CN115246764B - Clean production process of parachlorophenol - Google Patents
Clean production process of parachlorophenol Download PDFInfo
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- CN115246764B CN115246764B CN202211091551.4A CN202211091551A CN115246764B CN 115246764 B CN115246764 B CN 115246764B CN 202211091551 A CN202211091551 A CN 202211091551A CN 115246764 B CN115246764 B CN 115246764B
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- hydrogen peroxide
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- hydrochloric acid
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- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229940090668 parachlorophenol Drugs 0.000 title claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 zinc tetramine imine Chemical class 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000012044 organic layer Substances 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 18
- 150000002466 imines Chemical class 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011534 incubation Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000460 chlorine Substances 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000003780 insertion Methods 0.000 abstract description 3
- 230000037431 insertion Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 238000005660 chlorination reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007350 electrophilic reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a clean production process of p-chlorophenol, which belongs to the technical field of organic synthesis and comprises the following steps: under normal pressure, phenol, hydrogen peroxide and hydrochloric acid are used as raw materials, and a catalytic amount of zinc tetramine imine is used as a catalyst to prepare p-chlorophenol with high selectivity; the zinc tetradentate amine imine has larger steric hindrance and electronic cloud regulation capability, can effectively control the insertion trend and activity of chlorine atoms, and remarkably improves the selectivity; the hydrogen peroxide and the concentrated hydrochloric acid are used for preparing chlorine in situ, the hydrogen peroxide is clean and environment-friendly, the hydrochloric acid is cheap and easy to obtain, the hydrogen peroxide is used as a reaction reagent and a reaction solvent, the byproduct is water only, and the experimental process is clean and mild, and belongs to the technical field of green chemical synthesis.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a clean production process of parachlorophenol.
Background
The parachlorophenol has wide application, is an important chemical raw material of an organic synthesis and fine chemical intermediate, is widely applied to various fields of medicines, pesticides, solvents, dyes, pigments, mildew inhibitors, surfactants, spices and the like, and is one of products with high chlorine consumption.
The domestic p-chlorophenol industrialized production is mainly a direct chlorination method of phenol, namely, the direct electrophilic reaction of phenol is carried out by utilizing chlorine, and the method has the defects that the chlorination reaction is non-selective, rectification and purification are needed in the later stage, the utilization rate of chlorine atoms is low, a large amount of hydrochloric acid is produced as a byproduct, and raw material waste and environmental hazard are caused. After that, the literature reports that the introduction of a metal catalyst for phenol chlorination to increase its selectivity, such as copper chloride method, i.e. copper chloride as chlorine source and catalyst, and chlorine as oxidant, by the introduction of a metal catalyst, phenol chlorination selectivity is significantly improved, p/o-chloro=6: 1, the disadvantage is that the copper chloride is used in a large amount and the post-treatment is very troublesome. Later reports (RU 2340589) that hydrochloric acid is used as a chlorine source, hydrogen peroxide is used as an oxidant, and iron phthalocyanine is used as a catalyst to carry out phenol chlorination reaction to generate o/p-chlorophenol ratio=1.15:1, and the method consumes hydrochloric acid, hydrogen peroxide and byproduct water, is environment-friendly, but has low selectivity. Literature (Dalton trans., 2006, 3561-3575) reports a polystyrene-immobilized bis-salicylaldehyde vanadium catalyst (PS- [ VO (fsal-ohyba) ], which generates a para-brominated product content of 81% under H 2SO4/KBr/H2O2 system, although the above method provides a concept for us, a suitable metal complex, and catalysis can improve the selectivity of phenol chlorination.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a clean production process of p-chlorophenol, which takes zinc tetramine imine (LZn) as a catalyst, and the catalyst can effectively catalyze a hydrochloric acid and hydrogen peroxide system to realize high-selectivity chlorination of phenol.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
a clean production process of p-chlorophenol comprises the following steps:
(1) Adding concentrated hydrochloric acid with the mass concentration of 31%, phenol and catalyst tetradentate amine imine zinc into a reactor, dropwise adding hydrogen peroxide with the mass concentration of 30%, controlling the temperature of the reactor at 25-60 ℃ during dropwise adding, and continuing to perform heat preservation reaction for 1-4 h after the hydrogen peroxide is dropwise added;
the molar ratio of the phenol to the catalyst tetramine imine zinc is 1:0.001-0.1;
the mass ratio of the phenol to the concentrated hydrochloric acid is 1:20-40;
the molar ratio of the phenol to the hydrogen peroxide is 1.0-2.0;
The dropping speed of the hydrogen peroxide is 60-150 drops/min;
The structural formula of the catalyst tetradentate amine imine zinc is
；
(2) And after the reaction is finished, cooling to 25-30 ℃, standing for 0.5-1 h, layering, separating liquid to obtain an organic phase, washing the obtained organic phase with water for 3-5 times, merging the organic layers, and removing the water in the organic layers by rotary evaporation to obtain the parachlorophenol.
Preferably, the molar ratio of the phenol to the zinc tetramine imine of the catalyst in the step (1) is 1:0.05.
Preferably, in the step (1), the mass ratio of the phenol to the concentrated hydrochloric acid is 1:30.
Preferably, the molar ratio of the phenol to the hydrogen peroxide in the step (1) is 1:1.2.
Preferably, the reaction temperature in step (1) is 40 ℃.
Preferably, the dropping speed of the hydrogen peroxide in the step (1) is 120 drops/min.
Preferably, the incubation time in step (1) is 2 hours.
Wherein the catalyst is synthesized by a method of zinc tetramine imine (LZn) with reference to a document Polyhedron (2017) 206-210.
The synthetic route of the parachlorophenol is as follows:
。
compared with the prior art, the invention has the following advantages:
According to the clean production process of the p-chlorophenol, zinc tetradentate amine imine (LZn) is used as a catalyst, and the crystal structure of LZn shows that the chiral amine imine has large steric hindrance, so that the central metal is well protected, and the catalyst is prevented from being deactivated; meanwhile, the larger steric hindrance can effectively control the insertion trend of chlorine atoms, and the selectivity is obviously improved; the hydrogen peroxide and the concentrated hydrochloric acid are used for preparing chlorine in situ to realize the para-position high-selectivity chlorination, the consumed raw materials are hydrogen peroxide and hydrochloric acid, and the experimental process is clean and mild, and belongs to the technical field of green chemical synthesis.
The invention utilizes hydrogen peroxide and concentrated hydrochloric acid to prepare chlorine in situ, the hydrogen peroxide is clean and environment-friendly, the hydrochloric acid is cheap and easy to obtain, the byproduct is only water when being used as a reaction reagent and a reaction solvent, the reaction condition is mild, the selectivity is high, and the conversion rate is high, so that the method is a synthesis method suitable for industrialization.
Drawings
FIG. 1 is a crystal structure diagram of zinc tetramine imine as a catalyst used in the present invention.
FIG. 2 is an H 1 NMR chart of zinc tetramine imines as catalysts used in the present invention.
Detailed Description
The invention aims to provide a clean production process of p-chlorophenol, which is realized by the following technical scheme:
the invention is further described below in connection with specific embodiments.
Reference Polyhedron 121 (2017) 206-210 method wherein zinc tetramine imide (LZn) is used as catalyst
And (5) synthesizing. As shown in fig. 1, from the LZn crystal structure, the chiral amine imine has large steric hindrance, plays a good role in protecting central metal and prevents the catalyst from being deactivated; meanwhile, the larger steric hindrance can effectively control the insertion trend of chlorine atoms, the selectivity is obviously improved, and the H 1 NMR spectrum is shown in figure 2.
Example 1
9.41Kg of phenol, 2.95kg of catalyst tetramine imine zinc and 282.3% of concentrated hydrochloric acid with mass concentration of 31%
Adding 13.6kg of 30% hydrogen peroxide into a reactor, dropwise adding 13.6kg of hydrogen peroxide with the mass concentration at the dropwise adding speed of 120 drops/min, controlling the temperature of the reactor at 40 ℃ during dropwise adding, carrying out heat preservation reaction for 2h after dropwise adding, cooling to 25 ℃ after finishing the reaction, standing for 0.5h, layering, separating to obtain an organic phase, washing the obtained organic phase with water for 3 times, merging the organic layers, removing water in the organic layers by rotary evaporation to obtain 11.76kg of parachlorophenol, and measuring the purity of the parachlorophenol by HPLC (high performance liquid chromatography).
Example 2
Adding 9.41kg of phenol, 5.90kg of catalyst tetradentate amine imine zinc, 376.4 kg kg of concentrated hydrochloric acid with the mass concentration of 31% into a reactor, then dropwise adding 22.7kg of hydrogen peroxide with the mass concentration of 30% and the dropwise adding speed of 150 drops/min, controlling the temperature of the reactor at 60 ℃ during dropwise adding, carrying out heat preservation reaction for 4 hours after dropwise adding, cooling to 30 ℃ after finishing the reaction, standing for 1 hour, layering, separating liquid to obtain an organic phase, washing the obtained organic phase with water for 5 times, merging the organic layers, removing water in the organic layers by rotary evaporation to obtain 11.34kg of parachlorophenol, and measuring the parachlorophenol purity of 91.12% by HPLC.
Example 3
Adding 9.41kg of phenol, 0.59 kg kg of catalyst tetradentate amine imine zinc, 282.3 kg of concentrated hydrochloric acid with the mass concentration of 31% into a reactor, then dropwise adding 18.3kg of hydrogen peroxide with the mass concentration of 30% and the dropwise adding speed of 70 drops/min, controlling the temperature of the reactor at 60 ℃, carrying out heat preservation reaction for 2 hours after dropwise adding, cooling to 28 ℃ after the reaction is finished, standing for 1 hour, layering, separating liquid to obtain an organic phase, washing the obtained organic phase with water for 5 times, merging the organic layers, removing water in the organic layer by rotary evaporation, and obtaining 11.18kg of parachlorophenol, wherein the purity of the parachlorophenol is 90.23% by HPLC (high performance liquid chromatography).
Example 4
Adding 9.41kg of phenol, 0.059 kg kg of catalyst tetradentate amine imine zinc, 188.2kg of concentrated hydrochloric acid with the mass concentration of 31% into a reactor, then dropwise adding 11.3kg of hydrogen peroxide with the mass concentration of 30% and the dropwise adding speed of 60 drops/min, controlling the temperature of the reactor at 25 ℃, carrying out heat preservation reaction for 1h after the dropwise adding is finished, cooling to 25 ℃ after the reaction is finished, standing for 0.5h, layering, separating to obtain an organic phase, washing the obtained organic phase with water for 3 times, merging the organic layers, removing the water in the organic layer by rotary evaporation to obtain 10.15kg of parachlorophenol, and measuring the purity of the parachlorophenol 90.18% by HPLC.
Example 5
Adding 9.41kg of phenol, 2.95g of catalyst tetradentate amine imine zinc, 235.2 kg g of concentrated hydrochloric acid with the mass concentration of 31% into a reactor, then dropwise adding 15.8kg of hydrogen peroxide with the mass concentration of 30% and the dropwise adding speed of 80 drops/min, controlling the temperature of the reactor at 50 ℃, carrying out heat preservation reaction for 2 hours after dropwise adding, cooling to 28 ℃ after the reaction is finished, standing for 0.5h, layering, separating liquid to obtain an organic phase, washing the obtained organic phase with water for 3 times, merging the organic layer, removing water in the organic layer by rotary evaporation to obtain 10.97kg of parachlorophenol, and measuring the purity of the parachlorophenol by HPLC (high performance liquid chromatography).
Example 6
Adding 9.41kg of phenol, 4.42kg of catalyst tetradentate amine imine zinc, 329.3kg of concentrated hydrochloric acid with the mass concentration of 31% into a reactor, then dropwise adding 20.2kg of hydrogen peroxide with the mass concentration of 30% and the dropwise adding speed of 100 drops/min, controlling the temperature of the reactor at 40 ℃ during dropwise adding, carrying out heat preservation reaction for 2 hours after dropwise adding, cooling at 26 ℃ after the reaction is finished, standing for 0.75 hour, layering, separating liquid to obtain an organic phase, washing the obtained organic phase with water for 4 times, merging the organic layers, removing water in the organic layer by rotary evaporation, and obtaining 11.34kg of parachlorophenol, wherein the purity of the parachlorophenol is 91.0% by HPLC (high performance liquid chromatography).
Example 7
Adding 9.41kg of phenol, 1.48kg of catalyst tetramine imine zinc and 376.4 kg mass percent of concentrated hydrochloric acid into a reactor, then dropwise adding 13.6kg of 30 mass percent of hydrogen peroxide with the dropwise adding speed of 120 drops/min, controlling the temperature of the reactor at 30 ℃ during dropwise adding, preserving heat for 3h after dropwise adding, and cooling after the reaction is finished
Standing at 25deg.C for 0.9 hr, layering, separating to obtain organic phase, washing the obtained organic phase with water for 3 times, mixing organic layers, and rotary evaporating to remove water in the organic layers to obtain parachlorophenol 10.73kg, wherein the purity of parachlorophenol is 91.2% as determined by HPLC.
Claims (7)
1. A clean production process of p-chlorophenol is characterized in that: the method comprises the following steps:
(1) Adding concentrated hydrochloric acid with the mass concentration of 31%, phenol and catalyst tetradentate amine imine zinc into a reactor, dropwise adding hydrogen peroxide with the mass concentration of 30%, controlling the temperature of the reactor at 25-60 ℃ during dropwise adding, and continuing to perform heat preservation reaction for 1-4 h after the hydrogen peroxide is dropwise added;
the molar ratio of the phenol to the catalyst tetramine imine zinc is 1:0.001-0.1;
the mass ratio of the phenol to the concentrated hydrochloric acid is 1:20-40;
the molar ratio of the phenol to the hydrogen peroxide is 1.0-2.0;
The dropping speed of the hydrogen peroxide is 60-150 drops/min;
The structural formula of the catalyst tetradentate amine imine zinc is
；
(2) And after the reaction is finished, cooling to 25-30 ℃, standing for 0.5-1 h, layering, separating liquid to obtain an organic phase, washing the obtained organic phase with water for 3-5 times, merging the organic layers, and removing the water in the organic layers by rotary evaporation to obtain the parachlorophenol.
2. The clean production process of p-chlorophenol according to claim 1, wherein: the molar ratio of the phenol to the catalyst zinc tetramine imine in the step (1) is 1:0.05.
3. The clean production process of p-chlorophenol according to claim 1, wherein: in the step (1), the mass ratio of the phenol to the concentrated hydrochloric acid is 1:30.
4. The clean production process of p-chlorophenol according to claim 1, wherein: the molar ratio of the phenol to the hydrogen peroxide in the step (1) is 1:1.2.
5. The clean production process of p-chlorophenol according to claim 1, wherein: the temperature of the incubation reaction in step (1) is 40 ℃.
6. The clean production process of p-chlorophenol according to claim 1, wherein: the dropping speed of the hydrogen peroxide in the step (1) is 120 drops/min.
7. The clean production process of p-chlorophenol according to claim 1, wherein: the incubation time in step (1) is 2h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627758A (en) * | 2012-03-31 | 2012-08-08 | 济南大学 | Dual-core amine imine zinc catalyst and preparation method and application thereof |
| CN103936618A (en) * | 2014-04-16 | 2014-07-23 | 济南大学 | Chiral quadridentate nitrogen-zinc complex as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2340589C1 (en) * | 2007-07-18 | 2008-12-10 | Федеральное государственное унитарное предприятие "Государственный научный центр "Научно-исследовательский институт органических полупродуктов и красителей" (ФГУП "ГНЦ "НИОПИК") | Substituted iron phthalocyanines and method of obtaining chlor-derivatives of aromatic hydrocarbons |
| CN107963961A (en) * | 2017-12-13 | 2018-04-27 | 南京大学扬州化学化工研究院 | A kind of preparation method of parachlorophenol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627758A (en) * | 2012-03-31 | 2012-08-08 | 济南大学 | Dual-core amine imine zinc catalyst and preparation method and application thereof |
| CN103936618A (en) * | 2014-04-16 | 2014-07-23 | 济南大学 | Chiral quadridentate nitrogen-zinc complex as well as preparation method and application thereof |
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