CN116332792A - Preparation method of 2, 5-dichlorobenzonitrile - Google Patents
Preparation method of 2, 5-dichlorobenzonitrile Download PDFInfo
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- CN116332792A CN116332792A CN202310039090.4A CN202310039090A CN116332792A CN 116332792 A CN116332792 A CN 116332792A CN 202310039090 A CN202310039090 A CN 202310039090A CN 116332792 A CN116332792 A CN 116332792A
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- dichlorobenzonitrile
- reaction
- chlorine
- dichloro
- trichlorobenzyl
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- LNGWRTKJZCBXGT-UHFFFAOYSA-N 2,5-dichlorobenzonitrile Chemical compound ClC1=CC=C(Cl)C(C#N)=C1 LNGWRTKJZCBXGT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 azo isobutene Chemical compound 0.000 claims abstract description 9
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- ZULBFSSEZXLFIV-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-(chloromethyl)benzene Chemical compound ClCC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl ZULBFSSEZXLFIV-UHFFFAOYSA-N 0.000 claims description 13
- KFAKZJUYBOYVKA-UHFFFAOYSA-N 1,4-dichloro-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1Cl KFAKZJUYBOYVKA-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- OMZINLIPPVNUOG-UHFFFAOYSA-N 1,4-dichloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC(Cl)=CC=C1Cl OMZINLIPPVNUOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- YGFNEMXIPFLPFH-UHFFFAOYSA-N 1,4-dichlorobenzene hydrochloride Chemical compound Cl.ClC1=CC=C(Cl)C=C1 YGFNEMXIPFLPFH-UHFFFAOYSA-N 0.000 abstract 1
- 238000004176 ammonification Methods 0.000 abstract 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N iso-butene Natural products CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract 1
- OHDYZVVLNPXKDX-UHFFFAOYSA-N 2,3-dichlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1Cl OHDYZVVLNPXKDX-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000007265 chloromethylation reaction Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 2
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- KUWBYWUSERRVQP-UHFFFAOYSA-N 3,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1Cl KUWBYWUSERRVQP-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- LLMLNAVBOAMOEE-UHFFFAOYSA-N 2,3-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1Cl LLMLNAVBOAMOEE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003699 antiulcer agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Chemical group 0.000 description 1
- 229910052791 calcium Chemical group 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 2, 5-dichlorobenzonitrile, which belongs to the technical field of organic synthesis, wherein 2, 5-dichlorobenzene is heated to 110-130 ℃, benzoyl peroxide and azo isobutene are added as catalysts, chlorine is slowly introduced, when the content of the 2, 5-dichlorobenzene is less than or equal to 0.3%, chlorine introduction is stopped, nitrogen is introduced to drive off superfluous chlorine in the system, 2, 5-dichlorobenzene chloride solution is obtained, ammonium chloride and a catalyst are added, ammonification reaction is carried out at 200-230 ℃, when the content of the 2, 5-dichlorobenzene is less than 0.05%, the reaction is stopped, 2, 5-dichlorobenzonitrile reaction solution is obtained after the reaction is finished, and the 2, 5-dichlorobenzonitrile is obtained through reduced pressure rectification and tower top separation. The preparation method has the advantages of simple process flow, low cost, high yield and low pollution, and opens up a new route for preparing the 2, 5-dichlorobenzonitrile, thereby being beneficial to the development of downstream products of the 2, 5-dichlorobenzonitrile.
Description
Technical Field
The invention belongs to the technical field of dichlorobenzonitrile synthesis, and particularly relates to a preparation method of 2, 5-dichlorobenzonitrile.
Background
The dichlorobenzonitrile and the derivative thereof are important fine chemicals, can be widely used as raw materials and organic intermediates in industries such as pesticide bactericides, herbicides, preservatives, surfactants and the like. The main dichlorobenzonitrile compounds at present are 2, 4-dichlorobenzonitrile, 2, 6-dichlorobenzonitrile, 2, 5-dichlorobenzonitrile and 3, 4-dichlorobenzonitrile, wherein the research and study of the 2, 4-dichlorobenzonitrile, the 2, 6-dichlorobenzonitrile and the 3, 4-dichlorobenzonitrile are relatively complete, the synthetic method is relatively mature, but the 2, 5-dichlorobenzonitrile has fewer synthetic methods, the yield of the 2, 5-dichlorobenzonitrile is lower, and the development of the 2, 5-dichlorobenzonitrile is relatively deficient. 2, 5-dichlorobenzonitrile is a novel pesticide intermediate, is mainly used for synthesizing antiulcer drugs, and is also applied to engineering plastics, electronic materials, dyes and the like, so that the research on the processing route of 2, 5-dichlorobenzonitrile has important significance.
Currently, there are two main routes for the synthesis of dichlorobenzonitrile, the aldoxime process and the ammoxidation process. The aldoxime method uses dichlorobenzaldehyde as raw material, and hydroxylamine hydrochloride to produce oxime, then dehydrate to produce dichlorobenzonitrile, or uses dichlorotoluene to chloridize, hydrolyze to aldehyde, hydroxylamine and dehydrate to dichlorobenzonitrile, but most of these processes have the defects of long process flow, high cost, large waste water quantity, unstable yield and serious pollution, and are basically eliminated. The ammonia oxidation method is used for researching more processes at present, dichlorotoluene is used as a raw material, and the dichlorotoluene is obtained through gas phase ammoxidation under the action of a catalyst. However, the process for synthesizing 2, 5-dichlorobenzonitrile by an ammoxidation method has been reported very recently.
Patent CN 109912453B discloses a process for preparing 2, 5-dichlorobenzonitrile and a special catalyst, wherein p-dichlorobenzene and formaldehyde or/and paraformaldehyde are used as raw materials, under the action of chloromethylation and catalyst, the only chloromethylation product 2, 5-dichlorobenzyl chloride is obtained through chloromethylation reaction, and 2, 5-dichlorobenzyl chloride is used as the catalystThe raw materials, ammonia and oxygen are subjected to ammoxidation reaction under the action of a catalyst to obtain 2, 5-dichlorobenzonitrile, the yield of the 2, 5-dichlorobenzonitrile prepared by the reaction is high, the catalyst is a special ammoxidation catalyst, and the active components of the catalyst are as follows: v (V) a Cr b G c D d E e O x Wherein G is boron, phosphorus, molybdenum, titanium, nickel or bismuth; d is manganese, iron, cobalt, copper, zinc or tin; e is potassium, lithium, sodium, magnesium or calcium; a=1; b=0.2 to 3; c=0.1 to 1.2; d=0 to 0.6; e=0 to 0.5, the catalyst component is complex, not easy to obtain, and the cost is high.
In summary, it is of great importance to research a method for preparing 2,5 dichlorobenzonitrile with simple process, low cost and high yield.
Disclosure of Invention
Aiming at the problems of complex preparation process and high cost of the 2, 5-dichlorobenzonitrile in the prior art, the invention provides a preparation method of the 2, 5-dichlorobenzonitrile, which has the advantages of simple process flow, low cost, high yield and low pollution, is a new route for preparing the 2, 5-dichlorobenzonitrile, and is beneficial to the development of downstream products of the 2, 5-dichlorobenzonitrile.
The invention is realized by the following technical scheme:
a preparation method of 2, 5-dichlorobenzonitrile comprises the following steps:
(1) Chlorination: heating 2, 5-dichlorotoluene to 110-130 ℃, adding catalysts benzoyl peroxide and azoisobutylene, slowly introducing chlorine, stopping introducing chlorine when the content of the 2, 5-dichlorotoluene is less than or equal to 0.3%, and introducing nitrogen to drive off superfluous chlorine of the system to obtain 2, 5-dichloro trichlorobenzyl chloride solution;
(2) Ammoniation: adding ammonium chloride and a catalyst into the 2, 5-dichloro-trichlorobenzyl chloride solution in the step (1), carrying out ammoniation reaction at 200-230 ℃, stopping the reaction when the content of the 2, 5-dichloro-trichlorobenzyl is lower than 0.05%, and obtaining 2, 5-dichlorobenzonitrile reaction solution after the reaction is finished;
(3) And (3) rectifying: and (3) rectifying the 2, 5-dichlorobenzonitrile reaction liquid in the step (2) under reduced pressure, and separating at the tower top to obtain the 2, 5-dichlorobenzonitrile.
Preferably, the introducing rate of the chlorine in the step (1) is 250-400 ml/min.
Preferably, the adding amount of the benzoyl peroxide in the step (1) is 0.3-0.5% of the mass of the 2, 5-dichlorotoluene; the addition amount of the azo-isobutylene is 0.3-0.5% of the mass of the 2, 5-dichlorotoluene.
Preferably, the addition amount of the ammonium chloride in the step (2) is 20-25% of the mass of the 2, 5-dichloro-trichlorobenzyl chloride solution.
Preferably, the catalyst in step (2) is copper powder.
Preferably, the addition amount of the copper powder is 0.08-0.15% of the mass of the 2, 5-dichloro-trichlorobenzyl chloride solution.
Advantageous effects
The invention takes 2, 5-dichlorobenzene as raw material, 2, 5-dichlorobenzene is obtained through chlorination, then 2, 5-dichlorobenzonitrile is obtained through ammoniation and reduced pressure rectification, and the process flow for preparing 2, 5-dichlorobenzene has the advantages of simplicity, low cost, high yield and low pollution, thus developing a new route for preparing 2, 5-dichlorobenzonitrile and being beneficial to the development of downstream products of 2, 5-dichlorobenzonitrile.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
(1) Chlorination: 150g of 2, 5-dichlorotoluene is added into a 250mL four-neck flask with a thermometer, a stirring device and a tail gas absorbing device, the temperature is raised to 120 ℃, 0.5g of benzoyl peroxide and 0.5g of azoisobutylene serving as catalysts are added, the slow introduction of chlorine is started, the introduction rate of the chlorine is 300mL/min, when the content of the 2, 5-dichlorotoluene is less than or equal to 0.3%, the chlorine introduction is stopped, nitrogen is introduced to drive away the superfluous chlorine of the system, 245.4g of 2, 5-dichloro-trichlorobenzyl chloride solution is obtained, and the sampling analysis is carried out, wherein the content of the 2, 5-dichloro-trichlorobenzyl is 94.6%;
(2) Ammoniation: adding 50g of ammonium chloride and 0.24g of copper powder serving as a catalyst into the 2, 5-dichloro-trichlorobenzyl chloride solution in the step (1), carrying out ammoniation reaction at 220 ℃, stopping the reaction when the content of the 2, 5-dichloro-trichlorobenzyl is lower than 0.05%, and obtaining a 2, 5-dichlorobenzonitrile reaction solution after the reaction is finished;
(3) And (3) rectifying: the 2, 5-dichlorobenzonitrile reaction liquid in the step (2) is subjected to vacuum rectification, the 2, 5-dichlorobenzonitrile is obtained by tower top separation, the yield of the 2, 5-dichlorobenzonitrile is 97.8%, and the content of the 2, 5-dichlorobenzonitrile in the product is 99.5%.
Example 2
(1) Chlorination: 150g of 2, 5-dichlorotoluene is added into a 250mL four-neck flask with a thermometer, a stirring device and a tail gas absorbing device, the temperature is raised to 130 ℃, 0.5g of benzoyl peroxide and 0.7g of azoisobutylene serving as catalysts are added, the slow introduction of chlorine is started, the introduction rate of the chlorine is 300mL/min, when the content of the 2, 5-dichlorotoluene is less than or equal to 0.3%, the chlorine introduction is stopped, nitrogen is introduced to drive away the superfluous chlorine of the system, 246.1g of 2, 5-dichloro-trichlorobenzyl chloride solution is obtained, and the sampling analysis is carried out, and the content of the 2, 5-dichloro-trichlorobenzyl is 93.5%;
(2) Ammoniation: adding 50g of ammonium chloride and 0.3g of copper powder serving as a catalyst into the 2, 5-dichloro-trichlorobenzyl chloride solution in the step (1), carrying out ammoniation reaction at 230 ℃, stopping the reaction when the content of the 2, 5-dichloro-trichlorobenzyl is lower than 0.05%, and obtaining a 2, 5-dichlorobenzonitrile reaction solution after the reaction is finished;
(3) And (3) rectifying: the 2, 5-dichlorobenzonitrile reaction liquid in the step (2) is subjected to vacuum rectification, the 2, 5-dichlorobenzonitrile is obtained by tower top separation, the yield of the 2, 5-dichlorobenzonitrile is 95.8%, and the content of the 2, 5-dichlorobenzonitrile in the product is 99.3%.
Example 3
(1) Chlorination: 150g of 2, 5-dichlorotoluene is added into a 250mL four-neck flask with a thermometer, a stirring device and a tail gas absorbing device, the temperature is raised to 120 ℃, 0.7g of benzoyl peroxide and 0.7g of azoisobutylene serving as catalysts are added, the slow introduction of chlorine is started, the introduction rate of the chlorine is 300mL/min, when the content of the 2, 5-dichlorotoluene is less than or equal to 0.3%, the chlorine introduction is stopped, nitrogen is introduced to drive away the superfluous chlorine of the system, 245.1g of 2, 5-dichloro-trichlorobenzyl chloride solution is obtained, and the sampling analysis is carried out, and the content of the 2, 5-dichloro-trichlorobenzyl is 94.5%;
(2) Ammoniation: adding 50g of ammonium chloride and 0.25g of copper powder serving as a catalyst into the 2, 5-dichloro-trichlorobenzyl chloride solution in the step (1), carrying out ammoniation reaction at 200 ℃, stopping the reaction when the content of the 2, 5-dichloro-trichlorobenzyl is lower than 0.05%, and obtaining a 2, 5-dichlorobenzonitrile reaction solution after the reaction is finished;
(3) And (3) rectifying: the 2, 5-dichlorobenzonitrile reaction liquid in the step (2) is subjected to vacuum rectification, the 2, 5-dichlorobenzonitrile is obtained by tower top separation, the yield of the 2, 5-dichlorobenzonitrile is 84.3%, and the content of the 2, 5-dichlorobenzonitrile in the product is 99.5%.
Claims (6)
1. The preparation method of the 2, 5-dichlorobenzonitrile is characterized by comprising the following steps of:
(1) Chlorination: heating 2, 5-dichlorotoluene to 110-130 ℃, adding catalysts benzoyl peroxide and azoisobutylene, slowly introducing chlorine, stopping introducing chlorine when the content of the 2, 5-dichlorotoluene is less than or equal to 0.3%, and introducing nitrogen to drive off superfluous chlorine of the system to obtain 2, 5-dichloro trichlorobenzyl chloride solution;
(2) Ammoniation: adding ammonium chloride and a catalyst into the 2, 5-dichloro-trichlorobenzyl chloride solution in the step (1), carrying out ammoniation reaction at 200-230 ℃, stopping the reaction when the content of the 2, 5-dichloro-trichlorobenzyl is lower than 0.05%, and obtaining 2, 5-dichlorobenzonitrile reaction solution after the reaction is finished;
(3) And (3) rectifying: and (3) rectifying the 2, 5-dichlorobenzonitrile reaction liquid in the step (2) under reduced pressure, and separating at the tower top to obtain the 2, 5-dichlorobenzonitrile.
2. The method for producing 2, 5-dichlorobenzonitrile according to claim 1, wherein the introducing rate of chlorine gas in step (1) is 250 to 400 ml/min.
3. The method for producing 2, 5-dichlorobenzonitrile according to claim 1, wherein the amount of benzoyl peroxide added in the step (1) is 0.3 to 0.5% by mass of 2, 5-dichlorobenzene; the addition amount of the azo-isobutylene is 0.3-0.5% of the mass of the 2, 5-dichlorotoluene.
4. The method for producing 2, 5-dichlorobenzonitrile according to claim 1, wherein the amount of ammonium chloride added in the step (2) is 20 to 25% by mass of 2, 5-dichlorobenzyl chloride solution.
5. The process for producing 2, 5-dichlorobenzonitrile according to claim 1, wherein the catalyst in the step (2) is copper powder.
6. The method for preparing 2, 5-dichlorobenzonitrile according to claim 5, wherein the addition amount of copper powder is 0.08-0.15% of the mass of 2, 5-dichloro-trichlorobenzyl chloride solution.
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