CN108129318A - The preparation method of one kind 3,4- diacetoxy styrene - Google Patents
The preparation method of one kind 3,4- diacetoxy styrene Download PDFInfo
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- CN108129318A CN108129318A CN201810087308.2A CN201810087308A CN108129318A CN 108129318 A CN108129318 A CN 108129318A CN 201810087308 A CN201810087308 A CN 201810087308A CN 108129318 A CN108129318 A CN 108129318A
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- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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Abstract
This application involves a kind of preparation method of 3,4 diacetoxy styrene, this method includes：At a temperature of 60 70 DEG C, 3,4 4-dihydroxy benzaldehydes and malonic acid react under the conditions of existing at least one organic solvent and catalyst, and generation includes the first reaction mixture of 3,4 dihydroxycinnamic acids；80 90 DEG C are warming up to, making the first reaction mixture, the reaction was continued, and generation includes the second reaction mixture of 3,4 dihydroxy benzenes ethylene；The second reaction mixture is purified, obtains 3,4 dihydroxy benzenes ethylene；At a temperature of 10 20 DEG C, 3,4 dihydroxy benzenes ethylene and acetylation reagent reaction, generation include the third reaction mixture of 3,4 diacetoxy styrene；Third reaction mixture is purified, obtains 3,4 diacetoxy styrene.The application also provides a kind of preparation method of the acetyl derivatives of styrene.The advantageous effect of the application is that preparing raw material used is easy to get, at low cost, and synthesis condition is mild, simple process, and post processing flow is quick, is easy to industrialize.
Description
Technical field
This application involves technical field of organic synthesis.Specifically, this application involves one kind 3,4- diacetoxy benzene second
The preparation method of alkene.
Background technology
Photoresist, also known as photoresist refer to the irradiation by ultraviolet light, electron beam, ion beam, X ray etc. or spoke
It penetrates, the changed etch resistant thin-film material of solubility.It is exposed and developed and to make solubility increased be positive photo glue,
What solubility reduced is negative photoresist.By the difference of exposure light source and radiation source, it is ultraviolet photoresist (including ultraviolet to be divided into
Positive and negative type photoresist), deep ultraviolet light-sensitive lacquer, electron beam adhesive, X-ray glue, ion beam glue etc..Photoresist is production of integrated circuits
Required key material, up to the present optical lithography in the production of super large-scale integration still in occupation of predominantly
Position.
The acetyl derivatives of styrene, such as 3,4- diacetoxy styrene, are the fragrance with potential practicability
Compounds of group belongs to important high-molecular compound monomer, has and prepares the purposes such as resin, coating, electronic material, can be used for
Manufacture Other substrate materials.The method of the acetyl derivatives of known synthesizing styrene, for example, Japan Patent JP
Disclosed in 2009057294A, using 3,4-dihydroxycinnamic acid as raw material, two step one pot reactions, in 100 degrees Celsius or more high temperature
Decarboxylation obtains 3,4- dihydroxy benzenes ethylene and the acetylation that then cools down obtains 3,4- diacetoxy styrene, and distillation purifying obtains
To final products.It is also disclosed in United States Patent (USP) US5324804, at a temperature of 150 degrees Celsius, by caffeic acid two
Thermal decarboxylation synthesizes 3,4- dihydroxy benzenes ethylene in methylformamide.These methods be required for reaction reagent costly and/or
More harsh reaction condition, such as high temperature.
For this purpose, there is an urgent need in the art to a kind of preparation methods of the acetyl derivatives of new styrene to solve at least
State problem.
Invention content
The application's is designed to provide a kind of acetyl derivatives of new styrene, such as 3,4- diacetoxy benzene
The preparation method of ethylene, come solve it is above-mentioned in the prior art the technical issues of.
The application provides a kind of preparation method of the acetyl derivatives of styrene, including：
S1：At a temperature of 60-70 DEG C, the hydroxy derivatives and malonic acid of benzaldehyde at least one organic solvent and are urged
It is reacted under the conditions of agent is existing, the first reaction mixture of hydroxy derivatives of the generation comprising cinnamic acid,
The structure of the hydroxy derivatives of the benzaldehyde is as shown in the following general formula I：
The structure of the hydroxy derivatives of the cinnamic acid is as shown in the following general formula II：
Wherein, R1、R2、R3、R4And R5Independently selected from the following group：H、OH、OCH3, linear chain or branch chain C1-C10Alkyl；R1、R2、
R3、R4And R5At least one of be OH；
S2：80-90 DEG C is warming up to, making the first reaction mixture, the reaction was continued, generates the second reaction mixture；
S3：The second reaction mixture is purified, obtains the hydroxy derivatives of styrene, the knot of the hydroxy derivatives of the styrene
Structure is as shown in following general formula IIIs：
Wherein, R1、R2、R3、R4And R5Independently selected from the following group：H、OH、OCH3, linear chain or branch chain C1-C10Alkyl；R1、R2、
R3、R4And R5At least one of be OH；
S4：At a temperature of 10-20 DEG C, hydroxy derivatives and the acetylation reagent reaction of styrene, generation third reaction
Mixture；And
S5：Third reaction mixture is purified, obtains the acetyl derivatives of styrene, the acetyl derivatives of the styrene
Structure as shown in following general formulae IVs：
Wherein, R6、R7、R8、R9And R10Independently selected from the following group：H, O (C=O) CH3、OCH3Or linear chain or branch chain C1-C10Alkane
Base；R1、R2、R3、R4And R5At least one of be O (C=O) CH3。
In some embodiments, the acetyl derivatives of styrene are 3,4- diacetoxy styrene.
In some embodiments, the hydroxy derivatives of benzaldehyde are 3,4- 4-dihydroxy benzaldehydes.
In some embodiments, the hydroxy derivatives of cinnamic acid are 3,4-dihydroxycinnamic acid.
In some embodiments, the hydroxy derivatives of styrene are 3,4- dihydroxy benzenes ethylene.
In other embodiments, the acetyl derivatives of styrene may be monovinylphenyl styrene or two
Above acetoxy-styrene；In yet other embodiments, in diacetoxy styrene acetoxyl group the position of substitution
May be contraposition or meta position.Equally, the selection of the structure of reactant also needs to be adjusted according to the difference for preparing product structure.
The preparation method of one kind 3,4- diacetoxy styrene, including
S1：At a temperature of 60-70 DEG C, 3,4- 4-dihydroxy benzaldehydes and malonic acid are at least one organic solvent and catalysis
It is reacted under the conditions of agent is existing, generation includes the first reaction mixture of 3,4-dihydroxycinnamic acid；
S2：80-90 DEG C is warming up to, making the first reaction mixture, the reaction was continued, and generation includes 3,4- dihydroxy benzenes ethylene
Second reaction mixture；
S3：The second reaction mixture is purified, obtains 3,4- dihydroxy benzenes ethylene；
S4：At a temperature of 10-20 DEG C, 3,4- dihydroxy benzenes ethylene and acetylation reagent reaction, generation include 3,4- bis-
The third reaction mixture of acetoxy-styrene；And
S5：Third reaction mixture is purified, obtains 3,4- diacetoxy styrene.
In some embodiments, organic solvent is aprotic polar organic solvent, selected from n,N-Dimethylformamide
(DMF), N, N dimethyl acetamide, dimethyl sulfoxide, 1-Methyl-2-Pyrrolidone and its composition.
In some embodiments, catalyst is morpholine.
In some embodiments, at a temperature of step S1 is included in 18-25 DEG C, catalyst is added in into 3,4- dihydroxy
In the mixed liquor of benzaldehyde, malonic acid and organic solvent, 60-70 DEG C is warming up to, is reacted 18-25 hours, the first reaction of generation is mixed
Close object.
In some embodiments, step S2 includes being warming up to 80-90 DEG C, makes the first reaction mixture the reaction was continued 15-
20 hours, generate the second reaction mixture.
In some embodiments, the second reaction mixture is purified in step S3 to include：It steams in the second reaction mixture
After at least part organic solvent, ethyl acetate and activated carbon are added in, is filtered after being stirred 0.3-0.8 hours at 20-30 DEG C, concentration filter
Liquid obtains 3,4- dihydroxy benzenes ethylene.
In some embodiments, step S3 includes steaming the second reaction mixture at 58-62 DEG C by Rotary Evaporators
The organic solvent of middle 50-90%, wherein, before heating steams, polymerization inhibitor is added in the second reaction mixture, it is described
Polymerization inhibitor is selected from thiophene piperazine, hydroquinone, 1,4-benzoquinone, beta-phenyl naphthylamines, p-tert-Butylcatechol and methylene blue.
In some embodiments, step S4 includes mixing 3,4- dihydroxy benzenes ethylene and methyl tertiary butyl ether(MTBE), triethylamine
After closing stirring, at a temperature of 10-20 DEG C, the acetylation reagent is added in, is reacted 1.5-2.5 hours, generation third reaction is mixed
Close object.
In some embodiments, acetylation reagent is selected from acetic anhydride, chloroacetic chloride and acetic acid.
In some embodiments, third reaction mixture is purified in step S5 to include：At a temperature of 0-20 DEG C, add in
Ice water after isolating organic phase, using saturated sodium bicarbonate aqueous solution alkali cleaning at least twice, is washed using saturated common salt aqueous solution
At least once；At a temperature of 20-30 DEG C, activated carbon is added in the organic phase after being washed by alkali cleaning and salt, stirs 0.3-0.8
It is filtered after hour；It is recrystallized at least once after filtrate is dried using anhydrous cupric sulfate, obtains 3,4- diacetoxy benzene
Ethylene.
Compared with prior art, the advantageous effect of the application is that the preparation method of the application is obtained by using relatively easy
Arrive, price than relatively low raw material as reactant, using relatively mild reaction condition and relatively simple post-processing step, easily
In industrialization, more cheap product is obtained.
Description of the drawings
Fig. 1 shows the hydrogen nuclear magnetic resonance spectrogram of the product according to embodiment 1.
Specific embodiment
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
Weight is all based on, and test used and characterizing method are all synchronous with the submission date of the application with percentage.It is being applicable in
In the case of, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, disclosed by these special documents about in this field synthetic technology, product
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limiting value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between arbitrary high value.If for example, compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising the numerical value less than 1 or comprising
The range of score (such as 1.1,1.5 etc.) more than 1, then suitably by 1 unit regard as 0.0001,0.001,0.01 or
0.1.For including the range of the units less than 10 (such as 1 to 5), usually regarding 1 unit as 0.1., these are only intended to
The specific example of the content to be expressed, and all possible combination of the numerical value between cited minimum and peak is all
It is considered clear to record in this application.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, " hexane " either individually or collectively includes whole isomers of hexane).In addition, it unless explicitly stated otherwise, otherwise uses
"one", the noun that " one kind " or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise all in the application to use term "comprising"s, the composition of " comprising " or " having ", which can include, appoints
What additional additive, auxiliary material or compound.On the contrary, out to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process that do not specifically describe or list.Unless expressly stated, otherwise term "or" refers to
The separate member listed or any combination thereof.
Term defines
As used herein, term " alkyl " refers to forms after the hydrogen atom or group of alkane structure one monovalence of cancellation
Substituent group.
As used herein, term " linear chain or branch chain C1-C10Alkyl " refers to the carbon atom number of alkyl as 1-10, and alkyl
Carbon atom arrangement can be linear structure or branched structure.
As used herein, term " derivative " refers to a kind of hydrogen atom in simple compounds or atomic group by other atoms
Or atomic group replaces and derivative more complicated product.
As used herein, term " yield " refers to the product amount obtained in chemical reaction.Yield is typically expressed as reacting
The percentage of theoretical yield.
As used herein, term " polarity " refers to the solvent of the molecule with sizable permanent dipole moment.
As used herein, term " non-proton " refers in the solvent that cannot play unstable proton donor or receptor acting.
The acetyl derivatives of styrene
The acetyl derivatives of styrene used herein are not particularly limited.In this application, the acetyl of the styrene
Change the structure of derivative as shown in following general formulae IVs：
Wherein, R6、R7、R8、R9And R10Independently selected from the following group：H, O (C=O) CH3、OCH3Or linear chain or branch chain C1-C10Alkane
Base；R1、R2、R3、R4And R5At least one of be O (C=O) CH3。
In one embodiment, the acetyl derivatives of the styrene can be 3,4- diacetoxy styrene.
The hydroxy derivatives of benzaldehyde
The hydroxy derivatives of benzaldehyde used herein are not particularly limited.In this application, the hydroxyl of benzaldehyde derives
The structure of object is as shown in the following general formula I：
Wherein, R1、R2、R3、R4And R5Independently selected from the following group：H、OH、OCH3, linear chain or branch chain C1-C10Alkyl；R1、R2、
R3、R4And R5At least one of be OH.
At a temperature of 60-70 DEG C, the hydroxy derivatives and malonic acid of benzaldehyde are at least one organic solvent and catalysis
It is reacted under the conditions of agent is existing, the first reaction mixture of hydroxy derivatives of the generation comprising cinnamic acid.
The structure of the hydroxy derivatives of the cinnamic acid is as shown in the following general formula II：
Wherein, R1、R2、R3、R4And R5Independently selected from the following group：H、OH、OCH3, linear chain or branch chain C1-C10Alkyl；R1、R2、
R3、R4And R5At least one of be OH.
In some embodiments, the hydroxy derivatives of benzaldehyde are 3,4- 4-dihydroxy benzaldehydes；The hydroxyl of cinnamic acid spreads out
Biology is 3,4- dihydroxycinnamic acids.
The hydroxy derivatives of styrene
In some embodiments, 80-90 DEG C is warming up to, making the first reaction mixture, the reaction was continued, the second reaction of generation
Mixture；The second reaction mixture is purified, obtains the hydroxy derivatives of styrene, the structure of the hydroxy derivatives of the styrene is such as
Shown in the following general formula III：
Wherein, R1、R2、R3、R4And R5Independently selected from the following group：H、OH、OCH3, linear chain or branch chain C1-C10Alkyl；R1、R2、
R3、R4And R5At least one of be OH.
The hydroxy derivatives of styrene used herein are not particularly limited, in some embodiments, the hydroxyl of styrene
Radical derivative is 3,4- dihydroxy benzenes ethylene.
In some embodiments, at a temperature of 10-20 DEG C, the hydroxy derivatives and acetylation reagent of styrene are anti-
Should, generate third reaction mixture；Third reaction mixture is purified, obtains the acetyl derivatives of styrene.
With reference to above-mentioned reaction equation (1), this application discloses the preparation method of one kind 3,4- diacetoxy styrene, packets
It includes：
S1：At a temperature of 60-70 DEG C, 3,4- 4-dihydroxy benzaldehydes and malonic acid are at least one organic solvent and catalysis
It is reacted under the conditions of agent is existing, generation includes the first reaction mixture of 3,4-dihydroxycinnamic acid；
S2：80-90 DEG C is warming up to, making the first reaction mixture, the reaction was continued, and generation includes 3,4- dihydroxy benzenes ethylene
Second reaction mixture；
S3：The second reaction mixture is purified, obtains 3,4- dihydroxy benzenes ethylene；
S4：At a temperature of 10-20 DEG C, 3,4- dihydroxy benzenes ethylene and acetylation reagent reaction, generation include 3,4- bis-
The third reaction mixture of acetoxy-styrene；And
S5：Third reaction mixture is purified, obtains 3,4- diacetoxy styrene.
In some embodiments, organic solvent is aprotic polar organic solvent, selected from n,N-Dimethylformamide
(DMF), N, N dimethyl acetamide, dimethyl sulfoxide, 1-Methyl-2-Pyrrolidone and its composition.
In some embodiments, catalyst is morpholine.In presently filed embodiment, using morpholine decarboxylation compared to
Using potassium acetate decarboxylation, it can realize and be reacted under the reaction condition of milder, reduce energy consumption.
In some embodiments, at a temperature of step S1 is included in 18-25 DEG C, catalyst is added in into 3,4- dihydroxy
In the mixed liquor of benzaldehyde, malonic acid and organic solvent, 60-70 DEG C is warming up to, is reacted 18-25 hours, the first reaction of generation is mixed
Close object.
In some embodiments, step S2 includes being warming up to 80-90 DEG C, makes the first reaction mixture the reaction was continued 15-
20 hours, generate the second reaction mixture.
In embodiment described herein, it is easy to get and price is relatively low so that 3,4- 4-dihydroxy benzaldehydes and malonic acid are this
Raw material, in DMF under conditions of solvent, by two step one kettle ways, to take two 60-70 DEG C and 80-90 DEG C of different temperatures sections
Successive reaction generates 3,4-dihydroxycinnamic acid and 3,4- dihydroxy benzenes ethylene, and reaction temperature is relatively low, mild condition.And 3 are saved,
The separation baking step of 4- dihydroxycinnamic acids, simplifies reaction process.
In the heating process of step S1 and S2, it should be noted that temperature controls, temperature is excessively high to increase byproduct of reaction,
Reaction is made to become miscellaneous.Therefore reaction temperature is no more than 100 DEG C.
In some embodiments, the second reaction mixture is purified in step S3 to include：It steams in the second reaction mixture
After at least part organic solvent, ethyl acetate and activated carbon are added in, is filtered after being stirred 0.3-0.8 hours at 20-30 DEG C, concentration filter
Liquid obtains the 3,4- dihydroxy benzenes ethylene containing a small amount of DMF solvent.In some embodiments, during concentrating filtrate, filtrate
In ethyl acetate must be concentrated into qualified index (dissolvent residual ＜ 1%), if exceeded, the yield of product crystallization and pure can be reduced
Degree.
In some embodiments, step S3 includes steaming the second reaction mixture at 58-62 DEG C by Rotary Evaporators
The organic solvent of middle 50-90%, wherein, before heating steams, polymerization inhibitor is added in the second reaction mixture, it is described
Polymerization inhibitor is selected from thiophene piperazine, hydroquinone, 1,4-benzoquinone, beta-phenyl naphthylamines, p-tert-Butylcatechol and methylene blue.Compared with
In excellent embodiment, the concentration of the second reaction mixture is fallen 70% or so by Rotary Evaporators, avoids leading because of concentration overdrying
The intermediate crude product of cause goes bad.
In some embodiments, step S4 is included 3,4- dihydroxy benzenes ethylene and methyl tertiary butyl ether(MTBE) (MTBE), three
Ethamine (Et3N after) being mixed, at a temperature of 10-20 DEG C, the acetylation reagent is added in, is reacted 1.5-2.5 hours, it is raw
Into third reaction mixture.
In some embodiments, acetylation reagent is selected from acetic anhydride, chloroacetic chloride and acetic acid.
In some embodiments, third reaction mixture is purified in step S5 to include：At a temperature of 0-20 DEG C, add in
Ice water after isolating organic phase, using saturated sodium bicarbonate aqueous solution alkali cleaning three times to alkalescent (pH=7-8), uses saturation
Common salt aqueous solution washs at least once.At a temperature of 20-30 DEG C, activity is added in the organic phase after being washed by alkali cleaning and salt
Charcoal, stirring are filtered after 0.3-0.8 hours.It is filtered after filtrate is dried using anhydrous cupric sulfate, cools the filtrate to -50 ± 5 DEG C
White solid, filtering is precipitated in recrystallization.In some embodiments, contain after the filter cake directly concentration that low temperature recrystallization obtains
A large amount of water (being visually observed), need to be diluted, then dried with anhydrous sodium sulfate with methyl tert-butyl ether solvent, be filtered, and filtrate is dense
Contracting can obtain final products 3,4- diacetoxy styrene after being spin-dried for.In some embodiments, the three step total yields of this method
Rate is about more than 35%.
In acetylization reaction and the dry extraction process of subsequent washing, temperature should be controlled at 30 DEG C hereinafter, in order to avoid product
It is rotten.
Embodiment
Below in conjunction with the embodiment of the present invention, clear and complete description is carried out to technical scheme of the present invention.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.Actual conditions are not specified in the following example
Experimental method selects according to conventional methods and conditions or according to product manual.
Embodiment 1
In the present embodiment, 3,4- diacetoxies styrene is prepared by following methods：
942g 3,4- 4-dihydroxy benzaldehydes, 1064g malonic acid and 4710mL DMF are added in 20L four-hole bottles, stirred to molten
Liquid is in dark brown.At a temperature of 18-25 DEG C, 178.2g morpholines were added dropwise to four-hole bottle at 20 minutes or so.After completion of dropwise addition
60 DEG C are warming up to, reacts 22h, generation includes the first reaction mixture of 3,4-dihydroxycinnamic acid.
90 DEG C are warming up to, makes the first reaction mixture the reaction was continued 18h, generation includes the second of 3,4- dihydroxy benzenes ethylene
Reaction mixture.
The thiophene piperazine polymerization inhibitor of 200~500ppm is added in the second reaction mixture, using Rotary Evaporators at 60 DEG C
At a temperature of, the part DMF in the second reaction mixture is steamed, the concentration of the second reaction mixture is fallen 70% or so, is contained
The crude product of DMF.
2.5L ethyl acetate, above-mentioned crude product and 50g activated carbons containing DMF are added in into 5L four-hole bottles, is stirred at 20-30 DEG C
It is filtered after mixing 0.5 hour, concentration filtrate obtains 3, the 4- dihydroxy benzenes ethylene containing a small amount of DMF solvent.
2.5L methyl tertiary butyl ether(MTBE)s, 743g triethylamines and the above-mentioned 3,4- dihydroxy benzenes containing DMF are added in into 5L four-hole bottles
Ethylene mixes to solution in yellowish-brown emulsion.Temperature is controlled at 10-20 DEG C, by 1125g acetic anhydrides at 2 hours or so
The four-hole bottle is added dropwise to, is stirred for 2h, generates third reaction mixture.
Control temperature that 2.5L ice water was added dropwise to above-mentioned third reaction mixture in 0.5 hour or so, is isolated at 0-20 DEG C
The use of the saturated sodium bicarbonate aqueous solution alkali cleaning of 2.5L, 2L and 2L is in three times respectively alkalescent (pH=7- to solution after organic phase
8) washing of saturated common salt aqueous solution, is reused at least once.At a temperature of 20-30 DEG C, having after being washed by alkali cleaning and salt
50g activated carbons are added in machine phase, stirring is filtered after 0.5 hour.It is filtered after the drying of 50g anhydrous cupric sulfates is added in into filtrate, it will
Filtrate is cooled to -50 ± 5 DEG C of recrystallizations, and white solid, filtering is precipitated.It is dilute that filter cake adds in 1L methyl tert-butyl ether solvents after melting
It releases, adds the drying of 50g anhydrous sodium sulfates, filtering, filtrate concentration can obtain 521g yellow liquids, i.e. final products 3 after being spin-dried for,
4- diacetoxy styrene, yield 35%.
1H NMR：
Proton NMR data is obtained with 400MHz Bruker DRX.
As shown in Figure 1, with1H NMR analyze product 3,4- diacetoxy styrene,1H NMR(400MHz,CDCl3): δ
(ppm) 7.28 (1H, dd, J=8and 2Hz), 7.24 (1H, d, J=2Hz), 7.15 (1H, d, J=9Hz), 6.75 (1H, d, J
=18and 11Hz), 5.69 (1H, dd, J=18and 1Hz), 5.28 (1H, d, J=11Hz), 2.32
(3H,s),2.31(3H,s)。
Embodiment 2
In the present embodiment, 3,4- diacetoxies styrene is prepared by following methods：
942g 3,4- 4-dihydroxy benzaldehydes, 1064g malonic acid and 4710mL DMF are added in 20L four-hole bottles, stirred to molten
Liquid is in dark brown.At a temperature of 18-25 DEG C, 178.2g morpholines were added dropwise to four-hole bottle at 20 minutes or so.After completion of dropwise addition
70 DEG C are warming up to, reacts 22h, generation includes the first reaction mixture of 3,4-dihydroxycinnamic acid.
80 DEG C are warming up to, makes the first reaction mixture the reaction was continued 18h, generation includes the second of 3,4- dihydroxy benzenes ethylene
Reaction mixture.
The thiophene piperazine polymerization inhibitor of 200~500ppm is added in the second reaction mixture, using Rotary Evaporators at 60 DEG C
At a temperature of, the part DMF in the second reaction mixture is steamed, the concentration of the second reaction mixture is fallen 70% or so, is contained
The crude product of DMF.
2.5L ethyl acetate, above-mentioned crude product and 50g activated carbons containing DMF are added in into 5L four-hole bottles, is stirred at 20-30 DEG C
It is filtered after mixing 0.5 hour, concentration filtrate obtains 3, the 4- dihydroxy benzenes ethylene containing a small amount of DMF solvent.
2.5L methyl tertiary butyl ether(MTBE)s, 743g triethylamines and the above-mentioned 3,4- dihydroxy benzenes containing DMF are added in into 5L four-hole bottles
Ethylene mixes to solution in yellowish-brown emulsion.Temperature is controlled at 10-20 DEG C, by 1125g acetic anhydrides at 2 hours or so
The four-hole bottle is added dropwise to, is stirred for 2h, generates third reaction mixture.
Control temperature that 2.5L ice water was added dropwise to above-mentioned third reaction mixture in 0.5 hour or so, is isolated at 0-20 DEG C
The use of the saturated sodium bicarbonate aqueous solution alkali cleaning of 2.5L, 2L and 2L is in three times respectively alkalescent (pH=7- to solution after organic phase
8) washing of saturated common salt aqueous solution, is reused at least once.At a temperature of 20-30 DEG C, having after being washed by alkali cleaning and salt
50g activated carbons are added in machine phase, stirring is filtered after 0.5 hour.It is filtered after the drying of 50g anhydrous cupric sulfates is added in into filtrate, it will
Filtrate is cooled to -50 ± 5 DEG C of recrystallizations, and white solid, filtering is precipitated.It is dilute that filter cake adds in 1L methyl tert-butyl ether solvents after melting
It releases, adds the drying of 50g anhydrous sodium sulfates, filtering, filtrate concentration can obtain 550g yellow liquids, i.e. final products 3 after being spin-dried for,
4- diacetoxy styrene, yield 37%.
The Proton NMR data of products therefrom is consistent with embodiment 1.
The above-mentioned description to embodiment is understood that for the ease of those skilled in the art and using this Shen
Please.Person skilled in the art obviously easily can make various modifications, and described herein to these embodiments
General Principle is applied in other embodiments without paying performing creative labour.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and changes within all scope of the present application.
Claims (10)
1. one kind 3, the preparation method of 4- diacetoxy styrene, which is characterized in that 3, the 4- diacetoxies styrene
It is prepared by following methods：
S1：At a temperature of 60-70 DEG C, 3,4- 4-dihydroxy benzaldehydes and malonic acid are deposited at least one organic solvent and catalyst
It reacts under the conditions, generation includes the first reaction mixture of 3,4-dihydroxycinnamic acid；
S2：80-90 DEG C is warming up to, making first reaction mixture, the reaction was continued, and generation includes 3,4- dihydroxy benzenes ethylene
Second reaction mixture；
S3：Second reaction mixture is purified, obtains 3,4- dihydroxy benzenes ethylene；
S4：At a temperature of 10-20 DEG C, 3, the 4- dihydroxy benzenes ethylene and acetylation reagent reaction, generation include 3,4- bis-
The third reaction mixture of acetoxy-styrene；And
S5：The third reaction mixture is purified, obtains 3,4- diacetoxy styrene.
2. a kind of preparation method as described in claim 1, which is characterized in that the organic solvent is organic molten for aprotonic polar
Agent, selected from n,N-Dimethylformamide, N, N dimethyl acetamide, dimethyl sulfoxide, 1-Methyl-2-Pyrrolidone and its composition,
The catalyst is morpholine.
3. a kind of preparation method as described in claim 1, the method includes at a temperature of 18-25 DEG C, by catalyst plus
In the mixed liquor for entering 3, the 4- 4-dihydroxy benzaldehydes, malonic acid and organic solvent, 60-70 DEG C is warming up to, reaction 18-25 is small
When, generate first reaction mixture.
4. a kind of preparation method as described in claim 1 the method includes being warming up to 80-90 DEG C, makes first reaction
The reaction was continued 15-20 hours for mixture, generates second reaction mixture.
5. a kind of preparation method as described in claim 1, which is characterized in that purification second reaction mixture includes：It steams
Go out in second reaction mixture after at least partly described organic solvent, addition ethyl acetate and activated carbon, at 20-30 DEG C
At a temperature of, stirring is filtered after 0.3-0.8 hours, and concentration filtrate obtains 3, the 4- dihydroxy benzenes ethylene.
6. a kind of preparation method as claimed in claim 5, which is characterized in that institute is steamed at 58-62 DEG C by Rotary Evaporators
The organic solvent of 50-90% in the second reaction mixture is stated, wherein, it is mixed in the described second reaction before heating steams
Close in object and add in polymerization inhibitor, the polymerization inhibitor be selected from thiophene piperazine, hydroquinone, 1,4-benzoquinone, beta-phenyl naphthylamines, to tert-butyl o
Benzenediol and methylene blue.
7. a kind of preparation method as described in claim 1, the method includes by 3, the 4- dihydroxy benzenes ethylene and methyl
After tertbutyl ether, triethylamine are mixed, at a temperature of 10-20 DEG C, the acetylation reagent is added in, reaction 1.5-2.5 is small
When, generate the third reaction mixture.
8. a kind of preparation method as described in claim 1, which is characterized in that the acetylation reagent is selected from acetic anhydride, acetyl
Chlorine and acetic acid.
9. a kind of preparation method as described in claim 1, which is characterized in that purify the third reaction mixture and include：
At a temperature of 0-20 DEG C, ice water is added in, after isolating organic phase, uses saturated sodium bicarbonate aqueous solution alkali cleaning at least two
It is secondary, using the washing of saturated common salt aqueous solution at least once；
At a temperature of 20-30 DEG C, activated carbon is added in the organic phase after being washed by alkali cleaning and salt, stirs 0.3-0.8
It is filtered after hour；And
It is recrystallized at least once after filtrate is dried using anhydrous cupric sulfate, obtains 3, the 4- diacetoxies benzene second
Alkene.
A kind of 10. preparation method of the acetyl derivatives of styrene, which is characterized in that the acetyl derivatives of the styrene
It is prepared by following methods：
S1：At a temperature of 60-70 DEG C, the hydroxy derivatives and malonic acid of benzaldehyde are at least one organic solvent and catalyst
It is reacted under the conditions of existing, the first reaction mixture of hydroxy derivatives of the generation comprising cinnamic acid,
The structure of the hydroxy derivatives of the benzaldehyde is as shown in the following general formula I：
The structure of the hydroxy derivatives of the cinnamic acid is as shown in the following general formula II：
Wherein, R1、R2、R3、R4And R5Independently selected from the following group：H、OH、OCH3, linear chain or branch chain C1-C10Alkyl；R1、R2、R3、R4
And R5At least one of be OH；
S2：80-90 DEG C is warming up to, making first reaction mixture, the reaction was continued, generates the second reaction mixture；
S3：Second reaction mixture is purified, obtains the hydroxy derivatives of styrene, the hydroxy derivatives of the styrene
Structure is as shown in following general formula IIIs：
Wherein, R1、R2、R3、R4And R5Independently selected from the following group：H、OH、OCH3, linear chain or branch chain C1-C10Alkyl；R1、R2、R3、R4
And R5At least one of be OH；
S4：At a temperature of 10-20 DEG C, hydroxy derivatives and the acetylation reagent reaction of the styrene, generation third reaction
Mixture；And
S5：The third reaction mixture is purified, obtains the acetyl derivatives of styrene, the acetylation of the styrene derives
The structure of object is as shown in following general formulae IVs：
Wherein, R6、R7、R8、R9And R10Independently selected from the following group：H, O (C=O) CH3、OCH3Or linear chain or branch chain C1-C10Alkyl；
R1、R2、R3、R4And R5At least one of be O (C=O) CH3。
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| CN114773191A (en) * | 2022-04-29 | 2022-07-22 | 四川东材科技集团成都新材料有限公司 | Method for preparing p-acetoxystyrene by one-pot method |
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