CN107226775A - The method that the chloro- 3,5- xylenols of 4- are synthesized in continuous stream micro-pipe reactor - Google Patents
The method that the chloro- 3,5- xylenols of 4- are synthesized in continuous stream micro-pipe reactor Download PDFInfo
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- CN107226775A CN107226775A CN201610173033.5A CN201610173033A CN107226775A CN 107226775 A CN107226775 A CN 107226775A CN 201610173033 A CN201610173033 A CN 201610173033A CN 107226775 A CN107226775 A CN 107226775A
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- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Abstract
The invention belongs to organic fine synthesis field, it relate to synthesize 4- chloro- 3 in a kind of continuous stream micro-tubular reactor, the method of 5- xylenols, i.e. in the microreactor of control certain temperature, raw material 3 simultaneously, is continuously passed through in proportion, 5- xylenols, the hydrochloric acid solution of copper chloride, hydrogen peroxide, prepare CDMP.Method is simple, works well, compared with conventional method, intermittent reaction is changed into successive reaction, reaction time a few hours is foreshortened to about hundred seconds.
Description
Technical field
The invention belongs to organic fine synthesis field, it relate to synthesize 4- chloro- 3,5- in a kind of continuous stream micro-pipe reactor
The method of xylenol, i.e., in the microreactor of control certain temperature, simultaneously, be continuously passed through raw material 3,5- bis- in proportion
Methylphenol, the hydrochloric acid solution of copper chloride, hydrogen peroxide, prepare CDMP.
Background technology
MX (MX), white crystal, 63 ~ 66 DEG C of fusing point, available for phenolic resin processed, medicine, insecticide,
Dyestuff and explosive etc..CDMP (PCMX) is a kind of antimildew disinfectant of high-efficiency low-toxicity, to gram-negative
Property, Gram-positive, and the microorganism such as saccharomycete has the more killing of wide spectrum or inhibitory activity.In personal nursing (family
With sterilization), the field such as industrial (leather, wood mould) has a wide range of applications value.Solubility about 0.3% in water, it is conventional to add
Dosage 0.2% ~ 5%.Its structural formula is as follows：
Traditional PCMX synthesis techniques are as chlorinating agent, in organic solvent to 3,5- dimethyl using chlorine, chlorosulfuric acid etc.
Phenol (MX) carries out chlorination, and such as Chinese patent CN105037104A and CN104326881A is described use chlorine and sulphur respectively
Acyl chlorides is used as chlorinating agent.Personnel are pacified by the problem of both chlorinating agents have poisonous and harmful, dangerous larger in the industrial production
There is larger negative effect with environmental protection entirely.CN103351282A and CN103351282B is then provided one kind and made using oxygen
For oxidant, using hydrochloric acid as the method for chlorinating agent, laid particular emphasis in text and control the conversion ratio of reaction to be 50 ~ 90%, all reactions
Carried out in intermittent reaction equipment.Chinese invention patent CN101624333B also describes the synthetic route of a class PCMX, i.e.,
The catalyst system and catalyzing catalysis being made up of cupric salt and lower fatty acid, MX and oxidant and the chlorine-containing compound progress as chlorine source
Reaction is obtained, and reaction condition is 0-100 DEG C, 1-5atm.Reaction can be without using other organic solvents, or use aliphatic chlorine
Compound is as solvent, and the catalyst of the patent is mantoquita and the catalyst system and catalyzing of lower fatty acid composition, and reaction needs to remove after terminating
Solvent.Chinese invention patent CN101085722A provides a kind of industrialized process for preparing to chloro alkylphenol, this method
To carry out addition reaction generation with alkylphenol and chlorinating agent to chloro alkylphenol, the reaction is in -10 DEG C ~ 100 DEG C temperature
Carried out between degree and under co-catalyst effect, the co-catalyst is by metal chloride and machine sulfide, alkyl ether chemical combination
Thing is constituted.Chinese invention patent CN101823941A provides a kind of PCMX green synthesis process, using water as solvent, is used
Chlorinating agent be chlorosulfuric acid or chlorine, substrate MX is subjected to chlorination reaction by way of multistage temperature control.
World patent WO2012/136108 A1 describe the synthetic method of a class PCMX, and catalyst is made by cupric salt,
Reacted with MX, oxidant and chloride inorganic matter, in its claim, the consumption of cupric salt is the 10% ~ 60% of MX weight,
80 ~ 100 DEG C of reaction temperature.United States Patent (USP) 4245127 is introduced using organic sulfur compound and metal chloride as urging altogether
Agent, the reaction of chlorination 1- hydroxyl -3,5- dimethyl benzenes.The patent is discussed with thiophene phenol and lauryl mercaptan as organic sulfur respectively
Compound；Ferric trichloride, alchlor, and titanium tetrachloride constitute the system of co-catalyst as metal chloride, to sulfonyl
Chlorine and 1- hydroxyl -3,5- dimethyl benzenes carry out the influence of reaction synthesis 1- hydroxyl -3,5- dimethyl -4- chlorobenzenes.According to the patent
In the example that is previously mentioned, the product selectivity of maximum, i.e. 1- can be obtained as co-catalyst with titanium tetrachloride and lauryl mercaptan
Hydroxyl -3,5- dimethyl -4- chlorobenzenes reach 91.5%.It refer in Japanese Patent Laid-Open No. Sho 59-5132 with cupric salt as urging
Agent, hydrogen peroxide is as oxidant, with oxychlorination 1- hydroxyl -3,5- diformazan of the hydrochloric acid as chlorine source in the system of organic solvent
The method that base benzene synthesizes 1- hydroxyl -3,5- dimethyl -4- chlorobenzenes.But from the point of view of the experimental data that inventor provides, use this
The conversion ratio and very low, the highest theoretical yield of gained of selectivity of method（Conversion ratio * selectivity）Only 79.3%, Er Qiexu
Use the organic solvents such as Difluoroethane.
Continuous stream micro-tubular reactor is the special reactor of a class.The diameter of its passage is general in micron or grade,
It is significantly smaller than traditional reactor.Continuous flow reactor has the characteristics that：(1) due to channel width and depth in reactor
It is smaller, generally tens to hundreds of microns, greatly shorten the diffusion length between reactant, mass transfer velocity is fast, and reactant exists
It can be sufficiently mixed in the short time during flowing.(2) specific surface area of passage is generally 5000 ~ 50000m2m-3, and
In popular response container, specific surface area is about 100m2m-3, minority is 1000m2m-3.The specific surface area of passage is big, with very big
Heat exchanger effectiveness, even fierce exothermic reaction, abrupt release goes out a large amount of reaction heat can also remove in time, maintenance reaction temperature
Degree is in safe range.Because reaction-ure mixture is few, heat transfer is fast, is particularly suitable for use in studying abnormal fierce synthetic reaction and avoiding
The danger of blast.(3) when carrying out synthetic reaction in a continuous flow reactor, reactant ratio, temperature, pressure, reaction time
With the easy control of reaction conditions such as flow velocity.Reactant is reacted in flow process, and concentration is constantly reduced, and product concentration is not
Disconnected to improve, side reaction is less.
There is presently no the continuous conjunction that the chloro- 3,5- xylenols of the 4- in continuous stream micro-tubular reactor are mentioned in document
Into technique.
The content of the invention
The invention belongs to organic fine synthesis field, it relate to synthesize 4- chloro- 3 in a kind of continuous stream micro-tubular reactor,
The method of 5- xylenols, i.e., in the microreactor of control certain temperature, simultaneously, be continuously passed through raw material 3,5- in proportion
Xylenol, the hydrochloric acid solution of copper chloride, hydrogen peroxide, prepare CDMP.Method is simple, works well,
Compared with conventional method, intermittent reaction is changed to successive reaction, reaction time a few hours is foreshortened to about hundred seconds.
CDMP is synthesized in continuous current micro-reactor, it is characterised in that in the micro- of control certain temperature
In reactor, raw material MX, the hydrochloric acid solution of copper chloride, hydrogen peroxide simultaneously, are continuously passed through in proportion, are prepared
The chloro- 3,5- xylenols of 4-.
To achieve the above objectives, the technical scheme that the present invention is usually taken is as follows：4- is synthesized in continuous stream micro-pipe reactor
The method of chloro- MX, its feature simultaneously, is continuously passed through raw material 3 in proportion in continuous current micro-reactor,
The mol ratio of 5- xylenols, the hydrochloric acid solution of copper chloride, hydrogen peroxide, hydrogen peroxide and MX is 1.0 ~ 1.1,
The mol ratio of hydrochloric acid and MX is 1.0 ~ 1.1, prepares CDMP, gained reaction mixture
Countercurrent extraction equipment is quickly entered, continuously point liquid collects aqueous phase and organic phase respectively.
Usually, in the inventive method, the MX uses hot feed, and heating-up temperature maintains 70 DEG C.
The mol ratio of the hydrogen peroxide and 3,5- xylenols is 1.0 ~ 1.1.
The copper chloride（With CuCl2·2H O are counted）Addition be MX quality 5% ~ 20%, preferably
10%~15%；
The hydrochloric acid（In terms of HCl）Mol ratio with 3,5- xylenols is 1.0 ~ 1.1；
The reaction temperature that the reactor is maintained is 80 ~ 95 DEG C, preferably 88 ~ 90 DEG C；
Residence time of the reaction solution in micro passage reaction is 60 ~ 250s, preferably 120 ~ 150s；
The temperature of the countercurrent extraction equipment maintains 85 ~ 95 DEG C；
The mixed liquor is 60 ~ 120s in the residence time of countercurrent extraction equipment.
Beneficial effects of the present invention：
1st, in the present invention, the reaction time only needs several minutes, is significantly shorter than prior art a few hours；
2nd, in the present invention, in the absence of the material that security context risk is easily brought in the traditional handicrafts such as acyl chlorides or chlorine；
3rd, the present invention uses method for continuously synthesizing, compared with the reaction of existing batch tank, easy to operate, safety.
Brief description of the drawings
Fig. 1 is the structural representation of continuous current micro-reactor in present invention method.
Embodiment
Technical scheme is described in further detail with reference to embodiment, protection scope of the present invention is not limited to following
Embodiment.
Following examples use following flow：MX heating is molten into material A, weighs a certain amount of chlorination
Copper（CuCl2·2H₂O）Add dissolving with hydrochloric acid and be made into material B, hydrogen peroxide is material C（A, B, C only mark use, specific material
Without special sequence requirement）, it is certain that three strands of materials squeeze into setting in reactor as shown in Figure 1, reactor with pump simultaneously in proportion
Temperature, plate 1, plate 2, plate 3 are respectively three strands of materials preheating, it is preheated after three stock materials enter in follow-up reaction plate and carry out
Reaction, reactor caudal end egress receives reaction mass.Gained reaction mixture quickly enters use for laboratory countercurrent extraction equipment, even
Continuous point liquid collects aqueous phase and organic phase respectively.
Embodiment 1
244g3,5- xylenol are warming up to 70 DEG C of meltings, 238g30% hydrogen peroxide, 25g copper chlorides（CuCl2·2H₂O）Dissolving
In 219g35% hydrochloric acid, material MX in molar ratio：Hydrogen peroxide：Hydrochloric acid is 1：1.05：1.05 points of three bursts of entrance
Continuous stream micro-tubular reactor, reaction temperature sets 75 DEG C, and residence time 120s, reaction solution stops 100s in extraction equipment,
Extraction equipment temperature maintains 90 DEG C.Gained reaction solution is through liquid analysis of spectrum, the conversion ratio 98.59% of MX, and 4- is chloro-
MX content is 94.21%, and it is selectively 95.56%.
Embodiment 2
244g3,5- xylenol are warming up to 70 DEG C of meltings, 249g30% hydrogen peroxide, 40g copper chlorides（CuCl2·2H₂O）Dissolving
In 230g35% hydrochloric acid, material MX in molar ratio：Hydrogen peroxide：Hydrochloric acid is 1：1.1：1.1 points three strands enter company
Afterflow micro-tubular reactor, reaction temperature sets 78 DEG C, and residence time 180s, reaction solution stops 120s in extraction equipment, extraction
Taking equipment temperature maintains 95 DEG C.Gained reaction solution is through liquid analysis of spectrum, the conversion ratio 99.01% of MX, 4- chloro- 3,
5- dimethylphenol contents are 82.64%, and it is selectively 83.47%.
Embodiment 3
244g3,5- xylenol are warming up to 70 DEG C of meltings, 228g30% hydrogen peroxide, 20g copper chlorides（CuCl2·2H₂O）Dissolving
In 209g35% hydrochloric acid, material MX in molar ratio：Hydrogen peroxide：Hydrochloric acid is 1：1：1 point three strands enter continuous stream
Micro-tubular reactor, residence time 100s, reaction solution stops 60s in extraction equipment, and extraction equipment temperature maintains 95 DEG C.Gained
Reaction solution is through liquid analysis of spectrum, the conversion ratio 76.44% of MX, CDMP content
73.46%, it is selectively 96.12%.
The present invention uses method for continuously synthesizing, compared with the reaction of existing batch tank, easy to operate, safety, during reaction
Between only need several minutes, be significantly shorter than prior art a few hours.
Claims (10)
1. synthesizing the method for CDMP in a kind of continuous stream micro-pipe reactor, its feature is micro- anti-in continuous stream
Answer in device, raw material MX, the hydrochloric acid solution of copper chloride, hydrogen peroxide, hydrogen peroxide simultaneously, are continuously passed through in proportion
Mol ratio with MX is 1.0 ~ 1.1, and the mol ratio of hydrochloric acid and MX is 1.0 ~ 1.1, is prepared
CDMP, gained reaction mixture quickly enters countercurrent extraction equipment, continuously point liquid collect respectively aqueous phase and
Organic phase.
2. according to the method described in claim 1, it is characterised in that the addition of copper chloride is MX quality
5%~20%。
3. according to the method described in claim 1, it is characterised in that the addition of copper chloride is MX quality
10%~15%。
4. according to the method described in claim 1, it is characterised in that MX uses hot feed, heating-up temperature is maintained
70℃。
5. according to the method described in claim 1, it is characterised in that the reaction temperature that continuous current micro-reactor is maintained is 80-95
℃。
6. according to the method described in claim 1, it is characterised in that the reaction temperature that continuous current micro-reactor is maintained is 88-90
℃。
7. according to the method described in claim 1, it is characterised in that residence time of the reaction solution in continuous current micro-reactor be
60~250s。
8. according to the method described in claim 1, it is characterised in that residence time of the reaction solution in continuous current micro-reactor be
120~150s。
9. according to the method described in claim 1, it is characterised in that the temperature of countercurrent extraction equipment maintains 85 ~ 95 DEG C.
10. according to the method described in claim 1, it is characterised in that mixed liquor countercurrent extraction equipment residence time for 60 ~
120s。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610173033.5A CN107226775A (en) | 2016-03-24 | 2016-03-24 | The method that the chloro- 3,5- xylenols of 4- are synthesized in continuous stream micro-pipe reactor |
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| CN201610173033.5A CN107226775A (en) | 2016-03-24 | 2016-03-24 | The method that the chloro- 3,5- xylenols of 4- are synthesized in continuous stream micro-pipe reactor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112679362A (en) * | 2020-12-30 | 2021-04-20 | 东营安诺其纺织材料有限公司 | Extraction system and process for preparing 2, 4-dinitrochlorobenzene to generate acid phase |
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Cited By (2)
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| CN112679362A (en) * | 2020-12-30 | 2021-04-20 | 东营安诺其纺织材料有限公司 | Extraction system and process for preparing 2, 4-dinitrochlorobenzene to generate acid phase |
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