CN109134203A - A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation - Google Patents
A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation Download PDFInfo
- Publication number
- CN109134203A CN109134203A CN201811086480.2A CN201811086480A CN109134203A CN 109134203 A CN109134203 A CN 109134203A CN 201811086480 A CN201811086480 A CN 201811086480A CN 109134203 A CN109134203 A CN 109134203A
- Authority
- CN
- China
- Prior art keywords
- reaction
- paracide
- chlorophenesic acid
- round
- bottomed flask
- 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
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
One kind is by activated carbon containing iron catalysis Isosorbide-5-Nitrae-dichloro benzene hydroxylation preparation 2,5- chlorophenesic acid method, first with nitric acid, H2O2All kinds of active carbons of processing are carrier, and the active component Fe (NO of different quality is introduced by infusion process3)3, Fe/AC catalyst is made and is used for subsequent reactions.Using Isosorbide-5-Nitrae-dichloro-benzenes as substrate, acetonitrile is solvent, H for reaction2O2For oxidant.It reacts in the round-bottomed flask for be connected with reflux condensate device and carries out, wherein 30%H2O2For solution by the slow sample introduction of peristaltic pump constant speed or directly in disposable sample-adding to round-bottomed flask, reaction is persistently heated with stirring to certain time, and 2,5- chlorophenesic acid is made.Wherein, iron content is 0-0.5mmol/g in Fe/AC；Paracide and Fe/AC mass ratio are 1:0.1-1:0.5；Paracide and H2O2Molar ratio is 1:1.5-1:29.6；Reaction temperature is 30-80 DEG C；Reaction time is 10-300min.For the present invention in 0.20mmol/g Fe/HAC-j, the 6.63mmol paracide of optimal conditions 0.3g, 10mL acetonitrile is added at one time 10mL 30%H2O2, 2h is reacted in 60 DEG C, paracide conversion ratio is up to 70.9%, wherein 2,5- chlorophenesic acid yields are 39.5%, selectivity is 55.8%.Entire reaction process clean and effective, meets green development view.
Description
Technical field
The present invention relates to a kind of preparations of activated carbon containing iron and its catalysis Isosorbide-5-Nitrae-dichloro benzene hydroxylation to prepare 2,5- dichloro-benzenes
The method of phenol.
Background technique
2,5- chlorophenesic acids are a kind of important chemical intermediates, be widely used in prepare medicine intermediate, dyestuff intermediate,
Nitrogen fertilizer potentiating agent, leather fungicide, low toxicity herbicide dicamba etc..As emission reduction in recent years requires to be gradually increased, high toxicity
Herbicide (such as green sulphur is grand) is gradually limited, and the low-toxin farm chemicals dicamba demand for being widely used in production estimation is continuously increased, city
Field has good prospects.Therefore, as the important intermediate of dicamba 2, the demand of 5- chlorophenesic acid just increasingly increases.
The conventional method of 2,5- chlorophenesic acids mainly has 1,2,4- trichloro-benzene methods and 2,5- dichloroaniline method, and the latter one exist
With the most universal in industrial production.Then, on this Research foundation, 2,4- chlorophenesic acid isomerization process, adjacent chlorine have also been derived
Phenol chloridising and directly by benzene multistep reaction preparation the methods of 2,5- chlorophenesic acid.
Document (J. Am. Chem. Soc., 1952,74 (15) 3890-3891) reports one kind by 1,2,4- trichlorine
The method that benzene prepares 2,5- chlorophenesic acid, is added SO in substrate2It is molten with highly basic later as the ortho position of sulfonating agent protection-Cl
Liquid (NaOH) by-Cl hydrolyze generate hydroxyl, then 70% effect of sulfuric acid go down protecting group i.e. generate product.The method has higher receipts
Rate, but since preparation process needs strong acid and strong base, the high requirements on the equipment, and 1,2,4- trichlorophenol, 2,4,6,-T costs are higher, it is difficult to push away
Wide application.
Document (Chemical Manufacture and technology, 2010,17 (2) 16-17) reports one kind and prepares 2 by 2,5- dichloroaniline,
The method of 5- chlorophenesic acid.The method 2,5- dichloroaniline is raw material, and diazotising occurs under sulfuric acid and sodium nitrite effect and makees
With, then obtain product yield through high temperature preheating diazonium salt and hydrolysis and reach 90.2%.The method yield is higher, but diazotising is anti-
It should be carried out under the high temperature conditions with hydrolysis, energy consumption is higher, and soda acid dosage is big, keeps equipment perishable and is easy to produce
" three industrial wastes ".
Patent (CN201580065029) discloses one kind and passes through isomerization preparation 2,5- bis- by 2,4 dichloro phenol
The method of chlorophenol.It uses zeolite molecular sieve zsm-5 for catalyst, and water and acid are fed into isomerization zone at 200-280 DEG C
And isomerization product is obtained, highest obtains about 47% product yield.The method is higher to the accuracy requirement of charging, and in addition water is wanted
It is converted to the steam of fixed temperature, thus is difficult to control.
Patent (CN200610049124), which reports, a kind of prepares 2,5- chlorophenesic acid by one one-step hydroxylation of paracide
Method.It uses heteropoly acid, heteropolyacid salt or its support type to make catalyst, and acetone is solvent, H2O2For oxidant, 0-85 DEG C anti-
6-24h is answered, vacuum distillation obtains 2,5- chlorophenesic acid.The method route is simple, but presence separation is difficult, reaction efficiency is relatively low,
The poor problem of yield.
Patent (CN201610270712) discloses a kind of by different-phase catalyst catalysis oxidation paracide preparation 2,5- bis-
The method of chlorophenol.It uses SiO2, Al2O3, TiO2Deng for catalyst carrier, alum phosphorous oxides (VPOx) it is active component.Instead
Answer system using acetic acid as solvent, H2O2For oxidant, 12h is reacted in 30-40 DEG C.Reaction mixture, water are filtered after reaction
It washes, is catalyst and substrate in filter cake, is product in filtrate.Filtrate extracts through ethyl acetate, and revolving removes organic phase, collects dry
Dry spicule is 2,5- chlorophenesic acid.Reaction yield easy to operate, the separation letter that reaches as high as 39.3% method is calculated by weighing
Singly, but substrate and product are separated by way of directly washing, and not accurate enough by the quantitative manner of weighing, in addition the method
Reaction time is partially long, and reaction efficiency needs to be further increased.
In conclusion paracide is a kind of cheap preparation 2, the raw material of 5- chlorophenesic acid is former since the route is simple
Sub- utilization rate is high, meets " Green Chemistry " theory, and thus direct one-step hydroxylation generation 2,5- chlorophenesic acid, which has, greatly grinds
Study carefully meaning.But especially perfect, especially generally existing reaction time length, efficiency for the research of the system also it are not at present
Low problem.Therefore, it is carrier that the present invention, which has selected cheap active carbon (AC), and Fe is active component, is prepared for different iron content
Fe/AC is measured, the reaction of one one-step hydroxylation of paracide preparation 2,5- chlorophenesic acid is used for.The reaction system is molten with acetonitrile
Agent, 30% H2O2For oxidant, heats and reacted in reflux condensate device.In lower temperature and shorter time conditions
Under obtain product, and catalyst can directly be separated with liquid phase mixture by depressurizing to filter, and convenient for subsequent measurements and repeat to test
Progress.
Summary of the invention
The Fe/AC that the present invention is prepared for a kind of Cheap highly effective is catalyst, for being catalyzed the preparation of one one-step hydroxylation of dichloro-benzenes
2,5- chlorophenesic acid.The reaction is using acetonitrile as solvent, H2O2For oxidant, carried out under counterflow condition.It is pollution-free in relative clean
Under conditions of, obtain preferable catalytic effect.Correlated condition are as follows: iron content 0-0.5mmol/g；Paracide and Fe/AC matter
Amount compares 1:0.1-1:0.5；Paracide and H2O2Molar ratio is 1:1.5-1:29.6；30-80 DEG C of reaction temperature；Peristaltic pump is slow
H is added dropwise2O2Under the conditions of react 10-280min, disposably add H2O2Under the conditions of react 10-300min.
Optimal iron content is 0.20mmol/g in the present invention, and the optimum quality ratio of paracide and Fe/AC catalyst is
1:0.4, paracide and H2O2Optimum mole ratio be 1:14.8, optimal reaction temperature is 60 DEG C, and optimum reacting time is
120min, H2O2Best dosing method be disposably add.
Specific steps of the invention
The first step prepares the Fe/AC catalyst of different iron contents by infusion process.
Fe/AC catalyst, paracide, acetonitrile are sequentially added round-bottomed flask by second step, and reflux condensation mode dress is connect on flask
It sets, 30% H2O2Solution passes through different loading methods sample introductions to reaction system.Wherein, disposable sample introduction is direct before reaction starts
By a certain amount of 30% H2O2All it is added in round-bottomed flask.Peristaltic pump sample introduction is by 30% H2O2Solution is placed in conical flask, is led to
It crosses in peristaltic pump control sample introduction speed continuous sample introduction to round-bottomed flask.Setting value is arrived when water bath temperature is constant, by round-bottomed flask
It is placed in heating in pot, peristaltic pump is opened simultaneously, to guarantee H2O2Slow constant speed is added within the time of design.After reaction, circle
Bottom flask pulls out water-bath, cooled to room temperature, and decompression filters and obtains reaction mixture, washs simultaneously constant volume with acetonitrile solution,
It is quantified by high performance liquid chromatography, the initial paracide content based on addition calculates yield and selectivity of product etc..Specific meter
Calculation method is as follows:
Paracide conversion ratio=(amount of remaining paracide substance after the amount-reaction for the paracide substance being initially added)/
The amount * 100% of the substance for the paracide being initially added；
The amount * of 2,5- chlorophenesic acid yield=amount of the substance of 2,5- chlorophenesic acid/substance for the paracide being initially added
100%；
2,5- chlorophenesic acid selectivity=2,5- chlorophenesic acid yield/paracide conversion ratio * 100%.
Compared with the prior art the present invention has following features:
1) cheap and easily-available using active carbon as catalyst carrier, catalytic performance is good, there is biggish utilization space and stronger popularization
Potentiality.
2) Fe/AC method for preparing catalyst is simple, using equi-volume impregnating, this can be obtained in 80 DEG C of drying moisture and urges
Agent.Without roasting, energy consumption is lower.
3) catalyst is good to the catalytic performance of the reaction.60 DEG C of reaction 2h are the 2,5- chlorophenesic acid receipts that can reach 39.5%
Rate.Reaction temperature is low, and the time is short, energy-efficient.
4) H is used in reaction2O2For oxidant, the by-product of generation is water, meets Green Chemistry requirement.
Embodiment
The active carbon of 20-40 mesh is washed with deionized in beaker, constantly removes surface and floats the inorganic matters such as charcoal, until no longer
There is floating charcoal to generate.Washed active carbon is placed in 80 DEG C of baking ovens and dries 12 h, obtains AC.The AC of 10 g drying is weighed, and is prepared
The 10 mol/L HNO of 50 mL3Solution, the two are placed in round-bottomed flask, and spherical condensation tube is connect on round-bottomed flask, lead to tap water
Reflux condensation mode is carried out, round-bottomed flask is in 90 DEG C of oil bath heatings, and flow back 10 h.After, it stands overnight, is taken out by decompression within second day
The active carbon of nitric acid treatment is constantly washed with deionized in filter, until washing obtains absorbent charcoal carrier HAC to neutrality.Weigh phase
The HAC of homogenous quantities is in beaker, with the Fe (NO of various concentration3)3Solution is impregnated, in being stored at room temperature 12 h, be placed on
80 DEG C of baking ovens dry 12 h to get Fe/HAC catalyst.
The active carbon for taking each type, such as active fruit shell carbon, cocoanut active charcoal, rice hull active carbon, wild jujube active carbon, charcoal point
Son sieve is carrier, equally carries out above-mentioned acidification and dipping process (dipping iron content is 0.2 mmol/g), is respectively designated as
Fe/HAC-3, Fe/HAC-c, Fe/HAC-r, Fe/HAC-j and Fe/HAC-m.Take the commercial adamas activity of other different companies
Charcoal, Alfa active carbon, GENER active carbon are carrier, equally carry out above-mentioned dipping process (dipping iron content is 0.2mmol/g),
It is respectively designated as Fe/AC-adamas, Fe/AC-Alfa, Fe/AC-GENER.
Embodiment 1-8: the Fe/AC of each type of 0.4 g is added into round-bottomed flask respectively, 6.63 mmol are to dichloro
Benzene, 10 mL acetonitriles, 10 mL H2O2.Round-bottomed flask is placed in water bath when constant to 60 DEG C of water bath temperature and reacts 2 h.
Natural cooling after reaction, decompression separation catalyst, is washed with acetonitrile, and constant volume is in 100mL volumetric flask, using high performance liquid chromatography
Product is analyzed, table 1 is as a result listed in.
Table 1
| Embodiment | Catalyst | 2,5- chlorophenesic acid yield/% | 2,5- chlorophenesic acid selectivity/% | 1,4- chlorophenesic acid conversion ratio/% |
| 1 | Fe/HAC-3 | 37.3 | 49.4 | 75.4 |
| 2 | Fe/HAC-c | 37.1 | 58.9 | 63.0 |
| 3 | Fe/HAC-r | 28.2 | 39.6 | 71.0 |
| 4 | Fe/HAC-j | 39.5 | 55.8 | 70.9 |
| 5 | Fe/HAC-m | 19.6 | 27.3 | 71.7 |
| 6 | Fe/AC-adamas | 17.4 | 18.4 | 94.7 |
| 7 | Fe/AC-Alfa | 34.6 | 50.3 | 68.7 |
| 8 | Fe/AC-GENER | 13.4 | 18.2 | 73.8 |
Embodiment 9-16: carrying out condition optimizing by taking active fruit shell carbon as an example, and concrete operations are as follows.It is to carry with the shell of nitric acid treatment
The catalyst of the different iron contents of body is named as HAC (without Fe), Fe/HAC-1 (0.05mmol/g Fe), Fe/HAC- respectively
2 (0.10mmol/g Fe), Fe/HAC-3 (0.20mmol/g Fe), Fe/HAC-4 (0.30mmol/g Fe), Fe/HAC-5
(0.50mmol/g Fe).In addition the active fruit shell carbon for weighing 10 g drying, with the 10 mol/L H of 50 mL2O2Solution is in 90 DEG C
Reflux washing 10h, stands overnight and washs to neutrality, be named as H2O2-AC.0.3 g difference iron is added to round-bottomed flask respectively to contain
The Fe/AC(active fruit shell carbon of amount), 6.63mmol paracide, 10mL acetonitrile.10 mL, 30% H is added in conical flask2O2It is molten
Liquid is loaded by peristaltic pump uniform speed slow into round-bottomed flask, and round-bottomed flask is placed in water when constant to 60 DEG C of water bath temperature
Environment is bathed, peristaltic pump starts simultaneously at sample-adding, and 55 min are added, and are stirred for 5 min later.Natural cooling after reaction, decompression separation
Catalyst is washed with acetonitrile, and constant volume, using efficient liquid phase chromatographic analysis product, is as a result listed in table 2 in 100mL volumetric flask.
Table 2
| Embodiment | Catalyst | 2,5- chlorophenesic acid yield/% | 2,5- chlorophenesic acid selectivity/% | 1,4- chlorophenesic acid conversion ratio/% |
| 9 | AC | - | - | 1.5 |
| 10 | H2O2-AC | - | - | 1.5 |
| 11 | HAC | 8.6 | 26.1 | 33.0 |
| 12 | Fe/HAC-1 | 19.4 | 38.5 | 50.3 |
| 13 | Fe/HAC-2 | 19.9 | 37.6 | 52.9 |
| 14 | Fe/HAC-3 | 26.7 | 39.6 | 67.4 |
| 15 | Fe/HAC-4 | 22.5 | 28.0 | 80.4 |
| 16 | Fe/HAC-5 | 14.3 | 17.2 | 83.3 |
Embodiment 17-20: respectively into round-bottomed flask be added different quality Fe/HAC-3,6.63 mmol paracide, 10
ML acetonitrile.10 mL, 30% H is added in conical flask2O2Solution is loaded into round-bottomed flask by peristaltic pump uniform speed slow, works as water-bath
Round-bottomed flask is placed in water bath at constant to 60 DEG C of pot temperature, peristaltic pump starts simultaneously at sample-adding, and 55 min are added, Zhi Houzai
Stir 5 min.Natural cooling after reaction, decompression separation catalyst, is washed with acetonitrile, and constant volume is used in 100 mL volumetric flasks
As a result efficient liquid phase chromatographic analysis product is listed in table 3.
Table 3
| Embodiment | Fe/HAC-3 dosage/g | 2,5- chlorophenesic acid yield/% | 2,5- chlorophenesic acid selectivity/% | 1,4- chlorophenesic acid conversion ratio/% |
| 17 | 0.1 | 14.5 | 21.3 | 68.1 |
| 18 | 0.2 | 19.9 | 29.6 | 67.3 |
| 19 | 0.4 | 30.0 | 43.7 | 68.7 |
| 20 | 0.5 | 27.2 | 37.1 | 73.3 |
Embodiment 21-24: 0.4 g Fe/HAC-3,6.63 mmol paracide, 10 mL second are added into round-bottomed flask respectively
Nitrile.Different amounts of 30% H is added in conical flask2O2Solution is loaded into round-bottomed flask by peristaltic pump uniform speed slow, works as water-bath
Round-bottomed flask is placed in water bath at constant to 60 DEG C of temperature, peristaltic pump starts simultaneously at sample-adding, and 55 min are added, stirred again later
Mix 5 min.Natural cooling after reaction, decompression separation catalyst, is washed with acetonitrile, and constant volume is in 100 mL volumetric flasks, using height
Effect liquid phase chromatogram analyzes product, is as a result listed in table 4.
Table 4
| Embodiment | 30%H2O2Dosage/mL | 2,5- chlorophenesic acid yield/% | 2,5- chlorophenesic acid selectivity/% | 1,4- chlorophenesic acid conversion ratio/% |
| 21 | 1 | 2.6 | 6.9 | 37.1 |
| 22 | 5 | 18.5 | 34.8 | 53.0 |
| 23 | 15 | 27.1 | 33.2 | 81.6 |
| 24 | 20 | 22.3 | 27.2 | 81.9 |
Embodiment 25-28: 0.4 g Fe/HAC-3,6.63 mmol paracide, 10 mL second are added into round-bottomed flask respectively
Nitrile.30% H of 10 mL is added in conical flask2O2Solution is loaded by peristaltic pump uniform speed slow into round-bottomed flask, when water-bath pot temperature
Spend it is constant to set temperature when round-bottomed flask is placed in water bath, peristaltic pump starts simultaneously at sample-adding, and 55 min are added, Zhi Houzai
Stir 5 min.Natural cooling after reaction, decompression separation catalyst, is washed with acetonitrile, and constant volume is used in 100 mL volumetric flasks
As a result efficient liquid phase chromatographic analysis product is listed in table 5.
Table 5
| Embodiment | Reaction temperature/DEG C | 2,5- chlorophenesic acid yield/% | 2,5- chlorophenesic acid selectivity/% | 1,4- chlorophenesic acid conversion ratio/% |
| 25 | 30 | 12.7 | 29.8 | 42.7 |
| 26 | 50 | 16.6 | 25.5 | 65.3 |
| 27 | 70 | 26.0 | 33.2 | 78.4 |
| 28 | 80 | 20.8 | 24.4 | 85.3 |
Embodiment 29-35: 0.4 g Fe/HAC-3,6.63 mmol paracide, 10 mL second are added into round-bottomed flask respectively
Nitrile.30% H of 10 mL is added in conical flask2O2Solution is loaded by peristaltic pump uniform speed slow into round-bottomed flask, when water-bath pot temperature
Round-bottomed flask is placed in water bath when spending constant to 60 DEG C, peristaltic pump starts simultaneously at sample-adding, and 5 min add before setting time
It is complete, it is stirred for 5 min later.Natural cooling after reaction, decompression separation catalyst, is washed with acetonitrile, and constant volume holds in 100 mL
As a result measuring bottle is listed in table 6 using efficient liquid phase chromatographic analysis product.
Table 6
| Embodiment | Reaction time/min | 2,5- chlorophenesic acid yield/% | 2,5- chlorophenesic acid selectivity/% | 1,4- chlorophenesic acid conversion ratio/% |
| 29 | 10 | 15.7 | 25.8 | 61.0 |
| 30 | 30 | 22.2 | 36.1 | 61.5 |
| 31 | 45 | 26.7 | 40.3 | 66.4 |
| 32 | 90 | 30.5 | 42.1 | 72.4 |
| 33 | 120 | 30.9 | 41.0 | 75.3 |
| 34 | 240 | 12.1 | 14.1 | 85.7 |
| 35 | 280 | 12.4 | 14.5 | 85.3 |
Embodiment 36-44: 0.4 g Fe/HAC-3,6.63mmol paracide, 10 mL second are added into round-bottomed flask respectively
Nitrile, 10 mL H2O2.Round-bottomed flask is placed in water bath reaction certain time when constant to 60 DEG C of water bath temperature.Reaction
Natural cooling afterwards, decompression separation catalyst, is washed with acetonitrile, and constant volume is divided in 100 mL volumetric flasks using high performance liquid chromatography
As a result division object is listed in table 7.
Table 7
| Embodiment | Reaction time/min | 2,5- chlorophenesic acid yield/% | 2,5- chlorophenesic acid selectivity/% | 1,4- chlorophenesic acid conversion ratio/% |
| 36 | 10 | 25.2 | 51.2 | 49.2 |
| 37 | 30 | 30.4 | 52.3 | 58.2 |
| 38 | 60 | 32.6 | 52.4 | 62.3 |
| 39 | 90 | 35.1 | 51.2 | 68.5 |
| 40 | 120 | 37.3 | 49.4 | 75.4 |
| 41 | 150 | 19.1 | 25.2 | 75.8 |
| 42 | 200 | 14.9 | 19.5 | 76.7 |
| 43 | 260 | 14.3 | 18.3 | 78.0 |
| 44 | 300 | 14.3 | 17.6 | 81.4 |
Claims (9)
1. a kind of by activated carbon containing iron catalytic hydroxylation Isosorbide-5-Nitrae-dichloro-benzenes preparation 2,5- chlorophenesic acid method, it is characterised in that:
With nitric acid, H2O2The active carbon of processing is catalyst carrier, and the active component Fe (NO of different quality is introduced by infusion process3)3,
Fe/AC catalyst is made and is used for subsequent reactions.
2. reaction is using Isosorbide-5-Nitrae-dichloro-benzenes as substrate, acetonitrile is solvent, H2O2For oxidant.
It is carried out 3. reacting in the round-bottomed flask for be connected with reflux condensate device, wherein 30% H2O2Solution by peristaltic pump constant speed delay into
In sample or disposable sample-adding to round-bottomed flask, reaction is persistently heated with stirring to certain time, and 2,5- chlorophenesic acid is made.
4. the active carbon that the method is related to includes active fruit shell carbon, rice hull active carbon, cocoanut active charcoal and wild jujube active carbon etc..
5. method according to claim 1, it is characterised in that iron content is 0-0.05mmol/g in catalyst.
6. method according to claim 1, it is characterised in that paracide and Fe/AC mass ratio 1:0.1-1:0.5.
7. method according to claim 1, it is characterised in that paracide and H2O2Molar ratio is 1:1.5-1:29.6.
8. method according to claim 1, it is characterised in that reaction temperature is 30-80 DEG C.
9. method according to claim 1, feature is 10-300 min in the reaction time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811086480.2A CN109134203A (en) | 2018-09-18 | 2018-09-18 | A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811086480.2A CN109134203A (en) | 2018-09-18 | 2018-09-18 | A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109134203A true CN109134203A (en) | 2019-01-04 |
Family
ID=64814822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811086480.2A Pending CN109134203A (en) | 2018-09-18 | 2018-09-18 | A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134203A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642678A (en) * | 2019-10-29 | 2020-01-03 | 常州大学 | Method for preparing 2, 5-dichlorophenol by continuously oxidizing p-dichlorobenzene |
| CN110787832A (en) * | 2019-11-21 | 2020-02-14 | 怀化学院 | Preparation method and application of MOF-5-based microporous carbon catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648562A (en) * | 1994-08-03 | 1997-07-15 | Sandoz Ltd. | Oxidation process |
| CN101092332A (en) * | 2006-06-19 | 2007-12-26 | 四川大学 | Method for preparing methyl phenol from methylbenzene through catalytic oxidation in one step |
| CN102463124A (en) * | 2010-11-11 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing phenol from benzene by one-step method |
| CN104876805A (en) * | 2015-06-15 | 2015-09-02 | 江苏蓝丰生物化工股份有限公司 | Preparation process for mass production of 2, 5-dichlorophenol |
| CN107129426A (en) * | 2016-02-29 | 2017-09-05 | 南京工业大学 | Preparation method of 2, 5-dichlorophenol |
-
2018
- 2018-09-18 CN CN201811086480.2A patent/CN109134203A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648562A (en) * | 1994-08-03 | 1997-07-15 | Sandoz Ltd. | Oxidation process |
| CN101092332A (en) * | 2006-06-19 | 2007-12-26 | 四川大学 | Method for preparing methyl phenol from methylbenzene through catalytic oxidation in one step |
| CN102463124A (en) * | 2010-11-11 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing phenol from benzene by one-step method |
| CN104876805A (en) * | 2015-06-15 | 2015-09-02 | 江苏蓝丰生物化工股份有限公司 | Preparation process for mass production of 2, 5-dichlorophenol |
| CN107129426A (en) * | 2016-02-29 | 2017-09-05 | 南京工业大学 | Preparation method of 2, 5-dichlorophenol |
Non-Patent Citations (1)
| Title |
|---|
| 钟永科等: "活性炭载铁催化剂作用下几种典型芳烃一步氧化羟基化反应研究", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642678A (en) * | 2019-10-29 | 2020-01-03 | 常州大学 | Method for preparing 2, 5-dichlorophenol by continuously oxidizing p-dichlorobenzene |
| CN110787832A (en) * | 2019-11-21 | 2020-02-14 | 怀化学院 | Preparation method and application of MOF-5-based microporous carbon catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101973940B (en) | Continuously synthesizing method of sulfonic acid alkyl group ionic liquid | |
| CN105921161B (en) | A kind of catalyst and preparation method thereof preparing 2,5- chlorophenesic acids for paracide hydroxylating | |
| CN109134203A (en) | A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation | |
| CN102060738A (en) | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof | |
| CN103394370B (en) | Silica gel supported sulfonic acid dual-core ionic liquid catalyst, preparation method and application | |
| CN101773840B (en) | Method for hydrothermal synthesis of carbon-silicon composite solid acid catalyst | |
| CN102728403B (en) | Organic solid base catalyst for synthesizing alpha-cyanoethyl cinnamate, and preparation method and application thereof | |
| CN109761851A (en) | A kind of preparation method of isophthalodinitrile | |
| CN106946800B (en) | A kind of synthetic method of -2,4 (1H, 3H)-diketone of quinazoline and its derivative | |
| CN106892790A (en) | Method for preparing deuterated aniline compound by using microchannel reaction device | |
| CN106582749A (en) | Cs-VPO/SiO2 catalyst, preparation method therefor and use of Cs-VPO/SiO2 catalyst in preparation of acrylic acid through catalyzing condensation of acetic acid and trioxymethylene | |
| CN104383965A (en) | Metal-organic framework immobilized tungsten oxide catalyst for synthesizing glutaraldehyde and production method of metal-organic framework immobilized tungsten oxide catalyst | |
| CN106905350B (en) | The preparation method and its catalyst for preparing of a kind of thiazole simultaneously [3,2- α] pyridine derivate | |
| CN102432464A (en) | Continuous production process for dimethyl fumarate | |
| CN102259008B (en) | Solid acid catalyst for esterification reaction and preparation method thereof | |
| CN111943819A (en) | Method for preparing deca-dialdehyde intermediate | |
| CN105367535B (en) | A kind of method that green catalysis synthesizes 1,8 dioxo decahydro acridine derivatives | |
| CN107011211A (en) | A kind of preparation method of para-Phthalonitrile | |
| CN106554255A (en) | A kind of preparation method of 2,6 orcin | |
| CN111701621B (en) | Synthesis of coordination type zirconium o-benzenetrisol and application of coordination type zirconium o-benzenetrisol in preparation of cyclohexanol | |
| CN104525252A (en) | Immobilized ionic liquid solid acid catalyst and preparation method thereof | |
| CN109622031A (en) | The preparation method of 2- hydroxyphosphonoacetic acid zirconium and its application in furfuryl alcohol synthesis | |
| CN104525271A (en) | Ionic liquid supported magnetic iron oxide solid acid catalyst and preparation method thereof | |
| CN110016042B (en) | Method for preparing 1, 4-dihydropyrido [3, 2-c ] [5, 6-c ] dicoumarin derivative through catalysis | |
| WO2020186421A1 (en) | Coordinate zirconium phosphotungstate catalyst and use thereof in catalytic hydrogenation of furfural |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190104 |
|
| WD01 | Invention patent application deemed withdrawn after publication |