CN103408452A - Green synthesis process for p-chloro-o-nitroacetoanilide - Google Patents
Green synthesis process for p-chloro-o-nitroacetoanilide Download PDFInfo
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- CN103408452A CN103408452A CN2013103652110A CN201310365211A CN103408452A CN 103408452 A CN103408452 A CN 103408452A CN 2013103652110 A CN2013103652110 A CN 2013103652110A CN 201310365211 A CN201310365211 A CN 201310365211A CN 103408452 A CN103408452 A CN 103408452A
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- nitro
- chloracetyl
- acetanilide
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- ketene dimer
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Abstract
The invention discloses a green synthesis process for p-chloro-o-nitroacetoanilide. The process comprises the following steps of mixing a novel mixed catalyst system and p-chloro-o-nitroaniline, and enabling the novel mixed catalyst system and the p-chloro-o-nitroaniline to dissolve, wherein the mole ratio of the p-chloro-o-nitroaniline to diketene is 1: (1.05-1.5); finishing the dropwise adding operation of the diketene within 3h; and continuing to react at the temperature of 90 DEG C for 4h to obtain the p-chloro-o-nitroacetoanilide. The solubility of the p-chloro-o-nitroaniline in a solvent is improved, the yield of products is high, the reaction time is shortened, the solvent dosage is reduced, and no solid wastes are generated.
Description
Technical field
The present invention relates to the friendly process of a kind of synthetic adjacent nitro to the chloracetyl Acetanilide, belong to the compound preparing technical field.
Background technology
Adjacent nitro is a kind of faint yellow xln to the chloracetyl Acetanilide, is mainly used in the synthetic intermediate of weedicide and medicine.
US4636562 discloses take p-chloro-o-nitroaniline and is raw material, and triethylamine is catalyzer, and in benzene, reflux and drip the mixed solution of ketene dimer and benzene, after reaction finishes, the crude product ethyl alcohol recrystallization, this process recovery ratio is not high, and a large amount of waste liquids of recrystallization generation.
EP0280156 discloses a kind ofly take p-chloro-o-nitroaniline and is raw material, as under solvent, take Potassium monofluoride, is catalyzer, reaction at a certain temperature at acetic acid.The shortcoming of the method is that product purity is not high, and mother liquor can't be applied mechanically.
Summary of the invention
The object of the invention is to for deficiency of the prior art, the friendly process of a kind of synthetic adjacent nitro to the chloracetyl Acetanilide is provided.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to realize:
The friendly process of a kind of synthetic adjacent nitro to the chloracetyl Acetanilide, utilize novel hybrid catalyst system, carries out mixed dissolution with ortho-nitro-parachloroaniline, drips the ketene dimer reaction, makes adjacent nitro to the chloracetyl Acetanilide, and reaction equation is:
The mol ratio of described ortho-nitro-parachloroaniline and ketene dimer is 1:1.05～1.5, is added dropwise to complete ketene dimer in 3 hours, under 90 ℃, continues reaction 4 hours, namely makes adjacent nitro to the chloracetyl Acetanilide.
Preferably, the mol ratio of ortho-nitro-parachloroaniline and ketene dimer is 1:1.05～1.2, and the temperature that drips ketene dimer is 40-70 ℃, and time for adding is 1-2 hour, and soaking time is 1-3 hour.
The weight ratio of described ortho-nitro-parachloroaniline and novel mixed catalyst is 1:0.05.
The mixed catalyst of narrating is toluene, pyridine.
Beneficial effect of the present invention:
1) after using novel mixed catalyst, the solvability of ortho-nitro-parachloroaniline in solvent strengthened;
2) after using mixed solvent, without crystallization again, yield reaches 99%;
3) reaction times shortens;
4) mixed catalyst can be repeatedly used, and circulating mother liquor can be used more than 12 times, has reduced the usage quantity of solvent, produces without solid waste.
Embodiment
For making purpose of the present invention, technical scheme and beneficial effect more cheer and bright, the present invention adopts following specific embodiment to elaborate to technical scheme of the present invention.
In reactor, add mixed solvent, add toluene 1000kg, pyridine 0.4kg, after opening stirring, add p-chloro-o-nitroaniline 400kg, is warmed up to 60 ℃, starts to drip ketene dimer 250kg, is added dropwise to complete in 60 ℃, is added dropwise to complete follow-up continuation of insurance temperature 2 hours.After completion of the reaction, be cooled to 0 ℃, filter, filter cake gets final product through super-dry.Yield reaches 99%.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill of the present invention is modified or is equal to replacement technical scheme of the present invention; and not breaking away from aim and the scope of technical scheme, it all should be encompassed in claim scope of the present invention.
Claims (5)
1. one kind is synthesized the friendly process of adjacent nitro to the chloracetyl Acetanilide, it is characterized in that: utilize novel hybrid catalyst system, carry out mixed dissolution with ortho-nitro-parachloroaniline, drip the ketene dimer reaction, make adjacent nitro to the chloracetyl Acetanilide, reaction equation is:
2. the friendly process of a kind of synthetic adjacent nitro according to claim 1 to the chloracetyl Acetanilide, it is characterized in that: the mol ratio of described ortho-nitro-parachloroaniline and ketene dimer is 1:1.05～1.5, in 3 hours, be added dropwise to complete ketene dimer, under 90 ℃, continue reaction 4 hours, namely make adjacent nitro to the chloracetyl Acetanilide.
3. the friendly process of a kind of synthetic adjacent nitro according to claim 2 to the chloracetyl Acetanilide, it is characterized in that: the mol ratio of described ortho-nitro-parachloroaniline and ketene dimer is 1:1.05～1.2, the temperature that drips ketene dimer is 40-70 ℃, time for adding is 1-2 hour, and soaking time is 1-3 hour.
4. the friendly process of a kind of synthetic adjacent nitro according to claim 1 to the chloracetyl Acetanilide, it is characterized in that: the weight ratio of described ortho-nitro-parachloroaniline and novel mixed catalyst is 1:0.05.
5. according to the friendly process of the described a kind of synthetic adjacent nitro of claim 1 or 4 to the chloracetyl Acetanilide, it is characterized in that: the mixed catalyst of narrating is toluene, pyridine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2013103652110A CN103408452A (en) | 2013-08-19 | 2013-08-19 | Green synthesis process for p-chloro-o-nitroacetoanilide |
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| CN2013103652110A CN103408452A (en) | 2013-08-19 | 2013-08-19 | Green synthesis process for p-chloro-o-nitroacetoanilide |
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| CN103408452A true CN103408452A (en) | 2013-11-27 |
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| CN2013103652110A Pending CN103408452A (en) | 2013-08-19 | 2013-08-19 | Green synthesis process for p-chloro-o-nitroacetoanilide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292122A (en) * | 2014-09-05 | 2015-01-21 | 南通醋酸化工股份有限公司 | Method for reducing generation of by-product ethyl 3-(phenylamino)but-2-enoate in production of N-acetoacetanilide |
| CN105439894A (en) * | 2014-08-28 | 2016-03-30 | 江苏扬子江天悦新材料有限公司 | Preparation method of 3-carboxyl-4-hydroxy-acetoacetanilide |
| CN112961069A (en) * | 2021-02-08 | 2021-06-15 | 山东京博生物科技有限公司 | Preparation method of p-chloro-o-nitro-acetoacetanilide |
| CN113683526A (en) * | 2021-08-13 | 2021-11-23 | 京博农化科技有限公司 | Method for preparing p-chloro-o-nitroacetoacetanilide by using packed bed reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636562A (en) * | 1982-05-07 | 1987-01-13 | E. I. Du Pont De Nemours And Company | Process for preparing 6-halo-2-chloroquinoxaline |
| EP0280156A2 (en) * | 1987-02-25 | 1988-08-31 | Hoechst Aktiengesellschaft | Process for the preparation of acetoacetylarylamides-heteroarylamides respectively of deactived aromatic compounds |
| CN101177404A (en) * | 2007-11-30 | 2008-05-14 | 山东金城医药化工有限公司 | Method for preparing high-purity p-chloro-m-nitroacetoacetanilide |
| CN103224455A (en) * | 2013-04-19 | 2013-07-31 | 南通醋酸化工股份有限公司 | Preparation method for N-acetyl acetanilide |
-
2013
- 2013-08-19 CN CN2013103652110A patent/CN103408452A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636562A (en) * | 1982-05-07 | 1987-01-13 | E. I. Du Pont De Nemours And Company | Process for preparing 6-halo-2-chloroquinoxaline |
| EP0280156A2 (en) * | 1987-02-25 | 1988-08-31 | Hoechst Aktiengesellschaft | Process for the preparation of acetoacetylarylamides-heteroarylamides respectively of deactived aromatic compounds |
| CN101177404A (en) * | 2007-11-30 | 2008-05-14 | 山东金城医药化工有限公司 | Method for preparing high-purity p-chloro-m-nitroacetoacetanilide |
| CN103224455A (en) * | 2013-04-19 | 2013-07-31 | 南通醋酸化工股份有限公司 | Preparation method for N-acetyl acetanilide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439894A (en) * | 2014-08-28 | 2016-03-30 | 江苏扬子江天悦新材料有限公司 | Preparation method of 3-carboxyl-4-hydroxy-acetoacetanilide |
| CN104292122A (en) * | 2014-09-05 | 2015-01-21 | 南通醋酸化工股份有限公司 | Method for reducing generation of by-product ethyl 3-(phenylamino)but-2-enoate in production of N-acetoacetanilide |
| CN104292122B (en) * | 2014-09-05 | 2016-01-27 | 南通醋酸化工股份有限公司 | In the production of acetoacetanilide, reduce by product 3-(phenyl amino)-2-butylene acetoacetic ester generate method |
| CN112961069A (en) * | 2021-02-08 | 2021-06-15 | 山东京博生物科技有限公司 | Preparation method of p-chloro-o-nitro-acetoacetanilide |
| CN113683526A (en) * | 2021-08-13 | 2021-11-23 | 京博农化科技有限公司 | Method for preparing p-chloro-o-nitroacetoacetanilide by using packed bed reactor |
| CN113683526B (en) * | 2021-08-13 | 2023-06-30 | 山东京博农化科技股份有限公司 | Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor |
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Application publication date: 20131127 |