CN115819188B - 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-tertiary butyl-2- (alpha-methylbenzyl) phenol, and relates to the technical field of organic synthesis. 4-tertiary butyl phenol and styrene are used as reaction raw materials, and a liquid coordination complex is used as a catalyst and a solvent to perform one-pot reaction. By selecting different types of organic ligands, metal halides and liquid coordination complexes of the organic ligands and the halides, the synthetic process steps are simplified, and the limitation of volatile solvents on the reaction temperature in the reaction process is avoided. The method has the advantages that the reaction period is greatly shortened, higher product yield and purity can be achieved, the reaction rate is improved, the problem of solvent residue is avoided, a large amount of acid wastewater cannot be generated in the reaction process, and the solvent used in the post-treatment process of the product and the liquid coordination complex after the reaction is recycled, so that the method is more energy-saving and environment-friendly.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4-tertiary butyl-2- (alpha-methylbenzyl) phenol.
Background
Rubidium (Ru) and cesium (Cs) have larger atomic radius and ion radius, extremely active chemical properties and quite similar physical and chemical properties, and are obviously characterized by extremely large photoelectric threshold and extremely small electron work function, thus having excellent photoelectric characteristics. Because of the special physicochemical properties, rubidium and cesium chemicals have unique uses in various scientific research and technical application fields, which are difficult to replace by other metals. The increase in rubidium cesium yields results in a decrease in the price of the product, which in turn has also prompted the development of the rubidium 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 huge space still exists for application research and development of rubidium and cesium, and particularly, the application of rubidium and cesium resources in China, which is large in resource of rubidium and cesium, is quite different from the world advanced level in application development.
Industrial research on separation and purification of alkali metal rubidium cesium ions is mainly focused on precipitation, ion exchange and solvent extraction, wherein the solvent extraction method is the main method for extracting and recovering rubidium cesium from solution in the industry at present. The 4-tertiary butyl-2- (alpha-methylbenzyl) phenol (t-BAMBP) is an extracting agent 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 lithium extraction mother liquor of lepidolite, is systematically researched, and has industrial application and mature process.
the synthesis method of t-BAMBP comprises two methods, namely indirect synthesis and direct synthesis, wherein the main method in industry at present is direct synthesis, namely 4-tertiary butyl phenol and styrene are used as starting materials, and Lewis acids such as heteropolyacid, sulfonated resin, acidic liquid coordination complex and the like or acidic catalysts are used for catalysis to carry out Friedel-crafts alkylation.
The following problems are common in the traditional technology for directly synthesizing t-BAMBP by catalyzing 4-tert-butylphenol and styrene by using a Lewis acid catalyst:
(1) Incomplete reaction and low selectivity of main products;
(2) The catalyst is expensive;
(3) The reaction process uses volatile organic solvents, is not environment-friendly and the like.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of 4-tertiary butyl-2- (alpha-methylbenzyl) phenol, which aims to avoid using an organic solvent in the reaction process, optimize the process flow and improve the reaction selectivity and yield of products.
The invention is realized in the following way:
in a first aspect, the present invention provides a process for the preparation of 4-tert-butyl-2- (α -methylbenzyl) phenol comprising: taking 4-tertiary butyl phenol and styrene as reaction raw materials, and adopting a liquid coordination complex 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 at least one selected from aluminum chloride, zinc chloride, gallium chloride, tin dichloride and titanium chloride; the organic ligand is at least one of acetamide, N-methylacetamide, trioctylphosphorus oxide, 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.ltoreq.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 0.7:1.
In an alternative embodiment, the molar ratio of liquid coordination complex to 4-tert-butylphenol is from 2 to 4:1, the molar ratio of 4-tert-butylphenol to styrene is from 1:1 to 2;
preferably, the molar ratio of the liquid coordination complex to the 4-tert-butylphenol is from 2.5 to 3.5:1, and the molar ratio of the 4-tert-butylphenol to the styrene is from 1:1.2 to 1.8.
In an alternative embodiment, after 4-tertiary butyl phenol, styrene and a liquid coordination complex are mixed and dissolved, the mixture is reacted for 0.1 to 5 hours at a 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 organic phase and the liquid coordination complex phase are separated by low-temperature extraction after the reaction is completed, and the organic phase is concentrated and purified.
In an alternative embodiment, after the reaction is completed, cooling to 0-20 ℃, adding an extraction solvent for extraction, and carrying out 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 alternative embodiment, the extracted organic phase is distilled and purified under reduced pressure, and fractions within 160 ℃ to 190 ℃ under 0.8KPa to 1KPa are collected to obtain the 4-tertiary butyl-2- (alpha-methylbenzyl) phenol product.
In an alternative embodiment, the liquid coordination complex phase is recycled after a post-treatment comprising: pulping, separating and drying the liquid coordination complex phase and the post-treatment solvent.
In an alternative embodiment, 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 pulped, and after at least one liquid separation treatment, the obtained liquid coordination complex phase is dried in vacuum at a temperature of 80-130 ℃ for 8-10 h.
The invention has the following beneficial effects: the method uses 4-tertiary butyl phenol and styrene as reaction raw materials, and uses the liquid coordination complex as a catalyst and a solvent to perform one-pot reaction, so that the synthetic process steps are simplified, and the limitation of volatile solvents on the reaction temperature in the reaction process is avoided. Through the selection of the types and the proportions of the liquid coordination complex, the reaction period is greatly shortened, the higher product yield and purity can be achieved, the reaction rate is improved, the problem of solvent residue is avoided, a large amount of acid wastewater can not be generated in the reaction process, and the solvent used in the product after the reaction and the post-treatment process of the liquid coordination complex can be recycled, so that 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 dissolution performance, better in thermal stability and simpler in preparation process. Therefore, the preparation method provided by the invention has the advantages of simple process, easiness in operation, simplicity and convenience in synthesis of the liquid coordination complex catalyst, low requirements on production equipment, mild and easily-achieved reaction conditions, more contribution to industrial large-scale 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 that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
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 more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a preparation method of 4-tertiary butyl-2- (alpha-methylbenzyl) phenol, which creatively utilizes a liquid coordination complex as a catalyst and a solvent which are suitable for reaction, and carries out Friedel-crafts alkylation reaction on 4-tertiary butyl phenol and styrene to prepare the 4-tertiary butyl-2- (alpha-methylbenzyl) phenol. Specifically comprises the following steps:
s1, liquid coordination complex synthesis
The inventors have optimized the kinds of metal halides and organic ligands for synthesizing liquid coordination complexes using metal halides and organic ligands: 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 than one; the organic ligand is at least one selected from acetamide, N-methylacetamide, trioctyl phosphorus oxide, N-dimethyl acetamide, urea and thiourea, and can be one or more.
The metal halide and the organic ligand are selected within the above ranges, so that the prepared liquid coordination complex is suitable for the preparation method provided in the embodiment of the present invention. If the metal halide and the organic ligand are selected outside the above ranges, the liquid coordination complex cannot be synthesized, the reaction cannot be performed, or the yield is significantly lowered.
Further, the molar ratio of the organic ligand to the metal halide used for preparing the liquid coordination complex is n 1, and n is more than or equal to 0.5 and less than or equal to 1, and the liquid coordination complex prepared in the range is more suitable for the preparation method of the embodiment of the invention, so that the yield can be higher. In a preferred embodiment, the molar ratio of organic ligand to metal halide used to prepare the liquid coordination complex is from 0.6 to 0.7:1.
Specifically, the molar ratio of the organic ligand to the metal halide may be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or the like, or may be any value between the above adjacent values. The liquid coordination complex mainly comprises cations, neutral molecules and anions which are composed of metal elements (M) and organic ligands (L). Cationic examples are [ MCl ] 2 L 2 ] + 、[MCl 2 L] + Neutral molecules such as [ MCl ] 3 L]、[M 2 Cl 6 L]The anions being metal halide anions, e.g. [ MCl ] 4 ] - 、[M 2 Cl 7 ] - 、[M 3 Cl 10 ] - 。
The basic synthesis of liquid coordination complexes is known to those skilled in the art and reference is made to the preparation methods reported in [ Angewandte Chemie International Edition,2013,52 (48): 12582-12586 ].
S2 Friedel-crafts alkylation reaction
4-tertiary butyl phenol and styrene are used as reaction raw materials, and a liquid coordination complex is used as a catalyst and a solvent to perform 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 the volatile solvent on the reaction temperature is eliminated, and the reaction rate is improved.
In the actual operation process, 4-tertiary butyl phenol, styrene and a 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℃to 65℃and the reaction time is 0.2h to 1h. The liquid coordination complex can be added into a reaction kettle, then 4-tertiary butyl phenol and styrene are added, and then 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 ℃, etc. 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-tertiary butyl phenol is 2-4:1, and the molar ratio of the 4-tertiary butyl phenol to the styrene is 1:1-2. In a preferred embodiment, the molar ratio of liquid coordination complex to 4-tert-butylphenol is from 2.5 to 3.5:1, the molar ratio of 4-tert-butylphenol to styrene is from 1:1.2 to 1.8.
Specifically, the molar ratio of the liquid coordination complex to 4-tert-butylphenol may be 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, etc., and the molar ratio of 4-tert-butylphenol to styrene may be 1:1.0, 1:1.2, 1:1.5, 1:1.7, 1:2.0, etc.
S3, post-treatment
And (3) carrying out low-temperature extraction separation after the reaction is finished to obtain an organic phase and a liquid coordination complex phase, concentrating and purifying the organic phase to obtain a 4-tertiary butyl-2- (alpha-methylbenzyl) phenol product, and carrying out post-treatment on the liquid coordination complex phase for recycling.
In the actual operation process, after the reaction is completed, 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 completed to obtain an organic phase and a liquid coordination complex phase, concentrating the organic phase under reduced pressure to obtain light yellow liquid, pulping, separating liquid, drying the liquid coordination complex phase and another post-treatment solvent, and recycling. Therefore, the preparation method provided by the embodiment of the invention only uses a small amount of organic solvent in the low-temperature extraction and liquid coordination complex post-treatment processes of the product, but can be recycled, and a large amount of acid wastewater can not be generated in the reaction process, so that the preparation method is more energy-saving and environment-friendly.
In some embodiments, the extraction solvent is at least one selected from n-heptane, petroleum ether and n-hexane, and 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 within 160-190 ℃ under 0.8-1 KPa to obtain a 4-tertiary 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, and may be any one or more of the above. Mixing and pulping the liquid coordination complex phase with a post-treatment solvent, then carrying out at least one liquid separation treatment, and vacuum drying the obtained liquid coordination complex phase for 8-10 h at the temperature of 80-130 ℃.
Specifically, the liquid separation treatment may be 2 or 3 times, and is not limited herein. The amount of the post-treatment solvent used is not limited and may be equal to or slightly larger 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 ℃, etc.; the drying time may be 8 hours, 9 hours, 10 hours, etc.
In some embodiments, n-heptane and diethyl ether can be reused after simple distillation purification, and the repeated use has no effect after verification.
The inventor finds that the catalytic performance of the liquid coordination complex catalyst after vacuum drying is not obviously attenuated after 4 times of recycling, and the preparation process provided by the embodiment of the invention realizes recycling of raw materials and meets the requirements of energy conservation and environmental protection. The synthesis method provided by the embodiment of the invention uses the liquid coordination complex catalyst, has low saturated vapor pressure and good thermal stability, has good solubility to most substances, does not interact, is stable in water and air, has wider acidity adjustment range and catalytic performance, can be reused after being dried in vacuum, 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 requirements on production equipment, mild and easily achieved reaction conditions, high product yield, over 85 percent of reaction yield and over 95 percent of purity.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
In the following examples, liquid coordination complexes are shown as 0.6Ur-AlCl 3 For example, ur represents the organic ligand Urea, alCl 3 Represents the metal halide aluminum trichloride, 0.6 means that the molar ratio of urea to aluminum trichloride is 0.6.
In the following examples, the apparatus for performing High Performance Liquid Chromatography (HPLC) tests was a shimadzu LC-2030 type high performance liquid chromatograph, an ultraviolet-visible light detector, a Durashell C18 (L) column (250×4.6mm i.d.; particle size, 5 μm), column temperature: 30 ℃, detector wavelength: 254nm, mobile phase ratio: acetonitrile: water = 80:20, mobile phase flow rate: 1mL/min. equiv represents molar equivalent, and room temperature represents 4 to 30 ℃.
Example 1
This example provides a process for the preparation of 4-tert-butyl-2- (α -methylbenzyl) phenol comprising the steps of:
(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 purged with nitrogen, and mechanical stirring (200 rpm) was started and the oil bath temperature was set to 90 ℃. Adding urea (1.2 mol) into a three-necked flask for 4 times within 30min, and continuously reacting for 10h until the reaction is complete to obtain a clear and transparent ureA-Aluminum trichloride liquid coordination complex (0.6 Ur-AlCl) 3 ) Stored in a glove box for later use.
(2) Preparation
Accurately weighing 4-tertiary butyl phenol (1.5 mol), styrene (1.2 equiv.) and ureA-Aluminum trichloride liquid coordination complex (0.6 Ur-AlCl) 3 ) (2.5 equiv.) the mixture was placed in a three-necked flask with stirring, and the temperature was slowly raised to about 50deg.C after the 4-t-butylphenol was completely dissolved) The system was set to react at 65℃for 0.5h with heat preservation.
(3) Post-treatment
After the heat preservation reaction is finished, the liquid mixture after the reaction is cooled to 20 ℃, then n-heptane is added for stirring and extraction, and the organic phase is taken after liquid separation and dried by spinning to obtain 373.8g of pale yellow liquid. The pale yellow liquid obtained was distilled under reduced pressure, and a fraction at 160 to 190℃under 0.8KPa was collected to give the product 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (344.3 g, purity 95.3%) in 86% yield.
And 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 a liquid coordination complex phase, continuously repeatedly using the liquid coordination complex phase after vacuum drying at 100 ℃ for 10 hours, maintaining the process conditions in the same proportion as the first synthesis process, repeatedly using the liquid coordination complex phase for 4 times, and obtaining the product yield and purity results shown in the table 1, wherein the results show that the catalytic performance of the liquid coordination complex phase is not obviously attenuated after the liquid coordination complex phase is recycled for 4 times. The HPLC diagram of the product is shown in FIG. 1.
TABLE 1 cycle times of liquid coordination complex and catalytic effect
| Sequence 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 process for the preparation of 4-tert-butyl-2- (α -methylbenzyl) phenol comprising the steps of:
(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 purged with nitrogen, mechanical stirring (250 rpm) was turned on and the oil bath temperature was set to 80 ℃. Adding acetamide (1.8 mol) into a three-necked flask for 8 times within 30min, and continuously reacting for 8h until the reaction is complete to obtain a clear and transparent acetamide-aluminum trichloride liquid coordination complex (0.6 AA-AlCl) 3 ) Stored 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 coordination complex (0.6 AA-AlCl) 3 ) (3 equiv.) the flask was charged and stirring was turned on, and after the 4-t-butylphenol was slowly warmed to complete dissolution (about 40 ℃ C.), the system was set to react at 40 ℃ C. With heat preservation for 1h.
(3) Post-treatment
After the heat preservation reaction is finished, the liquid mixture after the reaction is cooled to 20 ℃, then n-heptane is added for stirring and extraction, and the organic phase is taken after liquid separation and dried by spinning to obtain 254.3g of pale yellow liquid. The pale yellow liquid obtained was distilled under reduced pressure, and fractions within 160-190℃at 0.8KPa were collected to give the product 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (224.8 g, purity 96.2%) in 85% yield.
Example 3
This example provides a process for the preparation of 4-tert-butyl-2- (α -methylbenzyl) phenol comprising the steps of:
(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 purged 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 a three-neck flask for 10 times within 30min, and continuously reacting for 12h until the reaction is complete to obtain clear and transparent trioctyloxyphosphor-gallium trichloride liquid coordination complex (0.7P) 888 O-GaCl 3 ) Stored in a glove box for later use.
(2) Preparation of 4-tert-butyl-2- (alpha-methylbenzyl) phenol
Accurately weighing 4-tertiary butyl phenol (0.2 mol), styrene (1.6 equiv.) and trioctyloxyphosphorus-gallium trichloride liquid coordination complex (0.7P) 888 O-GaCl 3 ) (2 equiv.) the flask was charged and stirring was turned on, and after the 4-t-butylphenol was slowly warmed to complete dissolution (about 40 ℃ C.), the system was set to react at 45 ℃ C. With heat preservation for 0.5h.
(3) Post-treatment
After the heat preservation reaction is finished, the liquid mixture after the reaction is cooled to 0 ℃, then n-heptane is added for stirring and extraction, and after liquid separation, an organic phase is taken and dried by spinning to obtain 62.1g of pale yellow liquid. The pale yellow liquid obtained was distilled under reduced pressure, and a fraction at 160 to 190℃under 0.8KPa was collected to give 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (46.1 g, purity 97.2%) as a product in 88% yield.
Example 4
This example provides a process for the preparation of 4-tert-butyl-2- (α -methylbenzyl) phenol comprising the steps of:
(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 purged with nitrogen, mechanical stirring (250 rpm) was turned on and the oil bath temperature was set to 80 ℃. N-methylacetamide (1.95 mol) was added to the three-necked flask in 8 portions within 30 minutesThe reaction is continued for 8 hours until the reaction is complete, and a clear and transparent N-methylacetamide-aluminum trichloride liquid coordination complex (0.65 NMA-AlCl) is obtained 3 ) Stored in a glove box for later use.
(2) Preparation of 4-tert-butyl-2- (alpha-methylbenzyl) phenol
Accurately weighing 4-tert-butylphenol (2 mol), styrene (1.3 equiv.) and N-methylacetamide-aluminum trichloride liquid coordination complex (0.65 NMA-AlCl) 3 ) (3.5 equiv.) was added to the three-necked flask and stirring was turned on, and after slowly warming to complete dissolution of 4-t-butylphenol (about 40 ℃ C.), the system was set to react at 60 ℃ for 0.8h with heat preservation.
(3) Post-treatment
After the heat preservation reaction is finished, the liquid mixture after the reaction is cooled to 5 ℃, then n-heptane is added for stirring and extraction, and the organic phase is taken after liquid separation and dried by spinning to obtain 494.6g of pale yellow liquid. The pale yellow liquid obtained was distilled under reduced pressure, and a fraction at 160 to 190℃under 0.8KPa was collected to give 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (460.1 g, purity 95.1%) as a product 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- (α -methylbenzyl) phenol (purity 95.2%) was obtained 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- (α -methylbenzyl) phenol (purity 97%) was obtained in 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-Aluminum trichloride liquid coordination Complex 0.5Ur-AlCl 3 。
The results show that: the product 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (purity 96%) was obtained in 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-Aluminum trichloride liquid coordination Complex 1.0Ur-AlCl 3 。
The results show that: no target product 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol was 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 completion of the reaction, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (256 g, purity 56.2%) was obtained in a yield of 37.7%.
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 completion of the reaction, 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol (292 g, purity 32.2%) was obtained in a yield of 24.7%.
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 liquid coordination complex catalyst is 1.2Ur-AlCl 3 。
The results show that: after the completion of the reaction, the formation of the target product (4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol) was 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 liquid coordination complex catalyst is 0.6AA-FeCl 3 。
The results show that: after the completion of the reaction, the formation of the target product (4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol) was 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 liquid coordination complex catalyst is 0.6 glycol-ZnCl 2 。
The results show that: after the completion of the reaction, the formation of the target product (4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol) was 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 is an equivalent amount of triethylamine hydrochloride.
The results show that: the product 4-tert-butyl-2- (α -methylbenzyl) phenol (purity 70%) was obtained in 62% yield.
In summary, the invention provides a preparation method of 4-tert-butyl-2- (alpha-methylbenzyl) phenol, which uses a liquid coordination complex as a catalyst and a solvent to catalyze 4-tert-butylphenol and styrene to react and synthesize. After the reaction is finished, adding a solvent to perform low-temperature extraction on the system, performing spin-drying on the extract after the 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 processing the liquid coordination complex for recycling. Has the following advantages:
(1) The raw materials of 4-tertiary butyl phenol, styrene and the liquid coordination complex are directly mixed and dissolved by adopting a one-pot method to react, 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 a solvent and a catalyst, so that the introduction of other impurities is reduced, the reaction risk is reduced, the limitation of the 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 acid wastewater can not be generated in the reaction process, and the method is more energy-saving and environment-friendly.
(4) The liquid coordination complex has the advantages of low cost, easy obtainment of organic ligands, insensitivity to air and easy storage 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 more than 85%, and the purity is more than 95%.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. 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 process for the preparation of 4-tert-butyl-2- (α -methylbenzyl) phenol, comprising: taking 4-tertiary butyl phenol and styrene as reaction raw materials, and adopting a liquid coordination complex as a catalyst and a solvent for reaction;
wherein the liquid coordination complex is synthesized with a metal halide and an organic ligand;
the liquid coordination complex is at least one selected from acetamide-aluminum chloride liquid coordination complex, N-methylacetamide-aluminum chloride liquid coordination complex, urea-zinc chloride liquid coordination complex and urea-titanium chloride liquid coordination complex; the molar ratio of the organic ligand and the metal halide used for preparing the liquid coordination complex is n 1, and n is more than or equal to 0.5 and less than 1;
the molar ratio of the liquid coordination complex to the 4-tertiary butyl phenol is 2-4:1, and the molar ratio of the 4-tertiary butyl phenol to the styrene is 1:1-2;
and after mixing and dissolving the 4-tertiary butyl phenol, the styrene and the liquid coordination complex, reacting for 0.1-5 h at the temperature of 30-100 ℃.
2. The method of producing according to claim 1, wherein the molar ratio of the organic ligand and the metal halide used for producing the liquid coordination complex is 0.6 to 0.7:1.
3. The production method according to claim 1 or 2, characterized in that the molar ratio of the liquid coordination complex to the 4-tert-butylphenol is 2.5 to 3.5:1, and the molar ratio of the 4-tert-butylphenol to the styrene is 1:1.2 to 1.8.
4. The preparation method according to claim 1, wherein the reaction temperature is 40-65 ℃ and the reaction time is 0.2-1 h.
5. The process according to claim 4, wherein the organic phase and the liquid coordination complex phase are separated by extraction at a low temperature after completion of the reaction, 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 ℃ to 20 ℃, an extraction solvent is added for extraction, and the organic phase is subjected to reduced pressure distillation and purification after the extraction and the liquid separation;
wherein the extraction solvent is at least one selected from n-heptane, petroleum ether and n-hexane.
7. The process according to claim 6, wherein the extracted organic phase is purified by distillation under reduced pressure, and a fraction of 0.8KPa to 1KPa at 160℃to 190℃is collected to obtain a 4-tert-butyl-2- (. Alpha. -methylbenzyl) phenol product.
8. The method of claim 5, wherein the liquid coordination complex phase is recycled after a post-treatment comprising: 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 method according to claim 9, wherein the liquid coordination complex phase is mixed with the post-treatment solvent and slurried, and then subjected to at least one liquid separation treatment, and the resulting liquid coordination complex phase is dried under vacuum at a temperature of 80 to 130 ℃ for 8 to 10 hours.
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| CN104262110A (en) * | 2014-09-11 | 2015-01-07 | 中南大学 | Method for preparing 4-tert-butyl-2-(alpha-methylbenzyl)phenol |
| CN112574006A (en) * | 2020-12-31 | 2021-03-30 | 江西赣锋循环科技有限公司 | Preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol |
| CN114230496A (en) * | 2021-12-15 | 2022-03-25 | 达高工业技术研究院(广州)有限公司 | Aromatic sulfinic acid compound and preparation method thereof |
| CN115124407A (en) * | 2022-09-02 | 2022-09-30 | 西陇科学股份有限公司 | Preparation method of 2, 5-ditert octyl hydroquinone |
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| RU2666139C2 (en) * | 2014-07-10 | 2018-09-06 | Релайэнс Индастриз Лимитед | Ionic liquid, adduct and methods of their obtaining |
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