CN101265219A - Method for preparing 4,4'-di(2,6-dinitro-4-trifluoromethylphenoxy)diphenyl sulfone - Google Patents
Method for preparing 4,4'-di(2,6-dinitro-4-trifluoromethylphenoxy)diphenyl sulfone Download PDFInfo
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- CN101265219A CN101265219A CNA2008100362971A CN200810036297A CN101265219A CN 101265219 A CN101265219 A CN 101265219A CN A2008100362971 A CNA2008100362971 A CN A2008100362971A CN 200810036297 A CN200810036297 A CN 200810036297A CN 101265219 A CN101265219 A CN 101265219A
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Abstract
The invention relates to a method of preparing 4, 4<1>-bis(2, 6-binitro-4-trifluoromethyl phenoxy) sulfobenzide. The method comprises the following steps: (1) the molar ratio between 4, 4<1>-dihydroxy diphenyl sulfone and 2, 6-binitro-4-trifluoromethylphenyl halides is 1.0:2.0 to 2.2, and the reflux and removing water reaction is performed in the salt forming agent and organic solvent system for 6 to 18 hours through heating; (2) reaction solution is concentrated, the reactant system is cooled, water is added in, and solid products are precipitated, filtered, washed, and dried, so that 4, 4<1>-bis(2, 6-binitro-4-trifluoromethyl phenoxy) sulfobenzide crystal is obtained. The operation of the method is simple, the product yield rate and the purity are high, the solvent is convenient to be recovered and can be used repeatedly, three wastes are fewer, and the method is environment-friendly and is suitable for the industrialized production.
Description
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) sulfobenzide.
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) sulfobenzide 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) sulfobenzide 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) sulfobenzide, 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).
The preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide of the present invention comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 4,4 '-dihydroxy diphenylsulphone 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) sulfobenzide 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 diphenylsulphone 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, and organic solvent and 4, the envelope-bulk to weight ratio of 4 '-dihydroxy diphenylsulphone are 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).
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 is the commercial run of preparation 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide, 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 diphenylsulphone, 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) sulfobenzide.
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 25.0 gram (0.10 moles) 4,4 '-dihydroxy diphenylsulphone, 59.5 gram (0.22 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 110.4 gram (0.80 mole) salt of wormwood, 1000 milliliters of N, dinethylformamide, 100 milliliters of benzene and 60 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 17 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 68.2 grams, 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide crystalline product, purity is 99.6%, obtain 4 according to reality, the amount of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide and theoretical amount (71.8 gram) calculate 4, the yield of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide is 95.0%.
Embodiment 2
With 25.0 gram (0.10 moles) 4,4 '-dihydroxy diphenylsulphone, 69.3 gram (0.22 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 55.2 gram (0.40 mole) salt of wormwood, 1600 milliliters of N, the N-N,N-DIMETHYLACETAMIDE, 260 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 62.8 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide crystalline product, purity is 99.5%, obtain 4 according to reality, the amount of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide and theoretical amount (71.8 gram) calculate 4, the yield of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide is 87.4%.
Embodiment 3
With 25.0 gram (0.10 moles) 4,4 '-dihydroxy diphenylsulphone, 54.1 gram (0.20 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 10.6 gram (0.10 mole) yellow soda ash, 640 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 1000 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 64.8 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide crystalline product, purity is 99.4%, according to 4,4 '-two (2 of reality acquisition, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of sulfobenzide and theoretical yield (71.8 gram), the yield that calculates 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide is 90.3%.
Embodiment 4
With 25.0 gram (0.10 moles) 4,4 '-dihydroxy diphenylsulphone, 11.8 gram (0.21 mole) potassium hydroxide, 880 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 260 milliliters of benzene and 140 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 64.4 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide crystalline product, purity is 99.6%, obtains 4,4 '-two (2 according to reality, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of sulfobenzide and theoretical amount (71.8 gram), the yield that calculates 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide is 89.7%.
Embodiment 5
With 25.0 gram (0.10 moles) 4,4 '-dihydroxy diphenylsulphone, 66.2 gram (0.21 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 80.0 gram (0.80 mole) saleratus, 400 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 200 milliliters of dimethyl sulfoxide (DMSO), 150 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 68.4 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide, purity is 99.6%, obtains 4,4 '-two (2 according to reality, 6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of sulfobenzide and theoretical amount (71.8 gram), the yield that calculates 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide is 95.2%.
Embodiment 6
With 25.0 gram (0.10 moles) 4,4 '-dihydroxy diphenylsulphone, 34.7 gram (0.11 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 27.1 gram (0.10 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 50.0 gram (0.50 mole) saleratus, 10.6 gram (0.10 mole) yellow soda ash, 125 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 1500 milliliters of benzene and 500 milliliters of dichlorobenzenes 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 62.3 grams 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide crystalline product, purity is 99.5%, according to 4 of reality acquisition, the amount of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide and theoretical yield (71.8 gram) calculate 4, the yield of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide is 86.7%.
Claims (9)
1.4 the preparation method of 4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 4,4 '-dihydroxy diphenylsulphone 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) sulfobenzide.
2. according to claim 14,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of sulfobenzide, 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 sulfobenzide 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) sulfobenzides, it is characterized in that: described salt forming agent and 4, the ratio of the mole number of 4 '-dihydroxy diphenylsulphone is 0.10～8.00: 1.00.
5. according to claim 14,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of sulfobenzide 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 1 or 54,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of sulfobenzide 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 1 or 54,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of sulfobenzide, 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. the preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide according to claim 1 or 5, it is characterized in that: described organic solvent and 4, the envelope-bulk to weight ratio of 4 '-dihydroxy diphenylsulphone are 5 milliliters～80 milliliters: 1 gram.
9. the preparation method of 4,4 '-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) sulfobenzide according to claim 1 is characterized in that: it is that temperature is 80 ℃～200 ℃ reaction that described reflux is divided the water reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591278B (en) * | 2009-07-03 | 2012-11-07 | 东华大学 | Method for preparing 4,4'-bis(4-nitro-2-trifluoromethylphenoxy)diphenylsulfone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101591278B (en) * | 2009-07-03 | 2012-11-07 | 东华大学 | Method for preparing 4,4'-bis(4-nitro-2-trifluoromethylphenoxy)diphenylsulfone |
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