CN117417305B - Synthesis method of high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine - Google Patents

Synthesis method of high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine Download PDF

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CN117417305B
CN117417305B CN202311382253.5A CN202311382253A CN117417305B CN 117417305 B CN117417305 B CN 117417305B CN 202311382253 A CN202311382253 A CN 202311382253A CN 117417305 B CN117417305 B CN 117417305B
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methoxyphenyl
dihydroxyphenyl
bis
triazine
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CN117417305A (en
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王荣
刘启发
***
廉云
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Anqing Kesi Chemical Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to the field of sunscreens, in particular to a synthesis method of high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine, which takes DCT and resorcinol as raw materials, and adds a solvent, a main catalyst and a cocatalyst to react at the temperature of 40-50 ℃, and after the reaction is finished, the high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine is obtained through post-treatment, compared with the prior art, the invention has the following beneficial effects: the invention adopts the combination of the main catalyst and the cocatalyst, thereby effectively increasing DCT selectivity, obviously increasing yield, greatly reducing impurity of the RET finished product, obviously increasing purity, and effectively improving the next reaction carried out by the intermediate.

Description

Synthesis method of high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine
Technical Field
The invention relates to the field of sunscreens, in particular to a method for synthesizing high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine.
Background
Tianlai S is an oil-soluble organic compound and is added into sunscreen emulsion to absorb ultraviolet rays. BASF and Ashland Inc are marketed under the trade names Tinosorb S and Escalol S, respectively. The S-radiation is a broad-area (broadband) UV absorber capable of absorbing UVB and UVA, and has two peaks at wavelengths 310 and 340nm, respectively. The light stability is extremely high, and even if 50MEDs are applied, 98.4% of the light can be kept without decomposition, mixing with other sunscreens such as avobenzone also inhibits their photodecomposition. The chemical structural formula is as follows:
2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine (RET) is a key intermediate for S, and has the following structural formula:
RET synthesis is currently mainly obtained by F-C reaction of 2, 4-dichloro-6- (4-methoxyphenyl) -1,3, 5-triazine (DCT) serving as a starting material and resorcinol. According to the existing process preparation method, the F-C reaction mainly uses Lewis acid, particularly aluminum chloride, as a catalytic system, uses a solvent of aluminum halide which can be dispersed such as sulfolane and the like to react, the aluminum chloride is high in dosage, after the reaction is finished, the aluminum chloride is directly hydrolyzed and filtered, a large amount of water is needed to be used for pickling and removing Lewis acid in the system to be neutral, a large amount of waste acid water is generated, a large amount of corrosive gas is generated in the reaction and washing process, the human body, the site environment, the safety and the environmental protection are greatly influenced, the requirements on mass production equipment are strict, the purity and the content of RET finally obtained are low, more impurities exist, the content of RET is unstable, and the S synthesis is unfavorable for the next step. The above materials are not beneficial to the industrialization requirements and do not meet the current green chemical production requirements.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for synthesizing high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine, which takes DCT and resorcinol as raw materials, adds a solvent, a main catalyst and a cocatalyst, reacts at the temperature of 40-50 ℃, and obtains the high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine through post-treatment after the reaction is finished.
Preferably, the main catalyst is aluminum trichloride.
Preferably, the cocatalyst is palladium chloride and S- (-) -1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine, and the molar ratio is 1:1.
Preferably, the solvent is used in a volume amount of 1 to 5L/mol based on the DCT molar amount.
Preferably, the mol ratio of DCT, resorcinol, main catalyst and cocatalyst is 1:1.05: (0.1-0.2): (0.01-0.05).
Preferably, the solvent is selected from any one of toluene, sulfolane and DMF.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the main catalyst and the cocatalyst are matched, so that the DCT selectivity is effectively increased, the yield is obviously increased, the impurity of the RET finished product is greatly reduced, the purity is obviously increased, and the next reaction with the intermediate is effectively promoted;
2. the micro cocatalyst is adopted, so that the consumption of the main catalyst aluminum trichloride is greatly reduced, the generation of post-treatment wastewater is effectively reduced, and the environment protection and the site environment are effectively improved;
3. the concentration, dissolution and crystallization are carried out for purification, so that the quality of RET finished products is effectively improved, RET impurity generation is reduced, a positive effect is generated on the synthesis of S-applied final products, the synthesis and quality control of the final finished products are more convenient, and the products have more market competitiveness;
4. the invention fundamentally solves the defects of more waste water, difficult treatment and poor field environment in the prior art, achieves stable reaction, is easy to operate, has more stable quality of finished products, increases corresponding economic benefits, greatly reduces environmental protection pressure and field environment, and makes the products more competitive.
Detailed Description
Unless otherwise indicated, parts in the present invention are parts by mass;
unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
A synthesis method of high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine comprises the steps of uniformly mixing 1mol of DCT, 1.05mol of resorcinol, 0.15mol of aluminum trichloride, 0.03mol of palladium chloride, 0.03mol of S- (-) -1,1 '-binaphthyl-2, 2' -diphenylphosphine and 2L of toluene under the protection of nitrogen, reacting at 40 ℃, sampling and detecting, after the reaction is finished, adding 1L of water each time, uniformly stirring, separating liquid, merging organic phases, distilling the organic phases, extracting toluene, adding 1L of 2-methyltetrahydrofuran into a distillation bottom, heating to 60 ℃, carrying out heat filtration, slowly cooling the filtrate to 5 ℃, adding 1g of seed crystal, stirring for 1h, carrying out suction filtration, drying a filter cake, and obtaining the high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine, wherein the purity is 99.6%, and the yield is 94.2%.
Example 2
This embodiment differs from embodiment 1 in that: 0.15mol of aluminum trichloride, the rest was identical to example 1, and the purity was 99.2% and the yield was 93.2% by calculation.
Example 3
This embodiment differs from embodiment 1 in that: 0.2 mol of aluminum trichloride, the rest was the same as in example 1, and the purity was 99.3% and the yield was 93.7% by calculation.
Example 4
This embodiment differs from embodiment 1 in that: 0.01mol of palladium chloride, 0.01mol of S- (-) -1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine, the rest of the preparation are identical to those of the example 1, and the purity is calculated to be 98.7% and the yield is calculated to be 90.3%.
Example 5
This embodiment differs from embodiment 1 in that: 0.05mol of palladium chloride, 0.05mol of S- (-) -1,1 '-binaphthyl-2, 2' -bisdiphenylphosphino-aluminum and the balance of the catalyst were identical to those in example 1, and the purity was 99.1% and the yield was 91.8%.
Comparative example 1
1mol DCT, 1.05mol resorcinol, 1mol aluminum trichloride and 2L toluene are uniformly mixed under the protection of nitrogen, reacted at 70 ℃, sampled and detected, after the reaction is finished, 1L water is added for 3 times, the mixture is stirred uniformly for each time, liquid is separated, an organic phase is combined, toluene is distilled and extracted from the organic phase, 1L 2-methyltetrahydrofuran is added into the distillation bottom, the temperature is raised to 60 ℃, the mixture is filtered by heat, the filtrate is slowly cooled to 5 ℃, seed crystals are added, stirring is carried out for 1h, suction filtration is carried out, and a filter cake is dried, thus obtaining 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine with purity of 90.2 percent and yield of 88.3 percent through calculation.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (4)

1. A method for synthesizing high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine is characterized by comprising the following steps: DCT and resorcinol are taken as raw materials, a solvent, a main catalyst and a cocatalyst are added for reaction at the temperature of 40-50 ℃, and after the reaction is finished, the high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine is obtained through post-treatment;
the main catalyst is aluminum trichloride;
the cocatalyst is composed of palladium chloride and S- (-) -1,1 '-binaphthyl-2, 2' -diphenylphosphine according to a molar ratio of 1:1.
2. The method for synthesizing high purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine according to claim 1, wherein the solvent volume amount is 1 to 5L/mol in terms of DCT molar amount.
3. The method for synthesizing high purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine according to claim 1, wherein the molar ratio of DCT, resorcinol, main catalyst, and cocatalyst is 1:1.05: (0.1-0.2): (0.01-0.05).
4. The method for synthesizing high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine according to claim 1, wherein the solvent is selected from any one of toluene, sulfolane and DMF.
CN202311382253.5A 2023-10-24 2023-10-24 Synthesis method of high-purity 2- (4-methoxyphenyl) -4, 6-bis (2, 4-dihydroxyphenyl) -1,3, 5-triazine Active CN117417305B (en)

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CN118084811A (en) * 2024-04-23 2024-05-28 安庆科思化学有限公司 Environment-friendly preparation method of sun-screening agent intermediate RET

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US5955060A (en) * 1995-11-23 1999-09-21 Ciba Specialty Chemicals Corporation Bis(resorcinyl)triazines useful as sunscreens in cosmetic preparations
CN109879822A (en) * 2019-04-23 2019-06-14 黄冈美丰化工科技有限公司 The preparation method of S intermediate is applied over a kind of ultraviolet absorbing agent day
WO2022253599A1 (en) * 2021-05-31 2022-12-08 Dsm Ip Assets B.V. Process for the preparation of bis-resorcinyl-triazines
CN115772133A (en) * 2022-11-29 2023-03-10 安徽英特美科技有限公司 Preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine

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US5955060A (en) * 1995-11-23 1999-09-21 Ciba Specialty Chemicals Corporation Bis(resorcinyl)triazines useful as sunscreens in cosmetic preparations
CN109879822A (en) * 2019-04-23 2019-06-14 黄冈美丰化工科技有限公司 The preparation method of S intermediate is applied over a kind of ultraviolet absorbing agent day
WO2022253599A1 (en) * 2021-05-31 2022-12-08 Dsm Ip Assets B.V. Process for the preparation of bis-resorcinyl-triazines
CN115772133A (en) * 2022-11-29 2023-03-10 安徽英特美科技有限公司 Preparation method of bis-ethylhexyloxyphenol methoxyphenyl triazine

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Wang Xueding等.Synthesis, Spectra, and Theoretical Investigations of 1,3,5-Triazine Compounds as Ultraviolet Rays Absorber Based on Time-Dependent Density Functional Calculations and three-Dimensional Quantitative Structure-Property Relationship.《Journal of Fluorescence》.2018,第28卷(第2期),第707-723页. *
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