CN100529190C - O-nitrophenol electrolyzing reduction process for preparing O-aminophenol - Google Patents
O-nitrophenol electrolyzing reduction process for preparing O-aminophenol Download PDFInfo
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- CN100529190C CN100529190C CNB2006101180115A CN200610118011A CN100529190C CN 100529190 C CN100529190 C CN 100529190C CN B2006101180115 A CNB2006101180115 A CN B2006101180115A CN 200610118011 A CN200610118011 A CN 200610118011A CN 100529190 C CN100529190 C CN 100529190C
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- nitrophenol
- aminophenol
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Abstract
The present invention relates to the process of electrolytically reducing o-nitrophenol in an H-type electrolytic bath for preparing o-aminophenol, and features that small amount of quaternary ammonium salt additive into the cathode chamber. In the electrolytic bath with copper plate cathode, lead plate anode, cathode solution of sodium hydroxide and anode solution of sulfuric acid, and at the conditions of reaction temperature of 30-80 deg.c and current density of 100-3000 A/sq m, the present invention can reach current efficiency and conversion rate over 70, over 20 percentage points higher than that of using non-alkaline solution as cathode solution or no additive.
Description
Technical field
The present invention relates to the preparation method of o-aminophenol, relate in particular to the method that the electrolysis o-nitrophenol prepares o-aminophenol.
Background technology
O-aminophenol (Ortho-Aminophenol) has another name called the 2-amino-phenol, and molecular formula is C
6H
7NO is a kind of important chemical intermediate, is widely used in dyestuff, medicine, press and biological technical field.At present, the production of o-aminophenol mainly is by reduction method, comprises the chemical reduction and the electrolytic reduction of o-nitrophenol.Wherein electrolytic reduction have with sulfuric acid as catholyte, have with sodium hydroxide as catholyte, as reference: Gao Quanchang etc. electrolytic process is synthesized Ortho-Aminophenol. chemical reagent, 1995,17:(6), 365～366,386.
The chemical reduction method productive rate is low, and product purity is low, and is difficult to separate, and pollutes greatlyyer, seldom is used now.And the current efficiency of electrolytic reduction and transformation efficiency are not high yet.Add phase-transfer catalyst and can improve the efficient of reaction, but can reduce degree of purity of production.Therefore, wish to get the electrolytic reaction and the highly purified product of higher conversion and current efficiency, need in reaction system, to add additive.
Summary of the invention
The object of the present invention is to provide a kind of mode that in reaction solution, adds trace mineral supplement to carry out the method that the direct electrolytic reduction of o-nitrophenol prepares o-aminophenol, to improve the current efficiency and the transformation efficiency of electrolytic process.
Design of the present invention is such:
(1) uses basic solution as electrolyte solution, thereby the raw material o-nitrophenol is existed with ionic species in solution.
(2) in cathode solution, add trace mineral supplement, reduce the electrode evolving hydrogen reaction, thereby improve the current efficiency and the transformation efficiency of o-aminophenol, need not again to separate again simultaneously.
According to above-mentioned design, the present invention proposes technical scheme as described below:
A kind of method of o-nitrophenol electrolytic reduction system o-aminophenol is characterized in that, described method is following steps:
1, the cathodic reduction of o-nitrophenol: with basic solution, raw material o-nitrophenol and additive mixing cathode compartment as the disposable whole input H grooves of catholyte, the concentration that makes raw material o-nitrophenol in the catholyte is 0.05～0.5mol/L, and content of additive is 0.005～1% of a raw material o-nitrophenol quality; The pH value of catholyte is 7～14, stirs with agitator anticathode liquid, is that 10%～30% sulphuric acid soln drops in the anolyte compartment as anolyte simultaneously with mass percent, the volume of anolyte is an amount of, under 30～80 ℃, logical direct current carries out electrolysis, and current density is 100～3000A/m
2, at this moment, the electro-reduction reaction that takes place on negative electrode is:
C
6H
5NO
3+6H
++6e
-→C
6H
7NO+2H
2O
After reaching the required theoretical electrolysis time of complete reaction conduction time, stop energising, take out catholyte;
Wherein, used additive is a quaternary ammonium salt, and its general formula is as follows:
Wherein R1, R2, R3, R4 are a kind of in methyl, ethyl, propyl group, butyl, heptyl, octyl group, dodecyl or the hexadecyl, and X is a kind of in halogen, hydroxide radical, nitrate radical, sulfate radical or the carbonate,
2, make o-aminophenol: the catholyte after the electrolysis in the step 1) is neutralized to neutrality, leaves standstill, suction filtration with cold distilled water washing 2 times, is product o-aminophenol solid after the drying.
In the technique scheme, the pH value of catholyte is preferred 10～14,
The total carbon atom number of quaternary ammonium salt additive is preferably 8～20;
Preferred 1000～the 2500A/m of current density
2
Using alkali solution is to keep the raw material o-nitrophenol to exist with ionic species in whole electrolytic process as the reason of electrolytic solution, so that additive plays a role.The pH value of catholyte will produce significant effects to the effect of reaction, when the pH value of catholyte is 7～14, be preferably at 10～14 o'clock, and the current efficiency of o-aminophenol and transformation efficiency have improved more than 20% during all than not doping.
The effect that additive adds mainly is: (1) combines with electrode, forms the positive charge layer at cathode surface, helps electronegative raw material ionic adsorption to electrode surface; (2) the electrostatic double layer current potential of change electrode surface reduces reaction required energy takes place; (3) form ion pair with the raw material ion, drag raw material arrival electrode surface and react.
The best total carbon atom number of additive is 8～20.Total carbon atom number can not form the good adsorption layer at electrode surface very little; Total carbon atom number is too many, and then the resistance that forms at electrode surface turns into too big, is unfavorable for the carrying out that reacts.
Content of additive is 0.005～1% of a raw material o-nitrophenol quality, and this content promptly can produce significantly influence to reaction efficiency, need not to carry out the separation of the finished product again again; Raw materials used o-nitrophenol is an analytical reagent, and its purity 〉=99% can reduce the anticathode pollution of impurity like this.。
Electrolysis temperature is 30～80 ℃, and temperature is crossed low the carrying out that react of will being unfavorable for, and the too high a large amount of generations that will cause side reaction of temperature.
Current density is 100～3000A/m
2, be preferably in 1000～2500A/m
2, electrolytic process is remained under the higher electrolytic efficiency, the transformation efficiency of final o-nitrophenol reaches more than 70%.
Above-mentioned electrolyzer is a conventional equipment.
Involved in the present invention to current efficiency and transformation efficiency be defined as:
The electric weight of current efficiency=theoretical electric weight/generation unit mole o-aminophenol actual consumption that generation unit mole o-aminophenol consumes
The o-nitrophenol amount (mol) of o-nitrophenol amount (the mol)/adding of transformation efficiency=react away
Beneficial effect
By above-mentioned disclosed technical scheme as seen, the present invention has following advantage:
At catholyte is under the alkaline condition, only need in the cathode compartment that electro-reduction reaction takes place, to add the micro-quaternary ammonium salt additive that is equivalent to raw materials quality 0.005～1%, just can make the o-nitrophenol electroreduction generate the current efficiency of o-aminophenol reaction and transformation efficiency and be greatly enhanced when not adding additive.
Description of drawings
Fig. 1 is the electrolyzer figure of o-nitrophenol electrolytic reduction system o-aminophenol.
1---anode 2---negative electrode 3---thermometer 4---H type electrolyzer
5---stirrer 6---agitator 7---ionic membrane 8---pads
Wherein: anode 1 is highly purified plate stereotype, and negative electrode 2 is plate copper coin.
Below in conjunction with accompanying drawing related content of the present invention is described in more detail. As seen from Figure 1, at first anolyte is joined the left end (anode chamber) of H groove 4, again with the right-hand member (cathode chamber) of the disposable whole input H grooves 4 of catholyte, and stir with magnetic stirring apparatus 6, then logical direct current carries out electrolysis, electro-reduction reaction occurs at negative electrode 2, generate the product o-aminophenol, and monitor the temperature of reaction with super constant temperature trough and thermometer, after electrolysis a period of time, catholyte is poured in the beaker into cooling from electrolytic cell, utilize the diazo-reaction analysis, the current efficiency that obtains ortho-nitrophenol reaches more than 70%. At last, catholyte is neutralized to neutrality, leaves standstill, suction filtration with cold distilled water washing 2 times, is product o-aminophenol solid after the drying.
The present invention is further illustrated by the following examples.As can be seen, behind the adding additive, the current efficiency and the transformation efficiency of reaction all descend in acidic solution from Comparative Examples 1 and Comparative Examples 2.Contrast as can be seen from Comparative Examples 3 and embodiment 1,2,3, behind the adding additive, the current efficiency and the transformation efficiency of reaction all are improved in basic solution.
Comparative Examples 1
All percentage compositions are the quality percentage composition among the embodiment.
As anode, dull and stereotyped copper is as negative electrode with dull and stereotyped lead, and wherein the copper coin usable floor area is 14cm
2(3.5 * 4cm).With ion-exchange membrane as barrier film.Anolyte was 20% sulphuric acid soln for 200ml concentration when electrolysis began, and catholyte is 20% sulphuric acid soln and 15 gram o-nitrophenols for 250ml concentration.Stir with magnetic stirring apparatus anticathode liquid.Institute's galvanization is 4.0A, and current density is 2857A/m
2The catholyte liquid temp is 60 ± 2 ℃.Be 4 hours 20 minutes actual conduction time.The electrolysis result is as follows:
| Bath voltage (V) | Catholyte volume (ml) | Current efficiency (%) | Transformation efficiency (%) | |
| Experiment 1 | 13.4 | 258.0 | 46.28 | 38.02 |
| Experiment 2 | 12.9 | 253.0 | 43.89 | 36.12 |
Comparative Examples 2
Electrode, anolyte, current density, electrolysis temperature, electrolysis time and barrier film are with embodiment 1.Catholyte was that 20% sulphuric acid soln, 15 gram o-nitrophenols and 9ml concentration are the tetrabutyl phosphonium bromide ammonium solution of 0.5g/L for 250ml concentration when electrolysis began.The electrolysis result is as follows:
| Bath voltage (V) | Catholyte volume (ml) | Current efficiency (%) | Transformation efficiency (%) | |
| Experiment 1 | 13.9 | 249.0 | 36.56 | 29.86 |
| Experiment 2 | 14.2 | 256.0 | 35.40 | 28.75 |
Comparative Examples 3
Electrode and barrier film are with embodiment 1.Anolyte was 15% sulphuric acid soln for 200ml concentration when electrolysis began, and catholyte is sodium hydroxide solution and the 6 gram o-nitrophenols of 2mol/L for 250ml concentration.Stir with magnetic stirring apparatus anticathode liquid.Institute's galvanization is 3.0A, and current density is 2143A/m
2The catholyte liquid temp is 50 ± 2 ℃.Be 2 hours 20 minutes actual conduction time.The electrolysis result is as follows:
| Bath voltage (V) | Catholyte volume (ml) | Current efficiency (%) | Transformation efficiency (%) | |
| Experiment 1 | 13.4 | 254.0 | 48.36 | 45.80 |
| Experiment 2 | 13.2 | 260.0 | 50.37 | 47.85 |
Embodiment 1
Electrode, anolyte, current density, electrolysis temperature, electrolysis time and barrier film are with Comparative Examples 3.Catholyte was that sodium hydroxide solution, 6 gram o-nitrophenols and the 9ml concentration of 2mol/L are the tetrabutyl phosphonium bromide ammonium solution of 0.5g/L for 250ml concentration when electrolysis began.The electrolysis result is as follows:
| Bath voltage (V) | Catholyte volume (ml) | Current efficiency (%) | Transformation efficiency (%) | |
| Experiment 1 | 13.4 | 254.0 | 83.47 | 79.19 |
| Experiment 2 | 13.2 | 259.0 | 85.13 | 80.77 |
Embodiment 2
Electrode, anolyte, current density, electrolysis temperature, electrolysis time and barrier film are with Comparative Examples 3.Catholyte was that sodium hydroxide solution, 6 gram o-nitrophenols and the 5ml concentration of 2mol/L are the tetramethyl ammonium hydroxide solution of 0.5g/L for 250ml concentration when electrolysis began.The electrolysis result is as follows:
| Bath voltage (V) | Catholyte volume (ml) | Current efficiency (%) | Transformation efficiency (%) | |
| Experiment 1 | 13.4 | 250.0 | 78.06 | 74.06 |
| Experiment 2 | 13.1 | 253.0 | 76.54 | 72.62 |
Embodiment 3
Electrode, anolyte, current density, electrolysis temperature, electrolysis time and barrier film are with Comparative Examples 3.Catholyte was that sodium hydroxide solution, 6 gram o-nitrophenols and the 5ml concentration of 2mol/L are the cetyl trimethylammonium bromide solution of 0.5g/L for 250ml concentration when electrolysis began.The electrolysis result is as follows:
| Bath voltage (V) | Catholyte volume (ml) | Current efficiency (%) | Transformation efficiency (%) | |
| Experiment 1 | 13.6 | 256.0 | 75.42 | 71.55 |
| Experiment 2 | 13.2 | 252.0 | 74.69 | 70.86 |
Claims (4)
1, a kind of method of o-nitrophenol electrolytic reduction system o-aminophenol is characterized in that, described method is following steps:
1), the cathodic reduction of o-nitrophenol: with basic solution, raw material o-nitrophenol and additive mix the cathode compartment as the disposable whole input H type electrolyzers of catholyte, the concentration that makes raw material o-nitrophenol in the catholyte is 0.05～0.5mol/L, content of additive is 0.005～1% of a raw material o-nitrophenol quality, the pH value of catholyte is 7～14, stir with agitator anticathode liquid, be that 10%～30% sulphuric acid soln drops in the anolyte compartment as anolyte simultaneously with mass percent, under 30～80 ℃, logical direct current carries out electrolysis, and current density is 100～3000A/m
2, at this moment, the electro-reduction reaction that takes place on negative electrode is:
C
6H
5NO
3+6H
++6e
-→C
6H
7NO+2H
2O
After reaching the required theoretical electrolysis time of complete reaction conduction time, stop energising, take out catholyte,
Wherein, used additive is a quaternary ammonium salt, and its general formula is as follows:
Wherein R1, R2, R3, R4 are a kind of in methyl, ethyl, propyl group, butyl, heptyl, octyl group, dodecyl or the hexadecyl, and X is a kind of in halogen, hydroxide radical, nitrate radical, sulfate radical or the carbonate; 2), get o-aminophenol: the catholyte after the electrolysis in the step 1) is neutralized to neutrality, leaves standstill, suction filtration with cold distilled water washing 2 times, is product o-aminophenol solid after the drying.
2, the method for o-nitrophenol electrolytic reduction system o-aminophenol as claimed in claim 1 is characterized in that, described method steps 1) in the pH value of catholyte be 10～14.
3, the method for o-nitrophenol electrolytic reduction system o-aminophenol as claimed in claim 1 is characterized in that, described method steps 1) in current density be 1000～2500A/m
2
4, the method for o-nitrophenol electrolytic reduction system o-aminophenol as claimed in claim 1 is characterized in that, described method steps 1) in the total carbon atom number of quaternary ammonium salt additive be 8～20.
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| CN100529190C true CN100529190C (en) | 2009-08-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747489A (en) * | 2019-11-07 | 2020-02-04 | 湖南大学 | Electroreduction preparation method of intermediate of anticancer drug gefitinib and analogue thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731650B (en) * | 2014-12-09 | 2018-04-03 | 南京理工大学 | Completely biological control nitrophenol enhanced electrochemical degradation method |
| CN114752952B (en) * | 2022-04-14 | 2024-07-19 | 浙江大学 | Electrocatalytic nitrogen fixation device and method for simultaneously generating nitric acid and ammonia double products |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1132617A (en) * | 1965-12-28 | 1968-11-06 | Miles Lab | Electrolytic reduction process using anhydrous electrolyte |
| US3475300A (en) * | 1966-02-02 | 1969-10-28 | Miles Lab | Process utilizing ion exchange membrane for electrolytic reduction of aromatic nitro compounds |
| GB1421118A (en) * | 1971-11-16 | 1976-01-14 | Albright & Wilson | Electrolytic reduction of nitrosophenols |
| CN1342785A (en) * | 2001-07-10 | 2002-04-03 | 华东理工大学 | Process for preparing p-aminophenol by electrolytic reduction of nitrobenzene |
-
2006
- 2006-11-03 CN CNB2006101180115A patent/CN100529190C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1132617A (en) * | 1965-12-28 | 1968-11-06 | Miles Lab | Electrolytic reduction process using anhydrous electrolyte |
| US3475300A (en) * | 1966-02-02 | 1969-10-28 | Miles Lab | Process utilizing ion exchange membrane for electrolytic reduction of aromatic nitro compounds |
| GB1421118A (en) * | 1971-11-16 | 1976-01-14 | Albright & Wilson | Electrolytic reduction of nitrosophenols |
| CN1342785A (en) * | 2001-07-10 | 2002-04-03 | 华东理工大学 | Process for preparing p-aminophenol by electrolytic reduction of nitrobenzene |
Non-Patent Citations (2)
| Title |
|---|
| "电解法合成邻氨基苯酚". 高全昌，陈拴虎，石进超.化学试剂，第17卷第6期. 1995 |
| "电解法合成邻氨基苯酚". 高全昌，陈拴虎，石进超.化学试剂，第17卷第6期. 1995 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747489A (en) * | 2019-11-07 | 2020-02-04 | 湖南大学 | Electroreduction preparation method of intermediate of anticancer drug gefitinib and analogue thereof |
| CN110747489B (en) * | 2019-11-07 | 2021-05-07 | 湖南大学 | Electroreduction preparation method of intermediate of anticancer drug gefitinib and analogue thereof |
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