CN102199075A - Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene - Google Patents
Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene Download PDFInfo
- Publication number
- CN102199075A CN102199075A CN2011100845339A CN201110084533A CN102199075A CN 102199075 A CN102199075 A CN 102199075A CN 2011100845339 A CN2011100845339 A CN 2011100845339A CN 201110084533 A CN201110084533 A CN 201110084533A CN 102199075 A CN102199075 A CN 102199075A
- Authority
- CN
- China
- Prior art keywords
- reaction
- hydroxyl
- cupric
- preparation
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene. The bivalent copper salt is used as a catalyst; 1-hydroxy-3, 5-dimethylbenzene, an oxidizing agent and a Cl-containing inorganic substance are reacted for obtaining without an organic solvent at the reaction temperature of 50 to 150 DEG C; the bivalent copper salt is occupied by weight of 0.5 % to 200% of 1-hydroxy-3,5-dimethylbenzene; the mole ratio of available oxygen amount, Cl-containing compound and 1-hydroxy-3,5- dimethylbenzene of the oxidizing agent is 1to 2:1to 1.5:1. The method has the advantages of simple operation, mild condition reaction. The obtained target product has the advantages of good selectivity and high conversion rate. Toxic gas can not be generated in the reaction process as well as no organic solvent is needed to be used, the environmental pollution can be obviously minimized. The invention provides 1-hydroxy-3, 5-dimethyl-4-chlorobenzene which is suitable for a large scale industrialized application.
Description
Technical field
The present invention relates to a kind of 1-hydroxyl-3, the preparation method of 5-dimethyl-4-chlorobenzene, be specifically related to a kind of under the condition that catalyzer and oxygenant exist, with chlorine-containing compound to 1-hydroxyl-3, the 5-dimethyl benzene carries out chlorination reaction and prepares 1-hydroxyl-3, the method for 5-dimethyl-4-chlorobenzene.
Background technology
1-hydroxyl-3,5-dimethyl-4-chlorobenzene (has another name called: 4-chloro-3, the 5-xylenol, CAS numbering: 88-04-0, english abbreviation: be a kind of important microbicide PCMX),, be widely used in industry and cosmetic industry as antiseptic-germicide, mould inhibitor, sterilizing agent, it is to bacterium, and mould and most of fungi have good restraining effect.In recent years, along with wreaking havoc of epidemic disease, people's health perception is more and more stronger, as a kind of traditional low toxicity sterilizing agent, and 1-hydroxyl-3,5-dimethyl-4-chlorobenzene also will have bigger development potentiality, and its structural formula is as follows:
Traditional 1-hydroxyl-3,5-dimethyl-4-chlorobenzene be to adopt sulfuryl chloride and 1-hydroxyl-3, and the 5-dimethyl benzene carries out the electrophilic substitution reaction preparation.1866, react with equimolar sulfuryl chloride and fused phenol from Dubois, the mankind have just known with the synthetic chlorophenic acid compounds (Z.F.Chem.705 (1866)) of sulfuryl chloride selectivity.But modern analytical technique shows, the selectivity of above-mentioned reaction and Dubois idea at that time is also inconsistent, and promptly in above-mentioned reaction process, he thinks that the selectivity of para-chlorophenol occupies an leading position.Eighties of last century mid-term, this catalyst for reaction system comprises divalence sulfide and metal halide, introduces in United States Patent (USP) 3920757.The organosulfur compound that a kind of optimum is provided in this patent is as catalyzer---phenyl ether, and carry out common catalysis with aluminum chloride.This catalyst system also is applied to other many using in the chlorination reaction of sulfuryl chloride as chlorizating agent simultaneously.The principal product that this catalyzed reaction obtained is the alkyl phenol compound of para-chloroaromatic.But there are some shortcomings in this catalyst system, particularly is applied in the commercial process this individual system all the more so.For example, the yield of product is difficult to reach the degree of anticipation, and is in addition, very limited according to the ratio of right/ortho position chloro product that patented method obtained, (the contraposition monochloro for product because have bigger industrial use, so general reaction with the contraposition monochloro for compound as the purpose product.) and in reaction, also can produce some unwanted isomer and many chlorinated secondary products, not only influence the purification of product, increased cost of disposal simultaneously.
United States Patent (USP) 4245127 introduces and uses organic sulfide and metal chloride as co-catalyst, chlorination 1-hydroxyl-3, the reaction of 5-dimethyl benzene.This patent has been discussed respectively and has been used thiophene phenol and Dodecyl Mercaptan as organic sulfide; Iron trichloride, aluminum chloride, and titanium tetrachloride forms the system of co-catalyst as metal chloride, to sulfuryl chloride and 1-hydroxyl-3, the 5-dimethyl benzene reacts synthetic 1-hydroxyl-3, the influence of 5-dimethyl-4-chlorobenzene.According to the example of being mentioned in this patent, can obtain maximum product selectivity with titanium tetrachloride and Dodecyl Mercaptan as co-catalyst, i.e. 1-hydroxyl-3,5-dimethyl-4-chlorobenzene reaches 91.5%.
Mention among the Chinese patent CN101085722A and a kind ofly promptly in reaction process, added one or more alkyl ether compounds as co-catalyst based on the improving one's methods of US4245127, bigger raising the selectivity of contraposition product.
Yet along with deepening continuously of ideas such as Sustainable development, chemistry in ecology and Green Chemistry, the human problem of environmental pollution that chemical process is produced is more and more paid attention to, and control is also more and more stricter.Because the synthetic 1-hydroxyl-3 of traditional technology, 5-dimethyl-4-chlorobenzene adopts sulfuryl chloride as the chlorine source, produce equimolar hydrogenchloride and sulfurous gas byproduct in process of production, so its Atom economy is extremely low, only is 26.3%.Two kinds of byproducts of this that is produced are the gas with severe corrosive, difficult treatment; Particularly sulfurous gas is low with the S-WAT recovery value that soda ash absorbs the back generation, and most producers adopts the method for directly discharging to handle, and not only processing unit, Infrastructure is caused corrosion, and environment is caused severe contamination.
In view of the above problems, the Japanese Patent spy opens to have mentioned among the clear 59-5132 and uses cupric salt as catalyzer, and hydrogen peroxide is used the oxychlorination 1-hydroxyl-3 of hydrochloric acid as the chlorine source as oxygenant in the system of organic solvent, the 5-dimethyl benzene synthesizes 1-hydroxyl-3, the method for 5-dimethyl-4-chlorobenzene.But from the experimental data that the contriver provides, use the transformation efficiency of this method and selectivity all very low, the highest theoretical yield of gained (transformation efficiency * selectivity) only is 79.3%, does not possess the value that commercialization is promoted, and needs with an organic solvent.Chinese patent application 200910044035.4 has proposed to use cupric salt and lower fatty acid as catalyst system, and oxidation chlorination gets 1-hydroxyl-3, the technology of 5-dimethyl-4-chlorobenzene.With lower fatty acid, perhaps lower fatty acid mixes the organic solvent as reaction with the chloro fat compounds of group in this invention.But the use of organic solvent not only can cause certain pollution to environment, and has increased production cost.
Summary of the invention
The purpose of this invention is to provide a kind of environmentally safe, product yield height, cost 1-hydroxyl-3 low, simple to operate, the preparation method of 5-dimethyl-4-chlorobenzene.
The objective of the invention is to realize in the following manner:
A kind of 1-hydroxyl-3, the preparation method of 5-dimethyl-4-chlorobenzene: make catalyzer by cupric salt, under the condition of organic solvent-free, with 1-hydroxyl-3,5-dimethyl benzene, oxygenant and chloride inorganics react and obtain, and temperature of reaction is 50-150 ℃; Described cupric salt accounts for 1-hydroxyl-3, the 0.5%-200% of 5-dimethyl benzene weight; The available oxygen amount of described oxygenant, chlorine-containing compound and 1-hydroxyl-3, the mol ratio of 5-dimethyl benzene consumption is: 1-2: 1-1.5: 1.
Described cupric salt is copper sulfate, cupric nitrate, copper carbonate, copper hydroxide, copper halide or the lipid acid mantoquita that contains 1-6 carbon atom.
Described copper halide is cupric chloride, cupric bromide or cupric iodide; The lipid acid mantoquita of the described 1-6 of a containing carbon atom is Tubercuprose, venus crystals or propionic acid copper.
Described cupric salt is anhydrous or has the mantoquita of crystal water.
The consumption of described cupric salt preferably accounts for 1-hydroxyl-3, the 10%-60% of 5-dimethyl benzene weight.
Described catalyzer can be replaced by the corresponding cuprous salt of above-mentioned cupric salt (as: cuprous chloride etc.); In reaction system, increase the amount that the cuprous salt oxidation is become the oxygenant and the butter of cupric salt with chlorination simultaneously.
Described oxygenant is oxygen, air or hydrogen peroxide.
Described chloride inorganics is hydrogenchloride or hydrochloric acid.
Described temperature of reaction is preferably 80-110 ℃; More preferably 90-100 ℃,
Reaction is preferably under the pressure 1-5atm condition to be carried out.
Can add entry during reaction, make the total amount of water account for 1-hydroxyl-3, the 5%-200% of 5-dimethyl benzene weight.
The available oxygen amount of described oxygenant is the part that can participate in oxidizing reaction in the oxygenant, and when for example adopting 30% hydrogen peroxide to be oxygenant, the O that can discharge in the hydrogen peroxide is the available oxygen amount.
Above-mentioned reaction system can be finished reaction in a reactor, also can be earlier with the cupric chloride (not being suitable for other mantoquitas) of capacity earlier and 1-hydroxyl-3, the 5-dimethyl benzene reacts, the cuprous chloride that produces is regenerated with oxygenant and hydrogenchloride or hydrochloric acid again, but on the angle of economy, adopt the effect of single stage method reaction better.
In the technical scheme of the present invention, cupric salt is to 1-hydroxyl-3, and the chlorination of 5-dimethyl benzene has tangible catalytic activity.Cupric salt used in the present invention comprises: copper sulfate, cupric nitrate, copper carbonate, copper hydroxide, cupric chloride, cupric bromide, cupric iodide, Tubercuprose, venus crystals or propionic acid copper or the like.The usage quantity of cupric salt is to the influence relation of being proportionate of speed of response, and promptly the catalyzer usage quantity is big more generally speaking, and the transformation efficiency of unit time reactant is high more.Consider the economic problems of reaction, for the first time usage quantity is controlled at 0.5%-200% be advisable (based on 1-hydroxyl-3, the weight of 5-dimethyl benzene); 10%-60% the best.Employed cupric salt catalyzer can be applied mechanically repeatedly in reaction process and can not influence speed of response.Also can in above-mentioned reaction system, add the corresponding cuprous salt of cupric salt and replace cupric salt, oxygenant that is added in itself and the reaction system and butter react and produce, just corresponding increasing and the oxygenant of its reaction and the amount of butter.
Employed oxygenant comprises oxygen, air and hydrogen peroxide among the present invention; Employed oxidant content (in available oxygen) and 1-hydroxyl-3, the mol ratio of 5-dimethyl benzene is between 1: 1 to 2: 1.In technical solution of the present invention, use hydrogen peroxide can obviously improve speed of response, but selectivity is not high; And use oxygen or air can obtain higher contraposition station-keeping ability.
The raw material that can be used as the chlorine source in the present invention comprises hydrogenchloride or hydrochloric acid.Employed chloride inorganics and 1-hydroxyl-3 among the present invention, the mol ratio of 5-dimethyl benzene is between 1: 1 to 1.5: 1.
When using hydrogen peroxide as oxygenant, reaction pressure is not obvious to the reaction influence; And when using oxygen or air as oxygenant, reaction pressure and the speed of response relation of being proportionate can be controlled at 1-5atm.Consider the economy of reaction, suitable pressure range can be controlled between the 1-2atm.
Water in the reaction system can be brought into by the technical hydrochloric acid that adds in the reaction process; If use hydrogenchloride as the chlorine source, can before reaction, add a certain amount of water, with the solubleness of increase hydrogenchloride in system, thereby improve reaction effect.In addition, reaction itself also can produce and the equimolar moisture of product (seeing reaction formula 1 and 2), when using the catalyzer of band crystal water, also can bring part moisture into, when using 30% hydrogen peroxide as oxygenant, also can bring a certain amount of moisture into.The total amount of water accounts for 1-hydroxyl-3, is advisable between the 5%-200% of 5-dimethyl benzene weight.Moisture is too many, can reduce the economy of reaction.
Reaction formula 1
Reaction formula 2
Having now utilizes cupric salt to be catalyzer, 1-hydroxyl-3, the 5-dimethyl benzene, oxygenant, chloride inorganics reaction generates 1-hydroxyl-3, all adopted organic solvent to react at low temperatures in the technology of 5-dimethyl-4-chlorobenzene, its purpose mainly is in order to make substrate 1-hydroxyl-3, the 5-dimethyl benzene is dissolved in organic phase, catalyzer in being beneficial to it and being soluble in the aqueous phase, oxygenant and chlorine-containing compound fully react, because solid-state 1-hydroxyl-3 under the low temperature, the 5-dimethyl benzene is difficult to the catalyzer with aqueous phase, oxygenant, chlorine-containing compound fully reacts, effectiveness affects to reaction is very big, so form a kind of thinking set in the field of study, substrate all will be dissolved in the organic solvent and just may carry out smoothly in such reaction.But the inventor is by discovering, under the situation of not adding organic solvent, as long as guarantee that by heating it is fully passable that substrate reacts with water under melted state.In view of reaction substrate 1-hydroxyl-3, the fusing point under the situation that water exists of 5-dimethyl benzene is more than 50 ℃, and temperature had been advisable more than 50 ℃ when therefore reaction began.Along with the carrying out of reaction, the fusing point of substrate can descend earlier, raises gradually then, is in melted state in order to guarantee substrate, and temperature of reaction should progressively raise, and guarantees that reaction substrate is in molten state, just help improving the yield of product so more.When raw material 1-hydroxyl-3, the transformation efficiency of 5-dimethyl benzene reaches 95% when above, and the fusing point of substrate in aqueous systems can be brought up to more than 90 ℃.High more from another one aspect temperature, speed of response is fast more, if but temperature is too high, surpassed the boiling point of water in the system, will produce the vaporization of water, and reaction substrate belongs to aldehydes matter, and therefore distillation easily reacts under reflux state, the vaporization of water can be entrained with large amount of organic, on condenser or pipeline, separate out, stop up condenser and pipeline, the influence operation; And, under reflux state, to react, the vaporization of water can be lost a large amount of heats, also is uneconomic on reacting totally.Therefore, temperature is too high to have certain influence to reaction yield, so when keeping high yield, temperature of reaction preferably is controlled at 80-110 ℃, is more preferably 90-100 ℃.
In sum, the invention provides a kind of new 1-hydroxyl-3, the synthetic method of 5-dimethyl-4-chlorobenzene adopts cupric salt as catalyzer, and hydrogenchloride or hydrochloric acid carry out the synthetic purpose product of oxi-chlorination as the chlorine source under the condition that oxygenant exists.This method is easy and simple to handle, reaction conditions is gentle, the purpose good product selectivity that obtains, the transformation efficiency height, and produce toxic gas in the reaction process hardly, do not need to use any organic solvent, can obviously reduce environmental pollution, be the 1-hydroxyl-3 that a kind of suitable heavy industrialization is used, 5-dimethyl-4-chlorobenzene preparation method.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
Add 122g (1.0mol) 1-hydroxyl-3 in three mouthfuls of reaction flasks of 500ml respectively, 5-dimethyl benzene, 51.2g copper chloride dihydrate, and 101.3g concentrated hydrochloric acid (HCl1.0mol); Load onto condenser, magnetic agitation, thermometer then, and oxygen-supplying tube.Reactant is heated to 90 ℃, aerating oxygen at the uniform velocity under whipped state.Temperature of reaction is controlled between 90-98 ℃, and reaction pressure is a normal pressure.Reaction is got upper organic phase GC detection level after finishing.The results are shown in Table 1.
Embodiment 2
Lower floor's water air distillation among the embodiment 1 is concentrated, steam 80g left and right sides moisture.Add 122g1-hydroxyl-3,5-dimethyl benzene, and 102g concentrated hydrochloric acid in the still bed material liquid; Load onto condenser, magnetic agitation, thermometer then, and oxygen-supplying tube.Reactant is heated to 90 ℃, aerating oxygen at the uniform velocity under whipped state.Temperature of reaction is controlled between 90-98 ℃, and reaction pressure is a normal pressure.Reaction after finishing is told lower floor's material, sampling GC detection level; The results are shown in Table 1.
Embodiment 3
Process of the test just changes hydrochloric acid into 1molHCl with embodiment 1, adds the 50g tap water in addition, and reaction pressure is controlled at 2atm, and reaction result sees Table 1:
Table 1 oxi-chlorination analytical results
Annotate: MX:1-hydroxyl-3,5-dimethyl benzene; OC:1-hydroxyl-3,5-dimethyl-2-chlorobenzene; DC:1-hydroxyl-3,5-dimethyl-2,4 dichloro benzene; PC:1-hydroxyl-3,5-dimethyl-4-chlorobenzene; Yield account form :=transformation efficiency * selectivity (down together).
Embodiment 4-5
Process of the test just is replaced by air with oxygen respectively with embodiment 1-2, and reaction result sees Table 2:
Table 2 oxi-chlorination analytical results
| Project | Reaction times | MX％ | OC％ | DC％ | PC％ | Selectivity | Transformation efficiency | Yield |
| Embodiment 4 | 20 hours | 1.04 | 2.58 | 2.25 | 94.16 | 95.14％ | 98.96％ | 94.15％ |
| Embodiment 5 | 24 hours | 1.18 | 2.89 | 2.19 | 93.74 | 94.86％ | 98.82％ | 93.74％ |
Embodiment 6-7
Process of the test just is replaced by 1.2mol 30% hydrogen peroxide with oxygen respectively with embodiment 1-2, and reaction result sees Table 3:
Table 3 oxi-chlorination analytical results
| Project | Reaction times | MX％ | OC％ | DC％ | PC％ | Selectivity | Transformation efficiency | Yield |
| Embodiment 6 | 4 hours | 0.99 | 6.78 | 7.54 | 86.69 | 85.53％ | 99.01％ | 84.68％ |
| Embodiment 7 | 4 hours | 1.08 | 5.99 | 7.55 | 85.38 | 86.31％ | 98.82％ | 85.38％ |
Embodiment 8-14
Process of the test just is replaced by cupric bromide, cupric iodide, formic acid ketone, neutralized verdigris, propionic acid copper, copper sulfate, cupric nitrate respectively with cupric chloride with embodiment 1, and experimental result is as follows:
Table 6 oxi-chlorination analytical results
Embodiment 15
Process of the test just is controlled at temperature of reaction between 110-115 ℃ with embodiment 1, and the condenser backflow phenomenon is very obvious in the reaction process, and the adularescent material gathers in prolong, reacts sampling after 8 hours, detects with GC, and the result is MX:0.98%; OC:3.25%; DC:2.98%; PC:92.79%.
Embodiment 16
Process of the test is with embodiment 1, and just the add-on with copper chloride dihydrate is increased to 102.4g, reacts sampling after 8 hours, detects with GC, and the result is MX:1.08%; OC:2.25%; DC:1.95%; PC:94.72%.
Claims (10)
1. 1-hydroxyl-3, the preparation method of 5-dimethyl-4-chlorobenzene is characterized in that, make catalyzer by cupric salt, under the condition of organic solvent-free, with 1-hydroxyl-3,5-dimethyl benzene, oxygenant and chloride inorganics react and obtain, and temperature of reaction is 50-150 ℃; Described cupric salt accounts for 1-hydroxyl-3, the 0.5%-200% of 5-dimethyl benzene weight; The available oxygen amount of described oxygenant, chlorine-containing compound and 1-hydroxyl-3, the mol ratio of 5-dimethyl benzene consumption is: 1-2: 1-1.5: 1.
2. preparation method according to claim 1 is characterized in that, described cupric salt is copper sulfate, cupric nitrate, copper carbonate, copper hydroxide, copper halide or the lipid acid mantoquita that contains 1-6 carbon atom.
3. preparation method according to claim 2 is characterized in that, described copper halide is cupric chloride, cupric bromide or cupric iodide; The lipid acid mantoquita of the described 1-6 of a containing carbon atom is Tubercuprose, venus crystals or propionic acid copper.
4. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that described cupric salt is anhydrous or has the mantoquita of crystal water.
5. preparation method according to claim 1 is characterized in that the consumption of described cupric salt accounts for 1-hydroxyl-3, the 10%-60% of 5-dimethyl benzene weight.
6. according to claim 4, it is characterized in that described catalyzer can be replaced by the corresponding cuprous salt of described cupric salt, in reaction system, increase the amount that the cuprous salt oxidation is become the oxygenant and the butter of cupric salt with chlorination simultaneously.
7. preparation method according to claim 1 is characterized in that, described oxygenant is oxygen, air or hydrogen peroxide.
8. preparation method according to claim 1 is characterized in that, described chloride inorganics is hydrogenchloride or hydrochloric acid.
9. preparation method according to claim 1 is characterized in that, described temperature of reaction is 80-110 ℃.
10. according to claim 1 or 9 described preparation methods, it is characterized in that described temperature of reaction is at 90-100 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100845339A CN102199075A (en) | 2011-04-02 | 2011-04-02 | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene |
| PCT/CN2012/073112 WO2012136108A1 (en) | 2011-04-02 | 2012-03-27 | Method for preparing 1-hydroxyl-3,5-dimethyl-4-chlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100845339A CN102199075A (en) | 2011-04-02 | 2011-04-02 | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102199075A true CN102199075A (en) | 2011-09-28 |
Family
ID=44660099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100845339A Pending CN102199075A (en) | 2011-04-02 | 2011-04-02 | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102199075A (en) |
| WO (1) | WO2012136108A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012136108A1 (en) * | 2011-04-02 | 2012-10-11 | 湖南利洁生物化工有限公司 | Method for preparing 1-hydroxyl-3,5-dimethyl-4-chlorobenzene |
| CN102775278A (en) * | 2012-07-27 | 2012-11-14 | 湖南利洁生物化工有限公司 | Crystallization and purification method of 1-hydroxyl-3,5-dimethyl-4-chlorobenzene |
| 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 |
| CN105037104A (en) * | 2015-06-02 | 2015-11-11 | 铜陵市恒兴化工有限责任公司 | Preparation method of 4-chloro-3,5-dimethylphenol |
| CN107226775A (en) * | 2016-03-24 | 2017-10-03 | 中国石油化工股份有限公司 | The method that the chloro- 3,5- xylenols of 4- are synthesized in continuous stream micro-pipe reactor |
| CN111440051A (en) * | 2020-04-03 | 2020-07-24 | 安徽中羰碳一工业技术有限责任公司 | Synthesis method of 4-chloro-3, 5-dimethylphenol |
| CN115433060A (en) * | 2022-10-31 | 2022-12-06 | 青岛科技大学 | Preparation method of monochlorophenol compound |
| CN115583869A (en) * | 2022-09-13 | 2023-01-10 | 安徽海华科技集团有限公司 | Selective oxidative chlorination method for phenolic compounds |
| CN115611710A (en) * | 2022-09-13 | 2023-01-17 | 安徽海华科技集团有限公司 | Method for improving oxidation chlorination efficiency of 3, 5-dimethylphenol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574329B (en) * | 2020-05-18 | 2022-09-20 | 万华化学集团股份有限公司 | Reactive distillation device and method for producing 4-chloro-3, 5-dimethylphenol |
Citations (4)
| 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 |
| US3916014A (en) * | 1972-08-03 | 1975-10-28 | Asahi Denka Kogyo Kk | Chlorination of aromatic compounds |
| JPS595132A (en) * | 1982-06-30 | 1984-01-12 | Hodogaya Chem Co Ltd | Preparation of 4-chloro-3,5-xylenol |
| CN101624333A (en) * | 2009-08-05 | 2010-01-13 | 湖南利洁生物化工有限公司 | 1-hydroxyl-3,5-dimethyl-4-chlorobenzene preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560554C (en) * | 2007-01-10 | 2009-11-18 | 胡汉忠 | Industrialized process for preparing to the chloro alkylphenol |
| 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 |
-
2011
- 2011-04-02 CN CN2011100845339A patent/CN102199075A/en active Pending
-
2012
- 2012-03-27 WO PCT/CN2012/073112 patent/WO2012136108A1/en active Application Filing
Patent Citations (4)
| 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 |
| US3916014A (en) * | 1972-08-03 | 1975-10-28 | Asahi Denka Kogyo Kk | Chlorination of aromatic compounds |
| JPS595132A (en) * | 1982-06-30 | 1984-01-12 | Hodogaya Chem Co Ltd | Preparation of 4-chloro-3,5-xylenol |
| CN101624333A (en) * | 2009-08-05 | 2010-01-13 | 湖南利洁生物化工有限公司 | 1-hydroxyl-3,5-dimethyl-4-chlorobenzene preparation method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012136108A1 (en) * | 2011-04-02 | 2012-10-11 | 湖南利洁生物化工有限公司 | Method for preparing 1-hydroxyl-3,5-dimethyl-4-chlorobenzene |
| CN102775278A (en) * | 2012-07-27 | 2012-11-14 | 湖南利洁生物化工有限公司 | Crystallization and purification method of 1-hydroxyl-3,5-dimethyl-4-chlorobenzene |
| CN102775278B (en) * | 2012-07-27 | 2014-03-05 | 湖南利洁生物化工有限公司 | Crystallization and purification method of 1-hydroxyl-3,5-dimethyl-4-chlorobenzene |
| 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 |
| CN105037104A (en) * | 2015-06-02 | 2015-11-11 | 铜陵市恒兴化工有限责任公司 | Preparation method of 4-chloro-3,5-dimethylphenol |
| CN107226775A (en) * | 2016-03-24 | 2017-10-03 | 中国石油化工股份有限公司 | The method that the chloro- 3,5- xylenols of 4- are synthesized in continuous stream micro-pipe reactor |
| CN111440051A (en) * | 2020-04-03 | 2020-07-24 | 安徽中羰碳一工业技术有限责任公司 | Synthesis method of 4-chloro-3, 5-dimethylphenol |
| CN115583869A (en) * | 2022-09-13 | 2023-01-10 | 安徽海华科技集团有限公司 | Selective oxidative chlorination method for phenolic compounds |
| CN115611710A (en) * | 2022-09-13 | 2023-01-17 | 安徽海华科技集团有限公司 | Method for improving oxidation chlorination efficiency of 3, 5-dimethylphenol |
| CN115611710B (en) * | 2022-09-13 | 2024-02-20 | 安徽海华科技集团有限公司 | Method for improving oxidation chlorination efficiency of 3, 5-dimethylphenol |
| CN115583869B (en) * | 2022-09-13 | 2024-04-23 | 安徽海华科技集团有限公司 | Selective oxidation chlorination method for phenolic compound |
| CN115433060A (en) * | 2022-10-31 | 2022-12-06 | 青岛科技大学 | Preparation method of monochlorophenol compound |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012136108A1 (en) | 2012-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102199075A (en) | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene | |
| CN101624333B (en) | 1-hydroxyl-3,5-dimethyl-4-chlorobenzene preparation method | |
| CN100560554C (en) | Industrialized process for preparing to the chloro alkylphenol | |
| CN106316809B (en) | A method of preparing perfluorethyl isopropyl ketone | |
| CN106336388B (en) | The synthetic method of benzofuran -2- (3H) -one | |
| CN103664511B (en) | Preparation method of 5-bromo-1,3-dichloro-2-fluorobenzene | |
| CN103601613A (en) | Preparation method of 3, 4, 5-trifluoro bromobenzene | |
| CN106916060A (en) | A kind of preparation method of high-purity parahydroxyacet-ophenone | |
| CN103351282B (en) | Preparing method for 4-chlorine-3,5-xylenol | |
| CN206033616U (en) | 1 continuou synthesy equipment of chlorobutane | |
| CN111440051A (en) | Synthesis method of 4-chloro-3, 5-dimethylphenol | |
| CN104211598B (en) | The preparation method of 2-(o-hydroxy-phenyl) cyclopropane-1-formic acid | |
| CN107337576B (en) | Normal temperature catalytic synthesis of 2-bromo-5-fluorobenzotrifluoride | |
| CN105152853A (en) | Method for preparing 2-bromine-5-fluorobenzotrifluoride | |
| CN101759613A (en) | Preparation method for perfluoroalkyl vikane | |
| CN110475764A (en) | The purification process of trifluoromethyl pyridine class | |
| de la Vega et al. | Selective para-bromination of toluene catalysed by Na-Y zeolite in the presence of an epoxide | |
| CN103483199B (en) | Preparation method of tetrafluoroterephthalate | |
| CN110615734B (en) | Industrialized synthesis method of o-aldehyde phenyl fatty acid | |
| CN104892403A (en) | Synthetic method of benzoic anhydride | |
| CN102363614B (en) | Method for synthesizing 2-bromothiophene | |
| CN115583869B (en) | Selective oxidation chlorination method for phenolic compound | |
| CN106829878B (en) | Dichloride sulphur preparing process and preparation facilities | |
| CN108191644A (en) | A kind of preparation method of chlorine difluoroacetic acid chloride | |
| CN107793298A (en) | A kind of preparation method of the aryl alkyl ethers of the multicomponent catalyst catalysis based on supported palladium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110928 |