CN108383689B - A kind of preparation method of 3,5- DI-tert-butylphenol compounds - Google Patents
A kind of preparation method of 3,5- DI-tert-butylphenol compounds Download PDFInfo
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
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- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
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- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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Abstract
The present invention relates to organic synthesis fields, and in particular to the preparation method of one kind 3,5- DI-tert-butylphenol compounds, comprising the following steps: 1) in organic solvent, 1,3- di-tert-butyl, alchlor, stirring is added, isopropanol, boron trifluoride etherate is added, heats, stirring；2) liquid separation, organic phase rectifying；3) 1,3- di-t-butyl -5- cumene, trifluoromethylbenzene, n-Hydroxyphthalimide, azodiisobutyronitrile, sodium carbonate, heating stirring are added in reaction flask；4) it is added dilute sulfuric acid into the reaction solution that step 3) obtains, heating stirring, stratification, organic phase obtains 3,5- di-tert-butyl phenolic product after rectifying, dry.Preparation method reaction condition provided by the invention is mild, preparation process is simple, product yield high.
Description
Technical field
The present invention relates to organic synthesis fields, in particular to the preparation method of one kind 3,5- DI-tert-butylphenol compounds.
Background technique
Alkyl phenol is mainly alkylated reaction and is generated by phenol and alkene, alcohol or halogenated hydrocarbons, and important alkyl phenol is in industry
It is mainly obtained by the alkylated reaction of phenol and alkene in production.Most importantly nonyl phenol, tert-butyl phenol in alkyl phenol
And octyl phenol.Tert-butyl phenolic compound is a kind of widely used substance, can be used as the anti-of the industries such as plastics, rubber, building materials
Oxidant and light stabilizer etc..3,5- DI-tert-butylphenol compounds are the important of petrochemical industry for manufacturing antioxidant and bright protective agent
The important source material of intermediate and fine chemistry industry.
The preparation method of phenolic compound mainly has the hydrolysis of halides, but synthesis is hydrolyzed using fragrant halides
Phenolic compound prepares alcohols material not as good as the hydrolysis of aliphatic halides and is so easy, and industrially generally requires and is heating when production
It can just be carried out under the operating condition of pressurization, reaction may be by benzyne intermediate process.In addition, when in the ortho para position of halogen
In the presence of having electron-withdrawing group, aromatic ring can be accelerated the generation of hydrolysis by short of electricity induced activation.In addition, there are also sulfonate
Alkali fusion, it is that aromatic sulfonic acid sodium salt has acidification after alkali fusion to obtain phenols again that the method, which is using the neutralization of arene-sulfonic acids sodium sulfite,
Compound.This method is applied to industrially produce phenol earliest.But this method uses strong acid and strong base as raw material or catalyst,
Reactant is very big to the pollution of environment, and reaction step is very long, and automated production rate is relatively low.In addition when in raw molecule
When containing functional groups such as carbonyl, halogen, amino, nitros, using the method in high temperature production phenolic compound, raw molecule
Functional group is easy to be influenced by the side reactions such as aoxidizing.Diazonium is made after obtaining aniline in diazonium salt method, aromatic hydrocarbon nitrification reduction again
Salt obtains phenol after diazonium salt hydrolysis.Hydrolyzing again after Grignard Reagent method, fragrant halides grignard reaction and borate effect can also
Obtain phenol.Alkylation of phenol method produces 3,5- DI-tert-butylphenol compounds, directly obtains reaction product, phenol by alkylating
Alkylation process it is easy to operate, but the selectivity reacted is very poor, and due to the orientation effect of hydroxyl, the new group that is added mainly is concentrated
On the ortho position of hydroxyl and contraposition, since the selectivity of production is too low, this method is not able to satisfy the needs of industrialized production.Isopropyl
Benzene method is a kind of method of very important synthesis phenolic compound.This method synthetic route mainly consists of three parts: alkyl
Change, oxidation, acidolysis.This method has many advantages, such as atom utilization height, and environmental pollution is small, but this method preparation process is more
Complexity, production process are more.
CN105198710A is related to the synthetic method of an inter-species tert-butyl phenol, includes the following steps: to tertiary butyl chloride
Benzene is raw material, and it is anti-to obtain 2-methyl-2-phenylpropane amine, diazotising, hydrolysis between the chloro- 4- tert-butyl -2- nitrobenzene of 1-, reduction generation by nitrification
A tert-butyl phenol should be obtained, the route raw material is cheap and easily-available, and each to walk unit process mild condition, post-processing is simple, and four steps are anti-
Answer total recovery high, the prospect with industrialized production.But the reaction has used a large amount of concentrated sulfuric acid and nitric acid, easily causes environment dirty
Dye.And 3,5- DI-tert-butylphenol compounds are due to tert-butyl phenol between being higher than there are the difficulty of two tert-butyls, preparation.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, provide a kind of reaction condition is mild, preparation process is simple,
The preparation method of the 3,5- DI-tert-butylphenol compounds of product yield high.
To achieve the goals above, the present invention provides the preparation method of one kind 3,5- DI-tert-butylphenol compounds, which is characterized in that
The following steps are included:
1) 1,3- di-tert-butyl, alchlor in organic solvent, is added, isopropanol, boron trifluoride second is added in stirring
Ether complexes, heating, are stirred to react 3-5 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, trifluoromethylbenzene obtained in step 2) are added in reaction flask, stirs
It mixes, n-Hydroxyphthalimide, azodiisobutyronitrile, sodium carbonate is added, is passed through air, heating stirring 15-18 hours, obtains
To the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) dilute sulphur is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Acid, after heating stirring 2-4 hours, stratification, organic phase obtains 3,5- di-tert-butyl phenolic product after rectifying, dry.
Further, the ratio between the amount of substance that 1,3- di-tert-butyl and isopropanol are added in step 1) is 3-5:1.
Further, the additional amount of isopropanol and the mass ratio of alchlor are 1:2.5-3.5 in step 1).
Further, the mass ratio of boron trifluoride etherate and alchlor is 0.07-0.12:1 in step 1).
Further, alchlor described in step 1) uses super in the preceding phosphoric acid solution for being first put into mass fraction and being 10%
It sonication 5-10 minutes, is used after filtration drying.
Further, organic solvent described in step 1) is one or both of petroleum ether, methylene chloride；It is described organic
Solvent is preferably petroleum ether.
Further, heating temperature is 60-80 DEG C in step 1).
The alkylated reaction of 1,3- di-tert-butyl and isopropanol belongs to reversible reaction, 1,3- di-t-butyl in reaction process
Hydrogen atom on benzene aromatic ring is lost replaced the isopropyl of hydroxyl, and isopropyl based products are formed, and in removal of alkylation reaction process
The isopropyl newly formed in middle isopropyl based products can be detached from from phenyl ring again under the influence of Louis acid catalysis acts on.Just,
Backward reaction constantly carries out that the reaction is promoted to be carried out continuously.Since the presence of tert-butyl on 1,3- di-tert-butyl improves benzene
The activity of ring, therefore it is easier to carry out the alkylation of isopropyl, while tert-butyl positions base as the first kind, there is positioning effect
It answers, when positive alkylated reaction carries out, isopropyl preferentially enters ortho position or contraposition on phenyl ring.With it is forward and inverse to reaction not
It is disconnected to carry out, since the steric hindrance of tert-butyl, isopropyl is all larger, metacompaund compared with ortho para position product, steric hindrance compared with
It is small, therefore the balance controlled reaction generates thermodynamically more stable metacompaund, finally a series of alkylations with remove alkane
Under the coefficient result of baseization, reaction forms stable product 1,3- di-t-butyl -5- cumene.Due to two on phenyl ring
Tert-butyl is bigger compared to some substituent group steric hindrances such as methyl, under thermodynamic (al) control, the final product 1 generated,
3- di-t-butyl -5- cumene is more stable.But it since there are biggish steric hindrances in 1,3- di-tert-butyl, is carrying out
When alkylated reaction, isopropyl is more inaccessibility to be added on phenyl ring, ultimately causes the yield of 1,3- di-t-butyl -5- cumene
It is lower.The present invention by alchlor using it is preceding be first put into mass fraction be 10% phosphoric acid solution in be ultrasonically treated 5-10 minutes,
It is used after filtration drying.Experimental study discovery, by the alchlor of the processing, catalytic activity is greatly improved.Meanwhile by three
Aluminium chloride and boron trifluoride etherate are used cooperatively, and the two synergistic effect, catalytic effect is more preferably.This may be due to trifluoro
Changing boron inherently has catalytic performance, but its catalytic activity is poor, and a small amount of boron trifluoride is added, and can activate phenyl ring, increases
The strong catalytic activity of alchlor.Furthermore the ratio of experimental study discovery boron trifluoride etherate and alchlor is to anti-
The amount that should influence the boron trifluoride very greatly, being such as added is excessive, and catalytic effect can be deteriorated, and the yield of product reduces.
Further, n-Hydroxyphthalimide and the mass ratio of sodium carbonate are 1:0.03-0.06 in step 3).
In the present invention, for the oxidation reaction in step 3), since the stability of product peroxide is poor, reaction temperature
The problems such as degree, reaction time etc. can all influence the progress of reaction, and causing the rate of by-product increase, oxidation reaction reduces.Due to
Activation energy needed for oxidation reaction is higher, and excessively high reaction temperature can be such that by-product increases again.The present invention is by being added N- hydroxyl
Phthalimide greatly reduces the activation energy of reaction, carry out reaction can under the conditions of lower temperature, but logical
It crosses the study found that individually adding n-Hydroxyphthalimide, reaction temperature is still higher.The present invention is in addition N- hydroxyl neighbour's benzene
On the basis of dicarboximide, and it is added to sodium carbonate, and defines the ratio of n-Hydroxyphthalimide and sodium carbonate
Example.Under n-Hydroxyphthalimide and the collective effect of sodium carbonate, reaction temperature is further decreased, the reaction time also into
One step shortens, while also ensuring higher yield.The addition of sodium carbonate can be enhanced the alkalinity of reaction system, improve N-
The catalytic performance of hydroxyphthalimide ensure that good product yield.
Further, heating temperature is 30-40 DEG C in step 3).
Further, heating temperature is 55-65 DEG C in step 4).
Further, the mass fraction of dilute sulfuric acid described in step 4) is 5-10%.
It is obtained by the present invention to have the beneficial effect that:
(1) preparation process of the present invention is simple, and reaction condition is mild, and reaction temperature is lower, is carried out in step 3) using air
Oxidation, compared to oxygen is used, price is more cheap and easily-available, and reduces security risk.
(2) acidolysis is carried out using dilute sulfuric acid in step 4) of the present invention, reduced using security risk caused by the concentrated sulfuric acid.
(3) alchlor and boron trifluoride etherate are used cooperatively by the present invention, and the two synergistic effect improves production
While object yield, keep reaction condition milder.
Specific embodiment
Embodiment 1
1) in reaction flask, 300mL petroleum ether, 285.5g (1.5mol) 1,3- di-tert-butyl, 75.15g trichlorine is added
Change aluminium (alchlor using it is preceding be first put into mass fraction be 10% phosphoric acid solution in be ultrasonically treated 10 minutes, after filtration drying
It uses, wherein ultrasonic power is 600W, and frequency 40KHz, temperature is 25 DEG C, work/intermittently than 3s/s), stirring at normal temperature 20 is divided
Clock is added 30.05g (0.5mol) isopropanol, 5.25g boron trifluoride etherate, is heated to 60 DEG C, is stirred to react 5 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.08gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.12g sodium carbonate, are passed through sky
Gas is heated to 30 DEG C, stirs 18 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 5% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 4 hours, stratification, organic phase obtains 3,5- after rectifying, dry
Di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 92.7%, samples to the reaction solution in step 1), passes through gas
Phase chromatographic quantitative analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 94.8%.
Embodiment 2
1) in reaction flask, 300mL petroleum ether, 475.8g (2.5mol) 1,3- di-tert-butyl, 105.18g trichlorine is added
Changing aluminium, (alchlor is made after filtration drying using being ultrasonically treated 5 minutes in the preceding phosphoric acid solution for being first put into mass fraction and being 10%
With, wherein ultrasonic power is 700W, and frequency 60KHz, temperature is 25 DEG C, work/intermittently than 2s/s), stirring at normal temperature 20 minutes,
30.05g (0.5mol) isopropanol, 12.62g boron trifluoride etherate is added, is heated to 80 DEG C, is stirred to react 3 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.5gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.27g sodium carbonate, are passed through sky
Gas is heated to 40 DEG C, stirs 15 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 10% dilute sulfuric acid, and after being heated to 65 DEG C, stirring 2 hours, stratification, organic phase obtains 3,5- after rectifying, dry
Di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 94.9%, samples to the reaction solution in step 1), passes through gas
Phase chromatographic quantitative analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 97.2%.
Embodiment 3
1) in reaction flask, 300mL petroleum ether, 380.6g (2.0mol) 1,3- di-tert-butyl, 90.15g trichlorine is added
Changing aluminium, (alchlor is made after filtration drying using being ultrasonically treated 8 minutes in the preceding phosphoric acid solution for being first put into mass fraction and being 10%
With, wherein ultrasonic power is 700W, and frequency 60KHz, temperature is 25 DEG C, work/intermittently than 2s/s), stirring at normal temperature 20 minutes,
30.05g (0.5mol) isopropanol, 6.31g boron trifluoride etherate is added, is heated to 60 DEG C, is stirred to react 4 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.2gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.21g sodium carbonate, are passed through sky
Gas is heated to 40 DEG C, stirs 16 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 8% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 3.5 hours, stratification, organic phase obtains 3 after rectifying, dry,
5- di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 92.3%, samples, passes through to the reaction solution in step 1)
Chromatogram ration analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 95.5%.
Embodiment 4
1) in reaction flask, 300mL petroleum ether, 380.6g (2.0mol) 1,3- di-tert-butyl, 90.15g trichlorine is added
Changing aluminium, (alchlor is made after filtration drying using being ultrasonically treated 8 minutes in the preceding phosphoric acid solution for being first put into mass fraction and being 10%
With, wherein ultrasonic power is 700W, and frequency 60KHz, temperature is 25 DEG C, work/intermittently than 2s/s), stirring at normal temperature 20 minutes,
30.05g (0.5mol) isopropanol, 10.82g boron trifluoride etherate is added, is heated to 60 DEG C, is stirred to react 4 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.2gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.21g sodium carbonate, are passed through sky
Gas is heated to 40 DEG C, stirs 16 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 8% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 3.5 hours, stratification, organic phase obtains 3 after rectifying, dry,
5- di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 90.9%, samples, passes through to the reaction solution in step 1)
Chromatogram ration analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 94.6%.
Comparative example 1
1) in reaction flask, 300mL petroleum ether, 380.6g (2.0mol) 1,3- di-tert-butyl, 96.08g trichlorine is added
Changing aluminium, (alchlor is made after filtration drying using being ultrasonically treated 8 minutes in the preceding phosphoric acid solution for being first put into mass fraction and being 10%
With, wherein ultrasonic power is 700W, and frequency 60KHz, temperature is 25 DEG C, work/intermittently than 2s/s), stirring at normal temperature 20 minutes,
30.05g (0.5mol) isopropanol is added, is heated to 60 DEG C, is stirred to react 4 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.2gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.21g sodium carbonate, are passed through sky
Gas is heated to 40 DEG C, stirs 16 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 8% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 3.5 hours, stratification, organic phase obtains 3 after rectifying, dry,
5- di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 82.4%, samples, passes through to the reaction solution in step 1)
Chromatogram ration analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 85.7%.
Comparative example 2
1) in reaction flask, 300mL petroleum ether, 380.6g (2.0mol) 1,3- di-tert-butyl, 102.27g trifluoro is added
Change diethyl etherate, stirring at normal temperature 20 minutes, 30.05g (0.5mol) isopropanol is added, is heated to 60 DEG C, it is small to be stirred to react 4
When；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.2gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.21g sodium carbonate, are passed through sky
Gas is heated to 40 DEG C, stirs 16 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 8% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 3.5 hours, stratification, organic phase obtains 3 after rectifying, dry,
5- di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 72.5%, samples, passes through to the reaction solution in step 1)
Chromatogram ration analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 77.3%.
Comparative example 3
1) in reaction flask, 300mL petroleum ether, 380.6g (2.0mol) 1,3- di-tert-butyl, 49.34g trichlorine is added
Changing aluminium, (alchlor is made after filtration drying using being ultrasonically treated 8 minutes in the preceding phosphoric acid solution for being first put into mass fraction and being 10%
With, wherein ultrasonic power is 700W, and frequency 60KHz, temperature is 25 DEG C, work/intermittently than 2s/s), stirring at normal temperature 20 minutes,
30.05g (0.5mol) isopropanol, 49.68g boron trifluoride etherate is added, is heated to 60 DEG C, is stirred to react 4 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.2gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.21g sodium carbonate, are passed through sky
Gas is heated to 40 DEG C, stirs 16 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 8% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 3.5 hours, stratification, organic phase obtains 3 after rectifying, dry,
5- di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 83.1%, samples, passes through to the reaction solution in step 1)
Chromatogram ration analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 84.9%.
Comparative example 4
1) in reaction flask, 300mL petroleum ether, 380.6g (2.0mol) 1,3- di-tert-butyl, 90.15g trichlorine is added
Change aluminium (alchlor is not ultrasonically treated in phosphoric acid solution using preceding), stirring at normal temperature 20 minutes, 30.05g is added
(0.5mol) isopropanol, 6.31g boron trifluoride etherate, are heated to 60 DEG C, are stirred to react 4 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.2gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, 0.21g sodium carbonate, are passed through sky
Gas is heated to 40 DEG C, stirs 16 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 8% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 3.5 hours, stratification, organic phase obtains 3 after rectifying, dry,
5- di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 83.7%, samples, passes through to the reaction solution in step 1)
Chromatogram ration analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 86.8%.
Comparative example 5
1) in reaction flask, 300mL petroleum ether, 380.6g (2.0mol) 1,3- di-tert-butyl, 90.15g trichlorine is added
Changing aluminium, (alchlor is made after filtration drying using being ultrasonically treated 8 minutes in the preceding phosphoric acid solution for being first put into mass fraction and being 10%
With, wherein ultrasonic power is 700W, and frequency 60KHz, temperature is 25 DEG C, work/intermittently than 2s/s), stirring at normal temperature 20 minutes,
30.05g (0.5mol) isopropanol, 6.31g boron trifluoride etherate is added, is heated to 60 DEG C, is stirred to react 4 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3-, bis- uncle
Butyl -5- cumene；
3) 1,3- di-t-butyl -5- cumene, 500mL fluoroform obtained in step 2) are added in another reaction flask
Base benzene, stirring are added 4.2gN- hydroxyphthalimide, 0.82g azodiisobutyronitrile, are passed through air, are heated to 40 DEG C,
Stirring 16 hours, obtains the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) quality is added into the reaction solution containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains
Score is 8% dilute sulfuric acid, and after being heated to 55 DEG C, stirring 3.5 hours, stratification, organic phase obtains 3 after rectifying, dry,
5- di-tert-butyl phenolic product.The yield of 3,5- DI-tert-butylphenol compounds is 84.1%, samples, passes through to the reaction solution in step 1)
Chromatogram ration analysis, the selectivity of 1,3- di-t-butyl -5- cumene are 94.1%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. one kind 3, the preparation method of 5- DI-tert-butylphenol compounds, which comprises the following steps:
1) 1,3- di-tert-butyl, alchlor in organic solvent, is added, isopropanol, boron trifluoride ether network is added in stirring
Object is closed, heating is stirred to react 3-5 hours；
2) reaction system after reaction, is down to room temperature, ice water, liquid separation is added, organic phase rectifying obtains 1,3- di-t-butyl-
5- cumene；
3) 1,3- di-t-butyl -5- cumene, trifluoromethylbenzene obtained in step 2) are added in reaction flask, stirring adds
Enter n-Hydroxyphthalimide, azodiisobutyronitrile, sodium carbonate, is passed through air, heating stirring 15-18 hours, is contained
There is the reaction solution of 1,3- di-t-butyl -5- hydrogen peroxide cumene；
4) dilute sulfuric acid is added into the reaction solution for containing 1,3- di-t-butyl -5- hydrogen peroxide cumene that step 3) obtains,
After heating stirring 2-4 hours, stratification, organic phase obtains 3,5- di-tert-butyl phenolic product after rectifying, dry；
Specifically, the mass ratio of boron trifluoride etherate and alchlor is 0.07-0.12:1 in step 1)；
Heating temperature is 30-40 DEG C in step 3).
2. the method according to claim 1, wherein 1,3- di-tert-butyl and isopropanol are added in step 1)
The ratio between amount of substance is 3-5:1.
3. the method according to claim 1, wherein in step 1) additional amount of isopropanol and alchlor matter
The ratio between amount is 1:2.5-3.5.
4. the method according to claim 1, wherein organic solvent described in step 1) is petroleum ether, dichloromethane
One or both of alkane.
5. the method according to claim 1, wherein heating temperature is 60-80 DEG C in step 1).
6. the method according to claim 1, wherein n-Hydroxyphthalimide and sodium carbonate in step 3)
Mass ratio be 1:0.03-0.06.
7. the method according to claim 1, wherein heating temperature is 55-65 DEG C in step 4).
8. method described in -7 any one according to claim 1, which is characterized in that the quality of dilute sulfuric acid described in step 4) point
Number is 5-10%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878255A (en) * | 1972-06-05 | 1975-04-15 | Phillips Petroleum Co | Process for preparing 3,5-dialkyl phenols |
| JPS61152635A (en) * | 1984-12-27 | 1986-07-11 | Mitsui Petrochem Ind Ltd | Production of 3,5-diisopropylphenol |
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2018
- 2018-03-29 CN CN201810269685.8A patent/CN108383689B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878255A (en) * | 1972-06-05 | 1975-04-15 | Phillips Petroleum Co | Process for preparing 3,5-dialkyl phenols |
| JPS61152635A (en) * | 1984-12-27 | 1986-07-11 | Mitsui Petrochem Ind Ltd | Production of 3,5-diisopropylphenol |
Non-Patent Citations (1)
| Title |
|---|
| Combining Homogeneous Catalysis with Heterogeneous Separation using Tunable Solvent Systems;Vittoria M.Blasucci;《J.Phys.Chem.A》;20090910;第114卷(第11期);第3936页 |
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