CN106083543A - One prepares the method for sun-screening agent intermediate 2,4 dihydroxy benaophenonel - Google Patents
One prepares the method for sun-screening agent intermediate 2,4 dihydroxy benaophenonel Download PDFInfo
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- CN106083543A CN106083543A CN201610416678.7A CN201610416678A CN106083543A CN 106083543 A CN106083543 A CN 106083543A CN 201610416678 A CN201610416678 A CN 201610416678A CN 106083543 A CN106083543 A CN 106083543A
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- resorcinol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
Abstract
The invention discloses the method that one prepares sun-screening agent intermediate 2,4 dihydroxy benaophenonel, the method is using resorcinol and benzenyl trichloride as raw material, carry out condensation reaction, prepare 2,4 dihydroxy benaophenonels, and reacted solvent is purified, recovery, the method is easy and simple to handle, preparation condition is gentle, environmental protection, prepared product quality is high, and wherein yield is 95%～98%, purity is 95%～99%, and isomer impurities is 1%～4%.
Description
Technical field
The invention belongs to daily-use chemical industry technical field, relate to the preparation method of a kind of organic intermediate, in particular to
The preparation method of the intermediate 2,4-DihydroxyBenzophenone of sun-screening agent ESCALOL 567.
Background technology
2,4-DihydroxyBenzophenone (2,4-dihydroxybenzophenone, BP-1), is called for short BP-1, again
Claiming ultra-violet absorber UV-0 (trade name UV-214), its structural formula is as shown in following formula I:
In faint yellow acicular crystal or white powder, molecular formula C under BP-1 room temperature13H10O3.BP-1 is long wave in genus
(290nm～400nm) ultra-violet absorber, utilizes its own molecular structure, converts light energy into heat energy, as ultra-violet absorber
It is widely used in cosmetic industry；And as industrial trade needing avoid photooxidation reaction to play the various of light stabilization
The additive of material, as polyvinyl chloride, polystyrene, epoxy resin, celluosic resin, unsaturated-resin, coating and not
The light stabilizer of saturated rubber etc.；It is alternatively arranged as synthesizing the raw material of other benzophenone ultraviolet absorbents.
Due to the specific use of ultra-violet absorber BP-1, the research in this field is always more active, in prior art, and BP-1
Synthetic route have following several:
(1) with resorcinol, chlorobenzoyl chloride as raw material, alchlor is catalyst condensation generation 2,4-dihydroxy hexichol
Ketone, such as: CN103073406A, in the method, the price of chlorobenzoyl chloride is higher, and can produce substantial amounts of useless containing aluminium during post processing
Water, easily causes environmental pollution, large-scale production relatively costly.
(2) resorcinol, benzenyl trichloride is utilized to carry out condensation reaction synthesis 2,4-DihydroxyBenzophenone for raw material, this
Method synthesis yield is high, and post processing is simple, such as: CN101628865A, CN101323564A etc..But the method can produce in a large number
Phenol wastewater 2-3 ton/ton, not only processing cost is high, and environmental pollution is serious.Owing to 2,4-DihydroxyBenzophenone is
Do ESCALOL 567 (sun-screening agent) important intermediate, thus 2,4-DihydroxyBenzophenone contaminated wastewater is asked
Topic becomes the very big stumbling-block of this sun-screening agent development.
Therefore, needing a kind of input cost of exploitation badly low, environmental pollution is little, and the preparation 2 that reaction yield is high, 4-dihydroxy two
The method of Benzophenone.
Content of the invention
In order to solve the problems referred to above, present inventor has performed and study with keen determination, it is found that: with resorcinol, trichloromethyl
Benzene is raw material, and water/alcohol is solvent, and condensation generates 2,4-DihydroxyBenzophenone, and through condition optimizing, the product purity obtaining is
95-99%, yield is 95-98%, and carries out certain process to the waste water producing after reaction, successfully achieves aqueous phase
Recycled, emits no waste water, environmental protection, decreases the pollution to environment, thus completes the present invention.
It is an object of the invention to provide following aspect:
(1) present invention provides a kind of method preparing sun-screening agent intermediate 2,4-DihydroxyBenzophenone, and the method includes
Following steps:
Step 1), add resorcinol and solvent in a kettle., in system, add benzenyl trichloride, carry out condensation anti-
Should；
Step 2), optionally cool down, filter, prepare thick product, be optionally purified, prepare 2,4-dihydroxy two
Benzophenone；
Step 3), the filtrate obtaining is post-processed, solvent recovery is applied mechanically.
(2) present invention also provides the 2,4-DihydroxyBenzophenone preparing according to said method, and wherein, reaction yield is
95%～98%；Purity is 95%～99%；Isomer impurities is 1%～4%.
The method preparing 2,4-DihydroxyBenzophenone providing according to the present invention, has the advantages that
(1) 2,4-DihydroxyBenzophenone prepared by the method that the present invention provides, its purity is 95%～99%, isomers
Impurity is 1%～4%, can be directly used for preparing sun-screening agent ESCALOL 567 etc., it is not necessary to extra rectifying, steaming
The purification process such as evaporate, saved cost；
(2) technological reaction mild condition of the present invention, reaction is homogeneous before this, after progressively separate out product, improve anti-
Product yield, by low temperature crystallization, the i.e. separable product of filtration；
(3) technique of the present invention carries out certain process to the waste water producing after reaction, successfully achieves aqueous phase
Recycled, emit no waste water, environmental protection, decrease the pollution to environment；
(4) method that the present invention provides also has the feature of simplicity, easily controllable and industrialized production.
Detailed description of the invention
Below by the present invention is described in detail, the features and advantages of the invention will illustrate with these and become more
For clear, clear and definite.
Word " exemplary " special here means " being used as example, embodiment or illustrative ".Here as " exemplary "
Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.
The present invention described below.
According to the first aspect of the invention, a kind of side preparing sun-screening agent intermediate 2,4-DihydroxyBenzophenone is provided
Method, it is characterised in that the method comprises the following steps:
Step 1), add resorcinol and the first solvent in a kettle., in system, add benzenyl trichloride, contract
Close reaction.
In the present invention, relate to benzenyl trichloride and be hydrolyzed to chlorobenzoyl chloride, thus the first solvent is aqueous solvent, and raw material
Benzenyl trichloride is water insoluble, therefore selects the first solvent for selecting organic solvent-water mixed solvent.
In described first solvent, organic solvent is selected from small molecular alcohol solvent, preferably methyl alcohol, ethanol, a kind of in isopropanol
Or multiple, more preferably ethanol, wherein, in the first solvent, the volume fraction of alcoholic solvent is 2%-20%, preferably 5%-15%, more excellent
Select 8%-12%.
In the preferred embodiment of the present invention, the organic solvent in the first solvent selects ethanol.Alcohol-water mixes
Solvent is being applicable to whole course of reaction, not only can disperse reactant well, and the use of ethanol can suppress isomers
The generation of impurity, after reaction completes, solvent is processed or reclaimer operation is simple, and solvent toxicity is little, operates safety.
The inventors discovered that, select step 1) described in the first solvent of ratio can be completely dissolved reaction in course of reaction
Raw material, and the precipitation of beneficially product 2,4-DihydroxyBenzophenone；If the volume content of organic solvent in the first solvent
Less than 2%, then the benzenyl trichloride adding dissolves insufficient, it is impossible to effectively contact with resorcinol, is unfavorable for reaction；If first
In solvent, the volume content of organic solvent is more than 20%, then reaction completes afterproduct and is difficult to precipitation, and organic solvent content improves,
Add production cost, increase the risk causing environmental pollution.
In the preferred embodiment of the present invention, first the first solvent having configured is joined in reactor, so
Rear addition resorcinol, starts stirring, makes resorcinol dissolve, and raise system reaction temperature, adds benzenyl trichloride, starts
React.Owing to solubility in the first solvent for the product 2,4-DihydroxyBenzophenone is less in course of reaction, with
The carrying out of reaction, product can be separated out by solvent, and beneficially reaction is carried out, and improves productivity.
In the present invention, the mass ratio of described resorcinol and the first solvent is the quality of resorcinol: the first solvent
Quality=1:2～1:16, preferably 1:4～1:8.The inventors discovered that, when the quality of resorcinol: the quality of the first solvent is less than
During 1:2, resorcinol content is high, may produce accessory substance when condensation reaction, reduces product yield；Matter when resorcinol
Amount: when the quality of the first solvent is more than 1:16, introduces too much solvent in reaction system, cause reaction raw materials concentration too low, instead
Answer rate reduction, and the waste of solvent can be caused, the increase of cost.
In the present invention in step 1, the ratio of described resorcinol and the mole of benzenyl trichloride be resorcinol mole
Amount: the mole=1:1～1:2 of benzenyl trichloride, preferably 1:1～1:1.5, more preferably 1:1～1:1.3；Wherein, resorcinol
Mole with the molar amount of its molecule, the mole of benzenyl trichloride is with the molar amount of its molecule.Step 1 of the present invention)
In, resorcinol II reacts according to the following formula with to benzenyl trichloride, (wherein TCMB is benzotrichloride)
From formula II, resorcinol is reacted by the chemical equivalent of 1:1 with benzenyl trichloride, for react fully into
OK, when carrying out condensation reaction, the present invention selects resorcinol another kind of raw material relative with benzenyl trichloride little over amount, preferably makes
Benzenyl trichloride is excessive, reduces the possibility that phenol wastewater pollutes, and when resorcinol and benzenyl trichloride mole it
Than during more than 1:2, benzenyl trichloride is excessive in a large number, and the yield of product no longer substantially increases, and reacts and terminate to deposit in rear system
At a large amount of benzenyl trichlorides, cause wastage of material.Preferably, after reaction terminates, excessive benzenyl trichloride is reclaimed, is used for
New reaction.
In the present invention, the feed postition of benzenyl trichloride is the mode of dropping, with the carrying out of stirring, benzenyl trichloride
Being dispersed in reaction system rapidly, thus it being excessive to avoid local concentration, make condensation reaction fully carry out, accessory substance is few, improves
The yield of condensation reaction.
In the present invention, add when a length of 0.5～5h, preferably 1～3h of benzenyl trichloride.Addition speed to benzenyl trichloride
Spend fast, dropping and the DeGrain that brings, and when adding the duration of benzenyl trichloride more than 5h, the quality of product is no longer
Substantially increase, but increase time cost.
When adding benzenyl trichloride, the temperature of system is 20～90 DEG C, preferably 40～70 DEG C.The inventors discovered that, reaction
When the temperature of system is 20～90 DEG C, condensation reaction can be quickly carried out, and in the product preparing, accessory substance is few.
In step 1 of the present invention) in, after adding benzenyl trichloride, insulation reaction is carried out to reaction system, the temperature of insulation reaction
Degree is 20～100 DEG C, preferably 50～90 DEG C, more preferably higher than carries out insulation reaction under dropping temperature.
The inventors discovered that, when the time of insulation reaction is less than 1h, condensation reaction carries out abundant not, in system still
There is the residue of a large amount of reaction raw materials, not only reduce the yield of product, and cause a large amount of wastes of raw material；Work as insulation reaction
Time more than 10h when, the yield of product no longer significantly improves, and not only loses time, and, when insulation reaction time continue
During prolongation, creating more accessory substance in system, therefore, it is 1～10h that the present invention selects the time of insulation reaction, preferably 3
～8h.
Step 2), cooling system, filters, prepares thick product, be optionally purified, prepare 2,4-dihydroxy hexichol first
Ketone.
By cooling system, making product separate out, temperature of reaction system is cooled to 0～30 DEG C, preferably 5～10 DEG C.This
It in bright, is not required to add other substance change systems composition, only by changing system temperature, the separation of product can be completed, thus
Avoid the introducing of other impurity in product.
In the present invention, system temperature cooldown rate is 10 DEG C/h～60 DEG C/h, preferably 15 DEG C/h～30 DEG C/h.Cooling speed
Rate is fast, and nucleus is quickly formed, and can produce many tiny nucleus, because not having enough time so that product molecule on nucleus
Adhere to and make crystal grow to very greatly, thus form many tiny crystal, cause crystal to separate difficulty with solution, and carry more
Impurity.The speed of cooling rate is very big to the qualitative effects of crystal, and in order to make crystal have certain granularity, the present invention selects cold
But speed is 10 DEG C/h～60 DEG C/h.
Step 2 of the present invention) in, filtering and be separated off liquid phase, the mode filtering is not specially limited by the present invention, can make
With any one filter type in prior art, such as natural filtration, filtration under diminished pressure etc., the present invention is preferably filtration under diminished pressure, a side
The speed of face filtration under diminished pressure is fast, on the other hand filtration under diminished pressure liquid phase substance is removed more thorough.
In a preferred embodiment, the thick product obtaining is purified.Simple filtration is likely to result in filter cake
Remain unreacted raw material completely, the impurity such as accessory substance of product in condensation reaction, after being purified filter cake, products therefrom
Purity significantly improve.The preferred recrystallization method of way of purification.
Recrystallization the second solvent used is selected from small molecular alcohol solvent or alcohol-water mixed solvent, preferably methyl alcohol, ethanol, isopropyl
Alcohol, alcohol-water (2:1～3:1, volume ratio).In a preferred embodiment, due to reaction raw materials and product 2,4-dihydroxy
Base benzophenone dissolves in alcohol-water (3:1, volume ratio), and after recrystallization, residual solvent easily reclaims, and toxicity is little, therefore
Second solvent preferred alcohol-water (3:1).
Recrystallization second solvent used and step 2) mass ratio of thick product for preparing is recrystallization the second solvent used
Quality: step 2) quality=5:1～20:1, preferably 5:1～15:1 of thick product that prepare.When the second solvent load is excessive, 2,
4-dihydroxy benaophenonel crystallization content is less, causes product to lose；When the second solvent load is too little, purification effect is inconspicuous.
The temperature of recrystallization is 0～30 DEG C, preferably 2～10 DEG C, more preferably 2～5 DEG C.
Optionally, the filter cake after recrystallization, filtration is dried, it is preferred to use vacuum drying method is dried,
Baking temperature is preferably 45 DEG C～80 DEG C, more preferably 55 DEG C～70 DEG C, such as 60 DEG C.
In the present invention, the purified rear 2,4-DihydroxyBenzophenone reaction yield preparing is 95%～98%, and purity is
95%～99%, isomer impurities is 1%～4%.
Step 3), the filtrate of thick product is post-processed, solvent recovery is applied mechanically.
The present invention has hydrogen chloride to produce in the condensation reaction, and system is acidity, and produces a large amount of chlorion.Preferably, exist
Before removing removing chloride, by the filtrate pH value of the thick product of alkaline matter regulation to 7～11, preferably 7～9.
In the present invention, described alkaline matter be selected from inorganic base and organic base, inorganic base selected from NaOH, potassium hydroxide,
Sodium carbonate, potassium carbonate etc., organic base is selected from methylamine, ethamine, triethylamine etc., preferably NaOH.Above-mentioned organic base or inorganic
Alkali is optionally directly added in filtrate or adds in filtrate after wiring solution-forming, by can be good be dissolved in filtrate for the purpose of, can
It is effectively neutralized reaction with filtrate.
In the present invention, the filtrate of thick product is post-processed, to realize the recycled of solvent.Post processing includes using
Filtrate is purified by absorption method, and described adsorbent has ion adsorption capacity.Conventional adsorbent includes:
1) inorganic adsorbent, including atlapulgite, activated carbon, diatomite or natural clay, its can effectively binding molecule or
Ion.Such as activated carbon, it is structurally irregular alignment due to microcrystalline carbon, has pore, when activation between interconnection
Can produce carbon tissue defects, therefore it is a kind of porous carbon, and bulk density is low, and specific surface area is big.The specific surface of normal activated carbon
Amass at 500～1700m2Between/g, there is very strong absorption property, including physical absorption and chemisorbed.
2) synthetic adsorbent, including ion exchange resin, ion exchange resin is (to have the work of exchange ion with functional group
Property group), there is network structure, insoluble macromolecular compound.In resin, the species of chemical active radical determines resin
Main character and classification.Ion exchange resin is divided into resin cation and the big class of resin anion (R.A.) two, they can respectively with molten
Cation in liquid and anion carry out ion exchange.Ion exchange resin aperture is less, it is adaptable to absorption inorganic ions.
Ion exchange resin of the present invention is selected from anion exchange resin, preferably strong-base anion-exchange resin, more
The preferably strong-base anion-exchange resin containing quaternary ammonium group, most preferably chlorine-based strong alkali anion exchange resin.
When being purified, the mass ratio of described ion exchange resin consumption and amount of filtrate is the matter of ion exchange resin
Amount: the quality=1:100～10:100 of filtrate, preferably 1:100～5:100, can complete the effective of chlorion within this range
Absorption.The quality of ion exchange resin: the quality of filtrate is less than 1:100, then ion exchange resin adsorption capacity is wanted less than purifying
Asking, in filtrate, chloride ion content is still higher；The quality of ion exchange resin: the quality of filtrate is more than 10:100, adsorption capacity
Reach requirement level, but ion exchange resin is excessive, adds production cost.
Optionally, described ion exchange resin is regenerated, recycle, 10 times can be not less than by access times.
The inventors discovered that, when temperature is less than 20 DEG C, does not reaches balance in the adsorption process short time, and rise high-temperature and can make
The rate of adsorption is accelerated, and the situation that adsorbance increases occurs, and when temperature is higher than 60 DEG C, desorption phenomenon is aggravated, thus the present invention
In, the temperature of adsorption reaction is 20 DEG C～60 DEG C, preferably 30 DEG C～50 DEG C.
The inventors discovered that, under the conditions of selected adsorbent and adsorption temp, be stirred during adsorption reaction, make
Adsorbent and filtrate are fully contacted, and are greatly improved adsorption efficiency, it is preferable that mixing time is 1h～6h, more preferably 2h～4h.
Recycling design is applied mechanically for lower batch of condensation reaction, it is preferable that when recycling design is applied mechanically, and adds appropriate fresh molten
Agent, it is highly preferred that solvent additional amount is the 10wt%～50wt%, preferably 20wt%～30wt% of solvent inventory first.
The inventors discovered that, if do not processed filtrate, directly applying mechanically condensation reaction, isomer impurities ratio in product
Higher, up to 10～15%, use after adsorption treatment, isomer impurities can be controlled in to react the same effect in the first batch be 1～
4%.The Isomers In Products impurity of preparation mainly identifies detection by LC-MS.
The invention provides the 2,4-DihydroxyBenzophenone preparing according to said method, wherein, described 2,4-dihydroxy
Benzophenone, reaction yield is 95%～98%, and purity is 95%～99%, and isomer impurities is 1%～4%.
Embodiment
Embodiment 1
(1) 660.6g 10% ethanol-water solution after reclaiming through primary first-order equation and 110.1g (1.0mol) resorcinol
Join in tetra-mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, start stirring, by body
System is heated to 60 DEG C, is slowly added dropwise 234.6g (1.2mol) benzenyl trichloride, after dropping finishes, continues under the conditions of 80 DEG C in 2h
Continuous insulation reaction 6h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
The thick product of 4-dihydroxy benaophenonel, with alcohol-water (3:1, volume ratio) quality: the quality=10:1 of thick product dissolves thick producing
Product, recrystallize, vacuum filtration at 5 DEG C, filter cake in-0.1MPa, 60 DEG C of dry 12h, obtain faint yellow acicular crystal 2,4-
Dihydroxy benaophenonel 210.1g, yield 98%, purity 98%, isomer impurities 2%.
(3) filtrate is neutralized to PH to 7 by NaOH solution, be subsequently adding filtrate weight 2% chlorion exchanger resin,
40 DEG C of stirring 3h, filter, and filtrate is directly overlapped and used condensation reaction.Filter cake i.e. chlorion exchanger resin can continue next batch
Absorption.
Embodiment 2
(1) 880.8g 20% ethanol-water solution after reclaiming through primary first-order equation and 110.1g (1.0mol) resorcinol
Join in tetra-mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, start stirring, by body
System is heated to 70 DEG C, is slowly added dropwise 234.6g (1.2mol) benzenyl trichloride, in 3h after dropping finishes, under the conditions of 60 DEG C
Continue insulation reaction 2h.
(2) after completion of the reaction, with 20 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
The thick product of 4-dihydroxy benaophenonel, with ethanol quality: the quality=15:1 of thick product dissolves thick product, carries out weight at 5 DEG C
Crystallization, vacuum filtration, filter cake in-0.1MPa, 60 DEG C of dry 12h, obtain faint yellow acicular crystal 2,4-DihydroxyBenzophenone
205.7g, yield 96%, purity 99%, isomer impurities 1%.
(3) filtrate is neutralized to PH to 8 by NaOH solution, be subsequently adding filtrate weight 5% chlorion exchanger resin,
30 DEG C of stirring 4h, filter, and filtrate is directly overlapped and used condensation reaction.Filter cake i.e. chlorion exchanger resin can continue next batch
Absorption.
Embodiment 3
(1) 660.6g 2% ethanol-water solution after reclaiming through primary first-order equation and 110.1g (1.0mol) resorcinol
Join in tetra-mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, start stirring, by body
System is heated to 60 DEG C, is slowly added dropwise 254.1g (1.3mol) benzenyl trichloride, after dropping finishes, continues under the conditions of 80 DEG C in 1h
Continuous insulation reaction 8h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
The thick product of 4-dihydroxy benaophenonel, with ethanol quality: the quality=5:1 of thick product dissolves thick product, heavily ties at 2 DEG C
Crystalline substance, vacuum filtration, filter cake in-0.1MPa, 60 DEG C of dry 12h, obtain faint yellow acicular crystal 2,4-DihydroxyBenzophenone
212.1g, yield 99%, purity 95%, isomer impurities 4%.
(3) filtrate is neutralized to PH to 7 by NaOH solution, be subsequently adding filtrate weight 3% chlorion exchanger resin,
50 DEG C of stirring 1h, filter, and filtrate is directly overlapped and used condensation reaction.Filter cake i.e. chlorion exchanger resin can continue next batch
Absorption.
Comparative example 1
(1) 660.6g 10% ethanol-water solution after reclaiming through primary first-order equation and 110.1g (1.0mol) resorcinol
Join in tetra-mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, start stirring, by body
System is heated to 60 DEG C, is slowly added dropwise 234.6g (1.2mol) benzenyl trichloride, after dropping finishes, continues under the conditions of 80 DEG C in 2h
Continuous insulation reaction 6h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
The thick product of 4-dihydroxy benaophenonel, with alcohol-water (3:1, volume ratio) quality: the quality=10:1 of thick product dissolves thick producing
Product, recrystallize, vacuum filtration at 5 DEG C, filter cake in-0.1MPa, 60 DEG C of dry 12h, obtain product after purification.
(3) filtrate is neutralized to PH to 7 by NaOH solution, be subsequently adding filtrate weight 2% atlapulgite, stir at 40 DEG C
Mixing 3h, filtering, filtrate is directly overlapped and is used condensation reaction.
Gained product after purification is faint yellow acicular crystal 2,4-DihydroxyBenzophenone 209.3g, yield 85%, purity
87%, isomer impurities 11%.It follows that use atlapulgite as adsorbent, isomer impurities content is higher, and impact is produced
The yield of product and post processing.
Comparative example 2
(1) 660.6g 10% ethanol-water solution after reclaiming through primary first-order equation and 110.1g (1.0mol) resorcinol
Join in tetra-mouthfuls of glass reaction bottles of 2000mL of belt stirrer, thermometer, addition funnel and condenser pipe, start stirring, by body
System is heated to 60 DEG C, is slowly added dropwise 234.6g (1.2mol) benzenyl trichloride, after dropping finishes, continues under the conditions of 80 DEG C in 2h
Continuous insulation reaction 6h.
(2) after completion of the reaction, with 30 DEG C/h rate of temperature fall cooling system temperature to 25 DEG C, vacuum filtration, filter cake is 2,
The thick product of 4-dihydroxy benaophenonel, with alcohol-water (3:1, volume ratio) quality: the quality=10:1 of thick product dissolves thick producing
Product, recrystallize, vacuum filtration at 5 DEG C, filter cake in-0.1MPa, 60 DEG C of dry 12h, obtain product after purification.
(3) filtrate is neutralized to PH to 7 by NaOH solution, be subsequently adding filtrate weight 2% activated carbon, 40 DEG C of stirrings
3h, filters, and filtrate is directly overlapped and used condensation reaction.
Gained product after purification is faint yellow acicular crystal 2,4-DihydroxyBenzophenone 211.8g, yield 89%, purity
90%, isomer impurities 7%.It follows that use activated carbon as adsorbent, isomer impurities content is higher, affects product
Yield and post processing.
Above in association with detailed description of the invention and exemplary example, the present invention is described in detail, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. the method preparing 2,4-DihydroxyBenzophenone, it is characterised in that the method comprises the following steps:
Step 1), add resorcinol and the first solvent in a kettle., in system, add benzenyl trichloride, carry out condensation anti-
Should；
Step 2), cooling system, filters, prepares thick product, be optionally purified, prepare product 2,4-dihydroxy hexichol first
Ketone；
Step 3), the filtrate of thick product is post-processed, solvent recovery is applied mechanically.
2. preparation method according to claim 1, it is characterised in that in step 1) in,
Described first solvent is alcohol-water mixed solvent, and wherein, alcoholic solvent is selected from small molecular alcohol, preferably methyl alcohol, ethanol, isopropyl
In alcohol one or more, more preferably ethanol；And/or
In described first solvent, the volume fraction of alcoholic solvent is 2%-20%, preferably 5%-15%, more preferably 8%-12%；With/
Or
The mass ratio of described resorcinol and solvent is the quality of resorcinol: the quality=1:2～1:16 of solvent, preferably 1:
4～1:8；And/or
The ratio of described resorcinol and the mole of benzenyl trichloride is the mole of resorcinol: the mole of benzenyl trichloride
=1:1～1:2, preferably 1:1～1:1.5, more preferably 1:1～1:1.3；Wherein, mole the rubbing with its molecule of resorcinol
That gauge, the mole of benzenyl trichloride is with the molar amount of its molecule.
3. preparation method according to claim 1 and 2, it is characterised in that in step 1) in,
When adding benzenyl trichloride, the temperature of system is 20～90 DEG C, preferably 40～70 DEG C；And/or
Add the mode for dropping for the mode of benzenyl trichloride；And/or
Add when a length of 0.5～5h, preferably 1～3h of benzenyl trichloride；And/or
The temperature of insulation reaction is 20～100 DEG C, preferably 50～90 DEG C；And/or
The time of insulation reaction is 1～10h, preferably 3～8h.
4. the preparation method according to one of claims 1 to 3, it is characterised in that step 2) in,
Temperature of reaction system is cooled to 0～30 DEG C, preferably 5～10 DEG C；And/or
Cooldown rate is 10 DEG C/h～60 DEG C/h, preferably 15 DEG C/h～30 DEG C/h；And/or
The method using recrystallization is purified；And/or
Recrystallization the second solvent used is selected from small molecular alcohol solvent or alcohol-water mixed solvent, preferably methyl alcohol, ethanol, isopropanol, second
Alcohol-water (2:1～3:1, volume ratio), more preferably alcohol-water (3:1, volume ratio)；And/or
Recrystallization second solvent used and step 2) mass ratio of thick product for preparing is the second solvent quality: step 2) prepare
The quality=5:1～20:1, preferably 5:1～15:1 of thick product；And/or
The temperature of recrystallization is 0～30 DEG C, preferably 2～10 DEG C, more preferably 2～5 DEG C.
5. the preparation method according to one of Claims 1 to 4, it is characterised in that step 3) in,
Filtrate pH value with the thick product of alkaline matter regulation；And/or
Described alkaline matter is selected from inorganic base and organic base, and inorganic base is selected from NaOH, potassium hydroxide, sodium carbonate, potassium carbonate
It is selected from methylamine, ethamine, triethylamine etc., preferably NaOH Deng, organic base；And/or
Regulating step 2) prepare system pH value to 7～11, preferably to 7～9.
6. the preparation method according to one of Claims 1 to 5, it is characterised in that step 3) in,
Described post processing includes using absorption method to be purified filtrate；And/or
Sorbent used selected from inorganic adsorbent and synthetic adsorbent, described inorganic adsorbent is selected from atlapulgite, activated carbon, silicon
Diatomaceous earth or natural clay, described synthetic adsorbent is selected from ion exchange resin.
7. preparation method according to claim 6, it is characterised in that
Described ion exchange resin is selected from anion exchange resin, preferably strong-base anion-exchange resin, more preferably contains quaternary ammonium
The strong-base anion-exchange resin of base, most preferably chlorine-based strong alkali anion exchange resin；And/or
The mass ratio of described ion exchange resin consumption and amount of filtrate is the quality of ion exchange resin: quality=1 of filtrate:
100～10:100, preferably 1:100～5:100；And/or
Optionally, described ion exchange resin can be recycled, and access times are not less than 10 times.
8. the preparation method according to claim 6 or 7, it is characterised in that
The temperature of adsorption reaction is 20 DEG C～60 DEG C, preferably 30 DEG C～50 DEG C；And/or
Optionally, adsorption reaction process is stirred；Preferably, mixing time is 1h～6h, more preferably 2h～4h；And/or
Optionally, recycling design is applied mechanically for lower batch of condensation reaction；Preferably, when recycling design is applied mechanically, add appropriate fresh
Solvent, it is highly preferred that solvent additional amount is the 10wt%～50wt%, preferably 20wt%～30wt% of solvent inventory first.
9. the method according to one of claim 1～8, it is characterised in that prepared 2,4-DihydroxyBenzophenone reaction
Yield is 95%～98%；Purity is 95%～99%；Isomer impurities is 1%～4%.
10. the 2,4-DihydroxyBenzophenone that the method according to one of claim 1～9 prepares, it is characterised in that
Reaction yield is 95%～98%；Purity is 95%～99%；Isomer impurities is 1%～4%.
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