CN103333204B - One class 9, the synthetic method of 9 '-spirobifluorene derivative - Google Patents
One class 9, the synthetic method of 9 '-spirobifluorene derivative Download PDFInfo
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- CN103333204B CN103333204B CN201310291849.4A CN201310291849A CN103333204B CN 103333204 B CN103333204 B CN 103333204B CN 201310291849 A CN201310291849 A CN 201310291849A CN 103333204 B CN103333204 B CN 103333204B
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Abstract
The invention discloses a class 9, the synthetic method of 9 '-spirobifluorene derivative, belong to organic chemical synthesis field.By the following method realize: under protection of inert gas, in methyl-tetrahydrofuran solvent with adjacent bromine halobenzene for raw material, at 50-100 DEG C with phenyl-magnesium-bromide effect after, react with bromo Fluorenone again, then through hydrolysis, filter, solid is closed loop synthetic bromide generation-9,9 '-spiral shell two fluorenes under acid catalysis; Then bromo-9,9 '-spiral shell two fluorenes and diphenylphosphine lithium Reactive Synthesis 9,9 '-spiral shell two fluorenes diphenylphosphine derivative.Synthetic method process of the present invention is simple, low in raw material price, is easy to get, and significantly reduces the production cost of series product in building-up process, has expanded fluorene derivatives as the application of intermediate in organic photoelectrical material design and synthesis.
Description
Technical field
The present invention relates to the synthetic method of a class organic phosphine derivatives, particularly relate to a class 9, the synthetic method of 9 '-spirobifluorene derivative, belong to organic chemical synthesis field.
Background technology
Electroluminescent organic material has that material selection range is wide, energy consumption is low, efficiency and luminosity is high, ultra-thin, all solidstate, fast response time, active illuminating and can the advantage such as large area flexible display, be expected to the core component becoming flat panel display of new generation, become one of the study hotspot in organic electronics and optoelectronic information field.Fluorenes class organic phosphine derivatives is the luminescent material that a class has broad prospect of application.Fluorenes has higher photo and thermal stability, and solid-state fluorenes fluorescence quantum efficiency is up to 60%-80%, and band-gap energy is greater than 2.90eV.Fluorenes structurally has certain modifiability, but the rigid plane biphenyl unit that fluorenes has makes again material easily form excimer when luminescence and produce longwave transmissions, have impact on the stability of the radiative saturated colour purity of device and glow color.For improving the comprehensive luminescent properties of fluorenes class material, the side chain that 2 or 7 of fluorenes are introduced large group or steric effect of having living space all proves one and effectively reduces interchain interaction, stops mixture to produce with the method for the thermostability and spectrum stability of improving polyfluorene.9,9 '-spiral shell two fluorenes diphenylphosphine derivative wherein represents.
At present, 9,9 '-spiral shell two fluorenes diphenylphosphine derivative usually with bromo-9,9 '-spiral shell two fluorenes be raw material at-70 DEG C with after n-Butyl Lithium effect with diphenyl phosphine chloride Reactive Synthesis.In this process raw materials used bromo-9,9 '-spiral shell two fluorenes all with 2-bromo biphenyl for Material synthesis.At present, on market, 2-bromo biphenyl is expensive, and supply is not enough, causes bromo-9,9 '-spiral shell two fluorenes to hold at high price, finally makes 9, and 9 '-spiral shell two fluorenes diphenylphosphine derivative is difficult to suitability for industrialized production, and then has influence on its potential application in luminescent material.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate, lower-cost synthesis 9, the method for 9 '-spirobifluorene derivative, meets industrial production demand.
For realizing the object of the invention, the present invention for Material synthesis bromo-9,9 '-spiral shell two fluorenes, then reacts obtained target compound with cheap adjacent bromine halobenzene with diphenylphosphine lithium.
Concrete grammar is as follows: under protection of inert gas; adjacent bromine halobenzene reacts with phenyl-magnesium-bromide in methyl-tetrahydrofuran solvent; after reaction terminates, by the diethyl ether solution of above-mentioned reaction solution instillation bromo Fluorenone, back flow reaction; through hydrolysis; obtain solid after filtration, solid is reacted in nitration mixture, after filtration, obtain crude solid; bromo-9,9 '-spiral shell two fluorenes is obtained through chromatography.Then bromo-9,9 '-spiral shell two fluorenes reacts with diphenylphosphine lithium in tetrahydrofuran solvent, obtains crude solid after filtration, obtains target product through chromatography.
Described bromo Fluorenone is 2-bromine Fluorenone and 2,7-dibromo fluorenone; Described nitration mixture is glacial acetic acid and hydrochloric acid mixture, and volume ratio is 100: 1.
Described target product structural formula is as follows:
In bromo-9,9 '-spiral shell two fluorenes building-up process, the adjacent bromine halobenzene of use is adjacent bromo-iodobenzene, o-dibromobenzene or adjacent bromochlorophene.
In bromo-9,9 '-spiral shell two fluorenes building-up process, the mol ratio of adjacent bromine halobenzene and phenyl-magnesium-bromide is between 1: 0.9-1.5, and preferably mol ratio is between 1: 1-1.3.
In bromo-9,9 '-spiral shell two fluorenes building-up process, the temperature of reaction of adjacent bromine halobenzene and phenyl-magnesium-bromide is between 50-100 DEG C, and preferably temperature of reaction is between 70-90 DEG C; The reaction times of adjacent bromine halobenzene and phenyl-magnesium-bromide is between 8-20h, and preferably the reaction times is between 10-15h.
The present invention uses adjacent bromine halobenzene to synthesize bromo-9,9 '-spiral shell two fluorenes as starting raw material, product structure warp
1hNMR characterizes.This synthesis technique is simple to operate, and use raw material is easy to get, cost is low, and compared with the synthetic method being raw material with directly using 2-bromo biphenyl, cost reduces by more than 60%, meets industrial production demand.
specific implementation method
For illustrating better the present invention, as follows for embodiment:
example 1:
Under argon shield, control temperature of reaction 100 DEG C, the methyltetrahydrofuran solution of adjacent for 10mL bromochlorophene (0.1mmol) is added dropwise in 5mL phenyl-magnesium-bromide (0.15mmol) methyltetrahydrofuran solution, stirring reaction 20h.Then by above-mentioned reaction solution instillation 10mL2-bromine Fluorenone (0.1mmol) diethyl ether solution, after back flow reaction 2h, hydrolysis, filter, solid reacts 4h at 75 DEG C in 5mL nitration mixture (glacial acetic acid and hydrochloric acid), filters, crude solid uses methylene dichloride-normal hexane mixed solvent to do eluent chromatography (200-300 order silica gel), obtain 2-bromo-9,9 '-spiral shell two fluorenes 30.0mg, yield 76.0%.Gained 2-bromo-9,9 '-spiral shell two fluorenes reacts with diphenylphosphine lithium (0.075mmol) in 10mL tetrahydrofuran solvent, after back flow reaction 5h, add methyl alcohol 10mL to reaction solution, filter to obtain solid, washing, solid crude product uses toluene-normal hexane mixed solvent to do eluent chromatography (200-300 order silica gel) and obtains target product phenylbenzene-2-(9,9 '-spiral shell two fluorenyl) phosphine 30.3mg, yield 81.1%.
bromo-9, the Structural Identification of 9 '-spiral shell two fluorenes:
1HNMR(300MHz，CDCl
3),δ/ppm：7.861-7.796（m，3H；ArH)，7.716-7.689(d，1H；J=8.1Hz；ArH)，7.500-7.468(dd，1H；J
1=8.1Hz；J
2=1.8Hz；ArH)，7.412-7.342(m，3H；ArH)，7.154-7.100(m，3H；ArH)，6.850-6.844(m，1H；J=1.8Hz；ArH)，6.738-6.710(m，3H；ArH)).
the Structural Identification of phenylbenzene-2-(9,9 '-spiral shell two fluorenyl) phosphine:
1HNMR(300MHz，CDCl
3),δ/ppm：8.282-8.257(d,1H；J=7.5Hz；ArH),7.851-7.713(m,6H；ArH),7.532-7.499(m,6H；ArH),7.420-7.164(m,4H；ArH),7.151-6.831(m,8H；ArH).
example 2
Under argon shield, control temperature of reaction 80 DEG C, the methyltetrahydrofuran solution of 10mL o-dibromobenzene (0.1mmol) is added dropwise in the methyltetrahydrofuran solution of 5mL phenyl-magnesium-bromide (0.11mmol), stirring reaction 12h.Then by above-mentioned reaction solution instillation 10mL2, in 7-dibromo fluorenone (0.1mmol) diethyl ether solution, after reflux 2h, hydrolysis, filters, solid reacts 4h at 75 DEG C in 5mL nitration mixture (glacial acetic acid and hydrochloric acid), filter, obtain solid and use methylene dichloride-normal hexane mixed solvent to do eluent chromatography (200-300 order silica gel) and obtain product 2,7-bis-bromo-9,9 '-spiral shell two fluorenes 36.2mg, yield 76.2%.Above-mentioned gained 2,7-bis-bromo-9,9 '-spiral shell two fluorenes reacts with diphenylphosphine lithium (0.15mmol) in tetrahydrofuran solvent, after backflow 12h, adds methyl alcohol to reaction solution, filtration obtains solid, washing, solid uses toluene-normal hexane mixed solvent to do eluent chromatography (200-300 order silica gel) and obtains target product 2,7-bis-(diphenylphosphine)-9,9'-spiral shell two fluorenes 35.9mg, yield 70.1%.
two bromo-9, the Structural Identification of 9 '-spiral shell two fluorenes:
1HNMR(300MHz，CDCl
3),δ/ppm：7.860-7.835（d，2H；J=7.5Hz；ArH)，7.679-7.652(d，2H；J=8.1Hz；ArH)，7.502-7.469(dd，2H；J
1=8.1Hz；J
2=1.7Hz；ArH)，7.404-7.402(d，2H；J=0.6Hz；ArH)，7.144(s，2H；ArH)，6.836-6.831(d，2H；J=1.5Hz；ArH)，6.732-6.707(d，2H；J=7.5Hz；ArH)).
the Structural Identification of 2,7-bis-(diphenylphosphine)-9,9'-spiral shell two fluorenes:
1HNMR(300MHz，CDCl
3),δ/ppm：8.208-8.182(d,2H；J=8.0Hz；ArH),7.871-7.753(m,14H；ArH),7.514-7.335(m,16H；ArH),7.147-7.122(m,2H；J=7.5Hz；ArH).
example 3:
Under argon shield, control temperature of reaction 50 DEG C, the methyltetrahydrofuran solution of adjacent for 10mL bromo-iodobenzene (0.1mmol) is added dropwise in the methyltetrahydrofuran solution of 5mL phenyl-magnesium-bromide (0.09mmol), stirring reaction 8h.Then by above-mentioned reaction solution instillation 5mL2-bromine Fluorenone (0.1mol) diethyl ether solution, after backflow 2h, hydrolysis, filtration obtains solid and react 4h at 75 DEG C in 10mL nitration mixture (glacial acetic acid and hydrochloric acid), filter, obtain solid and use methylene dichloride-normal hexane mixed solvent to do eluent chromatography (200-300 order silica gel), dry 2-bromo-9,9 '-spiral shell two fluorenes 30.9mg, yield 78.2%.Above-mentioned gained 2-bromo-9,9 '-spiral shell two fluorenes reacts with diphenylphosphine lithium (0.075mmol) in 5mL tetrahydrofuran (THF), after backflow 5h, add methyl alcohol and obtain solid, washing, filtration obtains solid and uses toluene-normal hexane mixed solvent to do eluent chromatography (200-300 order silica gel) and obtain phenylbenzene-2-(9,9 '-spiral shell two fluorenyl) phosphine 31.4mg, yield 80.5%.
Claims (2)
1. the class 9 that structural formula is following, the preparation method of 9 '-spirobifluorene derivative, it is characterized in that, under protection of inert gas, in methyltetrahydrofuran solution, with adjacent bromine halobenzene for raw material and phenyl-magnesium-bromide react, after end, reaction soln is instilled in the diethyl ether solution of bromo Fluorenone, back flow reaction, through hydrolysis, obtain solid after filtration, solid is reacted in nitration mixture; Obtain crude solid after filtration, obtain bromo-9,9 '-spiral shell two fluorenes through chromatography; Then bromo-9,9 '-spiral shell two fluorenes reacts with diphenylphosphine lithium in tetrahydrofuran solvent, obtains crude solid after filtration, is separated obtains target product through post; Described bromo Fluorenone is 2-bromine Fluorenone or 2,7-dibromo fluorenone;
；
Described adjacent bromine halobenzene is adjacent bromo-iodobenzene, o-dibromobenzene or adjacent bromochlorophene; The temperature of reaction of adjacent bromine halobenzene and phenyl-magnesium-bromide is 50-100 DEG C; The reaction times 8-20h of adjacent bromine halobenzene and phenyl-magnesium-bromide.
2. a class 9 as claimed in claim 1, the preparation method of 9 '-spirobifluorene derivative, is characterized in that, the mol ratio of adjacent bromine halobenzene and phenyl-magnesium-bromide is 1: 0.9-1.5.
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| CN105622334B (en) * | 2016-03-29 | 2018-01-16 | 河南省科学院化学研究所有限公司 | A kind of synthetic method of the fluorenes of 3 bromine, 9,9 ' spiral shell two |
| CN111548485B (en) * | 2020-06-17 | 2021-05-11 | 山西能源学院 | Conjugated microporous organic polymer and preparation method and application thereof |
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| CN101747374A (en) * | 2010-01-21 | 2010-06-23 | 中国科学院长春应用化学研究所 | Compound containing phosphorus-oxygen groups and organic electroluminescent device comprising compound containing phosphorus-oxygen groups and preparation method thereof |
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| CN102766033A (en) * | 2012-07-12 | 2012-11-07 | 上海师范大学 | Novel spirobifluorene compound 2,7-dimethyl-2',4-diacetyl spirobifluorene containing acetyl and preparation method and use thereof |
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Effective date of registration: 20160919 Address after: 457000 west section of Shengli Road, Henan, Puyang Patentee after: Puyang Huicheng Electronic Material Co., Ltd. Patentee after: Henan Academy of SciencesChemistry Institute Co., Ltd. Address before: 450002 Henan Province, Zhengzhou City Red Road No. 56 Patentee before: Henan Academy of SciencesChemistry Institute Co., Ltd. |