CN108285409A - A method of the Styrene and its derivatives of synthesis tert-butoxy substitution - Google Patents
A method of the Styrene and its derivatives of synthesis tert-butoxy substitution Download PDFInfo
- Publication number
- CN108285409A CN108285409A CN201810185891.0A CN201810185891A CN108285409A CN 108285409 A CN108285409 A CN 108285409A CN 201810185891 A CN201810185891 A CN 201810185891A CN 108285409 A CN108285409 A CN 108285409A
- Authority
- CN
- China
- Prior art keywords
- tert
- butoxy
- substitution
- group
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
Abstract
This application involves a kind of method of the Styrene and its derivatives of synthesis tert-butoxy substitution, the Styrene and its derivatives of the tert-butoxy substitution have the structure that the following general formula (I) indicates：
Description
Technical field
This application involves technical field of organic synthesis, and specifically, this application involves a kind of synthesis tert-butoxy substitutions
The method of Styrene and its derivatives.
Background technology
3- t-butoxystyrenes are important functional polymer compound, medicine, pesticide intermediate.Therefore, between research
The preparation method of t-butoxystyrene is of great significance.
At present the preparation method of the 3- t-butoxystyrenes of domestic report report almost without.United States Patent (USP)
US20020026084 and Japan Patent JP2002053515 reports, directly prepare grignard reagent 3- with 3- tert-butyl bromides (chlorine) benzene
Tert-butyl benzene bromine (chlorine) changes magnesium, and 3- tert-butoxy benzene second is prepared in the case where catalyst chlorine (bromine) changes ferrous effect with vinyl chloride
Alkene.But 3- tert-butyl bromides (chlorine) benzene is expensive, causes the synthetic method cost of the prior art higher.
For this purpose, there is an urgent need in the art to develop a kind of styrene and its derivative of low-cost synthesis tert-butoxy substitution
The method of object.
Invention content
The application's is designed to provide a kind of method of the Styrene and its derivatives of synthesis tert-butoxy substitution, to
Solve above-mentioned the problems of the prior art.The application, for main reaction raw materials, chooses methanesulfonic acid conduct with m-Chlorophenol, isobutene
Catalyst prepares 3- tert-butoxy-chlorobenzenes by etherification reaction；Then, 3- tertiary butyls chlorobenzene prepares grignard reagent 3- tert-butyl benzenes
Magnesium chloride, the nickelous ligand with vinyl chloride in Raney nickel Dppp (1,3- bis- (diphenylphosphine) propane) (are hereinafter abbreviated as
NiCl2(dppp)) under acting on, 3- t-butoxystyrenes are prepared by Kumada reactions.
It is raw material that the present processes, which select m-Chlorophenol cheap and easy to get, isobutene, and 3- tert-butoxies are first prepared
Chlorobenzene；Then final products 3- t-butoxystyrenes are obtained by the reaction by Kumada in 3- tert-butoxy-chlorobenzenes.The application provides
The preparation methods of complete 3- t-butoxystyrenes, raw material is simple and easy to get, catalyst n iCl2It is (dppp) i.e. cheap and easily-available,
High catalytic efficiency, reaction condition is mild, is suitable for industrialized production.
To achieve the goals above, the application provides following technical proposals.
In the first aspect, the application provides a kind of method of the Styrene and its derivatives of synthesis tert-butoxy substitution,
The Styrene and its derivatives of the tert-butoxy substitution have the structure that the following general formula (I) indicates：
In logical formula (I), group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2 and R4 difference is only
It is on the spot selected from hydrogen, C1-C3 alkyl or tert-butoxy, and at least one of group R2 and R4 are tert-butoxy, feature exists
In the method includes following step：
S1：At a temperature of 10-20 DEG C and in the presence of alkyl sulfonic acid catalyst, make halogenated phenol and its derivative
Object and isobutene carry out etherification reaction in the first solvent, obtain the halogenated benzene and its derivative of tert-butoxy substitution, wherein institute
Stating halogenated phenol and its derivative has structure shown in the following general formula (II)：
In logical formula (II), group X is halogen；Group R6, R8 and R10 are separately selected from hydrogen or C1-C3 alkyl；Base
Group R7 and R9 is separately selected from hydrogen, C1-C3 alkyl or hydroxyl, and at least one of R7 and R9 are hydroxyl；
The halogenated benzene and its derivative of the wherein described tert-butoxy substitution has structure shown in the following general formula (III)：
In logical formula (III), X is halogen, and group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2
It is separately selected from hydrogen, C1-C3 alkyl or tert-butoxy with R4, and at least one of group R2 and R4 are tertiary fourth oxygen
Base；And
S2：So that the halogenated benzene and its derivative that the tert-butoxy that step S1 is obtained replaces is reacted with magnesium, obtains being based on tertiary fourth
The grignard reagent of the halogenated benzene and its derivative of oxygroup substitution；And
S3：Under inert gas protection and deposit the halogeno-benzene for making to replace in the case of nickel catalysts based on tert-butoxy
And its grignard reagent of derivative is reacted with vinyl halides in the second solvent, is obtained with structure shown in logical formula (I)
The Styrene and its derivatives of tert-butoxy substitution.
In a kind of embodiment of first aspect, in step sl, the alkyl sulfonic acid catalyst is methanesulfonic acid.
In a kind of embodiment of first aspect, in step s3, the Raney nickel is freshly prepared NiCl2
(dppp)。
In a kind of embodiment of first aspect, first solvent includes toluene and/or dimethylbenzene；And/or described
Two solvents include tetrahydrofuran.
In a kind of embodiment of first aspect, the step S1 further includes at the end of the etherification reaction, to anti-
It answers addition lye in system that reaction is quenched, and unreacted raw material is removed using alkali liquid washing.
In a kind of embodiment of first aspect, the step S1 further includes passing through at the end of the etherification reaction
Filled column is evaporated under reduced pressure reaction mixture.
In a kind of embodiment of first aspect, in step s3, make the halogeno-benzene replaced based on tert-butoxy and its
It it is 20 ± 5 DEG C by reaction temperature control when the grignard reagent of derivative is reacted with vinyl halides in the second solvent.
In a kind of embodiment of first aspect, in step s3, make the halogeno-benzene replaced based on tert-butoxy and its
It it is 23 ± 3 DEG C by reaction temperature control when the grignard reagent of derivative is reacted with vinyl halides in the second solvent
In a kind of embodiment of first aspect, the step S3 further includes adding after the completion of reaction into reaction system
Enter diluted acid and removes excessive magnesium.
In a kind of embodiment of first aspect, the Styrene and its derivatives of the tert-butoxy substitution include uncle 3-
Butyl phenyl ether ethylene；The halogenated phenol and its derivative include m-Chlorophenol and/or m -bromoacetophenone；Or the tert-butoxy
The halogenated benzene and its derivative of substitution includes 3- tert-butoxy-chlorobenzenes and/or 3- tert-butoxy bromobenzenes.
In second aspect, the application provides a kind of method of the halogenated benzene and its derivative of synthesis tert-butoxy substitution,
The halogenated benzene and its derivative of the tert-butoxy substitution has structure shown in the following general formula (III)：
In logical formula (III), X is halogen, and group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2
It is separately selected from hydrogen, C1-C3 alkyl or tert-butoxy with R4, and at least one of group R2 and R4 are tertiary fourth oxygen
Base, which is characterized in that the method includes following step：
At a temperature of 10-20 DEG C and in the presence of alkyl sulfonic acid catalyst, make halogenated phenol and its derivative
Etherification reaction is carried out in the first solvent with isobutene, obtains the halogenated benzene and its derivative of tert-butoxy substitution, wherein described
Halogenated phenol and its derivative have structure shown in the following general formula (II)：
In logical formula (II), group X is halogen；Group R6, R8 and R10 are separately selected from hydrogen or C1-C3 alkyl；Base
Group R7 and R9 is separately selected from hydrogen, C1-C3 alkyl or hydroxyl, and at least one of R7 and R9 are hydroxyl.
Compared with prior art, the advantageous effect of the application is：(1) the application is starting with m-Chlorophenol, isobutene
Reaction raw materials, these raw materials and catalyst are cheap and easy to get；And Kumada reactions, selection are selected in the reaction of (2) the application second step
Property is good, can effectively reduce side reaction, catalyst n iCl2(dppp) high catalytic efficiency, it is cheap and easily-available.
Specific implementation mode
Below in conjunction with embodiments herein, clear and complete description is carried out to the technical solution of the application.
3- t-butoxystyrenes are a kind of important functional polymer compound, medicine intermediate and pesticide intermediates,
But the synthetic method cost of current 3- t-butoxystyrenes is higher, it is domestic then almost without reporting the synthesis side of the compound
Method.
The application, for main reaction raw materials, chooses methanesulfonic acid as catalyst, by being etherified instead with m-Chlorophenol, isobutene
3- tert-butoxy-chlorobenzenes should be prepared；Then, 3- tertiary butyls chlorobenzene prepares grignard reagent 3- tert-butyl benzene magnesium chlorides, exists with vinyl chloride
Raney nickel NiCl2(dppp) under acting on, 3- t-butoxystyrenes are prepared by Kumada reactions.
In the first aspect, the application provides a kind of method of the Styrene and its derivatives of synthesis tert-butoxy substitution,
The Styrene and its derivatives of the tert-butoxy substitution have the structure that the following general formula (I) indicates：
In logical formula (I), group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2 and R4 difference is only
It is on the spot selected from hydrogen, C1-C3 alkyl or tert-butoxy, and at least one of group R2 and R4 are tert-butoxy, feature exists
In the method includes following step：
S1：At a temperature of 10-20 DEG C and in the presence of alkyl sulfonic acid catalyst, make halogenated phenol and its derivative
Object and isobutene carry out etherification reaction in the first solvent, obtain the halogenated benzene and its derivative of tert-butoxy substitution, wherein institute
Stating halogenated phenol and its derivative has structure shown in the following general formula (II)：
In logical formula (II), group X is halogen；Group R6, R8 and R10 are separately selected from hydrogen or C1-C3 alkyl；Base
Group R7 and R9 is separately selected from hydrogen, C1-C3 alkyl or hydroxyl, and at least one of R7 and R9 are hydroxyl；
The halogenated benzene and its derivative of the wherein described tert-butoxy substitution has structure shown in the following general formula (III)：
In logical formula (III), X is halogen, and group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2
It is separately selected from hydrogen, C1-C3 alkyl or tert-butoxy with R4, and at least one of group R2 and R4 are tertiary fourth oxygen
Base；And
S2：So that the halogenated benzene and its derivative that the tert-butoxy that step S1 is obtained replaces is reacted with magnesium, obtains being based on tertiary fourth
The grignard reagent of the halogenated benzene and its derivative of oxygroup substitution；And
S3：Under inert gas protection and deposit the halogeno-benzene for making to replace in the case of nickel catalysts based on tert-butoxy
And its grignard reagent of derivative is reacted with vinyl halides in the second solvent, is obtained with structure shown in logical formula (I)
The Styrene and its derivatives of tert-butoxy substitution.
In second aspect, the application provides a kind of method of the halogenated benzene and its derivative of synthesis tert-butoxy substitution,
The halogenated benzene and its derivative of the tert-butoxy substitution has structure shown in the following general formula (III)：
In logical formula (III), X is halogen, and group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2
It is separately selected from hydrogen, C1-C3 alkyl or tert-butoxy with R4, and at least one of group R2 and R4 are tertiary fourth oxygen
Base, which is characterized in that the method includes following step：
At a temperature of 10-20 DEG C and in the presence of alkyl sulfonic acid catalyst, make halogenated phenol and its derivative
Etherification reaction is carried out in the first solvent with isobutene, obtains the halogenated benzene and its derivative of tert-butoxy substitution, wherein described
Halogenated phenol and its derivative have structure shown in the following general formula (II)：
In logical formula (II), group X is halogen；Group R6, R8 and R10 are separately selected from hydrogen or C1-C3 alkyl；Base
Group R7 and R9 is separately selected from hydrogen, C1-C3 alkyl or hydroxyl, and at least one of R7 and R9 are hydroxyl.
As used herein, term " C1-C3 alkyl " may include methyl, ethyl, propyl or isopropyl.
As used herein, term " halogen " may include chlorine, bromine, fluorine or iodine.
In a preferred embodiment, the alkyl sulfonic acid catalyst is methanesulfonic acid.In a preferred embodiment,
The Raney nickel may include freshly prepared NiCl2(dppp).In one embodiment, first solvent can be toluene
And/or dimethylbenzene.In another embodiment, second solvent can be tetrahydrofuran.
Embodiment 1
The present embodiment is related to, using m-Chlorophenol and isobutene as Material synthesis 3- tert-butoxy-chlorobenzenes, then passing through the tertiary fourths of 3-
Oxygroup chlorobenzene prepares grignard reagent, and 3- t-butoxystyrenes are synthesized with chloroethene alkene reaction.The reaction route of the present embodiment is such as
Shown in lower：
1. the first step：200g m-Chlorophenols are added in toluene at 20 ± 10 DEG C, start stirring until solid dissolved clarification, adds
Enter 5.5g methanesulfonic acids, then start to be passed through isobutene gas for 10-20 DEG C, there is more apparent exothermic phenomenon, is cooled down and kept by ice water
Interior temperature is between 10-20 DEG C.After about 2-3 hours, ventilation terminates, confined reaction system, and room temperature reaction is overnight.Reaction 17 hours
Analysis (middle control 1, raw material ＜ 20%) is sent in sampling afterwards, is post-processed after middle control is qualified.
The 20%NaOH solution of 1000ml is added to reaction solution, notices that temperature is less than 20 DEG C in control, stirs 15 points after adding
Clock, stratification, lower layer's water phase use the back extraction of 200ml toluene primary, merge organic phase again, and organic phase is washed with 20%NaOH solution again
It washs (500ml × 3), middle control is without raw material (middle control 2, raw material<0.1%) after, sodium sulphate drying is added.After filtering out drier, filtrate
1000ml single port bottles directly are poured into, evaporating toluene, (water pump vacuumizes, 200mm glass filler columns, oil bath 60-70
DEG C), remaining residue crude product is further continued for changing oil, and (oil pump vacuumizes the distillation of pumping vacuum decompression, 100-120 DEG C of oil bath, 300mm glass
Filled column), main distillate fraction (62-66 DEG C) is collected, 213g 3- tert-butoxy-chlorobenzenes (middle control 3, product >=99%) are obtained.Yield is：
74%.
2. second step：Under nitrogen protection, 216g magnesium chips is added in reaction bulb, in addition by the 3- tert-butoxies of 1100g
Chlorobenzene is dissolved in 1500g tetrahydrofurans and solution is made, and is then added in reaction bulb this solution about 5% (depending on inventory), adds
10mL 1 is added dropwise to flowing back in heat, and 2- Bromofumes cause, and after system causes, continue that remaining 3- tert-butoxy-chlorobenzenes and four are added dropwise
Hydrogen furans mixed solution, after 1 hour drips off, oil bath keeps 80-90 DEG C of reaction, sampling in 17 hours or so to send analysis (middle control
1, raw material<1%, intermediate ＞ 90%).After middle control is qualified, stop heating, being cooled to 30 ± 5 DEG C (directly cannot quickly be as cold as 30
± 5 DEG C), under nitrogen protection, 11g catalyst ns iCl is added2(dppp), after stirring its dissolving, interior temperature is in 23 ± 3 DEG C of conditions
Under, preprepared vinyl chloride 750g and tetrahydrofuran 1100g mixed liquors is added dropwise.Exothermic heat of reaction controls rate of addition, about
Drip off within 2.5 hours or so, keep the temperature 23 ± 3 DEG C of reaction 2.5h, after system is without apparent exothermic phenomenon, make system temperature rise to 25~
0.5h is reacted after 30 DEG C, analysis (middle control 2, intermediate are sent in sampling<10%, product ＞ 80%).
It is maintained between 10-20 DEG C, hydrochloric acid (without until magnesium powder) is added dropwise, then add 200mL ethyl acetate, stirring is stood
Layering, separates organic phase, water phase is extracted by 100mL ethyl acetate.Merge organic addition anhydrous sodium sulfate drying, filters out drying
11.6g phenothiazines are added in agent, and the resorcinol of 11.6g, 11.6g p-tert-Butylcatechols, 40 DEG C or less are spin-dried for solvent, obtain
1160g crude products (middle control 3, product>89%).Phenothiazine, resorcinol, p-tert-Butylcatechol can be used as in the present invention
Polymerization inhibitor, the double bond in 3- t-butoxystyrenes easily polymerize.
Crude product obtains crude product 840g by vacuum distillation (85 ± 2 DEG C of oil bath temperature, oil pump), with 500mm packed columns and
0.2cm stainless steel helices, oil temperature are increased to 110~115 DEG C and continue to be evaporated under reduced pressure, and temperature 38 DEG C of fractions in top are main distillate fraction at this time, altogether
Collect product 3- t-butoxystyrenes 680g, GC purity>99.0%. (middle control 4, product>99%), yield 65%.
Embodiment 2
The present embodiment is related to, using m -bromoacetophenone and isobutene as Material synthesis 3- tert-butoxy bromobenzenes, then passing through the tertiary fourths of 3-
Methoxyl bromobenzene prepares grignard reagent, and 3- t-butoxystyrenes are synthesized with chloroethene alkene reaction.The reaction route of the present embodiment with
Embodiment 1 it is similar, only use m -bromoacetophenone to substitute m-Chlorophenol as raw material.
1. the first step：270g m -bromoacetophenones are added in toluene at 20 ± 5 DEG C, start stirring until solid dissolved clarification, adds
Enter 5.5g methanesulfonic acids, then start to be passed through isobutene gas for 10-20 DEG C, there is more apparent exothermic phenomenon, is cooled down and kept by ice water
Interior temperature is between 10-20 DEG C.After about 2-3 hours, ventilation terminates, confined reaction system, and room temperature reaction is overnight.Reaction 17 hours
Analysis (middle control 1, raw material ＜ 20%) is sent in sampling afterwards, is post-processed after middle control is qualified.
The 20%NaOH solution of 1000ml is added to reaction solution, notices that temperature is less than 20 DEG C in control, stirs 15 points after adding
Clock, stratification, lower layer's water phase use the back extraction of 200ml toluene primary, merge organic phase again, and organic phase is washed with 20%NaOH solution again
It washs (500ml × 3), middle control is without raw material (middle control 2, raw material<0.1%) after, sodium sulphate drying is added.After filtering out drier, filtrate
1000ml single port bottles directly are poured into, evaporating toluene, (water pump vacuumizes, 200mm glass filler columns, oil bath 60-70
DEG C), remaining residue crude product is further continued for changing oil, and (oil pump vacuumizes the distillation of pumping vacuum decompression, 100-120 DEG C of oil bath, 300mm glass
Filled column), main distillate fraction (62-66 DEG C) is collected, 272g 3- tert-butoxies bromobenzene (middle control 3, product >=99%) is obtained.Yield is：
76%.
2. second step：Under nitrogen protection, 216g magnesium chips is added in reaction bulb, in addition by the 3- tert-butoxies of 1362g
Bromobenzene is dissolved in 1500g tetrahydrofurans and solution is made, and is then added in reaction bulb this solution about 5% (depending on inventory), adds
10mL 1 is added dropwise to flowing back in heat, and 2- Bromofumes cause, and after system causes, continue that remaining 3- tert-butoxies bromobenzene and four are added dropwise
Hydrogen furans mixed solution, after 1 hour drips off, oil bath keeps 80-90 DEG C of reaction, sampling in 17 hours or so to send analysis (middle control
1, raw material<1%, intermediate ＞ 90%).After middle control is qualified, stop heating, being cooled to 30 ± 5 DEG C (directly cannot quickly be as cold as 30
± 5 DEG C), under nitrogen protection, 11g catalyst ns iCl is added2(dppp), after stirring its dissolving, interior temperature is in 23 ± 3 DEG C of conditions
Under, preprepared vinyl chloride 750g and tetrahydrofuran 1100g mixed liquors is added dropwise.Exothermic heat of reaction controls rate of addition, about
Drip off within 2.5 hours or so, keep the temperature 23 ± 3 DEG C of reaction 2.5h, after system is without apparent exothermic phenomenon, make system temperature rise to 25~
0.5h is reacted after 30 DEG C, analysis (middle control 2, intermediate are sent in sampling<10%, product ＞ 80%).
It is maintained between 10-20 DEG C, hydrochloric acid (without until magnesium powder) is added dropwise, then add 200mL ethyl acetate, stirring is stood
Layering, separates organic phase, water phase is extracted by 100mL ethyl acetate.Merge organic addition anhydrous sodium sulfate drying, filters out drying
11.6g phenothiazines are added in agent, and 11.6g resorcinols, 11.6g p-tert-Butylcatechols, 40 DEG C or less are spin-dried for solvent, obtain
1160g crude products (middle control 3, product>89%).
Crude product obtains crude product 840g by vacuum distillation (85 ± 2 DEG C of oil bath temperature, oil pump), with 500mm packed columns and
0.2cm stainless steel helices, oil temperature are increased to 110~115 DEG C and continue to be evaporated under reduced pressure, and temperature 38 DEG C of fractions in top are main distillate fraction at this time, altogether
Collect product 3- t-butoxystyrenes 685g, GC purity>99.0%. (middle control 4, product>99%), yield 66%.
Above-mentioned is that this can be understood and applied for the ease of those skilled in the art to the description of embodiment
Application.Person skilled in the art obviously easily can make various modifications to these embodiments, and illustrating herein
General Principle be applied in other embodiments without paying performing creative labour.Therefore, the application is not limited to reality here
Example is applied, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
Improvement and modification all within scope of the present application.
Claims (11)
1. a kind of method of the Styrene and its derivatives of synthesis tert-butoxy substitution, the styrene of tert-butoxy substitution and
Its derivative has the structure that the following general formula (I) indicates：
In logical formula (I), group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2 and R4 are separately
Selected from hydrogen, C1-C3 alkyl or tert-butoxy, and at least one of group R2 and R4 are tert-butoxy, which is characterized in that institute
The method of stating includes the following steps：
S1：At a temperature of 10-20 DEG C and in the presence of alkyl sulfonic acid catalyst, make halogenated phenol and its derivative and
Isobutene carries out etherification reaction in the first solvent, the halogenated benzene and its derivative of tert-butoxy substitution is obtained, wherein the halogen
Substituting phenol and its derivative have structure shown in the following general formula (II)：
In logical formula (II), group X is halogen；Group R6, R8 and R10 are separately selected from hydrogen or C1-C3 alkyl；Group R7
It is separately selected from hydrogen, C1-C3 alkyl or hydroxyl with R9, and at least one of R7 and R9 are hydroxyl；
The halogenated benzene and its derivative of the wherein described tert-butoxy substitution has structure shown in the following general formula (III)：
In logical formula (III), X is halogen, and group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2 and R4
It is separately selected from hydrogen, C1-C3 alkyl or tert-butoxy, and at least one of group R2 and R4 are tert-butoxy；With
And
S2：So that the halogenated benzene and its derivative that the tert-butoxy that step S1 is obtained replaces is reacted with magnesium, obtains being based on tert-butoxy
The grignard reagent of the halogenated benzene and its derivative of substitution；And
S3：Under inert gas protection and deposit the halogeno-benzene for making to replace based on tert-butoxy in the case of nickel catalysts and its
The grignard reagent of derivative is reacted with vinyl halides in the second solvent, and the tertiary fourth with structure shown in logical formula (I) is obtained
The Styrene and its derivatives of oxygroup substitution.
2. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution as described in claim 1, which is characterized in that
In step S1, the alkyl sulfonic acid catalyst is methanesulfonic acid.
3. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In in step s3, the Raney nickel is freshly prepared NiCl2(dppp)。
4. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In first solvent includes toluene and/or dimethylbenzene；And/or second solvent includes tetrahydrofuran.
5. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In the step S1 further includes at the end of the etherification reaction lye being added into reaction system, reaction being quenched, and utilize alkali
Liquid washing removes unreacted raw material.
6. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In the step S1 further includes being evaporated under reduced pressure to reaction mixture by filled column at the end of the etherification reaction.
7. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In in step s3, making the grignard reagent of the halogenated benzene and its derivative replaced based on tert-butoxy with vinyl halides second
It it is 20 ± 5 DEG C by reaction temperature control when being reacted in solvent.
8. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In in step s3, making the grignard reagent of the halogenated benzene and its derivative replaced based on tert-butoxy with vinyl halides second
It it is 23 ± 3 DEG C by reaction temperature control when being reacted in solvent.
9. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In the step S3 further includes that diluted acid is added into reaction system after the completion of reaction to remove excessive magnesium.
10. the method for the Styrene and its derivatives of synthesis tert-butoxy substitution, feature exist as claimed in claim 1 or 2
In the Styrene and its derivatives of the tert-butoxy substitution include 3- t-butoxystyrenes；The halogenated phenol and its spread out
Biology includes m-Chlorophenol and/or m -bromoacetophenone；Or the halogenated benzene and its derivative of the tert-butoxy substitution includes uncle 3-
Butoxy chlorobenzene and/or 3- tert-butoxy bromobenzenes.
11. a kind of method of the halogenated benzene and its derivative of synthesis tert-butoxy substitution, the halogeno-benzene of the tert-butoxy substitution
And its derivative has structure shown in the following general formula (III)：
In logical formula (III), X is halogen, and group R1, R2 and R3 are separately selected from hydrogen or C1-C3 alkyl；Group R2 and R4
It is separately selected from hydrogen, C1-C3 alkyl or tert-butoxy, and at least one of group R2 and R4 are tert-butoxy,
It is characterized in that, the method includes following step：
At a temperature of 10-20 DEG C and in the presence of alkyl sulfonic acid catalyst, making halogenated phenol and its derivative and different
Butylene carries out etherification reaction in the first solvent, the halogenated benzene and its derivative of tert-butoxy substitution is obtained, wherein described halogenated
Phenol and its derivatives have structure shown in the following general formula (II)：
In logical formula (II), group X is halogen；Group R6, R8 and R10 are separately selected from hydrogen or C1-C3 alkyl；Group R7
It is separately selected from hydrogen, C1-C3 alkyl or hydroxyl with R9, and at least one of R7 and R9 are hydroxyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810185891.0A CN108285409B (en) | 2018-03-07 | 2018-03-07 | Method for synthesizing tert-butoxy substituted styrene and derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810185891.0A CN108285409B (en) | 2018-03-07 | 2018-03-07 | Method for synthesizing tert-butoxy substituted styrene and derivatives thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108285409A true CN108285409A (en) | 2018-07-17 |
| CN108285409B CN108285409B (en) | 2022-03-15 |
Family
ID=62833060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810185891.0A Active CN108285409B (en) | 2018-03-07 | 2018-03-07 | Method for synthesizing tert-butoxy substituted styrene and derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108285409B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082127A (en) * | 2023-02-07 | 2023-05-09 | 西安爱德克美新材料有限公司 | Preparation method of 4-tert-butoxy styrene |
| JP7407651B2 (en) | 2020-04-20 | 2024-01-04 | 東ソー・ファインケム株式会社 | Method for producing 3-acetoxystyrene |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053515A (en) * | 2000-08-09 | 2002-02-19 | Tosoh Corp | Tertiary butoxy styrene |
| EP1181017A1 (en) * | 1999-06-03 | 2002-02-27 | Pfizer Limited | Metalloprotease inhibitors |
| US20020026084A1 (en) * | 1998-01-30 | 2002-02-28 | Tosoh Corporation | Process for the production of styrene compound, and styrene compound free from biphenyl |
| CN1603293A (en) * | 2004-08-02 | 2005-04-06 | 常州市牛塘化工厂 | Process for preparing 4-tert-butoxy-chlorobenzene |
| CN101407452A (en) * | 2008-11-14 | 2009-04-15 | 浙江理工大学 | Process for synthesizing o-chloro-anisole |
| US20130280912A1 (en) * | 2012-04-23 | 2013-10-24 | Shin-Etsu Chemical Co., Ltd. | Silicon compound, silicon-containing compound, composition for forming resist underlayer film containing the same and patterning process |
-
2018
- 2018-03-07 CN CN201810185891.0A patent/CN108285409B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020026084A1 (en) * | 1998-01-30 | 2002-02-28 | Tosoh Corporation | Process for the production of styrene compound, and styrene compound free from biphenyl |
| EP1181017A1 (en) * | 1999-06-03 | 2002-02-27 | Pfizer Limited | Metalloprotease inhibitors |
| JP2002053515A (en) * | 2000-08-09 | 2002-02-19 | Tosoh Corp | Tertiary butoxy styrene |
| CN1603293A (en) * | 2004-08-02 | 2005-04-06 | 常州市牛塘化工厂 | Process for preparing 4-tert-butoxy-chlorobenzene |
| CN101407452A (en) * | 2008-11-14 | 2009-04-15 | 浙江理工大学 | Process for synthesizing o-chloro-anisole |
| US20130280912A1 (en) * | 2012-04-23 | 2013-10-24 | Shin-Etsu Chemical Co., Ltd. | Silicon compound, silicon-containing compound, composition for forming resist underlayer film containing the same and patterning process |
Non-Patent Citations (2)
| Title |
|---|
| HOLCOMBE等: "A new and specific method for the protection of phenols as the", 《JOURNAL OF ORGANIC CHEMISTRY(1986)》 * |
| 颉林等: "合成工艺条件对对叔丁氧基甲苯收率的影响", 《石化技术与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7407651B2 (en) | 2020-04-20 | 2024-01-04 | 東ソー・ファインケム株式会社 | Method for producing 3-acetoxystyrene |
| CN116082127A (en) * | 2023-02-07 | 2023-05-09 | 西安爱德克美新材料有限公司 | Preparation method of 4-tert-butoxy styrene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108285409B (en) | 2022-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107848917A (en) | The manufacture method of the trifluoro propene of 1 chlorine 2,3,3 | |
| CN108285409A (en) | A method of the Styrene and its derivatives of synthesis tert-butoxy substitution | |
| CN108017479A (en) | The manufacture method of aromatic compound | |
| CN104910036B (en) | A kind of containing continuous quaternary carbon center cyclopropane alpha-amino acid derivatives and synthetic method | |
| CN107417582B (en) | A kind of preparation method of E- alkenyl sulfone compound | |
| CN110330591B (en) | Porous organic polymer containing phosphine ligand and preparation method and application thereof | |
| JP2005238218A (en) | Palladium catalyst for carbon-carbon bond forming reaction and production method of olefin group-substituted aromatic compound using the palladium catalyst | |
| CN101633647A (en) | Method for synthesizing alpha-azyl aryl alkyl ketone compound with high selectivity and high yield | |
| CN105481639A (en) | Method for preparing biphenyl compound | |
| CN114956924A (en) | Method for synthesizing polyfluoro biaryl through series/coupling reaction | |
| JP4641839B2 (en) | Process for producing 4-methyl-3-trifluoromethylbenzoic acid | |
| JP4386729B2 (en) | Olefin arylation process | |
| CN108147972A (en) | A kind of preparation method of Wei Patawei intermediates and the like | |
| CN107108420A (en) | The manufacture method of alkene | |
| JP7405613B2 (en) | Method for producing fluorine-containing silane compound and fluorine-containing silane compound | |
| JP3552934B2 (en) | Method for producing benzoic acid amides | |
| JP5306336B2 (en) | Process for producing substituted heteroaromatic compounds | |
| CN106431824A (en) | Industrial production method of 3,3'-difluorobiphenyl | |
| CN109503338A (en) | A method of preparing cis- trifluoromethyl styrene compound | |
| CN114832862B (en) | Catalytic composition for coupling reaction and application of catalytic composition in preparation of isoquinoline-1, 3-dione compounds | |
| CN110683949B (en) | Method for preparing 9, 10-phenanthrene dicarboxylic ester compound | |
| CN106431823A (en) | Industrial production method of 3,3',4,4'-tetrafluorobiphenyl | |
| CN107325002A (en) | A kind of synthetic method using aryl carboxylic acid as the aryl halide of raw material | |
| CN112299937B (en) | Efficient preparation method of symmetrical diarylethene compound | |
| JP5058288B2 (en) | Process for producing olefin group-substituted aromatic compound using palladium catalyst for carbon-carbon bond formation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20181109 Address after: 221003 chemical agglomeration area of Pizhou Economic Development Zone, Xuzhou, Jiangsu Applicant after: B&C (Xuzhou) Chemical Co., Ltd. Address before: 201614 3M, 9 building, 1158 Central Road, Songjiang District, Shanghai. Applicant before: Shanghai Bo Chemical Technology Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |