CN107814695A - A kind of synthetic method of benzoic acid under 9 thiophene ketone compound for catalysis - Google Patents
A kind of synthetic method of benzoic acid under 9 thiophene ketone compound for catalysis Download PDFInfo
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- CN107814695A CN107814695A CN201711016188.9A CN201711016188A CN107814695A CN 107814695 A CN107814695 A CN 107814695A CN 201711016188 A CN201711016188 A CN 201711016188A CN 107814695 A CN107814695 A CN 107814695A
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- benzoic acid
- toluene
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- thiophene ketone
- synthetic method
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 41
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 40
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- -1 thiophene ketone compound Chemical class 0.000 title abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- 238000007539 photo-oxidation reaction Methods 0.000 abstract 1
- 239000003504 photosensitizing agent Substances 0.000 abstract 1
- 239000012453 solvate Substances 0.000 abstract 1
- GYICYQJEVCIYJY-UHFFFAOYSA-N thiophen-1-ylidenemethanone Chemical class O=C=S1C=CC=C1 GYICYQJEVCIYJY-UHFFFAOYSA-N 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 238000003810 ethyl acetate extraction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 1
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater 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
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- 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
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B01J35/39—
Abstract
The invention belongs to chemical technology field, the synthetic method of the benzoic acid under specially a kind of 9 thiophene ketone compound for catalysis.The inventive method includes：Using toluene as raw material, 9 thiophene ketone compounds are catalyst, without solvent, under room temperature, air conditionses, react 40 48h under visible light illumination, you can efficient to realize that toluene oxidation generates benzoic acid.The present invention can room temperature and it is solvent-free under the conditions of carry out toluene photooxidation method prepare benzoic acid, it is achieved thereby that the existing production technology that benzoic acid is prepared to toluene oxidation method is optimized and transformed；The present invention, as catalyst, reduces cost using visible light photosensitizer.The problem of energy consumption can be greatly reduced in the present invention, and the waste discharge for thoroughly solving the problems, such as to be brought by heavy metal and acetate solvate pollutes heavy-metal residual in environment and product, energy-conserving and environment-protective.The inventive method is compared with traditional production technology, whole power consumption, and equipment investment and overall cost of operation substantially reduce.
Description
Technical field
The invention belongs to chemical technology field, and in particular to the synthetic method of benzoic acid.
Background technology
Benzoic acid be the smell with benzene or formaldehyde flakey or acicular crystal, 122.13 DEG C of fusing point, 249 DEG C of boiling point,
Relative density 1.2659（15/4℃）, structural formula is：.Distilled rapidly at 100 DEG C, its steam has very strong stimulation
Property, cough is easily caused after suction.Water is slightly soluble in, is soluble in the organic solvents such as ethanol, ether.
Benzoic acid is mainly used in antimycotic and sterilization anti-corrosion, prevents for medicine, dye carrier, plasticizer, spices and food
The production of rotten agent etc., the performance improvement of phthalic resin coating is also used for, also serves as antirust agent, the agricultural chemicals of steel equipment.
Benzoic acid can be as production benzoic ether and the intermediate of phthalic acid ester, and benzoic ether and phthalic acid ester are
Important plasticizer.Bromobenzoic acid can be made through bromination reaction in benzoic acid, and m- bromobenzoic acid can be as electric photograph material
Adhesive.The intermediate of pharmacy and dyestuff is also used as, for producing plasticizer and spices etc..
At present, the technique that the whole world generally prepares benzoic acid using toluene thermal oxidation method.This method utilizes heavy metallic salt
Cobalt or manganese realize the oxidation of toluene, and final synthesizing benzoic acids as catalyst under conditions of HTHP.But this side
Method always there is high energy consumption, it is seriously polluted the problems such as.
With the proposition of energy-conserving and environment-protective concept, the having of being exposed of method of traditional toluene oxidation generation benzoic acid
The drawbacks of unsustainable development, is not received more and more by people.
Photochemistry, the science emerging as one, has been obtained for the development of high speed.Compared with traditional heat chemistry, light
Chemistry more clean energy-saving.Therefore, a kind of synthetic method of the benzoic acid under new illumination condition is urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to provide a kind of 9- thiophene ketone chemical combination that can be reduced environmental pollution, energy consumption is greatly reduced
The synthetic method of benzoic acid under thing catalysis.
The synthetic method of benzoic acid under 9- thiophene ketone compound for catalysis provided by the present invention, using organic photochemistry
Method, using toluene as raw material, 9- thiophene ketone compounds are catalyst, without solvent, room temperature（Such as 10-40 DEG C）, air bar
Under part, 40-48h is reacted under visible light illumination, you can efficient to realize that toluene oxidation generates benzoic acid.
Preferably, in the present invention, described 9- thiophene ketones compound catalyst is 4- phenyl -9- thienones, structural formula
For：。
Preferably, in the present invention, the dosage of described 9- thiophene ketone compounds is the 1-5% of toluene mass fraction.
Preferably, in the present invention, described visible ray is 4 800 W Projecting Lamps.
The inventive method, the scale iodine of 5-10 feather weight can be achieved.
The principle of the present invention is：4- phenyl -9- thienones are changed into excitation state under the irradiation of visible ray from ground state, it
Afterwards, being collided with reaction substrate toluene molecule even can pass to reaction substrate molecule, substrate molecule is reached high-energy
Excitation state, so as to which activating catalytic substrate molecule toluene makes it remove a hydrogen atom, corresponding benzyl radicalses intermediate is generated,
Subsequent benzyl radicalses are oxidized to benzaldehyde, the further oxidation by air generation benzene first of benzaldehyde under the oxidation of air
Acid.
The synthetic method of benzoic acid under 9- thiophene ketone compound for catalysis provided by the present invention, with traditional heat chemistry
Technique, which is compared, the advantages of notable：
First, reaction is carried out at ambient temperature, and compared with traditional heating production technology, energy consumption is greatly lowered.
Second, react and carried out under condition of no solvent, so as to solving in traditional handicraft due to making solvent using acetic acid
The all problems brought.Energy consumption is greatly reduced, serious pollution of the spent acid discharge to environment is solved, greatly reduces to equipment
Corrosivity, so as to replace titanium alloy material to manufacture reactor using stainless steel, greatly reduce equipment manufacturing costs.
3rd, using visible light catalyst rather than heavy metal catalyst, so as to thoroughly solve in traditional handicraft due to adopting
Heavy-metal residual problem in problem of environmental pollution, and product caused by with transition-metal catalyst.It means that this method
It is possible to be used directly to produce food even the benzoic acid product of pharmaceutical grade.This will substantially reduce the life of food and medicine level benzoic acid
Produce cost.Moreover, the more traditional toluene thermal oxidation method of catalyst cost decreases.
4th, the present invention uses air as oxidant source, further saves cost.
5th, the present invention post processing it is simple to operation, do not further relate to acetic acid and water separation and heavy metal to environment
Pollution.Acetic acid and heavy metal are free of in caused waste water, can easily carry out integrated treatment, and sensitising agent can reclaim
Utilize.
6th, the raw material that the production technology of benzoic acid provided by the present invention uses is single, improves the economy of technique,
And the conversion ratio of toluene, more than 99%, the yield of benzoic acid is more than 97%.
7th, the production method of benzoic acid provided by the present invention, as the energy, without thermal oxide, is located afterwards using visible ray
It is simple to manage equipment, the more existing oxidation production technology of whole power consumption reduces by more than 50%.
8th, the production method of benzoic acid provided by the present invention is without oxidation reaction tower, stripping tower, rectifying column, can be with
Titanium alloy material is replaced using stainless steel to manufacture reactor, the more traditional production technology of equipment investment reduces by more than 30%.
9th, the production method of benzoic acid provided by the present invention is without heavy metal catalyst, without solvent, without oxidation
Reaction tower, without stripping tower, without rectifying column, normal-temperature light can be carried out under shining, and overall cost of operation drops compared with traditional processing technology
Low more than 50%.
In a word, the energy-conserving and environment-protective new technology that this project will develop, thorough solution heavy metal pollution is asked on environmental protection
Topic and spent acid pollution problem；The benzoic acid for being expected to directly produce food and medicine level using this technology is produced in product quality
Product, so as to greatly improve value-added content of product.
Brief description of the drawings
Fig. 1 is benzoic acid nuclear magnetic spectrogram.
Embodiment
Embodiment 1
10kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 2% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 48 h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient
Liquid-phase chromatographic analysis, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen-oxygen is added in reactant mixture
Change sodium water solution to PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality 13.1kg, yield 99%.
Embodiment 2
10kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 3% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 46h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient liquid
Analysis of hplc, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydroxide is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 sodium water solution, recrystallizes,
Vacuum drying, nuclear-magnetism identification, product quality 13.0kg, yield 98%.
Embodiment 3
10kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 4% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 43h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient liquid
Analysis of hplc, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydroxide is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 sodium water solution, recrystallizes,
Vacuum drying, nuclear-magnetism identification, product quality is 13.1 kg, yield 99%.
Embodiment 4
10kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 5% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 40h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient liquid
Analysis of hplc, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydroxide is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 sodium water solution, recrystallizes,
Vacuum drying, nuclear-magnetism identification, product quality is 13.1 kg, yield 99%.
Embodiment 5
9kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 3% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 46h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient liquid
Analysis of hplc, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydroxide is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 sodium water solution, recrystallizes,
Vacuum drying, nuclear-magnetism identification, product quality 11.8kg, yield 99%.
Embodiment 6
9kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 2% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 48 h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient
Liquid-phase chromatographic analysis, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen-oxygen is added in reactant mixture
Change sodium water solution to PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 11.8 kg, yield 99%.
Embodiment 7
8kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 3% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 48 h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient
Liquid-phase chromatographic analysis, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen-oxygen is added in reactant mixture
Change sodium water solution to PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 10.5 kg, yield 99%.
Embodiment 8
8 kg toluene, the photochemical catalyst 4- phenyl -9- thienones of 5% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 40h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through efficient liquid
Analysis of hplc, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydroxide is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 sodium water solution, recrystallizes,
Vacuum drying, nuclear-magnetism identification, product quality is 10.5 kg, yield 99%.
Claims (4)
- A kind of 1. synthetic method of the benzoic acid under 9- thiophene ketone compound for catalysis, it is characterised in that using toluene as raw material, 9- Thienone compound is catalyst, under room temperature, air conditionses, reacts 40-48h under visible light illumination, that is, realizes toluene oxidation Generate benzoic acid.
- 2. the synthetic method of the benzoic acid under 9- thiophene ketone compound for catalysis according to claim 1, it is characterised in that Described 9- thiophene ketones compound catalyst is 4- phenyl -9- thienones, and structural formula is：。
- 3. the synthetic method of the benzoic acid under 9- thiophene ketone compound for catalysis according to claim 1, it is characterised in that The dosage of described 9- thiophene ketone compounds is the 1-5% of toluene mass fraction.
- 4. the synthetic method of the benzoic acid under 9- thiophene ketone compound for catalysis according to claim 1, it is characterised in that Described visible ray is 4 800 W Projecting Lamps.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152922A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination |
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- 2017-10-26 CN CN201711016188.9A patent/CN107814695A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152922A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination |
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