CN106748683A - A kind of method that 3,4 difluoro toluene continuous oxidation prepares 3,4 difluorobenzaldehydes - Google Patents
A kind of method that 3,4 difluoro toluene continuous oxidation prepares 3,4 difluorobenzaldehydes Download PDFInfo
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The method that 3,4 difluoro toluene continuous oxidations of one kind of the invention prepare 3,4 difluorobenzaldehydes, belongs to organic synthesis technology field.The method is that, with 3,4 difluoro toluene compounds are raw material, and one or more metal ion complexs of cobalt, molybdenum, bromine are catalyst, hydrogen peroxide is oxidant, and acetic acid is solvent, continuous by 3 in tubular reactor, the oxidation of 4 difluoro toluenes prepares the technology of 3,4 difluorobenzaldehydes.This method mild condition, the reaction time is short, and raw material availability is high, is capable of achieving the effective control in course of reaction, and safety and stability, continuous operation, production efficiency is high.
Description
Technical field
The invention belongs to organic synthesis technology field, it is related to one kind under liquid-phase reaction condition by 3,4- difluoro toluenes
The method that continuous oxidation prepares 3,4- difluorobenzaldehydes, is more specifically that, for substrate, hydrogen peroxide is oxidation with 3,4- difluoro toluenes
Agent, one or more metal ion complexs of cobalt, molybdenum, bromine are catalyst, and monocarboxylic acid is solvent, with different micro-structurals
Tubular reactor in continuous prepare 3,4- difluorobenzaldehyde products.
Background technology
3,4- difluorobenzaldehydes, molecular formula：C7H4F2O, molecular weight is 142.1, and finished product is colourless transparent liquid, boiling point 53-
55 DEG C, density 1.288g/ml is slightly soluble in hot alcohol and ether, water insoluble, can be volatilized with vapor.3,4- difluorobenzaldehydes are
One of important raw material of synthesis fine chemicals, for synthetic pesticide, medicine and liquid crystal material intermediate.
The main method of production 3,4- difluorobenzaldehydes is, by using 3,4- difluoro toluene chlorinations, to prepare 3,4- bis- at present
Fluorobenzyl chloride, then obtained through hydrolysis, specific reactions steps are as follows：
The above method is mainly by chlorination 3, and 4- difluoro toluenes obtain the fluorobenzyl chlorides of 3,4- bis- as raw material, then through hydrolysis
Reaction prepares 3,4- difluorobenzaldehydes.The defect that the method is present：First, need while chlorination to control chlorination depth and
Condition；Secondly, also need to add substantial amounts of catalyst to shorten the reaction time in hydrolysis；Finally, can not in reaction
The substantial amounts of spent acid waste water of generation for avoiding, production cost increases.And 3 are carried out using the continuous flow tubular reactor of ad hoc structure,
Continuous oxidation synthesis 3, the 4- difluorobenzaldehydes of 4- difluoro toluenes, can many-sided many deficiencies for solving existing process technology.
Tubular reactor is the general designation of the mini-reactor with micro-structural, compared with conventional reactor, tubular reactor
With small volume, specific surface area is big, easily amplifies, and process is continuous, and quick good mixing effect, heat-transfer effect is good, high temperature high voltage resistant etc.
Feature, the continuous flow tubular reactor using ad hoc structure can have to the mixing of reaction mass and mass transfer, diabatic process
Effect control.By the control of length and reaction time to tubular reactor, can further make the distribution of raw material and product
More optimize controllable；Can realize that substrate 3,4- difluoro toluenes enter tubular type in proportion with oxidant by the flow velocity for adjusting raw material pump
Reactor carries out reaction and greatly reduces back-mixing, further reduces the generation of side reaction, and the stability and target of oxidant are produced
The selectivity of thing is also greatly improved；By setting pressure safety valve in tubular reactor, in can in time giving off reactor
Excessive oxidant, it is ensured that the safety of reaction is carried out, and level of significance is minimized.The present invention uses the pipe reaction of ad hoc structure
Device carries out 3,4- difluoro toluene continuous oxidations and prepares the method for 3,4- difluorobenzaldehydes relative to conventional batch production method tool
There is unrivaled advantage, and an important approach can be provided for it industrializes quantity-produced improvement.
The content of the invention
The present invention is directed to not enough present on, there is provided one kind is in tubular reactor by the continuous oxygen of 3,4- difluoro toluenes
The method that change prepares 3,4- difluorobenzaldehydes.This method reaction time is short, and production efficiency is high, and mass transfer, heat transfer are optimized significantly,
Course of reaction is more stablized controllable.Further object of the present invention is, by process of the invention, realizes 3,4- bis-
Stablizing for toluene fluoride continuous oxidation is controllable, reduces the generation of accessory substance.Carried by the reinforcing and process optimization of mass-and heat-transfer process
The effective rate of utilization of reaction mass high, further reduces the usage amount of oxidant and catalyst and avoids during the course of the reaction
The use of co-catalyst, so that effectively save production cost and then the existing industrialized preparing process of improvement.
To achieve the above object, the technical solution adopted by the present invention is：
3,4- difluoro toluenes continuous oxidation is prepared 3,4- difluorobenzaldehydes by a kind of tubular reactor of use special construction
Method, carry out as steps described below：
(1) first at room temperature, by substrate 3,4- difluoro toluenes and part carboxylic acid solvent are with volume ratio 1:1 stirring mixing is equal
It is even, by oxidant and part carboxylic acid solvent with volume ratio 1:1 is well mixed, and then mixes metal complex and pours into 3,4- difluoros
Toluene-carboxylic acid solution, sodium salt is poured into hydrogen peroxide-carboxylic acid solution；By the required reaction time, two kinds of materials are calculated
It is different in flow rate, continuously squeezed into tubular reactor through measuring pump reacted into reaction zone after preheated mixing respectively, instead
Temperature is answered to be controlled by outer loop heat-exchange system；
(2) mol ratio of reaction mass is controlled by adjusting the method for flow velocity and weight calculation, by changing tubular reactor
0.5~15mm of internal diameter of the pipeline, 25~750ml of volume carry out the 60~2400s of residence time of control material hybrid reaction；Reacting
Cheng Hou, product exits into collecting tank from reactor end, and product rectification is separated, and unreacted 3,4- difluoro toluenes circulation is anti-
Should, product 3,4- difluorobenzaldehyde rectifying is collected after purification, wherein target product 3, and the yield of 4- difluorobenzaldehydes is up to 20%
~30%.
Wherein described catalyst is cobalt, molybdenum, bromine one or more metal complex catalysts, and it mainly includes：Acetic acid
Cobalt, cobalt oxalate, cobalt carbonate, cobalt naphthenate, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide etc., wherein being with oil-soluble catalyst
It is main, can fully be dissolved in 3,4- difluoro toluenes, its consumption and substrate 3, the mol ratio of 4- difluoro toluenes is in (0.001~0.30)
: 1, wherein preferred molar ratio is (0.01~0.25): 1.
Wherein described oxidant is hydrogen peroxide, and its solution concentration is calculated as 5%~65% with mass concentration, and preferred concentration is
10%~55%.Hydrogen peroxide is (1.0~10.0) with the preferred molar ratio of substrate 3,4- difluoro toluenes: 1.
Wherein described hydrogen peroxide, in tubular reactor, when hydrogen peroxide passes through reactor volume 50ml, hydrogen peroxide
Start it is rapid decompose, discharge a large amount of molecular oxygens, when it passes through 100ml, almost molecular oxygen form now should be anti-in 100ml
Answer the hydrogen peroxide that isoconcentration is additionally supplemented at volume to enter, reaction is participated in again.
Wherein described carboxylic acid solvent includes:Formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid etc..Wherein solvent and 3,4-
The volume ratio of difluoro toluene is in (1~8): 1.
Wherein described reaction temperature is 50~150 DEG C, and preferable reaction temperature is 70~130 DEG C, and reaction time is
60s~2400s.
In further technical scheme, the oxidant for having neither part nor lot in reaction is first quenched with difluoromethane sodium after completion of the reaction,
Then extracted by organic solvent, separated obtains target product after purification.
In above-mentioned technical proposal, the described reaction system difference in functionality such as including raw material storage tank, reaction zone, collection of products area
Region.Channel of reactor structure includes：Pipe once-through type channel design, cake formula pulse diameter varied narrow rectangular tube road structure, tiltedly
Square cake formula pulse diameter varied narrow rectangular tube road structure, enhancing mixed type cake formula narrow rectangular tube road structure and Corning's
Heart Cell channel designs.
The present invention has advantages below：
1st, the present invention uses a kind of mode of production of serialization, and the reaction time is short, and reaction condition is gentle, and process safety can
Control, production efficiency is high.
2nd, the present invention is capable of achieving the effective control to course of reaction by the tubular reactor made using different structure, makes
Product rests on the step of aldehyde alcohol one.
3rd, by the way that the utilization rate of its reaction rate and raw material greatly improved to mass transfer in course of reaction, heat transfer intensification,
And the usage amount of oxidant and catalyst is effectively reduced, and the use of co-catalyst is avoided, there is production cost
Effect is saved.
4th, the present invention is easy to operate, applied widely, and production is flexible, can be advised by the expanding production in parallel of reaction unit
Mould.
Brief description of the drawings
Fig. 1 is the process chart that 3,4- difluoro toluenes continuous oxidation of the present invention prepares 3,4- difluorobenzaldehydes.
Fig. 2 is continuous flow tubular reactor installation drawing used in the present invention：1st, 2- head tanks, 3,4- raw material measuring pumps,
5- preheating zones, 6,7- reaction zones, 8- products are quenched collecting region.
Fig. 3 is tubular reactor channel design schematic diagram used in the present invention, wherein a- once-through types channel design, b- circles
Cake formula pulse diameter varied narrow rectangular tube road, the oblique side cake formula pulse diameter varied narrow rectangular tube roads of c-, d- enhancings mixed type cake formula is flat
Pipeline, the Heart Cell structures microchannel of e-Corning.
Specific embodiment
Cobalt acetate and sodium molybdate are dissolved in the 1# tanks equipped with 3,4- difluoro toluenes and acetic acid, being pumped into 5# by 3# preheats
In reactor, pre- thermal reactor is heated to 50 DEG C；Sodium bromide is dissolved in the 2# tanks equipped with hydrogen peroxide and acetic acid, is pumped by 4#
Enter in the pre- thermal reactors of 6#, pre- thermal reactor is heated to 50 DEG C, then by two strands of preheating materials, be delivered in 7#, 8# reactor,
Temperature of reactor is set in temperature needed for reaction, and product flows out by 8# reactors, using 0 DEG C of cooling, collects products therefrom.
The present invention is described in detail with reference to embodiment, but the following examples are only the present invention preferably implementation method,
Protection scope of the present invention is not limited thereto, technology model of any one skilled in the art in present disclosure
In enclosing, technology according to the present invention scheme and its inventive concept are subject to equivalent substitute or change, should all cover in guarantor of the invention
Within the scope of shield.
Embodiment 1
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3b) once-through type passage+
Cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 2.02g cobalt acetates and 2.02g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.005:1,2.02g sodium bromides are dissolved in 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.005:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.33ml/min and 10.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 50
DEG C, residence time 60s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoro toluenes turn
Rate is 45.3%, and 3,4- difluorobenzaldehyde yields are 27.1%.
Embodiment 2
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3c) once-through type passage+
Oblique side cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determines according to flow velocity and reaction time with volume, exchanges heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.015:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 65
DEG C, residence time 200s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoro toluenes
Conversion ratio is 42.0%, and 3,4- difluorobenzaldehyde yields are 30.7%.
Embodiment 3
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3d) once-through type passage+
Enhancing mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.015:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, residence time 600s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoro first
Benzene conversion ratio is 42.8%, and 3,4- difluorobenzaldehyde yields are 28.2%.
Embodiment 4
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3b) once-through type passage+
Cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in 30%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.015:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.33ml/min and 10.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, residence time 900s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoro first
Benzene conversion ratio is 37.5%, and 3,4- difluorobenzaldehyde yields are 23.1%.
Embodiment 5
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3c) once-through type passage+
Oblique side cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determines according to flow velocity and reaction time with volume, exchanges heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in 30%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.015:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 95
DEG C, residence time 1200s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoro toluenes
Conversion ratio is 54.7%, and 3,4- difluorobenzaldehyde yields are 29.1%.
Embodiment 6
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3d) once-through type passage+
Enhancing mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.015:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, residence time 2000s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoros
Toluene conversion is 30.7%, and 3,4- difluorobenzaldehyde yields are 20.0%.
Embodiment 7
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3e) once-through type passage+
Corningde Heart Cell structures, internal diameter of the pipeline determines that heat transferring medium is with volume according to flow velocity and reaction time
Conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.015:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
120 DEG C, residence time 2200s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoros
Toluene conversion is 45.2%, and 3,4- difluorobenzaldehyde yields are 29.8%.
Embodiment 8
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3d) once-through type passage+
Enhancing mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml3,4- difluoro toluenes and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (3,4- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,4- difluoro toluenes)=0.015:1,3,4- difluoro toluene-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (3,4- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
150 DEG C, residence time 2400s.0 DEG C of cooling of outlet material, reaction solution is quenched with difluoromethane.Analyzed by GC, 3,4- difluoros
Toluene conversion is 37.9%, and 3,4- difluorobenzaldehyde yields are 21.1%.
Claims (6)
1. one kind 3, the method that 4- difluoro toluenes continuous oxidation prepares 3,4- difluorobenzaldehydes, it is characterised in that as steps described below
Carry out：
（1）At room temperature, by substrate 3,4- difluoro toluenes and part carboxylic acid solvent are with volume ratio 1:1 is uniformly mixed, and will aoxidize
Agent and part carboxylic acid solvent are with volume ratio 1:1 is well mixed, and then mixes metal complex and pours into 3,4- difluoro toluenes-carboxylic acid
Solution, sodium salt is poured into hydrogen peroxide-carboxylic acid solution；By the required reaction time, two kinds of not cocurrent flows of material are calculated
Speed, continuously squeezes into tubular reactor through measuring pump reacted into reaction zone after preheated mixing respectively, reaction temperature by
Outer loop heat-exchange system is controlled；
（2）The mol ratio of reaction mass is controlled by the method for adjusting flow velocity and weight calculation, by the pipeline for changing tubular reactor
0.5 ~ 15mm of internal diameter, 25 ~ 750ml of volume carrys out the residence time of control material hybrid reaction；After completion of the reaction, product is from reaction
Device end exits into collecting tank, and product rectification is separated, unreacted 3,4- difluoro toluenes circular response, product 3,4- difluorobenzenes
Formaldehyde rectification is collected after purification.
2. the method that a kind of 3,4- difluoro toluenes continuous oxidation according to claim 1 prepares 3,4- difluorobenzaldehydes, its
It is characterised by that described catalyst is cobalt, molybdenum, sodium one or more metal complex catalysts, it mainly includes：Cobalt acetate, grass
Sour cobalt, cobalt carbonate, cobalt naphthenate, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide etc., wherein based on oil-soluble catalyst, energy
Fully dissolved in 3,4- difluoro toluenes, its consumption and substrate 3, the mol ratio of 4- difluoro toluenes exists（0.001~0.30）: 1, its
Middle preferred molar ratio is（0.01~0.25）∶1.
3. the method that a kind of 3,4- difluoro toluenes continuous oxidation according to claim 1 prepares 3,4- difluorobenzaldehydes, its
Described oxidant being characterised by for hydrogen peroxide, its solution concentration is calculated as 5% ~ 65% with mass concentration, preferred concentration is 10% ~
55%, hydrogen peroxide and substrate 3, the preferred molar ratio of 4- difluoro toluenes is（1.0~10.0）∶1.
4. the method that a kind of 3,4- difluoro toluenes continuous oxidation according to claim 1 prepares 3,4- difluorobenzaldehydes, its
It is characterised by that described carboxylic acid solvent includes：Formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid;Wherein solvent and 3,4- difluoro first
The volume ratio of benzene exists（1~8）∶1.
5. the method that a kind of 3,4- difluoro toluenes continuous oxidation according to claim 1 prepares 3,4- difluorobenzaldehydes, its
It is characterised by：Reaction temperature is 50 ~ 150 DEG C, and preferable reaction temperature is 70 ~ 130 DEG C, reaction time 60s ~ 2400s.
6. the method that a kind of 3,4- difluoro toluenes continuous oxidation according to claim 1 prepares 3,4- difluorobenzaldehydes, its
It is characterised by that total overall reaction process is carried out continuously in the tubular reactor of ad hoc structure, the reaction system is stored up including raw material
The difference in functionality such as tank, reaction zone, collection of products region;Channel of reactor structure includes：Pipe once-through type channel design, cake formula
Pulse diameter varied narrow rectangular tube road structure, tiltedly side cake formula pulse diameter varied narrow rectangular tube road structure, enhancing mixed type cake formula square
The flat pipeline configuration of shape, cardioid channel design.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5473101A (en) * | 1991-06-21 | 1995-12-05 | Solvay Interox Limited | Oxidation of alkylaromatics |
| CN102432448A (en) * | 2011-11-07 | 2012-05-02 | 常州大学 | Method for preparing acetophenone by oxidizing ethylbenzene in continuous flow micro-channel reactor |
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2016
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| US5473101A (en) * | 1991-06-21 | 1995-12-05 | Solvay Interox Limited | Oxidation of alkylaromatics |
| CN102432448A (en) * | 2011-11-07 | 2012-05-02 | 常州大学 | Method for preparing acetophenone by oxidizing ethylbenzene in continuous flow micro-channel reactor |
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