). The yield of literature [1] is 65%, and the yield of literature [2] is 81%. Although the synthesis of dialkyl diboronated fluorene by this method has achieved good results without using any catalyst, it has some disadvantages as follows: (1) The reaction needs to be carried out in multiple steps. In the literature [1], the reaction has ...

Claims

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Application Information

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IPC IPC(8): C07F5/04B01J31/22B01J31/30
Inventor 李坚方志国
Owner 溧阳常大技术转移中心有限公司
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