CN106631728A - Method for preparing 3,5-difluorobenzaldehyde by 3,5-difluorotoluene continuous oxidation - Google Patents
Method for preparing 3,5-difluorobenzaldehyde by 3,5-difluorotoluene continuous oxidation Download PDFInfo
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- CN106631728A CN106631728A CN201610972094.8A CN201610972094A CN106631728A CN 106631728 A CN106631728 A CN 106631728A CN 201610972094 A CN201610972094 A CN 201610972094A CN 106631728 A CN106631728 A CN 106631728A
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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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- 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
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- 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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
- B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
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Abstract
The invention relates to a method for preparing 3,5-difluorobenzaldehyde by 3,5-difluorotoluene continuous oxidation, and belongs to the technical field of organic synthesis. The method belongs to a process technology being characterized in that a 3,5-difluorobenzaldehyde compound is used as a raw material; one or several metal ion complexes of cobalt, molybdenum and bromine are used as catalysts; hydrogen peroxide is used as an oxidizing agent; acetic acid is used as a solvent; the 3,5-difluorobenzaldehyde is continuously oxidized in a tubular reactor for preparing the 3,5-difluorobenzaldehyde. The method has the advantages that the conditions are mild; the reaction time is short; the raw material utilization rate is high; the effective control in the reaction process can be realized; safety and stability are realized; the continuous operation is realized; the production efficiency is high.
Description
Technical field
The invention belongs to organic synthesis technology field, is related to one kind under liquid-phase reaction condition by 3,5- difluoro toluenes
The method that continuous oxidation prepares 3,5- difluorobenzaldehydes, is more specifically that, for substrate, hydrogen peroxide is oxidation with 3,5- 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 3,5- difluorobenzaldehyde products.
Background technology
3,5- difluorobenzaldehydes, molecular formula：C7H4Cl2O, molecular weight is 142.1, and finished product is colourless to weak yellow liquid, is melted
Point is 17 DEG C, 61-63 DEG C of boiling point, 50 DEG C of flash-point.3,5- difluorobenzaldehydes are to synthesize one of important raw material of fine chemicals, are used
In synthetic dyestuffs, agricultural chemicals and medicine intermediate.
At present the main method of production 3,5- difluorobenzaldehydes is, by using 3,5- difluoro toluene chlorinations, to prepare 3,5- bis-
Fluorobenzyl chloride, then Jing hydrolysis and obtain, specific reactions steps are as follows：
Mainly by chlorination 3,5- difluoro toluenes obtain the fluorobenzyl chlorides of 3,5- bis- as raw material to said method, in the same of chlorination
When need to control the depth and condition of chlorination, and it also requires add substantial amounts of catalyst to shorten the chlorination reaction time, and sharp
Continuous oxidation synthesis 3, the 5- difluorobenzaldehydes of 3,5- difluoro toluenes are carried out with the continuous flow tubular reactor of ad hoc structure, can be many
Aspect solves many deficiencies of 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, can be had using the continuous flow tubular reactor of ad hoc structure to the mixing of reaction mass and mass transfer, diabatic process
Effect control.By the control of the length to tubular reactor and reaction time, the distribution of raw material and product can be further made
More optimize controllable；By adjusting the flow velocity of raw material pump substrate 3,5- difluoro toluenes are capable of achieving with oxidant in proportion into tubular type
Reactor carries out reaction and greatly reduces back-mixing, further reduces the generation of side reaction, and the stability of oxidant and target are produced
The selectivity of thing is also greatly improved；By arranging pressure safety valve in tubular reactor, can give off in time in reactor
Excessive oxidant, it is ensured that the safety of reaction is carried out, and level of significance is minimized.The present invention adopts the pipe reaction of ad hoc structure
Device carries out 3,5- difluoro toluene continuous oxidations and prepares the method for 3,5- difluorobenzaldehydes relative to conventional batch production method tool
There is unrivaled advantage, and quantity-produced improvement can be industrialized for it and one important approach is provided.
The content of the invention
The present invention is directed to not enough with present on, there is provided one kind is in tubular reactor by the continuous oxygen of 3,5- difluoro toluenes
The method that change prepares 3,5- 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 the process of the present invention, to realize 3,5- 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 high reaction mass, further reduces the usage amount of oxidant and catalyst and avoids during the course of the reaction
The use of co-catalyst, so as to effectively save production cost further improves existing industrialized preparing process.
For achieving the above object, the technical solution used in the present invention is：
3,5- difluoro toluenes continuous oxidation is prepared 3,5- difluorobenzaldehydes by a kind of tubular reactor of employing special construction
Method, carry out as steps described below：
(1) first at room temperature, by substrate 3,5- 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 pours metal complex mixing into 3,5- 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 squeeze into tubular reactor Jing 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 60～1600s of the time of staying of control material hybrid reaction；Reacting
Cheng Hou, product exits into collecting tank from reactor end, and product rectification is separated, and unreacted 3,5- difluoro toluenes circulation is anti-
Should, product 3,5- difluorobenzaldehyde rectifying is collected after purification, wherein target product 3, and the yield of 5- difluorobenzaldehydes is up to 20%
～35%.
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 dissolve in 3,5- difluoro toluenes, its consumption and substrate 3, the mol ratio of 5- difluoro toluenes (0.0025～
0.25): 1, wherein preferred molar ratio is (0.01～0.18): 1.
Wherein described oxidant is hydrogen peroxide, and its solution concentration is calculated as 5%～75% with mass concentration, and preferred concentration is
10%～60%.Hydrogen peroxide is (1.0～9.0) with the preferred molar ratio of substrate 3,5- 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 and additionally supplement at volume isocyatic hydrogen peroxide 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 3,5-
The volume ratio of difluoro toluene is in (1～12): 1.
Wherein described reaction temperature is 50～140 DEG C, and preferable reaction temperature is 75～125 DEG C, and reaction time is
60s～1600s.
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 after purification target product.
In above-mentioned technical proposal, described reaction system includes the difference in functionalitys such as 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 adopts 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 effectively reduce the usage amount of oxidant and catalyst, 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.
Description of the drawings
Fig. 1 is the process chart that 3,5- difluoro toluenes continuous oxidation of the present invention prepares 3,5- 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, and b- justifies
Cake formula pulse diameter varied narrow rectangular tube road, the oblique side cake formula pulse diameter varied narrow rectangular tube roads of c-, it is flat that d- strengthens mixed type cake formula
Pipeline, e-Corning Heart Cell structures microchannel.
Specific embodiment
Cobalt acetate and sodium molybdate are dissolved in the 1# tanks equipped with 3,5- difluoro toluenes and acetic acid, 5# preheatings are pumped into by 3#
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#
In entering the pre- thermal reactors of 6#, pre- thermal reactor is heated to 50 DEG C, then by two strands of preheating materials, in being delivered to 7#, 8# reactor,
Temperature of reactor is set in and reacts temperature required, and product, using 0 DEG C of cooling, collects products therefrom by flowing out in 8# reactors.
The present invention is described in detail with reference to embodiment, but the following examples are only the present invention preferably embodiment,
Protection scope of the present invention is not limited thereto, technology model of any those familiar with the art in present disclosure
In enclosing, technology according to the present invention scheme and its inventive concept in addition equivalent substitute or change should all cover the guarantor in the present invention
Within the scope of shield.
Embodiment 1
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, 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
For conduction oil.
(2) respectively 2.02g cobalt acetates and 2.02g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.005:1,2.02g sodium bromides are dissolved in into 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.005:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 5.33ml/min and 10.67ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 50
DEG C, time of staying 60s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoro toluenes turn
Rate is 31.3%, and 3,5- difluorobenzaldehyde yields are 24.1%.
Embodiment 2
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, 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) respectively 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in into 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.015:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 75
DEG C, time of staying 200s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoro toluenes
Conversion ratio is 29.0%, and 3,5- difluorobenzaldehyde yields are 20.7%.
Embodiment 3
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, conduit types are：(3a+3d) once-through type passage+
Strengthen mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline determines with volume according to flow velocity and reaction time, heat transferring medium
For conduction oil.
(2) respectively 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.015:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 600s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoro first
Benzene conversion ratio is 32.8%, and 3,5- difluorobenzaldehyde yields are 24.2%.
Embodiment 4
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, 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
For conduction oil.
(2) respectively 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in into 35%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.015:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 5.33ml/min and 10.67ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 600s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoro first
Benzene conversion ratio is 39.5%, and 3,5- difluorobenzaldehyde yields are 28.1%.
Embodiment 5
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, 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) respectively 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in into 35%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.015:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 600s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoro first
Benzene conversion ratio is 41.7%, and 3,5- difluorobenzaldehyde yields are 31.1%.
Embodiment 6
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, conduit types are：(3a+3d) once-through type passage+
Strengthen mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline determines with volume according to flow velocity and reaction time, heat transferring medium
For conduction oil.
(2) respectively 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in into 35%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.015:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 900s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoro first
Benzene conversion ratio is 37.7%, and 3,5- difluorobenzaldehyde yields are 21.0%.
Embodiment 7
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, 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) respectively 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.015:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
120 DEG C, time of staying 1200s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoros
Toluene conversion is 40.2%, and 3,5- difluorobenzaldehyde yields are 21.1%.
Embodiment 8
(1) device：Determine the connected mode of tubular reactor with reference to Fig. 2, conduit types are：(3a+3d) once-through type passage+
Strengthen mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline determines with volume according to flow velocity and reaction time, heat transferring medium
For conduction oil.
(2) respectively 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in into 200ml3,5- difluoro toluenes and 200ml acetic acid shapes
Into mixed solution, now n (cobalt acetate)：N (3,5- difluoro toluenes)=0.015:1,6.06g sodium bromides are dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (3,5- difluoro toluenes)=0.015:1,3,5- difluoro toluene-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat respectively with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump injection
In formula reactor, now n (H2O2)：N (3,5- difluoro toluenes)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
140 DEG C, time of staying 1600s.0 DEG C of cooling of outlet material, reactant liquor is quenched with difluoromethane.Through GC analyses, 3,5- difluoros
Toluene conversion is 35.9%, and 3,5- difluorobenzaldehyde yields are 22.7%.
Claims (6)
1. one kind 3, the method that 5- difluoro toluenes continuous oxidation prepares 3,5- difluorobenzaldehydes, it is characterised in that as steps described below
Carry out：
（1）Under room temperature, by substrate 3,5- 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 pours metal complex mixing into 3,5- difluoro toluenes-carboxylic acid
Solution, sodium salt is poured into hydrogen peroxide-carboxylic acid solution；By the required reaction time, the not cocurrent flow of two kinds of materials is calculated
Speed, continuously squeezes into tubular reactor Jing 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 adjusting the method for 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 time of staying 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 3,5- difluoro toluenes circular response, product 3,5- difluorobenzenes
Formaldehyde rectification is collected after purification.
2. the method that a kind of 3,5- difluoro toluenes continuous oxidation according to claim 1 prepares 3,5- 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 dissolve in 3,5- difluoro toluenes, its consumption and substrate 3, the mol ratio of 5- difluoro toluenes exists（0.0025~0.25）: 1, its
Middle preferred molar ratio is（0.01~0.18）∶1.
3. the method that a kind of 3,5- difluoro toluenes continuous oxidation according to claim 1 prepares 3,5- difluorobenzaldehydes, its
It is characterised by that described oxidant is hydrogen peroxide, its solution concentration is calculated as 5% ~ 75% with mass concentration, preferred concentration is 10% ~
60%, hydrogen peroxide and substrate 3, the preferred molar ratio of 5- difluoro toluenes is（1.0~9.0）∶1.
4. the method that a kind of 3,5- difluoro toluenes continuous oxidation according to claim 1 prepares 3,5- 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 3,5- difluoro first
The volume ratio of benzene exists（1~12）∶1.
5. the method that a kind of 3,5- difluoro toluenes continuous oxidation according to claim 1 prepares 3,5- difluorobenzaldehydes, its
It is characterised by：Reaction temperature is 50 ~ 140 DEG C, and preferable reaction temperature is 75 ~ 125 DEG C, reaction time 60s ~ 1600s.
6. the method that a kind of 3,5- difluoro toluenes continuous oxidation according to claim 1 prepares 3,5- 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 |
| CN102516052A (en) * | 2011-11-07 | 2012-06-27 | 常州大学 | Method for preparing acetophenone through ethyl benzene oxidation by using microchannel reactor |
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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 |
| CN102516052A (en) * | 2011-11-07 | 2012-06-27 | 常州大学 | Method for preparing acetophenone through ethyl benzene oxidation by using microchannel reactor |
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