CN106045840A - Synthetic process of 2-benzoylbenzoic acid - Google Patents
Synthetic process of 2-benzoylbenzoic acid Download PDFInfo
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- CN106045840A CN106045840A CN201610388717.7A CN201610388717A CN106045840A CN 106045840 A CN106045840 A CN 106045840A CN 201610388717 A CN201610388717 A CN 201610388717A CN 106045840 A CN106045840 A CN 106045840A
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- catalyst
- benzoyl
- chlorination
- benzoic acid
- aluminum chloride
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- 238000000034 method Methods 0.000 title claims abstract description 17
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 title abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 72
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 20
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 imidazole organic compounds Chemical class 0.000 claims abstract description 15
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 56
- 235000010233 benzoic acid Nutrition 0.000 claims description 29
- 239000005711 Benzoic acid Substances 0.000 claims description 28
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims 3
- 150000008065 acid anhydrides Chemical class 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- WOSQDCFVYQABKO-UHFFFAOYSA-N 1,2-benzoxazol-2-ium;chloride Chemical compound Cl.C1=CC=C2C=NOC2=C1 WOSQDCFVYQABKO-UHFFFAOYSA-N 0.000 description 1
- HHSNIRLXHJNXAK-UHFFFAOYSA-N 1,3-di(propan-2-yl)-2h-imidazole Chemical class CC(C)N1CN(C(C)C)C=C1 HHSNIRLXHJNXAK-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a synthetic process of 2-benzoylbenzoic acid. The synthetic process comprises following steps: step (1), imidazole organic compounds and anhydrous aluminum chloride in certain ratio are mixed, the reaction temperature is kept in a range of 5-15 DEG C, the reaction is performed until no gas is generated, and a catalyst A is obtained; step (2), excessive benzene is added to a reaction kettle, then a certain amount of phthalic anhydride and the catalyst A are added, the reaction temperature is 70-80 DEG C, the heat-preservation reaction is performed for 1-2 h, and then the temperature is decreased to 20-30 DEG C; step (3), diethyl ether is added to a reaction liquid obtained in the step (2) for extraction, and an upper solution and a lower solution are obtained; step (4), diluted hydrochloric acid is added to the upper solution obtained in the step (3) for acidolysis, diethyl ether is removed through evaporation, diluted hydrochloric acid is supplemented, the solution is cooled, crystals are separated out, suction filtration and drying are performed, and 2-benzoylbenzoic acid is obtained; step (5), the lower solution obtained in the step (3) is washed with normal hexane and subjected to vacuum drying, and the catalyst A is obtained. The synthetic process has the technical characteristics that the catalyst A can be recycled, and raw materials are saved.
Description
Technical field
The present invention relates to technical field of chemical synthesis, more specifically, it relates to the conjunction of a kind of o-benzoyl yl benzoic acid
Become technique.
Background technology
O-benzoyl yl benzoic acid is the important intermediate of organic synthesis, is the most former of production anthraquinone dyes intermediate
Material, is widely used in the industry such as dyestuff, papermaking.
Traditional method is the Lewis acid as catalyst such as the aluminum chloride with to several times of moles, urges in this course of reaction
Agent and reactant form complex, need catalytic amount big, and product needs hydrolysis, causes substantial amounts of pollution and waste.Existing
Application publication number is that the patent documentation (documents) of CN105541598A discloses in the middle of a kind of pungent medicine of hydrochloric acid benzisoxazole
The synthetic method of body o-benzoyl yl benzoic acid, with 2-carboxyl benzyl alcohol and phenol as raw material, Cu-lyt. closes for catalyst
Become o-benzoyl yl benzoic acid.The catalyst of the use in the method for both synthesis o-benzoyl yl benzoic acids all can not
Recycle, cause the biggest wasting of resources.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide the synthesis of a kind of o-benzoyl yl benzoic acid
Technique, its catalyst A used is reusable, economizes in raw materials.
For achieving the above object, the technical scheme is that
The synthesis technique of a kind of o-benzoyl yl benzoic acid, comprises the steps:
Step (1): imidazoles organic compound mixes with certain proportion with anhydrous Aluminum chloride, keep reaction temperature at 5～15 DEG C,
Until reaction terminates when generating without gas, obtain catalyst A；
Step (2): after the benzene of excess is added reactor, add a certain amount of phthalic anhydride and catalyst A, reaction temperature 70～80
DEG C, insulation reaction 1～2 hours, it is cooled to 20～30 DEG C；
Step (3): in step (2) in the reactant liquor of gained, adds ether extraction, respectively obtains upper solution and lower floor is molten
Liquid；
Step (4): add dilute hydrochloric acid acidolysis to the upper solution of step (3) gained, then boil off ether, be supplemented with dilute hydrochloric acid,
Cooling, separates out crystal, sucking filtration, is dried, obtains o-benzoyl yl benzoic acid；
Step (5): lower floor's solution of step (3) gained normal hexane washs, vacuum drying obtains catalyst A.
Preferably, in step (1), imidazoles organic compound is chlorination-1 to the present invention, 3-methylimidazole, chlorination-1-
Ethyl-3-methylimidazole, chlorination-1-propyl group-3-Methylimidazole., chlorination-1-butyl-3-Methylimidazole. or chlorination-1,3-two are different
Propyl imidazole.
The present invention preferably, in step (1) mol ratio of imidazoles organic compound and anhydrous Aluminum chloride be 1:1.5～
2.0。
Preferably, in step (1), imidazoles organic compound and anhydrous Aluminum chloride mol ratio are 1:1.75 to the present invention.
Preferably, in step (2), the mol ratio of benzene, phthalic anhydride and catalyst A is 3:1～1.5:0.1～0.5 to the present invention,
Wherein the mole of catalyst A presses the calculating of anhydrous Aluminum chloride mole.
Preferably, in step (2), the mol ratio of benzene, phthalic anhydride and catalyst A is 3:1:0.2, wherein catalyst A to the present invention
Mole press anhydrous Aluminum chloride mole calculate.
Preferably, in step (4), dilute hydrochloric acid is to be mixed by the water of 1 volume concentrated hydrochloric acid and 1 volume and be made into the present invention.
Compared with prior art, there is advantages that
(1) present invention is with imidazoles organic compound and anhydrous Aluminum chloride for Material synthesis catalyst A, and A is repeatable for this catalyst
Use, economize in raw materials.
(2) catalyst A has higher ion migration and diffusion velocity and stronger dissolving organic compound so that urge
Agent A more easily participates in the reaction between benzene, phthalic anhydride, therefore add the catalytic efficiency of catalyst A of the present invention with
And the reaction rate that benzene and phthalic anhydride react.
(3) in the present invention, chlorination-1,3-diisopropyl imidazoles is most preferred imidazoles organic compound.
(4) in the present invention, the preferred molar ratio of chlorination-1,3-diisopropyl imidazoles and anhydrous Aluminum chloride is 1:1.75.
(5) benzene, phthalic anhydride and catalyst A (mole of catalyst A is pressed anhydrous Aluminum chloride mole and calculated) in the present invention
Preferably mol ratio is 3:1:0.2.
Detailed description of the invention
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
The present embodiment can be made after reading this specification by member as required does not has the amendment of creative contribution, but as long as at this
All protected by Patent Law in the right of invention.
Embodiment one:
Chlorination-1,3-methylimidazole mixes for 1:1.5 ratio with both mol ratios with anhydrous Aluminum chloride, keeps reaction temperature
At 10 DEG C, until reaction terminates when generating without gas, obtain catalyst A；It is the benzene of 3:1:0.5, phthalic anhydride and catalysis by mol ratio
After agent A (mole of catalyst A is pressed anhydrous Aluminum chloride mole and calculated) adds reactor, control reaction temperature 75 DEG C, insulation
React 1.5 hours, be cooled to 25 DEG C；In the reactant liquor of gained, add ether extraction, respectively obtain upper solution and lower floor is molten
Liquid；Add dilute hydrochloric acid acidolysis to the upper solution of gained, then boil off ether, be supplemented with dilute hydrochloric acid, cooling, separate out crystal, take out
Filter, is dried, obtains o-benzoyl yl benzoic acid；Lower floor's solution normal hexane washs, and vacuum drying obtains catalyst A.
Embodiment two:
The difference of embodiment two and embodiment one is, imidazoles organic compound is chlorination-1-ethyl-3-methylimidazole.
Embodiment three:
The difference of embodiment three and embodiment one is, imidazoles organic compound is chlorination-1-propyl group-3-Methylimidazole..
Embodiment four:
The difference of embodiment four and embodiment one is, imidazoles organic compound is chlorination-1-butyl-3-Methylimidazole..
Embodiment five:
The difference of embodiment five and embodiment one is, imidazoles organic compound is chlorination-1,3-diisopropyl imidazoles.
Table 1
By table 1 it can be seen that embodiment five is optimum embodiment, its o-benzoyl yl benzoic acid produced has higher product
Rate and purity, catalyst A has the higher response rate simultaneously.Comparing embodiment one～five, other reaction condition is the most identical, uniquely
Variable be to employ different imidazoles organic compound, embodiment one～five employs chlorination-1,3-dimethyl miaow respectively
Azoles, chlorination-1-ethyl-3-methylimidazole, chlorination-1-propyl group-3-Methylimidazole., chlorination-1-butyl-3-Methylimidazole., chlorination-
1,3-diisopropyl imidazoles, therefore, chlorination-1,3-diisopropyl imidazoles is most preferred imidazoles organic compound.
Embodiment six～ten: with most preferred chlorination-1,3-diisopropyl imidazoles and anhydrous Aluminum chloride with different moles
Make catalyst A than reaction, prepare o-benzoyl yl benzoic acid.
Embodiment six:
Chlorination-1,3-diisopropyl imidazoles mixes for 1:1 ratio with both mol ratios with anhydrous Aluminum chloride, keeps reaction temperature
At 5 DEG C, until reaction terminates when generating without gas, obtain catalyst A；It is the benzene of 3:1:0.5, phthalic anhydride and catalyst by mol ratio
After A (mole of catalyst A is pressed anhydrous Aluminum chloride mole and calculated) adds reactor, controlling reaction temperature 80 DEG C, insulation is anti-
Answer 1 hour, be cooled to 20 DEG C；In the reactant liquor of gained, add ether extraction, respectively obtain upper solution and lower floor's solution；
Add dilute hydrochloric acid acidolysis to upper solution, then boil off ether, be supplemented with dilute hydrochloric acid, cooling, separate out crystal, sucking filtration, be dried,
To o-benzoyl yl benzoic acid；Lower floor's solution normal hexane washs, and vacuum drying obtains catalyst A.
Embodiment seven:
The difference of embodiment seven and embodiment six is, chlorination-1, and 3-diisopropyl imidazoles with the mol ratio of anhydrous Aluminum chloride is
1:1.7.
Embodiment eight:
The difference of embodiment eight and embodiment six is, chlorination-1, and 3-diisopropyl imidazoles with the mol ratio of anhydrous Aluminum chloride is
1:1.75.
Embodiment nine:
The difference of embodiment nine and embodiment six is, chlorination-1, and 3-diisopropyl imidazoles with the mol ratio of anhydrous Aluminum chloride is
1:1.8.
Embodiment ten:
The difference of embodiment ten and embodiment six is, chlorination-1, and 3-diisopropyl imidazoles with the mol ratio of anhydrous Aluminum chloride is
1:2.
Table 2
By table 2 it can be seen that embodiment eight is optimum embodiment, its o-benzoyl yl benzoic acid produced has higher product
Rate and purity, catalyst A has the higher response rate simultaneously.Comparing embodiment six～ten, other reaction condition is the most identical, uniquely
Variable be chlorination-1, the mol ratio of 3-diisopropyl imidazoles and anhydrous Aluminum chloride, therefore chlorination-1,3-diisopropyl imidazoles with
The preferred molar ratio of anhydrous Aluminum chloride is 1:1.75.
Embodiment 11～15: with the mol ratio of chlorination-1,3-diisopropyl imidazoles and anhydrous Aluminum chloride as 1:1.75
Reaction makes catalyst A, prepares o-benzoyl yl benzoic acid.
Embodiment 11:
Chlorination-1,3-diisopropyl imidazoles mixes for 1:1.75 ratio with both mol ratios with anhydrous Aluminum chloride, keeps reaction
Temperature, at 15 DEG C, until reaction terminates when generating without gas, obtains catalyst A；By mol ratio be the benzene of 3:1:0.2, phthalic anhydride and
After catalyst A (mole of catalyst A is pressed anhydrous Aluminum chloride mole and calculated) adds reactor, control reaction temperature 70 DEG C,
Insulation reaction 2 hours, is cooled to 30 DEG C；In reactant liquor, add ether extraction, respectively obtain upper solution and lower floor's solution；
Add dilute hydrochloric acid acidolysis to upper solution, then boil off ether, be supplemented with dilute hydrochloric acid, cooling, separate out crystal, sucking filtration, be dried,
To o-benzoyl yl benzoic acid；Lower floor's solution normal hexane washs, and vacuum drying obtains catalyst A.
Embodiment 12:
The difference of embodiment 12 and embodiment 11 is, (mole of catalyst A presses anhydrous chlorine for benzene, phthalic anhydride and catalyst A
Change aluminum mole calculate) mol ratio be 3:1.25:0.2.
Embodiment 13:
The difference of embodiment 13 and embodiment 11 is, (mole of catalyst A presses anhydrous chlorine for benzene, phthalic anhydride and catalyst A
Change aluminum mole calculate) mol ratio be 3:1.5:0.2.
Embodiment 14:
The difference of embodiment 14 and embodiment 11 is, (mole of catalyst A presses anhydrous chlorine for benzene, phthalic anhydride and catalyst A
Change aluminum mole calculate) mol ratio be 3:1:0.1.
Embodiment 15:
The difference of embodiment 15 and embodiment 11 is, (mole of catalyst A presses anhydrous chlorine for benzene, phthalic anhydride and catalyst A
Change aluminum mole calculate) mol ratio be 3:1:0.5.
Table 3
By table 3 it can be seen that embodiment 11 is optimum embodiment, its o-benzoyl yl benzoic acid produced has higher
Productivity and purity, catalyst A has the higher response rate simultaneously.Comparing embodiment 11～15, other reaction condition is homogeneous
With, unique variable be benzene, phthalic anhydride and catalyst A (mole of catalyst A is by the calculating of anhydrous Aluminum chloride mole) mole
Ratio, therefore benzene, phthalic anhydride and the preferred mol ratio of catalyst A (mole of catalyst A is pressed anhydrous Aluminum chloride mole and calculated)
For 3:1:0.2.
Comparative example one:
It is the benzene of 3:1:0.114, phthalic anhydride and chlorination-1 by mol ratio, after 3-diisopropyl imidazoles adds reactor, controls reaction
Temperature 70 C, insulation reaction 2 hours, it is cooled to 30 DEG C；In the reactant liquor of gained, add ether extraction, respectively obtain upper strata
Solution and lower floor's solution；Upper solution is carried out mass spectral analysis, there is no o-benzoyl yl benzoic acid.
Comparative example two:
It is after the benzene of 3:1:0.2, phthalic anhydride and anhydrous Aluminum chloride add reactor by mol ratio, controls reaction temperature 70 DEG C, insulation
React 2 hours, be cooled to 30 DEG C；In the reactant liquor of gained, add ether extraction, respectively obtain upper solution and lower floor is molten
Liquid；Upper solution carries out liquid-phase chromatographic analysis, and the productivity of o-benzoyl yl benzoic acid is 23%.
Embodiment 11, comparative example one and comparative example two are made comparisons, under identical reaction conditions, be used alone chlorination-
During 1,3-diisopropyl imidazoles, the productivity of o-benzoyl yl benzoic acid is zero；When being used alone anhydrous Aluminum chloride, although obtain neighbour
Benzoyl benzoic acid product, but its productivity obtained is the most undesirable；And by chlorination-1,3-diisopropyl imidazoles and anhydrous chlorine
When change aluminum is prepared as catalyst A, o-benzoyl yl benzoic acid obtains ideal productivity.Therefore, it can draw chlorination-1,3-
Diisopropyl imidazoles and anhydrous Aluminum chloride have synergism.This is likely due to chlorination-1,3-diisopropyl imidazoles has more
The catalyst A that negative current potential, broader electrochemical window, chlorination-1,3-diisopropyl imidazoles and anhydrous Aluminum chloride reaction generate
There is higher ion migration and diffusion velocity and stronger dissolving organic compound so that catalyst A more easily participates in
In the reaction between benzene, phthalic anhydride.
Claims (7)
1. the synthesis technique of an o-benzoyl yl benzoic acid, it is characterised in that comprise the steps:
Step (1): imidazoles organic compound mixes with certain proportion with anhydrous Aluminum chloride, keep reaction temperature at 5～15 DEG C,
Until reaction terminates when generating without gas, obtain catalyst A；
Step (2): after the benzene of excess is added reactor, add a certain amount of phthalic anhydride and catalyst A, reaction temperature 70～80
DEG C, insulation reaction 1～2 hours, it is cooled to 20～30 DEG C；
Step (3): in step (2) in the reactant liquor of gained, adds ether extraction, respectively obtains upper solution and lower floor is molten
Liquid；
Step (4): add dilute hydrochloric acid acidolysis to the upper solution of step (3) gained, then boil off ether, be supplemented with dilute hydrochloric acid,
Cooling, separates out crystal, sucking filtration, is dried, obtains o-benzoyl yl benzoic acid；
Step (5): lower floor's solution of step (3) gained normal hexane washs, vacuum drying obtains catalyst A.
The synthesis technique of o-benzoyl yl benzoic acid the most according to claim 1, it is characterised in that imidazoles in step (1)
Class organic compound is chlorination-1,3-methylimidazole, chlorination-1-ethyl-3-methylimidazole, chlorination-1-propyl group-3-methyl miaow
Azoles, chlorination-1-butyl-3-Methylimidazole. or chlorination-1,3-diisopropyl imidazoles.
The synthesis technique of o-benzoyl yl benzoic acid the most according to claim 1, it is characterised in that imidazoles in step (1)
Class organic compound is 1:1.5～2.0 with the mol ratio of anhydrous Aluminum chloride.
The synthesis technique of o-benzoyl yl benzoic acid the most according to claim 3, it is characterised in that imidazoles in step (1)
Class organic compound and anhydrous Aluminum chloride mol ratio are 1:1.75.
The synthesis technique of o-benzoyl yl benzoic acid the most according to claim 1, it is characterised in that benzene, benzene in step (2)
The mol ratio of acid anhydride and catalyst A is 3:1～1.5:0.1～0.5, and wherein the mole of catalyst A presses anhydrous Aluminum chloride mole
Calculate.
The synthesis technique of o-benzoyl yl benzoic acid the most according to claim 5, it is characterised in that benzene, benzene in step (2)
The mol ratio of acid anhydride and catalyst A is 3:1:0.2, and wherein the mole of catalyst A presses the calculating of anhydrous Aluminum chloride mole.
The synthesis technique of o-benzoyl yl benzoic acid the most according to claim 1, it is characterised in that dilute salt in step (4)
Acid is to be mixed by the water of 1 volume concentrated hydrochloric acid and 1 volume and be made into.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610388717.7A CN106045840A (en) | 2016-06-04 | 2016-06-04 | Synthetic process of 2-benzoylbenzoic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101805268A (en) * | 2010-03-25 | 2010-08-18 | 江苏大学 | Method for preparing acetyl salicylamide |
| CN103896756A (en) * | 2014-04-14 | 2014-07-02 | 河北工业大学 | Method of preparing o-benzoylbenzoic acid by acylation reaction of benzene and phthalic anhydride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101805268A (en) * | 2010-03-25 | 2010-08-18 | 江苏大学 | Method for preparing acetyl salicylamide |
| CN103896756A (en) * | 2014-04-14 | 2014-07-02 | 河北工业大学 | Method of preparing o-benzoylbenzoic acid by acylation reaction of benzene and phthalic anhydride |
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