CN116640041B - Method and system for preparing 4-bromodiphenyl and derivative thereof - Google Patents
Method and system for preparing 4-bromodiphenyl and derivative thereof Download PDFInfo
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- CN116640041B CN116640041B CN202310621860.6A CN202310621860A CN116640041B CN 116640041 B CN116640041 B CN 116640041B CN 202310621860 A CN202310621860 A CN 202310621860A CN 116640041 B CN116640041 B CN 116640041B
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- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 128
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 13
- 239000004305 biphenyl Substances 0.000 claims abstract description 13
- 239000012044 organic layer Substances 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims description 7
- 238000005452 bending Methods 0.000 claims description 4
- 229910001362 Ta alloys Inorganic materials 0.000 claims description 3
- 229910000856 hastalloy Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- 238000003860 storage Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- -1 4-propionyl-4-bromobiphenyl Chemical group 0.000 description 4
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- UUVKNCRMWPNBNM-UHFFFAOYSA-N 1-[4-(4-bromophenyl)phenyl]ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=C(Br)C=C1 UUVKNCRMWPNBNM-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical group ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical group CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical group CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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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
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a method and a system for preparing 4-bromodiphenyl and derivatives thereof, wherein hydrogen peroxide solution and hydrogen bromide solution are respectively and continuously pumped into a third reaction module EB L5 of a microchannel reactor, the reaction temperature is controlled to be 0-20 ℃ for 1-10 min, materials coming out of the third reaction module of the microchannel reactor flow into a pre-mixer H1, simultaneously, the diphenyl is pumped into a pre-mixer H1 to be mixed, then, solution in the pre-mixer H1 is pumped into a first reaction module group of the microchannel reactor, the temperature of the reaction module group is controlled to be 50-70 ℃ for 10-20 min, then, the solution in the first reaction module group is pumped into a pre-mixer H2, the solution is pumped into the pre-mixer H2, and after being mixed, the solution enters a second reaction module L1 to react, the temperature is controlled to be 10-30 ℃ for 1-2 min, and the materials enter a receiving tank C1 to be layered, and an organic layer is taken to obtain 4-bromodiphenyl.
Description
Technical Field
The application belongs to the technical field of preparation of 4-bromodiphenyl, and particularly relates to a system and a method for preparing 4-bromodiphenyl and derivatives thereof.
Background
In recent years, nematic liquid crystals have been widely used in the industries of lasers, aviation instruments, calculators, watches, and the like. The cyanobiphenyl liquid crystal has the advantages of good performance, best stability to light and heat, good moisture resistance, low valve voltage and the like, and is particularly suitable for displaying a torsion effect and a phase transition effect. The development of a new process of a cyanobiphenyl liquid crystal intermediate has great economic value.
The synthesis method of the cyanobiphenyl liquid crystal intermediate has been reported, and the liquid crystal intermediate is synthesized by using Friedel-Crafts acylation kettle type process, and has the defects of low yield, large subsequent acidification reaction heat and the like. Zhang Gao and the like report in engineering science and technology I and Xizan 710061 that 4-hydroxydiphenyl is used as a raw material, and a product is synthesized through 5 steps, so that the problems of complex process, safety, environmental protection and the like exist.
Therefore, the development of a safe, efficient and environment-friendly method and device for preparing the 4-bromobiphenyl and the derivatives thereof has important economic value.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
As one aspect of the present application, there is provided a process for preparing 4-bromodiphenyl and derivatives thereof, which comprises,
the hydrogen peroxide solution and the hydrogen bromide solution are respectively and continuously pumped into a third reaction module EBL5 of the micro-channel reactor, the reaction temperature is controlled to be 0-20 ℃ for 1-10 min, materials coming out of the third reaction module of the micro-channel reactor flow into a pre-mixer H1, biphenyl is pumped into the pre-mixer H1 to be mixed, the solution in the pre-mixer H1 is pumped into a first reaction module group of the micro-channel reactor, the temperature of the reaction module group is controlled to be 50-70 ℃ for 10-20 min, then the solution in the first reaction module group is pumped into a pre-mixer H2, the alkali solution is pumped into the pre-mixer H2, the mixed materials enter a second reaction module L1 to react at the temperature of 10-30 ℃ for 1-2 min, the materials enter a material receiving tank C1 to be layered, and the organic layer is taken to obtain the 4-bromobiphenyl.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: the micro-channel reactor is of a pipeline-shaped structure, inner components are coaxially arranged in the micro-channel reactor, the inner components are arranged at intervals by a plurality of inner component structures 1 and inner component structures 2, the inner component structures 1 are of a net-shaped structure, the inner component structures 2 are of a spiral structure, the spiral structure is formed by spirally bending sheet plates, the net-shaped structure is a plurality of layers, each layer is composed of a plurality of strip plates which are arranged in parallel, the strip plates of two adjacent layers are arranged in a crossed manner at a certain angle and are fixedly connected at an intersection point, and the outer edge of the net-shaped structure is matched with the inner diameter of a pipeline of the micro-channel reactor; the inner member is fixedly connected or detachably connected with the inner wall of the microchannel reactor.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: the strip plates of two adjacent layers are arranged in a 30-90-degree cross way.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: the inner diameter of the microchannel reactor is 0.5-6mm.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: after the 4-bromodiphenyl solution, the aluminum trichloride and the acyl chloride solution are respectively pumped into a pre-mixer H1 for mixing, the mixture is pumped into a first reaction module group of the micro-channel reactor for reaction, the reaction temperature is 50-80 ℃, the reaction time in the first reaction module group of the micro-channel reactor is 10-20 min, the materials and the acid liquor which come out of the first reaction module group of the micro-channel reactor are respectively pumped into a pre-mixer H2, then the materials and the acid liquor enter a second reaction module L1 of the micro-channel reactor for reaction, the reaction temperature is 10-30 ℃ and the reaction time is 1-2 min, the materials which come out of the second reaction module of the micro-channel reactor enter a material receiving tank C1 for layering, and the organic layer of the layer is taken down to obtain the 4-bromodiphenyl derivative.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: the mol ratio of biphenyl, hydrogen peroxide and hydrogen bromide is controlled to be 1:1.0-2.5:1.0-5.0.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: the mol ratio of the 4-bromodiphenyl, the aluminum chloride and the acyl chloride is controlled to be 1:1.0-3.0:1.0-3.0.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: the micro-channel reactor is made of one or more of tantalum alloy and hastelloy.
As a preferable scheme of the method for preparing 4-bromobiphenyl and its derivatives in the application: the flow rate of the liquid in the microchannel reactor is 1-1.5 m/min of linear velocity.
The application also provides a system for preparing 4-bromobiphenyl and derivatives thereof: the material storage tank A3 is connected with the feeding pump B4 through a one-way valve D3 and is connected with the inlet of the micro-channel reactor three-reaction module EBL5, the material storage tank A4 is connected with the feeding pump B5 through a one-way valve D4 and is connected with the inlet of the micro-channel reactor three-reaction module EBL5, the outlet of the micro-channel reactor three-reaction module EBL5 is connected to the mixer H1 through a valve Q5, the material storage tank A1 is connected with the feeding pump B1 and is connected with the pre-mixer H1 through a one-way valve D1, and the material storage tank A2 is connected with the feeding pump B2 and is connected with the pre-mixer H1 through a one-way valve D2; the outlet of the first reaction module group of the micro-channel reactor is connected with a pre-mixer H2 in front of a second reaction module L1 through a one-way valve D5, a storage tank A5 is connected with a feed pump B3 and is connected with the pre-mixer H2 through a one-way valve D7, the pre-mixer H2 is connected with the inlet of the second reaction module L1 through a valve K4, the outlet of the second reaction module L1 is connected with the inlet of a receiving kettle C1 through a one-way valve D6 and a back pressure valve BY1, and the outlet of the receiving kettle C1 is connected with a valve switch J1; the heat exchange device T1 is connected to the micro-channel reaction devices EBL1, EBL2, EBL3 and EBL4 through valves F1, F2 and F3 and F4 respectively, the heat exchange device T2 is connected to the micro-channel reaction device L1, and the heat exchange device T3 is connected to the micro-channel reaction device EBL5.
The application has the beneficial effects that: (1) According to the method for preparing the 4-bromodiphenyl and the derivative thereof, the 4-bromodiphenyl is prepared by adopting a three-strand feeding method of a micro-channel, and the 4-bromodiphenyl derivative is prepared by adopting a two-strand feeding method of the micro-channel, so that the operation is simple, the reaction rate is high, and the safety is high;
(2) The application further provides a device for preparing the 4-bromodiphenyl and the derivatives thereof by the micro-channel reactor, wherein the micro-channel reactor is internally provided with an inner member, the inner member comprises a grid structure and a spiral structure which are integrally designed, and two different structures in the inner member are used for enabling fluid turbulence to be more severe, so that the mass and heat transfer effects of the micro-channel reactor are improved, and the reaction efficiency is improved.
(3) The method for preparing the 4-bromodiphenyl and the derivative thereof greatly shortens the reaction time by adopting a micro-flow field reaction technology, shortens the bromination reaction from about 10 hours of kettle reaction to about 15 minutes, shortens the acylation reaction from about 10 hours of kettle reaction to about 15 minutes, and saves energy and is efficient.
(4) By the method for preparing the 4-bromodiphenyl and the derivative thereof, the 4-bromodiphenyl is reacted in a micro-channel reactor, the conversion rate is high, the purity of the prepared 4-bromodiphenyl is more than 98.0%, the yield is more than 93.0%, the purity of the derivative thereof is more than 98.0%, and the yield is more than 98.0%. Meanwhile, the application adopts the mode of arranging the internal components consisting of the grid structure and the spiral structure in the microchannel reactor, so that the yield is stable, and the yield error between different reactions is small.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a process flow diagram of a microchannel reactor of the application for preparing 4-bromobiphenyl and its derivatives.
FIG. 2 is a schematic diagram of the internal components of the microchannel reactor according to the present application.
FIG. 3 is a partial schematic representation of a microchannel reactor according to the present application.
FIG. 4 shows the nuclear magnetic resonance of 4-n-butyryl-4-bromobiphenyl obtained in example 1 of the present application 1 H NMR。
FIG. 5 shows the nuclear magnetism of the 4-propionyl-4-bromobiphenyl obtained in example 2 of the present application 1 H NMR。
FIG. 6 shows the nuclear magnetism of 4-acetyl-4-bromobiphenyl obtained in example 3 of the present application 1 H NMR。
FIG. 7 shows the nuclear magnetism of the 4-chloroacetyl-4-bromobiphenyl obtained in example 4 of the present application 1 H NMR。
In fig. 1: EBL1, EBL2, EBL3 and EBL4 are a first reaction module group of the micro-channel reactor, L1 is a second reaction module of the micro-channel reactor, EBL5 is a third reaction module of the micro-channel reactor, A1 is a biphenyl solution or 4-bromobiphenyl solution liquid storage tank, A2 is an acyl chloride solution liquid storage tank, A3 is a hydrogen peroxide solution liquid storage tank, A4 is a hydrogen bromide solution liquid storage tank, A5 is an alkaline solution or acid liquor liquid storage tank, B1 is a biphenyl solution or 4-bromobiphenyl solution storage feed pump, B2 is an acyl chloride solution feed pump, B3 is an alkaline solution or acid liquor feed pump, B3 is a hydrogen peroxide solution feed pump, B3 is a hydrogen bromide solution feed pump, C1 is a receiving tank, D1, D2, D3, D4, D5, D6 and D7 are check valves, T1 is a first reaction module group heat exchange device of the microchannel reactor, T2 is a second reaction module heat exchange device of the microchannel reactor, T3 is a third reaction module heat exchange device of the microchannel reactor, F1, F2, F3, F4, F5, F6, F7 and F8 are heat exchange medium flow valves, K1, K2, K3, K4, K5 and K6 are reaction plate inter-plate connection valves, Q1, Q2, Q3 and Q4 are back-pumping valves, H1 and H2 are premixers, BY1 is a back-pressure valve, and J1 is a receiving tank outlet switch.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof.
A system for preparing 4-bromodiphenyl and derivatives thereof by utilizing a microchannel reactor is shown in fig. 1, wherein a storage tank A3 is connected with a feed pump B4 and is connected with an inlet of a microchannel reactor three-reaction module EB L5 through a one-way valve D3, A4 is connected with a feed pump B5 and is connected with an inlet of a microchannel reactor three-reaction module EBL5 through a one-way valve D4, an outlet of the microchannel reactor three-reaction module EBL5 is connected to a mixer H1 through a valve Q5, the storage tank A1 is connected with the feed pump B1 and is connected with a pre-mixer H1 through a one-way valve D1, and the storage tank A2 is connected with the feed pump B2 and is connected with the pre-mixer H1 through a one-way valve D2. The first group of reaction modules of the microchannel reactor comprises four reaction modules (EBL 1, EBL2, EBL3, EBL 4): the first reaction module EBL1 inlet is connected with the pre-mixer H1, the first reaction module EBL1 outlet is connected with the second reaction module EBL2 inlet, the second reaction module EBL2 outlet is connected with the third reaction module EBL3 inlet, the third reaction module EBL3 outlet is connected with the fourth reaction module EBL4 inlet, the fourth reaction module EBL4 outlet is connected with the pre-mixer H2 in front of the second reaction module L1 through the one-way valve D5, the material storage tank A5 is connected with the feed pump B3 and is connected with the pre-mixer H2 through the one-way valve D7, the pre-mixer H2 is connected with the second reaction module L1 inlet through the valve K4, the second reaction module L1 outlet is connected with the material receiving kettle C1 inlet through the one-way valve D6 and the back pressure valve BY1, and the material receiving kettle C1 outlet is connected with the valve switch J1. The heat exchange device T1 is connected to the micro-channel reaction devices EBL1, EBL2, EBL3 and EBL4 through valves F1, F2 and F3 and F4 respectively, the heat exchange device T2 is connected to the micro-channel reaction device L1, and the heat exchange device T3 is connected to the micro-channel reaction device EBL5.
The application discloses a premixer, which refers to a containing space for mixing solutions, and particularly adopts a three-way pipe as the premixer, and is placed in front of a reaction module of a microchannel reactor for premixing the solutions. The heat exchange device refers to a temperature control device.
The reaction formula of the method is as follows:
in the following examples, the lye is 1w.t.% aqueous NaOH solution, the acid solution is 1w.t.% aqueous HCl solution, and the linear velocity of the solution in the microchannel reactor is 1.5m/min.
Example 1:
the proportion (molar ratio) is biphenyl to hydrogen peroxide to hydrogen bromide=1:1.5:3.0. 30w.t.% hydrogen bromide solution is added into a storage tank A3, a feed pump B4 pumps the hydrogen bromide solution into a three-way reaction module EBL5 of the micro-channel reactor through a one-way valve D3, 48w.t.% hydrogen bromide solution is added into the storage tank A4, the feed pump B5 pumps the hydrogen bromide solution into the three-way reaction module EBL5 of the micro-channel reactor through a one-way valve D4, the reaction time of the two solutions in the three-way reaction module EBL5 is 10min, the reaction temperature is 10 ℃, the reacted solution flows into a pre-mixer H1 through a valve Q5 (Q5 is opened and Q2 is closed), meanwhile, biphenyl solution is added into the storage tank A1, the biphenyl solution is pumped into the pre-mixer H1 through the one-way valve D1 through the feed pump B1, the mixed solution enters the first reaction module EBL1, the four reaction modules EBL2, the EBL3 and the EBL4 (the four reaction modules can be used independently or in series, the reaction is used in the case of serial connection), the reaction time in the first reaction module is 15min, the reaction temperature is 60 ℃, the pre-mixed solution enters the pre-mixer H2 through the one-way valve D5, the pre-mixer H2 is fed into the pre-mixer 1, the water enters the pre-mixer 1, and enters the pre-mixer 2.5 to the pre-mixer through the pre-mixer, and enters the water layer after the temperature 2.1 to enter the pre-mixer, and enters the water layer after the water into the pre-mixer 1. The yield of 4-bromodiphenyl oxide is 94.3+/-0.1%.
The raw material ratio (molar ratio) is 4-bromodiphenyl to aluminum trichloride to n-butyryl chloride=1:1.8:1.7. 4-bromodiphenyl solution and aluminum trichloride are added into a storage tank A1, a feed pump B1 pumps the solution into a pre-mixer H1 through a one-way valve D1, simultaneously n-butyryl chloride solution is added into a storage tank A2, a feed pump B2 pumps the solution into the pre-mixer H1 through a one-way valve D2 (Q5 is closed and Q2 is opened), after two are mixed, the solution enters into a first reaction module EBL1, EBL2, EBL3 and EBL4 (the four reaction modules can be independently used or can be used in series, the reaction is carried out in series for example), the residence time is 10min, the reaction temperature is 50 ℃, then the solution enters into a pre-mixer H2 through a one-way valve D5, at this time, 1% hydrochloric acid aqueous solution is added into the storage tank A5, the solution enters into the pre-mixer H2 through a one-way valve D7 through a feed pump B3, the two are mixed and then enter into a second reaction module L1 for reaction, the residence time is 1.5min, and the reaction temperature is 20 ℃. Layering in a receiving tank C1, and taking out the lower organic phase for post-treatment to obtain 4-n-butyryl-4-bromobiphenyl. The yield of the 4-n-butyryl-4-bromobiphenyl is 98.7+/-0.3 percent.
As shown in fig. 2, the microchannel reactor is internally and coaxially provided with inner members, the inner members are formed by a plurality of inner member structures 1 and inner member structures 2 which are arranged at intervals, the inner member structures 1 are in a net structure, the inner member structures 2 are in a spiral structure, the spiral structure is formed by spirally bending sheet-shaped plates, the net structure is a plurality of layers, each layer is formed by a plurality of parallel strip-shaped plates, the strip-shaped plates of two adjacent layers are arranged in a crossed manner at a certain angle and are fixedly connected at the crossing point, and the outer edge of the net structure is matched with the inner diameter of a pipeline of the microchannel reactor; the inner member is fixedly connected or detachably connected with the inner wall of the microchannel reactor. The working principle is that two different structures, namely a spiral structure and a reticular structure in the inner member are matched with each other, so that fluid turbulence is more severe, the mass transfer and heat transfer effects are further improved, the reaction efficiency is greatly improved, the reaction is stable, the product yield is stable, and the yield deviation is remarkably reduced.
The micro-channel reactor is of a pipeline-shaped structure, the micro-channel reactor is made of one or more of tantalum alloy and hastelloy, and the inner diameter of the micro-channel reactor is 0.5-6mm, preferably 0.5mm.
The flow rate of the liquid in the microchannel reactor is calculated according to the linear velocity parameter (flow rate/pipeline length), and when the inner member structure of the application is adopted, the solution is fully mixed when the linear velocity is 1-1.5 m/min.
Compared with the plate-shaped inner member prepared by arranging the bending sheets and the plate holes on the plate body, the inner member can enable the compound molecules in the solution to be in more sufficient contact, and the reaction yield is remarkably improved by arranging the inner member structure 1 and the inner member structure 2 at intervals.
Comparative example 1:
synthesizing 4-n-butyl-4-bromodiphenyl by kettle reaction, wherein the raw material ratio (molar ratio) is diphenyl to hydrogen peroxide to hydrogen bromide=1:1.5:3.0, the reaction time is 10 hours, and the reaction temperature is 60 ℃. The yield of the 4-bromodiphenyl oxide is 80.2+/-0.5 percent. The raw material ratio (molar ratio) is 4-bromodiphenyl to aluminum trichloride to n-butyryl chloride=1:1.8:1.7, the reaction time is 10 hours, the reaction temperature is 50 ℃, and the yield of 4-n-butyryl-4-bromodiphenyl is 78.4+/-0.2%.
Study example 1:
the proportion (molar ratio) is biphenyl to hydrogen peroxide to hydrogen bromide=1:1.5:3.0. 30w.t.% hydrogen bromide solution is added into a storage tank A3, a feed pump B4 pumps the hydrogen bromide solution into a three-way reaction module EBL5 of the micro-channel reactor through a one-way valve D3, 48w.t.% hydrogen bromide solution is added into the storage tank A4, the feed pump B5 pumps the hydrogen bromide solution into the three-way reaction module EBL5 of the micro-channel reactor through a one-way valve D4, the reaction time of the two solutions in the three-way reaction module EBL5 is 10min, the reaction temperature is 10 ℃, the reacted solution flows into a pre-mixer H1 through a valve Q5 (Q5 is opened and Q2 is closed), meanwhile, biphenyl solution is added into the storage tank A1, the biphenyl solution is pumped into the pre-mixer H1 through the one-way valve D1 through the feed pump B1, the mixed solution enters the first reaction module EBL1, the four reaction modules EBL2, the EBL3 and the EBL4 (the four reaction modules can be used independently or in series, the reaction is used in the case of serial connection), the reaction time in the first reaction module is 15min, the reaction temperature is 50 ℃, the pre-mixed solution enters the pre-mixer H2 through the one-way valve D5, the pre-mixer enters the pre-mixer H2, and enters the water layer 1 through the pre-mixer H2, and enters the pre-mixer 1, and enters the pre-mixer 2.5 to the pre-mixer, and enters the water layer 1 through the pre-mixer, and enters the water layer 1.2. The yield of 4-bromodiphenyl oxide is 89.2+/-0.3 percent.
The raw material ratio (molar ratio) is 4-bromodiphenyl to aluminum trichloride to n-butyryl chloride=1:1.8:1.7. 4-bromodiphenyl and aluminum trichloride solution are added into a storage tank A1, a feed pump B1 pumps the solution into a pre-mixer H1 through a one-way valve D1, acyl chloride solution is added into a storage tank A2 at the same time, a feed pump B2 pumps the solution into the pre-mixer H1 through a one-way valve D2 (Q5 is closed and Q2 is opened), after mixing, the solution enters into a first reaction module EBL1, EBL2, EBL3 and EBL4 (the four reaction modules can be independently used or can be used in series, the reaction is carried out in series for example), the residence time is 10min, the reaction temperature is 40 ℃, then the solution enters into a pre-mixer H2 through a one-way valve D5, at this time, 1% hydrochloric acid aqueous solution is added into the storage tank A5, the solution enters into the pre-mixer H2 through a one-way valve D7 through a feed pump B3, the two are mixed and then enter into a second reaction module L1 for reaction, the residence time is 1.5min, and the reaction temperature is 20 ℃. Layering in a receiving tank C1, and taking out the lower organic phase for post-treatment to obtain 4-n-butyryl-4-bromobiphenyl. The yield of 4-n-butyryl-4-bromobiphenyl was 94.8.+ -. 0.4%.
It is found that the reaction temperature has a certain influence on the reaction yield.
Example 2:
the acylating reagent of example 1 was replaced with propionyl chloride, with the remaining conditions being the same as in example 1. The yield of the product 4-propionyl-4-bromobiphenyl was 98.2%.
Example 3:
the acylating reagent of example 1 was replaced with acetyl chloride, with the remainder being the same as in example 1. The yield of the product 4-acetyl-4-bromobiphenyl is 98.6%.
Example 4:
the acylating reagent of example 1 was replaced with chloroacetyl chloride, with the remaining conditions being the same as in example 1. The yield of the product 4-chloroacetyl-4-bromobiphenyl is 84.2% +/-0.3%.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (9)
1. A process for preparing 4-bromobiphenyl, characterized by: comprising the steps of (a) a step of,
the hydrogen peroxide solution and the hydrogen bromide solution are respectively and continuously pumped into a third reaction module EBL5 of the micro-channel reactor, the reaction temperature is controlled to be 0-20 ℃ for 1-10 min, materials coming out of the third reaction module of the micro-channel reactor flow into a pre-mixer H1, meanwhile, after being pumped into the pre-mixer H1 for mixing, the solution in the pre-mixer H1 is pumped into a first reaction module group of the micro-channel reactor, the temperature of the reaction module group is controlled to be 50-70 ℃ for 10-20 min, then the solution in the first reaction module group is pumped into a pre-mixer H2, the alkali solution is pumped into the pre-mixer H2, the mixed materials enter a second reaction module L1 for reaction, the temperature is 10-30 ℃ for 1-2 min, the materials enter a material receiving tank C1 for layering, and the organic layer is taken to obtain the 4-bromodiphenyl.
2. The method according to claim 1, characterized in that: the micro-channel reactor is of a pipeline-shaped structure, inner components are coaxially arranged in the micro-channel reactor, the inner components are arranged at intervals by a plurality of inner component structures 1 and inner component structures 2, the inner component structures 1 are of a net-shaped structure, the inner component structures 2 are of a spiral structure, the spiral structure is formed by spirally bending sheet plates, the net-shaped structure is a plurality of layers, each layer is composed of a plurality of strip plates which are arranged in parallel, the strip plates of two adjacent layers are arranged in a crossed manner at a certain angle and are fixedly connected at an intersection point, and the outer edge of the net-shaped structure is matched with the inner diameter of a pipeline of the micro-channel reactor; the inner member is fixedly connected or detachably connected with the inner wall of the microchannel reactor.
3. The method according to claim 2, characterized in that: the strip plates of two adjacent layers are arranged in a 30-90-degree cross way.
4. A method according to any one of claims 1-3, characterized in that: the inner diameter of the microchannel reactor is 0.5-6mm.
5. A method according to any one of claims 1-3, characterized in that: the molar ratio of biphenyl, hydrogen peroxide and hydrogen bromide is controlled at 1: (1.0 to 2.5): (1.0 to 5.0).
6. A method according to any one of claims 1-3, characterized in that: the micro-channel reactor is made of one or more of tantalum alloy and hastelloy.
7. A method according to any one of claims 1-3, characterized in that: the flow speed of the liquid in the microchannel reactor is 1-1.5 m/min.
8. A process for preparing a 4-bromobiphenyl derivative characterized by: the method of claim 1 is used for preparing 4-bromodiphenyl, the obtained solution of 4-bromodiphenyl, aluminum trichloride and acyl chloride solution are respectively pumped into a pre-mixer H1 for mixing, then pumped into a first reaction module group of a micro-channel reactor for reaction, the reaction temperature is 50-80 ℃, the reaction time in the first reaction module group of the micro-channel reactor is 10-20 min, the materials coming out of the first reaction module group of the micro-channel reactor and acid liquor are respectively pumped into a pre-mixer H2, then the materials and acid liquor enter a second reaction module L1 of the micro-channel reactor for reaction, the reaction temperature is 10-30 ℃ and the time is 1-2 min, the materials coming out of the second reaction module of the micro-channel reactor enter a material receiving tank C1 for layering, and the organic layer at the lower layer is removed to obtain the 4-bromodiphenyl derivative.
9. The method according to claim 8, wherein: the molar ratio of the 4-bromobiphenyl, the aluminum trichloride and the acyl chloride is controlled to be 1: (1.0 to 3.0): (1.0 to 3.0).
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02169537A (en) * | 1988-12-23 | 1990-06-29 | Kanto Chem Co Inc | Fluorine-substituted biphenyl derivative |
| US6169186B1 (en) * | 1998-12-29 | 2001-01-02 | Dainippon Ink And Chemicals, Inc. | Bismaleimides comprising mesogenic groups |
| CN104557485A (en) * | 2015-01-13 | 2015-04-29 | 南京工业大学 | Application of micro-flow field reactor in Friedel-Crafts reaction |
| CN108129258A (en) * | 2018-01-18 | 2018-06-08 | 上海仁实医药科技有限公司 | A kind of synthesis technology of the bromo- 4`- pentylbiphenyls of 4- |
| CN112441900A (en) * | 2019-09-05 | 2021-03-05 | 浙江中科创越药业有限公司 | Preparation method of 4-biphenylacetic acid |
| CN112778117A (en) * | 2020-12-17 | 2021-05-11 | 江苏阿尔法药业有限公司 | Method for synthesizing 4- (4-fluorobenzoyl) butyric acid and analogue thereof in continuous flow microreactor |
| CN114230447A (en) * | 2021-12-31 | 2022-03-25 | 河南豫辰药业股份有限公司 | Continuous flow preparation method of 4' -fluoro-2-phenylacetophenone |
| CN114426501A (en) * | 2021-12-23 | 2022-05-03 | 山东艾孚特科技有限公司 | Preparation method of bromosartanbiphenyl based on aqueous phase reaction |
| CN115536489A (en) * | 2022-11-01 | 2022-12-30 | 济宁金汉斯环保材料股份有限公司 | Green preparation process of high-purity 4-bromobiphenyl |
| CN116078313A (en) * | 2023-04-11 | 2023-05-09 | 山东默锐科技有限公司 | Continuous bromoethane preparation system and preparation process |
-
2023
- 2023-05-30 CN CN202310621860.6A patent/CN116640041B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02169537A (en) * | 1988-12-23 | 1990-06-29 | Kanto Chem Co Inc | Fluorine-substituted biphenyl derivative |
| US6169186B1 (en) * | 1998-12-29 | 2001-01-02 | Dainippon Ink And Chemicals, Inc. | Bismaleimides comprising mesogenic groups |
| CN104557485A (en) * | 2015-01-13 | 2015-04-29 | 南京工业大学 | Application of micro-flow field reactor in Friedel-Crafts reaction |
| CN108129258A (en) * | 2018-01-18 | 2018-06-08 | 上海仁实医药科技有限公司 | A kind of synthesis technology of the bromo- 4`- pentylbiphenyls of 4- |
| CN112441900A (en) * | 2019-09-05 | 2021-03-05 | 浙江中科创越药业有限公司 | Preparation method of 4-biphenylacetic acid |
| CN112778117A (en) * | 2020-12-17 | 2021-05-11 | 江苏阿尔法药业有限公司 | Method for synthesizing 4- (4-fluorobenzoyl) butyric acid and analogue thereof in continuous flow microreactor |
| CN114426501A (en) * | 2021-12-23 | 2022-05-03 | 山东艾孚特科技有限公司 | Preparation method of bromosartanbiphenyl based on aqueous phase reaction |
| CN114230447A (en) * | 2021-12-31 | 2022-03-25 | 河南豫辰药业股份有限公司 | Continuous flow preparation method of 4' -fluoro-2-phenylacetophenone |
| CN115536489A (en) * | 2022-11-01 | 2022-12-30 | 济宁金汉斯环保材料股份有限公司 | Green preparation process of high-purity 4-bromobiphenyl |
| CN116078313A (en) * | 2023-04-11 | 2023-05-09 | 山东默锐科技有限公司 | Continuous bromoethane preparation system and preparation process |
Non-Patent Citations (1)
| Title |
|---|
| Jianping Lu，et al.."Pure Deep Blue Light-Emitting Diodes from Alternating Fluorene/Carbazole Copolymers by Using Suitable Hole-Blocking Materials".Macromolecules.2004,第37卷2442-2449，第2443页右栏第三段和第2444页scheme1. * |
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