CN106674016A - Method for synthesizing 2-chloro-5-nitrobenzoic acid through microchannel reactor - Google Patents
Method for synthesizing 2-chloro-5-nitrobenzoic acid through microchannel reactor Download PDFInfo
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- CN106674016A CN106674016A CN201611169012.2A CN201611169012A CN106674016A CN 106674016 A CN106674016 A CN 106674016A CN 201611169012 A CN201611169012 A CN 201611169012A CN 106674016 A CN106674016 A CN 106674016A
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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Abstract
The invention provides a method for synthesizing 2-chloro-5-nitrobenzoic acid through a microchannel reactor. The method comprises the steps of dissolving a raw material o-chlorobenzoic acid into concentrated sulfuric acid to obtain a material 1, and entering a preheating module; adopting fuming nitric acid and the concentrated sulfuric acid as a material 2 and a material 3, and entering another preheating module; preheating the material 1, the material 2 and the material 3, entering a reaction module group for reacting, collecting effluent reaction liquid, processing to obtain a crude product, and refining to obtain the product 2-chloro-5-nitrobenzoic acid. According to the method provided by the invention, the reaction time is shortened to a few minutes to a few seconds, the production energy consumption is reduced, and the reaction efficiency is remarkably improved. High-efficient mass and heat transfer efficiency ensures the reaction temperature to maintain within a setting range, the possibilities of temperature out of control, temperature runaway and even sharp reaction overflow or explosion caused by over-high local concentration do not exist, the intrinsic safety problem of the nitration reaction is solved fundamentally, and the reaction yield and the product purity are remarkably improved.
Description
Technical field
The present invention relates to organic synthesis field, and in particular to a kind of method of synthesis 2- chloro-5-nitrobenzoic acids
Background technology
2- chloro-5-nitrobenzoic acids are the conventional chemical intermediates of organic synthesis field, are mainly used as industrial dye and doctor
Medicine intermediate, structure is as follows：
It is the important intermediate for synthesizing mesalazine in medical synthesis field 2- chloro-5-nitrobenzoic acids, and in dyestuff work
Its structure is by that can regard the demand of conventional azo dyes, all things considered China medicine and dye industry in industry after modification
The extensive use for being increasingly increased to such chemical intermediate is laid a good foundation, thus its new process development and popularization are with wide
Market prospects.
The production technology of current 2- chloro-5-nitrobenzoic acids mainly has nitrification process and oxidizing process etc..
1) oxidizing process：
With the chloro- 5- nitrotoleunes of 2- as raw material, in the presence of HTHP catalyst by methyl oxidation be carboxyl
Obtain 2- chloro-5-nitrobenzoic acids, oxidant of the program using the conventional oxygen being extremely easy to get as reaction, but oxygen is helped
Combustion attribute causes the step oxidation reaction, and production safety hidden danger is very big at high temperature under high pressure, while the raw material and catalyst of step reaction
Price costly limits the extensive use of the method.
2) nitrification processes：
With 0-chloro-benzoic acid as initiation material, 2- chloro-5-nitrobenzoic acids are obtained by nitric acid nitrating single step reaction, this
It is to produce the topmost method of the product at present.Usual preparation method is by dissolution of raw material in the concentrated sulfuric acid, mixed acid nitrification to be added dropwise.
But because nitration reaction heat release is very violent, nitration mixture is added dropwise to be needed to carry out under cryogenic, and the viscosity of the concentrated sulfuric acid is greatly,
During material hybrid reaction it is careless slightly i.e. occur situations such as excessive local concentration, temperature runaway, coking occur, more severe patient by
Trigger violent oxidation reaction in the case where local concentration is too high in itrated compound and organic matter and slug or blast occur, therefore
Step nitration reaction operational risk in large-scale industrial production is very big.
The content of the invention
To overcome disadvantages mentioned above, the present invention to provide a kind of method that micro passage reaction synthesizes 2- chloro-5-nitrobenzoic acids,
The reactor compared with traditional reactor have mass-and heat-transfer efficiency high, it is easy to operate, can with the precise control reaction time, take up an area
The advantages of area is small, environmental protection is safe；The method is simple to operate, heat release is controllable, with short production cycle, and products obtained therefrom isomers
Few, high income, purity are high.
In the method for the synthesis 2- chloro-5-nitrobenzoic acids that the present invention is provided, using the peculiar design of micro passage reaction,
Chemical reaction can be accurately controlled in narrow and small glass modules, because contact specific surface area of the reaction road with heat exchange layer becomes
Greatly, thus material mass-and heat-transfer efficiency is increased substantially during the course of the reaction, so as to the mixing for realizing material can be in millisecond
Complete, based on above experimental design, even if the nitration reaction heat release of 0-chloro-benzoic acid is very violent, but in micro passage reaction
On remain able to ensure reaction temperature within the scope of setting, without temperature runaway and superheating phenomenon.In order to realize foregoing invention purpose,
Applicant provide following technical scheme：
Raw material 0-chloro-benzoic acid is dissolved in as material 1 in the concentrated sulfuric acid, into warm-up block；By fuming nitric aicd and dense sulphur
Respectively as material 2 and material 3, into another warm-up block, material 1,2,3 is carried out instead after preheating into reaction module group for acid
Should, the reaction solution of outflow is collected, treatment is obtained after crude product by being refining to obtain product 2- chloro-5-nitrobenzoic acids.
In a preferred scheme of the invention, reaction temperature described in above-mentioned steps is 0~50 DEG C, more preferably 0 DEG C；Material is pre-
Hot temperature is identical with reaction temperature；Total residence time of the material in reaction module group is 15s~90s.
In a preferred scheme of the invention, the mass fraction of the concentrated sulfuric acid described in above-mentioned steps is 98%, fuming nitric aicd
Mass fraction be 90%；0-chloro-benzoic acid is 1 with the mol ratio of nitric acid:1.0~1:1.5, more preferably 1:1.4.
In a preferred scheme of the invention, in the material 1 described in above-mentioned steps, 0-chloro-benzoic acid is dissolved in the dense of the concentrated sulfuric acid
It is 1mol/L~2mol/L to spend；Material 2 and material 3 enter another warm-up block, and the concentration that fuming nitric aicd is dissolved in the concentrated sulfuric acid is
1mol/L~3mol/L.
In a preferred scheme of the invention, the recrystallization solvent used by crude product refining described in above-mentioned steps for methyl alcohol-
Water, the vol/vol methanol of the two:Water=1:1~1:3, more preferably 1:1.
In a preferred scheme of the invention, the ratio between above steps material is controlled with measuring pump；It is described anti-
Answer the material of module and accessory for special glass, scribble the stainless steel metal or politef of anti-corrosion layer in it is a kind of with
On, the Maximum safe pressure that can be born is 1.5~1.8MPa；The warm-up block is the cardioid knot of straight type structure or Two In and One Out
Structure module；The reaction module is Two In and One Out or singly enters the heart-shaped structure module for singly going out, and the order of connection is warm-up block, two enter
One goes out the reaction module of structure, singly enters the reaction module for singly going out structure, and the reaction module of Two In and One Out structure is mixed after being used to preheat
Reaction is closed, singly entering singly to go out the reaction module of structure is used to extend reaction time.
The micro passage reaction for using includes warm-up block group and reaction module group, warm-up block group and reaction module group string
Connection, warm-up block group includes a warm-up block or two or more warm-up block in parallel, and reaction module group includes a reaction
Module or the reaction module of two or more series connection；The method for synthesizing 2- chloro-5-nitrobenzoic acids is comprised the following steps：
Understand for convenience, some preferred schemes of the invention are arranged as follows：
Reaction equation：
Raw material 0-chloro-benzoic acid is dissolved in the concentrated sulfuric acid as material 1, warm-up block 1, preheating temperature are entered through measuring pump A
Degree is identical with reaction temperature；Using 90% fuming nitric aicd and 98% concentrated sulfuric acid as material 2 and material 3, respectively through
Measuring pump B and measuring pump C enters warm-up block 2, and preheating temperature is identical with reaction temperature；Flowed after four modules are reacted
Go out reactor, collect the reaction solution of outflow, post processing with it is refined after obtain product 2- chloro-5-nitrobenzoic acids.
It is 1 that o-dichlorohenzene is adjusted by controlling the flow of measuring pump with the mol ratio of nitric acid:1.0~1:1.5, preferably 1:
1.4；Reaction temperature is 0~50 DEG C, preferably 0 DEG C；Residence time is 15s~90s.Crude product recrystallization solvent selects methanol-water, body
Product is than being methyl alcohol:Water=1:1~1:3, more preferably 1:1.
The microchannel reaction system that the program is used is made up of polylith module.The material of module and accessory be special glass,
Scribble stainless steel metal, politef of anti-corrosion layer etc..Reaction system can be anticorrosive, and the Maximum safe pressure of reaction is
1.5~1.8MPa.Module type is heart-shaped structure and straight trip structure, and straight trip structure is used for the preheating of material, and heart-shaped structure is divided into
Singly enter the hybrid reaction for singly going out and being used for after material is preheated and preheated with Two In and One Out two types, Two In and One Out, and singly enter singly to go out
For extend reaction residence time, reaction module number specifically determined by the residence time reacted.Connected mode for (with reference to
Fig. 2)：Material 1 is connected by warm-up block 1 with reaction module 3；Material 2 and material 3 by warm-up block 2 and warm-up block 1 simultaneously
Connection, connects with reaction module 3.
The method that this programme is provided has the advantages that：
1. the configuration of nitration mixture and nitration reaction can be completed in reaction module, it is not necessary to extra acid-proof proportioner
With strong acid transfer device, while the operation under confined space it also avoid acid mist that nitration mixture volatilizes in experimentation to operation
The infringement of personnel and the corrosion to equipment.
2. continuous flow reactor is changed into by traditional batch agitator, the reaction time shorten to a few minutes to several seconds
Clock, reduces energy consumption, significantly improves the efficiency of reaction.
3. efficient mass-and heat-transfer efficiency ensure that reaction temperature is maintained in setting range, too high in the absence of local concentration
Caused temperature control, temperature runaway even vigorous reaction slug or the possibility of blast, fundamentally solve the step nitration reaction
Essential safety problem.
4. the chloro- 3- nitrobenzoic acids of isomers 2- during temperature control more accurately ensure that course of reaction compared with Fu Shi reactors
Content will not increase because of local heating, and the yield of reaction and the purity of product are significantly raised.
5. the consumption of sulfuric acid and nitration mixture is reduced, the discharge of produced spent acid in industrial production is reduced, reduced to ring
The pollution in border and spent acid processing cost.
6. modularized design and good operability, although reactor holds liquid small volume, but the reaction of its continuous stream
Speciality but can guarantee that yield reaches the level of popular response kettle, greatly save the throwing of equipment floor space and human cost
Enter.
7., without enlarge-effect, it is not necessary to can be directly amplified in pilot scale, the amplification usually occurred in the absence of conventional reactor is difficult
Topic, produces flexible and safe, and reduce production link and fund input.
Brief description of the drawings
The module material circulation duct shape and structure schematic diagram of Fig. 1 lucite material micro passage reactions, wherein (a) is
Cardioid list enters and singly goes out module, and (b) is cardioid Two In and One Out module, and (c) is straight pattern block.
Fig. 2 reaction process and micro passage reaction annexation schematic diagram, wherein A, B, C are respectively measuring pump, and 1 is straight type
Warm-up block, 2 is cardioid Two In and One Out warm-up block, and 3 is cardioid Two In and One Out reaction module, for hybrid reaction after preheating,
4th, 5,6 respectively cardioid lists enter singly to go out reaction module.
Specific embodiment：
The preparation of 2- chloro-5-nitrobenzoic acids：
Comparative example：
Fuming nitric aicd 80g is weighed, in the concentrated sulfuric acid that control instills 600ml at 0~10 DEG C, about 3 hours completion of dropping,
Nitration mixture configuration finishes stand-by.
The 0-chloro-benzoic acid for weighing 120g is added in the concentrated sulfuric acid of 1000ml, stirring and dissolving, the nitration mixture that upper step is obtained
During temperature is slowly dropped into reaction system at 0~10 DEG C in control, about 6 hours completion of dropping are warming up to incubation at room temperature stirring 2 small
When, reaction is finished, and reaction system is slowly dropped into the mixture of ice and water of 5L, and temperature is no more than 30 DEG C in control, at room temperature
Insulated and stirred 1 hour, filtering, filter cake 800ml water washings, it is 1 then to add to 530ml volume ratios crude product:1 methanol-water
Recrystallized in solution, be filtrated to get wet product, be vacuum dried 12 hours at 50 DEG C, obtain 2- chloro-5-nitrobenzoic acid 116.6g, received
Rate 75.5%, liquid phase purity 98.1%.
Therefore, when synthesizing 2- chloro-5-nitrobenzoic acids in popular response kettle, nitration reaction needs to delay at low temperature
Slow to be added dropwise, time-consuming, due to there is the chloro- 3- nitrobenzoic acids of substantial amounts of isomers 2- to generate in the too high course of reaction of local temperature,
Yield and purity are all relatively low；The other production of feather weight is carried out in 500L reactors to the technique on this basis, as a result such as
Under：
0-chloro-benzoic acid feeds intake 50Kg, and the time for adding of the configuration of nitration mixture and nitration mixture is all in more than 12h, place in course of reaction
It is 72.3%, liquid phase purity 96.2% that 2- chloro-5-nitrobenzoic acids yield is obtained after reason is refined.
Data above illustrates that the technique is produced in traditional reactor and there is fairly obvious enlarge-effect.And it is micro- logical
What road reactor was utilized is the advantage of continuous stream reaction, the enlarge-effect in tank reactor above can be avoided, without pilot scale
And trial production, directly by the slitless connection of experiment to big production, realize continuous stable state production and essential safety.Herein below is company
The concrete operations of afterflow micro passage reaction：
Embodiment 1
(1) weighing 0-chloro-benzoic acid 120g adds into the concentrated sulfuric acid of 580ml stirring and dissolving as material 1, to weigh 80g's
Fuming nitric aicd weighs the concentrated sulfuric acid of 450ml as material 3 as material 2；
(2) flow velocity of control material 1 is 15ml/min；The flow velocity of control material 2 is 3min/min；The stream of control material 3
Speed is 12min/min；Reaction temperature is 0 DEG C, and 0-chloro-benzoic acid is 1 with the mol ratio of nitric acid:1.4；The residence time of reaction is
65s；
(3) after each stock material reaches stable state in reactor, the reaction solution from reactor outlet outflow is collected, with logical
As a example by entering material 1 (i.e. 450ml materials 1, the 0-chloro-benzoic acid of 95.0g) corresponding reaction solution of 30min, the reaction that will be collected into
Liquid is poured into the mixture of ice and water of 1.35L, is incubated at room temperature stirring 1 hour, filtering, filter cake 500ml water washings, by crude product
It is 1 to add to 560ml volume ratios:Recrystallized in 1 methanol-water solution, be filtrated to get wet product, 12 are vacuum dried at 50 DEG C small
When, obtain 2- chloro-5-nitrobenzoic acid 104.6g, yield 85.5%, liquid phase purity 99.6%.
In the screening and optimization process of technological parameter, the parameter such as concentration, mol ratio, residence time to reaction raw materials is entered
Go and groped, the relevant parameter of corresponding steps has been changed on the basis of the operating procedure of embodiment 1, other specification condition is constant,
Result is summarized as follows：
| Nitric acid mol ratio | Reaction temperature | Residence time | Yield | Purity |
| 1.4 | 0℃ | 62 seconds | 85.5% | 99.6% |
| 1.4 | 15℃ | 62 seconds | 83.9% | 99.4% |
| 1.4 | 50℃ | 62 seconds | 82.8% | 99.1% |
| 1.0 | 0℃ | 62 seconds | 82.1% | 98.5% |
| 1.5 | 0℃ | 62 seconds | 83.3% | 98.9% |
The above-mentioned description to specific illustrative embodiment of the invention be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that certain principles of the invention and its reality should
With so that those skilled in the art can realize and using a variety of exemplaries of the invention and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of method that micro passage reaction synthesizes 2- chloro-5-nitrobenzoic acids, it is characterised in that：By raw material 0-chloro-benzoic acid
It is dissolved in the concentrated sulfuric acid as material 1, into warm-up block；Using fuming nitric aicd and the concentrated sulfuric acid as material 2 and material 3,
Into another warm-up block, material 1,2,3 is reacted after preheating into reaction module group, collects the reaction solution of outflow, treatment
Obtain after crude product by being refining to obtain product 2- chloro-5-nitrobenzoic acids.
2. the method that micro passage reaction according to claim 1 synthesizes 2- chloro-5-nitrobenzoic acids, it is characterised in that：
The reaction temperature is 0~50 DEG C；Material preheating temperature is identical with reaction temperature；During total stop of the material in reaction module group
Between be 15s~90s.
3. the method that micro passage reaction according to claim 1 synthesizes 2- chloro-5-nitrobenzoic acids, it is characterised in that：
The reaction temperature is 0 DEG C；Material preheating temperature is identical with reaction temperature；Total residence time of the material in reaction module group be
15s~90s.
4. the method that the micro passage reaction according to Claims 2 or 3 synthesizes 2- chloro-5-nitrobenzoic acids, its feature exists
In：The mass fraction of the described concentrated sulfuric acid is 98%, and the mass fraction of fuming nitric aicd is 90%；0-chloro-benzoic acid rubs with nitric acid
You are than being 1:1.0~1:1.5.
5. the method that the micro passage reaction according to Claims 2 or 3 synthesizes 2- chloro-5-nitrobenzoic acids, its feature exists
In：The mass fraction of the described concentrated sulfuric acid is 98%, and the mass fraction of fuming nitric aicd is 90%；0-chloro-benzoic acid rubs with nitric acid
You are than being 1:1.4.
6. the method that the micro passage reaction according to claim 4 or 5 synthesizes 2- chloro-5-nitrobenzoic acids, its feature exists
In：In described material 1, the concentration that 0-chloro-benzoic acid is dissolved in the concentrated sulfuric acid is 1mol/L~2mol/L；Material 2 and material 3 enter
Another warm-up block, the concentration that fuming nitric aicd is dissolved in the concentrated sulfuric acid is 1mol/L~3mol/L.
7. the method that micro passage reaction according to claim 6 synthesizes 2- chloro-5-nitrobenzoic acids, it is characterised in that：
Recrystallization solvent used by described crude product refining is methanol-water, the vol/vol methanol of the two:Water=1:1~1:3.
8. the method that micro passage reaction according to claim 6 synthesizes 2- chloro-5-nitrobenzoic acids, it is characterised in that：
Recrystallization solvent used by described crude product refining is methanol-water, the vol/vol methanol of the two:Water=1:1.
9. the method that micro passage reaction according to claim 6 synthesizes 2- chloro-5-nitrobenzoic acids, it is characterised in that：
Ratio between each step material is controlled with measuring pump；The material of the reaction module and accessory be special glass, scribble it is resistance to
One or more of stainless steel metal or politef of corrosion layer, the Maximum safe pressure that can be born are 1.5~1.8MPa；
The warm-up block is the heart-shaped structure module of straight type structure or Two In and One Out；The reaction module is Two In and One Out or Dan Jindan
The heart-shaped structure module for going out, the order of connection is warm-up block, the reaction module of Two In and One Out structure, singly enters the reaction for singly going out structure
Module, the reaction module of Two In and One Out structure is used for hybrid reaction after preheating, and singly entering singly to go out the reaction module of structure is used to extend
Reaction time.
10. the method that micro passage reaction according to claim 8 synthesizes 2- chloro-5-nitrobenzoic acids, it is characterised in that：
The micro passage reaction for using includes warm-up block group and reaction module group, and warm-up block group is connected with reaction module group, preheats
Module group includes a warm-up block or two or more warm-up block in parallel, and reaction module group includes a reaction module or two
The reaction module of series connection more than individual；Material 1 is connected by warm-up block (1) with reaction module (3)；Material 2 and material 3 are by pre-
Thermal modules (2) are in parallel with warm-up block (1), connected with reaction module (3).
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| CN111253261A (en) * | 2020-03-02 | 2020-06-09 | 杭州沈氏节能科技股份有限公司 | Preparation method of 3, 5-dinitrobenzoic acid |
| CN112358400A (en) * | 2020-10-22 | 2021-02-12 | 烟台大学 | Method for synthesizing acifluorfen by nitration in microreactor |
| CN114195644A (en) * | 2021-12-14 | 2022-03-18 | 浙江工业大学 | Process and device for selective nitration of p-chlorobenzoic acid |
| CN114195644B (en) * | 2021-12-14 | 2023-11-14 | 浙江工业大学 | Process and device for selectively nitrifying p-chlorobenzoic acid |
| CN117603097A (en) * | 2023-11-29 | 2024-02-27 | 安徽泽升科技股份有限公司 | Method for rapidly preparing 2-bromo-5-nitrobenzenesulfonyl chloride |
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