CN101234987A - Method for preparing 4,4'-di(2,4-dinitrophenoxy)diphenyl ether - Google Patents
Method for preparing 4,4'-di(2,4-dinitrophenoxy)diphenyl ether Download PDFInfo
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- CN101234987A CN101234987A CNA2008100342588A CN200810034258A CN101234987A CN 101234987 A CN101234987 A CN 101234987A CN A2008100342588 A CNA2008100342588 A CN A2008100342588A CN 200810034258 A CN200810034258 A CN 200810034258A CN 101234987 A CN101234987 A CN 101234987A
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Abstract
The invention relates to a preparation method of 4, 4'-bis-(2, 4-dinitrophenoxy) diphenyl ether, comprising: (1) heating to reflux and segregate water for 3-18h to treat 4, 4'-dihydroxy diphenyl ester and 2, 4-dinitro halogenated benzene at a mol ratio of 1.0:2.0 to 2.2, in a system of salt forming agent and organic solvent; (2) concentrating reaction liquid, cooling the reactant system, adding water, precipitating solid product, filtering, washing and drying to obtain 4, 4'-bis-(2, 4-dinitrophenoxy) diphenyl ether crystal. The preparation method of 4, 4'-bis-(2, 4-dinitrophenoxy) diphenyl ether has simple operation, high yield and purity, wherein the solvent can be recovered easily and repeatedly used. The invention has low generation of three wastes and environment-friendly property, which is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation field of aromatic organic compounds, particularly relate to a kind of 4,4 '-preparation method of two (2,4-2,4-dinitrophenoxy base) 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 (2,4-2,4-dinitrophenoxy base) phenyl ether is one of important source material of synthetic aroma adoption dant monomer, 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 branching, can make the polyimide novel material that temperature resistant grade is higher, over-all properties is better.
Summary of the invention
The purpose of this invention is to provide a kind of 4,4 '-preparation method of two (2,4-2,4-dinitrophenoxy base) 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:
Wherein, X is a halogen atom, i.e. fluorine (F), chlorine (Cl), bromine (Br), iodine (I).
Of the present invention 4,4 '-preparation method of two (2,4-2,4-dinitrophenoxy base) phenyl ether, comprise the following steps:
(1) mol ratio be 1.0: 2.0～2.2 4,4 '-dihydroxy diphenyl ether and 2,4-dinitrobenzene halogeno-benzene, in salt forming agent, organic solvent system, reflux was divided water reaction 3～18 hours;
(2) concentration of reaction solution, the cooling reactant system adds water, separates out solid product, filter, washing, drying, obtain 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether crystal.
Described 2,4-dinitrobenzene halogeno-benzene is selected from 2,4-dinitrobenzene fluorobenzene, 2,4-dinitro-chloro-benzene, 2,4-dinitrobenzene bromobenzene, 2, one or more mixtures in the 4-dinitrobenzene 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 4,4 '-ratio of the mole number of 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, organic solvent and 4,4 '-envelope-bulk to weight ratio of dihydroxy diphenyl ether is 5 milliliters～80 milliliters: 1 restrains.
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).
It is that temperature is 80 ℃～200 ℃ reaction that described reflux is divided the water reaction.
Beneficial effect of the present invention:
(1) the present invention be preparation 4,4 '-commercial run of two (2,4-2,4-dinitrophenoxy base) 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) 4,4 '-reaction raw materials convenient sources such as dihydroxy diphenyl ether, cost is lower, is convenient to further apply.
Description of drawings
Figure is 4,4 '-molecular structure of two (2,4-2,4-dinitrophenoxy base) 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, 44.6 gram (0.22 mole) 2, the 4-dinitro-chloro-benzene, 110.4 gram (0.80 mole) salt of wormwood, 700 milliliters of N, dinethylformamide and 180 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 18 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 51.4 grams 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, purity is 99.2%, obtain 4 according to reality, 4 '-amount of two (2,4-2,4-dinitrophenoxy base) phenyl ether and theoretical amount (53.4 gram), calculate 4,4 '-yield of two (2,4-2,4-dinitrophenoxy base) phenyl ether is 96.3%.
Embodiment 2
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 54.4 gram (0.22 mole) 2,4-dinitrobenzene bromobenzene, 55.2 gram (0.40 mole) salt of wormwood, 150 milliliters of N,N-dimethylacetamide and 15 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 6 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 39.3 grams 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, purity is 99.0%, obtain 4 according to reality, 4 '-amount of two (2,4-2,4-dinitrophenoxy base) phenyl ether and theoretical amount (53.4 gram), calculate 4,4 '-yield of two (2,4-2,4-dinitrophenoxy base) phenyl ether is 73.6%.
Embodiment 3
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 40.5 gram (0.20 mole) 2, the 4-dinitro-chloro-benzene, 10.6 gram (0.10 mole) yellow soda ash, 120 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 100 milliliters of benzene and 45 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 16 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 46.7 grams 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, purity is 99.3%, according to 4,4 '-two (2 of reality acquisition, 4-2,4-dinitrophenoxy base) amount of phenyl ether and theoretical yield (53.4 gram), calculate 4,4 '-yield of two (2,4-2,4-dinitrophenoxy base) phenyl ether is 87.7%.
Embodiment 4
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 11.8 gram (0.21 mole) potassium hydroxide, 100 milliliters of N, dinethylformamide, 100 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 100 milliliters of benzene and 40 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 3 hours, add 40.9 gram (0.22 moles) 2,4-dinitrobenzene fluorobenzene, reacting by heating 2 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 47.2 grams 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, purity is 99.1%, obtains 4,4 '-two (2 according to reality, 4-2,4-dinitrophenoxy base) amount of phenyl ether and theoretical amount (53.4 gram), calculate 4,4 '-yield of two (2,4-2,4-dinitrophenoxy base) phenyl ether is 88.3%.
Embodiment 5
With 20.2 gram (0.10 moles) 4,4 '-dihydroxy diphenyl ether, 51.9 gram (0.21 mole) 2,4-dinitrobenzene bromobenzene, 80.0 gram (0.80 mole) saleratus, 300 milliliters of dimethyl sulfoxide (DMSO) and 100 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 50.8 grams 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether, purity is 99.5%, obtains 4,4 '-two (2 according to reality, 4-2,4-dinitrophenoxy base) amount of phenyl ether and theoretical amount (53.4 gram), calculate 4,4 '-yield of two (2,4-2,4-dinitrophenoxy base) phenyl ether is 95.1%.
Claims (9)
1.4,4 '-preparation method of two (2,4-2,4-dinitrophenoxy base) phenyl ether, comprise the following steps:
(1) mol ratio be 1.0: 2.0～2.2 4,4 '-dihydroxy diphenyl ether and 2,4-dinitrobenzene halogeno-benzene, in salt forming agent, organic solvent system, reflux was divided water reaction 3～18 hours;
(2) concentration of reaction solution, the cooling reactant system adds water, separates out solid product, filter, washing, drying, obtain 4,4 '-two (2,4-2,4-dinitrophenoxy base) phenyl ether crystal.
2. according to claim 14,4 '-two (2,4-2,4-dinitrophenoxy base) preparation method of phenyl ether, it is characterized in that: described 2,4-dinitrobenzene halogeno-benzene is selected from 2,4-dinitrobenzene fluorobenzene, 2,4-dinitro-chloro-benzene, 2,4-dinitrobenzene bromobenzene, 2, one or more mixtures in the 4-dinitrobenzene phenyl-iodide.
3. according to claim 14,4 '-two (2,4-2,4-dinitrophenoxy base) 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.
According to claim 1 or 3 described 4,4 '-preparation method of two (2,4-2,4-dinitrophenoxy base) phenyl ether, it is characterized in that: described salt forming agent and 4,4 '--the ratio of the mole number of dihydroxy diphenyl ether is 0.10～8.00: 1.00.
5. according to claim 14,4 '-two (2,4-2,4-dinitrophenoxy base) 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 (2,4-2,4-dinitrophenoxy base) 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 (2,4-2,4-dinitrophenoxy base) 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 1 or 54,4 '-preparation method of two (2,4-2,4-dinitrophenoxy base) phenyl ether, it is characterized in that: described organic solvent and 4,4 '-envelope-bulk to weight ratio of dihydroxy diphenyl ether is 5 milliliters～80 milliliters: 1 gram.
9. according to claim 14,4 '-preparation method of two (2,4-2,4-dinitrophenoxy base) phenyl ether, it is characterized in that: it is that temperature is 80 ℃～200 ℃ reaction that described reflux is divided the water reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217779A (en) * | 2020-03-05 | 2020-06-02 | 西安瑞联新材料股份有限公司 | Synthetic method of 3-methyl-4-nitro-dibenzofuran |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217779A (en) * | 2020-03-05 | 2020-06-02 | 西安瑞联新材料股份有限公司 | Synthetic method of 3-methyl-4-nitro-dibenzofuran |
| CN111217779B (en) * | 2020-03-05 | 2022-03-01 | 西安瑞联新材料股份有限公司 | Synthetic method of 3-methyl-4-nitro-dibenzofuran |
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Open date: 20080806 |