CN107382715A - A kind of parachlorobenzoyl chloride preparation method - Google Patents
A kind of parachlorobenzoyl chloride preparation method Download PDFInfo
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- CN107382715A CN107382715A CN201710609022.1A CN201710609022A CN107382715A CN 107382715 A CN107382715 A CN 107382715A CN 201710609022 A CN201710609022 A CN 201710609022A CN 107382715 A CN107382715 A CN 107382715A
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- added
- chlorine
- parachlorobenzoyl
- chlorotrichlormethyl
- parachlorotoluene
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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
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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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- Organic Chemistry (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of parachlorobenzoyl chloride preparation method, comprise the following steps：（1）, chlorination：Raw material parachlorotoluene is added in reactor, stirring, triethanolamine is added into reactor, stirs 30min；Thionyl chloride is added, is slowly heated up after stirring 10min, adds azodiisobutyronitrile, leads to chlorine reaction, obtains p-chlorotrichlormethyl；（2）, hydrolysis：By step（1）In obtained p-chlorotrichlormethyl input hydrolysis kettle, catalyst ferric trichloride is added, water is added dropwise, obtains parachlorobenzoyl chloride crude product；（3）, distillation：Parachlorobenzoyl chloride crude product is distilled to obtain product；Wherein, 30000 ~ 40000 parts of parachlorotoluene, 1 ~ 10 part of triethanolamine.Using parachlorotoluene as raw material, through chlorinated with chlorine, p-chlorotrichlormethyl is made, then hydrolyze, distill to obtain product；Being removed iron ion first with triethanolamine influences, and recycles thionyl chloride to be removed moisture influence, the chlorination reaction time is short, and byproduct of reaction is few, high income.
Description
Technical field
The invention belongs to a kind of parachlorobenzoyl chloride preparation method.
Background technology
With the fast development of high polymer material, parachlorobenzoyl chloride as a kind of important chemical intermediate increasingly by
To the concern of numerous researchers, its excellent performance obtains in medicine intermediate, dyestuff intermediate and preservative etc.
It is widely applied.
Existing preparation method is usually the warp using parachlorotoluene, chlorine, azodiisobutyronitrile, ferric trichloride, water as raw material
The steps such as superchlorination, hydrolysis, distillation produce qualified parachlorobenzoyl chloride；Tail gas high altitude discharge after washing, alkali cleaning washing, and
By-product hydrochloric acid, sodium hypochlorite.The shortcomings that preparation method：1st, the chlorination reaction time is grown.2nd, reaction side reaction is more, and impurity is more, production
Product yield is low.
The content of the invention
According to existing process technical deficiency, the present invention provides a kind of parachlorobenzoyl chloride preparation method, removes chlorination reaction
Iron ion and moisture influence, first with triethanolamine be removed iron ion influence, recycle thionyl chloride be removed
Moisture influences, then carries out chlorination reaction by catalyst of azodiisobutyronitrile.
The present invention provides a kind of parachlorobenzoyl chloride preparation method, comprises the following steps：
A kind of parachlorobenzoyl chloride preparation method, it is characterised in that：Utilize parachlorotoluene, chlorine, triethanolamine, the isobutyl of azo two
Nitrile, thionyl chloride, ferric trichloride are as raw material, through superchlorination, hydrolysis, distillation.Specific steps：
（1）, chlorination：Raw material parachlorotoluene is added in reactor, stirring, triethanolamine is added into reactor, is stirred
30min；Thionyl chloride is added, is slowly heated up after stirring 10min, adds azodiisobutyronitrile, leads to chlorine reaction, obtains to chlorine three
Chlorotoluene；
（2）, hydrolysis：By step（1）In obtained p-chlorotrichlormethyl input hydrolysis kettle, catalyst ferric trichloride is added, is added dropwise
Water, obtain parachlorobenzoyl chloride crude product；
（3）, distillation：Parachlorobenzoyl chloride crude product is distilled to obtain product；
Wherein, 30000 ~ 40000 parts of parachlorotoluene, 1 ~ 10 part of triethanolamine, 90 ~ 110 parts of thionyl chloride.
Reaction temperature has a great influence to chlorination reaction, and temperature is relatively low, and reaction speed is slow, reaction time length, reaction conversion
Rate is low；Temperature is high, and reaction is fast, but the catalyst reacted is easy to lose effect, stops reaction, preferred steps（1）Add chlorination
Sulfoxide, stirring are to slowly warm up to 100 ~ 110 DEG C after 10 minutes, add azodiisobutyronitrile, lead to chlorine, and reaction temperature control exists
120 ~ 130 DEG C obtain p-chlorotrichlormethyl.
Azodiisobutyronitrile and ferric trichloride use as catalyst in reaction, and in general, catalyst amount is higher, water
Solution reaction is faster, but yield advantage is relatively low, and preferably the mass ratio of azodiisobutyronitrile and parachlorotoluene is 1:150~170.It is described
Azodiisobutyronitrile is in step（2）The amount of middle ferric trichloride and the amount for obtaining p-chlorotrichlormethyl are closely bound up, preferably tri-chlorination
The mass ratio of iron and p-chlorotrichlormethyl is 1:1600~1800.
Step（2）The dosage of reclaimed water is how many very big on hydrolysis influence, and the dosage of water is more, and reaction can generate acid, production
Product yield is low；Opposite water is less, and reaction can be incomplete, and product quality is low, yield is low.It is preferred that the matter of water and p-chlorotrichlormethyl
Amount is than being 1:12~16.
Using parachlorotoluene as raw material, through chlorinated with chlorine, p-chlorotrichlormethyl is made, then hydrolyze, distill to obtain product in the present invention；
Go iron ions to influence first with triethanolamine, recycle thionyl chloride to go moisture removal to influence, then using azodiisobutyronitrile to urge
Agent carries out chlorination reaction, and the preparation method time of chlorinating mentioned using the present invention is short, and byproduct of reaction is few, high income.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is general based on the embodiment in the present invention, this area
The every other embodiment that logical technical staff is obtained under the premise of creative work is not made, belongs to protection of the present invention
Scope.The experimental method of unreceipted actual conditions in the following example, generally according to normal condition, or according to manufacturer
Proposed condition, unless stated otherwise, ratio and percentage are based on weight.
The raw materials used embodiment of the present invention is commercially available.
Embodiment 1
1st, chlorination：
3400kg parachlorotoluenes and 95kg thionyl chlorides are added to reactor, then adds 0.085kg triethanolamines and heat temperature raising 85
℃；
Azodiisobutyronitrile 20kg is weighed, first adds 0.5kg into system, remaining azodiisobutyronitrile is during the course of the reaction progressively
Addition；
Chlorine enters chlorine liquid carburetor by liquid-phase tube after the metering of liquid chlorine cylinder electronic scale, is vaporized hot water heating in device, liquid chlorine
Enter Chlorine Buffer Vessel after vaporization, filter is entered with 180kg/h, is finally passed through reactor；
Device for absorbing tail gas is opened, reactor tiny structure is kept, 120 DEG C of logical chlorine reactions 40 hours, adds catalyst per hour
Azodiisobutyronitrile 0.5kg, after chlorination reaction terminates, continue logical nitrogen and be incubated two hours, lead to cooling water to reacting kettle jacketing
Cooling, is down to 60 DEG C, reactor material is transferred into p-chlorotrichlormethyl crude product tank.
2nd, hydrolyze：Material is squeezed into measuring tank through transfering material pump and weighed in p-chlorotrichlormethyl crude product tank, obtains to the chloromethane of chlorine three
The actual mass of benzene is 3300kg, is added into hydrolysis kettle, and 1kg ferric trichlorides are added into hydrolysis kettle；
Water 220kg adds head tank, and inwardly adds 1kg ferric trichlorides；
A small amount of water is initially added into after 120 DEG C of heat temperature raising to be triggered, water is added dropwise into reactor with 22kg/h after initiation, and 12 is small
When it is interior be added dropwise, keep temperature in the kettle, sampling Detection does not hydrolyze p-chlorotrichlormethyl content as 0.04%, reaches terminal.
3rd, distill：The material of hydrolysis kettle is transferred to distillation still using vacuum, distilled using vacuum, content is more than
99% parachlorobenzoyl chloride income finished pot, after distillation, using nitrogen vacuum breaker, prevents moisture from entering system；
Absorb through falling-film absorber from the tail gas that chlorination reaction process comes and sold outside hydrochloric acid, through Alkali absorption into sodium hypochlorite, through two
Tail gas after level absorption tower absorbs carries out high altitude discharge；The tail gas come from hydrolysis kettle is made outside hydrochloric acid after falling-film absorber absorbs
Sell, then the high altitude discharge after two level alkali falling film absorption.
Embodiment 2
Prepared by the preparation method according to parachlorobenzoyl chloride in embodiment 2, only change the following ginseng of the following steps of embodiment 1
Number：
1st, chlorination：
3400kg parachlorotoluenes, 90kg thionyl chlorides and 0.1kg triethanolamines and 85 DEG C of heat temperature raising are added to reactor；
Claim first to add 0.5kg in oriented system, remaining azodiisobutyronitrile progressively adds during the course of the reaction；
Chlorine enters chlorine liquid carburetor by liquid-phase tube after the metering of liquid chlorine cylinder electronic scale, is vaporized hot water heating in device, liquid chlorine
Enter Chlorine Buffer Vessel after vaporization, filter is entered with certain flow 180kg/h, is finally passed through reactor；
Device for absorbing tail gas is opened, reactor tiny structure is kept, 125 DEG C of logical chlorine reactions 40 hours, adds catalyst per hour
Azodiisobutyronitrile 0.5kg, after chlorination reaction terminates, continue logical nitrogen and be incubated two hours, lead to cooling water to reacting kettle jacketing
Cooling, is down to 60 DEG C, reactor material is transferred into p-chlorotrichlormethyl crude product tank.
2nd, hydrolyze：Material is squeezed into measuring tank through transfering material pump and weighed in p-chlorotrichlormethyl crude product tank, obtains to the chloromethane of chlorine three
The actual mass of benzene is 3350kg, is added into hydrolysis kettle, and ferric trichloride 1.05kg is added into hydrolysis kettle；
Water 210kg adds water head tank, and inwardly adds 1kg ferric trichlorides；
Water is initially added into after 120 DEG C of heat temperature raising to be triggered, and water is added dropwise into reactor with 20kg/h after initiation, 12 hours
Inside it is added dropwise, keeps temperature in the kettle, it is 0.04% that sampling Detection, which does not hydrolyze p-chlorotrichlormethyl content, reaches terminal.
Embodiment 3
Prepared by the preparation method according to parachlorobenzoyl chloride in embodiment 3, only change the following ginseng of the following steps of embodiment 1
Number：
1st, chlorination：
3400kg parachlorotoluenes, 105kg thionyl chlorides and 0.11kg triethanolamines and 85 DEG C of heat temperature raising are added to reactor；
Azodiisobutyronitrile 20kg is weighed, first adds 0.5kg into system, remaining azodiisobutyronitrile is during the course of the reaction progressively
Addition；
Chlorine enters chlorine liquid carburetor by liquid-phase tube after the metering of liquid chlorine cylinder electronic scale, is vaporized hot water heating in device, liquid chlorine
Enter Chlorine Buffer Vessel after vaporization, filter is entered with certain flow 180kg/h, is finally passed through reactor；
Device for absorbing tail gas is opened, reactor tiny structure is kept, 130 DEG C of logical chlorine reactions 40 hours, adds catalyst per hour
Azodiisobutyronitrile 0.5kg, after chlorination reaction terminates, continue logical nitrogen and be incubated two hours, lead to cooling water to reacting kettle jacketing
Cooling, is down to 60 DEG C, reactor material is transferred into p-chlorotrichlormethyl crude product tank.
2nd, hydrolyze：Material is squeezed into measuring tank through transfering material pump and weighed in p-chlorotrichlormethyl crude product tank, obtains to the chloromethane of chlorine three
The actual mass of benzene is 3330kg, is added into hydrolysis kettle, and ferric trichloride 1kg is added into hydrolysis kettle；
Water 230kg adds water head tank, and inwardly adds 0.9kg ferric trichlorides；
Water is initially added into after 120 DEG C of heat temperature raising to be triggered, and water is added dropwise into reactor with 21kg/h after initiation, in 12 hours
It is added dropwise, keeps temperature in the kettle, it is 0.08% that sampling Detection, which does not hydrolyze p-chlorotrichlormethyl content, reaches terminal.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (5)
- A kind of 1. parachlorobenzoyl chloride preparation method, it is characterised in that：It is raw material using parachlorotoluene, chlorine, it is different with azo two Butyronitrile and ferric trichloride are catalyst, make auxiliary agent using triethanolamine, thionyl chloride in reaction, through superchlorination, hydrolysis, distill To product；Specific steps：（1）, chlorination：Raw material parachlorotoluene is added in reactor, stirring, triethanolamine is added into reactor, stirring half is small When；Thionyl chloride is added, stirring slowly heats up after ten minutes, adds azodiisobutyronitrile, leads to chlorine, obtains to the chloromethane of chlorine three Benzene；（2）, hydrolysis：By step（1）In obtained p-chlorotrichlormethyl input hydrolysis kettle, catalyst ferric trichloride is added, is added dropwise Water, obtain parachlorobenzoyl chloride crude product；Distillation：Parachlorobenzoyl chloride crude product is distilled to obtain product；Wherein, 30000 ~ 40000 parts of parachlorotoluene, 1 ~ 10 part of triethanolamine, 90 ~ 110 parts of thionyl chloride.
- A kind of 2. parachlorobenzoyl chloride preparation method according to claim 1, it is characterised in that：Step（1）Add chlorination Sulfoxide, stirring are to slowly warm up to 100 ~ 110 DEG C after 10 minutes, add azodiisobutyronitrile, lead to chlorine, and reaction temperature control exists 120~130℃。
- A kind of 3. parachlorobenzoyl chloride preparation method according to claim 2, it is characterised in that：Azodiisobutyronitrile with it is right The mass ratio of chlorotoluene is 1:150~170.
- A kind of 4. parachlorobenzoyl chloride preparation method according to claim 1, it is characterised in that：Ferric trichloride with to chlorine three The mass ratio of chlorotoluene is 1:1600~1800.
- A kind of 5. parachlorobenzoyl chloride preparation method according to claim 1, it is characterised in that：Water and p-chlorotrichlormethyl Mass ratio be 1:12~16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710609022.1A CN107382715A (en) | 2017-07-25 | 2017-07-25 | A kind of parachlorobenzoyl chloride preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710609022.1A CN107382715A (en) | 2017-07-25 | 2017-07-25 | A kind of parachlorobenzoyl chloride preparation method |
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| CN107382715A true CN107382715A (en) | 2017-11-24 |
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| CN201710609022.1A Pending CN107382715A (en) | 2017-07-25 | 2017-07-25 | A kind of parachlorobenzoyl chloride preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735680A (en) * | 2021-08-27 | 2021-12-03 | 江苏超跃化学有限公司 | Synthetic method of 2, 4-dichlorobenzyl chloride |
| CN115999481A (en) * | 2023-02-23 | 2023-04-25 | 山东道可化学有限公司 | Continuous production method of p-chlorobenzoyl chloride |
Citations (5)
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| CN1060650A (en) * | 1990-10-11 | 1992-04-29 | 陈敏哲 | United body method is produced to (neighbour) chlorobenzaldehyde, to (neighbour) chloro-benzoyl chloride |
| CN101671270A (en) * | 2008-09-11 | 2010-03-17 | 杭州澳赛诺化工有限公司 | Method for synthesizing cyanoacetylene derivatives |
| CN101947468A (en) * | 2010-06-03 | 2011-01-19 | 浙江康峰化工有限公司 | Composite catalyst and application |
| CN102180810A (en) * | 2011-03-10 | 2011-09-14 | 青岛科技大学 | Preparation method of 4-hydroxyphenylacetonitrile |
| CN106008197A (en) * | 2016-06-06 | 2016-10-12 | 山东福尔有限公司 | Preparation method for o-fluorobenzoyl chloride |
-
2017
- 2017-07-25 CN CN201710609022.1A patent/CN107382715A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060650A (en) * | 1990-10-11 | 1992-04-29 | 陈敏哲 | United body method is produced to (neighbour) chlorobenzaldehyde, to (neighbour) chloro-benzoyl chloride |
| CN101671270A (en) * | 2008-09-11 | 2010-03-17 | 杭州澳赛诺化工有限公司 | Method for synthesizing cyanoacetylene derivatives |
| CN101947468A (en) * | 2010-06-03 | 2011-01-19 | 浙江康峰化工有限公司 | Composite catalyst and application |
| CN102180810A (en) * | 2011-03-10 | 2011-09-14 | 青岛科技大学 | Preparation method of 4-hydroxyphenylacetonitrile |
| CN106008197A (en) * | 2016-06-06 | 2016-10-12 | 山东福尔有限公司 | Preparation method for o-fluorobenzoyl chloride |
Non-Patent Citations (1)
| Title |
|---|
| 于康平等: "对氯苯甲酰氯的合成", 《现代农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735680A (en) * | 2021-08-27 | 2021-12-03 | 江苏超跃化学有限公司 | Synthetic method of 2, 4-dichlorobenzyl chloride |
| CN115999481A (en) * | 2023-02-23 | 2023-04-25 | 山东道可化学有限公司 | Continuous production method of p-chlorobenzoyl chloride |
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Application publication date: 20171124 |