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A kind of method that catalyzes the synthesis of benzophosphole with pd nanoparticle

A technology of heterocyclopentadiene and benzophosphorus, which is applied in chemical instruments and methods, nanotechnology, catalyst activation/preparation, etc., and can solve problems such as complex reaction systems, cumbersome steps, and harsh reaction conditions

Inactive Publication Date: 2020-06-05
HENAN ACADEMY OF SCI CHEM RES INST CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these synthetic methods have some problems such as complicated steps, harsh reaction conditions, complex reaction systems, or special ligand-assisted catalysis. Therefore, it is urgent to develop a simple and efficient method for synthesizing benzophosphole
[0005] The simple and efficient catalytic synthesis of benzophospholene by Pd nanoparticles has not been reported so far

Method used

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  • A kind of method that catalyzes the synthesis of benzophosphole with pd nanoparticle
  • A kind of method that catalyzes the synthesis of benzophosphole with pd nanoparticle
  • A kind of method that catalyzes the synthesis of benzophosphole with pd nanoparticle

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Embodiment 1: Preparation of Pd nanoparticles

[0017] First add 2ml of ethanol solvent to a 10ml reaction bottle, then add 5mmol of aniline and 12.5mmol of tetrafluoroboric acid, add 12.5mmol of tert-butyl nitrite dropwise to the mixed solution under ice bath conditions, return to room temperature, react for 0.5h, and proceed to the reaction A small amount of ether was added to the solution, and a white precipitate was formed, which was filtered and dried to obtain 0.92 g (4.8 mmol) of phenyldiazotetrafluoroborate, with a yield of 96%; 4 mmol of phenyldiazotetrafluoroborate was added to a 250ml reaction flask salt (dissolved in 50ml tetrahydrofuran), then added 1mmol palladium acetate (dissolved in 50ml methanol), stirred at room temperature for 10min to 15min, the reaction solution became orange, and then added dropwise 5mmol sodium borohydride (dissolved in 50ml methanol) The solution was added dropwise and reacted at room temperature for 1 h until the reaction was c...

Embodiment 2

[0018] Embodiment 2: the preparation of reaction substrate I

[0019]

[0020] Under nitrogen protection, add 2mmol of compound (1) to a 50ml reaction flask, then add 10ml of anhydrous diethyl ether and 10ml of anhydrous tetrahydrofuran, lower the temperature of the system to -78°C, add 2.1mmol of n-butyllithium in n-hexane dropwise under nitrogen Solution (1.6M), after the dropwise addition, keep it warm at -78°C for 1 hour (reaction system 1), take another reaction bottle, add 10ml of anhydrous ether and 2.2mmol of aryl phosphorus dichloride, and cool down to -78°C ( Reaction system 2), add the solution of reaction system 1 into reaction system 2, and keep it warm for 15 minutes, then return to room temperature and continue the reaction for 1 hour, and add 20ml of water to the system. Extracted with ethyl acetate and spin-dried to obtain a crude product, which was purified by column chromatography to obtain the corresponding solid compound I with a yield of 84%-92%.

Embodiment 3

[0021] Embodiment 3: Preparation of benzophosphole target compound II (example is not limited to this)

[0022]

[0023] Preparation of Compound Ⅱ—01

[0024] Add 1 mmol of compound I-01 (R 1 = Ph, R 2 =Ph), 3ml of toluene solvent, 3mg of the Pd nanoparticles prepared above, reacted at 30°C for 0.5h, TLC detected that the reaction was complete, after extraction and drying, the solvent was distilled off under reduced pressure, and then purified by column chromatography to obtain 287mg (0.95 mmol) Compound II-01, white solid, yield 95%.

[0025]

[0026] The analysis data is: 1 H NMR (400MHz, CDCl 3 )δ:7.29-7.54(m,10H),7.60-7.80(5H); 13 CNMR (100MHz, CDCl 3 )δ:124.70(d,J PC =9.6Hz), 126.62, 128.95(d, J PC =12.4Hz), 128.96(d, J PC =10.8Hz), 128.97, 129.23, 129.96 (d, J PC =97.8Hz), 130.75, 132.27, 132.54, 132.75 (d, J PC =108.3Hz), 133.26, 136.58, 138.74 (d, J CP =94.2Hz,C),141.64(d,J PC = 28.2Hz); 31 PNMR (162MHz, CDCl 3 ) δ=39.3.

[0027] Preparation of Co...

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Abstract

The invention provides a novel method using Pd nano particles to catalytically synthesize benzophosphole and belongs to the field of organic synthesis. The method includes: the new Pd nano particles are synthesized first, a compound I is used as the reaction substrate, and cyclization is performed to obtain the target compound II as shown in the specification, wherein R1 and R2 represent phenyl, substituted phenyl or C1-5 alkyl. The method has the advantages that the method is good in selectivity, product yield can reach above 89%, industrial production is facilitated, and application of the benzophosphole in fields such as organic light-emitting functional materials (solar cells and organic light-emitting diodes), photochromic molecular switches and biological fluorescent probes.

Description

technical field [0001] The invention relates to a method for catalytically synthesizing benzophosphole by using Pd nanoparticles, which belongs to the field of organic synthesis. Background technique [0002] Phospholene has unique optical and electrochemical properties, and has a wide range of applications in the field of organic optoelectronic materials science. The phosphorus atom in the center of phospholene can be chemically modified to generate oxides, sulfides, transition Metal complexes, quaternary phosphonium salts, etc., especially oxides and sulfides, all exhibit high chemical and thermodynamic stability. As a special structure of phosphorole, benzophospholene is widely used in organic light-emitting functional materials (solar cells, organic light-emitting diodes), photochromic molecular switches, bioluminescent probes, etc. direction. [0003] Therefore, the method for synthesizing benzophosphole is getting more and more attention, but compared with the synthe...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/6568B01J23/44B01J37/16C09K11/06B82Y40/00
CPCB01J23/44B01J37/16B82Y40/00C07F9/65685C09K11/06C09K2211/1007C09K2211/1096
Inventor 刘长春张豫黎陈瑨霍萃萌王兰天柴存才魏爱勤代本才
Owner HENAN ACADEMY OF SCI CHEM RES INST CO LTD
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