CN115991642A - 2- (4) ， Synthesis method of-tert-butylbenzoyl) benzoic acid - Google Patents
2- (4) ， Synthesis method of-tert-butylbenzoyl) benzoic acid Download PDFInfo
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- CN115991642A CN115991642A CN202111214261.XA CN202111214261A CN115991642A CN 115991642 A CN115991642 A CN 115991642A CN 202111214261 A CN202111214261 A CN 202111214261A CN 115991642 A CN115991642 A CN 115991642A
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- tert
- butylbenzoyl
- benzoic acid
- aluminum trichloride
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- 238000001308 synthesis method Methods 0.000 title claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title 2
- 239000005711 Benzoic acid Substances 0.000 title 1
- 235000010233 benzoic acid Nutrition 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- KFTGETZSJFJXEO-UHFFFAOYSA-N 2-(4-tert-butylbenzoyl)benzoic acid Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1C(O)=O KFTGETZSJFJXEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 14
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000460 chlorine Substances 0.000 abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 abstract description 15
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- WMIQCCDZARURRI-UHFFFAOYSA-N 1,1-dichloroethane Chemical compound CC(Cl)Cl.CC(Cl)Cl WMIQCCDZARURRI-UHFFFAOYSA-N 0.000 description 1
- YWECCEXWKFHHQJ-UHFFFAOYSA-N 2-(4-chlorobenzoyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=C(Cl)C=C1 YWECCEXWKFHHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
2- (4' -tert-Butylbenzoyl) benzoic acid is an essential intermediate for the industrial production of 2-tert-butylanthraquinone, which is a very versatile organic intermediate. The invention provides a synthetic method of 2- (4' -tert-butylbenzoyl) benzoic acid, which comprises the following steps: benzene, dichloromethane, dichloroethane or a mixture thereof is taken as a solvent, phthalic anhydride (2) is added into the solvent, aluminum trichloride is slowly added into the solvent, and meanwhile tertiary butyl benzene (3) is added into the solvent dropwise after the reaction is finished, and the reaction solution is added into dilute hydrochloric acid or dilute sulfuric acid for hydrolysis; (4) After the hydrolysis is finished, removing the water layer, distilling the water layer, adding methanol or ethanol into the rest material liquid, filtering the separated material, and drying to obtain the 2- (4' -tert-butylbenzoyl) benzoic acid. The invention solves the problems of high chlorine content and lower product content in the product, has mild reaction conditions, reduces the wastewater treatment difficulty and has lower product cost.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for synthesizing 2- (4' -tert-butylbenzoyl) benzoic acid.
Background
2- (4' -tert-butylbenzoyl) benzoic acid is an essential intermediate for industrially producing 2-tert-butylanthraquinone, and 2-tert-butylanthraquinone is an organic intermediate with very wide application and is also a main auxiliary agent for synthesizing hydrogen peroxide. The reaction principle is as follows:
however, in the hydrogen peroxide synthesis process, the control on chlorine and sulfur is very strict, so that the chlorine content of 2-tertiary butyl anthraquinone is required to be less than 40ppm and the sulfur content is required to be less than 10ppm, and the chlorine source is mainly the chlorine content of 2- (4 '-tertiary butyl benzoyl) benzoic acid, so that how to prepare 2- (4' -tertiary butyl benzoyl) benzoic acid with lower chlorine content is an urgent problem to be solved in the industry.
The preparation method of the 2- (4' -tert-butylbenzoyl) benzoic acid in the prior art mainly comprises the following steps: the method 1 is that tert-butylbenzene and phthalic anhydride are used as raw materials, chlorobenzene, dichlorobenzene and the like are used as solvents, and Friedel-crafts acylation reaction is carried out under the condition that aluminum trichloride is used as a catalyst to prepare the catalyst; the method 2 comprises the steps of carrying out Friedel-crafts acylation reaction by taking chloroaluminate ionic liquid as a solvent; the method 3 uses solid zeolite molecular sieve as catalyst, and the reaction between phthalic anhydride and tert-butyl benzene is catalyzed at high temperature.
However, the above preparation methods have the following disadvantages, respectively: the method 1 uses tert-butylbenzene and phthalic anhydride as raw materials, chlorobenzene, dichlorobenzene and the like as solvents, and aluminum trichloride as a catalyst to carry out Friedel-crafts acylation reaction. The method is the most industrially used method at present, and the method has the greatest defects that chlorobenzene and dichlorobenzene participate in the reaction, so that the chlorine content in the synthesized 2- (4' -tert-butylbenzoyl) benzoic acid product is high, the product is unqualified due to the fact that the chlorine content in 2-tert-butylanthraquinone exceeds the standard, and the method has more isomers, low product content and low yield. In the method 2, chloroaluminate ionic liquid is used as a solvent for performing Friedel-crafts acylation reaction to prepare 2- (4' -tert-butylbenzoyl) benzoic acid, although the chlorine content is well controlled, the ionic liquid is difficult to prepare and recycle, and industrial application is difficult. The method 3 uses a solid zeolite molecular sieve as a catalyst, and the method is prepared by catalyzing phthalic anhydride and tert-butyl at a high temperature, and has the defect of severe reaction conditions, wherein the temperature is about 300-400 ℃ generally, the zeolite molecular sieve has low recycling rate, and the catalyst is difficult to recycle.
Disclosure of Invention
In order to solve the problems, the invention provides a synthetic method of 2- (4' -tert-butylbenzoyl) benzoic acid, which can well solve the chlorine content, can be industrially implemented, has mild production conditions and low cost. Compared with the prior art, the invention has the advantages that: the chlorinated aromatic hydrocarbon containing chlorine is not used as a solvent, so that the problem of high chlorine content in the product is solved. The reaction conditions are mild, and the temperature does not exceed 40 ℃. The COD of the generated wastewater is lower, and the wastewater treatment difficulty is reduced. The product yield is higher, the content exceeds 98 percent, and the product cost is lower than that of the prior method.
In order to achieve the above object, the present invention provides the following technical solutions:
benzene, methylene dichloride, dichloroethane or a mixture thereof is used as a solvent, phthalic anhydride is added at a certain temperature, the temperature of a reaction system is reduced to 5-15 ℃, aluminum trichloride is slowly added, tert-butylbenzene is added dropwise, the reaction is carried out for 2-4 hours after the tert-butylbenzene is added dropwise, the reaction solution is added into 3-6% hydrochloric acid or sulfuric acid for hydrolysis after the reaction is finished, a lower layer water layer is separated after the hydrolysis is finished, and the water layer is extracted once by using the solvent benzene, methylene dichloride and dichloroethane. The solvent is distilled out from the upper layer for reuse. Adding methanol or ethanol into the rest feed liquid for crystallization, filtering and drying to obtain 2- (4' -tert-butylbenzoyl) benzoic acid.
The synthesis method of the 2- (4' -tert-butylbenzoyl) benzoic acid has the following advantages:
1. the chlorinated aromatic hydrocarbon containing chlorine is not used as a solvent, and the synthesized product contains no chlorine, so that the problem of chlorine in the product is thoroughly solved.
2. The reaction adopts a solvent with the boiling point of 40-80 ℃, and the recovery of the solvent has low energy consumption and is easy to recover.
3. The reaction condition is mild, and the temperature is not more than 40 ℃.
4. The COD of the generated wastewater is lower, and the wastewater treatment difficulty is reduced.
5. By adopting the recrystallization method, the product yield is higher, the product quality is high, and the product cost is lower than that of the prior method.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
Example 1
The following raw materials were used in this example, see in particular table 1:
| sequence number | Raw material name | Dosage of | Percentage content |
| 1 | Tert-butylbenzene | 28g | 99.0% |
| 2 | Dichloroethane (dichloroethane) | 200g | 99.0% |
| 3 | Phthalic acidAnhydride(s) | 30g | 99.0% |
| 4 | Aluminum trichloride | 54g | 98.5% |
| 5 | Hydrochloric acid | 180g | 5% |
| 6 | Absolute ethyl alcohol | 250g | 99.5% |
The synthesis method of the 2- (4' -tert-butylbenzoyl) benzoic acid comprises the following steps:
1) 200g of dichloroethane, 30g of phthalic anhydride, starting stirring, starting a cooling system, cooling the system to 10 ℃, slowly adding 54g of aluminum trichloride, simultaneously dropwise adding 28g of tert-butylbenzene for about 1.5h, slowly increasing the system temperature along with the adding of the aluminum trichloride, controlling the system temperature to be not higher than 10-20 ℃, adding the aluminum trichloride, increasing the reaction temperature to 20-25 ℃ after the dropwise adding of the tert-butylbenzene, closing the cooling system, and continuously stirring for 2h to obtain a reaction solution.
2) 180g of 5% dilute hydrochloric acid is added into a 1000ml four-port reaction bottle, the reaction liquid is slowly put into hydrochloric acid for hydrolysis, the hydrolysis temperature is controlled to be not more than 75 ℃, and the temperature is controlled to be 70-75 ℃ after the hydrolysis is completed.
3) After the hydrolysis is finished, separating a lower water layer, extracting the water layer by using 20ml of dichloroethane, merging the water layer into an upper layer, distilling the upper layer at normal pressure to remove the dichloroethane, cooling, adding 250g of absolute ethyl alcohol when the temperature is 80 ℃, slowly reducing the system temperature, cooling to 20 ℃ by using ice water, precipitating a large amount of white solids in the system, and stirring for 30 minutes. Filtering and drying to obtain 55.75g of product with 96.5% yield. The content of 2- (4' -tert-butylbenzoyl) benzoic acid was 98.16% by detection, without any 2- (4-chlorobenzoyl) benzoic acid.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. A method for synthesizing 2- (4' -tert-butylbenzoyl) benzoic acid is characterized in that:
(1) Benzene, dichloromethane and dichloroethane or a mixture of any two solvents or a mixture of three solvents are used as solvents, phthalic anhydride is added into the solvents, and the mass ratio of the phthalic anhydride to the solvents is 1:3-10;
(2) Adding aluminum trichloride into the reaction liquid formed in the step (1), wherein the mass ratio of phthalic anhydride to aluminum trichloride is 1: 2-2.5, dropwise adding tert-butylbenzene, wherein the mass ratio of phthalic anhydride to tert-butylbenzene is 1:1-1.2;
(3) After the reaction is finished, adding the reaction solution into dilute hydrochloric acid or dilute sulfuric acid for hydrolysis;
(4) After the hydrolysis is finished, separating a water layer, distilling the liquid after the water layer is removed, cooling the rest liquid, adding methanol or ethanol, cooling, and filtering and drying the obtained white solid.
2. The synthesis method according to claim 1, wherein: and (3) maintaining the temperature of the reaction liquid in the step (1) at 5-40 ℃.
3. The synthesis method according to claim 1, wherein: the aluminum trichloride is added in the step (2) in a divided manner, the time is 1-2 h, and the mass ratio of the aluminum trichloride to the phthalic anhydride is 1:2-2.5.
4. The synthesis method according to claim 1, wherein: the concentration of sulfuric acid or hydrochloric acid for hydrolysis in the step (3) is 3-6%, the reaction temperature is controlled to be not more than 75 ℃, and the mass ratio of the sulfuric acid or sulfuric acid to the aluminum trichloride is 1:3.5-5.
5. The synthesis method according to claim 1, wherein: the mass ratio of the methanol or the ethanol to the 2- (4' -tert-butylbenzoyl) benzoic acid in the step (4) is 1:3 to 10.
6. The synthesis method according to claim 1, wherein: the temperature of the reaction solution in the step (1) is kept at 5-40 ℃, aluminum trichloride is added in the step (2) in a fractional manner, the adding time is 1-2 h, the mass ratio of the added aluminum trichloride to phthalic anhydride is 1:2-2.5, the concentration of sulfuric acid or hydrochloric acid for hydrolysis in the step (3) is 3-6%, the reaction temperature is controlled to be not more than 75 ℃, the mass ratio of hydrochloric acid or sulfuric acid to aluminum trichloride is 1:3.5-5, and the mass ratio of methanol or ethanol to 2- (4' -tert-butylbenzoyl) benzoic acid in the step (4) is 1: 3-10, the filtering temperature is 15-25 ℃, and the drying temperature is 100-130 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111214261.XA CN115991642A (en) | 2021-10-19 | 2021-10-19 | 2- (4) ， Synthesis method of-tert-butylbenzoyl) benzoic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111214261.XA CN115991642A (en) | 2021-10-19 | 2021-10-19 | 2- (4) ， Synthesis method of-tert-butylbenzoyl) benzoic acid |
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| Publication Number | Publication Date |
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| CN115991642A true CN115991642A (en) | 2023-04-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202111214261.XA Pending CN115991642A (en) | 2021-10-19 | 2021-10-19 | 2- (4) ， Synthesis method of-tert-butylbenzoyl) benzoic acid |
Country Status (1)
| Country | Link |
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| CN (1) | CN115991642A (en) |
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2021
- 2021-10-19 CN CN202111214261.XA patent/CN115991642A/en active Pending
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