CN108191681A - The technique of one-step synthesis method 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline - Google Patents
The technique of one-step synthesis method 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline Download PDFInfo
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- CN108191681A CN108191681A CN201810029523.7A CN201810029523A CN108191681A CN 108191681 A CN108191681 A CN 108191681A CN 201810029523 A CN201810029523 A CN 201810029523A CN 108191681 A CN108191681 A CN 108191681A
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- China
- Prior art keywords
- hydroxyethylaminos
- dihydroxy ethyl
- ethyl aniline
- nitros
- nitro
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- 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
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- 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
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
Abstract
The present invention relates to a kind of techniques of 3 nitro of one-step synthesis method, 4 hydroxyethylamino N, N dihydroxy ethyl aniline, include the following steps：(1) using 2 nitro Isosorbide-5-Nitrae phenylenediamines as raw material, under catalyst, ammonolysis reaction is carried out with ethylene oxide, obtains 3 nitro, 4 hydroxyethylamino N, N dihydroxy ethyl aniline crude product；The crude product of 4 hydroxyethylamino N, N dihydroxy ethyl aniline of (2) 3 nitro obtains 3 nitro, 4 hydroxyethylamino N, N dihydroxy ethyl aniline highly finished product by purifying.The present invention reduces the reaction time while product quality quality is improved, reduces cost, safety easy to operate, cleans production, environmental protection, high efficiency, product is made to be more suitable for producing in enormous quantities.
Description
Technical field
The present invention relates to a kind of preparation method of chemical intermediate, more particularly, to a kind of one-step synthesis method 3- nitros -4-
The technique of hydroxyethylamino-N, N- dihydroxy ethyl aniline.
Background technology
3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyls aniline is a kind of common chemical industry for producing amino benzenes compounds
Raw material, for medicine, dyestuff intermediate, with the fast development of medicine and dyestuff industry, 3- nitro -4- hydroxyethylaminos-N, N-
Dihydroxy ethyl is all applied in various fields, also can be more and more to the demand of the substance.
Preparation method report about 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline is less, and the prior art is general
It is prepared using 3- nitro -4- fluoroanilines and ethylene oxide ammonolysis, hydroxyethylamino method, under above-mentioned preparation method mainly has
Step is stated 1. using ethylene oxide as ammonolysis reagent；2. methanol is used as medium；3. using water as medium, urged in disodium hydrogen phosphate
Change effect is lower to carry out aminolysis.
Verification to above scheme simultaneously optimizes, when finding using sodium dihydrogen phosphate series of products as ammonolysis, rear
Phosphorus-containing wastewater is more intractable in processing procedure, is not easy industrialized production, use 3- nitro -4- fluoroanilines for raw material production cost too
Height, market competition are in a disadvantageous position.
Invention content
Of the existing technology in order to overcome the problems, such as, the present invention provides the one of a kind of low cost, green and highly effective and safe
The technique that footwork synthesizes 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline.
A kind of technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline, includes the following steps：
(1) using 2- nitros-Isosorbide-5-Nitrae-phenylenediamine as raw material, under catalyst, ammonolysis reaction is carried out with ethylene oxide, is obtained
To 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline crude products；
(2) crude product of 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline obtains 3- nitro -4- hydroxyl second by purifying
Amino-N, N- dihydroxy ethyl aniline highly finished product.
Preferably, in step (1), the catalyst is copper powder, one kind in cuprous oxide, stannous chloride, copper sulphate.
Preferably, the weight ratio of the 2- nitros-Isosorbide-5-Nitrae-phenylenediamine, ethylene oxide, catalyst is 1：0.4~0.8：
0.01~0.05.
Preferably, ammonolysis reaction uses 50% methanol aqueous solution as reaction dissolvent.
Preferably, the temperature of ammonolysis reaction is 15~70 DEG C.
Preferably, the time of ammonolysis reaction is 4~15h.
Preferably, in step (2), the purifying is specially：50% methanol that crude product is added in 8~15 times of volumes is water-soluble
Liquid, the activated carbon of 0.5~1.5 times of weight are warming up to 60~80 DEG C of decolorations, and 3- nitro -4- hydroxyls are obtained by filtration after being cooled to room temperature
Ethylamino-N, N- dihydroxy ethyl aniline highly finished product.
Preferably, the catalyst be copper powder, the 2- nitros-Isosorbide-5-Nitrae-phenylenediamine, ethylene oxide, copper powder weight ratio
It is 1：0.6：0.025.
Preferably, the technique of one-step synthesis method 3- nitro -4- hydroxyethylaminos-N, N- the dihydroxy ethyl aniline, packet
Include following step：
(1) in the 2L four-hole boiling flasks equipped with thermometer, blender, 50% methanol aqueous solution of 1000ml is added in, is opened
Stirring when temperature is stabilized to 64 DEG C, adds in 80g 2- nitro p-phenylenediamines and 2g copper powders, maintains the temperature at 64~66 DEG C, leads to
Enter ethylene oxide 48g, the time is 12 hours, 20 DEG C is then cooled to, in 20~25 DEG C of insulated and stirred 5h, feed liquid mistake after the completion
Filter obtains 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline crude products after clear water washing；
(2) crude product is added in 50% methanol aqueous solution of 10 times of volumes, the activated carbon of 1 times of weight is warming up to 70~72 DEG C
Decoloration, 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline highly finished product are obtained by filtration after being cooled to room temperature.
Synthetic route of the present invention is as follows：
The present invention reduces the reaction time while product quality quality is improved, reduces cost, safety easy to operate, makes production
Product production cleans, environmental protection, high efficiency, and product is made to be more suitable for producing in enormous quantities.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but invention which is intended to be protected is not limited to
This.
Embodiment 1
In the 2L four-hole boiling flasks equipped with thermometer, blender, 50% methanol aqueous solution of 1000ml is added in, unlatching is stirred
It mixes, when temperature is stabilized to 64 DEG C, adds in 80g 2- nitro p-phenylenediamines and 2g copper powders, maintain the temperature at 64~66 DEG C, be passed through
Ethylene oxide 48g reacts 12 hours, is then cooled to 20 DEG C, and in 20~25 DEG C of insulated and stirred 5h, feed liquid after the completion filters,
3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline crude products are obtained after clear water washing.Crude product is added in the 50% of 10 times of volumes
Methanol aqueous solution, the activated carbon of 1 times of weight are warming up to 70~72 DEG C of decolorations, sterling are obtained by filtration after being cooled to room temperature.Yield
95%, purity 99.8%.
Embodiment 2~4
Concrete operations obtain embodiment 2~4, the comparison with embodiment 1 with reference to embodiment 1 under the conditions of different catalysts
The results are shown in Table 1：
Table 1
| Catalyst | Yield % | Purity % | |
| Embodiment 1 | Copper powder | 95 | 99.8 |
| Embodiment 2 | Cuprous oxide | 85 | 99.5 |
| Embodiment 3 | Stannous chloride | 90 | 99.2 |
| Embodiment 4 | Copper sulphate | 83 | 99.5 |
Embodiment 5~8
It is allocated as with system as catalyst, changes 2- nitros-Isosorbide-5-Nitrae-phenylenediamine, ethylene oxide, catalyst weight ratio, ammonolysis temperature
Degree, the ammonolysis time obtains embodiment 5~8, as shown in table 2 with the comparing result of embodiment 1：
Table 2
Claims (9)
1. a kind of technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline, it is characterised in that including under
State step：
(1) using 2- nitros-Isosorbide-5-Nitrae-phenylenediamine as raw material, under catalyst, ammonolysis reaction is carried out with ethylene oxide, obtains 3-
Nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline crude product；
(2) crude product of 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline by purifying obtain 3- nitro -4- hydroxyethylaminos -
N, N- dihydroxy ethyl aniline highly finished product.
2. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 1,
It is characterized in that：In step (1), the catalyst is copper powder, one kind in cuprous oxide, stannous chloride, copper sulphate.
3. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 1,
It is characterized in that：2- nitros -1,4- the phenylenediamines, ethylene oxide, catalyst weight ratio be 1：0.4~0.8：0.01~
0.05。
4. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 1,
It is characterized in that：Ammonolysis reaction uses 50% methanol aqueous solution as reaction dissolvent.
5. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 1,
It is characterized in that：The temperature of ammonolysis reaction is 15~70 DEG C.
6. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 1,
It is characterized in that：The time of ammonolysis reaction is 4~15h.
7. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 4,
It is characterized in that：In step (2), the purifying is specially：By crude product add in 8~15 times of volumes 50% methanol aqueous solution, 0.5
The activated carbon of~1.5 times of weight is warming up to 60~80 DEG C of decolorations, be cooled to after room temperature be obtained by filtration 3- nitro -4- hydroxyethylaminos -
N, N- dihydroxy ethyl aniline highly finished product.
8. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 2,
It is characterized in that：The catalyst be copper powder, the 2- nitros-Isosorbide-5-Nitrae-phenylenediamine, ethylene oxide, copper powder weight ratio be 1：
0.6：0.025.
9. the technique of one-step synthesis method 3- nitros -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline according to claim 1,
It is characterized by comprising following step：
(1) in the 2L four-hole boiling flasks equipped with thermometer, blender, 50% methanol aqueous solution of 1000ml is added in, opens stirring,
When temperature is stabilized to 64 DEG C, 80g 2- nitro p-phenylenediamines and 2g copper powders are added in, 64~66 DEG C is maintained the temperature at, is passed through epoxy
Ethane 48g, time are 12 hours, are then cooled to 20 DEG C, and in 20~25 DEG C of insulated and stirred 5h, feed liquid after the completion filters, clearly
3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline crude products are obtained after water washing；
(2) crude product is added in 50% methanol aqueous solution of 10 times of volumes, the activated carbon of 1 times of weight is warming up to 70~72 DEG C of decolorations,
3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline highly finished product are obtained by filtration after being cooled to room temperature.
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| CN201810029523.7A CN108191681A (en) | 2018-01-12 | 2018-01-12 | The technique of one-step synthesis method 3- nitro -4- hydroxyethylaminos-N, N- dihydroxy ethyl aniline |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2750327A (en) * | 1953-06-01 | 1956-06-12 | Lever Brothers Ltd | Process of dyeing animal fibers and dyes and dyeing compositions therefor |
| US3944612A (en) * | 1967-11-02 | 1976-03-16 | Clairol Incorporated | 4-Fluoro-3-nitro anilines |
| US5414128A (en) * | 1991-12-14 | 1995-05-09 | Cassella Ag | Process for the preparation of N-substituted nitro-p-phenylenediamines |
-
2018
- 2018-01-12 CN CN201810029523.7A patent/CN108191681A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2750327A (en) * | 1953-06-01 | 1956-06-12 | Lever Brothers Ltd | Process of dyeing animal fibers and dyes and dyeing compositions therefor |
| US3944612A (en) * | 1967-11-02 | 1976-03-16 | Clairol Incorporated | 4-Fluoro-3-nitro anilines |
| US5414128A (en) * | 1991-12-14 | 1995-05-09 | Cassella Ag | Process for the preparation of N-substituted nitro-p-phenylenediamines |
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Address after: 311228 Linjiang Industrial Park, Xiaoshan District, Zhejiang, Hangzhou Applicant after: Zhejiang DINGLONG Technology Co.,Ltd. Address before: 311228 Linjiang Industrial Park, Xiaoshan District, Zhejiang, Hangzhou Applicant before: ZHEJIANG DINGLONG TECHNOLOGY Co.,Ltd. |
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