CN101234978A - Method for preparing 2,2-di[4-(2,4-dinitrophenoxy)-3,5-dimethylphenyl]propane - Google Patents

Method for preparing 2,2-di[4-(2,4-dinitrophenoxy)-3,5-dimethylphenyl]propane Download PDF

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CN101234978A
CN101234978A CNA2008100342499A CN200810034249A CN101234978A CN 101234978 A CN101234978 A CN 101234978A CN A2008100342499 A CNA2008100342499 A CN A2008100342499A CN 200810034249 A CN200810034249 A CN 200810034249A CN 101234978 A CN101234978 A CN 101234978A
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dimethylphenyl
propane
preparation
dinitrophenoxy base
organic solvent
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虞鑫海
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Donghua University
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Donghua University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention relates to a preparation method of 2, 2-bis-[4-(2, 4-dinitrophenoxy)-3, 5-dimethylphenyl] propane, comprising: (1) heating to reflux and segregate water for 6-18h to treat 2, 2-bis(4-hydroxy-3, 5-dimethylphenyl) propane and 2, 4-dinitro halogenated benzene at a mol ratio of 1.0:2.0-2.2, in a system of a salt forming agent and an organic solvent; (2) concentrating reaction liquid, cooling the reactant system, adding water, precipitating solid product, filtering, immerging and drying to obtain 2, 2-bis-[4-(2, 4-dinitrophenoxy)-3, 5-dimethylphenyl] propane. The preparation method of 2, 2-bis-[4-(2, 4-dinitrophenoxy)-3, 5-dimethylphenyl] propane 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

2, the preparation method of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-
Technical field
The invention belongs to the preparation field of aromatic organic compounds, particularly relate to a kind of 2, the preparation method of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-.
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).
2, two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-are 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.
Summary of the invention
The purpose of this invention is to provide a kind of 2, the preparation method of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-, 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 2, the preparation method of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 2, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane and 2 of 2-, 4-dinitrobenzene halogeno-benzene, in salt forming agent, organic solvent system, reflux is 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 2, two [4-(2,4-2,4-dinitrophenoxy base)-3,5-3,5-dimethylphenyl] the propane crystal of 2-.
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 2, the ratio of the mole number of two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2-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, volume ratio is 1: 0.05～10, organic solvent and 2, the envelope-bulk to weight ratio of two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2-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).
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 preparation 2, the commercial run of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-, 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;
Reaction raw materials convenient sources such as two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of (4) 2,2-, cost is lower, is convenient to further apply.
Description of drawings
Fig. 1 is 2, the molecular structure of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-.
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 28.4 gram (0.10 moles) 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 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, and concentration of reaction solution reclaims solvent to recycle, the cooling reactant system, add water, separate out solid product, hot wash 2～3 times, dry, obtain 2 of 59.8 grams, the two [4-(2,4-2,4-dinitrophenoxy base)-3 of 2-, the 5-3,5-dimethylphenyl] the propane crystalline product, purity is 99.2%, obtains 2 according to reality, and 2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] amount of propane and theoretical amount (61.6 gram), calculate 2,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3,5-3,5-dimethylphenyl] yield of propane is 97.1%.
Embodiment 2
With 28.4 gram (0.10 moles) 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 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, and concentration of reaction solution reclaims solvent to recycle, the cooling reactant system, add water, separate out solid product, hot wash 2～3 times, dry, obtain 53.8 grams 2, the two [4-(2,4-2,4-dinitrophenoxy base)-3 of 2-, the 5-3,5-dimethylphenyl] the propane crystalline product, purity is 99.1%, obtains 2 according to reality, and 2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] amount of propane and theoretical amount (61.6 gram), calculate 2,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3,5-3,5-dimethylphenyl] yield of propane is 87.3%.
Embodiment 3
With 28.4 gram (0.10 moles) 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 40.5 gram (0.20 mole) 2, the 4-dinitro-chloro-benzene, 10.6 gram (0.10 mole) yellow soda ash, 90 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 100 milliliters of benzene and 50 milliliters of dichlorobenzenes are put into reactor, stir, and reflux divides the water reaction after 16 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separate out solid product, hot wash 2～3 times, drying obtains 53.3 grams 2,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] the propane crystalline product, purity is 99.0%, according to 2 of reality acquisition, amount of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-and theoretical yield (61.6 gram), calculate 2, the yield of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-is 86.5%.
Embodiment 4
With 28.4 gram (0.10 moles) 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 40.9 gram (0.22 mole) 2,4-dinitrobenzene fluorobenzene, 11.8 gram (0.21 mole) potassium hydroxide, 20 milliliters of N, dinethylformamide, 150 milliliters of benzene and 10 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, hot wash 2～3 times, drying, obtain 57.6 grams 2, two [4-(2,4-2,4-dinitrophenoxy base)-3,5-3,5-dimethylphenyl] the propane crystalline products of 2-, obtain 2 according to reality, amount of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-and theoretical amount (61.6 gram), calculate 2, the yield of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-is 93.5%.
Embodiment 5
With 28.4 gram (0.10 moles) 2, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2-, 51.9 gram (0.21 mole) 2,4-dinitrobenzene bromobenzene, 80.0 gram (0.80 mole) saleratus, 300 milliliters of dimethyl sulfoxide (DMSO), 100 milliliters of benzene and 10 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, hot wash 2～3 times, drying obtains 60.5 grams 2, and 2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane, obtain 2 according to reality, 2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] amount of propane and theoretical amount (61.6 gram), calculate 2,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3,5-3,5-dimethylphenyl] yield of propane is 98.3%.

Claims (9)

1.2 the preparation method of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 2, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane and 2 of 2-, 4-dinitrobenzene halogeno-benzene, in salt forming agent, organic solvent system, reflux is 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 2, two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-.
2. according to claim 12,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] preparation method of propane, 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 12,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] preparation method of propane, it 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 claim 1 or 3 described 2, the two [4-(2,4-2,4-dinitrophenoxy base)-3 of 2-, the 5-3,5-dimethylphenyl] preparation method of propane, it is characterized in that: described salt forming agent and 2, the ratio of the mole number of two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2-is 0.10～8.00: 1.00.
5. according to claim 12, the preparation method of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-, it 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 52,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] preparation method of propane, it 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 52,2-is two, and [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] preparation method of propane, 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 52, the two [4-(2,4-2,4-dinitrophenoxy base)-3 of 2-, the 5-3,5-dimethylphenyl] preparation method of propane, it is characterized in that: described organic solvent and 2, the envelope-bulk to weight ratio of two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2-is 5 milliliters～80 milliliters: 1 gram.
9. according to claim 12, the preparation method of two [4-(2,4-2,4-dinitrophenoxy base)-3, the 5-3,5-dimethylphenyl] propane of 2-is characterized in that: it is that temperature is 80 ℃～200 ℃ reaction that described reflux is divided the water reaction.
CNA2008100342499A 2008-03-05 2008-03-05 Method for preparing 2,2-di[4-(2,4-dinitrophenoxy)-3,5-dimethylphenyl]propane Pending CN101234978A (en)

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