CN117943125A - Metal catalyst and preparation method thereof, and preparation method of 2,3, 5-trimethylhydroquinone diester - Google Patents
Metal catalyst and preparation method thereof, and preparation method of 2,3, 5-trimethylhydroquinone diester Download PDFInfo
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- -1 2,3, 5-trimethylhydroquinone diester Chemical class 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 48
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000012345 acetylating agent Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 14
- 239000003377 acid catalyst Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229930003427 Vitamin E Natural products 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229940046009 vitamin E Drugs 0.000 description 3
- 235000019165 vitamin E Nutrition 0.000 description 3
- 239000011709 vitamin E Substances 0.000 description 3
- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical compound CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a metal catalyst and a preparation method thereof, and a preparation method of 2,3, 5-trimethylhydroquinone diester. The method uses the metal catalyst to replace the conventional preparation process of the acid catalyst, adopts low-cost air as an oxide source, has simple reaction route and high product yield, and avoids the problem of material corrosion caused by the acid catalyst. In addition, the crude 2,3, 5-trimethylhydroquinone diester is separated and purified by a continuous rectification scheme, the separation process is simple, and the problem of product loss in filtrate in the traditional crystallization process is avoided.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a metal catalyst and a preparation method thereof, and a preparation method of 2,3, 5-trimethylhydroquinone diester.
Background
Vitamin E has the effects of resisting aging, improving immunity and the like in human bodies, and is widely applied to the fields of foods, medicines, cosmetics and the like. 2,3, 5-trimethylhydroquinone diester is an important intermediate for synthesizing vitamin E, the optimization of the preparation process is critical to the development of the vitamin E industry, and the traditional preparation process mainly comprises a trimethylphenol method, a pseudotrimethylbenzene method and an isophorone method.
The tricresyl process uses tricresyl as material and strong alkali as catalyst, and is prepared through high temperature and high pressure reaction. The 2,4, 6-trimethylphenol adopted by the route has high price and high production cost, and is difficult to realize industrial production.
The preparation process of the pseudocumene method comprises the steps of taking propylene as an alkylating reagent, and then sulfonating, alkali melting and dealkylating to synthesize TMHQ. The method has mild conditions, long route, poor reaction selectivity and difficult purification and separation.
The isophorone method is to obtain trimethylhydroquinone diester by taking acetone as an initial raw material and carrying out polymerization, isomerization, oxidation and rearrangement. The method has complex synthetic route, uses strong acid as a catalyst, has high equipment corrosion risk and high industrial production cost.
Patent CN1241559a reports that the process route is simple, but the cost of raw materials is high, and the strong acid used for catalysis can cause the generation of a large amount of wastewater, and the cost of industrial three-waste treatment and equipment corrosion prevention investment are high, by using oxo isophorone as raw material and using strong acid such as perchloric acid, sulfuric acid or fluorosulfonic acid as catalyst.
Patent CN1273963a reports that the product yield obtained by separating and purifying the oxo-isophorone as raw material through crystallization, secondary reaction of crystallization filtrate and other means after the reaction is only 88%.
The development of a novel preparation method of 2,3, 5-trimethylhydroquinone diester with mild reaction conditions, low production cost and high yield has very positive significance.
Disclosure of Invention
The invention aims to provide a novel metal catalyst and a preparation method thereof, and a preparation method of 2,3, 5-trimethylhydroquinone diester. The method uses the metal catalyst to replace the conventional preparation process of the acid catalyst, adopts low-cost air as an oxide source, has simple reaction route and high product yield, and avoids the problem of material corrosion caused by the acid catalyst.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In a first aspect of the present invention, there is provided a metal catalyst having the structure:
in a second aspect of the present invention, a method for preparing a metal catalyst is provided, wherein N1, N2-dimethyl-1, 2-dinaphthylamine is used as a ligand, and the metal catalyst is prepared by reacting with copper salt under alkaline conditions:
preferably, the preparation method of the metal catalyst comprises the following steps:
(1) Dissolving a ligand N1, N2-dimethyl-1, 2-dinaphthylamine and a base in an organic solvent;
(2) And (3) adding copper salt into the ligand solution in an inert atmosphere for reaction, filtering and washing by adopting an organic solvent to obtain the metal catalyst.
Preferably, the ligand N1, N2-dimethyl-1, 2-dinaphthylamine has the following structural formula:
Preferably, the base in step 1) is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, preferably potassium carbonate; the mass ratio of the alkali dosage to the ligand is 1:50-200, preferably 1:80-130;
preferably, the organic solvent in the step 1) is one or more of methanol, ethanol, ethylene glycol and benzyl alcohol, preferably ethylene glycol; the mass ratio of the organic solvent to the ligand is 1:0.02-0.1, preferably 1:0.05-0.08;
Preferably, the copper salt in step 2) is one or more of copper acetate, copper chloride, copper sulfate, preferably copper chloride; the mass ratio of the copper salt to the ligand is 1:5-25, preferably 1:10-15; the reaction temperature is 80-250 ℃, preferably 150-210 ℃.
The third aspect of the invention provides a preparation method of 2,3, 5-trimethylhydroquinone diester, which uses trimellitic benzene as a raw material, air as an oxidizing substance and acetic anhydride as an acetylating reagent, and the 2,3, 5-trimethylhydroquinone diester is produced by reaction under the action of the metal catalyst.
Preferably, the mass ratio of the added amount of acetic anhydride to the pseudocumene is 1:1.5-5, preferably 1:2-4;
Preferably, the mass ratio of the metal catalyst to the pseudocumene is 1:50-200, preferably 1:80-120;
Preferably, the pressure of the air after being introduced is 0.1-0.5mPa, the flow rate is 2-10L/min, preferably 0.15-0.3mPa, and 5-8L/min;
preferably, the reaction temperature is 80-150 ℃, preferably 100-120 ℃;
preferably, the preparation method comprises the following steps: mixing and dissolving the pseudocumene and the solvent, and heating for preheating;
Then adding a metal catalyst, and then introducing air to react to obtain 2,3, 5-trimethylhydroquinone diester;
preferably, the preheating temperature is 30-60 ℃, preferably 40-50 ℃.
After the reaction is finished, the catalyst is filtered out, and the solvent is removed by reduced pressure distillation to obtain the crude trimethylhydroquinone diester.
The reduced pressure distillation temperature is 80-150 ℃, the vacuum degree is 20-80kPa, preferably 100-120 ℃ and 30-60kPa;
Preferably, the crude 2,3, 5-trimethylhydroquinone diester is rectified by continuous rectification to obtain the high-purity 2,3, 5-trimethylhydroquinone diester product.
Preferably, the continuous rectification comprises the steps of:
a) Adding the bottom liquid into a rectifying tower, reducing the vacuum degree in the rectifying tower, and continuously adding the crude 2,3, 5-trimethylhydroquinone diester into the rectifying tower kettle after the temperature of the tower kettle is raised to 75-120 ℃, preferably 90-110 ℃;
b) At a vacuum level of 0.05 to 0.4kPa, preferably 0.1 to 0.2kPa; the 2,3, 5-trimethylhydroquinone diester is purified by rectification at a temperature of 100-300 ℃, preferably 150-250 ℃.
Preferably, the bottom-laying liquid in the step a) adopts one or more of trimellitic benzene and acetic anhydride, preferably acetic anhydride;
preferably, the mass ratio of the bottom liquid to the crude 2,3, 5-trimethylhydroquinone diester in step a) is 1:1.5-5, preferably 1:2-3;
Preferably, the 2,3, 5-trimethylhydroquinone diester feed temperature in step a) is from 100 to 200 ℃, preferably from 150 to 180 ℃;
Preferably, the vacuum in step a) is reduced to 50-90kPa, preferably 60-80kPa;
Preferably, the crude 2,3, 5-trimethylhydroquinone diester in step a) is fed at a rate of from 5 to 100g/min, preferably from 20 to 80g/min;
Condensing and refluxing the steam at the top of the rectifying tower, refluxing part of the reflux liquid to the rectifying tower, and collecting part of the reflux liquid to a product kettle;
preferably, the reflux ratio of the rectifying tower is controlled at 1:0.05-0.2, preferably 1:0.1-0.15.
The invention has the beneficial effects that:
taking pseudocumene as a raw material, continuously introducing air into a reaction system under the action of a metal catalyst to prepare a 2,3, 5-trimethylhydroquinone diester product with the selectivity more than 95%, and adopting low-cost air as an oxide source, so that the reaction route is simple, the product yield is high, and the problem of material corrosion caused by an acid catalyst is avoided;
The 2,3, 5-trimethylhydroquinone diester crude product can be purified by a continuous rectification scheme to obtain a high-purity and high-yield 2,3, 5-trimethylhydroquinone diester product, the separation process is simple, and the problem of product waste in filtrate in the traditional crystallization process is avoided.
Detailed Description
The technical scheme of the present invention is further described below by way of specific examples, but is not limited thereto.
N1, N2-dimethyl-1, 2-dinaphthylamine CAS1309366-57-1, shanghai Bi Co., ltd
Nuclear magnetic test conditions: 0.05g of the metal catalyst was weighed, added to 5ml of deuterated chloroform for dissolution, and the sample was sampled and tested using a Jeol-ECZ400S nuclear magnetic test instrument.
Example 1
The metal catalyst was prepared as follows:
50g of N1, N2-dimethyl-1, 2-dinaphthylamine and 0.50g of sodium carbonate are respectively weighed into 1000g of ethylene glycol solvent, replaced by nitrogen, then 4.2g of copper chloride is added into the solvent, the temperature is raised to 200 ℃ and reflux is carried out for 3 hours, suction filtration is carried out, the ethylene glycol is adopted for washing, and 50g of the obtained metal catalyst is separated. The data of the nuclear magnetic analysis are as follows: 13 C NMR (101 MHz, chlorine-d) delta 137.5,130.6,128.6,125.8,125.6,122.9,78,75.5,66,44.4,31ppm.
2,3, 5-Trimethylhydroquinone diester preparation and separation process:
300g of pseudocumene is weighed into a reaction kettle, 150g of acetic anhydride is added for mixing and dissolving, the temperature is raised to 45 ℃ for preheating, 3g of metal catalyst is added into the reaction kettle, 0.3mPa of air is introduced for reaction, air is introduced at the flow rate of 5L/min for reaction, the temperature is continuously raised to 100 ℃ for reaction, when the pseudocumene conversion rate is more than or equal to 99%, the reaction is finished, the catalyst is filtered, and the solvent is removed by reduced pressure distillation at 100 ℃ and 50kPa for obtaining the crude product of 2,3, 5-trimethylhydroquinone diester.
The crude 2,3, 5-trimethylhydroquinone diester prepared above is heated to 150 ℃ for feeding, 250g of pseudocumene is added into the rectifying tower kettle for heating to 90 ℃, the pressure is reduced to 70kPa for preheating the rectifying tower to 90 ℃. And then adding the crude trimethylhydroquinone diester heated to 150 ℃ into a rectifying tower kettle at a speed of 20g/min, continuously reducing the vacuum degree to 0.2kPa, heating the tower kettle to 180 ℃, regulating the reflux ratio to 1:0.1 for extraction after the reflux is stable, analyzing the extracted components, wherein the purity of the 2,3, 5-trimethylhydroquinone diester is 99.8%, and the product yield is 95.6% after accounting by using pseudocumene.
Example 2
The metal catalyst was prepared as follows:
50g of N1, N2-dimethyl-1, 2-dinaphthylamine and 0.63g of potassium carbonate are respectively weighed into 835g of methanol solvent, replaced by nitrogen, then 3.3g of copper acetate is added into the solvent, the temperature is raised to 150 ℃ and reflux is carried out for 5 hours, and then suction filtration and methanol washing are carried out, thus 46g of obtained metal catalyst is separated.
2,3, 5-Trimethylhydroquinone diester preparation and separation process:
Weighing 250g of pseudocumene in a reaction kettle, adding 61g of acetic anhydride for mixing and dissolving, heating to 55 ℃ for preheating, adding 2.5g of metal catalyst in the reaction kettle, then introducing 0.2mPa of air for reaction, introducing air at a flow rate of 7L/min, continuously heating to 120 ℃ for reaction, filtering out the catalyst after the reaction is finished when the pseudocumene conversion rate is more than or equal to 99%, and distilling under reduced pressure at 120 ℃ and 60kPa to remove the solvent to obtain a 2,3, 5-trimethylhydroquinone diester crude product.
And heating the prepared crude 2,3, 5-trimethylhydroquinone diester to 190 ℃ to prepare for feeding, adding 200g of acetic anhydride into a rectifying tower kettle, heating to 100 ℃, reducing the pressure to 80kPa, and preheating the rectifying tower. And then adding the heated crude 2,3, 5-trimethylhydroquinone diester into a rectifying tower kettle at a speed of 30g/min, continuously reducing the vacuum degree to 0.15kPa, heating the tower kettle to 200 ℃, adjusting the reflux ratio to 1:0.2 for extraction after the reflux is stable, analyzing the extracted components, wherein the purity of the 2,3, 5-trimethylhydroquinone diester is 99.9%, and the product yield is 96.0% after accounting for pseudocumene.
Example 3
The metal catalyst was prepared as follows:
50g of N1, N2-dimethyl-1, 2-dinaphthylamine and 0.33g of potassium bicarbonate are respectively weighed into 500g of ethanol solvent, replaced by nitrogen, then 2.0g of copper sulfate is added into the solvent, the temperature is raised to 180 ℃ and reflux is carried out for 3.5h, suction filtration is carried out, ethanol washing is adopted, and 43g of the obtained metal catalyst is separated.
Weighing 250g of pseudocumene in a reaction kettle, adding 165g of acetic anhydride for mixing and dissolving, heating to 40 ℃ for preheating, adding 1.6g of metal catalyst in the reaction kettle, then introducing 0.2mPa of air for reaction, introducing air at a flow rate of 10L/min, continuously heating to 90 ℃ for reaction, filtering out the catalyst after the reaction is finished when the pseudocumene conversion rate is more than or equal to 99%, and distilling under reduced pressure at 90 ℃ and 30kPa to remove the solvent to obtain a 2,3, 5-trimethylhydroquinone diester crude product.
And heating the prepared crude 2,3, 5-trimethylhydroquinone diester to 120 ℃ for feeding, adding 100g of acetic anhydride into a rectifying tower kettle, heating to 110 ℃, reducing the pressure to 80kPa, and preheating the rectifying tower. And then adding the heated crude 2,3, 5-trimethylhydroquinone diester into a rectifying tower kettle at a speed of 50g/min, continuously reducing the vacuum degree to 0.1kPa, heating the tower kettle to 220 ℃, regulating the reflux ratio to 1:0.05 for extraction after the reflux is stable, analyzing the extracted components, wherein the purity of the 2,3, 5-trimethylhydroquinone diester is 99.8%, and the product yield is 97.1% after accounting for pseudocumene.
Example 4
The metal catalyst was prepared as follows:
50g of N1, N2-dimethyl-1, 2-dinaphthylamine and 1g of sodium carbonate are respectively weighed into 625g of benzyl alcohol solvent, replaced by nitrogen, 6.3g of copper acetate is added into the solvent, the temperature is raised to 220 ℃ and reflux is carried out for 6 hours, suction filtration is carried out, benzyl alcohol is adopted for washing, and 45g of the obtained metal catalyst is separated.
Weighing 200g of pseudocumene in a reaction kettle, adding 40g of acetic anhydride for mixing and dissolving, heating to 60 ℃ for preheating, adding 4g of metal catalyst in the reaction kettle, introducing 0.3mPa of air for reaction, introducing air at a flow rate of 6L/min, continuously heating to 100 ℃ for reaction, filtering out the catalyst after the reaction is finished when the pseudocumene conversion rate is more than or equal to 99%, and distilling under reduced pressure at 90 ℃ and 60kPa to remove the solvent to obtain a2, 3, 5-trimethylhydroquinone diester crude product.
And heating the prepared crude 2,3, 5-trimethylhydroquinone diester to 100 ℃ for feeding, adding 120g of acetic anhydride into a rectifying tower kettle, heating to 120 ℃, reducing the pressure to 60kPa, and preheating the rectifying tower. And then adding the heated crude 2,3, 5-trimethylhydroquinone diester into a rectifying tower kettle at a speed of 60g/min, continuously reducing the vacuum degree to 0.05kPa, heating the tower kettle to 200 ℃, regulating the reflux ratio to 1:0.1 for extraction after the reflux is stable, analyzing the extracted components, wherein the purity of the 2,3, 5-trimethylhydroquinone diester is 99.9%, and the product yield is 97.3% after accounting for pseudocumene.
Comparative example 1
Weighing 200g of pseudocumene in a reaction kettle, adding 40g of acetic anhydride for mixing and dissolving, heating to 60 ℃ for preheating, adding 4g of copper acetate as a catalyst in the reaction kettle, introducing 0.3mPa of air for reaction, introducing air at a flow rate of 6L/min, continuously heating to 100 ℃ for reaction, wherein the reaction time is 20h, the pseudocumene conversion rate is 17%, and the reaction liquid is sampled and analyzed to generate no 2,3, 5-trimethylhydroquinone diester.
Claims (10)
1. A metal catalyst characterized by the following structure:
2. The preparation method of the metal catalyst comprises the step of reacting N1, N2-dimethyl-1, 2-dinaphthylamine serving as a ligand with copper salt under an alkaline condition to prepare the metal catalyst.
3. The preparation method according to claim 2, wherein the preparation method of the metal catalyst is as follows:
(1) Adding the ligand N1, N2-dimethyl-1, 2-dinaphthylamine and a base into an organic solvent;
(2) Adding copper salt into the ligand solution in inert atmosphere for reaction, filtering and washing to obtain a metal catalyst;
Preferably, the ligand N1, N2-dimethyl-1, 2-dinaphthylamine has the following structural formula:
4. a process according to claim 3, wherein the base in step 1) is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, preferably potassium carbonate;
Preferably, the mass ratio of the base to the ligand is 1:50-200, preferably 1:80-130;
Preferably, the organic solvent in the step 1) is one or more of methanol, ethanol, ethylene glycol and benzyl alcohol, preferably ethylene glycol;
Preferably, the mass ratio of the organic solvent to the ligand is 1:0.02-0.1, preferably 1:0.05-0.08.
5. The method according to claim 3, wherein the copper salt in step 2) is one or more of copper acetate, copper chloride, copper sulfate, preferably copper chloride;
preferably, the mass ratio of copper salt to ligand is 1:5-25, preferably 1:10-15;
Preferably, the reaction temperature is 80-250 ℃, preferably 150-210 ℃.
6. A process for preparing 2,3, 5-trimethylhydroquinone diester, which comprises reacting a starting material of trimellitic benzene with air as an oxidizing substance and acetic anhydride as an acetylating agent with the metal catalyst according to claim 1 or the metal catalyst prepared by the process according to any one of claims 2 to 5 to produce 2,3, 5-trimethylhydroquinone diester.
7. The preparation method according to claim 6, wherein the mass ratio of the addition amount of acetic anhydride to the pseudocumene is 1:1.5-5, preferably 1:2-4;
Preferably, the mass ratio of the metal catalyst to the pseudocumene is 1:50-200, preferably 1:80-120;
Preferably, the pressure of the air after being introduced is 0.1-0.5mPa, the flow rate is 2-10L/min, preferably 0.15-0.3mPa, and 5-8L/min;
preferably, the reaction temperature is 80-150 ℃, preferably 100-120 ℃.
8. The preparation method according to claim 6, characterized in that the preparation method comprises the steps of: mixing and dissolving the pseudocumene and the solvent, and heating for preheating; then adding a metal catalyst, and then introducing air to react to obtain 2,3, 5-trimethylhydroquinone diester;
preferably, the preheating temperature is 30-60 ℃, preferably 40-50 ℃;
preferably, after the reaction is finished, the catalyst is filtered out, and the solvent is removed by reduced pressure distillation to obtain the crude trimethylhydroquinone diester.
Preferably, the reduced pressure distillation temperature is 80-150 ℃, the vacuum degree is 20-80kPa, preferably 100-120 ℃,30-60kPa;
Preferably, the crude 2,3, 5-trimethylhydroquinone diester is rectified by continuous rectification to obtain the high-purity 2,3, 5-trimethylhydroquinone diester product.
9. The method of claim 8, wherein the continuous rectification comprises the steps of:
a) Adding the bottom liquid into a rectifying tower, reducing the vacuum degree in the rectifying tower, and continuously adding the crude 2,3, 5-trimethylhydroquinone diester into the rectifying tower kettle after the temperature of the tower kettle is raised to 75-120 ℃, preferably 90-110 ℃;
b) At a vacuum level of 0.05 to 0.4kPa, preferably 0.1 to 0.2kPa; the 2,3, 5-trimethylhydroquinone diester is purified by rectification at a temperature of 100-300 ℃, preferably 150-250 ℃.
10. The method according to claim 9, wherein the base fluid in step a) is one or more of trimellitic benzene and acetic anhydride, preferably acetic anhydride;
preferably, the mass ratio of the bottom liquid to the crude 2,3, 5-trimethylhydroquinone diester in step a) is 1:1.5-5, preferably 1:2-3;
Preferably, the 2,3, 5-trimethylhydroquinone diester feed temperature in step a) is from 100 to 200 ℃, preferably from 150 to 180 ℃;
Preferably, the vacuum in step a) is reduced to 50-90kPa, preferably 60-80kPa;
Preferably, the crude 2,3, 5-trimethylhydroquinone diester in step a) is fed at a rate of from 5 to 100g/min, preferably from 20 to 80g/min;
preferably, the reflux ratio of the rectifying tower is controlled at 1:0.05-0.2, preferably 1:0.1-0.15.
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