CN101270055A - Method for preparing 3,5-bis(2,6-di-nitryl-4-trifluoromethyl phenoxy group) methylbenzene - Google Patents

Method for preparing 3,5-bis(2,6-di-nitryl-4-trifluoromethyl phenoxy group) methylbenzene Download PDF

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CN101270055A
CN101270055A CNA2008100369542A CN200810036954A CN101270055A CN 101270055 A CN101270055 A CN 101270055A CN A2008100369542 A CNA2008100369542 A CN A2008100369542A CN 200810036954 A CN200810036954 A CN 200810036954A CN 101270055 A CN101270055 A CN 101270055A
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dinitrobenzene
toluene
trifluoromethylphenopendant
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虞鑫海
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Donghua University
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Abstract

The present invention relates to a preparation method of 3, 5-bi (2, 6-dinitro-4-trifluoromethyl phenoxy) toluene. The preparation method comprises the following steps: (1) 3, 5-dihydroxy toluene and 2, 6-dinitro-4-trifluoromethyl halogenated benzene with the molar ratio of 1.0 : 2.0 to 2.2 are put in the system of salt-forming agent and organic solvent for 6 to 18 hours with heated reflux reaction and water diversion; (2) the reaction solution is concentrated; the reaction system is cooled; water is added; solid products are separated, filtered, washed and dried to prepare the crystals of the 3, 5-bi (2, 6-dinitro-4-trifluoromethyl phenoxy) toluene. The preparation method has the advantages of simple operation, high yield of the product, high purity of the product, convenient recovery of the solvent that can be used repeatedly, less three-waste, less environmental pollution, and suitability for the industrial production.

Description

3, the preparation method of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-
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 6-dinitrobenzene-4-4-trifluoromethylphenopendant) 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 6-dinitrobenzene-4-4-trifluoromethylphenopendant) 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 system of high cladodification, can make the polyimide novel material that temperature resistant grade is higher, over-all properties is better.
But 3, the preparation method of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-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 3, the preparation method of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) 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:
Figure A20081003695400031
Figure A20081003695400041
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 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 3,5-orcin 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 3, two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) the toluene crystal of 5-.
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 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, strong polar non-proton organic solvent and 3, and the envelope-bulk to weight ratio of 5-orcin 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).
The temperature of described reaction is 80 ℃～180 ℃.
Beneficial effect of the present invention:
(1) the present invention is preparation 3, the commercial run of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) 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 6-dinitrobenzene-4-4-trifluoromethylphenopendant) 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, 54.1 gram (0.20 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 55.2 gram (0.40 mole) salt of wormwood, 42.4 gram (0.40 mole) yellow soda ash, 990 milliliters of N, dinethylformamide, 99 milliliters of benzene are put into reactor, stir, reflux divides the water reaction after 6 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 3 of 54.6 grams, and 5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene crystalline product, purity is 99.5%.Obtain 3 according to reality, amount of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-and theoretical amount (59.2 gram) calculate 3, and the yield of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-is 92.2%.
Embodiment 2
With 12.4 gram (0.10 moles) 3, the 5-orcin, 69.3 gram (0.22 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 55.2 gram (0.40 mole) salt of wormwood, 600 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 100 milliliters of N, the N-N,N-DIMETHYLACETAMIDE, 600 milliliters of benzene and 100 milliliters of dimethylbenzene 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 55.9 grams 3, and 5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) crystalline product of toluene, its purity is 99.7%.Obtain 3 according to reality, amount of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-and theoretical amount (59.2 gram) calculate 3, and the yield of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-is 94.5%.
Embodiment 3
With 12.4 gram (0.10 moles) 3, the 5-orcin, 54.1 gram (0.20 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 10.6 gram (0.10 mole) yellow soda ash, 65 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 900 milliliters of benzene, 300 milliliters of toluene and 100 milliliters of dichlorobenzenes 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 41.7 grams 3, and 5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene crystalline product, purity is 99.0%, and according to 3 of reality acquisition, 5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) amount of toluene and theoretical yield (59.2 gram), calculate 3, the yield of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-is 70.5%.
Embodiment 4
With 12.4 gram (0.10 moles) 3, the 5-orcin, 11.8 gram (0.21 mole) potassium hydroxide, 360 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 160 milliliters of N, dinethylformamide, 450 milliliters of benzene and 30 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 6 hours, adds 55.9 gram (0.22 moles) 2,6-dinitrobenzene-4-trifluoromethyl fluorobenzene, continue reaction after 9 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 40.1 grams 3, two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) the toluene crystalline products of 5-, purity is 99.4%, obtain 3 according to reality, amount of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-and theoretical amount (59.2 gram) calculate 3, the yield of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-is 67.8%.
Embodiment 5
With 12.4 gram (0.10 moles) 3, the 5-orcin, 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, 150 milliliters of N, dinethylformamide, 100 milliliters of dimethyl sulfoxide (DMSO), 500 milliliters of benzene and 60 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 12 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 56.7 grams 3, two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-, purity is 99.6%, obtain 3 according to reality, amount of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-and theoretical amount (59.2 gram) calculate 3, the yield of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-is 95.8%.
Embodiment 6
With 24.8 gram (0.20 moles) 3, the 5-orcin, 54.1 gram (0.20 mole) 2,6-dinitrobenzene-4-trifluoromethyl chlorinated benzene, 66.2 gram (0.21 mole) 2,6-dinitrobenzene-4-trifluoromethyl bromobenzene, 80.0 gram (0.80 mole) saleratus, 10.6 gram (0.10 mole) yellow soda ash, 1200 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 120 milliliters of benzene are put into reactor, stir, reflux divides the water reaction after 8.5 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 107.2 grams 3, two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-, purity is 99.6%, obtain 3 according to reality, amount of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-and theoretical amount (118.4 gram) calculate 3, the yield of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-is 90.5%.

Claims (9)

1.3 the preparation method of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-comprises the following steps:
(1) mol ratio be 1.0: 2.0～2.2 3,5-orcin 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 3, two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-.
2. according to claim 13,5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of toluene, 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 13,5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of toluene 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 3, the preparation method of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) 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.
5. according to claim 13,5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of toluene 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 53,5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of toluene 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 53,5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of toluene, 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 5 or 7 described 3,5-two (2,6-dinitrobenzene-4-4-trifluoromethylphenopendant) preparation method of toluene is characterized in that: described strong polar non-proton organic solvent and 3, the envelope-bulk to weight ratio of 5-orcin are 5 milliliters～80 milliliters: 1 gram.
9. according to claim 13, the preparation method of two (2, the 6-dinitrobenzene-4-4-trifluoromethylphenopendant) toluene of 5-, it is characterized in that: the temperature of described reaction is 80 ℃～180 ℃.
CNA2008100369542A 2008-05-04 2008-05-04 Method for preparing 3,5-bis(2,6-di-nitryl-4-trifluoromethyl phenoxy group) methylbenzene Pending CN101270055A (en)

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