CN106187787B - A kind of preparation method of 2- amino -4- chlorodiphenyl ether - Google Patents
A kind of preparation method of 2- amino -4- chlorodiphenyl ether Download PDFInfo
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- CN106187787B CN106187787B CN201610517329.4A CN201610517329A CN106187787B CN 106187787 B CN106187787 B CN 106187787B CN 201610517329 A CN201610517329 A CN 201610517329A CN 106187787 B CN106187787 B CN 106187787B
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Abstract
The invention discloses a kind of preparation methods of 2- amino -4- chlorodiphenyl ether, the following steps are included: dispersing 2- nitro -4- chlorodiphenyl ether, Iron trichloride hexahydrate and active carbon in ethyl alcohol, then plus alkali adjusts pH to 7~9, hydrazine hydrate is added dropwise in a heated condition and carries out reduction reaction, after reaction, the 2- amino -4- chlorodiphenyl ether is obtained after post treatment.The preparation method reaction condition is mild, easily-controllable, and consersion unit is simple, and used catalyst and solvent can be recycled repeatedly, environmentally friendly, stable product quality, and purity is good, and high income is advantageously implemented large-scale production.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of -4 chlorodiphenyl ether of hydrazine hydrate reduction 2- nitro preparation 2- amino -
The method of 4- chlorodiphenyl ether.
Background technique
2- amino -4- chlorodiphenyl ether (CAS:93-67-4,5-Chloro-2-phenoxyaniline, molecular weight:
219.67), structural formula is as follows:
2- amino -4- chlorodiphenyl ether is a kind of important acid dyes intermediate, mainly for the production of Acid Red 249, acid
Red 149, Blue VRS 28 of property etc.,
The reduction that current 2- amino -4- chlorodiphenyl ether generally passes through -4 chlorodiphenyl ether of 2- nitro is prepared, mainly have with
Lower two methods:
(1) iron powder reducing method, the disadvantage of the method are exactly to need using a large amount of iron powders, generate a large amount of iron cement, dirty
Dye is serious, very unfriendly to environment.
(2) catalytic hydrogenation method, the method is environmentally friendly, three-waste free pollution, but due to hydroconversion condition harshness, risk compared with
Height, therefore the requirement to equipment is very high, once invests larger, unfavorable commercial introduction.
The Chinese patent application of 103086897 A of Publication No. CN discloses a kind of hydrazine hydrate reduction o-aminodiphenyl ether
The method for preparing o-nitrodiphenyl ether, the method steps are as follows: in reaction flask, o-aminodiphenyl ether, catalyst and water is added,
It stirs, be warming up to 70-100 DEG C, in the hydrazine hydrate that concentration is 85% in 1-2 hours, is added dropwise, keep the temperature 3-6 hours, reaction terminates
Afterwards, it is down to room temperature, concentrated hydrochloric acid is slowly added dropwise under stirring, tune pH value is 1-2, filtering, washing, the cooling of filtrate ice bath, 0-5 DEG C of stirring
Under, 30% sodium hydroxide is slowly instilled, adjusting pH value is 7, has precipitating to generate, and filters after continuing cooling 1 hour, obtains adjacent aminodiphenyl
Ether.
Summary of the invention
The present invention provides a kind of preparation methods of 2- amino -4- chlorodiphenyl ether, and the preparation method is easy to operate, meanwhile,
Reaction efficiency is high.
A kind of preparation method of 2- amino -4- chlorodiphenyl ether, comprising the following steps:
It disperses 2- nitro -4- chlorodiphenyl ether, Iron trichloride hexahydrate and active carbon in ethyl alcohol, then plus alkali adjusts pH to 7
~9, hydrazine hydrate is added dropwise in a heated condition and carries out reduction reaction, after reaction, obtains the 2- amino-after post treatment
4- chlorodiphenyl ether.
In the present invention, replaces water as reaction dissolvent by using ethyl alcohol, reduce the side reaction of reduction reaction, improve
Reaction yield.Meanwhile by the direct in the reaction system of reduction reaction, the operation is more convenient.
The reaction equation of the reduction reaction is as follows:
In the present invention, the quality of the Iron trichloride hexahydrate is the 10%~20% of 2- nitro -4- chlorodiphenyl ether quality, living
Property charcoal and Iron trichloride hexahydrate mass ratio be 0.5~2:1.The catalyst of the dosage can guarantee reaction with the progress of higher efficiency.
Preferably, the volume mass ratio of the ethyl alcohol and 2- nitro -4- chlorodiphenyl ether is 1-5ml/g.
Preferably, the alkali is liquid alkaline, piece alkali, sodium bicarbonate, soda ash or ammonium hydroxide.
Preferably, the molar ratio of the 2- nitro -4- chlorodiphenyl ether and hydrazine hydrate is 1:1.5~2.
Preferably, heating temperature is 80-90 DEG C, hydrazine hydrate time for adding is 2~3 hours, and the reaction time is 3~4 small
When.
Preferably, the post-processing includes: filtering reacting liquid while hot, obtained solid catalyst recovery；
Obtained filtrate adds water and stirs layering, obtains product by being distilled to recover ethyl alcohol, evaporated mother liquor.
Preferably, directly adding adjusting PH with base value when recovery, do not need that Iron trichloride hexahydrate and active carbon is added.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) conversion ratio of reaction is improved as reaction dissolvent by using ethyl alcohol, and ethyl alcohol can return after completion of the reaction
Receipts are applied, and waste water caused by aqueous phase reactions is substantially reduced；
(2) reaction condition is mild, easily-controllable, and consersion unit is simple, and used catalyst can be recycled repeatedly, to environment friend
Good, stable product quality, purity is good, high income, is advantageously implemented large-scale production.
Specific embodiment
Implement to be intended to illustrate invention rather than limitation of the invention further below.
Embodiment 1
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity is added
Charcoal 5g is stirred and is adjusted pH value to 7.3 with 7g liquid alkaline (sodium hydrate aqueous solution that mass percent concentration is 30%), is warming up to
80-90 DEG C, it is 85% hydrazine hydrate 13g that mass percent concentration, which is slowly added dropwise, in system at reflux, is dripped off within about 2 hours, after
Continuous reflux is filtered while hot after 3 hours, after filtrate is distilled to recover alcohol, is added water and stirred 30 minutes, and it is shallow that standing liquid separation obtains 24.85g
Brown oil product, 2- amino -4- chlorodiphenyl ether purity are 99.04%, content 98.65%, product yield 92.82%.
Embodiment 2
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity is added
Charcoal 5g stirs and adjusts pH value to 9.5 with 9g liquid alkaline (30%), is warming up to 80-90 DEG C, system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 13g, is dripped off within about 2 hours, is filtered while hot after continuing reflux 3 hours, after filtrate is distilled to recover alcohol, is added
Water stirs 30 minutes, stands liquid separation and obtains 21.88g dark-brown product, 2- amino -4- chlorodiphenyl ether purity is 94.74%, content
It is 91.55%, product yield 75.85%.
Embodiment 3
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity is added
Charcoal 5g stirs and adjusts pH value to 7.5 with 7g liquid alkaline (30%), is warming up to 80-90 DEG C, system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 12g, is dripped off within about 2 hours, is filtered while hot after continuing reflux 3 hours, after filtrate is distilled to recover alcohol, is added
Water stirs 30 minutes, stands liquid separation and obtains 22.80g light brown product, 2- amino -4- chlorodiphenyl ether purity is 98.76%, content
It is 95.77%, product yield 82.27%.
Embodiment 4
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity is added
Charcoal 5g stirs and adjusts pH value to 7.1 with 7g liquid alkaline (30%), is warming up to 80-90 DEG C, system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 14g, is dripped off within about 2 hours, is filtered while hot after continuing reflux 3 hours, after filtrate is distilled to recover alcohol, is added
Water stirs 30 minutes, stands liquid separation and obtains 23.94g light brown product, 2- amino -4- chlorodiphenyl ether purity is 98.47%, content
It is 96.63%, product yield 87.59%.
Embodiment 5
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 3g, activity is added
Charcoal 5g stirs and adjusts pH value to 7.3 with 4.2g liquid alkaline (30%), is warming up to 80-90 DEG C, system is slowly dripped at reflux
Adding concentration is 85% hydrazine hydrate 13g, is dripped off within about 2 hours, is filtered while hot after continuing reflux 3 hours, after filtrate is distilled to recover alcohol,
It adds water and stirs 30 minutes, stands liquid separation and obtain 22.11g dark-brown product, 2- amino -4- chlorodiphenyl ether purity only has 52.58%.
Embodiment 6
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 6g, activity is added
Charcoal 5g stirs and adjusts pH value to 7.5 with 8.4g liquid alkaline (30%), is warming up to 80-90 DEG C, system is slowly dripped at reflux
Adding concentration is 85% hydrazine hydrate 13g, is dripped off within about 2 hours, is filtered while hot after continuing reflux 3 hours, after filtrate is distilled to recover alcohol,
It adds water and stirs 30 minutes, stands liquid separation and obtain 24.58g light brown oil product, 2- amino -4- chlorodiphenyl ether purity is
98.89%, content 98.23%, product yield 91.40%.
Embodiment 7
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity is added
Charcoal 3g stirs and adjusts pH value to 7.1 with 7g liquid alkaline (30%), is warming up to 80-90 DEG C, system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 13g, is dripped off within about 2 hours, is filtered while hot after continuing reflux 3 hours, after filtrate is distilled to recover alcohol, is added
Water stirs 30 minutes, stands liquid separation and obtains 23.80g light brown oil product, and 2- amino -4- chlorodiphenyl ether purity is 98.09%,
Content is 97.00%, product yield 87.41%.
Embodiment 8
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity is added
Charcoal 5g stirs and adjusts pH value to 8.2 with 7.2g liquid alkaline (30%), is warming up to 80-90 DEG C, system is slowly dripped at reflux
Adding concentration is 85% hydrazine hydrate 13g, is dripped off within about 2 hours, is filtered while hot after continuing reflux 3 hours, and catalyst, filtrate distillation are recycled
It after recovered alcohol, adds water and stirs 30 minutes, stands liquid separation and obtain 23.83g light brown oil product, 2- amino -4- chlorodiphenyl ether
Purity is 95.12%, content 96.78%, product yield 87.32%.
Embodiment 9
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL is added, applies and is recycled in embodiment 8
Catalyst, and with 30% hydrochloric acid adjust pH value to 8.1, be warming up to 80-90 DEG C, concentration is slowly added dropwise in system at reflux
It for 85% hydrazine hydrate 13g, drips off within about 2 hours, is filtered while hot after continuing reflux 3 hours, recycle catalyst, filtrate is distilled to recover wine
It after essence, adds water and stirs 30 minutes, stands liquid separation and obtain 24.89g light brown oil product, 2- amino -4- chlorodiphenyl ether purity is
97.90%, content 95.48%, product yield 89.98%.
Embodiment 10
In reaction flask, 2- nitro -4- chlorodiphenyl ether 30g, industrial alcohol 90mL is added, applies and is recycled in embodiment 9
Catalyst, and with 30% hydrochloric acid adjust pH value to 8.1, be warming up to 80-90 DEG C, concentration is slowly added dropwise in system at reflux
It for 85% hydrazine hydrate 13g, drips off within about 2 hours, is filtered while hot after continuing reflux 3 hours, after filtrate is distilled to recover alcohol, water is added to stir
It mixes 30 minutes, stands liquid separation and obtain 25.16g light brown oil product, 2- amino -4- chlorodiphenyl ether purity is 97.90%, content
It is 98.42%, product yield 93.76%.
Claims (3)
1. a kind of preparation method of 2- amino -4- chlorodiphenyl ether, which comprises the following steps:
It disperses 2- nitro -4- chlorodiphenyl ether, Iron trichloride hexahydrate and active carbon in ethyl alcohol, then plus alkali adjusts pH to 7~9,
Hydrazine hydrate is added dropwise in a heated condition and carries out reduction reaction, after reaction, obtains the 2- amino -4- chlorine after post treatment
Diphenyl ether；
The alkali is liquid alkaline, piece alkali, sodium bicarbonate, soda ash or ammonium hydroxide；
The post-processing includes: filtering reacting liquid while hot, obtained solid catalyst recovery；
Obtained filtrate adds water and stirs layering, obtains product by being distilled to recover ethyl alcohol, evaporated mother liquor；
Directly add adjusting PH with base value when recovery, do not need that Iron trichloride hexahydrate and active carbon is added,
The molar ratio of the 2- nitro -4- chlorodiphenyl ether and hydrazine hydrate is 1: 1.5~2,
The mass ratio of the Iron trichloride hexahydrate and 2- nitro -4- chlorodiphenyl ether is 1:6~1:5, activated carbon and Iron trichloride hexahydrate
Mass ratio is 0.5~2: 1.
2. the preparation method of 2- amino -4- chlorodiphenyl ether according to claim 1, which is characterized in that the ethyl alcohol and 2-
The volume mass ratio of nitro -4- chlorodiphenyl ether is 1-5ml/g.
3. the preparation method of 2- amino -4- chlorodiphenyl ether according to claim 1, which is characterized in that heating temperature 80-
90 DEG C, hydrazine hydrate time for adding is 2~3 hours, and the reaction time is 3~4 hours.
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| CN107739312B (en) * | 2017-11-13 | 2020-02-18 | 安徽省化工设计院 | Process and system for producing amine ether by reducing nitroether with hydrazine hydrate |
| CN110003025A (en) * | 2019-04-29 | 2019-07-12 | 天津华津制药有限公司 | The preparation method of 1- [2- hydroxyl -3- amino -5- (benzyloxy) phenyl]-ethyl ketone |
| CN113717035B (en) * | 2021-09-13 | 2024-03-26 | 江苏禾本生化有限公司 | Recycling method of difenoconazole waste intermediate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125027A (en) * | 1974-08-14 | 1976-11-01 | Oosakashi | Novel process for reduction of aromatic nitro compounds |
| EP0065668A2 (en) * | 1981-05-22 | 1982-12-01 | CELAMERCK GmbH & Co. KG | Urea derivatives, their preparation and use |
| CN103086897A (en) * | 2011-10-27 | 2013-05-08 | 天津药物研究院 | Method for preparing o-oxydianiline from reducing o-nitrophenyl ether by hydrazine hydrate |
| CN103539712A (en) * | 2013-10-12 | 2014-01-29 | 浙江闰土研究院有限公司 | P-aminophenyl-beta-hydroxyethyl sulfide preparation method |
| CN103539680A (en) * | 2013-10-23 | 2014-01-29 | 浙江闰土研究院有限公司 | Clean production process of 6-chloro-2,4-dinitroaniline |
-
2016
- 2016-06-29 CN CN201610517329.4A patent/CN106187787B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125027A (en) * | 1974-08-14 | 1976-11-01 | Oosakashi | Novel process for reduction of aromatic nitro compounds |
| EP0065668A2 (en) * | 1981-05-22 | 1982-12-01 | CELAMERCK GmbH & Co. KG | Urea derivatives, their preparation and use |
| CN103086897A (en) * | 2011-10-27 | 2013-05-08 | 天津药物研究院 | Method for preparing o-oxydianiline from reducing o-nitrophenyl ether by hydrazine hydrate |
| CN103539712A (en) * | 2013-10-12 | 2014-01-29 | 浙江闰土研究院有限公司 | P-aminophenyl-beta-hydroxyethyl sulfide preparation method |
| CN103539680A (en) * | 2013-10-23 | 2014-01-29 | 浙江闰土研究院有限公司 | Clean production process of 6-chloro-2,4-dinitroaniline |
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