CN101234979B - Method for preparing 3,5-di(2,4-dinitrophenoxy)toluene - Google Patents
Method for preparing 3,5-di(2,4-dinitrophenoxy)toluene Download PDFInfo
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- CN101234979B CN101234979B CN2008100342501A CN200810034250A CN101234979B CN 101234979 B CN101234979 B CN 101234979B CN 2008100342501 A CN2008100342501 A CN 2008100342501A CN 200810034250 A CN200810034250 A CN 200810034250A CN 101234979 B CN101234979 B CN 101234979B
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Abstract
The invention relates to a preparation method of 3, 5-bis-(2, 4-dinitrophenoxy) toluene, comprising: (1) heating to reflux and segregate water for 3-18h to treat 3, 5-dihydroxy toluene 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 3, 5-bis-(2, 4-dinitrophenoxy) toluene. The preparation method of 3, 5-bis-(2, 4-dinitrophenoxy) toluene 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 3, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-.
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).
3, two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-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 resin 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 3, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-, 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 3, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 3,5-orcin 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 gets 3, two (2,4-2,4-dinitrophenoxy base) the toluene crystal of 5-.
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 3, the ratio of the mole number of 5-orcin 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 3, the envelope-bulk to weight ratio of 5-orcin 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 preparation 3, the commercial run of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-, 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 (4) 3,5-orcins, cost is lower, is convenient to further apply.
Description of drawings
Fig. 1 is 3, the molecular structure of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-.
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 12.4 gram (0.10 moles) 3, the 5-orcin, 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, hot wash 2～3 times, drying, obtain 3 of 43.0 grams, two (2,4-2,4-dinitrophenoxy base) the toluene crystalline products of 5-, purity is 99.4%, obtain 3 according to reality, amount of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-and theoretical amount (45.6 gram) calculate 3, the yield of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-is 94.2%.
Embodiment 2
With 12.4 gram (0.10 moles) 3, the 5-orcin, 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 3 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 33.9 grams 3, two (2,4-2,4-dinitrophenoxy base) the toluene crystalline products of 5-, purity is 98.7%, obtain 3 according to reality, amount of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-and theoretical amount (45.6 gram) calculate 3, the yield of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-is 74.3%.
Embodiment 3
With 12.4 gram (0.10 moles) 3, the 5-orcin, 40.5 gram (0.20 mole) 2, the 4-dinitro-chloro-benzene, 10.6 gram (0.10 mole) yellow soda ash, 96 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 36 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, hot wash 2～3 times, drying obtains 41.6 grams 3, and 5-two (2,4-2,4-dinitrophenoxy base) toluene crystalline product, purity is 99.1%, and according to 3 of reality acquisition, 5-two (2,4-2,4-dinitrophenoxy base) amount of toluene and theoretical yield (45.6 gram), calculate 3, the yield of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-is 91.2%.
Embodiment 4
With 12.4 gram (0.10 moles) 3,5-orcin, 11.8 gram (0.21 mole) potassium hydroxide, 120 milliliters of N, dinethylformamide, 100 milliliters of benzene and 20 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 3 hours, adds 40.9 gram (0.22 moles) 2,4-dinitrobenzene fluorobenzene, reacting by heating 3 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 39.9 grams 3, two (2,4-2,4-dinitrophenoxy base) the toluene crystalline products of 5-, purity is 99.3%, obtain 3 according to reality, amount of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-and theoretical amount (45.6 gram) calculate 3, the yield of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-is 87.6%.
Embodiment 5
With 12.4 gram (0.10 moles) 3, the 5-orcin, 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, hot wash 2～3 times, drying obtains 41.7 grams 3, and 5-two (2,4-2,4-dinitrophenoxy base) toluene, purity is 99.1%, obtains 3 according to reality, and 5-two (2,4-2,4-dinitrophenoxy base) amount of toluene and theoretical amount (45.6 gram), calculate 3, the yield of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-is 91.5%.
Claims (4)
1.3 the preparation method of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 3,5-orcin and 2,4-dinitrobenzene halogeno-benzene, in salt forming agent, organic solvent system, reflux was divided water reaction 3～18 hours;
Described 2,4-dinitrobenzene halogeno-benzene is selected from 2,4-dinitro-chloro-benzene, 2, one or more mixtures in the 4-dinitrobenzene bromobenzene;
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 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; Wherein, 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; 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);
(2) concentration of reaction solution, the cooling reactant system adds water, separates out solid product, filter, washing, drying gets 3, two (2,4-2,4-dinitrophenoxy base) the toluene crystal of 5-.
2. according to claim 13, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-, it is characterized in that: described salt forming agent and 3, the ratio of the mole number of 5-orcin is 0.10～8.00: 1.00.
3. according to claim 13, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-, it is characterized in that: described organic solvent and 3, the envelope-bulk to weight ratio of 5-orcin are 5 milliliters～80 milliliters: 1 restrains.
4. according to claim 13, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) toluene of 5-is characterized in that: it is that temperature is 80 ℃～200 ℃ reaction that described reflux is divided the water reaction.
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| CN2008100342501A CN101234979B (en) | 2008-03-05 | 2008-03-05 | Method for preparing 3,5-di(2,4-dinitrophenoxy)toluene |
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| CN2008100342501A CN101234979B (en) | 2008-03-05 | 2008-03-05 | Method for preparing 3,5-di(2,4-dinitrophenoxy)toluene |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314339A (en) * | 2000-03-21 | 2001-09-26 | 上海市合成树脂研究所 | Method for preparing 1,3-di-(-3-nitrophenoxy) benzene |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314339A (en) * | 2000-03-21 | 2001-09-26 | 上海市合成树脂研究所 | Method for preparing 1,3-di-(-3-nitrophenoxy) benzene |
Non-Patent Citations (5)
| Title |
|---|
| JOHN D. REINHEIMER等.Aromatic Nucleophilic Substitution Reaction inQualitativeOrganic Chemistry : The Reaction of 2,4-Dinitrofluorobenzene with Phenols.J. Org. Chem.22卷.1957,22卷1743-1745页. * |
| Wolfgang Wildenhain等.英文标题Thin-layer chromatographic separation of phenoliccompounds as 2,4-dinitrophenyl ethers.Journal of Chromatography19 2.1965,19(2),438-440. * |
| WolfgangWildenhain等.英文标题Thin-layerchromatographicseparationofphenoliccompoundsas2 4-dinitrophenyl ethers.Journal of Chromatography19 2.1965 |
| 姚跃良等.4-[3-(4-氨基苯氧基)苯氧基]苯胺的合成研究.化学世界2007年 4期.2007,2007年(4期),228-231页. |
| 姚跃良等.4-[3-(4-氨基苯氧基)苯氧基]苯胺的合成研究.化学世界2007年 4期.2007,2007年(4期),228-231页. * |
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