CN101289397A - Method for preparing 4,4', di(2,6-dinitro-4-trifluoromethyl phenoxy)diphenyl ether - Google Patents

Method for preparing 4,4', di(2,6-dinitro-4-trifluoromethyl phenoxy)diphenyl ether Download PDF

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CN101289397A
CN101289397A CNA2008100369519A CN200810036951A CN101289397A CN 101289397 A CN101289397 A CN 101289397A CN A2008100369519 A CNA2008100369519 A CN A2008100369519A CN 200810036951 A CN200810036951 A CN 200810036951A CN 101289397 A CN101289397 A CN 101289397A
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dinitrobenzene
trifluoromethylphenopendant
phenyl ether
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trifluoromethyl
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虞鑫海
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Donghua University
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Abstract

The invention relates to a preparation method of 4, 4'-bis (2, 6-dinitro-4-trifluoromethyl phenoxy) diphenyl ether, including the following steps: (1) in salifying agents and the organic solvent system, 4, 4'-dihydroxy diphenyl ether and 2, 6-dinitro-4-trifluoromethyl halogeno benzene with a molar ratio of 1.0:2.0 to 2.2 carry on heating reflux water reaction for six to eighteen hours; (2) the reaction liquid is condensed; the reactant system is cooled; water is added to precipitate solid product; after filtered, washed and dried, the crystal of 4, 4'- bis(2, 6-dinitro-4 trifluoromethyl phenoxy) diphenyl ether is obtained. The method of the invention has the advantages of simple operation, high yield and purity of products, convenient recovery of solvent, repeated use, fewer three wastes, friendly environment and applicable to the industrial production.

Description

The preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether
Technical field
The invention belongs to the preparation field of aromatic organic compounds, particularly relate to a kind of preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether.
Background technology
Aromatic polyimide has excellent thermostability, chemical stability, anti-nuclear radiation, excellent mechanical property, electric property and organic solvent resistance, has obtained widespread use in space flight and aviation, electronics microelectronics, field such as electric.Because characteristics such as it these are high temperature resistant, high strength, anticorrosive, good insulating, film-forming process are simple, thereby be a kind of good functional materials, can satisfy the performance requriements of LCD (liquid-crystal display).
4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether is one of synthetic monomeric important source material of high cladodification aromatic polyimide, the i.e. important source material of the polynary primary amine of aromatic series.The polynary primary amine of aromatic series can be used to prepare the polyimide system of high cladodification, can make the polyimide novel material that temperature resistant grade is higher, over-all properties is better.
But the preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether does not have disclosed patent or bibliographical information at present as yet.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether, this method technology is simple, cost is low, environmental friendliness, purity and yield height, is applicable to industrial production.
Chemical equation of the present invention is as follows:
Figure A20081003695100031
Wherein, X is a halogen atom, i.e. fluorine (F), chlorine (Cl), bromine (Br), iodine (I).
The preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether of the present invention comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 4,4 '-dihydroxy diphenyl ether and 2,6-dinitrobenzene-4-trifluoromethyl halogeno-benzene, in salt forming agent, organic solvent system, reflux was divided water reaction 6～18 hours;
(2) concentration of reaction solution, the cooling reactant system adds water, separates out solid product, filter, washing, drying gets 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether crystal.
Described 2,6-dinitrobenzene-4-trifluoromethyl halogeno-benzene is selected from 2,6-dinitrobenzene-4-trifluoromethyl fluorobenzene, 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 2, one or more mixtures in 6-dinitrobenzene-4-trifluoromethyl phenyl-iodide.
Described salt forming agent is selected from one or more mixtures in Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Magnesium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, the calcium hydroxide.
Described salt forming agent and 4, the ratio of the mole number of 4 '-dihydroxy diphenyl ether is 0.10～8.00: 1.00.
Described organic solvent is the mixture of water-insoluble organic solvent and strong polar non-proton organic solvent, and volume ratio is 1: 0.05～10, strong polar non-proton organic solvent and 4, and the envelope-bulk to weight ratio of 4 '-dihydroxy diphenyl ether is 5 milliliters～80 milliliters: 1 gram.
Described water-insoluble organic solvent is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene.
Described strong polar non-proton organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
The temperature of described reaction is 80 ℃～180 ℃.
Beneficial effect of the present invention:
(1) the present invention is the commercial run of preparation 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether, and product yield and purity are all higher;
(2) simple to operate, reaction process is carried out under normal pressure, does not relate to also not producing corrosives, equipment is not had particular requirement, less investment;
(3) organic solvent uses kind few, and reclaims conveniently, Recycling repeatedly, and the three wastes are few, and are environmentally friendly;
(4) 4, reaction raw materials convenient sources such as 4 '-dihydroxy diphenyl ether, cost is lower, is convenient to further apply.
Description of drawings
Fig. 1 is 4, the molecular structure of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 59.5 gram (0.22 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 110.4 gram (0.80 mole) salt of wormwood, 1200 milliliters of N, dinethylformamide, 180 milliliters of benzene and 60 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 10 hours, concentration of reaction solution reclaims solvent to recycle the cooling reactant system, add water, separate out solid product, with hot wash 2～3 times, drying, obtain 4 of 64.8 grams, 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether crystalline product, purity is 99.7%, obtain 4 according to reality, the amount of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether and theoretical amount (67.0 gram) calculate 4, the yield of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether is 96.7%.
Embodiment 2
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 69.3 gram (0.22 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 10.0 gram (0.10 mole) saleratus, 10.6 gram (0.10 mole) yellow soda ash, 55.2 gram (0.40 mole) salt of wormwood, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 600 milliliters of N, the N-N,N-DIMETHYLACETAMIDE, 100 milliliters of benzene and 30 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 15 hours, concentration of reaction solution reclaims solvent to recycle the cooling reactant system, add water, separate out solid product, with hot wash 2～3 times, drying, obtain 61.2 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether crystalline product, purity is 99.6%, obtain 4 according to reality, the amount of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether and theoretical amount (67.0 gram) calculate 4, the yield of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether is 91.4%.
Embodiment 3
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 54.1 gram (0.20 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 10.6 gram (0.10 mole) yellow soda ash, 110 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 2000 milliliters of benzene and 200 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 10 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separates out solid product, with hot wash 2～3 times, drying obtains 55.2 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether crystalline product, purity is 99.7%, according to 4,4 '-two (2 of reality acquisition, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of phenyl ether and theoretical yield (67.0 gram), the yield that calculates 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether is 82.4%.
Embodiment 4
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 11.8 gram (0.21 mole) potassium hydroxide, 1000 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 300 milliliters of benzene and 50 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 6 hours, add 55.9 gram (0.22 moles) 2,6-dinitrobenzene-4-trifluoromethyl fluorobenzene, reflux 8 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separates out solid product, with hot wash 2～3 times, drying obtains 52.0 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether crystalline product, purity is 99.8%, obtains 4,4 '-two (2 according to reality, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of phenyl ether and theoretical amount (67.0 gram), the yield that calculates 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether is 77.6%.
Embodiment 5
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 66.2 gram (0.21 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 80.0 gram (0.80 mole) saleratus, 600 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 300 milliliters of dimethyl sulfoxide (DMSO), 250 milliliters of benzene and 50 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 18 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separates out solid product, with hot wash 2～3 times, drying obtains 60.5 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether, purity is 99.5%, obtains 4,4 '-two (2 according to reality, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of phenyl ether and theoretical amount (67.0 gram), the yield that calculates 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether is 90.3%.
Embodiment 6
With 40.4 gram (0.20 moles) 4,4 '-dihydroxy diphenyl ether, 59.5 gram (0.22 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 66.2 gram (0.21 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 110.4 gram (0.80 mole) salt of wormwood, 3200 milliliters of N, dinethylformamide, 320 milliliters of benzene and 160 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 10 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separates out solid product, with hot wash 2～3 times, drying obtains 4,4 '-two (2 of 128.9 grams, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether crystalline product, purity is 99.7%, obtains 4,4 '-two (2 according to reality, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of phenyl ether and theoretical amount (134.0 gram), the yield that calculates 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether is 96.2%.

Claims (9)

1.4 the preparation method of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 4,4 '-dihydroxy diphenyl ether and 2,6-dinitrobenzene-4-trifluoromethyl halogeno-benzene, in salt forming agent, organic solvent system, reflux was divided water reaction 6～18 hours;
(2) concentration of reaction solution, the cooling reactant system adds water, separates out solid product, filter, washing, drying gets 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether.
2. according to claim 14,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of phenyl ether, it is characterized in that: described 2,6-dinitrobenzene-4-trifluoromethyl halogeno-benzene is selected from 2,6-dinitrobenzene-4-trifluoromethyl fluorobenzene, 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 2, one or more mixtures in 6-dinitrobenzene-4-trifluoromethyl phenyl-iodide.
3. according to claim 14,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of phenyl ether is characterized in that: described salt forming agent is selected from one or more mixtures in Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Magnesium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, the calcium hydroxide.
4. according to the preparation method of claim 1 or 3 described 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether, it is characterized in that: described salt forming agent and 4, the ratio of the mole number of 4 '-dihydroxy diphenyl ether is 0.10～8.00: 1.00.
5. according to claim 14,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of phenyl ether is characterized in that: described organic solvent is the mixture of water-insoluble organic solvent and strong polar non-proton organic solvent, and volume ratio is 1: 0.05～10.
6. according to claim 54,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of phenyl ether is characterized in that: described water-insoluble organic solvent is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene.
7. according to claim 54,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of phenyl ether, it is characterized in that: described strong polar non-proton organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
8. according to claim 5 or 7 described 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of phenyl ether is characterized in that: described strong polar non-proton organic solvent and 4, the envelope-bulk to weight ratio of 4 '-dihydroxy diphenyl ether are 5 milliliters～80 milliliters: 1 gram.
9. the preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) phenyl ether according to claim 1, it is characterized in that: the temperature of described reaction is 80 ℃～180 ℃.
CNA2008100369519A 2008-05-04 2008-05-04 Method for preparing 4,4', di(2,6-dinitro-4-trifluoromethyl phenoxy)diphenyl ether Pending CN101289397A (en)

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