CN104447230A - Method for preparing 4-methoxystyrene - Google Patents
Method for preparing 4-methoxystyrene Download PDFInfo
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Abstract
The invention relates to a method for preparing 4-methoxystyrene. The method comprises the following steps: (1) dissolving 4-methoxyacetophenone into an ethanol solvent, adding a reducer and performing reduction reaction to obtain an intermediate 1-(4-methoxyphenyl) ethanol; and (2) performing dehydration reaction on the intermediate obtained in step (1) under the catalysis of a dehydrating agent, and distilling at the same time to obtain a rough 4-methoxystyrene product. The method for preparing the 4-methoxystyrene is readily available in raw materials, simple in process, high in reaction yield and high in product purity, and a polymerization inhibitor is not needed, so that the problems that the requirement for raw materials is strict, the post treatment is difficult, polymerization is easily caused in the reaction, the production is discontinuous, the requirement for production equipment is strict and the like in the existing synthetic method are solved, and the method can be effectively applied to production practice.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to a kind of preparation method of 4-methoxy styrene.
Background technology
Styrene compound is the important monomer of synthetic polystyrene resin, and each substituting group on phenyl ring can give obtained polystyrene resin various different character, is widely used in the fields such as material, medicine intermediate, tackiness agent, coating, sunscreen.The expelling water of substituted polystyrene compound and the displacement of reservoir oil are all fine.Be a kind of excellent corrosion resistant material to the polymkeric substance of methoxy styrene, be widely used in information industry, the bibliographical information of its synthetic method is more, specific as follows.
Providing in patent DE2317525 and EP128984 with ethylbenzene is raw material, obtains cinnamic method through catalytic dehydrogenating reaction.The shortcoming of the method is that yield is low, crude product purity difference, separating-purifying difficulty, and requires high to production unit.
Provide in patent US3636182 to replace toluene and monochloro methane reacts the method preparing substituted phenylethylene 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.
Providing in patent US005489731A with p-methoxybenzyl alcohol is raw material, reacts the obtained method to methoxy styrene with triphenyl phosphorus, formaldehyde, Hydrogen bromide by Wittig.Wittig reagent is prepared loaded down with trivial details, and service requirements is very high; And use gaseous state one monobromethane in reaction, need special conversion unit.This synthetic route expensive raw material price, aftertreatment is also more loaded down with trivial details.
Be raw material with p-methoxy-acetophenone in patent CN1660743A, through potassium borohydride reduction, then carry out esterification with sal enixum, obtain methoxy styrene finally by eliminative reaction.This synthetic route is made up of three-step reaction, and reaction scheme is long, needs a large amount of sal enixums and cyclohexane solvent.And more difficult generation is reacted in the method final step, yield is extremely low, crude product purity difference, is not suitable for industry's enlarging production.
Be raw material with p-methoxy-acetophenone in patent CN101747162A, through potassium borohydride reduction, then carry out esterification with sal enixum, finally in Pintsch process pipe, eliminative reaction occurs and obtain methoxy styrene.When there is Pintsch process eliminative reaction in the method, transformation efficiency is extremely low, in Pintsch process pipe product be easily polymerized, poor yields, and containing a large amount of unreacted raw material and etherificate by product completely in crude product.
In patent CN103922902A with to anisole ethanol for raw material, in Pintsch process pipe, there is dehydration reaction obtain methoxy styrene.When there is Pintsch process eliminative reaction in the method, transformation efficiency is better, but product can not be avoided to be polymerized in Pintsch process pipe, can not obtain high purity product.
In sum, lack in the existing synthetic method of 4-methoxy styrene that a kind of technique is simple, cheaper starting materials is easy to get, without the synthetic route of especial equipment requirements, shortage obtains the method for high purity product.
Summary of the invention
For problems of the prior art, the object of this invention is to provide a kind of preparation method of 4-methoxy styrene, described preparation method's raw material is easy to get, and technique is simple, and product yield is high, purity is high and can continuous seepage.
To achieve these goals, the invention provides a kind of preparation method of 4-methoxy styrene, comprise the following steps:
(1) 4-methoxyacetophenone is dissolved in alcoholic solvent, adds reductive agent and carry out reduction reaction, obtain intermediate 1-(4-p-methoxy-phenyl) ethanol;
(2) in step (1), gained intermediate 1-(4-p-methoxy-phenyl) ethanol carries out dehydration reaction under dewatering agent catalysis, and distillation simultaneously obtains crude product 4-methoxy styrene.
Wherein, step (3) is also comprised: gained crude product 4-methoxy styrene in step (2) is obtained product through rectifying.
Wherein, described alcoholic solvent to be methyl alcohol, ethanol or volume fraction be 95% aqueous ethanolic solution; Described reductive agent is lithium aluminum hydride, sodium borohydride or POTASSIUM BOROHYDRIDE, preferred POTASSIUM BOROHYDRIDE.
Wherein, described dewatering agent is sal enixum, activated alumina, silicon oxide, phosphoric acid or sulfuric acid, preferably sulfuric acid hydrogen potassium.
Wherein, the mol ratio of described 4-methoxyacetophenone and reductive agent is 1:0.25 ~ 1:0.35, and preferred molar ratio is 1:0.3; The mol ratio of described intermediate 1-(4-p-methoxy-phenyl) ethanol and dewatering agent is 1:0.00002 ~ 1:0.001, preferred 1:0.0001.
Wherein, in described step (1), reduction reaction temperature is 20 ~ 80 DEG C, preferably 30 ~ 50 DEG C; Reaction times is 1 ~ 3 h; In described step (1), reaction also comprises distillation process after terminating, and distillation temperature is 90 ~ 110 DEG C, and vacuum tightness is 0.2 ~ 1 mmHg.
Wherein, in described step (2), dehydration reaction temperature is 150 ~ 220 DEG C, preferably 160 ~ 190 DEG C.
Wherein, in described step (2), distillation procedure is specially: water pump underpressure distillation, and intermediate is added drop-wise in reaction flask by constant pressure funnel, and while reacting, distillation obtains product; Wherein intermediate rate of addition is 10 ~ 30 mL/min.
Wherein, in described step (2), distillation pressure is 20 ~ 50 mmHg, preferably 25 ~ 35 mmHg.
Wherein, in described step (3), rectification temperature is 50 ~ 90 DEG C, and rectifying pressure is 0 ~ 1 mmHg.
The invention provides one with 4-methoxyacetophenone for raw material, obtain intermediate 1-(4-p-methoxy-phenyl) ethanol by the reduction reaction under reductive agent effect, then the synthetic method of dehydration reaction preparing product 4-methoxy styrene occurs under sal enixum effect.
The preparation method of 4-methoxy styrene of the present invention, in step (1), reduction reaction gained intermediate need pass through distilation, object is to remove completely the impurity such as excessive reductant wherein and boronate complex, avoids producing subsequent reactions bringing out the impacts such as polymerization.In step (2), 1-(4-p-methoxy-phenyl) ethanol is progressively added dropwise in reaction flask, dewatering agent is disposable to add in reaction flask, speed of response is controlled by regulating the rate of addition of 1-(4-p-methoxy-phenyl) ethanol, if drip too fast, then have side reaction to occur, reduce productive rate and the purity of gained crude product; If dripped slow, then caused time upper unnecessary waste.
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 the need to adding stopper, solve that existing synthetic method Raw requirement is harsh, aftertreatment is difficult, reaction is easily polymerized, producing can not continuously and the problem such as production unit requirement harshness, described preparation method can be effectively applied to production practice.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
The invention provides a kind of preparation method of 4-methoxy styrene, comprise the following steps:
(1) 4-methoxyacetophenone being dissolved in volume fraction is in the ethanol of 95%, stirs, and heat up, add reductive agent in batches and carry out reduction reaction, temperature of reaction is 20 ~ 80 DEG C, and the reaction times is 1 ~ 3 h.After reaction terminates, add isopyknic water with ethanol, fully stir, remove excessive reductive agent and reductive agent reaction gained complex compound.Then through extraction into ethyl acetate, separatory, drying also concentrates organic phase.Distillation, distillation temperature is 90 ~ 110 DEG C, and vacuum tightness is 0 ~ 1 mmHg, obtains intermediate 1-(4-p-methoxy-phenyl) ethanol.
(2) in advance by oil bath pan heating temperatures to setting temperature of reaction 150 ~ 220 DEG C, then sal enixum and a small amount of 1-(4-p-methoxy-phenyl) ethanol are added in reaction flask, most 1-(4-p-methoxy-phenyl) ethanol adds in constant pressure funnel, is added dropwise in reaction flask carries out dehydration reaction with the speed of 10 ~ 30 mL/min.After reacting 5 min, start water pump underpressure distillation, distillation pressure is 20 ~ 50 mmHg, and while generation dehydration reaction, distillation obtains crude product, and in crude product, 4-methoxy styrene content is greater than 98%.
(3) in step (2), gained crude product is through undue water, drying and rectifying, and rectification temperature is 50 ~ 90 DEG C, and rectifying pressure is 0 ~ 1 mmHg, obtains the product that 4-methoxy styrene content is greater than 99.5%.
Wherein, described reductive agent is lithium aluminum hydride, sodium borohydride or POTASSIUM BOROHYDRIDE, preferred POTASSIUM BOROHYDRIDE.
Wherein, described dewatering agent is sal enixum, activated alumina, silicon oxide, phosphoric acid or sulfuric acid, preferably sulfuric acid hydrogen potassium.
Wherein, the mol ratio of described 4-methoxyacetophenone and reductive agent is 1:0.25 ~ 1:0.35, and preferred molar ratio is 1:0.3; The mol ratio of described intermediate 1-(4-p-methoxy-phenyl) ethanol and dewatering agent is 1:0.00002 ~ 1:0.001, preferred 1:0.0001.
Wherein, temperature of reaction preferably 30 ~ 50 DEG C in described step (1).
Wherein, dehydration reaction temperature preferably 160 ~ 190 DEG C in described step (2).
Wherein, distillation pressure preferably 25 ~ 35 mmHg in described step (2).
Embodiment 1
A reduction reaction: be add the 4-methoxyacetophenone of 2 kg in the there-necked flask of 10L and 4 L volume fractions are the ethanol of 95% at capacity.After heating in water bath to 30 DEG C, add POTASSIUM BOROHYDRIDE totally 240 g in batches.Add rear maintenance bath temperature constant, continue reaction 3 h, monitored by gas-chromatography, determine, without after 4-methoxyacetophenone residue, to add 4 L tap water termination reactions, after stirring 45 min, start extraction.First time adds 4.5 L extraction into ethyl acetate, and residue aqueous phase adds 0.5 L extraction into ethyl acetate twice again.Merge organic phase, add anhydrous sodium sulfate drying 3 h that massfraction is organic phase quality 5%.Filter, filtrate is revolved and is steamed except desolventizing, obtains 1.993 kg crude intermediate.Carry out distilation (distillation temperature is 100 DEG C, vacuum tightness 1mmHg) again, obtain 1-(4-p-methoxy-phenyl) ethanol of 1.9 kg, detecting its purity through GC is 99.45%, and yield is 95%.
B dehydration reaction: first by oil bath pan heating temperatures to 190 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 0.2 g sal enixum is 1-(4-p-methoxy-phenyl) ethanol adding 500g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 25mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 17 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, obtains the moisture crude product of 4.65 kg, and after point water, obtain 4.082 kg crude products, yield is 93%, and wherein the content of 4-methoxy styrene is 98.46%.
C rectifying: be the 4-methoxy styrene crude product adding 4 kg in the there-necked flask of 5 L at capacity, add 20 cm rectifying columns, liquid temperature controls at 75 DEG C, and oil pump vacuumizes, vacuum tightness pressure controller regulates and remains on 0.8mmHg.Distill complete after 8 h, obtain main distillate fraction 3.85 kg, 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 whole process three-step reaction is 85%.
Embodiment 2
A reduction reaction: be add the 4-methoxyacetophenone of 2 kg in the there-necked flask of 10 L and 4 L volume fractions are the ethanol of 95% at capacity.After heating in water bath to 30 DEG C, add POTASSIUM BOROHYDRIDE totally 185 g in batches.Add rear maintenance bath temperature constant, continue reaction 5 h, monitored by gas-chromatography, determine, without after 4-methoxyacetophenone residue, to add 4 L tap water termination reactions, after stirring 45 min, start extraction.First time adds 4.5 L extraction into ethyl acetate, and residue aqueous phase adds 0.5 L extraction into ethyl acetate twice again.Merge organic phase, add anhydrous sodium sulfate drying 3 h that massfraction is organic phase quality 5%.Filter, filtrate is revolved and is steamed except desolventizing, obtains 1.996 kg crude intermediate.Carry out distilation (distillation temperature is 100 DEG C, vacuum tightness 0.5mmHg) again, obtain 1.91 kg1-(4-p-methoxy-phenyl) ethanol, detecting its purity through GC is 99.45%, and yield is 95.5%.
B dehydration reaction: first by oil bath pan heating temperatures to 190 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 0.2 g sal enixum is 1-(4-p-methoxy-phenyl) ethanol adding 500g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 30mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 17 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, obtains the moisture crude product of 4.65 kg, and after point water, obtain 4.01 kg crude products, yield is 93%, and wherein the content of 4-methoxy styrene is 98.7%.
C rectifying: be the 4-methoxy styrene crude product adding 4.01 kg in the there-necked flask of 5 L at capacity, add 20 cm rectifying columns, liquid temperature controls at 75 DEG C, and oil pump vacuumizes, vacuum tightness pressure controller regulates and remains on 0.8mmHg.Distill complete after 8 h, obtain main distillate fraction 3.84 kg, 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 whole process three-step reaction is 84.8%.
Embodiment 3
A reduction reaction: be add the 4-methoxyacetophenone of 2 kg in the there-necked flask of 10 L and 4 L volume fractions are the ethanol of 95% at capacity.After heating in water bath to 50 DEG C, add POTASSIUM BOROHYDRIDE totally 40 g in batches.Add rear maintenance bath temperature constant, continue reaction 5 h, monitored by gas-chromatography, determine, without after 4-methoxyacetophenone residue, to add 4 L tap water termination reactions, after stirring 45 min, start extraction.First time adds 4.5 L extraction into ethyl acetate, and residue aqueous phase adds 0.5 L extraction into ethyl acetate twice again.Merge organic phase, add anhydrous sodium sulfate drying 3 h that massfraction is organic phase quality 5%.Filter, filtrate is revolved and is steamed except desolventizing, obtains 1.99 kg crude intermediate.Carry out distilation (distillation temperature is 100 DEG C, vacuum tightness 1mmHg) again, obtain 1.91 kg1-(4-p-methoxy-phenyl) ethanol, detecting its purity through GC is 99.3%, and yield is 95.5%.
Step b is identical with embodiment 1 with step c.
Embodiment 4
A reduction reaction: be add the 4-methoxyacetophenone of 2 kg in the there-necked flask of 10 L and 4 L volume fractions are the ethanol of 95% at capacity.After heating in water bath to 80 DEG C, add POTASSIUM BOROHYDRIDE totally 40 g in batches.Add rear maintenance bath temperature constant, continue reaction 5 h, monitored by gas-chromatography, determine, without after 4-methoxyacetophenone residue, to add 4 L tap water termination reactions, after stirring 45 min, start extraction.First time adds 4.5 L extraction into ethyl acetate, and residue aqueous phase adds 0.5 L extraction into ethyl acetate twice again.Merge organic phase, add anhydrous sodium sulfate drying 3 h that massfraction is organic phase quality 5%.Filter, filtrate is revolved and is steamed except desolventizing, obtains 1.75kg crude intermediate.Carry out distilation (distillation temperature is 100 DEG C, vacuum tightness 1mmHg) again, obtain 1.65 kg1-(4-p-methoxy-phenyl) ethanol, detecting its purity through GC is 98.7%, and yield is 82.5%.
Step b is identical with embodiment 1 with step c.
Embodiment 5
Step a is identical with embodiment 1.
B dehydration reaction: first by oil bath pan heating temperatures to 190 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 0.4 g sal enixum is 1-(4-p-methoxy-phenyl) ethanol adding 500 g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 35mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 17 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, and after point water, obtain 4.022 kg crude products, 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 reaction: first by oil bath pan heating temperatures to 190 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 0.2 g sal enixum is 1-(4-p-methoxy-phenyl) ethanol adding 500 g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 30mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 40 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, and after point water, obtain 3.682 kg crude products, 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 reaction: first by oil bath pan heating temperatures to 220 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 0.2 g sal enixum is 1-(4-p-methoxy-phenyl) ethanol adding 500 g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 30mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 40 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, and after point water, obtain 3.700 kg crude products, 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 reaction: first by oil bath pan heating temperatures to 190 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 0.2 g sal enixum is 1-(4-p-methoxy-phenyl) ethanol adding 500 g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 30mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 40 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, and after point water, obtain 3.940 kg crude products, 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 reaction: first by oil bath pan heating temperatures to 190 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 4 g sal enixums are 1-(4-p-methoxy-phenyl) ethanol adding 500g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 45mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 17 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, and after point water, obtain 3.100 kg crude products, 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 reaction: first by oil bath pan heating temperatures to 190 DEG C, be 1-(4-p-methoxy-phenyl) ethanol adding 30 g in the there-necked flask of 1 L in advance at capacity, 0.45 g sal enixum is 1-(4-p-methoxy-phenyl) ethanol adding 500g in the constant pressure funnel of 5 L at capacity.After oil bath pan rises to design temperature, there-necked flask is put into oil bath pan, build vacuum distillation apparatus, start water pump underpressure distillation (pressure 25mmHg).Control 1-(4-p-methoxy-phenyl) ethanol is slowly instilled in reaction flask by constant pressure funnel with the speed of 17 mL/min, after 1-(4-p-methoxy-phenyl) ethanol in constant pressure funnel adds, continuing 1-(4-p-methoxy-phenyl) ethanol adding 4.47 kg, adding thermal distillation without the need to stopping.Reaction terminates to stop distillation, and after point water, obtain 4.200 kg crude products, 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 is identical with embodiment 1 with step b.
C rectifying: be the 4-methoxy styrene crude product adding 4 kg in the there-necked flask of 5 L at capacity, add 20 cm rectifying columns, liquid temperature controls at 90 DEG C, and oil pump vacuumizes, vacuum tightness pressure controller regulates and remains on 0.8mmHg.Distill complete after 8 h, obtain main distillate fraction 3.78 kg, 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: be add the 4-methoxyacetophenone of 2 kg in the there-necked flask of 10 L and 4 L volume fractions are the ethanol of 95% at capacity.After heating in water bath to 30 DEG C, add POTASSIUM BOROHYDRIDE totally 140 g in batches.Add rear maintenance bath temperature constant, continue reaction 15 h, monitored by gas-chromatography, determine, without after 4-methoxyacetophenone residue, to add 4 L tap water termination reactions, after stirring 45 min, start extraction.First time adds 4.5 L extraction into ethyl acetate, and residue aqueous phase adds 0.5 L extraction into ethyl acetate twice again.Merge organic phase, add anhydrous sodium sulfate drying 3 h that massfraction is organic phase quality 5%.Filter, filtrate is revolved and is steamed except desolventizing, obtains 1.44 kg crude intermediate.Carry out air distillation purification again, obtain 1.22 kg1-(4-p-methoxy-phenyl) ethanol, detecting its purity through GC is 97.3%, and yield is 61%.
Step b is identical with embodiment 1 with step c.
Comparative example 2
Step a is identical with embodiment 1 with step b.
C rectifying: be the 4-methoxy styrene crude product adding 4 kg in the there-necked flask of 5 L at capacity, add 20 cm rectifying columns, liquid temperature controls at 100 DEG C, and oil pump vacuumizes, vacuum tightness pressure controller regulates and remains on 0.8mmHg.Distill complete after 8 h, obtain main distillate fraction 3.85 kg, yield is 28%, and product extent of polymerization is serious, percent polymerization about 70%.The content being detected wherein 4-methoxy styrene by GC is 98.3%.Products obtained therefrom appearance colorless is transparent.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, 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, all belong to the scope of protection of present invention.
Claims (10)
1. a preparation method for 4-methoxy styrene, is characterized in that, comprises the following steps:
(1) 4-methoxyacetophenone is dissolved in alcoholic solvent, adds reductive agent and carry out reduction reaction, obtain intermediate 1-(4-p-methoxy-phenyl) ethanol;
(2) in step (1), gained intermediate 1-(4-p-methoxy-phenyl) ethanol carries out dehydration reaction under dewatering agent catalysis, and distillation simultaneously obtains crude product 4-methoxy styrene, reaction equation:
。
2. preparation method according to claim 1, is characterized in that, also comprises step (3): gained crude product 4-methoxy styrene in step (2) is obtained product through rectifying.
3. preparation method according to claim 1 and 2, is characterized in that, described alcoholic solvent to be methyl alcohol, ethanol or volume fraction be 95% aqueous ethanolic solution.
4. preparation method according to claim 1 and 2, is characterized in that, described reductive agent is lithium aluminum hydride, sodium borohydride or POTASSIUM BOROHYDRIDE, preferred POTASSIUM BOROHYDRIDE; The mol ratio of described 4-methoxyacetophenone and reductive agent is 1:0.25 ~ 1:0.35, and preferred molar ratio is 1:0.3.
5. preparation method according to claim 1 and 2, is characterized in that, described dewatering agent is sal enixum, activated alumina, silicon oxide, phosphoric acid or sulfuric acid, preferably sulfuric acid hydrogen potassium; The mol ratio of described intermediate 1-(4-p-methoxy-phenyl) ethanol and dewatering agent is 1:0.00002 ~ 1:0.001, preferred 1:0.0001.
6. preparation method according to claim 1 and 2, is characterized in that, in described step (1), reduction reaction temperature is 20 ~ 80 DEG C, preferably 30 ~ 50 DEG C; Reaction times is 1 ~ 3 h; In described step (1), reaction also comprises distillation process after terminating, and distillation temperature is 90 ~ 110 DEG C, and vacuum tightness is 0.2 ~ 1 mmHg.
7. preparation method according to claim 1 and 2, is characterized in that, in described step (2), dehydration reaction temperature is 150 ~ 220 DEG C, preferably 160 ~ 190 DEG C.
8. preparation method according to claim 1 and 2, is characterized in that, in described step (2), distillation procedure is specially: underpressure distillation, and intermediate is added drop-wise in reaction flask, and while reacting, distillation obtains product; Wherein intermediate rate of addition is 10 ~ 30 mL/min.
9. preparation method according to claim 8, is characterized in that, in described step (2), distillation pressure is 20 ~ 50 mmHg, preferably 25 ~ 35 mmHg.
10. preparation method according to claim 1 and 2, is characterized in that, in described step (3), rectification temperature is 50 ~ 90 DEG C, and rectifying pressure is 0 ~ 1mmHg.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109553511A (en) * | 2018-12-28 | 2019-04-02 | 江南大学 | Parahydroxyacet-ophenone one-step method realizes the method that hydrogenation reaction coupling dehydration prepares 4-Vinyl phenol |
| CN110527005A (en) * | 2019-08-06 | 2019-12-03 | 中山大学 | A kind of super high molecular weight poly- (4- alkoxystyrene) and preparation method thereof |
| CN112811991A (en) * | 2021-02-01 | 2021-05-18 | 惠泽化学科技(濮阳)有限公司 | Synthesis method of p-methoxystyrene |
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| CN1660743A (en) * | 2004-12-15 | 2005-08-31 | 上海大学 | Method for synthesizing 4-methoxy styrene |
| CN101747162A (en) * | 2009-12-25 | 2010-06-23 | 南京工业大学 | Synthesis process of p-methoxystyrene |
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| CN1660743A (en) * | 2004-12-15 | 2005-08-31 | 上海大学 | Method for synthesizing 4-methoxy styrene |
| CN101747162A (en) * | 2009-12-25 | 2010-06-23 | 南京工业大学 | Synthesis process of p-methoxystyrene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553511A (en) * | 2018-12-28 | 2019-04-02 | 江南大学 | Parahydroxyacet-ophenone one-step method realizes the method that hydrogenation reaction coupling dehydration prepares 4-Vinyl phenol |
| CN109553511B (en) * | 2018-12-28 | 2021-08-10 | 江南大学 | Method for preparing p-hydroxystyrene by coupling hydrogenation reaction and dehydration reaction with p-hydroxyacetophenone one-step method |
| CN110527005A (en) * | 2019-08-06 | 2019-12-03 | 中山大学 | A kind of super high molecular weight poly- (4- alkoxystyrene) and preparation method thereof |
| CN110527005B (en) * | 2019-08-06 | 2021-01-22 | 中山大学 | Ultra-high molecular weight poly (4-alkoxy styrene) and preparation method thereof |
| CN112811991A (en) * | 2021-02-01 | 2021-05-18 | 惠泽化学科技(濮阳)有限公司 | Synthesis method of p-methoxystyrene |
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