CN101284788B - Preparation method of 2,3-di(2,4-dinitro phenoxy)naphthalin - Google Patents
Preparation method of 2,3-di(2,4-dinitro phenoxy)naphthalin Download PDFInfo
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- CN101284788B CN101284788B CN2008100384646A CN200810038464A CN101284788B CN 101284788 B CN101284788 B CN 101284788B CN 2008100384646 A CN2008100384646 A CN 2008100384646A CN 200810038464 A CN200810038464 A CN 200810038464A CN 101284788 B CN101284788 B CN 101284788B
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Abstract
The invention relates to a method for preparing 2,3-bis(2,4-dinitro phenoxyl) albocarbon. The method comprises the following steps: firstly, 2,3-dinitro halogeno benzene and 2,4-dinitro halogeno benzene in the mol ratio of 1.0:2.0-2.2 are subjected to heating reflux and water diversion reaction in a salt forming agent and an organic solvent system for 3 to 18 hours; secondly, the reacted liquor is concentrated, the reactant system is cooled down, water is added to separate the solid product out, filtering, cleaning and drying are performed to obtain the 2,3-bis(2,4-dinitro phenoxyl) albocarbon. The method has the advantages that the operation is simple, the product recovery rate and the purity are high, the solvent recovery is convenient, the solvent can be used repeatedly, the three wastes are less, the environment is not polluted, and the method 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 2, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-.
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 (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-are one of synthetic monomeric important source material of high branching 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 2, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-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 2, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-, 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 (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 2,3-naphthalenediol 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 2, two (2,4-2,4-dinitrophenoxy base) the naphthalene crystal of 3-.
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, salt forming agent and 2, the ratio of the mole number of 3-naphthalenediol 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 2, the envelope-bulk to weight ratio of 3-naphthalenediol 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 2, the commercial run of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-, 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) 2,3-naphthalenediols, cost is lower, is convenient to further apply.
Description of drawings
Fig. 1 is 2, the molecular structure of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-.
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 16.0 gram (0.10 moles) 2, the 3-naphthalenediol, 44.6 gram (0.22 mole) 2, the 4-dinitro-chloro-benzene, 110.4 gram (0.80 mole) salt of wormwood, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 500 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 2 of 44.3 grams, two (2,4-2,4-dinitrophenoxy base) the naphthalene crystalline products of 3-, purity is 99.1%, obtain 2 according to reality, amount of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-and theoretical amount (49.2 gram) calculate 2, the yield of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is 90.1%.
Embodiment 2
With 16.0 gram (0.10 moles) 2, the 3-naphthalenediol, 54.4 gram (0.22 mole) 2,4-dinitrobenzene bromobenzene, 55.2 gram (0.40 mole) salt of wormwood, 150 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 150 milliliters of N,N-dimethylacetamide, 100 milliliters of benzene 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 38.8 grams 2, two (2,4-2,4-dinitrophenoxy base) the naphthalene crystalline products of 3-, purity is 99.5%, obtain 2 according to reality, amount of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-and theoretical amount (49.2 gram) calculate 2, the yield of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is 78.9%.
Embodiment 3
With 16.0 gram (0.10 moles) 2, the 3-naphthalenediol, 40.5 gram (0.20 mole) 2, the 4-dinitro-chloro-benzene, 10.6 gram (0.10 mole) yellow soda ash, 180 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 80 milliliters of benzene and 30 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 34.5 grams 2, and 3-two (2,4-2,4-dinitrophenoxy base) naphthalene crystalline product, purity is 99.1%, and according to 2 of reality acquisition, 3-two (2,4-2,4-dinitrophenoxy base) amount of naphthalene and theoretical yield (49.2 gram), calculate 2, the yield of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is 70.2%.
Embodiment 4
With 16.0 gram (0.10 moles) 2,3-naphthalenediol, 11.8 gram (0.21 mole) potassium hydroxide, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 80 milliliters of N, dinethylformamide, 150 milliliters of benzene and 80 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, with hot wash 2～3 times, drying, obtain 44.7 grams 2, two (2,4-2,4-dinitrophenoxy base) the naphthalene crystalline products of 3-, purity is 99.3%, obtain 2 according to reality, amount of two (2, the 4-nitrophenoxy) naphthalenes of 3-and theoretical amount (49.2 gram) calculate 2, the yield of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is 90.8%.
Embodiment 5
With 16.0 gram (0.10 moles) 2, the 3-naphthalenediol, 51.9 gram (0.21 mole) 2,4-dinitrobenzene bromobenzene, 80.0 gram (0.80 mole) saleratus, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 300 milliliters of dimethyl sulfoxide (DMSO), 100 milliliters of benzene 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 46.7 grams 2, and 3-two (2,4-2,4-dinitrophenoxy base) naphthalene, purity is 99.3%, obtains 2 according to reality, and 3-two (2,4-2,4-dinitrophenoxy base) amount of naphthalene and theoretical amount (49.2 gram), calculate 2, the yield of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is 95.0%.
Embodiment 6
With 16.0 gram (0.10 moles) 2, the 3-naphthalenediol, 44.6 gram (0.22 mole) 2, the 4-dinitro-chloro-benzene, 13.8 gram (0.01 mole) salt of wormwood, 70 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 10 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 12 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 2 of 14.9 grams, and 3-two (2,4-2,4-dinitrophenoxy base) naphthalene crystalline product, purity is 99.0%, obtains 2 according to reality, and 3-two (2,4-2,4-dinitrophenoxy base) amount of naphthalene and theoretical amount (49.2 gram), calculate 2, the yield of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is 30.2%.
Embodiment 7
With 16.0 gram (0.10 moles) 2, the 3-naphthalenediol, 44.6 gram (0.22 mole) 2, the 4-dinitro-chloro-benzene, 27.6 gram (0.20 mole) salt of wormwood, 63.6 gram (0.60 mole) yellow soda ash, 51 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 10 milliliters of N, dinethylformamide and 1219 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 11 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 2 of 27.9 grams, two (2,4-2,4-dinitrophenoxy base) the naphthalene crystalline products of 3-, purity is 99.0%, obtain 2 according to reality, amount of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-and theoretical amount (49.2 gram) calculate 2, the yield of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is 56.7%.
Claims (9)
1. 2, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 2,3-naphthalenediol 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 2, two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-.
2. according to claim 12,3-two (2,4-2,4-dinitrophenoxy base) preparation method of naphthalene, 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 12,3-two (2,4-2,4-dinitrophenoxy base) preparation method of naphthalene 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 preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-, it is characterized in that: described salt forming agent and 2, the ratio of the mole number of 3-naphthalenediol is 0.10～8.00: 1.00.
5. according to claim 12, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-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 52,3-two (2,4-2,4-dinitrophenoxy base) preparation method of naphthalene 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 52,3-two (2,4-2,4-dinitrophenoxy base) preparation method of naphthalene, 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 preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-, it is characterized in that: described organic solvent and 2, the envelope-bulk to weight ratio of 3-naphthalenediol are 5 milliliters～80 milliliters: 1 restrains.
9. according to claim 12, the preparation method of two (2, the 4-2,4-dinitrophenoxy base) naphthalenes of 3-is characterized in that: it is that temperature is 80 ℃～200 ℃ reaction that described reflux is divided the water reaction.
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Non-Patent Citations (6)
| Title |
|---|
| PEDRO A. LEHMANN F.CHARACTERIZATION OF PHENOLS AS THEIR 2,4-DINITROPHENYL ETHERS.《Analytica Chimica Acta》.1971,第54卷(第2期),321-336. * |
| PEDRO A. LEHMANN F.Conformations of highly hindered aryl ethers. XVIII. Neighboring-ring anisotropy effects in poly(2,4-dinitrophenoxy)benzenes.《Tetrahedron》.1974,第30卷(第6期), * |
| PEDROA.LEHMANNF.CHARACTERIZATIONOFPHENOLSASTHEIR2 4-DINITROPHENYL ETHERS.《Analytica Chimica Acta》.1971 |
| PEDROA.LEHMANNF.Conformationsofhighlyhinderedarylethers.XVIII.Neighboring-ringanisotropyeffectsinpoly(2 4-dinitrophenoxy)benzenes.《Tetrahedron》.1974 |
| 严辉等.1 4-双(4-氨基苯氧基)苯的合成及其聚酰亚胺在挠性覆铜板中的应用.《湖北省化学化工学会2006年年会暨循环经济专家论坛论文集》.2006 |
| 严辉等.1,4-双(4-氨基苯氧基)苯的合成及其聚酰亚胺在挠性覆铜板中的应用.《湖北省化学化工学会2006年年会暨循环经济专家论坛论文集》.2006,91-93. * |
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