CN109369550A - A kind of preparation method of triazine-based ultraviolet absorbent - Google Patents
A kind of preparation method of triazine-based ultraviolet absorbent Download PDFInfo
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- CN109369550A CN109369550A CN201811525408.5A CN201811525408A CN109369550A CN 109369550 A CN109369550 A CN 109369550A CN 201811525408 A CN201811525408 A CN 201811525408A CN 109369550 A CN109369550 A CN 109369550A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
Abstract
The present invention relates to 2, (2- hydroxyl -4- the butoxy phenyl) -6- of 4- bis- (2,4- dibutoxy phenyl) -1,3, the preparation method of 5- triazine, this method comprises the following steps: (1) under the action of mating type solid-carried catalyst, reaction generates compound of formula I 2,4 for Cyanuric Chloride and resorcinol, 6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines；(2) under the action of phase transfer catalyst and lye, reaction generates target compound for compound of formula I and butyl halide；(1) mating type solid-carried catalyst simplifies the separating technology of reaction mass, it is only necessary to which filtering solid catalyst can reach separating effect, reduce the generation of a large amount of aluminium containing salt acid waste waters；(2) technique is simplified using Catalyzed By Phase-transfer Catalyst etherification reaction, without harsh anhydrous condition, compared with traditional Williamson etherification reaction, it is possible to reduce largely, be difficult to isolated complex salt waste.
Description
Technical field
The invention belongs to field of material technology, are related to ultraviolet absorbing agent 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6-
The preparation of (2,4- dibutoxy phenyl) -1,3,5- triazine.
Background technique
Ultraviolet light in daylight can be divided into UV-A (315-400nm) according to the difference of wavelength, UV-B (285-315nm), UV-
Three wave bands of C (200-285nm).Fiber, plastics, artificial rubber and other high molecular materials of exposure in the sunlight, due to inhaling
The energy for having received its ultraviolet light, has caused Auto-oxidation reaction, cause polymer aging, degradation so that the appearance of product and
Physical mechanical property degenerates.Ultraviolet absorbing agent is most generally used at present to the protection of ultraviolet light, ultraviolet absorbing agent is inhaled
It receives high-energy ultraviolet light and carries out energy conversion, energy is discharged or consumed in the form of thermal energy or harmless Low emissivity, thus anti-
Only sunlight or other artificial ultraviolet lights cause the degradation of polymer and reduce the harm to human body.Triazine-based ultraviolet absorbent
Anti-light, hot, oxygen or ring in the industries such as plastics, coating, dyestuff, fiber, windshield, cosmetics, drug, sun-screening agent
Power destruction in border, which has, stablizes and protects application.The kind of triazine-based ultraviolet absorbent mainly includes UV-1164, UV-1577, UV-
400, UV-405, UV-460 etc..
UV-460, i.e. 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- dibutoxy phenyl) -1,3,5-triazines,
Its preparation is usually that Friedel-Crafts first occurs in the presence of alchlor with resorcinol by Cyanuric Chloride to react
To 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines intermediate products, intermediate product carries out ether with halogenated alkane (BuX) again
Change reaction and obtain purpose product (reaction equation is as follows).
Wherein, intermediate is prepared with following three kinds of methods:
(1) solvent method: the solvent of use is nitrobenzene, tetrachloroethanes, dichloroethanes, petroleum alkane and ethers etc., patent
US3224708 uses nitro benzene solvent, and reaction temperature is at 90-95 DEG C, product 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-
Triazine crude yield is higher than 90%, the solvent that the technique of last century the seventies development where the chemical research of Shanxi uses
It is equally nitrobenzene, the midbody product yield that pilot scale obtains is 72%.It is using the maximum feature of nitro benzene solvent: toxicity
Greatly, boiling point is high, aftertreatment technology is complicated, environmental pollution is serious.Other solvents it is poor for applicability be not able to satisfy equally reaction after
The reasonable demand of science and engineering skill；
(2) solid phase method: the resorcinol, Cyanuric Chloride, trichlorine with solid material that department of chemistry of Northeast Normal University releases
The solid phase method of change aluminium reacts, although solving Solvent, equally brings and reacts incomplete, reacts uncontrollable, equipment corruption
Erosion, the disadvantage that explosive, hydrogen chloride gas overflows, dust is big, product ash content is big；
(3) suspension method: referring to the advantage and disadvantage of solvent method and solid phase method, the alkane low using toxicity, boiling point is suitable, halogenated hydrocarbons
Solvent, resorcinol, Cyanuric Chloride, alchlor suspension are reacted wherein and at a relatively high temperature, conducive to material point
It dissipates, reaction heat transfer, prepares intermediate in this approach and relatively easily control reaction process and simplify aftertreatment technology.Patent
The technology of preparing that US3118887 is introduced is similarly.
The preparation of 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- dibutoxy phenyl) -1,3,5- triazine is special
Sharp DE19750906 (US6284821, CN97123135.4) is described: starting material 2,4,6- tri- (2,4- dihydroxy phenyl)-
1,3,5-triazines and halogenated (chlorine, bromine) butane in the presence of basic matterial, carry out alkane in solvent DMF, glycol ethers solvent
Oxygen glycosylation reaction obtains purpose product, basic matterial NaOH, KOH, Na2CO3、K2CO3Deng, reactant 2,4,6- tri- (2,4- bis-
Hydroxy phenyl) molar ratio of -1,3,5-triazines and butyl halide is not less than 1:4, and it is same as the molar ratio of basic matterial to be not less than
1:4。
In the preparation of 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- dibutoxy phenyl) -1,3,5- triazine
Cheng Zhong, due to having used a large amount of alchlor, solid alkaloid substance, it will a large amount of waste water and trade waste are generated, to rear
The environmental protection treatment of phase brings greatly difficulty, be easy to cause the pollution of environment.
In view of this, (2- hydroxyl -4- the butoxy phenyl) -6- of 2,4- bis- (2,4- dibutoxy phenyl) -1 that exploitation is new,
The process of preparing of 3,5- triazines overcomes its existing defect and deficiency, can be high in actual course of industrialization
Effect, environmental protection are necessary.
Summary of the invention
It is an object of the invention to overcome defect of the existing technology, one kind 2,4- bis- (2- hydroxyl -4- butoxy is provided
Phenyl) -6- (2,4- dibutoxy phenyl) -1,3,5-triazines preparation method, this method urged using mating type solid-carried catalyst
Change Friedel-Crafts reaction, Catalyzed By Phase-transfer Catalyst etherification reaction, overcome in the prior art complex technical process, make
With and generate and largely be easy to cause the acid of environmental pollution, the defect of alkaline matter, there is reaction yield high, waste and sewage production
It is raw to measure less, be suitable for industrialized advantage.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation of 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- dibutoxy phenyl) -1,3,5- triazine
Method, reaction equation is as follows,
Include the following steps:
(1) Cyanuric Chloride and resorcinol have the γ-Al of alchlor in load2O3The effect of mating type solid-carried catalyst
Under, reaction generates compound of formula I；
(2) compound of formula I and butyl halide BuX react production IIization under the action of phase transfer catalyst and lye
Close object.
Preferably, the mating type solid-carried catalyst is prepared with the following method: removing γ-Al2O3In moisture,
Obtain dry γ-Al2O3；γ-Al after drying2O3With alchlor according to (3-10): 1 weight ratio is carried out at 50~150 DEG C
Immobilized reaction, gained reaction solution are mating type solid-carried catalyst.
The preparating mechanism of the mating type solid-carried catalyst is as follows:
Preferably, when preparing mating type solid-carried catalyst, γ-Al2O3It is dry using following operation: by γ-Al2O3
It is placed in alkane, in aromatic hydrocarbon solvent, reflux dewatering.The alkane, aromatic hydrocarbon solvent are selected from hexamethylene, normal heptane, toluene, diformazan
One of benzene, preferably normal heptane.
Preferably, γ-Al2O3Mass volume ratio with solvent is 1:(2~4) (g/ml).
Preferably, γ-Al2O3Using macropore or mesoporous class γ-Al2O3, granularity mesh number is in 20-100 mesh.It is preferred that using big
Hole class, granularity mesh number are the γ-Al of 40-80 mesh2O3.Macropore of the present invention refers to that aperture is greater than 50nm, mesoporous to refer to
Aperture is 2-50nm.
Preferably, when preparing mating type solid-carried catalyst, γ-Al2O3With reacting with carbon tetrachloride, chlorine for alchlor
One of imitative, nitrobenzene is solvent, preferably nitrobenzene.These solvents have higher boiling, and immobilized anti-of catalyst can be improved
It answers temperature, accelerate immobilized rate, shorten the immobilized time.
Preferably, γ-the Al after dry2O3Weight ratio with alchlor is (4-6): 1.
Preferably, the mass volume ratio of alchlor and reaction dissolvent is 1:(8-10) (g/ml).
Preferably, γ-Al2O3Immobilized reaction temperature with alchlor is 80-120 DEG C.
Preferably, γ-Al2O3The immobilized reaction time with alchlor is 5-72h (preferably 7-9h).
As the preferable technical solution of the present invention, the preparation of mating type solid-carried catalyst is using following operation: by γ-Al2O3
It is placed in normal heptane, reflux dewatering, it is dry, obtain dry γ-Al2O3；According to γ-Al2O3Weight ratio with alchlor is
(3-10): 1, the two is placed in nitrobenzene, 5-72h is reacted under the conditions of 50~150 DEG C, gained reaction solution is that mating type is solid
Carried catalyst.
As the present invention more preferably technical solution, the preparation of mating type solid-carried catalyst is using following operation: by large aperture,
Granularity mesh number is the γ-Al of 40-80 mesh2O3It is placed in normal heptane, reflux dewatering 1-3h, in 100 DEG C of dryings after filtering, obtains drying
γ-Al2O3；According to γ-Al2O3It is (4-6) with the weight ratio of alchlor: 1, the two is placed in nitrobenzene, in 80~
7-9h is reacted under the conditions of 120 DEG C, gained reaction solution is the mating type solid-carried catalyst.
Preferably, step (1) carries out in nitro benzene solvent.Preferably, the volume mass of nitrobenzene and Cyanuric Chloride ratio
For 5:1 (ml/g).
Preferably, in step (1), Cyanuric Chloride, resorcinol, alchlor molar ratio be 1.0:(3.0-3.1):
(1.5-1.8)。
Preferably, the reaction temperature of step (1) is 20-120 DEG C.
Preferably, the reaction time of step (1) is 5-10h.
As preferably operation of the invention, the operation of step (1) are as follows: with molar ratio computing, according to Cyanuric Chloride: isophthalic two
Phenol: alchlor=1.0:(3.0-3.1): (1.5-1.8) feeds intake, the mating type that aforementioned any method is prepared
Solid-carried catalyst, Cyanuric Chloride, resorcinol are put into reaction vessel, in 20-120 DEG C of reaction 5-10h.
Method of the present invention further includes the steps that the reaction solution obtained to step (1) post-processes, and locates after described
Reason are as follows: filtering reacting liquid depressurizes prolapse solvent, obtains aqueous suspension to remove solid catalyst, through filtering, washing, drying,
Obtain compound of formula I crude product.
Method of the present invention further includes the steps that carrying out crystal refining, the crystallization to the compound of formula I crude product
The recrystallisation solvent of purification is dimethylformamide, it is highly preferred that the volumetric usage (mL) of recrystallisation solvent is the 5- of crude product weight (g)
10 times.
Preferably, the phase transfer catalyst is tetrabutylammonium bromide and polyethers -800 in step (2).More preferably, four fourth
The dosage of base ammonium bromide is the 1%~5% of compound of formula I, and the dosage of polyethers -800 is the 1%~5% of compound of formula I.
Preferably, the butyl halide is 1-chlorobutane or 1- bromobutane in step (2).
Preferably, compound of formula I and the molar ratio of butyl halide are 1:(4.0~4.2).
Preferably, the lye is NaOH, KOH, Na in step (2)2CO3、K2CO3Aqueous solution one kind, preferably make
With NaOH aqueous solution.
Preferably, the molar ratio of solute is 1:(3~5 in compound of formula I and lye).
Preferably, step (2) carries out in a solvent, one of the solvent selection toluene, dimethylbenzene.
Preferably, the reaction temperature of step (2) is 20-120 DEG C, preferably 70-80 DEG C.
As preferably operation of the invention, the operation of step (2) are as follows: with molar ratio computing, according to compound of formula I: halogenated fourth
Alkane: solute=1.0:(4.0-4.2 in lye): 4.0 feed intake, and compound of formula I, butyl halide, lye are put into reactor
In, the polyethers -800 of the tetrabutylammonium bromide and 1%~5% that account for compound of formula I weight 1~5% is added, is carried out in 70-80 DEG C
Etherification reaction.
It invention further preferably includes the step of post-processing to the reaction solution of step (2), the post-processing is to anti-
Answer liquid carry out liquid separation, wash, decolourize, crystallization, gained crystallized product be 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,
4- dibutoxy phenyl) -1,3,5- triazine.
As the preferable technical solution of the present invention, described method includes following steps:
(1) mating type solid-carried catalyst is prepared: by γ-Al2O3It is placed in normal heptane, reflux dewatering, through drying, obtains drying
γ-Al2O3；According to γ-Al2O3It is (3-10) with the weight ratio of alchlor: 1, the two is placed in nitrobenzene, in 50~
5-78h is reacted under the conditions of 150 DEG C, gained reaction solution is the mating type solid-carried catalyst；
(2) preparation of compounds of formula I: with molar ratio computing, according to Cyanuric Chloride: resorcinol: alchlor=1.0:(3.0-
3.1): (1.5-1.8) feeds intake, mating type solid-carried catalyst that aforementioned any method is prepared, Cyanuric Chloride,
Benzenediol is put into reaction vessel, in 20-120 DEG C, reacts 5-10h to get compound of formula I；
(3) preparation formula II compound: with molar ratio computing, according to compound of formula I: butyl halide: solute=1.0 in lye:
(4.0-4.2): 4.0 feed intake, and by compound of formula I, butyl halide, lye investment reactor, addition accounts for compound of formula I weight
1~5% tetrabutylammonium bromide and 1%~5% polyethers -800 are measured, in 70-80 DEG C of progress etherification reaction to get Formula II chemical combination
Object.
On the basis of common knowledge of the art, each preferred version of the invention can be combined with each other to get of the invention each
Preferred embodiment.
The present invention relates to the commercially available acquisition of raw materials and reagents.
The present invention achieves following good effect: (1) mating type solid-carried catalyst simplifies the separating technology of reaction mass,
Reaction mass is not required to the operation such as hydrolyst, washing, separation, it is only necessary to and filtering solid catalyst can reach separating effect,
Reduce the generation of a large amount of aluminium containing salt acid waste waters；(2) technique is simplified using Catalyzed By Phase-transfer Catalyst etherification reaction, be not necessarily to
Harsh anhydrous condition, compared with traditional Williamson etherification reaction, it is possible to reduce largely, be difficult to isolated complex salt
Waste.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Operation involved in embodiment
It unless otherwise specified, is this field customary technical operation.The embodiment of the present invention is only to schematically illustrate, those skilled in the art
It is appreciated that being adjusted in the parameter area that the present invention arranges to partial parameters according to operation identical with following embodiment
It is whole, the effect essentially identical with embodiment can be obtained.
The preparation of solid-carried catalyst reaction solution
(1) dry γ-Al2O3: to device blender, thermometer, water segregator, reflux condenser 500ml four-hole bottle in plus
Enter the γ-Al of large aperture, 40-80 mesh2O3100g, is added normal heptane solvent 300mL, and stirring is warming up to reflux temperature (about 100
DEG C), through water segregator reflux dewatering 2h, 100 DEG C of dry 2h are filtered afterwards, obtain dry γ-Al2O3。
(2) it prepares solid-carried catalyst reaction solution: feeding intake according to the inventory of table 1, it is anti-that solid-carried catalyst is made respectively
Answer liquid A, solid-carried catalyst reaction solution B and solid catalyst reaction liquid C.Operation are as follows: to device blender, thermometer, returned cold
Condenser, nitrogen conduit, hydrogen chloride absorption conduit 500mL four-hole bottle in be added it is dry after γ-Al2O3, nitrobenzene, start and stir
Addition alchlor is mixed, nitrogen is passed through, the hydrogen chloride gas of generation is absorbed in absorption plant by conduit, reacted at 80 DEG C
1h, after be warming up to 120 DEG C in 2h, keep the temperature 5h to get solid-carried catalyst reaction solution.
Table 1: the inventory of solid-carried catalyst reaction solution is prepared
Embodiment 1
(1) crude intermediate is prepared: to device blender, thermometer, reflux condenser, nitrogen conduit, hydrogen chloride absorption
Cyanuric Chloride 18.5g (0.1mol), resorcinol 33g (0.3mol), nitrobenzene are added in the 1000ml four-hole bottle of conduit
92.5mL is passed through after nitrogen gas stirring is warming up to material whole dissolution and is cooled to 20 DEG C, solid-carried catalyst reaction solution A, reaction is added
Heat release is gradually warmed up, and the hydrogen chloride gas of generation is absorbed through absorption plant, is to slowly warm up to 80 DEG C of heat preservations 2h, 100 DEG C of heat preservation 2h,
120 DEG C of heat preservation 6h (total 10h) are cooled to 80 DEG C, and filtering removal solid catalyst, nitrobenzene 20ml washes twice catalyst, washes
Liquid is incorporated into reaction solution；Vacuum distillation abjection nitrobenzene obtains aqueous pulpous state liquid, and filtering, hot water washing are three times, dry, obtain
Intermediate product 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5- triazine crude product 40g.
(2) crude intermediate refines: the crude product of step (1) being added in 500mL four-hole bottle, DMF 280mL, stirring is added
80 DEG C or more are warming up to, material all dissolves, slow cooling under environment temperature ,≤70 DEG C of precipitation crystalline solids, and water-bath is cooled to
30 DEG C, 2h is kept the temperature, filtering, DMF washing are secondary, obtain yellow crystalline solid and obtain 29.5g intermediate product 2,4,6- tri- after dry
(2,4- dihydroxy phenyl) -1,3,5-triazines, yield 72.84% (in terms of Cyanuric Chloride), purity (HPLC) >=99%, fusing point >
300℃。
(3) prepare target product: to device blender, thermometer, reflux condenser, nitrogen conduit 500ml four-hole bottle
Middle (2,4- the dihydroxy phenyl) -1,3,5- triazine of intermediate product 2,4,6- tri- 20.3g being added after step (2) purification
(0.05mol), toluene 60.9ml, stirring are warming up to 50 DEG C of materials and all dissolve, and are passed through nitrogen, tetrabutylammonium bromide is added
0.203g, -800 1.015g of polyethers are stirred as 20% sodium hydroxide solution of 40g (0.2mol) is added after homogeneous liquid, are warming up to
70 DEG C, start that 1-chlorobutane 18.5g (0.2mol) is added dropwise, 1h is added dropwise, in 74-76 DEG C of insulation reaction, the tracking of period HPLC
It detects, stops reaction when material composition no longer changes after 8h.Liquid separation is stood, 50-60 DEG C of washing is secondary, removes toluene, must be concentrated
Liquid.30mL toluene is added into concentrate at 90-100 DEG C and is cooled to≤70 DEG C of addition methanol 60mL at dissolved clarification transparent liquid, drops
Temperature to≤40 DEG C of solid materials are precipitated, and cold bath is cooled to≤20 DEG C, keeps the temperature 2h.Filtering, methanol washing three times, it is dry, obtain
Purpose product 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- Dibutoxy Benzene of yellow or slight yellow powdery solid
Base) -1,3,5-triazines, weight 22.1g, yield 70.3% (with intermediate), purity (HPLC) 98.1%, fusing point 98.1-
99.1℃。
Embodiment 2
(1) crude intermediate is prepared: to device blender, thermometer, reflux condenser, nitrogen conduit, hydrogen chloride absorption
Cyanuric Chloride 18.5g (0.1mol), resorcinol 34.1g (0.31mol), nitrobenzene are added in the 1000ml four-hole bottle of conduit
92.5mL is passed through after nitrogen gas stirring is warming up to material whole dissolution and is cooled to 20 DEG C, solid-carried catalyst reaction liquid C, reaction is added
Heat release is gradually warmed up, and the hydrogen chloride gas of generation is absorbed through absorption plant, is to slowly warm up to 100 DEG C of heat preservation 5h, is cooled to 80 DEG C,
Filtering removal solid catalyst, nitrobenzene 20ml*2 are washed twice, and washing lotion is incorporated into reaction solution；Vacuum distillation abjection nitro
Benzene obtains aqueous pulpous state liquid, and filtering, hot water washing are three times, dry, obtain intermediate product 2,4,6- tri- (2,4- dihydroxy phenyl)-
1,3,5- triazine crude product 40g.
(2) crude intermediate refines: the crude product that step (1) is obtained is added in 500mL four-hole bottle, and DMF 320mL is added,
Stirring is warming up to 80 DEG C or more, and material all dissolves, slow cooling under environment temperature ,≤70 DEG C of precipitation crystalline solids, water-bath drop
Temperature keeps the temperature 2h to 30 DEG C, and filtering, DMF washing are secondary, obtains yellow crystalline solid and obtains 33.2g intermediate product 2 after dry,
4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines, yield 81.98% (in terms of Cyanuric Chloride), purity (HPLC) >=99%,
300 DEG C of fusing point ﹥.
(3) prepare target product: to device blender, thermometer, reflux condenser, nitrogen conduit 500mL four-hole bottle
Middle (2,4- the dihydroxy phenyl) -1,3,5- triazine of intermediate product 2,4,6- tri- 20.3g being added after step (2) purification
(0.05mol), toluene 101.5mL, stirring are warming up to 50 DEG C of materials and all dissolve, and are passed through nitrogen, tetrabutylammonium bromide is added
1.015g, -800 0.203g of polyethers are stirred as 20% sodium hydroxide solution of 40g (0.2mol) is added after homogeneous liquid, are warming up to
70 DEG C, start dropwise addition 1-chlorobutane 19.43g (0.21mol) 1h and be added dropwise, in 74-76 DEG C of insulation reaction, the tracking of period HPLC
It detects, stopping reaction when material composition no longer changes after 6h, standing liquid separation, 50-60 DEG C of washing is secondary.Toluene after removing washing
Toluene in reaction solution, obtains concentrate.Toluene 30mL is added into dissolved clarification transparent liquid into concentrate at 90-100 DEG C, be cooled to≤
70 DEG C of addition methanol 60ml are cooled to≤40 DEG C of solid materials and are precipitated, and cold bath is cooled to≤20 DEG C, keeps the temperature 2h.Filtering, methanol
Washing three times, it is dry, obtain the purpose product 2 of yellow or slight yellow powdery solid, 4- bis- (2- hydroxyl -4- butoxy phenyl) -
6- (2,4- dibutoxy phenyl) -1,3,5-triazines, weight 25.2g, yield 80.13% (with intermediate), purity (HPLC)
98.6%, 98.5-99.4 DEG C of fusing point.
Embodiment 3
(1) crude intermediate is prepared: to device blender, thermometer, reflux condenser, nitrogen conduit, hydrogen chloride absorption
Cyanuric Chloride 18.5g (0.1mol), resorcinol 33.5g (0.3045mol), nitrobenzene are added in the 1000ml four-hole bottle of conduit
92.5mL is passed through after nitrogen gas stirring is warming up to material whole dissolution and is cooled to 20 DEG C, solid-carried catalyst reaction solution B, reaction is added
Heat release is gradually warmed up, and the hydrogen chloride gas of generation is absorbed through absorption plant, is to slowly warm up to 80 DEG C of heat preservations 2h, 100 DEG C of heat preservation 1h,
110 DEG C of heat preservation 5h (total 8h) are cooled to 80 DEG C, and filtering removal solid catalyst, nitrobenzene 20ml*2 is washed twice, and washing lotion merges
Into reaction solution；Vacuum distillation abjection nitrobenzene obtains aqueous pulpous state liquid, and filtering, hot water washing are three times, dry, obtain intermediate production
Object 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5- triazine crude product 41g.
(2) crude intermediate refines: the crude product that step (1) is obtained is added in 500mL four-hole bottle, and DMF 300ml is added,
Stirring is warming up to 80 DEG C or more, and material all dissolves, slow cooling under environment temperature ,≤70 DEG C of precipitation crystalline solids, water-bath drop
Temperature keeps the temperature 2h to 30 DEG C, and filtering, DMF washing are secondary, obtains yellow crystalline solid and obtains 30.6g intermediate product 2 after dry,
4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines, yield 75.56% (in terms of Cyanuric Chloride), purity (HPLC) >=99%,
300 DEG C of fusing point ﹥.
(3) prepare target product: to device blender, thermometer, reflux condenser, nitrogen conduit 500mL four-hole bottle
Middle (2,4- the dihydroxy phenyl) -1,3,5- triazine of intermediate product 2,4,6- tri- 20.3g being added after step (2) purification
(0.05mol), dimethylbenzene 80mL, stirring are warming up to 50 DEG C of materials and all dissolve, and are passed through nitrogen, tetrabutylammonium bromide is added
0.6g, -800 0.5g of polyethers stir as 20% sodium hydroxide solution of 40g (0.2mol) is added after homogeneous liquid, are warming up to 70 DEG C,
Start dropwise addition 1-chlorobutane 19g (0.205mol) 1h to be added dropwise, in 78-80 DEG C of insulation reaction, period HPLC tracing detection, 7h
Stop reaction when material composition no longer changes afterwards, stand liquid separation, 50-60 DEG C of washing is secondary.Toluene reaction solution after removing washing
In toluene, obtain concentrate.Toluene 30ml is added into dissolved clarification transparent liquid into concentrate at 90-100 DEG C, is cooled to≤70 DEG C and adds
Enter methanol 60ml, be cooled to≤40 DEG C of solid materials and be precipitated, cold bath is cooled to≤20 DEG C, keeps the temperature 2 hours.Filtering, methanol are washed
Wash three times, it is dry, obtain the purpose product 2 of yellow or slight yellow powdery solid, 4- bis- (2- hydroxyl -4- butoxy phenyl) -6-
(2,4- dibutoxy phenyl) -1,3,5-triazines, 24.1 grams of weight, yield 76.63% (with intermediate), purity (HPLC)
98.4%, 98.2-99 DEG C of fusing point.
Embodiment 4
According to intermediate product 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines of any acquisition of embodiment 1-3, use
In 1- bromobutane etherification reaction.
To device blender, thermometer, reflux condenser, nitrogen conduit 500ml four-hole bottle in be added purification after in
Between 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines 20.3g (0.05mol) of product, toluene 60.9ml, stirring is warming up to
50 DEG C of materials all dissolve, and are passed through nitrogen, and tetrabutylammonium bromide 0.203g, -800 1.015g of polyethers is added, stirs as homogeneous liquid
40g20% sodium hydroxide solution (0.2mol) is added afterwards, is warming up to 70 DEG C, starts that 1- bromobutane 27.4g (0.2mol) 1h is added dropwise
It is added dropwise, in 76-78 DEG C of insulation reaction, period HPLC tracing detection stops reaction when material composition no longer changes after 8h, quiet
Liquid separation is set, 50-60 DEG C of washing is secondary.The toluene in toluene reaction solution after removing washing, obtains concentrate.At 90-100 DEG C to dense
Toluene 30ml is added in contracting liquid into dissolved clarification transparent liquid, is cooled to≤70 DEG C of addition methanol 60ml, is cooled to≤40 DEG C of solid materials
It is precipitated, cold bath is cooled to≤20 DEG C, keeps the temperature 2 hours.Filtering, methanol washing three times, it is dry, obtain yellow or slight yellow powdery
The purpose product 2 of solid, 4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- dibutoxy phenyl) -1,3,5-triazines, weight
23.1 grams of amount, yield 73.45% (with intermediate), purity (HPLC) 98.2%, 98.1-98.9 DEG C of fusing point.
Embodiment 5
According to intermediate product 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines of any acquisition of embodiment 1-3, use
In 1- bromobutane etherification reaction.
To device blender, thermometer, reflux condenser, nitrogen conduit 500ml four-hole bottle in be added purification after in
Between product 2,4,6- tri- (2,4- dihydroxy phenyl) 20.3 grams of -1,3,5-triazines (0.05mol), toluene 101.5ml, stirring heating
It is all dissolved to 50 DEG C of materials, is passed through nitrogen, tetrabutylammonium bromide 1.015g, -800 0.203g of polyethers is added, it is homogeneous for stirring
20% sodium hydroxide solution of 40g (0.2mol) is added after liquid, is warming up to 70 DEG C, starts that 1- bromobutane 28.8g is added dropwise
(0.21mol) 1h is added dropwise, in 78-80 DEG C of insulation reaction, period HPLC tracing detection, when material composition no longer changes after 6h
Stop reaction, stand liquid separation, 50-60 DEG C of washing is secondary.The toluene in toluene reaction solution after removing washing, obtains concentrate.?
90-100 DEG C toluene 30ml is added into concentrate into dissolved clarification transparent liquid, is cooled to≤70 DEG C of addition methanol 60ml, be cooled to≤
40 DEG C of solid materials are precipitated, and cold bath is cooled to≤20 DEG C, keep the temperature 2h.Filtering, methanol washing three times, it is dry, obtain yellow or
(2- hydroxyl -4- the butoxy phenyl) -6- of purpose product 2,4- bis- (2,4- dibutoxy phenyl) -1,3 of slight yellow powdery solid,
5- triazine, 26.2 grams of weight, yield 83.31% (with intermediate), purity (HPLC) 98.4%, 98.3-99.1 DEG C of fusing point.
Comparative experiments example
To device blender, thermometer, reflux condenser, nitrogen conduit, hydrogen chloride absorption conduit 1000ml four-hole bottle
Middle addition Cyanuric Chloride 18.5g (0.1mol), resorcinol 33g (0.3mol), nitrobenzene 200ml are passed through nitrogen gas stirring heating
20 DEG C are cooled to after to material all dissolution, is added aluminum trichloride (anhydrous) 20g (0.15mol), exothermic heat of reaction is gradually warmed up, and is generated
Hydrogen chloride gas absorbed through absorption plant, be to slowly warm up to 95 DEG C of heat preservation 6h, reaction was completed.Reaction solution is poured into ice under stirring
In 2.0% dilute hydrochloric acid of 500g of water-bath cooling, it is lower than 20 DEG C of stirring 2h, is warming up to 40 DEG C or more after the dilution of 5000g water, stands
Liquid separation, 5000g water repeat washing twice.Obtain the nitrobenzene solution containing a small amount of water.
In vacuum distillation apparatus, 130-170 DEG C of temperature, pressure 0.06-0.09MPa (gauge pressure) recycles nitrobenzene 220ml.
Be cooled to 90 DEG C hereinafter, plus water 200g, at 80-100 DEG C of temperature, the distillation of pressure 0.05-0.07MPa (gauge pressure) reduced steam is de-
Remaining nitrobenzene out.Aqueous pulpous state liquid is obtained, filtering, hot water washing are secondary, obtain 2,4,6- tri- (2,4- dihydroxy of intermediate product
Phenyl) -1,3,5-triazines crude product, weight 40g after drying.
Intermediate product 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5- triazine crude product after being dried is added
In 500mL four-hole bottle, DMF 300ml is added, stirring is warming up to 80 DEG C or more, and material all dissolves, and slowly drops under environment temperature
Temperature ,≤70 DEG C of precipitation crystalline solids, water-bath are cooled to 30 DEG C, keep the temperature 2h, and filtering, DMF washing are secondary, and it is solid to obtain yellow crystal
Body after dry, obtains 30.4g intermediate product 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines, yield 75.06% (with
Cyanuric Chloride meter), purity (HPLC) >=99%, 300 DEG C of fusing point ﹥.
To device blender, thermometer, reflux condenser, nitrogen conduit 500ml four-hole bottle in be added purification after in
Between 2,4,6- tri- (2,4- dihydroxy phenyl) -1,3,5-triazines 20.3g (0.05mol) of product, DMF150ml, stirring be warming up to 80
DEG C material all dissolves, and is passed through nitrogen, is added solid water-free potassium carbonate 27.6g (0.2mol), at 80 DEG C, starts that 1- bromine fourth is added dropwise
Alkane 27.4g (0.2mol) 1h is added dropwise, and in 100-110 DEG C of insulation reaction, period HPLC tracing detection, material composition is not after 6h
Stop reaction when changing again, filtering, DMF washing three times, remove waste solid salt, acetic acid is neutralized to after filtrate, cleaning solution merging
PH value display is neutral, and decompression deviates from and recycles whole DMF.
After addition toluene 100ml dissolves concentrate, 50-60 DEG C of 50g washing is secondary.Toluene reaction solution after washing, adds
Enter active carbon 1.5g in 80-90 DEG C of stirring 1h, filters carbon removal, a small amount of toluene washing is secondary.Obtained toluene solution normal pressure, decompression
(0.05-0.07MPa) (gauge pressure), 110-140 DEG C of temperature is deviate from and recycles toluene.
Toluene 30ml is added into dissolved clarification transparent liquid into concentrate at 90-100 DEG C, is cooled to≤70 DEG C of addition methanol
60ml is cooled to≤40 DEG C of solid materials and is precipitated, and cold bath is cooled to≤20 DEG C, keeps the temperature 2 hours.Filtering, methanol washing three times,
It is dry, obtain the purpose product 2 of yellow or slight yellow powdery solid, 4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- bis-
Butoxy phenyl) -1,3,5-triazines, weight 24.2g, yield 76.95% (with intermediate), purity (HPLC) 97.6%, melt
97.9-98.8 DEG C of point.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of preparation side of 2,4- bis- (2- hydroxyl -4- butoxy phenyl) -6- (2,4- dibutoxy phenyl) -1,3,5- triazine
Method, it is characterised in that: reaction equation is as follows,
Include the following steps:
(1) Cyanuric Chloride and resorcinol have the γ-Al of alchlor in load2O3Under the action of mating type solid-carried catalyst, instead
Compound of formula I should be generated；
(2) compound of formula I and butyl halide react production II compound under the action of phase transfer catalyst and lye.
2. according to the method described in claim 1, it is characterized by: the mating type solid-carried catalyst is prepared with the following method
It forms: removing γ-Al2O3In moisture, obtain dry γ-Al2O3；γ-Al after drying2O3With alchlor according to (3-
10): 1 weight ratio carries out immobilized reaction at 50~150 DEG C, and gained reaction solution is mating type solid-carried catalyst.
3. method according to claim 1 or 2, it is characterised in that: γ-Al2O3Using macropore or mesoporous class γ-Al2O3,
Granularity mesh number is in 20-100 mesh.
4. according to the method described in claim 2, it is characterized by: dry γ-Al2O3Operation are as follows: by γ-Al2O3It is placed in alkane
In hydrocarbon, aromatic hydrocarbon solvent, reflux dewatering；The alkane, aromatic hydrocarbon solvent are in hexamethylene, normal heptane, toluene, dimethylbenzene
It is a kind of.
5. method according to claim 1-3, it is characterised in that: γ-Al2O3With reacting with four for alchlor
One of chlorination carbon, chloroform, nitrobenzene are solvent.
6. according to the method described in claim 1, it is characterized by: in step (1), Cyanuric Chloride, resorcinol, alchlor
Molar ratio be 1.0:(3.0-3.1): (1.5-1.8).
7. method according to claim 1-5, it is characterised in that: the reaction temperature of step (1) is 20-120 DEG C.
8. according to the method described in claim 1, it is characterized by: the phase transfer catalyst is tetrabutyl bromine in step (2)
Change ammonium and polyethers -800；Preferably, the dosage of tetrabutylammonium bromide is the 1%~5% of compound of formula I, the dosage of polyethers -800
It is the 1%~5% of compound of formula I.
9. according to the method described in claim 1, it is characterized by: in step (2), mole of compound of formula I and butyl halide
Than for 1:(4.0~4.2)；And/or the lye is NaOH, KOH, Na2CO3、K2CO3Aqueous solution one kind；And/or step
Suddenly (2) carry out in a solvent, one of the solvent selection toluene, dimethylbenzene；And/or the reaction temperature of step (2) is
20-120℃。
10. the method according to claim 1, wherein including the following steps:
(1) mating type solid-carried catalyst is prepared: by γ-Al2O3It is placed in normal heptane, reflux dewatering, through drying, obtains dry γ-
Al2O3；According to γ-Al2O3Weight ratio with alchlor is (3-10): 1, the two is placed in nitrobenzene, in 50~150 DEG C
Under the conditions of react 5-78h, gained reaction solution is the mating type solid-carried catalyst；
(2) preparation of compounds of formula I: with molar ratio computing, according to Cyanuric Chloride: resorcinol: alchlor=1.0:(3.0-
3.1): (1.5-1.8) feeds intake, mating type solid-carried catalyst that aforementioned any method is prepared, Cyanuric Chloride,
Benzenediol is put into reaction vessel, in 20-120 DEG C, reacts 5-10h to get compound of formula I；
(3) preparation formula II compound: with molar ratio computing, according to compound of formula I: butyl halide: solute=1.0:(4.0- in lye
4.2): 4.0 feed intake, will compound of formula I, butyl halide, lye investment reactor in, addition account for compound of formula I weight 1~
5% tetrabutylammonium bromide and 1%~5% polyethers -800, in 70-80 DEG C of progress etherification reaction to get Formula II compound.
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