CN107915659A - A kind of synthetic method of 3,4 dichlorobenzonitrile - Google Patents
A kind of synthetic method of 3,4 dichlorobenzonitrile Download PDFInfo
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- CN107915659A CN107915659A CN201711116630.5A CN201711116630A CN107915659A CN 107915659 A CN107915659 A CN 107915659A CN 201711116630 A CN201711116630 A CN 201711116630A CN 107915659 A CN107915659 A CN 107915659A
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- dichlorobenzonitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
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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
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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Abstract
The invention discloses a kind of synthetic method of 3,4 dichlorobenzonitriles, include the following steps：(1) with 1,2 dichloro-benzenes for raw material, catalyst A is added, bromine is added dropwise after heating, rear insulation reaction is added dropwise, it is post-treated to obtain 3,4 dichloro-bromobenzenes；(2) after mixing cuprous cyanide, catalyst B and solvent, 3,4 dichloro-bromobenzene dilutions are added dropwise after heating, rear insulation reaction is added dropwise, it is post-treated to obtain 3,4 dichlorobenzonitriles.This method, as raw material, obtains 3,4 dichlorobenzonitriles, for molar yield up to more than 85%, purity >=98%, this method cost of material is low, is adapted to industrialized production using 1,2 dichloro-benzenes through bromination, cyaniding two-step reaction.
Description
Technical field
The invention belongs to pesticide, medicine intermediate preparation field, and in particular to the synthetic method of 3,4- dichlorobenzonitriles.
Background technology
3,4- difluorobenzonilyiles are the important intermediates for preparing herbicide cyhalofop-butyl, the herbicide high-efficiency low-toxicity low-residual,
To rice class crop very safety and grassy weed can be prevented and kill off with excellent selectivity.And 3,4- dichlorobenzonitriles are synthesis 3,
The raw material of 4- difluorobenzonilyiles, so 3,4- dichlorobenzonitriles have larger application value in pesticide field, its synthetic method is increasingly
It is concerned by people.
Specifically, 3,4- dichlorobenzonitriles have many synthetic methods, according to the difference of starting material, can be divided into following several
Kind：
(1) one kind with 3,4- dichlorotoleune for raw material, under the action of catalyst ammoxidation synthesis 3,4- dichlorobenzonitriles, this
Kind mode is used by most domestic.But since 3,4- dichlorotoleune is the accessory substance of production 2,4-DCT, in master
After product 2,4-DCT demand slows down, the supply of 3,4- dichlorotoleune is limited by the production of 2,4-DCT.
(2) one kind through thionyl chloride chlorination, then amidatioon, then uses protochloride with 3,4- dichlorobenzoic acids for starting material
Sulfone dehydration synthesis 3,4- dichlorobenzonitriles.This method starting material is expensive, and production process step is more, gives off a large amount of sulfur dioxide and chlorine
Change hydrogen.
(3) one kind generates oxime, then be dehydrated generation 3,4- dichloros with 3,4- dichlorobenzaldehydes for starting material with hydroxylamine hydrochloride
Cyanophenyl, but starting material is very rare, it is expensive.
Due to the rapid development of cyhalofop-butyl, the market has openings of 3,4- dichlorobenzonitriles finds one kind more than 1000 tons/year
It is new can industrialized production method it is imperative.Above-mentioned synthesis technique has their own characteristics each, but has some disadvantages, main
The problem of be raw material supply there are it is larger the problem of, therefore develop a kind of new synthesis 3, the method for 4- dichlorobenzonitriles.
The content of the invention
For the above-mentioned prior art, there are problem, the synthetic method of present invention offer one kind 3,4- dichlorobenzonitriles, this method
There can be shorter synthetic route, raw material is easy to get, and yield height, cost is low and less pollution.
The technical solution adopted by the present invention is as follows：
The synthetic method of one kind 3,4- dichlorobenzonitriles, includes the following steps：
(1) bromination
With 1,2- dichloro-benzenes for raw material, catalyst A is added, bromine is added dropwise after heating, rear insulation reaction is added dropwise, after
Handle to obtain 3,4- dichloro-bromobenzenes；
(2) cyaniding
After cuprous cyanide, catalyst B and solvent are mixed, 3,4- dichloro-bromobenzene dilutions are added dropwise after heating, are added dropwise
Insulation reaction afterwards, it is post-treated to obtain 3,4- dichlorobenzonitriles.
As raw material, 3,4- dichlorobenzonitriles are obtained through bromination, cyaniding two-step reaction using 1,2- dichloro-benzenes for this method, mole
For yield up to more than 85%, purity >=98%, this method cost of material is low, is adapted to industrialized production.
The synthetic route of the present invention is as follows：
In step (1), the catalyst A is iron powder or ferric trichloride, and the dosage of catalyst A is 1,2- dichloro-benzenes quality
1~15%；Specific catalyst is selected, can not only accelerate bromination reaction speed, while can significantly control the life of accessory substance
Into reduction content of isomer.
The 1,2- dichloro-benzenes and bromine add molar ratio as 1.0~1.3：1,30~75 are first warming up to before dropwise addition
℃；
Preferably, step (1) carries out under the conditions of lucifuge, and lucifuge condition is conducive to obtain the yield of higher；
Preferably, the rate of addition of bromine is 0.2~0.3mL/min, and bromine dropwise adding speed is preferably slow, prevents bromine dropwise adding mistake
Bromine is caused to be accumulated soon, so as to generate the even more bromo substitution accessory substances of two bromos；
In step (1), reaction temperature is 30~75 DEG C, and the reaction time is 1~4h；The too low then reaction speed of reaction temperature compared with
Slowly, reaction temperature is excessive, and by-products content increase, preferably, reaction temperature is 45~60 DEG C, the reaction time is 1.5~3h；
In step (1), the post processing includes adding sodium sulfite solution and dichloromethane extraction is washed.
In step (2), the catalyst B is L-PROLINE or hydration 1,10- ferrosins, and the dosage of catalyst B is 3,
5 ‰~the 2% of 4- dichloro-bromobenzene quality；
The solvent is N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAC) or dimethyl sulfoxide (DMSO)
(DMSO), preferably, the solvent is DMF.
In step (2), the molar ratio that adds of 3,4- dichloro-bromobenzenes and cuprous cyanide is 1:1.0~1.3；
In step (2), reaction temperature is 100~150 DEG C, and the reaction time is 2~4h；The too low then reaction speed of reaction temperature
Relatively slow, after reaction temperature is higher than 130 DEG C, impurity showed increased, conversion ratio and yield are relatively low, preferably, reaction temperature is
110~130 DEG C.
Compared with prior art, the invention has the advantages that：The present invention provides a 3,4- dichlorobenzonitrile is new
Synthetic method, reactions steps are shorter, and raw material is cheap and easy to get, and reaction condition is gently controllable, have very big industrial applications before
Scape.
Embodiment
Embodiment 1
(1) bromination
By 26.2g 1,2- dichloro-benzenes is mixed with 2.75g iron powders, is heated to 45 DEG C, is slowly dripped with the speed of 0.2mL/min
Add 26g bromines, insulation reaction 2h is added dropwise, after reaction, add sodium sulfite solution and dichloromethane extraction is washed, after precipitation
Crude product 41.6g is obtained, 1,2- dichloro-benzenes 5.5%, isomers 2,3- dichloro-bromobenzenes 2.1%, height boiling (mainly dibromo are contained in crude product
Or more bromination products, it is rear same) 0.6%, rectifying, collects 100~110 DEG C of cut recoveries under -0.09~-0.1MPa, collect -
160~165 DEG C of cuts under 0.09~-0.1MPa, up to 3,4- dichloro-bromobenzene fine work 33.2g, 3,4- dichloro-bromobenzene purity are
98.5%, molar yield 90.3%.
(2) cyaniding
By 5.4g cuprous cyanides, 0.1g L-PROLINEs and 25g DMF are mixed and heated to 128 DEG C, and 3,4- dichloro-bromobenzenes are added dropwise
Dilution (mixed solution of 11.3g 3,4- dichloro-bromobenzene and 10g DMF), is added dropwise insulation reaction 3h, and reaction terminates through water
Product 8.3g, 3,4- dichlorobenzonitrile purity 98.2%, molar yield 96.5% are obtained after washing layering.
Embodiment 2
(1) bromination
By 26.2g 1,2- dichloro-benzenes is mixed with 2.75g iron powders, is heated to 75 DEG C, is slowly dripped with the speed of 0.25mL/min
Add 26g bromines, insulation reaction 2h is added dropwise, after reaction, add sodium sulfite solution and dichloromethane extraction is washed, after precipitation
Crude product 41.3g is obtained, contains 1,2 dichloro-benzenes 4.8% in crude product, isomers 2,3- dichloro-bromobenzenes 2.0%, height boiling 5.2%, rectifying,
100~110 DEG C of cut recoveries under -0.09~-0.1MPa are collected, collects and is evaporated for 160~165 DEG C under -0.09~-0.1MPa
Point, up to 3,4- dichloro-bromobenzene fine work 31.5g, 3,4- dichloro-bromobenzene purity are 98.3%, molar yield 85.7%.
(2) cyaniding
By 5.4g cuprous cyanides, 0.1g L-PROLINEs and 25g DMF are mixed and heated to 150 DEG C, and 3,4- dichloro-bromobenzenes are added dropwise
Dilution (mixed solution of 11.3g 3,4- dichloro-bromobenzene and 10g DMF), is added dropwise insulation reaction 3h, and reaction terminates through water
Product 9.7g is obtained after washing layering, multiple high impurity peaks occurs, 3,4- dichlorobenzonitrile purity are 37.89%, and molar yield is (folding
It is pure) 42.5%.
Embodiment 3
(1) bromination
26.2g o-dichlorohenzenes are mixed with 0.59g ferric trichlorides, 45 DEG C is heated to, is slowly dripped with the speed of 0.3mL/min
Add 26g bromines, insulation reaction 2h is added dropwise, after reaction, add sodium sulfite solution and dichloromethane extraction is washed, after precipitation
Crude product 41.1g is obtained, contains 1,2 dichloro-benzenes 5.0% in crude product, isomers 2,3- dichloro-bromobenzenes 1.0%, height boiling 2.6%, rectifying,
100~110 DEG C of cut recoveries under -0.09~-0.1MPa are collected, collects and is evaporated for 160~165 DEG C under -0.09~-0.1MPa
Point, up to 3,4- dichloro-bromobenzene fine work 33.1g, 3,4- dichloro-bromobenzene purity are 98.5%, molar yield 90.0%.
(2) cyaniding
By 5.4g cuprous cyanides, 0.1g hydration 1,10- ferrosins and 25g DMF are mixed and heated to 128 DEG C, 3,4- bis- are added dropwise
Chloro-bromobenzene dilution (mixed solution of 11.3g 3,4- dichloro-bromobenzene and 10g DMF), is added dropwise insulation reaction 3h, reaction knot
Beam obtains product 8.1g after washing is layered, and 3,4- dichlorobenzonitrile purity are 98.0%, molar yield 94.2%.
Embodiment 4
(1) bromination
26.2g o-dichlorohenzenes are mixed with 0.59g ferric trichlorides, 75 DEG C is heated to, is slowly dripped with the speed of 0.2mL/min
Add 26g bromines, insulation reaction 2h is added dropwise, after reaction, add sodium sulfite solution and dichloromethane extraction is washed, after precipitation
Crude product 40.9g is obtained, contains 1,2 dichloro-benzenes 4.5% in crude product, isomers 2,3- dichloro-bromobenzenes 1.2%, height boiling 5.6%, rectifying,
100~110 DEG C of cut recoveries under -0.09~-0.1MPa are collected, collects and is evaporated for 160~165 DEG C under -0.09~-0.1MPa
Point, up to 3,4- dichloro-bromobenzene fine work 31.8g, 3,4- dichloro-bromobenzene purity are 98.0%, molar yield 86.5%.
(2) cyaniding
By 5.4g cuprous cyanides, 0.1g hydration 1,10- ferrosins and 25g DMF are mixed and heated to 150 DEG C, 3,4- bis- are added dropwise
Chloro-bromobenzene dilution (mixed solution of 11.3g 3,4- dichloro-bromobenzene and 10g DMF), is added dropwise insulation reaction 3h, reaction knot
Beam obtains product 8.5g after washing is layered, and 3,4- dichlorobenzonitrile purity are 82.6%, and (pure) molar yield is 81.6%.
Comparative example 1
(1) bromination
By 26.2g 1,2- dichloro-benzenes and input reaction bulb, are heated to 45 DEG C, are slowly added dropwise with the speed of 0.25mL/min
26g bromines, are added dropwise, insulation reaction 5h, and sampling is controlled in reaction solution, and 3,4- dichloro-bromobenzene conversion ratios are 75%, and reaction is slower.
(2) cyaniding
5.4g cuprous cyanides and 25g DMF are mixed and heated to 128 DEG C, 3,4- dichloro-bromobenzene dilutions (11.3g is added dropwise
The mixed solution of 3,4- dichloro-bromobenzenes and 10g DMF), insulation reaction 6h is added dropwise, reaction terminates to obtain after washing is layered
Product 6.8g, 3,4- dichlorobenzonitrile purity 98.3%, molar yield 79.1%.
Comparative example 2
Compared with Example 1, differ only in step (1), the rate of addition of bromine is 1.5mL/min, due to bromine
Rate of addition is too fast, causes bromine to be accumulated, and temperature rise is too fast, and by-products content is higher, is added dropwise, insulation reaction 2h, instead
Answer and sampling is controlled in liquid, 3,4- dichloro-bromobenzene conversion ratios are 68%, containing isomers 2,3- dichloro-bromobenzenes 9%, height boiling 18%.
Claims (8)
1. one kind 3, the synthetic method of 4- dichlorobenzonitriles, it is characterised in that include the following steps：
(1) bromination
With 1,2- dichloro-benzenes for raw material, catalyst A is added, bromine is added dropwise after heating, rear insulation reaction is added dropwise, it is post-treated
Obtain 3,4- dichloro-bromobenzenes；
(2) cyaniding
After cuprous cyanide, catalyst B and solvent are mixed, 3,4- dichloro-bromobenzene dilutions are added dropwise after heating, are protected after being added dropwise
Temperature reaction, it is post-treated to obtain 3,4- dichlorobenzonitriles.
2. the synthetic method of 3,4- dichlorobenzonitriles according to claim 1, it is characterised in that in step (1), the catalysis
Agent A is iron powder or ferric trichloride, and the dosage of catalyst A is the 1~15% of 1,2- dichloro-benzenes quality.
3. the synthetic method of 3,4- dichlorobenzonitriles according to claim 1, it is characterised in that 1, the 2- dichloro-benzenes and bromine
Element adds molar ratio as 1.0~1.3：1,30~75 DEG C are first warming up to before dropwise addition.
4. the synthetic method of 3,4- dichlorobenzonitriles according to claim 1, it is characterised in that in step (1), reaction temperature
For 30~75 DEG C, the reaction time is 1~4h.
5. the synthetic method of 3,4- dichlorobenzonitriles according to claim 1, it is characterised in that in step (2), the catalysis
Agent B is L-PROLINE or hydration 1,10- ferrosins, and the dosage of catalyst B is 5 ‰~the 2% of 3,4- dichloro-bromobenzene quality.
6. the synthetic method of 3,4- dichlorobenzonitriles according to claim 1, it is characterised in that in step (2), 3,4- dichloros
The molar ratio that adds of bromobenzene and cuprous cyanide is 1:1.0~1.3.
7. the synthetic method of 3,4- dichlorobenzonitriles according to claim 1, it is characterised in that in step (2), reaction temperature
For 100~150 DEG C, the reaction time is 2~4h.
8. the synthetic method of 3,4- dichlorobenzonitriles according to claim 7, it is characterised in that in step (2), reaction temperature
For 110~130 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784928A (en) * | 2022-12-08 | 2023-03-14 | 济宁正东化工有限公司 | Method for synthesizing 3,4-dichlorobenzonitrile |
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| CN102875276A (en) * | 2012-10-24 | 2013-01-16 | 大连理工大学 | Method for preparing cyan aromatic hydrocarbon by using aryl bromide |
| CN103922892A (en) * | 2014-04-04 | 2014-07-16 | 福州大学 | Method for preparing 3,4-dichloro bromobenzene |
| CN104140347A (en) * | 2014-07-15 | 2014-11-12 | 大连理工大学 | Method for preparing iodo-substituted aromatic compounds by virtue of iodination of bromine on aromatic ring |
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| CN1162305A (en) * | 1994-10-17 | 1997-10-15 | 诺瓦提斯公司 | Process for ereparation of substituted 3-aminobenzonitriles |
| CN1810775A (en) * | 2006-02-21 | 2006-08-02 | 唐保清 | Prepn process of 4-amino-2-trifluoromethyl benzonitrile |
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| CN102875276A (en) * | 2012-10-24 | 2013-01-16 | 大连理工大学 | Method for preparing cyan aromatic hydrocarbon by using aryl bromide |
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| CN115784928A (en) * | 2022-12-08 | 2023-03-14 | 济宁正东化工有限公司 | Method for synthesizing 3,4-dichlorobenzonitrile |
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