CN115819188A - Preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol - Google Patents
Preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol Download PDFInfo
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Abstract
The invention discloses a preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol, and relates to the technical field of organic synthesis. 4-tert-butylphenol and styrene are used as reaction raw materials, and a liquid coordination complex is simultaneously used as a catalyst and a solvent to carry out one-pot reaction. By selecting different organic ligands, metal halides and liquid coordination complexes with the ratio of the organic ligands to the halides, the steps of the synthesis process are simplified, and the limitation of a volatile solvent to the reaction temperature in the reaction process is avoided. The reaction period is greatly shortened, the yield and the purity of the product are high, the reaction rate is improved, the problem of solvent residue is avoided, a large amount of acidic wastewater cannot be generated in the reaction process, the product after the reaction and the solvent used in the liquid coordination complex post-treatment process can be recycled, and the method is more energy-saving and environment-friendly.
Description
Technical Field
The invention relates to the technical field of organic synthesis, and particularly relates to a preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol.
Background
Rubidium (Ru) and cesium (Cs) elements have larger atomic radius and ionic radius, have extremely active chemical properties, are quite close to the physical and chemical properties of the elements, and have the remarkable characteristics of extremely large photoelectric threshold and extremely small electron work function, so that the elements have excellent photoelectric characteristics. Due to the special physicochemical properties of the rubidium and cesium, the rubidium and cesium chemicals have unique uses which other metals are difficult to replace in various scientific research and technical application fields. The increase of the yield of rubidium and cesium leads to a reduction of the price of the product, which in turn promotes the development of the rubidium and cesium industry. Rubidium and cesium are widely and deeply researched in the fields of photoelectric materials, atomic frequency standards, laser materials, synthesis catalysis and the like, but the application research and development of rubidium and cesium still have huge space, particularly China which is a large country of rubidium and cesium resources has a considerable difference with the world advanced level in the aspect of utilization of rubidium and cesium resources, particularly application and development.
The industrial research on the separation and purification of rubidium and cesium ions of alkali metals mainly focuses on precipitation, ion exchange and solvent extraction, wherein the solvent extraction method is the current main method for industrially extracting and recovering rubidium and cesium from solution. 4-tert-butyl-2- (alpha-methylbenzyl) phenol (t-BAMBP) is an extractant with excellent performance for separating and purifying Ru and Cs, has high rubidium and cesium extraction efficiency and good separation performance, is used for separating and purifying rubidium and cesium in a lepidolite lithium extraction mother liquor to obtain systematic research, has industrial application and mature process.
the synthesis method of t-BAMBP comprises two methods of indirect synthesis and direct synthesis, and the current mainstream method in industry is a direct synthesis method, namely 4-tert-butylphenol and styrene are used as starting raw materials, and Friedel-crafts alkylation is carried out by catalysis of heteropolyacid, sulfonated resin, acidic liquid coordination complex and other Lewis acid or acidic catalysts.
The traditional process for directly synthesizing t-BAMBP by catalyzing 4-tert-butylphenol and styrene by using a Lewis acid catalyst generally has the following problems:
(1) Incomplete reaction and low selectivity of main products;
(2) The catalyst is expensive;
(3) Volatile organic solvent is used in the reaction process, and the method is not green enough.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol, aiming at avoiding using an organic solvent in the reaction process, optimizing the process flow and simultaneously improving the reaction selectivity and yield of the product.
The invention is realized by the following steps:
in a first aspect, the present invention provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, comprising: 4-tert-butylphenol and styrene are used as reaction raw materials, and a liquid coordination complex is simultaneously used as a catalyst and a solvent for reaction;
wherein the liquid coordination complex is synthesized by metal halide and organic ligand;
the metal halide is selected from at least one of aluminum chloride, zinc chloride, gallium chloride, tin dichloride and titanium chloride; the organic ligand is at least one selected from acetamide, N-methylacetamide, trioctylphosphine, trioctyloxyphosphine, N-dimethylacetamide, urea and thiourea;
the molar ratio of the organic ligand and the metal halide used for preparing the liquid coordination complex is n:1,0.5 which is not less than n < 1.
In an alternative embodiment, the molar ratio of organic ligand to metal halide used to prepare the liquid coordination complex is from 0.6 to 0.7.
In an alternative embodiment, the liquid coordination complex has a molar ratio to 4-tert-butylphenol of from 2 to 4;
preferably, the molar ratio of the liquid coordination complex to 4-tert-butylphenol is 2.5 to 3.5.
In an optional embodiment, 4-tert-butylphenol, styrene and the liquid coordination complex are mixed and dissolved and then react for 0.1 to 5 hours at the temperature of between 30 and 100 ℃;
preferably, the reaction temperature is 40-65 ℃, and the reaction time is 0.2-1 h.
In an alternative embodiment, the reaction is followed by low temperature extractive separation to obtain an organic phase and a liquid coordination complex phase, and the organic phase is concentrated and purified.
In an optional embodiment, after the reaction is finished, cooling to 0-20 ℃, adding an extraction solvent for extraction, and performing reduced pressure distillation and purification on an organic phase after extraction and liquid separation;
wherein the extraction solvent is at least one selected from n-heptane, petroleum ether and n-hexane.
In an optional embodiment, the extracted organic phase is subjected to reduced pressure distillation and purification, and fractions within 160-190 ℃ under 0.8-1 KPa are collected to obtain a 4-tert-butyl-2- (alpha-methylbenzyl) phenol product.
In an alternative embodiment, the liquid coordination complex phase is recycled after post-treatment, the post-treatment comprising: and (4) pulping, separating and drying the liquid coordination complex phase and the post-treatment solvent.
In alternative embodiments, the post-treatment solvent is selected from at least one of diethyl ether, ethyl acetate, and dichloromethane.
In an alternative embodiment, the liquid coordination complex phase is mixed with a post-treatment solvent and is beaten, then at least one time of liquid separation treatment is carried out, and the obtained liquid coordination complex phase is dried in vacuum for 8 to 10 hours at the temperature of 80 to 130 ℃.
The invention has the following beneficial effects: 4-tert-butylphenol and styrene are used as reaction raw materials, and a liquid coordination complex is simultaneously used as a catalyst and a solvent to carry out one-pot reaction, so that the synthesis process steps are simplified, and the limitation of a volatile solvent to the reaction temperature in the reaction process is avoided. Through the selection of the type and the proportion of the liquid coordination complex, the reaction period is greatly shortened, the yield and the purity of a product are higher, the reaction rate is improved, the problem of solvent residue is avoided, a large amount of acidic wastewater cannot be generated in the reaction process, the product after the reaction and the solvent used in the post-treatment process of the liquid coordination complex can be recycled, and the method is more energy-saving and environment-friendly.
Compared with the ionic liquid prepared by the traditional ligand, the liquid coordination complex adopted by the invention is stable in water and air, easy to store, better in solubility property, more excellent in thermal stability and simpler in preparation process. Therefore, the preparation method provided by the invention has the advantages of simple and easy operation, simple and convenient synthesis of the liquid coordination complex catalyst, low requirement on production equipment, mild and easily-achieved reaction conditions, contribution to industrial scale-up production and better industrial application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an HPLC chart of the product obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides a preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol, and the inventor creatively utilizes a liquid coordination complex as a catalyst and a solvent suitable for reaction at the same time to carry out Friedel-crafts alkylation reaction on 4-tert-butyl phenol and styrene to prepare the 4-tert-butyl-2- (alpha-methylbenzyl) phenol. Specifically, the method comprises the following steps:
s1, liquid coordination complex synthesis
The liquid coordination complex is synthesized by using metal halide and organic ligand, and the inventor optimizes the types of the metal halide and the organic ligand: the metal halide is at least one selected from aluminum chloride, zinc chloride, gallium chloride, tin dichloride and titanium chloride, and can be one or more; the organic ligand is at least one selected from acetamide, N-methylacetamide, trioctylphosphine, trioctyloxyphosphine, N-dimethylacetamide, urea and thiourea, and may be one or more.
The metal halide and the organic ligand are selected within the above ranges, and the liquid coordination complex obtained by the preparation can be suitably used in the preparation method provided in the embodiment of the present invention. If the selection of the metal halide and the organic ligand is outside the above range, the liquid complex cannot be synthesized, the reaction cannot proceed, or the yield is significantly reduced.
Further, the molar ratio of the organic ligand to the metal halide used for preparing the liquid coordination complex is n:1,0.5 ≦ n < 1, and the liquid coordination complex prepared in this range is more suitable for the preparation method of the embodiment of the present invention, enabling higher yield. In a preferred embodiment, the molar ratio of organic ligand to metal halide used to prepare the liquid coordination complex is 0.6 to 0.7.
Specifically, the molar ratio of the organic ligand to the metal halide may be 0.5. The liquid coordination complex mainly contains cations, neutral molecules and anions consisting of metal elements (M) and organic ligands (L). Examples of cations are [ MCl 2 L 2 ] + 、[MCl 2 L] + Neutral molecules, for example, [ MCl 3 L]、[M 2 Cl 6 L]The anion being a metal halide anion, such as [ MCl 4 ] - 、[M 2 Cl 7 ] - 、[M 3 Cl 10 ] - 。
It should be noted that the basic synthesis method of liquid coordination complexes is well known to those skilled in the art, and reference may be made to the preparation method reported in [ Angewandte Chemie International Edition,2013,52 (48): 12582-12586 ].
S2 Friedel-crafts alkylation reaction
4-tert-butylphenol and styrene are used as reaction raw materials, and a liquid coordination complex is simultaneously used as a catalyst and a solvent to carry out one-pot reaction. The liquid coordination complex is used as a solvent and a catalyst, so that the introduction of other impurities is reduced, the limitation of a volatile solvent on the reaction temperature is eliminated, and the reaction rate is improved.
In the actual operation process, 4-tert-butylphenol, styrene and liquid coordination complex are mixed and dissolved in a reaction kettle and react for 0.1 to 5 hours at the temperature of between 30 and 100 ℃. In a preferred embodiment, the reaction temperature is 40-65 ℃ and the reaction time is 0.2-1 h. The liquid coordination complex can be firstly added into a reaction kettle, then 4-tert-butylphenol and styrene are added, the temperature is raised for dissolution, and the constant temperature reaction is carried out after the dissolution.
Specifically, the reaction temperature may be 30 ℃, 40 ℃, 50 ℃, 60 ℃, 65 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or the like. The reaction time may be 0.1h, 0.5h, 1.0h, 2.0h, 3.0h, 4.0h, 5.0h, etc.
The inventor optimizes the dosage of each raw material to further improve the yield of the reaction: the molar ratio of the liquid coordination complex to the 4-tert-butylphenol is 2 to 4, the molar ratio of 1, 4-tert-butylphenol to styrene is 1:1 to 2. In a preferred embodiment, the molar ratio of the liquid coordination complex to 4-tert-butylphenol is from 2.5 to 3.5.
Specifically, the molar ratio of the liquid coordination complex to 4-tert-butylphenol may be 2.0.
S3, post-processing
After the reaction is finished, low-temperature extraction separation is carried out to obtain an organic phase and a liquid coordination complex phase, the organic phase is used for concentration and purification to obtain a 4-tert-butyl-2- (alpha-methylbenzyl) phenol product, and the liquid coordination complex phase is recycled after post-treatment.
In the actual operation process, after the reaction is finished, cooling to 0-20 ℃ (such as 0 ℃,5 ℃, 10 ℃, 15 ℃,20 ℃ and the like), adding an extraction solvent for extraction, separating liquid after the extraction is finished to obtain an organic phase and a liquid coordination complex phase, concentrating the organic phase under reduced pressure to obtain a light yellow liquid, and pulping, separating liquid and drying the liquid coordination complex phase and another post-treatment solvent for recycling. Therefore, the preparation method provided by the embodiment of the invention only uses a small amount of organic solvent in the processes of low-temperature extraction of the product and post-treatment of the liquid coordination complex, but can be recycled, and a large amount of acidic wastewater is not generated in the reaction process, so that the preparation method is more energy-saving and environment-friendly.
In some embodiments, the extraction solvent is selected from at least one of n-heptane, petroleum ether, and n-hexane, which may be any one or more of the above. And (3) carrying out reduced pressure distillation and purification on the extracted organic phase, and collecting fractions at 160-190 ℃ under 0.8-1 KPa to obtain a 4-tert-butyl-2- (alpha-methylbenzyl) phenol product.
In some embodiments, the post-treatment solvent is selected from at least one of diethyl ether, ethyl acetate, and dichloromethane, which may be any one or more of the above. Mixing the liquid coordination complex phase with a post-treatment solvent, pulping, performing at least one liquid separation treatment, and vacuum-drying the obtained liquid coordination complex phase at the temperature of 80-130 ℃ for 8-10 h.
Specifically, the liquid separation treatment may be performed 2 times or 3 times, and is not limited herein. The amount of post-treatment solvent is not limited, and may be equivalent to or slightly greater than the mass of the liquid coordination complex phase. Specifically, the drying temperature of the liquid coordination complex phase may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ and the like; the drying time can be 8h, 9h, 10h and the like.
In some embodiments, n-heptane and diethyl ether, after simple distillation purification, can be reused, and it was verified that repeated use three times has no effect.
The inventor finds that the catalytic performance of the liquid coordination complex catalyst after vacuum drying is not obviously attenuated after the liquid coordination complex catalyst is recycled for 4 times, and the preparation process provided by the embodiment of the invention realizes the recycling of raw materials and meets the requirements of energy conservation and environmental protection. The synthesis method of the embodiment of the invention uses the liquid coordination complex catalyst, has low saturated vapor pressure, good thermal stability, good solubility performance for most substances without interaction, stability in water and air, wider acidity regulation interval and catalytic performance, and repeated use after vacuum drying, greatly reduces the production cost and increases the economic benefit.
On the whole, the preparation method provided by the embodiment of the invention has the advantages of short reaction period, simple and convenient synthesis of the liquid coordination complex catalyst, low requirement on production equipment, mild and easily-achieved reaction conditions and high product yield, the reaction yield is over 85 percent, and the purity is over 95 percent.
The features and properties of the present invention are described in further detail below with reference to examples.
In the following examples, liquid coordination complexes are shown by the method as 0.6Ur-AlCl 3 For example, ur represents the organic ligand Urea, alCl 3 Represents the metal halide aluminium trichloride, 0.6 represents the molar ratio of urea to aluminium trichloride of 0.6.
In the following examples, the instruments for performing High Performance Liquid Chromatography (HPLC) tests were Shimadzu LC-2030 type high performance liquid chromatograph, UV-visible light detector, durashell C18 (L) column (250X 4.6mm i.d.; particle size, 5 μm), column temperature: 30 ℃, detector wavelength: 254nm, mobile phase ratio: acetonitrile: water =80, mobile phase flow rate: 1mL/min. equiv. means molar equivalent, room temperature means 4 ℃ to 30 ℃.
Example 1
This example provides a method for preparing 4-tert-butyl-2- (α -methylbenzyl) phenol, including the following steps:
(1) Preparation of Urea-aluminum trichloride liquid coordination Complex (0.6 Ur-AlCl) 3 )
Anhydrous aluminum chloride (2 mol) was accurately weighed into a three-necked flask charged with nitrogen blanket, mechanical stirring (200 rpm) was turned on and the oil bath temperature was set to 90 ℃. Adding urea (1.2 mol) into a three-neck flask in 30min for 4 times, and continuing to react for 10h until the reaction is complete to obtain clear and transparent urea-aluminum trichloride liquid coordination complex (0.6 Ur-AlCl) 3 ) And storing the product in a glove box for later use.
(2) Preparation of
Accurately weighing a liquid coordination complex (0.6 Ur-AlCl) of 4-tert-butylphenol (1.5 mol), styrene (1.2 equiv.) and urea-aluminum trichloride 3 ) (2.5 equiv.) was added to the three-necked flask and stirred, and the temperature was slowly raised until 4-t-butylphenol was completely dissolved (about 50 ℃ C.), and the system was set to keep the temperature at 65 ℃ for 0.5 hour.
(3) Post-treatment
After the heat preservation reaction is finished, cooling the liquid mixture after the reaction to 20 ℃, then adding n-heptane for stirring and extraction, separating liquid, taking an organic phase, and spin-drying to obtain light yellow liquid 373.8g. The obtained light yellow liquid is collected and distilled under reduced pressure, and fractions within 160-190 ℃ under 0.8KPa are collected to obtain the product 4-tert-butyl-2- (alpha-methylbenzyl) phenol (344.3 g, purity 95.3%) with yield 86%.
Adding a certain amount of diethyl ether into the liquid coordination complex obtained by extraction and liquid separation after the reaction is finished, pulping, standing for layering, separating liquid, collecting the liquid coordination complex phase, continuously and repeatedly using after vacuum drying for 10h at 100 ℃, keeping the process conditions in the same proportion with the first synthesis process, repeatedly using for 4 times, and obtaining the product yield and purity results shown in table 1. The HPLC profile of the product is shown in FIG. 1.
TABLE 1 number of liquid coordination complexes recycled and catalytic effect
| Serial number | Yield (%) | Purity (%) |
| 1 | 86 | 95.3 |
| 2 | 87 | 94.6 |
| 3 | 85 | 96.2 |
| 4 | 84 | 95.7 |
Example 2
This example provides a method for preparing 4-tert-butyl-2- (α -methylbenzyl) phenol, including the following steps:
(1) Preparation of acetamide-aluminum trichloride liquid coordination complex (0.6 AA-AlCl) 3 )
Anhydrous aluminum chloride (3 mol) was accurately weighed into a three-necked flask charged with nitrogen blanket, mechanical stirring (250 rpm) was turned on and the oil bath temperature was set to 80 ℃. Adding acetamide (1.8 mol) into three-neck flask in 30min for 8 times, and reacting for 8 hr until the reaction is complete to obtain clear and transparent acetamide-aluminum trichloride liquid coordination complex (0.6 AA-AlCl) 3 ) And storing the product in a glove box for later use.
(2) Preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol
Accurately weighing 4-tert-butylphenol (1 mol), styrene (1.5 equiv.) and acetamide-aluminum trichloride liquid to prepareSite complex (0.6 AA-AlCl) 3 ) (3 equiv.) was added to the three-necked flask and stirring was turned on, and the temperature was slowly raised until 4-t-butylphenol was completely dissolved (about 40 ℃ C.), and the system was set to keep the temperature at 40 ℃ for 1 hour.
(3) Post-treatment
After the reaction is finished by keeping the temperature, cooling the liquid mixture after the reaction to 20 ℃, adding n-heptane for stirring and extracting, separating the liquid, taking the organic phase, and spin-drying to obtain 254.3g of light yellow liquid. The obtained pale yellow liquid was collected and distilled under reduced pressure, and fractions at 160 to 190 ℃ under 0.8KPa were collected to obtain 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (224.8 g, purity 96.2%) as a product, with a yield of 85%.
Example 3
This embodiment provides a method for preparing 4-tert-butyl-2- (α -methylbenzyl) phenol, including the following steps:
(1) Preparation of trioctyloxyphosphorus-gallium trichloride liquid coordination complex (0.7P) 888 O-GaCl 3 )
Anhydrous gallium chloride (0.5 mol) was accurately weighed into a three-necked flask charged with nitrogen, mechanical stirring (250 rpm) was turned on and the oil bath temperature was set to 80 ℃. Adding gallium chloride (0.35 mol) into three-neck flask in 30min 10 times, and reacting for 12 hr until the reaction is complete to obtain clear and transparent trioctyloxyphosphorus-gallium trichloride liquid coordination complex (0.7P) 888 O-GaCl 3 ) And storing in the glove box for later use.
(2) Preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol
Accurately weighing liquid coordination complex (0.7P) of 4-tert-butylphenol (0.2 mol), styrene (1.6 equiv.) and trioctyloxyphosphorus-gallium trichloride 888 O-GaCl 3 ) (2 equiv.) was added to the three-necked flask, stirring was started, and the temperature was slowly raised until 4-t-butylphenol was completely dissolved (about 40 ℃ C.), and the system was set to keep the temperature at 45 ℃ for 0.5 hour.
(3) Post-treatment
After the reaction is finished by keeping the temperature, cooling the liquid mixture after the reaction to 0 ℃, then adding n-heptane for stirring and extraction, separating the liquid, taking the organic phase, and spin-drying to obtain 62.1g of light yellow liquid. The obtained pale yellow liquid was collected and distilled under reduced pressure, and fractions at 160 to 190 ℃ under 0.8KPa were collected to obtain 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (46.1 g, purity 97.2%) as a product with a yield of 88%.
Example 4
This example provides a method for preparing 4-tert-butyl-2- (α -methylbenzyl) phenol, including the following steps:
(1) Preparation of N-methylacetamide-aluminum trichloride liquid coordination complex (0.65 NMA-AlCl) 3 )
Anhydrous aluminum chloride (3 mol) was accurately weighed into a three-necked flask charged with nitrogen blanket, mechanical stirring (250 rpm) was turned on and the oil bath temperature was set to 80 ℃. Adding N-methylacetamide (1.95 mol) into a three-neck flask in 30min for 8 times, and continuing to react for 8h until the reaction is complete to obtain clear and transparent N-methylacetamide-aluminum trichloride liquid coordination complex (0.65 NMA-AlCl) 3 ) And storing the product in a glove box for later use.
(2) Preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol
Accurately weighing a liquid coordination complex (0.65 NMA-AlCl) of 4-tert-butylphenol (2 mol), styrene (1.3 equiv.) and N-methylacetamide-aluminum trichloride 3 ) (3.5 equiv.) was added to the three-necked flask and stirred, and the temperature was slowly raised until 4-t-butylphenol was completely dissolved (about 40 ℃ C.), and the system was set to keep the temperature at 60 ℃ for 0.8 hour.
(3) Post-treatment
After the heat preservation reaction is finished, cooling the liquid mixture after the reaction to 5 ℃, then adding n-heptane for stirring and extraction, separating the liquid, taking the organic phase, and spin-drying to obtain 494.6g of light yellow liquid. The resulting pale yellow liquid was collected and distilled under reduced pressure, and fractions at 160 to 190 ℃ under 0.8KPa were collected to give 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (460.1 g, purity 95.1%) in 86% yield.
Example 5
This example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 1 only in that: step (1) preparation of 0.6Ur-ZnCl 2 A liquid coordination complex.
The results show that: the product, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, was obtained (purity 95.2%) in 85.1% yield.
Example 6
This example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 1 only in that: step (1) preparation of 0.6Ur-TiCl 4 A liquid coordination complex.
The results show that: the product, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, was obtained in 97% purity and 89% yield.
Example 7
This example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 1 only in that: preparation of urea-aluminium trichloride liquid coordination complex 0.5Ur-AlCl 3 。
The results show that: the product, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, was obtained in 96% purity and 88% yield.
Example 8
This example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 1 only in that: preparation of urea-aluminium trichloride liquid coordination complex 1.0Ur-AlCl 3 。
The results show that: the target product, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, was not detected.
Comparative example 1
This comparative example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 1 only in that: the molar ratio of 4-tert-butylphenol to styrene was 1:3.
The results show that: after the reaction was completed, the product, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, (256 g, 56.2% purity) was obtained in 37.7% yield.
Comparative example 2
This comparative example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 1 only in that: the reaction temperature was 130 ℃.
The results show that: after the reaction was completed, the product, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (292 g, purity 32.2%) was obtained in 24.7% yield.
Comparative example 3
This comparative example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 1 only in that: the selected liquid coordination complex catalyst is 1.2Ur-AlCl 3 。
The results show that: after the reaction is finished, the generation of the target product (4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol) is not detected.
Comparative example 4
This comparative example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 2 only in that: the selected liquid coordination complex catalyst is 0.6AA-FeCl 3 。
The results show that: after the reaction is finished, the generation of the target product (4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol) is not detected.
Comparative example 5
This comparative example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 2 only in that: the selected liquid coordination complex catalyst is 0.6 ethylene glycol-ZnCl 2 。
The results show that: after the reaction is finished, the generation of the target product (4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol) is not detected.
Comparative example 6
This comparative example provides a process for the preparation of 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, which differs from example 2 only in that: the organic ligand adopts equivalent triethylamine hydrochloride.
The results show that: the product, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol, was obtained in a purity of 70% and a yield of 62%.
In summary, the invention provides a preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol, which takes a liquid coordination complex as a catalyst and a solvent at the same time to catalyze 4-tert-butyl phenol and styrene to react and synthesize. And after the reaction is finished, adding a solvent to perform low-temperature extraction on the system, performing spin-drying on the extraction liquid after extraction to obtain light yellow liquid, performing reduced pressure distillation on the light yellow liquid, collecting fractions at a specific temperature to obtain a pure product, and treating the liquid coordination complex for recycling. Has the following advantages:
(1) The raw materials of 4-tert-butylphenol, styrene and the liquid coordination complex are directly mixed and dissolved by a one-pot method for reaction, so that the process steps are optimized, and the equipment investment is reduced.
(2) In the reaction process, the liquid coordination complex is used as both a solvent and a catalyst, so that the introduction of other impurities is reduced, the reaction risk is reduced, the limitation of a volatile solvent on the reaction temperature is eliminated, and the reaction rate is improved.
(3) Only a small amount of organic solvent is used in the low-temperature extraction process of the product, but the organic solvent can be recycled, so that the problem of solvent residue is avoided, a large amount of acidic wastewater cannot be generated in the reaction process, and the method is more energy-saving and environment-friendly.
(4) The liquid coordination complex organic ligand is cheap and easy to obtain, is not sensitive to air, and is easy to store and use.
(5) The synthesis method has the advantages of high reaction speed, high yield and high purity of the product 4-tert-butyl-2- (alpha-methylbenzyl) phenol, the reaction yield is over 85 percent, and the purity is over 95 percent.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing 4-tert-butyl-2- (alpha-methylbenzyl) phenol, which is characterized by comprising the following steps: 4-tert-butylphenol and styrene are used as reaction raw materials, and a liquid coordination complex is simultaneously used as a catalyst and a solvent for reaction;
wherein the liquid coordination complex is synthesized from a metal halide and an organic ligand;
the metal halide is selected from at least one of aluminum chloride, zinc chloride, gallium chloride, tin dichloride and titanium chloride; the organic ligand is at least one of acetamide, N-methylacetamide, trioctylphosphine, trioctyloxyphosphine, N-dimethylacetamide, urea and thiourea;
the molar ratio of the organic ligand to the metal halide used to prepare the liquid coordination complex is n:1,0.5 ≤ n < 1.
2. The method according to claim 1, wherein the molar ratio of the organic ligand to the metal halide used for preparing the liquid coordination complex is 0.6 to 0.7.
3. The method of claim 1 or 2, wherein the molar ratio of the liquid coordination complex to the 4-tert-butylphenol is 2 to 4:1, and the molar ratio of the 4-tert-butylphenol to the styrene is 1:1 to 2;
preferably, the molar ratio of the liquid coordination complex to the 4-tert-butylphenol is 2.5 to 3.5, and the molar ratio of the 4-tert-butylphenol to the styrene is 1.2 to 1.8.
4. The preparation method of claim 1, wherein the 4-tert-butylphenol, the styrene and the liquid coordination complex are mixed and dissolved, and then reacted at 30 to 100 ℃ for 0.1 to 5 hours;
preferably, the reaction temperature is 40-65 ℃, and the reaction time is 0.2-1 h.
5. The method according to claim 4, wherein the reaction is completed and then the organic phase and the liquid coordination complex phase are separated by low-temperature extraction, and the organic phase is concentrated and purified.
6. The preparation method according to claim 5, wherein after the reaction is completed, the temperature is reduced to 0-20 ℃, an extraction solvent is added for extraction, and the organic phase is subjected to reduced pressure distillation and purification after extraction and liquid separation;
wherein the extraction solvent is selected from at least one of n-heptane, petroleum ether and n-hexane.
7. The preparation method of claim 6, wherein the extracted organic phase is subjected to reduced pressure distillation purification, and fractions within 160-190 ℃ at 0.8-1 KPa are collected to obtain the 4-tert-butyl-2- (alpha-methylbenzyl) phenol product.
8. The method of claim 5, wherein the liquid coordination complex phase is recycled after post-treatment, the post-treatment comprising: and (4) pulping, separating and drying the liquid coordination complex phase and the post-treatment solvent.
9. The method according to claim 8, wherein the post-treatment solvent is at least one selected from the group consisting of diethyl ether, ethyl acetate and dichloromethane.
10. The preparation method according to claim 9, wherein the liquid coordination complex phase is mixed with the post-treatment solvent and beaten, and after at least one liquid separation treatment, the obtained liquid coordination complex phase is vacuum-dried at a temperature of 80 ℃ to 130 ℃ for 8 hours to 10 hours.
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