CN104447230B - A kind of preparation method of 4-methoxy styrene - Google Patents
A kind of preparation method of 4-methoxy styrene Download PDFInfo
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Abstract
The preparation method that the present invention relates to a kind of 4-methoxy styrene, comprises the following steps: 4-methoxyacetophenone is dissolved in alcoholic solvent by (1), adds reducing agent and carries out reduction reaction, obtains intermediate 1-(4-methoxyphenyl) ethanol；(2) in step (1), gained intermediate carries out dehydration under dehydrant catalysis, and distillation simultaneously obtains crude product 4-methoxy styrene.4-methoxy styrene preparation method provided by the invention, raw material is easy to get, technique is simple, reaction yield is high, product purity is high, and without adding polymerization inhibitor, solve that existing synthetic method Raw requirement is harsh, post processing difficulty, reaction easily polymerization, producing can not continuously and produce the problems such as equipment requirements harshness, it is possible to be effectively applied to production practices.
Description
Technical field
The present invention relates to organic synthesis field, the preparation method being specifically related to a kind of 4-methoxy styrene.
Background technology
Styrene compound is the important monomer of synthetic polystyrene resin, and each substituent group on phenyl ring can give prepared polystyrene resin various different character, is widely used in the fields such as material, medicine intermediate, binding agent, coating, sunscreen cream.The expelling water of substituted polystyrene compound and the displacement of reservoir oil are all fine.Polymer to methoxy styrene is a kind of excellent corrosion-resistant material, is widely used in information industry, and the bibliographical information of its synthetic method is more, and concrete grammar has:
1, providing in patent DE2317525 and EP128984 with ethylo benzene for raw material, catalyzed dehydrogenation reaction obtains cinnamic method.The shortcoming of the method is that yield is low, crude product purity difference, separating-purifying difficult, and high to producing equipment requirements；
2, patent US3636182 provides to replace toluene and the monochloro methane method that substituted phenylethylene is prepared in reaction under 700 DEG C of high temperature.The method is high to equipment requirements, severe reaction conditions, and described method side reaction is many, be easily polymerized under high temperature, dangerous high, is unfavorable for safety in production；
3, patent US005489731A provides with P-methoxybenzyl alcohol for raw material, reacted, with triphenyl phosphorus, formaldehyde, hydrobromic acid, the method prepared methoxy styrene by Wittig.Wittig reagent is prepared loaded down with trivial details, and instructions for use is significantly high；And in reacting, use gaseous state one Celfume, it is necessary to special consersion unit.This synthetic route expensive raw material price, post processing is also cumbersome；
4, with acetanisole for raw material in patent CN1660743A, through potassium borohydride reduction, then carry out esterification with potassium acid sulfate, be obtained by reacting methoxy styrene through eliminating after.This synthetic route is made up of three-step reaction, and reaction scheme is long, it is necessary to substantial amounts of potassium acid sulfate and cyclohexane solvent.And the method final step to react more difficult generation, yield extremely low, crude product purity difference, be not suitable for industry's enlarging production；
5, with acetanisole for raw material in patent CN101747162A, through potassium borohydride reduction, then carry out esterification with potassium acid sulfate, finally occur elimination to be obtained by reacting methoxy styrene in Pintsch process pipe.The method occurs Pintsch process eliminate conversion ratio during reaction extremely low, in Pintsch process pipe product be easily polymerized, poor yields, and containing a large amount of unreacteds raw material completely and etherificate by-product in crude product；
6, in patent CN103922902A with to methoxybenzene ethanol for raw material, in Pintsch process pipe occur dehydration obtain methoxy styrene.The method occurs Pintsch process eliminate conversion ratio during reaction better, but cannot be avoided product and be polymerized in Pintsch process pipe, high purity product can not be obtained；
In sum, the existing synthetic method of 4-methoxy styrene lacks a kind of technique is simple, cheaper starting materials is easy to get, without the synthetic route of especial equipment requirements, the method that shortage obtains high purity product.
Summary of the invention
Solve the technical problem that
For problems of the prior art, the preparation method that it is an object of the invention to provide a kind of 4-methoxy styrene, described preparation method raw material is easy to get, and technique is simple, and product yield is high, purity is high and can produce continuously.
Technical scheme
To achieve these goals, the preparation method that the present invention provides a kind of 4-methoxy styrene, comprise the following steps:
(1) 4-methoxyacetophenone is dissolved in alcoholic solvent, adds reducing agent and carry out reduction reaction, obtain intermediate 1-(4-methoxyphenyl) ethanol；
(2) in step (1), gained intermediate 1-(4-methoxyphenyl) ethanol carries out dehydration under dehydrant catalysis, and distillation simultaneously obtains crude product 4-methoxy styrene；
Wherein, step (3) is also included: gained crude product 4-methoxy styrene in step (2) is obtained product through rectification；
Wherein, described alcoholic solvent is methanol, ethanol or volume fraction is the ethanol water of 95%；Described reducing agent is lithium aluminium hydride reduction, sodium borohydride or potassium borohydride, it is preferable that potassium borohydride；
Wherein, described dehydrant is potassium acid sulfate, activated alumina, silicon oxide, phosphoric acid or sulphuric acid, it is preferable that potassium acid sulfate；
Wherein, the mol ratio of described 4-methoxyacetophenone and reducing agent is 1:0.25～1:0.35, it is preferable that mol ratio is 1:0.3；The mol ratio of described intermediate 1-(4-methoxyphenyl) ethanol and dehydrant is 1:0.00002～1:0.001, it is preferable that 1:0.0001；
Wherein, in described step (1), reduction reaction temperature is 20～80 DEG C, it is preferable that 30～50 DEG C；Response time is 1～3h；In described step (1), reaction also includes distillation process after terminating, and vapo(u)rizing temperature is 90～110 DEG C, and vacuum is 0.2～1mmHg；
Wherein, in described step (2), dehydration temperature is 150～220 DEG C, it is preferable that 160～190 DEG C；
Wherein, distillation procedure in described step (2) is particularly as follows: water pump decompression distillation, and intermediate is added drop-wise in reaction bulb by constant pressure funnel, and while reacting, distillation obtains product；Wherein intermediate rate of addition is 10～30mL/min；
Wherein, in described step (2), distillation pressure is 20～50mmHg, it is preferable that 25～35mmHg；
Wherein, in described step (3), rectification temperature is 50～90 DEG C, and rectification pressure is 0～1mmHg.
The invention provides a kind of with 4-methoxyacetophenone for raw material, obtain intermediate 1-(4-methoxyphenyl) ethanol by the reduction reaction under reducing agent effect, then occur dehydration to prepare the synthetic method of product 4-methoxy styrene under potassium acid sulfate effect.
The preparation method of 4-methoxy styrene of the present invention, in step (1), reduction reaction gained intermediate need to pass through distilation, purpose is in that to completely remove the impurity such as excessive reductant therein and boronate complex, it is to avoid produce to bring out the impacts such as polymerization on subsequent reactions.In step (2), 1-(4-methoxyphenyl) ethanol is progressively added dropwise in reaction bulb, in the disposable addition reaction bulb of dehydrant, response speed is controlled by regulating the rate of addition of 1-(4-methoxyphenyl) ethanol, if dripping too fast, then have side reaction to occur, reduce productivity and the purity of gained crude product；If dripping slow, then cause time upper unnecessary waste.
Beneficial effect
4-methoxy styrene preparation method provided by the present invention, raw material is easy to get, technique is simple, reaction yield is high, product purity is high, and without adding polymerization inhibitor, solve that existing synthetic method Raw requirement is harsh, post processing difficulty, reaction easily polymerization, producing can not continuously and produce the problems such as equipment requirements harshness, described preparation method is effectively applied to production practices.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
The preparation method that the present invention provides a kind of 4-methoxy styrene, comprises the following steps:
(1) 4-methoxyacetophenone is dissolved in the ethanol that volume fraction is 95%, stirring, heat up, add reducing agent in batches and carry out reduction reaction, reaction temperature is 20～80 DEG C, and the response time is 1～3h.After reaction terminates, add and the isopyknic water of ethanol, be sufficiently stirred for, remove excessive reducing agent and reducing agent reaction gained complex.Then through extraction into ethyl acetate, separatory, dry and concentrate organic facies.Distillation, vapo(u)rizing temperature is 90～110 DEG C, and vacuum is 0～1mmHg, obtains intermediate 1-(4-methoxyphenyl) ethanol；
(2) in advance by oil bath pan heating temperatures to setting reaction temperature 150～220 DEG C, then potassium acid sulfate and a small amount of 1-(4-methoxyphenyl) ethanol are added in reaction bulb, most 1-(4-methoxyphenyl) ethanol adds in constant pressure funnel, is added dropwise in reaction bulb with the speed of 10～30mL/min and carries out dehydration.After reaction 5min, starting water pump decompression distillation, distillation pressure is 20～50mmHg, and while there is dehydration, distillation obtains crude product, and in crude product, 4-methoxy styrene content is more than 98%；
(3) in step (2), gained crude product is through undue water, dry and rectification, and rectification temperature is 50～90 DEG C, and rectification pressure is 0～1mmHg, obtains the 4-methoxy styrene content product more than 99.5%；
Wherein, described reducing agent is lithium aluminium hydride reduction, sodium borohydride or potassium borohydride, it is preferable that potassium borohydride；
Wherein, described dehydrant is potassium acid sulfate, activated alumina, silicon oxide, phosphoric acid or sulphuric acid, it is preferable that potassium acid sulfate；
Wherein, the mol ratio of described 4-methoxyacetophenone and reducing agent is 1:0.25～1:0.35, it is preferable that mol ratio is 1:0.3；The mol ratio of described intermediate 1-(4-methoxyphenyl) ethanol and dehydrant is 1:0.00002～1:0.001, it is preferable that 1:0.0001；
Wherein, reaction temperature preferably 30～50 DEG C in described step (1)；
Wherein, dehydration temperature preferably 160～190 DEG C in described step (2)；
Wherein, distillation pressure preferably 25～35mmHg in described step (2).
Embodiment 1
A reduction reaction: the 4-methoxyacetophenone and the 4L volume fraction that add 2kg in the there-necked flask that capacity is 10L are the ethanol of 95%.Heating in water bath is to after 30 DEG C, adding potassium borohydride 240g altogether in batches.Keep bath temperature constant after adding, continue reaction 3h, monitored by gas chromatogram, it is determined that after remaining without 4-methoxyacetophenone, add 4L tap water and terminate reaction, after stirring 45min, start to extract.First time adds 4.5L extraction into ethyl acetate, and residue aqueous phase adds 0.5L extraction into ethyl acetate twice.Merge organic facies, add the dry 3h of anhydrous sodium sulfate that mass fraction is organic facies quality 5%.Filtering, filtrate rotation is evaporated off solvent, obtains 1.993kg crude intermediate.Carrying out distilation (vapo(u)rizing temperature is 100 DEG C, vacuum 1mmHg) again, obtain 1-(4-methoxyphenyl) ethanol of 1.9kg, detecting its purity through GC is 99.45%, and yield is 95%；
B dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.2g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 25mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 17mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains the moisture crude product of 4.65kg, obtains 4.082kg crude product after point water, and yield is 93%, and wherein the content of 4-methoxy styrene is 98.46%；
C rectification: add the 4-methoxy styrene crude product of 4kg in the there-necked flask that capacity is 5L, add 20cm rectifying column, liquid temperature controls at 75 DEG C, oil pump evacuation, and vacuum pressure controller regulates and is maintained at 0.8mmHg.Distilling complete after 8h, obtain main distillate fraction 3.85kg, yield is 96.3%, and the content being detected wherein 4-methoxy styrene by GC is 99.75%.Products obtained therefrom appearance colorless is transparent；
The total recovery of this synthetic method overall process three-step reaction is 85%.
Embodiment 2
A reduction reaction: the 4-methoxyacetophenone and the 4L volume fraction that add 2kg in the there-necked flask that capacity is 10L are the ethanol of 95%.Heating in water bath is to after 30 DEG C, adding potassium borohydride 185g altogether in batches.Keep bath temperature constant after adding, continue reaction 5h, monitored by gas chromatogram, it is determined that after remaining without 4-methoxyacetophenone, add 4L tap water and terminate reaction, after stirring 45min, start to extract.First time adds 4.5L extraction into ethyl acetate, and residue aqueous phase adds 0.5L extraction into ethyl acetate twice.Merge organic facies, add the dry 3h of anhydrous sodium sulfate that mass fraction is organic facies quality 5%.Filtering, filtrate rotation is evaporated off solvent, obtains 1.996kg crude intermediate.Carrying out distilation (vapo(u)rizing temperature is 100 DEG C, vacuum 0.5mmHg) again, obtain 1.91kg1-(4-methoxyphenyl) ethanol, detecting its purity through GC is 99.45%, and yield is 95.5%；
B dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.2g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 30mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 17mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains the moisture crude product of 4.65kg, obtains 4.01kg crude product after point water, and yield is 93%, and wherein the content of 4-methoxy styrene is 98.7%；
C rectification: add the 4-methoxy styrene crude product of 4.01kg in the there-necked flask that capacity is 5L, add 20cm rectifying column, liquid temperature controls at 75 DEG C, oil pump evacuation, and vacuum pressure controller regulates and is maintained at 0.8mmHg.Distilling complete after 8h, obtain main distillate fraction 3.84kg, yield is 96.3%, and the content being detected wherein 4-methoxy styrene by GC is 99.70%.Products obtained therefrom appearance colorless is transparent；
The total recovery of this synthetic method overall process three-step reaction is 84.8%.
Embodiment 3
A reduction reaction: the 4-methoxyacetophenone and the 4L volume fraction that add 2kg in the there-necked flask that capacity is 10L are the ethanol of 95%.Heating in water bath is to after 50 DEG C, adding potassium borohydride 40g altogether in batches.Keep bath temperature constant after adding, continue reaction 5h, monitored by gas chromatogram, it is determined that after remaining without 4-methoxyacetophenone, add 4L tap water and terminate reaction, after stirring 45min, start to extract.First time adds 4.5L extraction into ethyl acetate, and residue aqueous phase adds 0.5L extraction into ethyl acetate twice.Merge organic facies, add the dry 3h of anhydrous sodium sulfate that mass fraction is organic facies quality 5%.Filtering, filtrate rotation is evaporated off solvent, obtains 1.99kg crude intermediate.Carrying out distilation (vapo(u)rizing temperature is 100 DEG C, vacuum 1mmHg) again, obtain 1.91kg1-(4-methoxyphenyl) ethanol, detecting its purity through GC is 99.3%, and yield is 95.5%；
Step b and step c is identical with embodiment 1.
Embodiment 4
A reduction reaction: the 4-methoxyacetophenone and the 4L volume fraction that add 2kg in the there-necked flask that capacity is 10L are the ethanol of 95%.Heating in water bath is to after 80 DEG C, adding potassium borohydride 40g altogether in batches.Keep bath temperature constant after adding, continue reaction 5h, monitored by gas chromatogram, it is determined that after remaining without 4-methoxyacetophenone, add 4L tap water and terminate reaction, after stirring 45min, start to extract.First time adds 4.5L extraction into ethyl acetate, and residue aqueous phase adds 0.5L extraction into ethyl acetate twice.Merge organic facies, add the dry 3h of anhydrous sodium sulfate that mass fraction is organic facies quality 5%.Filtering, filtrate rotation is evaporated off solvent, obtains 1.75kg crude intermediate.Carrying out distilation (vapo(u)rizing temperature is 100 DEG C, vacuum 1mmHg) again, obtain 1.65kg1-(4-methoxyphenyl) ethanol, detecting its purity through GC is 98.7%, and yield is 82.5%；
Step b and step c is identical with embodiment 1.
Embodiment 5
Step a is identical with embodiment 1；
B dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.4g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 35mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 17mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains 4.022kg crude product after point water, and yield is 91.6%, and wherein the content of 4-methoxy styrene is 98.42%；
Step c is identical with embodiment 1.
Embodiment 6
Step a is identical with embodiment 1；
B dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.2g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 30mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 40mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains 3.682kg crude product after point water, and yield is 84%, and wherein the content of 4-methoxy styrene is 95.42%；
Step c is identical with embodiment 1.
Embodiment 7
Step a is identical with embodiment 1；
B dehydration: first by oil bath pan heating temperatures to 220 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.2g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 30mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 40mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains 3.700kg crude product after point water, and yield is 84.3%, and wherein the content of 4-methoxy styrene is 98.12%；
Step c is identical with embodiment 1.
Embodiment 8
Step a is identical with embodiment 1；
B dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.2g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 30mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 40mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains 3.940kg crude product after point water, and yield is 89.8%, and wherein the content of 4-methoxy styrene is 96.52%；
Step c is identical with embodiment 1.
Embodiment 9
Step a is identical with embodiment 1；
B dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 4g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 45mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 17mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains 3.100kg crude product after point water, and yield is 70.6%, and wherein the content of 4-methoxy styrene is 98.92%；
Step c is identical with embodiment 1.
Embodiment 10
Step a is identical with embodiment 1；
B dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.45g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L.After oil bath pan rises to design temperature, there-necked flask is put in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation (pressure 25mmHg).Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 17mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation.Reaction terminates to stop distillation, obtains 4.200kg crude product after point water, and yield is 95.7%, and wherein the content of 4-methoxy styrene is 98.72%.
Step c is identical with embodiment 1.
Embodiment 11
Step a and step b is identical with embodiment 1；
C rectification: add the 4-methoxy styrene crude product of 4kg in the there-necked flask that capacity is 5L, add 20cm rectifying column, liquid temperature controls at 90 DEG C, oil pump evacuation, and vacuum pressure controller regulates and is maintained at 0.8mmHg.Distilling complete after 8h, obtain main distillate fraction 3.78kg, yield is 94.5%, and the content being detected wherein 4-methoxy styrene by GC is 99.52%.Products obtained therefrom appearance colorless is transparent.
Comparative example 1
A reduction reaction: the 4-methoxyacetophenone and the 4L volume fraction that add 2kg in the there-necked flask that capacity is 10L are the ethanol of 95%.Heating in water bath is to after 30 DEG C, adding potassium borohydride 140g altogether in batches.Keep bath temperature constant after adding, continue reaction 15h, monitored by gas chromatogram, it is determined that after remaining without 4-methoxyacetophenone, add 4L tap water and terminate reaction, after stirring 45min, start to extract.First time adds 4.5L extraction into ethyl acetate, and residue aqueous phase adds 0.5L extraction into ethyl acetate twice.Merge organic facies, add the dry 3h of anhydrous sodium sulfate that mass fraction is organic facies quality 5%.Filtering, filtrate rotation is evaporated off solvent, obtains 1.44kg crude intermediate.Carrying out air-distillation purification again, obtain 1.22kg1-(4-methoxyphenyl) ethanol, detecting its purity through GC is 97.3%, and yield is 61%；
Step b and step c is identical with embodiment 1.
Comparative example 2
Step a and step b is identical with embodiment 1；
C rectification: add the 4-methoxy styrene crude product of 4kg in the there-necked flask that capacity is 5L, add 20cm rectifying column, liquid temperature controls at 100 DEG C, oil pump evacuation, and vacuum pressure controller regulates and is maintained at 0.8mmHg.Distilling complete after 8h, obtain main distillate fraction 3.85kg, yield is 28%, and product extent of polymerization is serious, aggregate rate about 70%.The content being detected wherein 4-methoxy styrene by GC is 98.3%.Products obtained therefrom appearance colorless is transparent.
Although, above use generality explanation, detailed description of the invention and test, the present invention is described in detail, but on basis of the present invention, it is possible to it is made some modifications or improvements, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (2)
1. a preparation method for 4-methoxy styrene, specifically comprises the following steps that
A, reduction reaction: the 4-methoxyacetophenone and the 4L volume fraction that add 2kg in the there-necked flask that capacity is 10L are the ethanol of 95%；Heating in water bath is to after 30 DEG C, adding potassium borohydride 240g altogether in batches；Keep bath temperature constant after adding, continue reaction 3h, monitored by gas chromatogram, it is determined that after remaining without 4-methoxyacetophenone, add 4L tap water and terminate reaction, after stirring 45min, start to extract；First time adds 4.5L extraction into ethyl acetate, and residue aqueous phase adds 0.5L extraction into ethyl acetate twice；Merge organic facies, add the dry 3h of anhydrous sodium sulfate that mass fraction is organic facies quality 5%；Filtering, filtrate rotation is evaporated off solvent, obtains 1.993kg crude intermediate；Carrying out distilation again, vapo(u)rizing temperature is 100 DEG C, and vacuum is 1mmHg, obtains 1-(4-methoxyphenyl) ethanol of 1.9kg, and detecting its purity through GC is 99.45%, and yield is 95%；
B, dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.2g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L；After oil bath pan rises to design temperature, being put into by there-necked flask in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation, distillation pressure is 25mmHg；Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 17mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation；Reaction terminates to stop distillation, obtains the moisture crude product of 4.65kg, obtains 4.082kg crude product after point water, and yield is 93%, and wherein the content of 4-methoxy styrene is 98.46%；
C, rectification: add the 4-methoxy styrene crude product of 4kg in the there-necked flask that capacity is 5L, add 20cm rectifying column, liquid temperature controls at 75 DEG C, oil pump evacuation, and vacuum pressure controller regulates and is maintained at 0.8mmHg；Distilling complete after 8h, obtain main distillate fraction 3.85kg, yield is 96.3%, and the content being detected wherein 4-methoxy styrene by GC is 99.75%, and products obtained therefrom appearance colorless is transparent；The total recovery of three-step reaction is 85%.
2. a preparation method for 4-methoxy styrene, specifically comprises the following steps that
A, reduction reaction: the 4-methoxyacetophenone and the 4L volume fraction that add 2kg in the there-necked flask that capacity is 10L are the ethanol of 95%；Heating in water bath is to after 30 DEG C, adding potassium borohydride 185g altogether in batches；Keep bath temperature constant after adding, continue reaction 5h, monitored by gas chromatogram, it is determined that after remaining without 4-methoxyacetophenone, add 4L tap water and terminate reaction, after stirring 45min, start to extract；First time adds 4.5L extraction into ethyl acetate, and residue aqueous phase adds 0.5L extraction into ethyl acetate twice；Merge organic facies, add the dry 3h of anhydrous sodium sulfate that mass fraction is organic facies quality 5%；Filtering, filtrate rotation is evaporated off solvent, obtains 1.996kg crude intermediate；Carrying out distilation again, vapo(u)rizing temperature is 100 DEG C, and vacuum is 0.5mmHg, obtains 1-(4-methoxyphenyl) ethanol of 1.91kg, and detecting its purity through GC is 99.45%, and yield is 95.5%；
B, dehydration: first by oil bath pan heating temperatures to 190 DEG C, the there-necked flask that capacity is 1L is previously added 1-(4-methoxyphenyl) ethanol of 30g, 0.2g potassium acid sulfate, adds 1-(4-methoxyphenyl) ethanol of 500g in the constant pressure funnel that capacity is 5L；After oil bath pan rises to design temperature, being put into by there-necked flask in oil bath pan, build vacuum distillation apparatus, start water pump decompression distillation, distillation pressure is 30mmHg；Control 1-(4-methoxyphenyl) ethanol slowly to be instilled in reaction bulb by constant pressure funnel with the speed of 17mL/min, after 1-(4-methoxyphenyl) ethanol in constant pressure funnel adds, continuously add 1-(4-methoxyphenyl) ethanol of 4.47kg, it is not necessary to stop adding thermal distillation；Reaction terminates to stop distillation, obtains the moisture crude product of 4.65kg, obtains 4.01kg crude product after point water, and yield is 93%, and wherein the content of 4-methoxy styrene is 98.7%；
C, rectification: add the 4-methoxy styrene crude product of 4.01kg in the there-necked flask that capacity is 5L, add 20cm rectifying column, liquid temperature controls at 75 DEG C, oil pump evacuation, and vacuum pressure controller regulates and is maintained at 0.8mmHg；Distilling complete after 8h, obtain main distillate fraction 3.84kg, yield is 96.3%, and the content being detected wherein 4-methoxy styrene by GC is 99.70%, and products obtained therefrom appearance colorless is transparent；The total recovery of three-step reaction is 84.8%.
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