CN107915618A - A kind of synthetic method of benzoic acid using illumination as 9 thiophene ketone compound for catalysis of condition - Google Patents
A kind of synthetic method of benzoic acid using illumination as 9 thiophene ketone compound for catalysis of condition Download PDFInfo
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- CN107915618A CN107915618A CN201711023196.6A CN201711023196A CN107915618A CN 107915618 A CN107915618 A CN 107915618A CN 201711023196 A CN201711023196 A CN 201711023196A CN 107915618 A CN107915618 A CN 107915618A
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- benzoic acid
- illumination
- toluene
- thiophene ketone
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- 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
Abstract
The invention belongs to the synthetic method of chemical technology field, specially a kind of benzoic acid using illumination as 9 thiophene ketone compound for catalysis of condition.The method of the present invention includes：Using toluene as raw material, 9 thiophene ketone compounds are catalyst, without solvent, under room temperature, air conditions, react 40 48h under visible light illumination, you can efficient to realize that toluene oxidation generates benzoic acid.The method of the present invention 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 conservation and environmental protection.The method of the present invention 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：.Distil rapidly at 100 DEG C, its steam has very strong thorn
Swash property, cough is easily caused after suction.Water is slightly soluble in, is soluble in the organic solvents such as ethanol, ether.
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.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 high temperature and pressure.But this side
Method always there is high energy consumption, it is seriously polluted the problems such as.
With the proposition of energy conservation and environmental protection concept, the having of being exposed of method of traditional toluene oxidation generation benzoic acid
The drawbacks of unsustainable development, is not accepted by people more and more.
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 it is a kind of can reduce environmental pollution, be greatly reduced energy consumption using illumination as condition 9-
The synthetic method of the benzoic acid of thiophene ketone compound for catalysis.
The synthetic method of benzoic acid provided by the present invention using illumination as condition 9- thiophene ketone compound for catalysis, uses
The method of organic photochemistry, specifically using toluene as raw material, 9- thiophene ketone compounds are catalyst, without solvent, room temperature（Such as
10-40℃）, react 40-48h under air conditions, can efficiently realize that toluene oxidation generates benzoic acid under visible light illumination.
A kind of synthesis side using illumination as the benzoic acid under condition 9- thiophene ketone compound for catalysis provided by the present invention
Method, it is characterised in that the synthetic method can realize the scale iodine of 5-10 feather weight.
Preferably, in the present invention, the 9- thiophene ketones compound catalyst is 2- methoxyl group -9- thienones, it is tied
Structure formula is：。
Preferably, in the present invention, the dosage of the 9- thiophene ketone compounds is the 1-5% of toluene mass fraction.
Preferably, in the present invention, it is 4 800 W Projecting Lamps that the visible ray, which shines,.
Synthetic method provided by the invention using illumination as the benzoic acid under condition 9- thiophene ketone compound for catalysis can be real
The scale iodine of existing 5-10 feather weight.
The principle of the present invention is：2- methoxyl group -9- thienones are changed into excitation state under the irradiation of visible ray from ground state, it
Afterwards, colliding with reaction substrate toluene molecule even can pass to reaction substrate molecule, substrate molecule is reached high-energy
Excitation state, so that activating catalytic substrate molecule toluene makes it remove a hydrogen atom, generates corresponding benzyl radicals intermediate,
Subsequent benzyl radicals are oxidized to benzaldehyde, the further oxidation by air generation benzene first of benzaldehyde under the oxidation of air
Acid.
Synthetic method provided by the present invention using illumination as the benzoic acid under condition 9- thiophene ketone compound for catalysis, with
Traditional thermochemical processes, which are compared, the advantages of notable：
First, reaction carries 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 that solve in traditional handicraft due to making solvent using acetic acid and
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 manufacture reaction kettle instead of titanium alloy material 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 production 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 photosensitizer can recycle
Utilize.
6th, the raw material that the production method 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
Reaction kettle is manufactured instead of titanium alloy material using stainless steel, 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 carry out under shining, and overall cost of operation is dropped compared with traditional processing technology
Low more than 50%.
In short, the energy conservation and environmental protection new technology that this project will develop, asks thorough solution heavy metal pollution 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
The toluene of 9kg, the photochemical catalyst 2- methoxyl group -9- thienones of 2% mass fraction, in sky are added in the reaction kettle of 50 L
Atmosphere encloses middle stirring, at a temperature of 25 DEG C, reacts 48 h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reaction mixture
To PH to be neutral, ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality 11.8kg, yield 99%.
Embodiment 2
The toluene of 9kg, the photochemical catalyst 2- methoxyl group -9- thienones of 3% mass fraction, in sky are added in the reaction kettle of 50 L
Atmosphere encloses middle stirring, at a temperature of 25 DEG C, reacts 46h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reaction mixture
To PH to be neutral, ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality 11.8kg, yield 99%.
Embodiment 3
The toluene of 9kg, the photochemical catalyst 2- methoxyl group -9- thienones of 4% mass fraction, in sky are added in the reaction kettle of 50 L
Atmosphere encloses middle stirring, at a temperature of 25 DEG C, reacts 45h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reaction mixture
To PH to be neutral, ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 11.8 kg, yield 99%.
Embodiment 4
The toluene of 9kg, the photochemical catalyst 2- methoxyl group -9- thienones of 5% mass fraction, in sky are added in the reaction kettle of 50 L
Atmosphere encloses middle stirring, at a temperature of 25 DEG C, reacts 40h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reaction mixture
To PH to be neutral, ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality 11.8kg, yield 99%.
Embodiment 5
The toluene of 10kg, the photochemical catalyst 2- methoxyl group -9- thienones of 3% mass fraction, in sky are added in the reaction kettle of 50 L
Atmosphere encloses middle stirring, at a temperature of 25 DEG C, reacts 48 h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reaction mixture
To PH to be neutral, ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 13.1 kg, yield 99%.
Embodiment 6
The toluene of 10kg, the photochemical catalyst 2- methoxyl group -9- thienones of 4% mass fraction, in sky are added in the reaction kettle of 50 L
Atmosphere encloses middle stirring, at a temperature of 25 DEG C, reacts 47h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reaction mixture
To PH to be neutral, ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 13.1 kg, yield 99%.
Embodiment 7
Add the toluene of 10 kg in the reaction kettle of 50 L, the photochemical catalyst 2- methoxyl group -9- thienones of 5% mass fraction,
Stirred in air atmosphere, at a temperature of 25 DEG C, react 45h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, warp
Efficient liquid phase chromatographic analysis, the generation of only single product benzoic acid, toluene conversion is more than 99%.Added in reaction mixture
Sodium hydrate aqueous solution is neutrality to PH, and ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2, heavy
Crystallization, vacuum drying, nuclear-magnetism identification, product quality 13.1kg, yield 99%.
Embodiment 8
The toluene of 8kg, the photochemical catalyst 2- methoxyl group -9- thienones of 3% mass fraction, in sky are added in the reaction kettle of 50 L
Atmosphere encloses middle stirring, at a temperature of 25 DEG C, reacts 45h under the irradiation of 4 800 W Projecting Lamps.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reaction mixture
To PH to be neutral, ethyl acetate extraction and recovery photosensitizer, water layer adds dilute hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 10.5 kg, yield 99%.
Claims (4)
1. the synthetic method of a kind of benzoic acid using illumination as condition 9- thiophene ketone compound for catalysis, it is characterised in that with first
Benzene is raw material, and 9- thiophene ketone compounds are catalyst, under room temperature, air conditions, reacts 40-48h under visible light illumination, i.e.,
Realize that toluene oxidation generates benzoic acid.
2. the synthesis side according to claim 1 using illumination as the benzoic acid under condition 9- thiophene ketone compound for catalysis
Method, it is characterised in that the 9- thiophene ketones compound catalyst is 2- methoxyl group -9- thienones, its structural formula is：。
3. the synthetic method of the benzoic acid according to claim 1 using illumination as condition 9- thiophene ketone compound for catalysis,
It is characterized in that, the dosage of the 9- thiophene ketone compounds is the 1-5% of toluene mass fraction.
4. the synthetic method of the benzoic acid according to claim 1 using illumination as condition 9- thiophene ketone compound for catalysis,
It is characterized in that, the visible ray, which shines, uses 4 800 W Projecting Lamps.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167390A (en) * | 2020-03-17 | 2020-05-19 | 北京双子动力科技发展有限公司 | Preparation device and preparation method of linear triatomic hydrogen high-energy rocket fuel |
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| CN104447271A (en) * | 2014-11-14 | 2015-03-25 | 复旦大学 | Method for synthesizing benzoic acid through alcohol catalysis under condition of illumination |
| CN105061185A (en) * | 2015-07-20 | 2015-11-18 | 复旦大学 | Method for catalytic synthesis of benzoic acid by use of anthraquinone under lighting condition |
| CN105152905A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid through thioxanthene catalysis under condition of illumination |
| 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
- 2017-10-26 CN CN201711023196.6A patent/CN107915618A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810754A (en) * | 2005-01-27 | 2006-08-02 | 中国科学院化学研究所 | Alkylbenzene photooxidizing process with oxygen to prepare aromatic aldehyde and aromatic acid |
| JP2012056851A (en) * | 2010-09-04 | 2012-03-22 | Nagoya Industrial Science Research Inst | Method for producing aromatic carboxylic acid compound |
| CN103910623A (en) * | 2014-03-03 | 2014-07-09 | 复旦大学 | Preparation method for benzoic acid |
| CN104447271A (en) * | 2014-11-14 | 2015-03-25 | 复旦大学 | Method for synthesizing benzoic acid through alcohol catalysis under condition of illumination |
| CN105061185A (en) * | 2015-07-20 | 2015-11-18 | 复旦大学 | Method for catalytic synthesis of benzoic acid by use of anthraquinone under lighting condition |
| CN105152905A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid through thioxanthene catalysis under condition of illumination |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111167390A (en) * | 2020-03-17 | 2020-05-19 | 北京双子动力科技发展有限公司 | Preparation device and preparation method of linear triatomic hydrogen high-energy rocket fuel |
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Application publication date: 20180417 |