CN107739315A - The processing method of 3-acetylaminoaniline hydrochloride mother liquor - Google Patents
The processing method of 3-acetylaminoaniline hydrochloride mother liquor Download PDFInfo
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- CN107739315A CN107739315A CN201710954708.4A CN201710954708A CN107739315A CN 107739315 A CN107739315 A CN 107739315A CN 201710954708 A CN201710954708 A CN 201710954708A CN 107739315 A CN107739315 A CN 107739315A
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- mother liquor
- processing method
- hydrogen chloride
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- 0 CC(Nc1cc(*)ccc1)=O Chemical compound CC(Nc1cc(*)ccc1)=O 0.000 description 1
- UQVKNKXDSWRQJE-UHFFFAOYSA-N CC(Nc1cccc(NC(C)=O)c1)=O Chemical compound CC(Nc1cccc(NC(C)=O)c1)=O UQVKNKXDSWRQJE-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N Nc1cccc(N)c1 Chemical compound Nc1cccc(N)c1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of processing method of the mother liquor of 3-acetylaminoaniline hydrochloride.The processing method, it comprises the following steps：At 75~95 DEG C, by the mother liquor and hydrogen chloride, reaction is hydrolyzed, obtains treatment fluid, you can；Mass percentage content of the hydrogen chloride in the mother liquor is 9~14%；Containing the component that mass percent is following in the mother liquor, 2~9% hydrogen chloride, 25~60% acetic acid, 2.2~10.3% m-phenylene diamine (MPD)s, 5.7~15% m-acetamidoanilines, 7.8~15% diacetylamino aniline, remaining is water.The processing method of the mother liquor of the present invention eliminates mother liquor distillation concentrate and the acetum process that steams, subsequent process do not have to carry out adding acetic acid substantially, you can recycled simplifies technical process in the amidation process of next step, more green；The basic free of losses of material, yield further improve, up to more than 98%；It is recyclable to apply mechanically.
Description
Technical field
The present invention relates to a kind of processing method of 3-acetylaminoaniline hydrochloride mother liquor.
Background technology
3-acetylaminoaniline hydrochloride, it can produce the purple coupling components of disperse dyes such as 93#, amino second between use
During anilide hydrochloride, first with, with hydrochloride, it is a kind of critically important dispersed dye coupling component in 30% liquid caustic soda
Intermediate.
The preparation technology of existing 3-acetylaminoaniline hydrochloride is：Water and m-phenylene diamine (MPD) are added into reaction pot, is made molten
Solution；30% hydrochloric acid is added, half an hour is stirred, then adds acetic acidreaction.Reaction temperature is high, and energy consumption is big, and reaction needs after terminating
Want very long decrease temperature crystalline process.On salt acid molecule on one of which amino, play a part of protect amino, and another
Amino obtains acetylamino, has just obtained 3-acetylaminoaniline hydrochloride with aceticanhydride, acetic acid reaction,
The synthesis of 3-acetylaminoaniline hydrochloride, the mother liquor that conventional technique obtains needs to be evaporated under reduced pressure concentrate, through concentrate
Mother liquid coming afterwards is covered for next group.
Due to still containing substantial amounts of hydrochloric acid, acetic acid, raw material m-phenylene diamine (MPD), product m-acetamino benzene in the mother liquor of this reaction
Diacetylamino aniline between amine, and accessory substance.By the water in mother liquor in progress subtractive process is evaporated under reduced pressure, hydrochloric acid has volatilization
Property, and acetic acid and water are distilled off together into azeotropic mixture；There are complex steps in mother liquor still-process, operation is not simple enough
Just, high energy consumption, the problems such as cycle is long.
The content of the invention
The technical problems to be solved by the invention are to overcome 3-acetylaminoaniline hydrochloride in existing technology female
When liquid recycles, the problem of reaction temperature height, complex steps, high energy consumption, long cycle, and an inter-species amino second is provided
The processing method of anilide hydrochloride mother liquor.This method saves mother liquor distillation concentrate process so that the mother liquor after processing can follow
Ring set is used, and high income, and whole technical process is simplified.
The invention provides a kind of processing method of the mother liquor of 3-acetylaminoaniline hydrochloride, it comprises the following steps：
At 75~95 DEG C, by the mother liquor and hydrogen chloride, reaction is hydrolyzed, obtains treatment fluid, you can；The hydrogen chloride is described
Mass percentage content in mother liquor is 9~14%；Contain hydrogen chloride, acetic acid, m-phenylene diamine (MPD), m-acetamino in the mother liquor
Aniline, a diacetylamino aniline.
Containing the component that mass percent is following in the mother liquor, 2~9% hydrogen chloride, 25~60% acetic acid, 2.2~
10.3% m-phenylene diamine (MPD) (abbreviation raw material), 5.7~15% m-acetamidoanilines (abbreviation product), 7.8~15% diacetyl
Amino aniline (abbreviation accessory substance), remaining is water；It is preferred that containing the component that mass percentage content is following in the mother liquor, 2
~7% hydrogen chloride, 30~50% acetic acid, 2.2~5.8% m-phenylene diamine (MPD)s, 6.0~10% m-acetamidoanilines, 8.0~
13.4% diacetylamino aniline, remaining is water.
The content of hydrogen chloride can be the conventional method control in this area, for example, when hydrogen cloride concentration is less than 9~14%,
Adding hydrochloric acid or be passed through hydrogen chloride gas, in the present invention, the concentration of the hydrochloric acid is preferably 25%~37%, more preferably for 30%~
37%.
The temperature of the hydrolysis is preferably 80~90 DEG C.
In the treatment fluid, it is preferred that hydrogen chloride is 9~14%, acetic acid is 30~50%, m-acetamidoaniline<
2%, a diacetylamino aniline<2%, content is mass percent.
The processing method of the mother liquor of the 3-acetylaminoaniline hydrochloride, further can also include the steps of：At 0 DEG C
~5 DEG C, by the treatment fluid and the mixture of m-phenylene diamine (MPD), amidation process is carried out with aceticanhydride, obtains 3-acetylaminoaniline
Hydrochloride, you can.
In the amidation process, described mixture can be that this area is conventional, for example, solution or suspension, this hair
Preferably the m-phenylene diamine (MPD) is dissolved in the treatment fluid in bright and obtained.
In the amidation process, the dosage of the m-phenylene diamine (MPD) is such reaction routine of this area, in the present invention, institute
State in mixture, the molar ratio of the m-phenylene diamine (MPD) and the hydrogen chloride in the treatment fluid is preferably (0.9~1.2):1；
More preferably it is (1~1.1):1.
In the amidation process, the dosage of the aceticanhydride is such reaction routine of this area, in the present invention, the vinegar
The molar ratio of acid anhydride and the m-phenylene diamine (MPD) is preferably (0.9~1.2):1；More preferably it is (1~1.1):1.
In the amidation process, the aceticanhydride is preferably to be added in described mixture by dropwise addition mode.
In the amidation process, the process of the reaction can use in this area routine monitoring method (such as
TLC, HPLC or NMR) it is monitored, as reaction end when typically being disappeared using m-phenylene diamine (MPD) or no longer reacted.
After the amidation process terminates, following post-processing step may also include：Solid is separated out, filtering, obtains an amino
Antifebrin hydrochloride.
It is preferred that after the amidation process terminates, the disposing mother liquor that is obtained after filtering can be by above-mentioned processing method and institute
State amidation process recycled.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：The preparation method of the present invention, (1) are saved mother liquor distillation concentrate process, subtracted
Few energy consumption；(2) most of accessory substance in mother liquor is raw material through hydrolysis, then by mother liquid recycle, simplifies technical process,
It is more green；(3) acetum need not be steamed, acetic acid is stayed in mother liquor, and subsequent process does not have to be added substantially, subtracts
Lack supplies consumption, reduce cost；(4) mother liquor after handling, amidation process is carried out in low temperature, without making acetic acid flow back,
Process environments are improved, while the basic free of losses of material, product yield are further enhanced, up to more than 98%；(5) mother liquor
Can be according to the method for the present invention, recycled.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
Embodiment 1
The stirring of 500ml four-hole bottles adds 150g50% acetic acid, and stirring adds 54.0g m-phenylene diamine (MPD)s, at 15~25 DEG C, uses
59.88g hydrochloric acid (32%) is added dropwise within 30 minutes, stirring ice bath after material dissolution is cooled to 0~5 DEG C.Added at 0~5 DEG C with 4~5h
Enter 53.6g aceticanhydrides.Continue to react 1h, sampling detection, raw material 0.71%, 3-acetylaminoaniline hydrochloric acid at this temperature after adding
Salt 90.2%, a diacetylamino aniline 8.04%, filtering, obtain 3-acetylaminoaniline hydrochloride wet cake 96.3g, purity
98.91%, amino value 84.57%, yield 88.21%, mother liquor 205.3g (raw material 14.23%, 3-acetylaminoaniline hydrochloride
35.76%th, a diacetylamino aniline 47.5%) cover for next group.
Embodiment 2
Mother liquor 150g (hydrochloric acid 2.98%, acetic acid 56.48%, raw material 2.9%, product in embodiment 1 are added in flask
7.5%, accessory substance 9.74%；HPLC purity：Raw material 14.23%, product 35.76%, accessory substance 47.5%), add 63.4g salt
Sour (32%), stirring are warming up to 80 DEG C.1h is incubated at 80~90 DEG C.60 DEG C are cooled to, sampling detects the content of hydrochloric acid and acetic acid,
Content of hydrochloric acid 11.6%, acetic acid 39.7%, sampling detection HPLC purity：Raw material 91.37%, product 2.36%, accessory substance
5.88%.54g m-phenylene diamine (MPD)s, stirring and dissolving are put into, while is cooled to 0~5 DEG C.58.3g aceticanhydrides are added dropwise with 4~5h, after adding
2h is incubated at 0~5 DEG C, detects HPLC purity, product 90.61%, accessory substance 9.02%.After terminal, filtering, an amino second is obtained
Anilide hydrochloride wet cake 108.6g, HPLC purity 99.12%, amino value 84.13%, yield 98.22%, mother liquor 189.7g
(hydrochloric acid 2.55%, acetic acid 55.34%, raw material 2.8%, product 6.9%, accessory substance 8.37%, HPLC：Raw material 15.65%, production
Thing 37.16%, accessory substance 46.22%), cover for next group.
Embodiment 3
Mother liquor 150g (mother liquor that embodiment 2 obtains) is added in flask, adds 63.4g hydrochloric acid (32%), stirring is warming up to
80℃.1h is incubated at 80~90 DEG C.60 DEG C are cooled to, sampling detects the content of hydrochloric acid and acetic acid, content of hydrochloric acid 11.3%, acetic acid
For 38.9%, sampling detection HPLC purity：Raw material 92.31%, product 3.36%, accessory substance 4.13%.Put into 54g isophthalic two
Amine, stirring and dissolving, while it is cooled to 0~5 DEG C.58.3g aceticanhydrides are added dropwise with 4~5h, are incubated 2h, detection after adding at 0~5 DEG C
HPLC purity, product 90.33%, accessory substance 8.62%.After terminal, filtering, 3-acetylaminoaniline hydrochloride wet cake is obtained
107.6g, purity 99.01%, amino value 84.45%, yield 98.32%, mother liquor 191.3g (hydrochloric acid 3.12%, acetic acid
56.05%, HPLC：Raw material 11.05%, product 44.21%, accessory substance 43.16%), cover for next group.
Embodiment 4
Mother liquor 150g (mother liquor that embodiment 3 obtains) is added in flask, adds 63.4g hydrochloric acid (32%), stirring is warming up to
80℃.1h is incubated at 80~90 DEG C.60 DEG C are cooled to, sampling detects the content of hydrochloric acid and acetic acid, content of hydrochloric acid 11.7%, acetic acid
For 39.4%, sampling detection HPLC purity：Raw material 92.18%, product 4.31%, accessory substance 3.16%.Put into 54g isophthalic two
Amine, stirring and dissolving, while it is cooled to 0~5 DEG C.58.3g aceticanhydrides are added dropwise with 4~5h, are incubated 2h, detection after adding at 0~5 DEG C
HPLC purity, product 90.57%, accessory substance 8.97%.After terminal, filtering, 3-acetylaminoaniline hydrochloride wet cake is obtained
108.1g, HPLC purity 99.03%, amino value 84.27%, yield 98.56%, mother liquor 189.9g (hydrochloric acid 2.88%, acetic acid
54.71%, HPLC：Raw material 9.22%, product 47.31%, accessory substance 42.53%), cover for next group.
Comparative example 1
Mother liquor 150g (hydrochloric acid 2.98%, acetic acid 56.48%, raw material 2.9%, product in embodiment 1 are added in flask
7.5%, accessory substance 9.74%；HPLC purity：Raw material 14.23%, product 35.76%, accessory substance 47.5%), add 63.4g salt
Sour (32%), is stirred at room temperature 1h, sampling detection hydrochloric acid and acetic acid content, content of hydrochloric acid 11.3%, and acetic acid content is
38.9%, sampling detection HPLC purity：Raw material 13.85%, product 39.31%, accessory substance 46.58%.Put into 54g isophthalic two
Amine, stirring and dissolving, while it is cooled to 0~5 DEG C.58.3g aceticanhydrides are added dropwise with 4-5h, are incubated 1h, detection after adding at 0~5 DEG C
HPLC purity, product 9.99%, accessory substance 5.73%, raw material 82.04%.Filtering, obtains wet cake 106.9g, product 2.94%,
Raw material 96.4%, mother liquor 192.6g.
Claims (10)
1. a kind of processing method of the mother liquor of 3-acetylaminoaniline hydrochloride, it is characterised in that comprise the following steps：75~
At 95 DEG C, by the mother liquor and hydrogen chloride, reaction is hydrolyzed, obtains treatment fluid, you can；The hydrogen chloride is in the mother liquor
Mass percentage content be 9~14%；In the mother liquor containing hydrogen chloride, acetic acid, m-phenylene diamine (MPD), m-acetamidoaniline,
Between diacetylamino aniline.
2. processing method as claimed in claim 1, it is characterised in that the mother liquor contains the following group of mass percentage content
Point：2~9% hydrogen chloride, 25~60% acetic acid, 2.2~10.3% m-phenylene diamine (MPD)s, 5.7~15% m-acetamidoanilines, 7.8
~15% diacetylamino aniline, remaining is water；
And/or in the treatment fluid, hydrogen chloride is 9~14%, acetic acid is 30~50%, m-acetamidoaniline<2%, two
Acetylaminoaniline<2%, content is mass percent.
3. processing method as claimed in claim 2, it is characterised in that the mother liquor contains the following group of mass percentage content
Point：2~7% hydrogen chloride, 30~50% acetic acid, 2.2~5.8% m-phenylene diamine (MPD)s, 6.0~10% m-acetamidoanilines, 8.0~
13.4% diacetylamino aniline, remaining is water.
4. processing method as claimed in claim 1, it is characterised in that the temperature of the hydrolysis is 80~90 DEG C；
And/or by adding hydrochloric acid or being passed through hydrogen chloride gas makes the hydrogen chloride content be maintained at 9~14%.
5. processing method as claimed in claim 4, it is characterised in that the concentration of the hydrochloric acid is 25%~37%, preferably
For 30%~37%.
6. the processing method as described in any one of Claims 1 to 5, it is characterised in that further comprising the steps of：0 DEG C~5
DEG C, by the treatment fluid and the mixture of m-phenylene diamine (MPD), amidation process is carried out with aceticanhydride, obtains 3-acetylaminoaniline hydrochloric acid
Salt, you can.
7. processing method as claimed in claim 6, it is characterised in that described mixture is solution or suspension；
And/or the molar ratio of the m-phenylene diamine (MPD) and the hydrogen chloride in the treatment fluid is (0.9~1.2):1；
And/or the molar ratio of the aceticanhydride and the m-phenylene diamine (MPD) is (0.9~1.2):1；
And/or the aceticanhydride is to be added to by dropwise addition mode in described mixture.
8. processing method as claimed in claim 7, it is characterised in that described mixture is to be dissolved in the m-phenylene diamine (MPD)
Obtained in the treatment fluid；
And/or the molar ratio of the m-phenylene diamine (MPD) and the hydrogen chloride in the treatment fluid is (1~1.1):1；
And/or the molar ratio of the aceticanhydride and the m-phenylene diamine (MPD) is (1~1.1):1.
9. processing method as claimed in claim 6, it is characterised in that after the amidation process terminates, in addition to it is following after
Processing step：Solid is separated out, filtering, obtains 3-acetylaminoaniline hydrochloride, you can.
10. processing method as claimed in claim 6, it is characterised in that after the amidation process terminates, obtained after filtering
Disposing mother liquor, processing method carries out recycled as described in claim 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710954708.4A CN107739315A (en) | 2017-10-13 | 2017-10-13 | The processing method of 3-acetylaminoaniline hydrochloride mother liquor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710954708.4A CN107739315A (en) | 2017-10-13 | 2017-10-13 | The processing method of 3-acetylaminoaniline hydrochloride mother liquor |
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| CN201710954708.4A Withdrawn CN107739315A (en) | 2017-10-13 | 2017-10-13 | The processing method of 3-acetylaminoaniline hydrochloride mother liquor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358411A (en) * | 2020-11-16 | 2021-02-12 | 浙江迪邦化工有限公司 | Process and system for continuously producing m-aminoacetanilide hydrochloride under high temperature and pressure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328133A (en) * | 2008-07-26 | 2008-12-24 | 浙江龙盛染料化工有限公司 | Synthetic method of m-amino acetanilide |
| CN102617389A (en) * | 2012-02-29 | 2012-08-01 | 浙江闰土股份有限公司 | Synthetic method of N, N-diethyl-3-propionylaminoaniline |
| CN105461572A (en) * | 2014-12-29 | 2016-04-06 | 浙江龙盛集团股份有限公司 | Clean technology for continuously synthesizing 2,4-dinitro-6-chloroaniline |
-
2017
- 2017-10-13 CN CN201710954708.4A patent/CN107739315A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328133A (en) * | 2008-07-26 | 2008-12-24 | 浙江龙盛染料化工有限公司 | Synthetic method of m-amino acetanilide |
| CN102617389A (en) * | 2012-02-29 | 2012-08-01 | 浙江闰土股份有限公司 | Synthetic method of N, N-diethyl-3-propionylaminoaniline |
| CN105461572A (en) * | 2014-12-29 | 2016-04-06 | 浙江龙盛集团股份有限公司 | Clean technology for continuously synthesizing 2,4-dinitro-6-chloroaniline |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358411A (en) * | 2020-11-16 | 2021-02-12 | 浙江迪邦化工有限公司 | Process and system for continuously producing m-aminoacetanilide hydrochloride under high temperature and pressure |
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