CN109956863A - The synthesis technology of chlorobenzoyl chloride - Google Patents
The synthesis technology of chlorobenzoyl chloride Download PDFInfo
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- CN109956863A CN109956863A CN201711406883.6A CN201711406883A CN109956863A CN 109956863 A CN109956863 A CN 109956863A CN 201711406883 A CN201711406883 A CN 201711406883A CN 109956863 A CN109956863 A CN 109956863A
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- chlorobenzoyl chloride
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- toluene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
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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
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of synthesis technologies of chlorobenzoyl chloride, belong to the preparation technical field of chlorobenzoyl chloride.The present invention the following steps are included: (1) LED light source irradiation under, side reaction inhibitor is first added, then chlorine is passed through in toluene and is reacted, be made tri-chlorination benzyl crude product；The wavelength of the LED light source is 520nm~650nm；The side reaction inhibitor is the mixture of 4,6- dinitro -2- sec-butyl phenol and aniline；(2) benzoic acid is added, under the action of catalyst, the resulting tri-chlorination benzyl crude product of a dropping step (1) is reacted at 110~120 DEG C, and chlorobenzoyl chloride crude product is made；(3) vacuum distillation purification is carried out to the resulting chlorobenzoyl chloride crude product of step (2), chlorobenzoyl chloride fine work is made.Operation of the present invention is simple, and reaction time is short, and reaction temperature is low, and low energy consumption, and product yield and purity is high, production cost is low, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of synthesis technologies of chlorobenzoyl chloride, belong to the preparation technical field of chlorobenzoyl chloride.
Background technique
Chlorobenzoyl chloride is the important intermediate for preparing dyestuff, fragrance, organic peroxide, drug and resin, is also used for
Among photography and the production of artificial tannic acid.Using toluene as in the technique of Material synthesis chlorobenzoyl chloride, the reaction time is mainly concentrated
In the synthesis of tri-chlorination benzyl, and the rate of Benzyl Side-Chain Chloride reaction is lower in the prior art, because side reaction leads to tri-chlorination
The low yield of benzyl, so cause relatively low using toluene as the reaction rate of the entire technique of Material synthesis chlorobenzoyl chloride, yield is low,
Energy consumption is high, causes environmental pollution to a certain extent.
There are two types of than more typical synthetic method, thermal chemical reaction and light-catalyzed reaction at present for tri-chlorination benzyl.Heat chemistry is anti-
Answering method is that toluene is heated to 140 DEG C or more and carries out side chain in the presence of no illumination has catalyst such as ammonium chloride
Chlorination.The reaction simplifies consersion unit, and catalyst ammonium chloride is cheap and easily-available, but the reaction time is long, and yield is low, by-product
It is more.
Light-catalyzed reaction method is that toluene is carried out liquid phase side chain chlorination, reaction under ultraviolet light or other light sources irradiation
Device temperature gradually rises up to 180 DEG C, and the reaction time is generally in 12h or more.Common catalyst is azo-bis-isobutyl cyanide, tri-chlorination
Phosphorus and peroxide etc..The problem is that light source power consumption is big, the efficiency of light energy utilization is low, and light source life is shorter, and catalyst is anti-to master
The catalytic efficiency answered is not high, and catalyst or corrosivity toxicity is big or nature is unstable, with the presence of risk such as explosions.
Summary of the invention
Easy to operate the purpose of the present invention is to provide a kind of synthesis technology of chlorobenzoyl chloride, reaction time is short, reaction
Temperature is low, and low energy consumption, and product yield and purity is high, production cost is low, is suitble to industrialized production.
The synthesis technology of chlorobenzoyl chloride of the present invention, comprising the following steps:
(1) under LED light source irradiation, side reaction inhibitor is first added, then chlorine is passed through in toluene and is reacted, make
Obtain tri-chlorination benzyl crude product；The wavelength of the LED light source is 520nm~650nm；The side reaction inhibitor is 4,6- dinitro-
The mixture of 2- sec-butyl phenol and aniline；
(2) benzoic acid is added, under the action of catalyst, the resulting tri-chlorination benzyl crude product of a dropping step (1) is 110~120
It is reacted at DEG C, chlorobenzoyl chloride crude product is made；Used catalyst is ferric trichloride, zinc chloride or silica；
(3) vacuum distillation purification is carried out to the resulting chlorobenzoyl chloride crude product of step (2), chlorobenzoyl chloride fine work is made.
The LED light source has wave-length coverage narrow (520nm~650nm), energy concentration, moderate strength, service life length, aggregation
The features such as light beam.
The side reaction inhibitor is the mixture of 4,6- dinitro -2- sec-butyl phenol and aniline, and mixing mass ratio is
1.5~3:2~5.
The dosage of the side reaction inhibitor is the 0.02%~0.08% of toluene quality.
The molar ratio of the chlorine and toluene is 3.0:1~3.5:1.
The reaction temperature of step (1) is 80~130 DEG C, and the reaction time is 6~8h.
The molar ratio of the tri-chlorination benzyl crude product and benzoic acid is 1:1.01~1:1.05.
In step (2), catalyst amount is the 0.1%~0.5% of benzoic acid Mass.
The reaction time of step (2) is 1~2h.
In step (3), pressure when vacuum distillation is 10~30mmHg, and temperature is 80~110 DEG C.
In the synthesis technology of step (1) tri-chlorination benzyl of the present invention, the mechanism of Catalytic Chlorination of Toluene Side Chain method is as follows:
The Cl under LED light source irradiation2Homolysis occurs, breaking of covalent bonds generates chlorine radical Cl, chlorine radical and benzene
Substitution reaction occurs for ring pendant methyl hydrogen, and forms a new free radical under LED light source effect, and iterative cycles accelerate
The progress entirely reacted.Side reaction inhibitor is added simultaneously, the generation for effectively inhibiting monochlor(in)ate benzyl high temperature polymerization to react extends
Its induction period in polymerization promotes Benzyl Side-Chain Chloride to react the progress that deepens continuously, effectively increases reaction rate and product yield, most
Tri-chlorination benzyl crude product is obtained eventually.
Using toluene as in the technique of Material synthesis chlorobenzoyl chloride, the reaction time is concentrated mainly on the synthesis of tri-chlorination benzyl
In, the present invention effectively accelerates Benzyl Side-Chain Chloride reaction rate, the yield of tri-chlorination benzyl is improved, to improve entire work
The reaction rate of skill, reduces energy consumption, reduces environmental pollution, and the tail gas of generation recycles after being handled with buck etc., gained
Product purity is higher, has the requirement of industrialized production.
Compared with prior art, the invention has the following advantages:
(1) present invention synthesizes tri-chlorination benzyl using photocatalytic method, only uses light source and is catalyzed, and side reaction inhibition is added
Agent is not added with catalyst, avoids and causes corrosivity toxicity is big or itself property is unstable to have the danger such as explosion using catalyst
Dangerous influence；
(2) present invention is using LED light as light source, and 520~650nm of wavelength effectively concentrates light source, and illumination depth is good,
Greatly improve light source utilization rate；
(3) compound side reaction inhibitor is added in the present invention, more effectively prevents the side reactions such as monochlor(in)ate benzyl polymerization
Occur；
(4) operation of the present invention is simple, and reaction time is short, and reaction temperature is lower, and low energy consumption, and product yield and purity is high (are received
Rate >=96.8%, purity >=99.7%), production cost is low, is suitble to industrialized production.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended to limit implementation of the invention.
Raw materials used is commercial product.
Embodiment 1
Be added 100g toluene in reaction flask, 0.02g inhibitor (4,6- dinitro -2- sec-butyl phenols and aniline it is mixed
Conjunction mass ratio is 1.5:2), 80 DEG C are first warming up to, starts logical chlorine under LED light (wavelength is 520nm~650nm) irradiation, with
Reaction is slowly heated up, and final temperature control is at 130 DEG C, coreaction 6h, and reaction 0~3h chlorine flowrate is 50g/h, with chlorine
Change degree is constantly deepened, and 4~6h chlorine flowrate is 30g/h, and tri-chlorination benzyl crude product 210g is obtained at the end of reaction, and purity is
97.2%, yield 96.2%.
50g benzoic acid is weighed, the above-mentioned reaction of 81.2g resulting trichlorine is added dropwise in 0.25g zinc chloride at a temperature of 130 ± 5 DEG C
Change benzyl crude product, 0.5h is dripped off, and keeps the temperature 0.5h after emission-free generation, is evaporated under reduced pressure in 20mmHg, is obtained chlorobenzoyl chloride fine work 112g, pure
Degree 99.7%, yield 96.8%.
Embodiment 2
Be added 200g toluene in reaction flask, 0.08g inhibitor (4,6- dinitro -2- sec-butyl phenols and aniline it is mixed
Conjunction mass ratio is 1.5:4), under LED light (wavelength be 520nm~650nm) irradiation, chlorine is led at 100 ± 10 DEG C, with react into
Row slowly heating, coreaction 8h, 0~3h chlorine flowrate are 85g/h, and 4h chlorine flowrate is controlled in 70g/h, 5~6h chlorine flowrate
55g/h, 7~8h chlorine flowrate are 45g/h.Tri-chlorination benzyl crude product 424g, purity 97.1% are obtained at the end of reaction, yield is
97.5%.
100g benzoic acid is weighed, the above-mentioned reaction of 168g resulting three is added dropwise in 0.1g ferric trichloride at a temperature of 130 ± 5 DEG C
Benzyl chloride crude product, 1h are dripped off, and keep the temperature 0.5h after emission-free generation, are evaporated under reduced pressure in 15mmHg, are obtained chlorobenzoyl chloride fine work 224g, pure
Degree is 99.8%, yield 97.1%.
Embodiment 3
Be added 150g toluene in reaction flask, 0.05g inhibitor (4,6- dinitro -2- sec-butyl phenols and aniline it is mixed
Conjunction mass ratio is 2:5), under LED light (wavelength be 520nm~650nm) irradiation, 110 ± 10 DEG C of slowly heatings, coreaction 7h, 0
~3h chlorine flowrate is 70g/h, and 4~5h chlorine flowrate is 45g/h, and 6~7h chlorine flowrate is 35g/h.It is obtained slightly at the end of reaction
Product tri-chlorination benzyl 317g, purity 97.5%, yield 97.4%.
80g benzoic acid is weighed, the above-mentioned reaction of 126g resulting trichlorine is added dropwise in 0.3g silica at a temperature of 130 ± 5 DEG C
Change benzyl crude product, 0.5h is dripped off, and keeps the temperature 0.5h after emission-free generation, is evaporated under reduced pressure in 30mmHg, is obtained chlorobenzoyl chloride fine work 181g, pure
Degree is 99.7%, yield 97.5%.
Embodiment 4
80g the toluene, (mixing of 4,6- dinitro -2- sec-butyl phenols and aniline of 0.03g inhibitor are added in reaction flask
Mass ratio is 2.5:4), under LED light (wavelength be 520nm~650nm) illumination, 115 ± 5 DEG C of slowly heatings, coreaction 6h, 0
~3h chlorine flowrate is 45g/h, and 4~5h chlorine flowrate is 30g/h, and 6h chlorine flowrate is 20g/h.Crude product three is obtained at the end of reaction
Benzyl chloride 170g, purity 97.3%, yield 97.6%.
50g benzoic acid is weighed, the above-mentioned reaction of 84g resulting tri-chlorination is added dropwise in 0.15g zinc chloride at a temperature of 130 ± 5 DEG C
Benzyl crude product, 0.5h are dripped off, and keep the temperature 0.5h after emission-free generation, are evaporated under reduced pressure in 10mmHg, are obtained chlorobenzoyl chloride fine work 114g, purity
It is 99.8%, yield 98.0%.
Claims (7)
1. a kind of synthesis technology of chlorobenzoyl chloride, it is characterised in that the following steps are included:
(1) under LED light source irradiation, side reaction inhibitor is first added, then chlorine is passed through in toluene and is reacted, be made three
Benzyl chloride crude product；The wavelength of the LED light source is 520nm~650nm；The side reaction inhibitor is that 4,6- dinitro -2- is secondary
The mixture of butylphenol and aniline；
(2) benzoic acid is added, under the action of catalyst, the resulting tri-chlorination benzyl crude product of a dropping step (1) is at 110~120 DEG C
It is reacted, chlorobenzoyl chloride crude product is made；Used catalyst is ferric trichloride, zinc chloride or silica；
(3) vacuum distillation purification is carried out to the resulting chlorobenzoyl chloride crude product of step (2), chlorobenzoyl chloride fine work is made.
2. the synthesis technology of chlorobenzoyl chloride according to claim 1, it is characterised in that: 4,6- dinitro -2- sec-butylbenzenes
The mixing mass ratio of phenol and aniline is 1.5~3:2~5.
3. the synthesis technology of chlorobenzoyl chloride according to claim 1 or 3, it is characterised in that: the dosage of side reaction inhibitor
It is the 0.02%~0.08% of toluene quality.
4. the synthesis technology of chlorobenzoyl chloride according to claim 1, it is characterised in that: the molar ratio of chlorine and toluene is
3.0:1~3.5:1.
5. the synthesis technology of chlorobenzoyl chloride according to claim 1, it is characterised in that: the reaction temperature of step (1) is 80
~130 DEG C, the reaction time is 6~8h.
6. the synthesis technology of chlorobenzoyl chloride according to claim 1, it is characterised in that: tri-chlorination benzyl crude product and benzoic acid
Molar ratio is 1:1.01~1:1.10.
7. the synthesis technology of chlorobenzoyl chloride according to claim 1, it is characterised in that: in step (2), catalyst amount is
The 0.1%~0.5% of benzoic acid Mass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711406883.6A CN109956863A (en) | 2017-12-22 | 2017-12-22 | The synthesis technology of chlorobenzoyl chloride |
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| CN201711406883.6A CN109956863A (en) | 2017-12-22 | 2017-12-22 | The synthesis technology of chlorobenzoyl chloride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651673A (en) * | 2021-07-01 | 2021-11-16 | 烟台泰和新材料股份有限公司 | Preparation method of aromatic side chain methyl chloride |
| CN114656330A (en) * | 2022-04-07 | 2022-06-24 | 河南特格纳特科技有限公司 | Preparation method of trichlorotoluene and trichlorotoluene |
| CN114702380A (en) * | 2022-04-07 | 2022-07-05 | 河南特格纳特科技有限公司 | Method for co-producing p-chlorobenzoyl chloride and caproyl chloride and acyl chloride products thereof |
| CN115010584A (en) * | 2022-06-13 | 2022-09-06 | 南京师范大学 | Method for synthesizing arone by oxidizing benzyl tertiary carbon broken bond under catalysis of iron |
-
2017
- 2017-12-22 CN CN201711406883.6A patent/CN109956863A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651673A (en) * | 2021-07-01 | 2021-11-16 | 烟台泰和新材料股份有限公司 | Preparation method of aromatic side chain methyl chloride |
| CN114656330A (en) * | 2022-04-07 | 2022-06-24 | 河南特格纳特科技有限公司 | Preparation method of trichlorotoluene and trichlorotoluene |
| CN114702380A (en) * | 2022-04-07 | 2022-07-05 | 河南特格纳特科技有限公司 | Method for co-producing p-chlorobenzoyl chloride and caproyl chloride and acyl chloride products thereof |
| CN114656330B (en) * | 2022-04-07 | 2024-03-15 | 河南特格纳特科技有限公司 | Preparation method of trichlorotoluene and trichlorotoluene thereof |
| CN114702380B (en) * | 2022-04-07 | 2024-03-19 | 河南特格纳特科技有限公司 | Method for co-producing p-chlorobenzoyl chloride and hexanoyl chloride and acyl chloride product thereof |
| CN115010584A (en) * | 2022-06-13 | 2022-09-06 | 南京师范大学 | Method for synthesizing arone by oxidizing benzyl tertiary carbon broken bond under catalysis of iron |
| CN115010584B (en) * | 2022-06-13 | 2023-12-12 | 南京师范大学 | Method for synthesizing aromatic ketone by iron-catalyzed oxidation of tertiary carbon bond breaking of benzyl position |
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Application publication date: 20190702 |