CN112321520B - One-pot synthesis process of bis-ethylhexyloxyphenol methoxyphenyl triazine - Google Patents
One-pot synthesis process of bis-ethylhexyloxyphenol methoxyphenyl triazine 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
- C07D251/24—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
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Abstract
The invention discloses a preparation method of a process for synthesizing bis-ethylhexyloxyphenol methoxyphenyl triazine by a one-pot method, wherein toluene and benzonitrile are used as a dispersion system of aluminum trichloride during the synthesis of RET so as to reduce the toxic influence of sulfone solvents on human bodies; after the RET is synthesized, directly crushing the system, dissolving the RET in N, N-dimethylformamide, carrying out etherification reaction with chloroisooctane by taking weak base carbonate as an acid-binding agent, and directly washing with water to remove waste salt generated in the step after the etherification is finished. The process fundamentally solves the problems of large amount of water washing and particular difficulty in filtration in the RET synthesis process, and directly uses the RET reaction system to carry out reflux and water diversion for etherification reaction, so that the selectivity of the etherification of the bis-ethylhexyloxyphenol methoxyphenyl triazine is also improved to a certain extent, the bis-ethylhexyloxyphenol methoxyphenyl triazine finished product with the chromatographic purity of more than 99 percent is finally obtained, and the total yield of two steps reaches more than 85.5 percent.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine by one-pot synthesis.
Background
Bis-ethylhexyloxyphenol methoxyphenyl triazine, also known as Tinosorb S, with the trade name Bemotrizinol, abbreviated as BTZ, CAS number: 187393-00-6, formula: c38H49N3O5Molecular weight: 627.81g/mol, the chemical structural formula is as follows:
the bis-ethylhexyloxyphenol methoxyphenyl triazine is an oil-soluble organic compound, is added into sunscreen milk to absorb ultraviolet rays, is a wide-area ultraviolet absorbent, can absorb UVB to UVA, and has two absorption peaks at the wavelengths of 310 nm and 340nm respectively. It has extremely high photostability, even if 50MEDs (minimum tanning dose, which varies from person to person) are administered, for example, a person who has developed a red swelling phenomenon on the skin by irradiating ultraviolet rays for 20 minutes, and a minimum tanning dose for 20 minutes, can maintain the 98.4% level of ultraviolet rays without decomposition, and can inhibit their photolysis by mixing with other sunscreens such as avobenzone.
The existing synthesis process of bis-ethylhexyloxyphenol methoxyphenyl triazine mainly takes 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine and resorcinol as raw materials, a sulfone solvent is used for synthesizing an intermediate 2, 6- (2, 4-dihydroxyphenyl) -4- (4-methoxyphenyl) - [1, 3, 5] triazine (RET for short), and then a large amount of water is used for washing until the RET is neutral so as to remove aluminum trichloride; in addition, a toluene-nitrile solvent is used as a reaction solvent, after the reaction is finished, a large amount of tap water is still needed to wash RET so as to remove aluminum trichloride, and in the washing process, due to the existence of aluminum trichloride and toluene, the filtering rate is very slow, the synthesis of RET is seriously influenced, and a large amount of generated waste water aggravates the environment-friendly treatment capacity; after being dried, the obtained intermediate is used for synthesizing bis-ethylhexyloxyphenol methoxyphenyl triazine, N-dimethylformamide is mainly used as a solvent, alkali is used as an acid-binding agent, and halogenated isooctane is used for acidification reaction, under the condition of strong alkali, the halogenated isooctane serving as a raw material is seriously damaged, the etherification selectivity of bis-ethylhexyloxyphenol methoxyphenyl triazine is unfavorable, and when bromo-substituted isooctane and iodo-substituted isooctane are used, the raw material cost is high, and bromide and iodide generated need to be treated.
For the reasons mentioned above, it is highly desirable to provide an economical and environmentally friendly process for preparing bis-ethylhexyloxyphenol methoxyphenyl triazine.
Disclosure of Invention
In order to overcome the problems, the inventor of the invention carries out intensive research and researches a preparation method of a process for synthesizing bis-ethylhexyloxyphenol methoxyphenyl triazine by a one-pot method, and when RET is synthesized, toluene and benzonitrile are taken as a dispersion system of aluminum trichloride so as to reduce the toxic effect of sulfone solvents on human bodies; after the RET is synthesized, directly crushing the system, dissolving the RET in N, N-dimethylformamide, carrying out etherification reaction with chloroisooctane by taking weak base carbonate as an acid-binding agent, and directly washing with water to remove waste salt generated in the step after the etherification is finished. The process fundamentally solves the problems of large amount of water washing and particular difficulty in filtration in the RET synthesis process, and directly uses a RET reaction system to carry out reflux water diversion for etherification reaction, so that the selectivity of the etherification of the bis-ethylhexyloxyphenol methoxyphenyl triazine is also improved to a certain extent, and finally the bis-ethylhexyloxyphenol methoxyphenyl triazine finished product with the chromatographic purity of more than 99 percent is obtained, and the total yield of two steps reaches more than 85.5 percent, thereby completing the invention.
Specifically, the present invention aims to provide the following:
in a first aspect, a one-pot synthesis process for bis-ethylhexyloxyphenol methoxyphenyl triazine is provided, which comprises the following steps:
step 1, preparing RET;
and 2, carrying out etherification reaction on RET, and treating to obtain a target product.
Wherein, step 1 comprises the following substeps:
step 1-1, adding 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine, resorcinol and an organic solvent into a reactor;
and step 1-2, heating for reaction to obtain RET.
Wherein, in the step 1-1,
adding a catalyst into the reactor, wherein the catalyst is Lewis acid or protonic acid, preferably Lewis acid, and comprises one or more of aluminum trichloride, ferric trichloride, titanium tetrachloride, zinc chloride, boron trifluoride and antimony trichloride, and more preferably aluminum trichloride;
the organic solvent is an aromatic hydrocarbon compound, such as one or more selected from benzonitrile, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, and chlorobenzene; preferably a mixture of benzonitrile and toluene.
Wherein, in the step 1-2, the heating temperature is 50 to 80 ℃, preferably 55 to 75 ℃, and more preferably 60 to 70 ℃.
Wherein, step 2 comprises the following substeps:
step 2-1, dissolving the RET obtained in the step 1, and adjusting the pH value;
step 2-2, carrying out etherification reaction on the solution obtained in the step 2-1;
and 2-3, after the reaction is finished, carrying out subsequent treatment to obtain the bis-ethylhexyloxyphenol methoxyphenyl triazine.
In step 2-1, the chemical reagent for dissolving RET is an organic solvent, preferably a polar organic solvent, including one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, and methyl pyrrolidone, more preferably N, N-dimethylformamide.
Wherein, in the step 2-2, a catalyst is added to the solution obtained in the step 2-1, wherein the catalyst is carbonate, bicarbonate, hydrochloride or hydroxyapatite, preferably carbonate, bicarbonate or hydrochloride of alkali metal, alkaline earth metal or ammonium, such as one or more of magnesium chloride, potassium bicarbonate, potassium carbonate, sodium bicarbonate and ammonium bicarbonate.
Wherein, in step 2-3, the subsequent processing comprises:
step 2-3-1, recovering the solvent under reduced pressure, adding the organic solvent, stirring, standing and layering;
and 2-3-2, desolventizing, crystallizing, recrystallizing and drying the organic layer to obtain a finished product.
In the step 2-3-1, the organic solvent comprises aromatic hydrocarbons, aliphatic hydrocarbons, ketones and the like; preferably aromatic hydrocarbons with benzene ring, including benzene, toluene, ethylbenzene, xylene, etc.; more preferably toluene.
In a second aspect, there is provided bis-ethylhexyloxyphenol methoxyphenyl triazine obtained according to the synthesis process of the first aspect, having a chromatographic purity of greater than 99%.
The invention has the advantages that:
1. the invention fundamentally solves the problem of difficult RET reaction caused by uneven dispersion of aluminum trichloride in Friedel-crafts reaction; and fundamentally solves the problems of difficult filtration and generation of a large amount of wastewater in the RET post-treatment process.
2. The one-pot method for synthesizing the bis-ethylhexyloxyphenol methoxyphenyl triazine reduces the post-treatment process of RET, the obtained RET is directly used for synthesizing the bis-ethylhexyloxyphenol methoxyphenyl triazine, and the etherification selectivity of the bis-ethylhexyloxyphenol methoxyphenyl triazine is also improved unexpectedly.
3. The process for synthesizing the bis-ethylhexyloxyphenol methoxyphenyl triazine has the advantages that the generated impurities are low; after the reaction is finished, a small amount of tap water is used for quenching the reaction, the generation of wastewater is reduced, the RET obtained by the Friedel-crafts reaction is directly dissolved by N, N-dimethylformamide, the problem of difficult treatment of the Friedel-crafts reaction is reduced, and the problems of a large amount of wastewater generated and overlong separation time during the separation of the Friedel-crafts reaction RET are thoroughly solved.
4. The etherification of the bis-ethylhexyloxyphenol methoxyphenyl triazine is carried out in a water dividing mode, so that the etherification selectivity of the bis-ethylhexyloxyphenol methoxyphenyl triazine is greatly improved; after the etherification of the bis-ethylhexyloxyphenol methoxyphenyl triazine is finished, the solvent is directly recovered, and then the organic solvent toluene is added for direct water washing, so that the operation of the whole process is more convenient and safer.
5. The method synthesizes the bis-ethylhexyloxyphenol methoxyphenyl triazine by a one-pot method, and the generated waste salt is directly washed by water and removed in the post-treatment process of the bis-ethylhexyloxyphenol methoxyphenyl triazine, so that the actual operation difficulty is greatly reduced, the operation is easier, a large amount of time and waste water are saved, the corresponding economic benefit is increased, and the environmental protection pressure is reduced.
Drawings
FIG. 1 shows a LC-MS diagram of bis-ethylhexyloxyphenol methoxyphenyl triazine obtained in example 1 of the present invention.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
According to the present invention, a first aspect provides a one-pot synthesis process of bis-ethylhexyloxyphenol methoxyphenyl triazine, which comprises the following steps:
step 1, preparing RET.
In a further preferred embodiment, step 1 comprises the following sub-steps:
step 1-1, 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine, resorcinol, and an organic solvent are added to a reactor.
In the step 1-1, a catalyst is added into the reactor, wherein the catalyst is Lewis acid or protonic acid, preferably Lewis acid, and comprises one or more of aluminum trichloride, ferric trichloride, titanium tetrachloride, zinc chloride, boron trifluoride and antimony trichloride, and more preferably aluminum trichloride.
In the invention, the preferred catalyst is aluminum trichloride, which has the strongest catalytic effect, is beneficial to system dispersion, and has lower market price than other catalysts, thus having great advantages in the synthesis of RET.
In the invention, when the catalyst is added, the temperature of the reaction system is raised, and meanwhile, the temperature of the reaction system is ensured to be lower than 60 ℃, preferably lower than 50 ℃, more preferably 25-30 ℃, and the temperature rise is favorable for reducing the viscosity of the reaction system and fully performing the subsequent reaction. Preferably, the catalyst is added in small amount and multiple times in batches, so that the system temperature change is small, the safety control is easy, and the impurity change caused by overtemperature can be reduced.
In step 1-1, an organic solvent is added to the reactor as an inert solvent while providing a reaction system for the reaction. The organic solvent is an aromatic hydrocarbon compound, such as one or more selected from benzonitrile, toluene, ethylbenzene, ortho-xylene, meta-xylene, para-xylene, chlorobenzene; preferably a mixture of benzonitrile and toluene.
In the invention, the research of the inventor finds that the toluene-benzonitrile is used as a reaction system to replace a sulfone solvent used in the traditional process for preparing RET, so that the influence of the solvent on the toxicity of a human body can be reduced, and simultaneously, the catalyst in the system can be ensured to be a uniform system in the reaction process, the uniform reaction is facilitated, the thorough reaction is facilitated, and the impurity content is lower.
Wherein the mass ratio of the toluene to the benzonitrile is 0.5-2:1-5, preferably 1-2: 2-4, more preferably 1: 4, the inventors have found that when the mass ratio of the toluene to the benzonitrile is 0.5-2:1-5, especially 1: 4, the reaction process is most stable, and the content of impurities generated at the end of the reaction is minimized.
In the invention, the reactants are preferably added into the reactor under the protection of inert gas, and subsequent reaction is carried out, wherein the subsequent reaction comprises argon, nitrogen, helium and the like; more preferably nitrogen.
In step 1-1, the reactor is not limited to any vessel in which a reaction can be carried out, and preferably, the reactor is a flask, and more preferably, the reactor is a four-neck flask, so that the addition is facilitated at any time during the reaction.
And step 1-2, heating for reaction to obtain RET.
In step 1-2, the temperature of the reaction system is adjusted to 50 to 80 ℃, preferably 55 to 75 ℃, more preferably 60 to 70 ℃.
In the step 1-2, the Friedel-crafts reaction is carried out, and the Friedel-crafts reaction has strict requirements on temperature, and the inventor researches show that when the temperature of a reaction system is 50-80 ℃, particularly 60-70 ℃, the conversion rate of 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine is highest, and the selectivity of RET is highest.
In step 1-2, when the reaction is finished, quenching the reaction by using a quenching agent to obtain the product RET. Preferably, the quenching agent is tap water, more preferably pre-cooled tap water. In the present invention, the reaction solution is continuously cooled using a quenching agent to remove heat emitted during quenching and, at the same time, to reduce the generation of waste water.
In step 1-2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine generates carbenium ion under the action of a catalyst, and then electrophilic substitution reaction is carried out with resorcinol, so that RET is obtained.
In a further preferred embodiment, the reaction occurring in step 2 is as shown in formula (1):
and 2, carrying out etherification reaction on RET, and treating to obtain a target product.
In a further preferred embodiment, said step 2 comprises the following sub-steps:
and 2-1, dissolving the RET obtained in the step 1, and adjusting the pH value.
Wherein, the chemical reagent for dissolving RET is an organic solvent, preferably a polar organic solvent, comprising one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and methyl pyrrolidone, more preferably N, N-dimethylformamide.
In the invention, N, N-dimethylformamide is preferably used as an organic reagent for dissolving RET, the N, N-dimethylformamide has good dissolving capacity and stable chemical property, and in addition, the RET obtained by Friedel-crafts reaction is directly dissolved by the N, N-dimethylformamide, so that the problem of difficult treatment of the traditional Friedel-crafts reaction is reduced, and the problems of large amount of wastewater generation and overlong filtering time during the separation of the Friedel-crafts reaction RET are thoroughly solved.
In step 2-1, after dissolution of RET, the resulting solution is adjusted to a slightly alkaline pH, and the selected agent comprises a base, a basic salt, preferably a basic salt, including basic carbonate, basic complex salts, more preferably a weak base carbonate such as potassium bicarbonate.
In the invention, the Friedel-crafts reaction can generate an acid substance of hydrogen chloride, so that the Friedel-crafts reaction system is acidic, and the pH is preferably adjusted to be alkalescent in order to reduce the influence of the Friedel-crafts reaction acidic system on a late etherification catalyst, and meanwhile, the inventor finds that the pH is adjusted to be alkalescent by using weak base carbonate, the pH is 7-9, preferably 7-8, more preferably 7-7.5, the accurate feeding of the late etherification catalyst is facilitated, and the etherification end point is easier to control.
And 2-2, carrying out etherification reaction on the solution obtained in the step 2-1.
In the present invention, the solution obtained in step 2-1 is refluxed to remove water contained in the solution, and halogenated isooctane, preferably chlorinated isooctane, is added to the solution to carry out an etherification reaction.
In the invention, chloro-isooctane is preferably used for etherification reaction, so that other halogens are prevented from being introduced, and even other side reactions are prevented from being generated, and unnecessary troubles for subsequent further treatment are prevented.
In step 2-2, a catalyst is added to the solution obtained in step 2-1, said catalyst also acting as an acid-binding agent, said catalyst being a carbonate, bicarbonate or hydrochloride or hydroxyapatite, preferably an alkali metal, alkaline earth metal or ammonium carbonate, bicarbonate or hydrochloride, for example one or more of magnesium chloride, potassium bicarbonate, potassium carbonate, sodium bicarbonate and ammonium bicarbonate, more preferably a weak base carbonate such as potassium carbonate or the like.
In the invention, because acid gas hydrogen chloride is correspondingly generated in the etherification reaction process, and the reaction can be promoted to move to the right only by timely transferring the gas out of the system, an acid binding agent is preferably added in the reaction.
In the invention, if strong base is used as an acid-binding agent, the hydrolysis rate is obviously accelerated under the alkaline condition because chlorine element is very active, so that more side reactions are generated, and the reaction is very violent and is difficult to control.
In the invention, weak base carbonate is preferably used as an acid-binding agent, so that the influence of strong base used in etherification reaction in the traditional process on aluminum trichloride and halogenated isooctane in a system is reduced, the generation of byproducts in the target product bis-ethylhexyloxyphenol methoxyphenyl triazine is favorably reduced, and the yield is correspondingly improved.
In a further preferred embodiment, the weak base carbonate used in step 2-1 and step 2-2 contains the same cation, such as potassium bicarbonate and potassium carbonate.
And (3) refluxing the solution obtained in the step (2-1), adding halogenated isooctane and optionally adding a catalyst, then heating the system again to reflux, and carrying out water diversion reaction to the end point.
In a further preferred embodiment, the etherification reaction that occurs in step 2-2 is as shown in formula (2):
and 2-3, after the reaction is finished, carrying out subsequent treatment to obtain the bis-ethylhexyloxyphenol methoxyphenyl triazine.
In a further preferred embodiment, the post-processing comprises:
and 2-3-1, recovering the solvent under reduced pressure, adding the organic solvent, stirring, standing and layering.
In step 2-3-1, after the etherification reaction is finished, the pressure of a water pump is adjusted, and the solvents of toluene, halogenated isooctane and dissolved RET organic solvent are recovered under reduced pressure.
In the invention, after the reaction is finished, the solvent is recovered, thereby reducing the generation of three wastes, saving resources and reducing energy consumption.
In step 2-3-1, after the solvent is recovered, the remaining solution contains aluminum trichloride, potassium salt, etc., and therefore, further processing is required, and an organic solvent is added to the remaining solution to dissolve the mixture, followed by stirring.
In step 2-3-1, the organic solvent comprises aromatic hydrocarbons, aliphatic hydrocarbons, ketones, and the like; preferably aromatic hydrocarbons with benzene rings, including benzene, toluene, ethylbenzene, xylene, etc.; more preferably, the solvent is toluene.
In the invention, a toluene dissolution product is preferred, which contributes to improving the quality of the target product bis-ethylhexyloxyphenol methoxyphenyl triazine.
In the invention, preferably, tap water is added while an organic solvent is added, salts are easy to dissolve in water, aluminum trichloride is also soluble in water, water and the organic solvent are added into the rest solution, stirring is carried out to ensure that molecules and ions in the solution are fully mixed, because the solubility of the bis-ethylhexyloxyphenol methoxyphenyl triazine in toluene is far higher than that in water, obvious layering phenomenon can occur after stirring and standing, impurities such as salts are contained in a water layer, an organic layer mainly comprises toluene and the bis-ethylhexyloxyphenol methoxyphenyl triazine, and in order to further improve the quality of the bis-ethylhexyloxyphenol methoxyphenyl triazine, the organic layer solution is preferably washed for 2-3 times.
In the invention, after the etherification reaction is finished and the solvent is removed, the product is dissolved in the organic solvent toluene, and the aluminum trichloride and the salts are removed by washing with water, so the operation is convenient, the control is easy, and the salts in the system are removed more thoroughly.
And 2-3-2, desolventizing, crystallizing, recrystallizing and drying the organic layer to obtain a finished product.
In a further preferred embodiment, the finished product of the bis-ethylhexyloxyphenol methoxyphenyl triazine is obtained by further processing, desolventizing, crystallizing, recrystallizing and drying the organic layer.
According to the invention, the second aspect provides the bis-ethylhexyloxyphenol methoxyphenyl triazine prepared by the synthesis process of the first aspect, and the chromatographic purity of the bis-ethylhexyloxyphenol methoxyphenyl triazine is more than 99%.
The invention provides a process preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine, which comprises the steps of taking toluene and benzonitrile as a dispersion system of aluminum trichloride, taking 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine and resorcinol as raw materials, synthesizing RET through Friedel-crafts reaction, dissolving the RET of the system by N, N-dimethylformamide, taking weak base carbonate as an acid binding agent, carrying out etherification reaction with chloroisooctane, and carrying out subsequent treatment to obtain a bis-ethylhexyloxyphenol methoxyphenyl triazine finished product with the chromatographic purity of more than 99 percent, wherein the yield of the bis-ethylhexyloxyphenol methoxyphenyl triazine obtained by the method can reach more than 85.5 percent; the method has the advantages of less three wastes, simple operation, easy control and easy realization of industrialization.
Examples
Example 1
Under the protection of nitrogen, 40g of 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine, 250g of toluene, 100g of benzonitrile and 35.2g of resorcinol were charged in a dry and clean 1000ml four-neck flask.
After the feeding is finished, heating the system to 25-30 ℃, slowly adding 47.9g of aluminum trichloride into the system for multiple times, keeping the adding temperature of the aluminum trichloride to be lower than 60 ℃, after the aluminum trichloride is added, keeping the temperature of 60-70 ℃ for reaction to the end point, and cooling the system to room temperature to obtain RET. Adding 40g of tap water into the obtained RET, uniformly stirring, adding 500g N, N-dimethylformamide into the system, heating to dissolve, and adding potassium bicarbonate to adjust the pH value of the system to 7-8.
Adding 75.4g of potassium carbonate, heating to reflux, removing water in the system, cooling to 50-60 ℃, adding 81.3g of chloroisooctane, heating again, refluxing, and carrying out water diversion reaction to the end point.
And after the etherification reaction is finished, cooling to 30-40 ℃, regulating the vacuum to-0.01 MPa by a water pump, recovering the solvent under reduced pressure until the kettle temperature is 140 ℃, after the solvent recovery is finished, cooling the system to 50-60 ℃, adding 200g of toluene and 200g of tap water, keeping the temperature, stirring until the solvent is completely dissolved, removing a water layer, and continuously washing an organic layer twice by 100g of tap water.
The oil layer is desolventized, crystallized, recrystallized and dried to obtain 83.7g of finished bis-ethylhexyloxyphenol methoxyphenyl triazine with the chromatographic purity of 99.4 percent, and the LC-MS diagram is shown in figure 1.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention.
Claims (8)
1. A one-pot synthesis process of bis-ethylhexyloxyphenol methoxyphenyl triazine is characterized by comprising the following steps:
step 1, preparing RET; the method comprises the following substeps:
step 1-1, adding 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine, resorcinol and an organic solvent into a reactor; adding a catalyst into the reactor, wherein the catalyst is Lewis acid; the organic solvent is a mixture of cyanobenzene and toluene, and the mass ratio of the toluene to the cyanobenzene is 0.5-2: 1-5;
adding reactants into a reactor under the protection of inert gas, and carrying out subsequent reaction;
step 1-2, heating to 50-80 ℃ for reaction to obtain RET;
step 2, carrying out etherification reaction on RET, and processing to obtain a target product, wherein the method comprises the following substeps:
step 2-1, dissolving the RET obtained in the step 1, and adjusting the pH value; the RET is dissolved in an organic solvent which is one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and methyl pyrrolidone;
step 2-2, carrying out etherification reaction on the solution obtained in the step 2-1, wherein the etherification reaction is to reflux the solution obtained in the step 2-1, add chloroisooctane and add a catalyst, then heat the system again to reflux, carry out water diversion reaction to the end point, and the catalyst is one or more of magnesium chloride, potassium bicarbonate, potassium carbonate, sodium bicarbonate and ammonium bicarbonate;
step 2-3, after the reaction is finished, carrying out subsequent treatment to obtain bis-ethylhexyloxyphenol methoxyphenyl triazine; the subsequent processing comprises:
step 2-3-1, recovering the solvent under reduced pressure, adding the organic solvent, stirring, standing and layering; the organic solvent is benzene, toluene, ethylbenzene or xylene, and tap water is added while the organic solvent is added;
and 2-3-2, desolventizing, crystallizing, recrystallizing and drying the organic layer to obtain a finished product, wherein RET is as follows:
2. the process of claim 1, wherein in step 1-1, the catalyst is one or more of aluminum trichloride, ferric trichloride, titanium tetrachloride, zinc chloride, boron trifluoride and antimony trichloride.
3. The process of claim 2, wherein in step 1-1, the catalyst is aluminum trichloride.
4. The process according to claim 1, wherein the heating temperature in step 1-2 is 55-75 ℃.
5. The process according to claim 4, wherein the heating temperature in step 1-2 is 60-70 ℃.
6. The process of claim 1, wherein in step 2-1, the chemical reagent that dissolves RET is N, N-dimethylformamide.
7. The process of claim 1, wherein in step 2-2, the catalyst is potassium carbonate.
8. The process of claim 1, wherein in step 2-3-1, the organic solvent is toluene.
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| CN113149919B (en) * | 2021-05-07 | 2022-01-11 | 湖北师范大学 | Etherification synthesis method of ultraviolet absorbent Tianlaishi S |
| CN113429359B (en) * | 2021-06-24 | 2023-11-24 | 黄冈美丰化工科技有限公司 | Preparation method of high-purity bis-ethylhexyloxyphenol methoxyphenyl triazine |
| CN115894390A (en) * | 2021-09-30 | 2023-04-04 | 安徽圣诺贝化学科技有限公司 | Preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine sun-screening agent by high-selectivity etherification |
| 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 |
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