CN105001027A - Fluorne compound preparing method - Google Patents
Fluorne compound preparing method Download PDFInfo
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- CN105001027A CN105001027A CN201510442486.9A CN201510442486A CN105001027A CN 105001027 A CN105001027 A CN 105001027A CN 201510442486 A CN201510442486 A CN 201510442486A CN 105001027 A CN105001027 A CN 105001027A
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Abstract
The invention belongs to the chemical field and relates to a fluorne compound preparing method, in particular to a method for preparing a fluorne compound by means of 9-fluorenone and a phenolic compound under the condition that heteropolyacid is used as a catalyst. By the adoption of the fluorne compound preparing method, oxidation of a phenolic reactant is avoided; the use amount of the catalyst is small, reaction is stable, the liquidity of materials is high, the reaction yield is high, and the number of byproducts is small.
Description
Technical field
The invention belongs to chemical field, specifically relate to the preparation method of fluorenes based compound.
Background technology
Fluorenes and derivatives class material thereof, be mainly rigid plane biphenyl structural, has higher thermostability and photochemical stability, shows photoelectric properties and the biological activity of many uniquenesses.If the fluorescence quantum efficiency of solid-state fluorenes is up to 60% ~ 80%, band-gap energy is greater than 2.90eV; There is in molecule larger conjugation absorbing wavelength; There is more obvious electroluminescent, photoluminescence (phosphorescence and fluorescence) phenomenon; Its 2,7 and 9 carbon are easy to carry out structural modification and introduce the electronic structure that multiple functional group can change material, there is again good modifiability simultaneously; Fluorenes itself is one of product separation of coal tar in addition, and output is large, and cheap, raw material is easy to get.Therefore, the multi-field extensive application such as compound of fluorene class photoelectric material, solar cell, biological medicine.
But to the modification of assorted fluorenes different loci, the effective conjugate length of molecule will be caused, molecular configuration, Energy of molecular orbitals, molecule crystallographic texture produces larger difference, as biphenyl aromatic ring system is introduced fluorenes system, the number of further increase conjugate unit and kind, increase effectively the conjugate length of molecule, reduce intermolecular π – π stacking, as bisphenol fluorene, its by a large amount of in condensation reaction, in particular for preparation, there is high heat resistance, good optical property, the epoxy resin of good flame retardant properties, poly-ammonia is cruel, poly-carbonic acid is cruel, poly-cruel, poly aromatic fat, the polycondensation products such as polyethers or polyether.After introducing this structure of bisphenol fluorene in epoxy resin, because rigidity improves, thermotolerance improves greatly than traditional bisphenol A epoxide resin (D G EBA).Also epoxy curing agent can be prepared with this kind of material, as bisphenol fluorene diglycidylether (D G EBF), Schutlz has prepared bisphenol fluorene diglycidylether (D G EBF) at first and has found that this resin mellic acid three is joined or after two (4 one aminophenyl) alum (DDM) solidification, Heat of Formation is oxidized highly stable material.
At present, the production method mainly sulfuric acid process of bisphenol fluorene is prepared.This method with 96% one 98% sulfuric acid as condensation catalyst, by phenol: Fluorenone: the ratio of components of sulfuric acid (mol ratio) 4:1:0.5, first phenol, Fluorenone are thrown in reactor, stir and keep temperature of reaction below 30 DEG C, then dropwise sulfuric acid is added, maintain the temperature at 30-70 DEG C, then add the method that appropriate thin base propionic acid is cocatalyst bisphenol fluorene synthesizing.This method is easy to operate, but in preparation process one be use the vitriol oil pollute the environment; Two is if when phenol content is too much, easily remains phenol, needs to reclaim separately; If phenol content deficiency, easily produce by product list phenol body, its structural formula is:
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes the preparation method of fluorenes based compound, by changing catalyzer, reaching and improving the productive rate of reaction product and the object of protection of the environment.
For solving the problems of the technologies described above, the present invention proposes the preparation method of fluorenes based compound, adopt 9 ?Fluorenone and phenolic compound under heteropolyacid is the condition of catalyzer, prepare fluorenes based compound, described fluorenes based compound possesses following structural formula,
In formula, Ar is
As the preferred technical solution of the present invention, described 9 ?the consumption of Fluorenone, phenolic compound and heteropolyacid be respectively m mole 9 ?Fluorenone, the phenolic compound of n mole and the heteropolyacid of k mole, wherein m:n:k is 1:(2 ~ 6): (0.1 ~ 0.7).
As the present invention's further optimal technical scheme, described 9 ?the consumption of Fluorenone, phenolic compound and heteropolyacid to be preferably m:n:k be 1:3:0.5.
As the present invention's further optimal technical scheme, described heteropolyacid is phosphorus vanadic acid, germanium vanadic acid, arsenic vanadic acid, phosphorus niobic acid, germanium niobic acid, silicomolybdic acid, silicotungstic acid, phospho-molybdic acid, titanium molybdic acid, germanium molybdic acid, arsenic molybdic acid, tin molybdic acid, phospho-wolframic acid, germanotungstic acid, stannotungstic acid, molybdovanaphosphoric acid, tungstovanadophosphoric acid, germanium tungsten vanadic acid, P-Mo-Wo-V acid, Ge-Mo-Wo-V acid, P-Mo-Wo acid or P-Mo-Nb acid.
As the preferred technical scheme of the present invention, described heteropolyacid is preferably phospho-wolframic acid, silicotungstic acid, molybdovanaphosphoric acid, tungstovanadophosphoric acid or P-Mo-Wo-V acid.
As the present invention's further optimal technical scheme, described phenolic compound be phenol, pyrocatechol, ortho-cresol, Phenoxyethanol, phenyl o-phenyl phenol or 2 ?naphthols.
As the present invention's further optimal technical scheme, reaction carries out in organic solvent toluene or dimethylbenzene, the mole dosage of organic solvent be 9 ?7 ~ 16 times of mole dosage of Fluorenone.
As the present invention's further optimal technical scheme, reaction carries out in the temperature range of 70 DEG C ~ 120 DEG C, and the reaction times is 2h.
As the present invention's further optimal technical scheme, also comprise and reacted product is cleaned with acetone in the temperature range of 30 DEG C ~ 40 DEG C, and dry.
Beneficial effect of the present invention
Heteropolyacid is adopted to replace the vitriol oil to be that catalyzer has following advantage: (1), the vitriol oil have strong oxidizing property, easily reactant phenols is oxidized, by-product isomer is increased, reduce yield, and use heteropolyacid just there is no this side effect, be more preferably phospho-wolframic acid; (2), sulfuric acid needs after the reaction to wash by massive laundering or washes with alkali neutralization again, and aftertreatment bothers, and wastewater flow rate is large, and " phospho-wolframic acid " is soluble in water, and consumption is few, just can remove after reaction with a small amount of water; (3), with the vitriol oil make catalyst reaction violent, quick heating, wayward, material easily lumps, and uses " phospho-wolframic acid " for catalyzer, and consumption is few, reacting balance, and material fluidity is good, and reaction yield is high, and by-product is few.
Accompanying drawing explanation
The color atlas of fluorenes based compound is obtained prepared by accompanying drawing 1 the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.Following instance is only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention, and the person skilled in the art in this field can make some nonessential improvement and adjustment according to foregoing invention content to the present invention.
Embodiment 1
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 7mol dimethylbenzene, 1mol 9 ?Fluorenone and 3mol phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.5mol phospho-wolframic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 70 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.98mol, product yield is 98%.
The structural formula of products therefrom is as follows:
In formula I, Ar is
Embodiment 2
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 16mol toluene, 1mol 9 ?Fluorenone, 2mol phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.1mol silicotungstic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 90 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 40 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.999mol, product yield is 99.9%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 3
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 8mol toluene, 1mol 9 ?Fluorenone, 6mol pyrocatechol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.7mol molybdovanaphosphoric acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 100 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 35 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 4
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
By 15mol toluene 1mol 9 ?Fluorenone, 0.4mol ortho-cresol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.15mol tungstovanadophosphoric acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 95 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 40 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.989mol, product yield is 98.9%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 5
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 10mol toluene 1mol 9 ?Fluorenone, 4mol ortho-cresol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.6mol P-Mo-Wo-V acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 110 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 40 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 6
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 13mol toluene, 1mol 9 ?Fluorenone, 3.5mol ortho-cresol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.23mol germanium vanadic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 120 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 38 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.985mol, product yield is 98.5%.
The structural formula I of products therefrom is as follows:
In formula, Ar is
Embodiment 7
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 14mol dimethylbenzene, 1mol 9 ?Fluorenone, 5.2mol Phenoxyethanol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.23mol arsenic vanadic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise 115 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 39 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.991mol, product yield is 99.1%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 8
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 8.5mol dimethylbenzene, 1mol 9 ?Fluorenone, 2.9mol Phenoxyethanol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.5mol phosphorus niobic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise 115 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 39 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula I of products therefrom is as follows:
In formula, Ar is
Embodiment 9
Concrete scheme of the present invention is: the preparation method of fluorenes based compound, comprises the steps:
A. by 12.5mol toluene, 1mol 9 ?Fluorenone, 3.7mol Phenoxyethanol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.5mol germanium niobic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise 115 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 39 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.995mol, product yield is 99.5%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 10
The preparation method of fluorenes based compound, comprises the steps:
A. by 14.5mol toluene, 1mol 9 ?Fluorenone and 3.6mol phenyl o-phenyl phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.54mol silicomolybdic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 70 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.98mol, product yield is 98%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 11
The preparation method of fluorenes based compound, comprises the steps:
A. by 8mol toluene, 1mol 9 ?Fluorenone and 4.3mol phenyl o-phenyl phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.7mol phospho-molybdic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 80 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 33 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.98mol, product yield is 98%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 12
The preparation method of fluorenes based compound, comprises the steps:
A. by 9.5mol dimethylbenzene, 1mol 9 ?Fluorenone and 4.1mol phenyl o-phenyl phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.45mol titanium molybdic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 95 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 13
The preparation method of fluorenes based compound, comprises the steps:
A. by 10mol dimethylbenzene, 1mol 9 ?Fluorenone and 2.8mol phenyl o-phenyl phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.35mol germanium molybdic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 90 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.995mol, product yield is 99.5%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 14
The preparation method of fluorenes based compound, comprises the steps:
A. by 11mol dimethylbenzene, 1mol 9 ?Fluorenone and 3mol phenyl o-phenyl phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.45mol arsenic molybdic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 100 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.996mol, product yield is 99.6%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 15
The preparation method of fluorenes based compound, comprises the steps:
A. by 12mol toluene, 1mol 9 ?Fluorenone and 2.6mol phenyl o-phenyl phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.7mol arsenic molybdic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 120 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 36 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.991mol, product yield is 99.1%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 16
The preparation method of fluorenes based compound, comprises the steps:
A. by 13mol dimethylbenzene, 1mol 9 ?Fluorenone and 6mol phenyl o-phenyl phenol add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.56mol tin molybdic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 90 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 31 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.998mol, product yield is 99.8%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 17
The preparation method of fluorenes based compound, comprises the steps:
A. by 10mol dimethylbenzene, 1mol 9 ?Fluorenone and 4mol 2 ?naphthols add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.35mol germanotungstic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 95 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 18
The preparation method of fluorenes based compound, comprises the steps:
A. by 13mol dimethylbenzene, 1mol 9 ?Fluorenone and 3.2mol 2 ?naphthols add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.15mol stannotungstic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 87 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 33 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 19
The preparation method of fluorenes based compound, comprises the steps:
A. by 10mol dimethylbenzene, 1mol 9 ?Fluorenone and 3mol 2 ?naphthols add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.15mol germanium tungsten vanadic acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 90 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 20
The preparation method of fluorenes based compound, comprises the steps:
A. by 14.2mol dimethylbenzene, 1mol 9 ?Fluorenone and 5.1mol 2 ?naphthols add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.35mol Ge-Mo-Wo-V acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 97 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 30 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 21
The preparation method of fluorenes based compound, comprises the steps:
A. by 13mol dimethylbenzene, 1mol 9 ?Fluorenone and 5mol 2 ?naphthols add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.24mol Ge-Mo-Wo-V acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 73 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 36 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 22
The preparation method of fluorenes based compound, comprises the steps:
A. by 13mol dimethylbenzene, 1mol 9 ?Fluorenone and 3.2mol 2 ?naphthols add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.24mol P-Mo-Nb acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 98 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 31 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 23
The preparation method of fluorenes based compound, comprises the steps:
A. by 12mol dimethylbenzene, 1mol 9 ?Fluorenone and 3.45mol 2 ?naphthols add reactor, stir said mixture, make it be uniformly dissolved;
B. in reaction vessel, dropwise add 0.25mol P-Mo-Wo acid, make catalyzer, promote the carrying out of condensation reaction;
C. reacting by heating container, makes solution temperature in container rise to 99 DEG C, isothermal reaction 2h;
D. in cooling reactor to reactor, solution temperature is low to moderate room temperature, then filters, and gets its filter cake;
E. be the acetone solution of 37 DEG C by above-mentioned filter cake temperature, filter, get its filtrate;
F. by above-mentioned filtrate low rate mixing, make its crystallisation by cooling, when temperature is low to moderate room temperature, filter, obtain white crystal,
G. dried by above-mentioned white crystal, both obtained fluorenes based compound 0.99mol, product yield is 99%.
The structural formula of products therefrom is as follows:
In formula, Ar is
Embodiment 1 ?obtain the color atlas of product as accompanying drawing 1 prepared by 23, the analytical results of stratographic analysis is as shown in the table.
Analytical results
Claims (9)
1. the preparation method of fluorenes based compound, is characterized in that: adopt 9 ?Fluorenone and phenolic compound under heteropolyacid is the condition of catalyzer, prepare fluorenes based compound, described fluorenes based compound possesses following structural formula,
In formula, Ar is
2. the preparation method of fluorenes based compound according to claim 1, it is characterized in that: described 9 ?the consumption of Fluorenone, phenolic compound and heteropolyacid be respectively m mole 9 ?Fluorenone, the phenolic compound of n mole and the heteropolyacid of k mole, wherein m:n:k is 1:(2 ~ 6): (0.1 ~ 0.7).
3. the preparation method of fluorenes based compound according to claim 2, is characterized in that: described 9 ?the consumption of Fluorenone, phenolic compound and heteropolyacid to be preferably m:n:k be 1:3:0.5.
4. the preparation method of the fluorenes based compound according to claim 1,2 or 3, is characterized in that: described heteropolyacid is phosphorus vanadic acid, germanium vanadic acid, arsenic vanadic acid, phosphorus niobic acid, germanium niobic acid, silicomolybdic acid, silicotungstic acid, phospho-molybdic acid, titanium molybdic acid, germanium molybdic acid, arsenic molybdic acid, tin molybdic acid, phospho-wolframic acid, germanotungstic acid, stannotungstic acid, molybdovanaphosphoric acid, tungstovanadophosphoric acid, germanium tungsten vanadic acid, P-Mo-Wo-V acid, Ge-Mo-Wo-V acid, P-Mo-Wo acid or P-Mo-Nb acid.
5. the preparation method of fluorenes based compound according to claim 4, is characterized in that: described heteropolyacid is preferably phospho-wolframic acid, silicotungstic acid, molybdovanaphosphoric acid, tungstovanadophosphoric acid or P-Mo-Wo-V acid.
6. the preparation method of the fluorenes based compound according to claim 1,2 or 3, is characterized in that: described phenolic compound be phenol, pyrocatechol, ortho-cresol, Phenoxyethanol, phenyl o-phenyl phenol or 2 ?naphthols.
7. the preparation method of the fluorenes based compound according to claim 1,2 or 3, is characterized in that: reaction carries out in organic solvent toluene or dimethylbenzene, the mole dosage of organic solvent be 9 ?7 ~ 16 times of mole dosage of Fluorenone.
8. the preparation method of the fluorenes based compound according to claim 1,2 or 3, is characterized in that: its reaction carries out in the temperature range of 70 DEG C ~ 120 DEG C, and the reaction times is 2h.
9. the preparation method of the fluorenes based compound according to claim 1,2 or 3, is characterized in that: also comprise and cleaning with acetone in the temperature range of 30 DEG C ~ 40 DEG C reacted product, and dry.
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| CN110894181A (en) * | 2018-09-12 | 2020-03-20 | 中国石油化学工业开发股份有限公司 | Preparation method of bisphenol fluorene compound |
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