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Spiro biimidazole molecule as well as preparation method and application thereof

A biimidazole and molecular technology, applied in novel spirocyclic biimidazole organic small molecules, in the field of its synthesis, can solve the problem of no report of biimidazole molecules, and achieve the effect of fast fading rate

Active Publication Date: 2017-08-01
HUAZHONG UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

On the other hand, biimidazole-based photochromic and fluorescent switching materials have been reported one after another, but so far, biimidazole molecules with long-lived phosphorescence have not been reported.

Method used

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  • Spiro biimidazole molecule as well as preparation method and application thereof
  • Spiro biimidazole molecule as well as preparation method and application thereof
  • Spiro biimidazole molecule as well as preparation method and application thereof

Examples

Experimental program
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preparation example Construction

[0034] Specifically, the preparation method of such spirocyclic biimidazole molecules comprises the following steps:

[0035] (1) Dissolve diaryl ketone, carbon tetrabromide, and triphenylphosphine in toluene at a molar ratio of 1:2~4:4~8, heat to 100~140°C and reflux for 1~4 days, and the reaction is complete Afterwards, the solvent was spin-dried, and the residue was separated by silica gel column chromatography, and then the collected product was recrystallized from ethanol to obtain 1,1'-dibromo-2,2'-diarylethene;

[0036] (2) 1,1'-dibromo-2,2'-diarylethene obtained in step (1) and o-benzaldehyde phenylboronic acid, potassium carbonate and zero-valent palladium catalyst according to the molar ratio of 1:2~4: 4-8: 0.05-0.1 dissolved in a mixed solution of toluene and water, reacted for 12-24 hours at 90-110°C under a nitrogen atmosphere, after the reaction was complete, extracted the aqueous phase with dichloromethane, combined the organic phases, Then the solvent was spin...

example 1

[0043] X, R in formula (1) 1 and R 2 When both are H, the spiro biimidazole molecule is a benzophenone-spiro biimidazole molecule, and its synthesis includes the following four synthetic steps, such as figure 1 Shown:

[0044] 1) Preparation of 1,1'-dibromo-2,2'-diphenylethylene

[0045] In a 500ml single-necked round bottom flask, benzophenone (3.04g, 16,68mmol), carbon tetrabromide (11.06g, 33.36mmol), triphenylphosphine (17.53g, 66.84mmol), etc. were dissolved in toluene ( 250ml), heated to 140°C and refluxed for 4 days. After the reaction was complete, the solvent was spin-dried, and the residue was separated by column chromatography on silica gel, and then the collected product was recrystallized from ethanol to obtain 4.91 g of white crystals, with a yield of 87.1%. That is, the target molecule 1,1'-dibromo-2,2'-diphenylethylene can be obtained according to the following general formula

[0046]

[0047] 2) Synthesis of 2,2'-diphenyl-benzaldehyde

[0048] In a 2...

Embodiment 2

[0060] When X = S, R 1 =OCH 3 ,R 2 When =H, the synthesis of thioxanthone-spiro biimidazole comprises the following four synthetic steps: as Figure 7 , Figure 7 It is a synthetic route map of 4,4'-methoxy-thioxanthone-spirocyclic biimidazole molecule;

[0061] 1) Preparation of thioxanthone dibromoethylene

[0062] In a 500ml single-necked round bottom flask, dissolve thioxanthone (3.00g, 14.15mmol), carbon tetrabromide (13.91g, 42.45mmol), triphenylphosphine (22.25g, 84.9mmol), etc. in toluene (250ml) , heated to 140°C and refluxed for 2 days. After the reaction was complete, the solvent was spin-dried, and the residue was separated by column chromatography on silica gel, and then the collected product was recrystallized with ethanol to obtain 3.80 g of white crystals, with a yield of 73.4%. That is, the target molecule 1,1'-dibromo-2,2'-thioxanthoneethylene can be obtained according to the following general formula

[0063]

[0064] 2) Synthesis of thioxanthone-(...

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Abstract

The invention discloses a preparation method and application of a spiro biimidazole molecule and a relevant derivative. Diphenyl ketone or a derivative thereof is taken as a raw material, and a corresponding dibromo aromatic ring olefin product is prepared by Corey-Fuchs reaction; then the product and o-formaldehyde phenylboronic acid generate Suzuki reaction to obtain geminal-ortho aldehyde substituted tetraryl ethylene; then the geminal-ortho aldehyde substituted tetraryl ethylene generates Leuckart reaction with benzil or a derivative thereof in acetic acid and ammonium acetate to obtain geminal-ortho tetraphenyl ethylene-triphenyl imidazole; finally, under the oxidation of K3Fe(CN)6 / KOH, the spiro biimidazole molecule is obtained by free radical cyclization addition. The molecule shows phosphorescence emitting behavior with longer service life (1.6 seconds) under low temperature (77K). The 3D spiro molecule may provide guidance for preparing a long-service-life room temperature phosphorescence small organic molecule material.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and more specifically relates to a novel spirocyclic biimidazole organic small molecule, its synthesis method and application. Background technique [0002] There are many kinds of organic photochromic materials, including a new type of molecular switch that uses hexaarylbiimidazole (HABI for short) as a matrix to generate free radicals under light. The traditional biimidazole molecular design, because the two molecules of imidazole radicals are separated from each other after exposure to light, has slow fading and poor anti-fatigue performance, so it cannot be practically applied. In recent years, the intramolecular bridge-modified biimidazole molecules designed by bridge molecules have been proved to have extremely fast fading rates (J.Am.Chem.Soc.2004,126,6526-6527; J.Am.Chem .Soc.2009 131,4227–4229; J.Am.Chem.Soc.2014,136,3796-3799; J.Am.Chem.Soc.2015,137,4952-4955) and anomalous negative ph...

Claims

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Application Information

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IPC IPC(8): C07D471/22C07D495/22C09K11/06C09K9/02
CPCC07D471/22C07D495/22C09K9/02C09K11/06C09K2211/1007C09K2211/1029C09K2211/1044C09K2211/1092
Inventor 朱明强龚文亮熊祖劲陈泽强华琼新
Owner HUAZHONG UNIV OF SCI & TECH
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