CN106187787A - A kind of preparation method of 2 amino 4 chlorodiphenyl ethers - Google Patents
A kind of preparation method of 2 amino 4 chlorodiphenyl ethers Download PDFInfo
- Publication number
- CN106187787A CN106187787A CN201610517329.4A CN201610517329A CN106187787A CN 106187787 A CN106187787 A CN 106187787A CN 201610517329 A CN201610517329 A CN 201610517329A CN 106187787 A CN106187787 A CN 106187787A
- Authority
- CN
- China
- Prior art keywords
- amino
- preparation
- chlorodiphenyl ether
- chlorodiphenyl
- ether
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses the preparation method of a kind of 2 amino 4 chlorodiphenyl ethers, comprise the following steps: 2 nitro 4 chlorodiphenyl ethers, Iron trichloride hexahydrate and activated carbon are scattered in ethanol, then alkali regulation pH to 7～9 is added, dropping hydrazine hydrate carries out reduction reaction in a heated condition, after reaction terminates, obtain 2 described amino 4 chlorodiphenyl ethers through post processing.This preparation method reaction condition is gentle, easily-controllable, and consersion unit is simple, and used catalyst and solvent can repeatedly recycle, environmentally friendly, constant product quality, and purity is good, and yield is high, is advantageously implemented large-scale production.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of hydrazine hydrate reduction 2-nitro-4 chlorodiphenyl ether prepare 2-amino-
The method of 4-chlorodiphenyl ether.
Background technology
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 stain intermediate, mainly for the production of Acid Red 249, acid
Property is red 149, Blue VRS 28 etc.,
Current 2-amino-4-chlorodiphenyl ether is typically prepared by the reduction of 2-nitro-4 chlorodiphenyl ether, mainly have with
Lower two kinds of methods:
(1) iron powder reducing method, the disadvantage of the method needs to use a large amount of iron powder exactly, produces substantial amounts of iron cement, dirty
Dye is serious, the most unfriendly to environment.
(2) catalytic hydrogenation method, the method is environmentally friendly, three-waste free pollution, but owing to hydroconversion condition is harsh, danger is relatively
Height, therefore the requirement to equipment is the highest, once invests relatively big, unfavorable commercial introduction.
The Chinese patent application of Publication No. CN 103086897 A discloses a kind of hydrazine hydrate reduction o-aminodiphenyl ether
The method preparing o-nitrodiphenyl ether, the method step is as follows: in reaction bulb, adds o-aminodiphenyl ether, catalyst and water,
Stirring, be warming up to 70-100 DEG C, in 1-2 hour, dropping concentration is the hydrazine hydrate of 85%, is incubated 3-6 hour, and reaction terminates
After, it to be down to room temperature, under stirring, slowly drip concentrated hydrochloric acid, tune pH value is 1-2, filters, washes, and filtrate ice bath is lowered the temperature, 0-5 DEG C of stirring
Under, slowly instill 30% sodium hydroxide, adjusting pH value is 7, has precipitation to generate, and filters, obtain adjacent ADP after continuing cooling 1 hour
Ether.
Summary of the invention
The invention provides the preparation method of a kind of 2-amino-4-chlorodiphenyl ether, this preparation method is easy and simple to handle, meanwhile,
Reaction efficiency is high.
The preparation method of a kind of 2-amino-4-chlorodiphenyl ether, comprises the following steps:
2-nitro-4-chlorodiphenyl ether, Iron trichloride hexahydrate and activated carbon are scattered in ethanol, then add alkali regulation pH to 7
～9, dropping hydrazine hydrate carries out reduction reaction in a heated condition, after reaction terminates, through post processing obtain described 2-amino-
4-chlorodiphenyl ether.
In the present invention, by using ethanol to replace water as reaction dissolvent, reduce the side reaction of reduction reaction, improve
Reaction yield.Meanwhile, by direct in the reaction system of reduction reaction, operate easier.
The reaction equation of this reduction reaction is as follows:
In the present invention, the quality of described Iron trichloride hexahydrate is the 10%～20% of 2-nitro-4-chlorodiphenyl ether quality, lives
Property charcoal and Iron trichloride hexahydrate mass ratio be 0.5～2:1.The catalyst of this consumption ensure that reaction is carried out with higher efficiency.
As preferably, the volume mass of described ethanol and 2-nitro-4-chlorodiphenyl ether is than for 1-5ml/g.
As preferably, described alkali is liquid caustic soda, sheet alkali, sodium bicarbonate, soda or ammonia.
As preferably, described 2-nitro-4-chlorodiphenyl ether is 1:1.5～2 with the mol ratio of hydrazine hydrate.
As preferably, heating-up temperature is 80-90 DEG C, and hydrazine hydrate time for adding is 2～3 hours, and the response time is 3～4 little
Time.
As preferably, described post processing includes: filtered while hot reactant liquor, the solid catalyst recovery obtained；
The filtrate obtained is through Distillation recovery ethanol, and evaporated mother liquor adds water and stirs layering, obtains product.
As preferably, during recovery, directly add adjusting PH with base value, it is not necessary to add Iron trichloride hexahydrate and activated carbon.
Compared with the existing technology, beneficial effects of the present invention is embodied in:
(1) by using ethanol as reaction dissolvent, improve the conversion ratio of reaction, and ethanol can return after completion of the reaction
Receipts are applied mechanically, and are substantially reduced waste water produced by aqueous phase reactions；
(2) reaction condition is gentle, easily-controllable, and consersion unit is simple, and used catalyst can repeatedly recycle, to environment friend
Good, constant product quality, purity is good, and yield is high, is advantageously implemented large-scale production.
Detailed description of the invention
Hereinafter implement to be intended to illustrate rather than limitation of the invention further.
Embodiment 1
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity
Charcoal 5g, stirs and with 7g liquid caustic soda (mass percent concentration is the sodium hydrate aqueous solution of 30%) regulation pH value to 7.3, is warming up to
80-90 DEG C, it is 85% hydrazine hydrate 13g that system is slowly added dropwise mass percent concentration at reflux, within about 2 hours, drips off, continues
Continuing filtered while hot after refluxing 3 hours, after filtrate recovery of alcohol distillation, add water stirring 30 minutes, and it is shallow that standing separatory obtains 24.85g
Brown oil product, 2-amino-4-chlorodiphenyl ether purity is 99.04%, and content is 98.65%, and product yield is 92.82%.
Embodiment 2
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity
Charcoal 5g, stirs and with 9g liquid caustic soda (30%) regulation pH value to 9.5, is warming up to 80-90 DEG C, and system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 13g, within about 2 hours, drips off, filtered while hot after continuing to reflux 3 hours, after filtrate recovery of alcohol distillation, adds
Water stirs 30 minutes, stands separatory and obtains 21.88g dark-brown product, and 2-amino-4-chlorodiphenyl ether purity is 94.74%, content
Being 91.55%, product yield is 75.85%.
Embodiment 3
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity
Charcoal 5g, stirs and with 7g liquid caustic soda (30%) regulation pH value to 7.5, is warming up to 80-90 DEG C, and system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 12g, within about 2 hours, drips off, filtered while hot after continuing to reflux 3 hours, after filtrate recovery of alcohol distillation, adds
Water stirs 30 minutes, stands separatory and obtains 22.80g light brown product, and 2-amino-4-chlorodiphenyl ether purity is 98.76%, content
Being 95.77%, product yield is 82.27%.
Embodiment 4
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity
Charcoal 5g, stirs and with 7g liquid caustic soda (30%) regulation pH value to 7.1, is warming up to 80-90 DEG C, and system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 14g, within about 2 hours, drips off, filtered while hot after continuing to reflux 3 hours, after filtrate recovery of alcohol distillation, adds
Water stirs 30 minutes, stands separatory and obtains 23.94g light brown product, and 2-amino-4-chlorodiphenyl ether purity is 98.47%, content
Being 96.63%, product yield is 87.59%.
Embodiment 5
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 3g, activity
Charcoal 5g, stirs and with 4.2g liquid caustic soda (30%) regulation pH value to 7.3, is warming up to 80-90 DEG C, and system is the most slowly dripped
Adding concentration is 85% hydrazine hydrate 13g, within about 2 hours, drips off, filtered while hot after continuing to reflux 3 hours, after filtrate recovery of alcohol distillation,
Add water stirring 30 minutes, stands separatory and obtains 22.11g dark-brown product, and 2-amino-4-chlorodiphenyl ether purity only has 52.58%.
Embodiment 6
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 6g, activity
Charcoal 5g, stirs and with 8.4g liquid caustic soda (30%) regulation pH value to 7.5, is warming up to 80-90 DEG C, and system is the most slowly dripped
Adding concentration is 85% hydrazine hydrate 13g, within about 2 hours, drips off, filtered while hot after continuing to reflux 3 hours, after filtrate recovery of alcohol distillation,
Add water stirring 30 minutes, stands separatory and obtains 24.58g light brown oil product, and 2-amino-4-chlorodiphenyl ether purity is
98.89%, content is 98.23%, and product yield is 91.40%.
Embodiment 7
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity
Charcoal 3g, stirs and with 7g liquid caustic soda (30%) regulation pH value to 7.1, is warming up to 80-90 DEG C, and system is slowly added dropwise at reflux
Concentration is 85% hydrazine hydrate 13g, within about 2 hours, drips off, filtered while hot after continuing to reflux 3 hours, after filtrate recovery of alcohol distillation, adds
Water stirs 30 minutes, stands separatory and obtains 23.80g light brown oil product, and 2-amino-4-chlorodiphenyl ether purity is 98.09%,
Content is 97.00%, and product yield is 87.41%.
Embodiment 8
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, Iron trichloride hexahydrate 5g, activity
Charcoal 5g, stirs and with 7.2g liquid caustic soda (30%) regulation pH value to 8.2, is warming up to 80-90 DEG C, and system is the most slowly dripped
Adding concentration is 85% hydrazine hydrate 13g, within about 2 hours, drips off, filtered while hot after continuing to reflux 3 hours, reclaims catalyst, and filtrate is distilled
After recovered alcohol, add water stirring 30 minutes, stands separatory and obtains 23.83g light brown oil product, 2-amino-4-chlorodiphenyl ether
Purity is 95.12%, and content is 96.78%, and product yield is 87.32%.
Embodiment 9
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, apply mechanically in embodiment 8 and reclaim
Catalyst, and with 30% hydrochloric acid regulation pH value to 8.1, be warming up to 80-90 DEG C, system is slowly added dropwise concentration at reflux
It is 85% hydrazine hydrate 13g, within about 2 hours, drips off that filtered while hot after continuing to reflux 3 hours reclaims catalyst, filtrate Distillation recovery wine
After essence, add water stirring 30 minutes, stands separatory and obtains 24.89g light brown oil product, and 2-amino-4-chlorodiphenyl ether purity is
97.90%, content is 95.48%, and product yield is 89.98%.
Embodiment 10
In reaction flask, add 2-nitro-4-chlorodiphenyl ether 30g, industrial alcohol 90mL, apply mechanically in embodiment 9 and reclaim
Catalyst, and with 30% hydrochloric acid regulation pH value to 8.1, be warming up to 80-90 DEG C, system is slowly added dropwise concentration at reflux
It is 85% hydrazine hydrate 13g, within about 2 hours, drips off that filtered while hot after continuing to reflux 3 hours, after filtrate recovery of alcohol distillation, adds water and stirs
Mixing 30 minutes, stand separatory and obtain 25.16g light brown oil product, 2-amino-4-chlorodiphenyl ether purity is 97.90%, content
Being 98.42%, product yield is 93.76%.
Claims (8)
1. the preparation method of a 2-amino-4-chlorodiphenyl ether, it is characterised in that comprise the following steps:
2-nitro-4-chlorodiphenyl ether, Iron trichloride hexahydrate and activated carbon are scattered in ethanol, then add alkali regulation pH to 7～9,
Dropping hydrazine hydrate carries out reduction reaction in a heated condition, after reaction terminates, obtains described 2-amino-4-chlorine through post processing
Diphenyl ether.
The preparation method of 2-amino-4-chlorodiphenyl ether the most according to claim 1, it is characterised in that six described water chlorine
Change quality is 2-nitro-4-chlorodiphenyl ether quality the 10%～20% of ferrum, activated carbon and Iron trichloride hexahydrate mass ratio be 0.5～
2:1.
The preparation method of 2-amino-4-chlorodiphenyl ether the most according to claim 1, it is characterised in that described ethanol and 2-
The volume mass of nitro-4-chlorodiphenyl ether is than for 1-5ml/g.
The preparation method of 2-amino-4-chlorodiphenyl ether the most according to claim 1, it is characterised in that described alkali is liquid
Alkali, sheet alkali, sodium bicarbonate, soda or ammonia.
The preparation method of 2-amino-4-chlorodiphenyl ether the most according to claim 1, it is characterised in that described 2-nitro-
4-chlorodiphenyl ether is 1:1.5～2 with the mol ratio of hydrazine hydrate.
The preparation method of 2-amino-4-chlorodiphenyl ether the most according to claim 1, it is characterised in that heating-up temperature is 80-
90 DEG C, hydrazine hydrate time for adding is 2～3 hours, and the response time is 3～4 hours.
The preparation method of 2-amino-4-chlorodiphenyl ether the most according to claim 1, it is characterised in that described post processing
Including: filtered while hot reactant liquor, the solid catalyst recovery obtained；
The filtrate obtained is through Distillation recovery ethanol, and evaporated mother liquor adds water and stirs layering, obtains product.
The preparation method of 2-amino-4-chlorodiphenyl ether the most according to claim 7, it is characterised in that straight during recovery
Connect and add adjusting PH with base value, it is not necessary to add Iron trichloride hexahydrate and activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610517329.4A CN106187787B (en) | 2016-06-29 | 2016-06-29 | A kind of preparation method of 2- amino -4- chlorodiphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610517329.4A CN106187787B (en) | 2016-06-29 | 2016-06-29 | A kind of preparation method of 2- amino -4- chlorodiphenyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106187787A true CN106187787A (en) | 2016-12-07 |
| CN106187787B CN106187787B (en) | 2019-01-22 |
Family
ID=57464714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610517329.4A Active CN106187787B (en) | 2016-06-29 | 2016-06-29 | A kind of preparation method of 2- amino -4- chlorodiphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106187787B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739312A (en) * | 2017-11-13 | 2018-02-27 | 安徽省化工设计院 | A kind of technique and system that amidogen ether is produced using hydrazine hydrate reduction nitre ether |
| 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 |
| CN113717035A (en) * | 2021-09-13 | 2021-11-30 | 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739312A (en) * | 2017-11-13 | 2018-02-27 | 安徽省化工设计院 | A kind of technique and system that amidogen ether is produced using hydrazine hydrate reduction nitre ether |
| 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 |
| CN113717035A (en) * | 2021-09-13 | 2021-11-30 | 江苏禾本生化有限公司 | Recycling method of difenoconazole waste intermediate |
| CN113717035B (en) * | 2021-09-13 | 2024-03-26 | 江苏禾本生化有限公司 | Recycling method of difenoconazole waste intermediate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106187787B (en) | 2019-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103420918B (en) | Simple and convenient preparation method of key intermediate (2-methyl-4-amino-5-amino methyl pyrimidine) for vitamin B1 | |
| CN101891649B (en) | Novel 3-cyano methyl benzoate preparing method | |
| CN101560183B (en) | Method for preparing 5-bromo-2-methylpyridine | |
| CN105294534B (en) | Industrialized method for preparing aplidine and intermediate thereof | |
| CN109232178B (en) | Novel method for preparing high-purity hydroxytyrosol | |
| CN106187787A (en) | A kind of preparation method of 2 amino 4 chlorodiphenyl ethers | |
| CN101955484A (en) | Method for synthesizing naloxone or naltrexone | |
| CN109369545B (en) | Synthesis process of 2-methyl-5-pyrazine formate | |
| CN103724279B (en) | One step to form the loop prepares the convenient synthetic method of 2-methyl-4-amino-5-amino methylpyrimidine | |
| CN104478790A (en) | Preparation method of S-type apremilast | |
| CN103396318B (en) | Synthetic process for 2,4-dinitroanisole | |
| CN104592163A (en) | Synthetic method of chiral 2-phenylpyrrolidine | |
| CN104710402B (en) | Dicyclohexyl crown ether synthesis method | |
| CN103694094A (en) | 5-chloro-2-pentanone preparation method | |
| CN113200876A (en) | Synthesis process of p-aminophenol | |
| CN101735023A (en) | Method for preparing 3-bromo-5-chlorophenol | |
| CN108383718A (en) | The preparation method of one kind 2,4,5- trifluoro benzene acetic acids | |
| CN106478422B (en) | A kind of preparation method of paranitrophenylacetic acid | |
| CN102718662A (en) | Method for preparing cinacalcet hydrochloride | |
| CN100497318C (en) | Method for preparing 2,4,6-trichloro pyrimidine | |
| CN105017044A (en) | Preparation method of trans-4-aminomethylcyclohexanecarboxylic acid | |
| CN104892371A (en) | Method for producing glycol dimethyl ether | |
| CN102757390B (en) | Method for preparing 2-methoxy-4-diazanyl-5-fluoropyrimidine | |
| CN103755706B (en) | A kind of environment-friendly preparation method synthesizing folic acid | |
| CN105348285A (en) | Low-cost and high-yield adenine preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |