CN105037104A - Preparation method of 4-chloro-3,5-dimethylphenol - Google Patents
Preparation method of 4-chloro-3,5-dimethylphenol Download PDFInfo
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- CN105037104A CN105037104A CN201510297455.9A CN201510297455A CN105037104A CN 105037104 A CN105037104 A CN 105037104A CN 201510297455 A CN201510297455 A CN 201510297455A CN 105037104 A CN105037104 A CN 105037104A
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- preparation
- cdmp
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- cupric chloride
- chlorine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- 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
Abstract
The invention discloses a preparation method of 4-chloro-3,5-dimethylphenol, which comprises the following steps: by using cupric chloride as a chlorinating agent and catalyst and chlorine as an oxidizer, reacting 3,5-dimethylphenol, cupric chloride, chlorine and hydrochloric acid at 90-120 DEG C for 4-8 hours, and after the reaction finishes, rectifying the product to obtain the 4-chloro-3,5-dimethylphenol. The method does not use any solvent in the reaction process; the purity of the rectified 4-chloro-3,5-dimethylphenol can reach 99% or above, and thus, the rectified 4-chloro-3,5-dimethylphenol can satisfy the quality requirements of the industry; the components have favorable separating effects; the unreacted 3,5-dimethylphenol can be reutilized; and the method can easily control the utilization ratio of the 3,5-dimethylphenol through the reaction conditions, and can easily implement industrialization.
Description
Technical field
The invention belongs to a kind of sterilant preparing technical field, be specifically related to a kind of preparation method of CDMP.
Background technology
4-chloro-3,5-xylenol (i.e. chlorxylone, be called for short PCMX) be a kind ofly be acknowledged as efficient, wide spectrum and the sterilant of safety, be first-selected sterilant through U.S. FDA certification, can be used as antimildew and antibacterial agent and be widely used in medical disinfecting or personal-care supplies, also can be used for the industrial circles such as glue, coating, paint, weaving, leather, papermaking as sanitas and mould inhibitor.Along with human consumer's preventing and the increase of health consciousness microbial contamination, greatly have stimulated the demand of the toxic product that disappears.Especially in China, the improvement of people's education level and manufacturer's standard has in recent years changed the idea of human consumer, makes them seek the product of high-quality and long quality-guarantee period.Manufacturers, by processing and preparing, constantly increases making for meeting popular demand as possible of microbiological manipulation product.
Once having in documents and materials to mention uses copper chloride dihydrate as chlorizating agent, oxidation chlorination synthesis CDMP.General oxygenant has hydrogen peroxide, oxygen.Use hydrogen peroxide as oxygenant in Japanese Patent Laid-Open No. Sho 59-5132, but low from experimental data yield, be not suitable for industrial production.Use oxygen as oxygenant in patent 201310286303.X, controlled the generation of dipolymer by the transformation efficiency controlling MX, but be difficult to control in actual industrial production, want Real-Time Monitoring, add the workload of analysis, and then increase cost.
From above-mentioned document, want the industrial production of carrying out CDMP that a kind of reaction conditions must be found to be easy to control, yield is high, is easy to industrialized synthetic method.
Summary of the invention
According to above the deficiencies in the prior art, the present invention proposes a kind of 4-chloro-3, the preparation method of 5-xylenol, by controlling the transformation efficiency that the usage quantity of cupric chloride, acidity, temperature of reaction and reaction times controls to react, improve 4-chloro-3, the selectivity of 5-xylenol, solves the difficult problem that preparation process yield is not high, need Real-Time Monitoring, is applicable to industrial production.
To achieve these goals, the technical scheme that the present invention takes is:
A preparation method for CDMP, described preparation method makes chlorizating agent and catalyzer by cupric chloride, chlorine makes oxygenant, is 90-120 DEG C in temperature of reaction, and 3,5-xylenol, chlorine and hydrochloric acid reaction 4-8 hour, after reaction terminates, carry out rectifying to product and obtain.
The concrete steps of described preparation method are as follows:
Step one: add 3 in four-hole boiling flask, 5-xylenol and cupric chloride, the consumption of cupric chloride is 3, the 20%-50% of the weight of 5-xylenol, add the concentrated hydrochloric acid that massfraction is 36% again, concentrated hydrochloric acid consumption is the 150%-280% of the weight of MX, load onto agitator, thermometer, condenser and ventpipe, condensator outlet connects device for absorbing tail gas;
Step 2: open heating jacket, heating makes temperature of reaction be 90-120 DEG C, and under whipped state, at the uniform velocity pass into chlorine, the reaction times is 4-8 hour;
Step 3: after reaction terminates, carries out rectifying to reaction product and obtains.
Preferably, the consumption of described cupric chloride is the 30-40% of MX weight.
Preferably, the 180%-250% of described massfraction to be the consumption of the concentrated hydrochloric acid of 36% be MX weight.
Preferably, described step 2 temperature of reaction is 110 DEG C.
Preferably, described cupric chloride is anhydrous or has the cupric chloride of crystal water.
Preferably, the described step 2 reaction times is 6 hours.
Preferably, the speed that passes into passing into chlorine described in is 0.3L/min.
Preferably, described stir speed (S.S.) under whipped state is 300-400r/min.
Beneficial effect of the present invention is: invent and do not use solvent in reaction process, and the purity obtaining CDMP after rectifying can reach more than 99%, the specification of quality of industry can be met, the separating effect of each component is fine, and unreacted MX can be used by secondary returning.Reaction conditions of the present invention is easy to the utilization ratio controlling MX, is easy to industrialization.
Embodiment
Below by the description to embodiment, to manufacturing process of the present invention and operation using method etc., be described in further detail, have more complete, accurate and deep understanding to help those skilled in the art to inventive concept of the present invention, technical scheme.
Embodiment 1
Add 1200g3 in the four-hole boiling flask of 5000ml, 5-xylenol, 366g anhydrous cupric chloride, the massfraction of 2710g is the concentrated hydrochloric acid of 36%, then loads onto agitator, thermometer, condenser and ventpipe.Condensator outlet connects device for absorbing tail gas.Open heating jacket and agitator, reactant is heated to 100 DEG C, under whipped state, at the uniform velocity pass into chlorine, the speed that passes into of chlorine is 0.2-0.4L/min, reacts 6 hours.Stirring velocity is 300-400r/min, and the speed that passes into of preferred chlorine is 0.3L/min.After reaction terminates, reaction product is carried out rectifying, obtains CDMP, through gas chromatographic analysis, the purity of product CDMP is 99.2%.The yield of CDMP is 80.36%.
Embodiment 2
Add 1200g3 in the four-hole boiling flask of 5000ml, 5-xylenol, 366g anhydrous cupric chloride, the massfraction of 2710g is the concentrated hydrochloric acid of 36%, then loads onto agitator, thermometer, condenser and ventpipe.Condensator outlet connects device for absorbing tail gas.Open heating jacket and agitator, reactant is heated to 110 DEG C, under whipped state, at the uniform velocity pass into chlorine, the speed that passes into of chlorine is 0.2-0.4L/min, reacts 6 hours.Stirring velocity is 300-400r/min, and the speed that passes into of preferred chlorine is 0.3L/min.After reaction terminates, reaction product is carried out rectifying, obtains CDMP, through gas chromatographic analysis, the purity of product CDMP is 99.3%.The yield of CDMP is 81.71%.
Embodiment 3
Add 1200g3 in the four-hole boiling flask of 5000ml, 5-xylenol, 366g anhydrous cupric chloride, the massfraction of 2710g is the concentrated hydrochloric acid of 36%, then loads onto agitator, thermometer, condenser and ventpipe.Condensator outlet connects device for absorbing tail gas.Open heating jacket and agitator, reactant is heated to 120 DEG C, under whipped state, at the uniform velocity pass into chlorine, the speed that passes into of chlorine is 0.2-0.4L/min, reacts 6 hours.Stirring velocity is 300-400r/min, and the speed that passes into of preferred chlorine is 0.3L/min.After reaction terminates, reaction product is carried out rectifying, obtains CDMP, through gas chromatographic analysis, the purity of product CDMP is 99.1%.The yield of CDMP is 72.38%.
Embodiment 4
Add 1200g3 in the four-hole boiling flask of 5000ml, 5-xylenol, 366g anhydrous cupric chloride, the massfraction of 2281g is the concentrated hydrochloric acid of 36%, then loads onto agitator, thermometer, condenser and ventpipe.Condensator outlet connects device for absorbing tail gas.Open heating jacket and agitator, reactant is heated to 110 DEG C, under whipped state, at the uniform velocity pass into chlorine, the speed that passes into of chlorine is 0.2-0.4L/min, reacts 6 hours.Stirring velocity is 300-400r/min, and the speed that passes into of preferred chlorine is 0.3L/min.After reaction terminates, reaction product is carried out rectifying, obtains CDMP, through gas chromatographic analysis, the purity of product CDMP is 99.5%.The yield of CDMP is 79.37%.
Embodiment 5
Add 1200g3 in the four-hole boiling flask of 5000ml, 5-xylenol, 366g anhydrous cupric chloride, the massfraction of 3250g is the concentrated hydrochloric acid of 36%, then loads onto agitator, thermometer, condenser and ventpipe.Condensator outlet connects device for absorbing tail gas.Open heating jacket and agitator, reactant is heated to 110 DEG C, under whipped state, at the uniform velocity pass into chlorine, the speed that passes into of chlorine is 0.2-0.4L/min, reacts 6 hours.Stirring velocity is 300-400r/min, and the speed that passes into of preferred chlorine is 0.3L/min.After reaction terminates, reaction product is carried out rectifying, obtains CDMP, through gas chromatographic analysis, the purity of product CDMP is 99.5%.The yield of CDMP is 81.56%.
Embodiment 6
Add 1200g3 in the four-hole boiling flask of 5000ml, 5-xylenol, 366g anhydrous cupric chloride, the massfraction of 3250g is the concentrated hydrochloric acid of 36%, then loads onto agitator, thermometer, condenser and ventpipe.Condensator outlet connects device for absorbing tail gas.Open heating jacket and agitator, reactant is heated to 110 DEG C, at the uniform velocity passes into chlorine at whipped state, the speed that passes into of chlorine is 0.2-0.4L/min, reacts 4 hours.Stirring velocity is 300-400r/min, and the speed that passes into of preferred chlorine is 0.3L/min.After reaction terminates, reaction product is carried out rectifying, obtains CDMP, through gas chromatographic analysis, the purity of product CDMP is 99.3%.The yield of CDMP is 75.24%.
Embodiment 7
Add 1200g3 in the four-hole boiling flask of 5000ml, 5-xylenol, 366g anhydrous cupric chloride, the massfraction of 3250g is the concentrated hydrochloric acid of 36%, then loads onto agitator, thermometer, condenser and ventpipe.Condensator outlet connects device for absorbing tail gas.Open heating jacket and agitator, reactant is heated to 110 DEG C, under whipped state, at the uniform velocity pass into chlorine, the speed that passes into of chlorine is 0.2-0.4L/min, reacts 8 hours.Stirring velocity is 300-400r/min, and the speed that passes into of preferred chlorine is 0.3L/min.After reaction terminates, reaction product is carried out rectifying, obtains CDMP, through gas chromatographic analysis, the purity of product CDMP is 99.7%.The yield of CDMP is 81.63%.
From testing above, utilize cupric chloride to make chlorizating agent and catalyzer, chlorine makes oxygenant, by 3,5-xylenol, chlorine and hydrochloric acid reaction obtain 4-chloro-3, the reaction of 5-xylenol is within the scope of 90-120 DEG C in temperature, along with temperature raises, 4-chloro-3,5-xylenol yield increases, and raise after temperature is raised to 110 DEG C, yield then declines again.In the scope that concentrated hydrochloric acid consumption is the 150%-280% of the weight of MX, along with the rising of concentrated hydrochloric acid content, yield increases, and raises after concentrated hydrochloric acid content is elevated to certain value again, and yield declines.Reaction times, along with the growth in reaction times, yield increased in 4-8 hours window, but after certain hour, yield will no longer change.
Above to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the improvement of the various unsubstantialities that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all within protection scope of the present invention without to improve.The protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (9)
1. a 4-chloro-3, the preparation method of 5-xylenol, it is characterized in that: make chlorizating agent and catalyzer by cupric chloride, chlorine makes oxygenant, be 90-120 DEG C in temperature of reaction, MX, cupric chloride, chlorine and hydrochloric acid reaction 4-8 hour, after reaction terminates, rectifying is carried out to product and obtains.
2. the preparation method of CDMP according to claim 1, is characterized in that, the concrete steps of described preparation method are as follows:
Step one: add 3 in four-hole boiling flask, 5-xylenol and cupric chloride, the consumption of cupric chloride is 3, the 20%-50% of the weight of 5-xylenol, add the concentrated hydrochloric acid that massfraction is 36% again, massfraction be 36% concentrated hydrochloric acid consumption be the 150%-280% of the weight of MX, load onto agitator, thermometer, condenser and ventpipe, condensator outlet connects device for absorbing tail gas;
Step 2: open heating jacket, heating makes temperature of reaction be 90-120 DEG C, and under whipped state, at the uniform velocity pass into chlorine, the reaction times is 4-8 hour;
Step 3: after reaction terminates, carries out rectifying to reaction product and obtains.
3. CDMP preparation method according to claim 2, is characterized in that: the consumption of described cupric chloride is the 30%-40% of the weight of MX.
4. CDMP preparation method according to claim 2, is characterized in that: the 180%-250% of described massfraction to be the consumption of the concentrated hydrochloric acid of 36% be MX weight.
5. CDMP preparation method according to claim 2, is characterized in that: described step 2 temperature of reaction is 110 DEG C.
6. the preparation method of CDMP according to claim 2, is characterized in that: described cupric chloride is anhydrous or has the cupric chloride of crystal water.
7. the preparation method of CDMP according to claim 2, is characterized in that: the described step 2 reaction times is 6 hours.
8. the preparation method of CDMP according to claim 2, is characterized in that: described in pass into chlorine the speed that passes into be 0.2-0.4L/min.
9. the preparation method of CDMP according to claim 2, is characterized in that: described stir speed (S.S.) under whipped state is 300-400r/min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1240829A (en) * | 1967-10-04 | 1971-07-28 | Reckitt & Colmann Prod Ltd | Improvements in or relating to the chlorination of phenols |
| US4245127A (en) * | 1975-10-31 | 1981-01-13 | Seitetsu Kagaku Co., Ltd. | Process for chlorinating xylenols |
| CN101085722A (en) * | 2007-01-10 | 2007-12-12 | 胡汉忠 | Industrial preparation method for p-chloroalkylphenols |
| CN102199075A (en) * | 2011-04-02 | 2011-09-28 | 湖南利洁生物化工有限公司 | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene |
| CN103214350A (en) * | 2013-04-10 | 2013-07-24 | 淮阴师范学院 | Preparation method of chloroxylenol |
| CN103351282A (en) * | 2013-07-09 | 2013-10-16 | 湖南利洁生物化工有限公司 | Preparing method for 4-chlorine-3,5-xylenol |
| CN103351283A (en) * | 2013-06-17 | 2013-10-16 | 江苏焕鑫高新材料科技有限公司 | Preparation method of parachlorometaxylenol |
| CN104326881A (en) * | 2014-10-16 | 2015-02-04 | 荣成青木高新材料有限公司 | Preparation method of 3,5-dimethyl-4-chlorophenol |
-
2015
- 2015-06-02 CN CN201510297455.9A patent/CN105037104A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1240829A (en) * | 1967-10-04 | 1971-07-28 | Reckitt & Colmann Prod Ltd | Improvements in or relating to the chlorination of phenols |
| US4245127A (en) * | 1975-10-31 | 1981-01-13 | Seitetsu Kagaku Co., Ltd. | Process for chlorinating xylenols |
| CN101085722A (en) * | 2007-01-10 | 2007-12-12 | 胡汉忠 | Industrial preparation method for p-chloroalkylphenols |
| CN102199075A (en) * | 2011-04-02 | 2011-09-28 | 湖南利洁生物化工有限公司 | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene |
| CN103214350A (en) * | 2013-04-10 | 2013-07-24 | 淮阴师范学院 | Preparation method of chloroxylenol |
| CN103351283A (en) * | 2013-06-17 | 2013-10-16 | 江苏焕鑫高新材料科技有限公司 | Preparation method of parachlorometaxylenol |
| CN103351282A (en) * | 2013-07-09 | 2013-10-16 | 湖南利洁生物化工有限公司 | Preparing method for 4-chlorine-3,5-xylenol |
| CN104326881A (en) * | 2014-10-16 | 2015-02-04 | 荣成青木高新材料有限公司 | Preparation method of 3,5-dimethyl-4-chlorophenol |
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Application publication date: 20151111 |