CN105348029A - Preparation method of cyclic di-p-xylyene - Google Patents
Preparation method of cyclic di-p-xylyene Download PDFInfo
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- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
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Abstract
The invention discloses a preparation method of cyclic di-p-xylyen. The method mainly includes the steps of: taking p-xylene as the starting raw material, performing bromination to obtain p-methylbenzyl bromide, and then carrying out reaction with triethylamine to obtain a corresponding quaternary ammonium salt, and finally adding the quaternary ammonium salt into a system containing a mixed solvent, alkali liquor and a mixed catalyst dropwise, and carrying out reaction for certain period of time to obtain cyclic di-p-xylyene, and finally performing aftertreatment to obtain a cyclic di-p-xylyene pure product. The method provided by the invention has the advantages of cheap and easily available raw materials, short reaction time, strong continuity, high yield, high purity and small solvent consumption, etc., and can be used for large-scale production.
Description
Technical field
The present invention relates to the preparation method of organic compound, particularly relate to the preparation of ParyleneN film raw material p-Xylol ring disome.
Background technology
Parylene series thin film is a state-of-the-art class thin-film material in the world today.Owing to having the excellent physicals such as mechanical, electrical, hot; good chemical stability; biocompatibility; and the characteristic such as protection from fumes, mildew-resistant, protection against the tide, therefore Parylene film is obtained for widespread use at numerous areas such as medicine, military affairs, space flight, automobile, microelectronic industry and historical relic's protections.ParyleneN film is the important member in Parylene series thin film, is to be polymerized by chemical vacuum gas phase deposition technology by p-Xylol ring disome, and its preparation process is shown below.
In view of excellent properties and the widespread use of ParyleneN film, thus the preparation of raw material p-Xylol ring disome also seems particularly important.Usually, the preparation method of p-Xylol ring disome is important comprises Hofmann null method and pyrolysis method.US Patent No. 3149175 reports the method that pyrolysis method prepares p-Xylol ring disome, its advantage is that reaction raw materials is easy to get and the simple feature of reaction process, but subject matter is present in severe reaction conditions, the aspects such as the large and product yield of energy consumption is low, thus limit popularization and the use of this production method.Comparatively conventional synthetic method is Huffman null method, the method mainly with to methyl benzyl chloride for starting raw material prepares p-Xylol ring disome, advantage is the feature that reaction raw materials is easy to get, reaction process is simple, production cost is low, but the productive rate of product has much room for improvement.Therefore, the p-Xylol ring disome preparing high yield by Huffman null method becomes priority fields of study.The synthetic technological condition of the patents such as US4532369 and US4795838 to p-Xylol ring disome is improved, and yield increases, but yield still has very large room for promotion.It is starting raw material that CN101811925 patent adopts methyl benzyl chloride, p-Xylol ring disome is obtained through series reaction synthesis, have that solvent load is few, reaction conditions is gentle and yield reaches 80% with first-class feature, but required reaction raw materials still costly in reaction process, employ price phase-transfer catalyst costly, and operate discontinuous.
The invention provides a kind of can the preparation method of continuous industrial production p-Xylol ring disome, solve that productive rate in prior art is low, high in cost of production problem, achieve high yield under mild reaction conditions and produce p-Xylol ring disome.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of can the method for suitability for industrialized production p-Xylol ring disome, the method reaction raw materials is cheap and easy to get, simple to operate, and the reaction times is short, reaction conditions is gentle, yield is high.Its characteristic is to take p-Xylol as starting raw material, obtains product through bromination, salify and ring-closure reaction process, has that reaction raw materials is easy to get, cheap, productive rate is high and value added high.
Technical scheme: the preparation method of a kind of p-Xylol ring disome of the present invention comprises the steps:
1) take p-Xylol as starting raw material, obtain after bromination methyl bromobenzyl, and then react obtained corresponding quaternary ammonium salt to triethylamine;
2) in the system of organic solvent, alkali lye and catalyzer existence, drip above-mentioned quaternary ammonium salt, prepare p-Xylol ring disome after reaction, obtain p-Xylol ring disome sterling by purification processes.
Wherein:
Describedly obtained by p-Xylol and bromine reaction methyl bromobenzyl, bromine is generated by massfraction 40% aqueous solution of hydrogen bromide and the reaction of 30 ~ 90 DEG C, massfraction 30% hydrogen peroxide, wherein preferably 70 DEG C.
Described quaternary ammonium salt, its preparation method is react methyl bromobenzyl and triethylamine, and temperature of reaction is 0 ~ 70 DEG C, wherein preferably 20 DEG C.
Described organic solvent is one or more in DMF, N,N-dimethylacetamide, tetramethylene sulfone, benzene, toluene, acetone or oil of mirbane.
Described organic solvent wherein preferred DMF and toluene uses simultaneously, and its volume ratio is (1 ~ 100): 1, wherein preferred 60:1.
Described alkali lye is one or more in organometallic lithium compounds, grignard reagent, sodium alkoxide, potassium alcoholate.
Described alkali lye preferred alcohol sodium, sodium ethylate: the mass ratio of quaternary ammonium salt is (0.5 ~ 5): 1, wherein preferred 1.5:1.
Described catalyzer is one or more in polyethers, quinones, tetraphenyl halogenation phosphine class, polyethylene glycols.
The preferred quinones of described catalyzer and polyethylene glycols use simultaneously, naphthoquinones: poly(oxyethylene glycol) 400=1:1 (mass ratio); The mass ratio of catalyzer and quaternary ammonium salt is (0.001 ~ 0.2): 1, wherein preferred 0.005:1.
Beneficial effect: hinge structure of the present invention, has the following advantages:
(1) the present invention prepares p-Xylol ring disome and can be used for scale operation, and products obtained therefrom purity is high, and productive rate is high;
(2) starting raw material used in the present invention is p-Xylol, and reaction raw materials is cheap and easy to get;
(3) reaction process of the present invention can be continuously produced;
(4) solvent used in the present invention is mixed solvent, and required quantity of solvent is few, and reaction effect is good;
(5) catalyzer used herein is catalyst compounded, owing to reaching " synergistic effect ", is greatly shortened in the reaction times.
Embodiment
Chemical equation of the present invention is as follows:
The invention provides a kind of preparation method of p-Xylol ring disome, preparation method is as follows:
Take p-Xylol as initial reactant, through bromination reaction preparation to methyl bromobenzyl, be then prepared into quaternary ammonium salt, at a certain temperature, in the mixed system containing alkali lye, catalyzer, solvent, drip quaternary ammonium salt, and then raise temperature of reaction, insulation reaction 10h.Carry out post-processing operation, can obtain p-Xylol ring disome, the yield of this compound reaches 86%, and purity reaches 99%.
In such scheme, to the preparation of methyl bromobenzyl, be under UV-irradiation, obtained by p-Xylol and bromine reaction.
In such scheme, the preparation of quaternary ammonium salt is at room temperature, adds triethylamine water (33%) solution, stirs and obtains for 2 hours.This quaternary ammonium salt can be directly used in next step reaction.
In such scheme, prepare the method for bromine for drip hydrogen peroxide (30%) in Hydrogen bromide (40%) solution, and then be heated to (30 ~ 90) DEG C.
In such scheme, post-processing operation, is suction filtration while hot, is then washed to neutrality; A small amount of gac adds in toluene together with solid matter, stirring and refluxing 1 hour at 80 DEG C.Suction filtration is to remove insolubles while hot, and then crystallisation by cooling post-drying obtains p-Xylol ring disome.
In such scheme, preparing main material mol ratio in methyl bromobenzyl process is p-Xylol: Hydrogen bromide: hydrogen peroxide=1:(0.1 ~ 6): (0.1 ~ 5).Wherein preferred p-Xylol: Hydrogen bromide: hydrogen peroxide=1:0.6:0.5.
In such scheme, described alkali lye is one or more the wherein preferred alcohol sodium in organometallic lithium compounds, grignard reagent, sodium alkoxide and potassium alcoholate, and the mass ratio of sodium ethylate and quaternary ammonium salt is 1:1 ~ 10:1, wherein preferred 1.5:1.
In such scheme, described catalyzer is one or more in polyethers, quinones, tetraphenyl halogenation phosphine class, polyethylene glycols, and wherein preferably quinones and polyethylene glycols use simultaneously, and mass ratio is naphthoquinones: poly(oxyethylene glycol) 400=1:1.The mass ratio of catalyzer and quaternary ammonium salt is (0.001 ~ 0.2): 1, wherein preferred 0.005:1.
In such scheme, described solvent is one or more in amides, aromatic hydrocarbons, ketone and heterocyclic, and wherein preferably DMF and toluene use simultaneously, and its volume ratio is (1 ~ 100): 1, wherein preferred 60:1.
Below by embodiment, the present invention will be further described.Should be understood that following examples are only not used in for illustration of the present invention to limit the scope of the invention.In addition, after the content of having read the present invention's instruction, those skilled in the art can do various amendment to the present invention, and these forms fall within the application's appending claims limited range equally.
Embodiment 1:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g sodium ethylate, N, dinethylformamide 60mL, toluene 1mL, naphthoquinones and each 0.23g of poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 29.86g, yield is 86%.
Embodiment 2:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 30 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 0 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that massfraction is 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add sodium ethylate 44.85g, N, N-N,N-DIMETHYLACETAMIDE 40mL, tetramethylene sulfone 21mL, naphthoquinones and each 0.23g of poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 13.19g, yield is 38%.
Embodiment 3:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that massfraction is 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add sodium ethylate 448.53g, benzene 51mL, toluene 10mL, naphthoquinones and each 0.23g of poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, then be warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 21.52g, yield is 62%.
Embodiment 4
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 90 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 0 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g ethyl group magnesium bromide, acetone 20mL, oil of mirbane 40mL, naphthoquinones and each 0.23g of poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, then be warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 8.33g, yield is 24%.
Embodiment 5:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 70 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g potassium ethylate, N, dinethylformamide 60.4mL, toluene 0.6mL, polyglycol ether 0.46g, is heated to 95 DEG C, then drips obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 27.74g, yield is 80%.
Embodiment 6:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add butyllithium 134.56g, N, dinethylformamide 30mL, toluene 30mL, naphthoquinones and each 0.23g of poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 18.03g, yield is 52%.
Embodiment 7:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g sodium ethylate, N, dinethylformamide 60mL, toluene 1mL, naphthoquinones and each 0.045g of poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 9.01g, yield is 26%.
Embodiment 8:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g sodium ethylate, N, dinethylformamide 60.4mL, toluene 0.6mL, naphthoquinones and each 9g of poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 29.12g, yield is 84%.
Embodiment 9:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g sodium ethylate, tetramethylene sulfone 61mL, tetraphenylphosphonium chloride 0.46g, is heated to 95 DEG C, then drips obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 12.48g, yield is 36%.
Embodiment 10:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g sodium ethylate, N, dinethylformamide 60.4mL, toluene 0.6mL, naphthoquinones 0.45g, is heated to 95 DEG C, then drips obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, be then warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 15.60g, yield is 45%.
Embodiment 11:
To in the four-hole boiling flask that prolong, thermometer and constant pressure funnel are housed, successively adding 35g p-Xylol, 20mL tetracol phenixin and 40g massfraction is the Hydrogen bromide of 40%, is then slowly heated to 70 DEG C.Under the condition of ultra violet lamp, drip the hydrogen peroxide 30g of 30%, time for adding is 1 hour, after dropwising, and reacts 5 hours, separatory at 70 DEG C, can containing the organic phase to methyl bromobenzyl.At 20 DEG C of temperature, in this organic phase, add the triethylamine aqueous solution that enough massfractions are 33%, react 2 hours, gained quaternary ammonium salt solution is transferred in dropping funnel.In the four-hole boiling flask that condensing works, thermometer and stirring are housed, add 134.56g sodium ethylate, acetone 60.4mL, toluene 0.6mL, 0.45g poly(oxyethylene glycol) 400, be heated to 95 DEG C, then drip obtained quaternary ammonium salt solution slowly, time for adding is 1.5 hours, in the process dripped, be divided into liquid 50mL, then be warming up to 110 DEG C, react 9 hours at such a temperature.After completion of the reaction, suction filtration, is washed to neutrality, is then dissolved in benzene by gained filter cake at 80 DEG C, adds a small amount of gac simultaneously, stirs 0.5 hour.By suction filtration while hot, crystallisation by cooling, drying operation, obtain p-Xylol ring disome 13.87g, yield is 40%.
Claims (9)
1. a preparation method for p-Xylol ring disome, is characterized in that the method comprises the steps:
1) take p-Xylol as starting raw material, obtain after bromination methyl bromobenzyl, and then react obtained corresponding quaternary ammonium salt to triethylamine;
2) in the system of organic solvent, alkali lye and catalyzer existence, drip above-mentioned quaternary ammonium salt, prepare p-Xylol ring disome after reaction, obtain p-Xylol ring disome sterling by purification processes.
2. the preparation method of a kind of p-Xylol ring disome according to claim 1, it is characterized in that: describedly to be obtained by p-Xylol and bromine reaction methyl bromobenzyl, bromine is generated by massfraction 40% aqueous solution of hydrogen bromide and the reaction of 30 ~ 90 DEG C, massfraction 30% hydrogen peroxide.
3. the preparation method of a kind of p-Xylol ring disome according to claim 1, is characterized in that: described quaternary ammonium salt, and its preparation method is react methyl bromobenzyl and triethylamine, and temperature of reaction is 0 ~ 70 DEG C, wherein preferably 20 DEG C.
4. the preparation method of a kind of p-Xylol ring disome according to claim 1, is characterized in that: described organic solvent is one or more in DMF, N,N-dimethylacetamide, tetramethylene sulfone, benzene, toluene, acetone or oil of mirbane.
5. the preparation method of a kind of p-Xylol ring disome according to claim 4, is characterized in that: described organic solvent wherein preferred DMF and toluene uses simultaneously, and its volume ratio is (1 ~ 100): 1, wherein preferred 60:1.
6. the preparation method of a kind of p-Xylol ring disome according to claim 1, is characterized in that: described alkali lye is one or more in organometallic lithium compounds, grignard reagent, sodium alkoxide, potassium alcoholate.
7. the preparation method of a kind of p-Xylol ring disome according to claim 6, is characterized in that: described alkali lye preferred alcohol sodium, sodium ethylate: the mass ratio of quaternary ammonium salt is (0.5 ~ 5): 1, wherein preferred 1.5:1.
8. the preparation method of a kind of p-Xylol ring disome according to claim 1, is characterized in that: described catalyzer is one or more in polyethers, quinones, tetraphenyl halogenation phosphine class, polyethylene glycols.
9. the preparation method of a kind of p-Xylol ring disome according to claim 8, is characterized in that: the preferred quinones of described catalyzer and polyethylene glycols use simultaneously, naphthoquinones: polyoxyethylene glycol mass ratio is 400=1:1; The mass ratio of catalyzer and quaternary ammonium salt is (0.001 ~ 0.2): 1, wherein preferred 0.005:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106986742A (en) * | 2017-04-05 | 2017-07-28 | 常州市骏佳化工有限公司 | Four chloro paraxylene ring disome synthetic methods |
| CN111269077A (en) * | 2020-04-02 | 2020-06-12 | 上海蕲鑫新材料科技有限公司 | Synthetic method of 2,3,4, 5-tetramethyl-p-xylene ring dimer |
| CN113307714A (en) * | 2021-06-18 | 2021-08-27 | 安徽苏乐医药材料有限公司 | Preparation method of parylene N |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986742A (en) * | 2017-04-05 | 2017-07-28 | 常州市骏佳化工有限公司 | Four chloro paraxylene ring disome synthetic methods |
| CN106986742B (en) * | 2017-04-05 | 2020-08-04 | 常州市骏佳化工有限公司 | Synthesis method of tetrachloro-p-xylene cyclic dimer |
| CN111269077A (en) * | 2020-04-02 | 2020-06-12 | 上海蕲鑫新材料科技有限公司 | Synthetic method of 2,3,4, 5-tetramethyl-p-xylene ring dimer |
| CN113307714A (en) * | 2021-06-18 | 2021-08-27 | 安徽苏乐医药材料有限公司 | Preparation method of parylene N |
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