CN110372620A - A kind of preparation method of ultraviolet absorbing agent UV-1600 intermediate - Google Patents
A kind of preparation method of ultraviolet absorbing agent UV-1600 intermediate Download PDFInfo
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- 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
- C07D251/22—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 two ring carbon atoms
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Abstract
The present invention provides a kind of preparation method of ultraviolet absorbing agent UV-1600 intermediate, especially ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3, the preparation method of 5- triazine, for this method using Cyanuric Chloride and biphenyl as raw material, alchlor is catalyst, HCl gas is co-catalyst, Friedel-Crafts alkylation is carried out, 2,4- bis- (4- xenyl) -6- chloro- 1 is obtained, 3,5- triazine, the latter carry out friedel-craft with resorcinol again and react, and obtain target product.The preparation method of ultraviolet absorbing agent UV-1600 intermediate of the present invention, using HCl gas as co-catalyst, the catalytic activity of catalyst system is greatly improved, the yield of product can be greatly improved, provides a new process route for the industrialized production of UV-1600.
Description
Technical field
The invention belongs to high molecular material function additive fields, more particularly, in a kind of ultraviolet absorbing agent UV-1600
The preparation method of mesosome 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,5- triazine.
Background technique
It is ultraviolet compared to the widest benzotriazole and benzophenone ultraviolet absorbent, triazines applied at present
Light absorbers are newer a kind of products, and there is this kind of product high efficiency (additive amount is few and effect is good), low color (to make its application
Face is wider), high processing temperature, preferable compatibility (good dispersion, and molecule itself is easy to be chemically modified) and excellent
The advantages that broad spectrum activity (molar absorption coefficient with higher in the ultraviolet light range of UVA and UVB), the above advantage makes
Triazine-based ultraviolet absorbent becomes the developing direction of ultraviolet absorbing agent.Its basic structure is as follows:
Wherein, R1, R2, R3, R4Mostly alkyl or H, such as UV-1164, UV-1577, R5Mostly alkyl or hydroxy ether etc. are such as UV-
400, UV-405.
UV-1600 (Tinuvin1600, No. CAS: 204583-39-1), structure is as follows, is the newest research and development of German BASF
The extraordinary triazines effective UV light absorbers of sale are released and commercially produced, there is extremely low volatility, very high ultraviolet
Line absorption efficiency, with the good compatibility of various polymeric substrates, do not influence it is transparent, do not influence to colour, and required additive amount ratio
Traditional ultraviolet absorbing agent is lower.Therefore, UV-1600 is known as " being entire industry tree in terms of durability, long-term weatherability
Found a new benchmark ", performance has surmounted current ultraviolet absorbing agent most of on the market.
Even to this day, still seldom for the report of the synthesis technology of UV-1600, main difficulty is wherein mesosome 2,
4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,5-triazines preparation, traditional triazine-based ultraviolet absorbent,
As UV-1164, UV-400, UV-405 (three's intermediate having the same) and UV-460, their intermediate all use friedel-craft
Alkylation process, industrial production exploitativeness is high, but in the intermediate of UV-1600, the substituent group position biphenyl on triazine ring 2,4,
Reactivity ratio's meta-xylene of biphenyl and Cyanuric Chloride is far short of what is expected, and without selectivity, is difficult through control biphenyl and trimerization
Therefore the molar ratio of chlorine cyanogen is received very big to control the quantity of biphenyl substituent group on triazine ring using friedel-craft alkylation process
Limitation.Currently, the preparation of UV-1600 intermediate, is mainly the following method:
(1) Grignard Reagent method, reaction route are as follows:
What document report was more at present is still Grignard Reagent method, but this technique requires THF water content very high, processing
Difficulty is high, and flash-point is very low (- 17 DEG C), and than relatively hazardous when production, therefore, the preparation of this technique first two steps, Grignard Reagent is passed
Family name's reagent is reacted with Cyanuric Chloride, is difficult to industrialized production substantially.In addition, Grignard Reagent is very active, hardly possible storage, and water,
Carbon dioxide can react, and react quickly, so being likely to cause the drop of material effective content in the process to feed intake
It is low, measure it accurately relatively difficult.Specific document is visible: Jingxi Huagong, 28 (3), 284-288；2011, WO
2011067282 etc..
(2) palladium chtalyst method, route are as follows:
The selectivity of palladium chtalyst method is good, and synthesis condition is also relatively mild, but maximum drawback be exactly palladium catalyst compared to
Conventional catalyst wants expensive very much (first step reaction palladium catalyst used is more expensive), although each reaction aequum is few
(3mol%), but its molecular weight is larger, causing actually to feed intake, quality is many, and cost is too high.Similar reaction can refer to patent KR
2016132724。
(3) it is cyclized method, route is as follows:
This method and step is more, and triazine ring is by obtaining after two intermediate reactions cyclization, and intermediate is all
Individual process route is needed to go to synthesize, and some raw materials, somewhat expensive such as 4- cresotinic acid amide, comprehensive each step, this
Not only long but also cost is very high for route, and industrial production exploitativeness is not high.The method can refer to patent US6255438.
Currently, UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,5-triazines work
The problems such as skill route, there is high risks, Gao Chengben, finds the industry that danger coefficient is low, operation difficulty is small, at low cost
It is very necessary to change route.
Summary of the invention
In view of this, the present invention is directed to propose a kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl)-
6- (2,4- dihydroxy) phenyl -1,3,5-triazines preparation method, including make Cyanuric Chloride and biphenyl in catalyst alchlor
In the presence of co-catalyst hydrogen chloride gas, the step of carrying out Friedel-Crafts alkylation, generate type I compound；
Inventor has found by many experiments, and in the preparation process of compound of formula I, HCl gas is not added, reacts almost very
Hardly possible carries out, and using alchlor as catalyst, HCl gas is co-catalyst, can greatly improve the catalytic activity of catalyst system, significantly
Improve reaction rate, reaction depth.
The dosage present invention of HCl gas is not specially limited, and is kept excessive, is continually fed into HCl gas in reaction process.?
In a kind of specific embodiment, under normal temperature and pressure, can control the flow of HCl gas is 20-60cm3/ min (preferably 30-
40cm3/min)。
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,
The preparation method of 5- triazine, it is characterised in that: including making Cyanuric Chloride and biphenyl in catalyst alchlor and co-catalyst chlorine
In the presence of changing hydrogen, the step of carrying out Friedel-Crafts alkylation, generate type I compound；
As a currently preferred embodiment, the preparation of type I compound carries out in a solvent, and the solvent is selected from
One or more of chlorobenzene, o-dichlorohenzene, nitrobenzene.
As a currently preferred embodiment, in the preparation process of type I compound, biphenyl is first dissolved in solvent
It is interior, then be added dropwise into the solution dissolved with Cyanuric Chloride.
As the preferred embodiment of the present invention, in the preparation process of type I compound, the quality of biphenyl and solvent
Than for 1:(2-5).
As a currently preferred embodiment, the preparation of compound of formula I carries out at a temperature of 0-30 DEG C.
As the preferred embodiment of the present invention, in the preparation process of compound of formula I, Cyanuric Chloride, biphenyl and
The molar ratio of alchlor is 1:(2-2.5): (1.5-3).
As a currently preferred embodiment, in the preparation process of compound of formula I, by Cyanuric Chloride and tri-chlorination
Aluminium is dissolved in solvent, is cooled to 0-3 DEG C under inert gas shielding；Hydrogen chloride gas is passed through to system and is added dropwise containing the molten of biphenyl
Liquid, maintenance system temperature is 0-3 DEG C during dropwise addition；After completion of dropwise addition, be warming up to 15-30 DEG C the reaction was continued to get.Here
Solvent refers to one or more of chlorobenzene above-mentioned, o-dichlorohenzene, nitrobenzene.Inert gas is preferably nitrogen.
Preferably, the solution containing biphenyl refers to that biphenyl is dissolved in the formation of solvent in the preparation process of above-mentioned compound of formula I
Solution.
Preferably, the time for adding of the solution containing biphenyl is 1-4h.
Preferably, being passed through hydrogen chloride gas in the preparation process of above-mentioned compound of formula I to system and dripping containing biphenyl
Being warming up to 15-30 DEG C again after solution, after prior to 0-3 DEG C reaction a period of time, the reaction was continued.Wherein, described " a period of time " can
Think 0.5-1.5h, preferably 1h.More preferably, it is reacted after heating in 30 DEG C.
Preferably, the preparation process of above-mentioned compound of formula I, further includes that the reaction liquid that will heat up after reacting is post-processed
Process.The post-processing is first mutually separated reaction liquid, is carried out crystallization treatment to organic phase later, can be obtained type I compound.
Specifically: the method that reaction liquid is mutually separated are as follows: reaction solution is poured into diluted acid, water phase is separated, it is right
Organic phase carries out crystallization treatment.
Crystallization as the preferred embodiment of the present invention, during the preparation post-reaction treatment of compound of formula I
Solvent is at least one of methanol, ethyl alcohol, propyl alcohol, isopropanol.
As a currently preferred embodiment, which further includes making after the completion of type I compound preparation
The step of type I compound is reacted under the action of catalyst alchlor with resorcinol, II compound of production；
More specifically, II compound of formula preparation the following steps are included:
1) type I compound of formula ratio and alchlor are dissolved in solvent, react a period of time after stirring heating；
2) recycling design after filtering drying, solid is refined using recrystallisation solvent, obtains II compound of formula.
Preferably, the type I compound of formula ratio and alchlor are added in another reaction vessel in step 1), then
The solvent of formula ratio is added, stirring is warming up to 85-100 DEG C；Preferably, stirring is warming up to 90-95 DEG C herein.
Preferably, the reaction of step 1) carries out in a solvent, the solvent and the solvent phase used when preparation of compounds of formula I
Together.
Preferably, in step 1), reaction time 2-4h, preferably 3h.
Preferably, in step 2), the method for recycling design are as follows: reaction solution is poured into diluted acid, is heated up, steam distillation,
Recycling design.
As a currently preferred embodiment, in the preparation process of II compound of formula, type I compound, isophthalic two
Phenol, alchlor three molar ratio be 1:(1-1.1): (1-1.2).
As a currently preferred embodiment, during the preparation post-reaction treatment of II compound of formula, Ye Jibu
It is rapid 2) in, with one or more of toluene, dimethylbenzene, chlorobenzene be Formula II compound recrystallisation solvent.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined with each other each preferably to get the present invention
Example.
The present invention relates to the commercially available acquisition of raw materials and reagents.
Compared with the existing technology, preparation method of the invention, has the advantage that
(1) synthesis of intermediate 2,4- bis- (4- xenyl) -6- chloro-1,3,5-triazines uses friedel-craft alkylation process, avoids
The risk of Grignard Reagent method and higher operation difficulty, the cost of catalyst is much lower compared with palladium catalyst, and process route
Short, exploitativeness is high, is suitble to industrialized production.
(2) subtractive process of the chloro- 1,3,5- triazine of intermediate 2,4- bis- (4- xenyl) -6- is simple, easy.
(3) post-processing and essence of target product 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,5- triazine
Process processed is simple, efficient.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
Comparative example
A kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,
The preparation method of 5- triazine, specific as follows:
Step 1: 27.6g (0.15mol) Cyanuric Chloride, 40.0g (0.30mol) alchlor are weighed, is added sequentially to
It is rear to be added 250ml chlorobenzene in 1000ml four-hole bottle, nitrogen protection, after four-hole bottle is placed in ice-water bath, be cooled to 0-3 DEG C；Afterwards
Start the chlorobenzene solution (biphenyl 46.26g, 0.3mol are dissolved in 150ml chlorobenzene) that biphenyl is added dropwise, time for adding 1h, dropping temperature
Always it is 0-3 DEG C, reacts 1h after dripping at a temperature of this, move back ice-water bath, be warming up to 30 DEG C, react 3h at T=30 DEG C；
Stop reaction, after reaction solution is poured at 30 DEG C in the dilute hydrochloric acid of 100ml 3%, separate water phase, organic phase is directly in 300ml
White solid is precipitated in alcohol crystallization in methanol, filters, obtains white solid 5.5-6g, yield about 10%, HPLC purity 94-95%.
Step 2: 15g (35.7mmol) 2,4- bis- (4- xenyl) -6- chloro-1,3,5-triazines, 5.3g are weighed
(39.3mmol) alchlor and 3.93g (35.7mmol) resorcinol, are added in 250ml four-hole bottle, rear that 75ml chlorine is added
Benzene, stirring are warming up to 90-95 DEG C, stop reaction after reacting 3h；System is poured into the dilute hydrochloric acid of 100ml 3%, is heated up, water
Chlorobenzene is recycled in steam distillation, filters, and drying, solid refines with toluene, obtains target product yellow solid 13.8g, yield 78%,
HPLC purity 98%, MS (MOLDI TOF) m/z (C33H23N3O2)[M]+=493.57, measured value 495.29.
Embodiment 1
A kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,
The preparation method of 5- triazine, specific as follows:
Step 1: 27.6g (0.15mol) Cyanuric Chloride, 40.0g (0.30mol) alchlor are weighed, is added sequentially to
It is rear to be added 250ml chlorobenzene in 1000ml four-hole bottle, nitrogen protection, after four-hole bottle is placed in ice-water bath, be cooled to 0-3 DEG C；Afterwards
Start to be passed through HCl gas and starting into system the chlorobenzene solution of biphenyl to be added dropwise (biphenyl 46.26g, 0.3mol are dissolved in 150ml chlorine
Benzene), time for adding 1h, dropping temperature is 0-3 DEG C always, reacts 1h after dripping at a temperature of this, moves back ice-water bath, is risen
Temperature to 30 DEG C, gradually deepen by reaction process system color, has ultimately become reddish black, has reacted 3h at T=30 DEG C, rear to stop leading to
HCl gas；Stop reaction, after reaction solution is poured at 30 DEG C in the dilute hydrochloric acid of 100ml 3wt%, separate water phase, organic phase
White solid is precipitated in the alcohol crystallization directly in 300ml methanol, filters, obtains white solid 35.5-36g, yield 58-60%,
HPLC purity 94-95%, 2,4,6- tri- (4- xenyl) -1,3,5-triazines containing 3.5-4.0wt%.
Step 2: 15g (35.7mmol) 2,4- bis- (4- xenyl) -6- chloro-1,3,5-triazines, 5.3g are weighed
(39.3mmol) alchlor and 3.93g (35.7mmol) resorcinol, are added in 250ml four-hole bottle, rear that 75ml chlorine is added
Benzene, stirring are warming up to 90-95 DEG C, stop reaction after reacting 3h；System is poured into the dilute hydrochloric acid of 100ml 3wt%, is heated up,
Steam distillation recycles chlorobenzene, filters, and drying, solid is refined with toluene, obtains target product yellow solid 14.5g, yield
82%, HPLC purity 98%, MS (MOLDI TOF) m/z (C33H23N3O2)[M]+=493.57, measured value 495.29.
Embodiment 2
A kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,
The preparation method of 5- triazine, specific as follows:
Step 1: 27.6g (0.15mol) Cyanuric Chloride, 40.0g (0.30mol) alchlor are weighed, is added sequentially to
It is rear to be added 250ml chlorobenzene in 1000ml four-hole bottle, nitrogen protection, after four-hole bottle is placed in ice-water bath, be cooled to 0-3 DEG C；Afterwards
Start to be passed through into system HCl gas and starting be added dropwise biphenyl chlorobenzene solution (biphenyl 57.82g, 0.375mol is dissolved in
180ml chlorobenzene), time for adding 1h, dropping temperature is 0-3 DEG C always, reacts 1h after dripping at a temperature of this, moves back deicing
Water-bath is warming up to 15 DEG C, and reaction process system color is gradually deepened, and has ultimately become reddish black, has reacted 3h at T=15 DEG C, after
Stop logical HCl gas；Stop reaction, after reaction solution is poured at 15 DEG C in the dilute hydrochloric acid of 100ml 3wt%, separate water phase,
White solid is precipitated in organic phase alcohol crystallization directly in 300ml methanol, filters, obtains white solid 33g, yield 55%, HPLC
Purity 95.4%, 2,4,6- tri- (4- xenyl) -1,3,5-triazines containing 3.4wt%.
Step 2: 15g (35.7mmol) 2,4- bis- (4- xenyl) -6- chloro-1,3,5-triazines, 5.3g are weighed
(39.3mmol) alchlor and 3.93g (35.7mmol) resorcinol, are added in 250ml four-hole bottle, rear that 75ml chlorine is added
Benzene, stirring are warming up to 90-95 DEG C, stop reaction after reacting 3h；System is poured into the dilute hydrochloric acid of 100ml 3wt%, is heated up,
Steam distillation recycles chlorobenzene, filters, and drying, solid is refined with toluene, obtains target product yellow solid 14.5g, yield
82%, HPLC purity 98%.
Embodiment 3
A kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,
The preparation method of 5- triazine, specific as follows:
Step 1: 27.6g (0.15mol) Cyanuric Chloride, 40.0g (0.30mol) alchlor are weighed, is added sequentially to
It is rear to be added 250ml o-dichlorohenzene in 1000ml four-hole bottle, nitrogen protection, after four-hole bottle is placed in ice-water bath, be cooled to 0-3
℃；Start to be passed through into system afterwards HCl gas and starting be added dropwise biphenyl o-dichlorobenzene solution (biphenyl 50.88g, 0.33mol,
It is dissolved in 150ml o-dichlorohenzene), time for adding 1h, dropping temperature is 0-3 DEG C always, 1h is reacted after dripping at a temperature of this,
Ice-water bath is moved back, is warming up to 30 DEG C, reaction process system color is gradually deepened, and has ultimately become reddish black, anti-at T=30 DEG C
3h is answered, it is rear to stop logical HCl gas；Stop reaction, after reaction solution is poured at 30 DEG C in the dilute hydrochloric acid of 100ml 3wt%, point
White solid is precipitated in water phase out, organic phase alcohol crystallization directly in 300ml ethyl alcohol, filters, obtains white solid 34g, yield
53.9%, HPLC purity 94.4%, 2,4,6- tri- (4- xenyl) -1,3,5-triazines containing 5wt%.
Step 2: 15g (35.7mmol) 2,4- bis- (4- xenyl) -6- chloro-1,3,5-triazines, 5.3g are weighed
(39.3mmol) alchlor and 3.93g (35.7mmol) resorcinol, are added in 250ml four-hole bottle, rear that 75ml neighbour is added
Dichloro-benzenes, stirring are warming up to 90-95 DEG C, stop reaction after reacting 3h；System is poured into the dilute hydrochloric acid of 100ml 3wt%, is risen
Temperature, steam distillation recycle o-dichlorohenzene, filter, and drying, solid diformazan benzene refining obtains target product yellow solid 13g,
Yield 73.8%, HPLC purity 98%.
Embodiment 4
A kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,
The preparation method of 5- triazine, specific as follows:
Step 1: 27.6g (0.15mol) Cyanuric Chloride, 40.0g (0.30mol) alchlor are weighed, is added sequentially to
It is rear to be added 250ml nitrobenzene in 1000ml four-hole bottle, nitrogen protection, after four-hole bottle is placed in ice-water bath, be cooled to 0-3 DEG C；
Start to be passed through HCl gas and starting afterwards into system the nitrobenzene solution of biphenyl to be added dropwise (biphenyl 46.26g, 0.3mol, are dissolved in
150ml nitrobenzene), time for adding 1h, dropping temperature is 0-3 DEG C always, 1h is reacted after dripping at a temperature of this, after remove
Ice-water bath is warming up to 30 DEG C, and reaction process system color is gradually deepened, and has ultimately become reddish black, has reacted 3h at T=30 DEG C,
Stop logical HCl gas afterwards；Stop reaction, after reaction solution is poured at 30 DEG C in the dilute hydrochloric acid of 100ml 3wt%, separate water
White solid is precipitated in phase, organic phase alcohol crystallization directly in 300ml ethyl alcohol, filters, obtains white solid 35g, yield 54%,
HPLC purity 94.8%, 2,4,6- tri- (4- xenyl) -1,3,5-triazines containing 4.5wt%.
Step 2: 15g (35.7mmol) 2,4- bis- (4- xenyl) -6- chloro-1,3,5-triazines, 5.3g are weighed
(39.3mmol) alchlor and 3.93g (35.7mmol) resorcinol, are added in 250ml four-hole bottle, rear that 75ml nitre is added
Base benzene, stirring are warming up to 90-95 DEG C, stop reaction after reacting 3h；System is poured into the dilute hydrochloric acid of 100ml 3wt%, is risen
Temperature, steam distillation recycle nitrobenzene, filter, and drying, solid diformazan benzene refining obtains target product yellow solid 14g, receive
Rate 79.5%, HPLC purity 98%.
Embodiment 5
A kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,
The preparation method of 5- triazine, specific as follows:
Step 1: 27.6g (0.15mol) Cyanuric Chloride, 40.0g (0.30mol) alchlor are weighed, is added sequentially to
It is rear to be added 250ml chlorobenzene in 1000ml four-hole bottle, nitrogen protection, after four-hole bottle is placed in ice-water bath, be cooled to 0-3 DEG C；Afterwards
Start to be passed through HCl gas and starting into system the chlorobenzene solution of biphenyl to be added dropwise (biphenyl 46.26g, 0.3mol are dissolved in 150ml chlorine
Benzene), time for adding 1h, dropping temperature is 0-3 DEG C always, reacts 1h after dripping at a temperature of this, moves back ice-water bath, is risen
Temperature to 30 DEG C, gradually deepen by reaction process system color, has ultimately become reddish black, has reacted 3h at T=30 DEG C, rear to stop leading to
HCl gas；Stop reaction, after reaction solution is poured at 30 DEG C in the dilute hydrochloric acid of 100ml 3wt%, separate water phase, organic phase
White solid is precipitated in the alcohol crystallization directly in 300ml isopropanol, filters, obtains white solid 36g, yield 57.1%, HPLC is pure
Degree 95.5%, 2,4,6- tri- (4- xenyl) -1,3,5-triazines containing 4wt%.
Step 2: 15g (35.7mmol) 2,4- bis- (4- xenyl) -6- chloro-1,3,5-triazines, 5.3g are weighed
(39.3mmol) alchlor and 3.93g (35.7mmol) resorcinol, are added in 250ml four-hole bottle, rear that 75ml chlorine is added
Benzene, stirring are warming up to 90-95 DEG C, stop reaction after reacting 3h；System is poured into the dilute hydrochloric acid of 100ml 3wt%, is heated up,
Steam distillation recycles chlorobenzene, filters, and drying, solid diformazan benzene refining obtains target product yellow solid 14.5g, yield
82%, HPLC purity 98%.
It should be noted that " reaction process system color is gradually deepened, and red and black has been ultimately become in the above various embodiments
Color ", this is that alchlor and raw material form complex compound, and reddish black is the color of complex compound.It should also be noted that, above each
In embodiment, the flow that flow is converted under normal temperature and pressure that is passed through of HCl gas at reaction conditions is 20- in step 1
60cm3/min。
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 (10)
1. a kind of ultraviolet absorbing agent UV-1600 intermediate 2,4- bis- (4- xenyl) -6- (2,4- dihydroxy) phenyl -1,3,5-
The preparation method of triazine, it is characterised in that: including making Cyanuric Chloride and biphenyl in catalyst alchlor and co-catalyst chlorination
In the presence of hydrogen, the step of carrying out Friedel-Crafts alkylation, generate type I compound；
2. preparation method according to claim 1, it is characterised in that: the preparation of type I compound carries out in a solvent, described
Solvent is selected from one or more of chlorobenzene, o-dichlorohenzene, nitrobenzene；
Preferably, first biphenyl is dissolved in solvent, then is added dropwise into the solution dissolved with Cyanuric Chloride；
It is further preferred that the mass ratio of biphenyl and solvent is 1:(2-5).
3. preparation method according to claim 1 or 2, it is characterised in that: the preparation of compound of formula I is at a temperature of 0-30 DEG C
It carries out.
4. preparation method according to claim 3, it is characterised in that: Cyanuric Chloride and alchlor are dissolved in solvent,
0-3 DEG C is cooled under inert gas shielding；Hydrogen chloride gas is passed through to system and the solution containing biphenyl is added dropwise, and is tieed up during being added dropwise
Holding system temperature is 0-3 DEG C；After completion of dropwise addition, be warming up to 15-30 DEG C the reaction was continued to get.
5. preparation method according to claim 1-4, it is characterised in that: Cyanuric Chloride, biphenyl and alchlor
Molar ratio be 1:(2-2.5): (1.5-3).
6. preparation method according to claim 1-5, it is characterised in that: during post-reaction treatment, with methanol,
At least one of ethyl alcohol, propyl alcohol, isopropanol are the recrystallisation solvent of compound of formula I.
7. preparation method according to claim 1-6, it is characterised in that: further include making type I compound and isophthalic
The step of diphenol reacts under the action of catalyst alchlor, II compound of production；
8. preparation method according to claim 7, it is characterised in that: type I compound, resorcinol, alchlor three
Molar ratio be 1:(1-1.1): (1-1.2).
9. preparation method according to claim 7 or 8, it is characterised in that: the synthesis temperature of II compound of formula is 85-100
DEG C, preferably 90-95 DEG C.
10. according to the described in any item preparation methods of claim 7-9, it is characterised in that: during post-reaction treatment, with first
One or more of benzene, dimethylbenzene, chlorobenzene are the recrystallisation solvent of Formula II compound.
Priority Applications (2)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892548A (en) * | 2020-07-24 | 2020-11-06 | 利安隆（中卫）新材料有限公司 | Process for preparing 2,4, 6-tris (2-hydroxy-4-n-hexyloxyaryl) -1,3, 5-triazine and intermediates thereof |
| CN112028846A (en) * | 2020-09-28 | 2020-12-04 | 中昊(大连)化工研究设计院有限公司 | Method for preparing high-purity ultraviolet absorber intermediate |
| WO2021022731A1 (en) * | 2019-08-07 | 2021-02-11 | 天津利安隆新材料股份有限公司 | Method for preparing intermediate of ultraviolet light absorber uv-1600 |
| CN113087678A (en) * | 2021-03-31 | 2021-07-09 | 中昊(大连)化工研究设计院有限公司 | Synthetic method of ultraviolet absorbent UV-1600 |
| CN113214173A (en) * | 2021-04-27 | 2021-08-06 | 烟台新特路新材料科技有限公司 | Multifunctional triazine ultraviolet absorbent with thioether antioxidant structure and preparation method thereof |
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| CN115073388B (en) * | 2022-07-14 | 2023-03-03 | 四川沃肯精细化工有限公司 | Preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine |
| CN116178289A (en) * | 2022-12-26 | 2023-05-30 | 天津利安隆新材料股份有限公司 | Method for synthesizing triazine compound by etherification |
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| KR102044942B1 (en) * | 2016-05-02 | 2019-11-14 | 삼성에스디아이 주식회사 | Compound for organic optoelectric device and organic optoelectric device and display device |
| CN110372620B (en) * | 2019-08-07 | 2021-06-22 | 天津利安隆新材料股份有限公司 | Preparation method of ultraviolet absorbent UV-1600 intermediate |
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| CN1326447A (en) * | 1998-11-17 | 2001-12-12 | Cytec技术有限公司 | Process for preparing triazines using combination of lewis acids and reaction promoters |
| CN1774426A (en) * | 2003-03-24 | 2006-05-17 | 西巴特殊化学制品控股公司 | Symmetrical triazine derivatives |
| WO2011067282A1 (en) * | 2009-12-05 | 2011-06-09 | Bayer Materialscience Ag | Polycarbonate compositions with a phenolically substituted triazine derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021022731A1 (en) * | 2019-08-07 | 2021-02-11 | 天津利安隆新材料股份有限公司 | Method for preparing intermediate of ultraviolet light absorber uv-1600 |
| CN111892548A (en) * | 2020-07-24 | 2020-11-06 | 利安隆（中卫）新材料有限公司 | Process for preparing 2,4, 6-tris (2-hydroxy-4-n-hexyloxyaryl) -1,3, 5-triazine and intermediates thereof |
| CN111892548B (en) * | 2020-07-24 | 2023-12-01 | 利安隆（中卫）新材料有限公司 | Process for preparing 2,4, 6-tris (2-hydroxy 4-n-hexyloxyaryl) -1,3, 5-triazines and intermediates thereof |
| CN112028846A (en) * | 2020-09-28 | 2020-12-04 | 中昊(大连)化工研究设计院有限公司 | Method for preparing high-purity ultraviolet absorber intermediate |
| CN113087678A (en) * | 2021-03-31 | 2021-07-09 | 中昊(大连)化工研究设计院有限公司 | Synthetic method of ultraviolet absorbent UV-1600 |
| CN113214173A (en) * | 2021-04-27 | 2021-08-06 | 烟台新特路新材料科技有限公司 | Multifunctional triazine ultraviolet absorbent with thioether antioxidant structure and preparation method thereof |
| CN113214173B (en) * | 2021-04-27 | 2022-08-02 | 烟台新特路新材料科技有限公司 | Multifunctional triazine ultraviolet absorbent with thioether antioxidant structure and preparation method thereof |
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| WO2021022731A1 (en) | 2021-02-11 |
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