CN107652198B - Process for preparing acetanilide - Google Patents
Process for preparing acetanilide Download PDFInfo
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- CN107652198B CN107652198B CN201710929028.7A CN201710929028A CN107652198B CN 107652198 B CN107652198 B CN 107652198B CN 201710929028 A CN201710929028 A CN 201710929028A CN 107652198 B CN107652198 B CN 107652198B
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- aniline
- acetanilide
- catalyst
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- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229960001413 acetanilide Drugs 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229960000583 acetic acid Drugs 0.000 claims abstract description 25
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 25
- 238000010992 reflux Methods 0.000 claims abstract description 23
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000021736 acetylation Effects 0.000 claims abstract description 18
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 16
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 13
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical group [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000005457 ice water Substances 0.000 claims description 14
- 239000002274 desiccant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000012345 acetylating agent Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 description 36
- 238000000967 suction filtration Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 150000008061 acetanilides Chemical class 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- GRDXCFKBQWDAJH-UHFFFAOYSA-N 4-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=C(S(Cl)(=O)=O)C=C1 GRDXCFKBQWDAJH-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBDYPDHUODKDRK-UHFFFAOYSA-N n-acetyl-n-phenylacetamide Chemical compound CC(=O)N(C(C)=O)C1=CC=CC=C1 KBDYPDHUODKDRK-UHFFFAOYSA-N 0.000 description 1
- NQRLPDFELNCFHW-UHFFFAOYSA-N nitroacetanilide Chemical class CC(=O)NC1=CC=C([N+]([O-])=O)C=C1 NQRLPDFELNCFHW-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 p-nitroanilides Chemical class 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940085790 synthetic camphor Drugs 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical class CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of acetanilide. The preparation method of the acetanilide comprises the following steps: uniformly mixing aniline, an acetylation reagent, a dehydrating agent and a catalyst, heating to 100-120 ℃, performing reflux reaction for 3-4 hours at the temperature, and cooling to separate out a product; the acetylation reagent is prepared by mixing glacial acetic acid and N, N-dimethylacetamide in a molar ratio of 1: 2-4, the dehydrating agent is dicyclohexylcarbodiimide, and the catalyst is sodium amide and/or ammonium chloride. Compared with the prior art, the method improves the yield of the acetanilide by changing the type of the acetylation reagent and adding the dehydrating agent and the catalyst, and the yield can reach more than 98 percent.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method of acetanilide.
Background
Acetanilide is a raw material of sulfonamides and can be used as an analgesic, antipyretic and preservative. Acetanilides are also used to make dye intermediates such as p-nitroacetanilides, p-nitroanilides, p-phenylenediamines, and p-esters. It is used in large quantities for the manufacture of p-acetamido-benzenesulfonyl chloride in world war II. Acetanilides are also used in the manufacture of thioacetamides. Can be used as rubber vulcanization accelerator, stabilizer for fiber grease coating, stabilizer for hydrogen peroxide, and synthetic camphor. Therefore, the synthesis process of the acetanilide has important significance in practical application.
The literature reports that the following methods are commonly used for synthesizing acetanilide: (1) refluxing aniline and excess glacial acetic acid together; (2) refluxing aniline, glacial acetic acid, acetic anhydride and a small amount of zinc powder; (3) stirring aniline, acetyl chloride and triethylamine together at room temperature; (4) aniline and equimolar hydrochloric acid are first prepared into aniline chloride, acetic anhydride is then added, sodium acetate solution is then added and the mixture is stirred. In the above methods, (1) and (2) need to reflux and continuously evaporate the generated water, the operation is complicated, the reaction is slow when glacial acetic acid is used as an acetylation reagent, the reaction is difficult to control when acetic anhydride is used as the acetylation reagent, the diacetyl aniline is generated, and the yield is low. (3) Although the method is short in time consumption and low in reaction temperature, acetyl chloride is expensive and easy to hydrolyze, and has a lot of byproducts and low yield. (4) The method needs to consume a large amount of sodium acetate, thereby not only causing the waste of time and reagents, but also greatly increasing the cost.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of acetanilide, which solves the problem of low yield of the existing process.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the acetanilide comprises the following steps:
uniformly mixing aniline, an acetylation reagent, a dehydrating agent and a catalyst, heating to 100-120 ℃, performing reflux reaction for 3-4 hours at the temperature, and cooling to separate out a product;
the acetylation reagent is prepared by mixing glacial acetic acid and N, N-dimethylacetamide in a molar ratio of 1: 2-4, the dehydrating agent is dicyclohexylcarbodiimide, and the catalyst is sodium amide or ammonium chloride or a mixture of the sodium amide and the ammonium chloride.
Compared with the prior art, the method improves the yield of the acetanilide by changing the type of the acetylation reagent and adding the dehydrating agent and the catalyst.
In the invention, the glacial acetic acid is low in price and low in acetylation activity, but the acetylation selectivity is high, so that the yield is high; the N, N-dimethylacetamide has high activity, and the N, N-dimethylacetamide and glacial acetic acid jointly acetylate aniline to produce a synergistic effect, so that the yield is improved, and the reaction time is shortened. Dicyclohexylcarbodiimide (DCC) as a dehydrating agent can absorb water generated by the reaction in time to promote the reaction to be carried out in a forward direction, so that the reaction efficiency is improved; meanwhile, the activity of the acetylation reagent is not reduced by the dicyclohexylcarbodiimide. Sodium amide and ammonium chloride are mainly used to increase the reaction rate.
According to statistics, the preparation method can achieve the following effects: the yield of the acetanilide reaches more than 98 percent within 3-4 hours of reaction time.
The preparation method can be further improved to achieve more technical effects:
preferably, the catalyst is sodium amide.
The sodium amide not only can catalyze the reaction, but also has the dehydration capability, can promote the reaction to be complete, and reduces the waste of raw materials.
Preferably, the molar ratio of the acetylation reagent to the aniline is 1.5-2: 1.
The molar ratio of the acetylation reagent to the aniline not only affects the reaction rate, but also easily generates byproducts if the mixture ratio is improper, and through investigation, when the molar ratio of the acetylation reagent to the aniline is 1.5-2: 1, the reaction yield is high, and the reaction time is short.
Preferably, the molar ratio of the dehydrating agent to the aniline is 0.8-1.2: 1.
In the present invention, it is preferable that the molar ratio of the dehydrating agent to the aniline is 0.8 to 1.2:1, for example, 0.8:1, 0.9:1, 1:1, 1.1:1, or 1.2: 1.
Preferably, the molar ratio of the catalyst to the aniline is 1-1.5: 1.
In order to improve the yield of the acetanilide in a shorter time, the molar ratio of the catalyst to the aniline is preferably 1 to 1.5:1, such as 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5: 1.
Preferably, the temperature of the reflux reaction is 110-120 ℃.
In order to avoid decomposition or oxidation of the raw materials or generation of byproducts, the temperature of the reflux reaction is preferably 110 to 120 ℃, for example, 110 ℃, 112 ℃, 115 ℃, 117 ℃, 119 ℃, and 120 ℃.
Preferably, the acetylation reagent is glacial acetic acid and N, N-dimethylacetamide which are mixed according to a molar ratio of 1: 2-3.
When glacial acetic acid and N, N-dimethylacetamide are mixed in a molar ratio of 1:2 to 3, the synergistic effect is more excellent, for example, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, etc.
Preferably, a drying agent is also added during the reflux reaction.
The drying agent combines the double functions of the dehydrating agent, so that the dehydrating effect is improved, and the reaction rate is further improved.
Preferably, the desiccant is calcium chloride or calcium sulfate.
Preferably, the cooling method comprises the following steps: the ice water was added repeatedly and cooled.
In summary, compared with the prior art, the invention achieves the following technical effects:
(1) the yield of the acetanilide is improved;
(2) the reaction time is relatively short;
(3) the reaction temperature is low;
(4) simple process and easy industrial popularization.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Synthesis of acetanilide
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.3%.
Example 2
The main difference from example 1 is the molar ratio between glacial acetic acid and N, N-dimethylacetamide, which is as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.15mol of glacial acetic acid, 0.45mol of N, N-dimethylacetamide and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.7%.
Example 3
The main difference from example 1 is the molar ratio between glacial acetic acid and N, N-dimethylacetamide, which is as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.12mol of glacial acetic acid, 0.48mol of N, N-dimethylacetamide and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.1%.
Example 4
The main difference from example 1 is the catalyst used, specifically as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of sodium amide, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.9%.
Example 5
The main difference from example 1 is the catalyst used, specifically as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.2mol of ammonium chloride, 0.1mol of sodium amide, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensation tube, stirring, heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.2%.
Example 6
The main difference from example 1 is the amount of catalyst used, which is specified below.
The first step is as follows:
adding 0.3mol of aniline, 0.45mol of ammonium chloride, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide and 0.36mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.4%.
Example 7
The main difference from example 1 is the amount of acetylating agent used, as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.1mol of glacial acetic acid, 0.35mol of N, N-dimethylacetamide and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 99.1%.
Example 8
The main difference from example 1 is the amount of dicyclohexylcarbodiimide used, which is as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide and 0.36mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.4%.
Example 9
The main difference from example 1 is that the drying method is more diversified, as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide, 0.24mol of dicyclohexylcarbodiimide and 10mg of calcium chloride sealed in a bag into a round-bottom flask, installing an air condensation tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 98.8%.
Comparative example 1
The difference from example 1 is that N, N-dimethylacetamide is not used, as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.6mol of glacial acetic acid and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condenser tube, stirring, heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 89.5%.
Comparative example 2
The only difference from example 1 is the dehydrating reagent used, as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of ammonium chloride, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide and 0.24mol of cyclohexane into a round-bottom flask, installing an air condenser tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 91.3%.
Comparative example 3
The difference from example 1 is in the catalyst used, specifically as follows.
The first step is as follows:
adding 0.3mol of aniline, 0.3mol of p-toluenesulfonic acid, 0.2mol of glacial acetic acid, 0.4mol of N, N-dimethylacetamide and 0.24mol of dicyclohexylcarbodiimide into a round-bottom flask, installing an air condensing tube, stirring and heating to 120 ℃, refluxing for 3 hours, stopping heating after the reaction is completed, and naturally cooling to room temperature.
The second step is that:
adding ice water into the reaction liquid in the first step, standing, performing suction filtration when no solid is separated out, continuously cooling the filtrate to below 0 ℃, separating out the solid again, performing suction filtration, combining the solids obtained by the two suction filtration, washing with water, and drying to obtain white needle-shaped crystals, wherein the yield is 89.2%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. The preparation method of the acetanilide is characterized by comprising the following steps of:
uniformly mixing aniline, an acetylation reagent, a dehydrating agent and a catalyst, heating to 100-120 ℃, performing reflux reaction for 3-4 hours at the temperature, and cooling to separate out a product;
the acetylation reagent is prepared by mixing glacial acetic acid and N, N-dimethylacetamide in a molar ratio of 1: 2-4, the dehydrating agent is dicyclohexylcarbodiimide, and the catalyst is sodium amide or ammonium chloride or a mixture of the sodium amide and the ammonium chloride;
the molar ratio of the acetylation reagent to the aniline is 1.5-2: 1;
the molar ratio of the catalyst to the aniline is 1-1.5: 1;
the molar ratio of the dehydrating agent to the aniline is 0.8-1.2: 1;
and a drying agent is also added during the reflux reaction, and the drying agent is calcium chloride or calcium sulfate.
2. The method for producing acetanilide according to claim 1, wherein the catalyst is sodium amide.
3. The method for producing acetanilide according to claim 1, wherein the temperature of the reflux reaction is 110 to 120 ℃.
4. The method for producing acetanilide according to claim 1, wherein the acetylating agent is glacial acetic acid and N, N-dimethylacetamide, and the mixture is mixed in a molar ratio of 1:2 to 3.
5. The method for preparing acetanilide according to claim 1, wherein the cooling method comprises: the ice water was added repeatedly and cooled.
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| CN105017029A (en) * | 2015-07-15 | 2015-11-04 | 蚌埠中实化学技术有限公司 | Preparation method of p-bromoaniline |
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| CN105017029A (en) * | 2015-07-15 | 2015-11-04 | 蚌埠中实化学技术有限公司 | Preparation method of p-bromoaniline |
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