CN116332786B - Preparation process of compound acetamide - Google Patents
Preparation process of compound acetamide Download PDFInfo
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- CN116332786B CN116332786B CN202310190618.8A CN202310190618A CN116332786B CN 116332786 B CN116332786 B CN 116332786B CN 202310190618 A CN202310190618 A CN 202310190618A CN 116332786 B CN116332786 B CN 116332786B
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 145
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000002148 esters Chemical class 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 17
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 33
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 32
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical group CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000010533 azeotropic distillation Methods 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 53
- -1 hydroxy, protected amino Chemical group 0.000 description 10
- 150000001263 acyl chlorides Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000003857 carboxamides Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- VSQUZVLNMULDCY-UHFFFAOYSA-N [O].C1=CC=NC=C1 Chemical compound [O].C1=CC=NC=C1 VSQUZVLNMULDCY-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000005236 alkanoylamino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of compound preparation, in particular to a preparation process of compound acetamide. Which comprises the following steps: adding enough deionized water and ethanol into a reaction kettle, stirring, and adding a catalyst into the reaction kettle to azeotropically generate azeotropic liquid; taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating at normal pressure to generate intermediate liquid; after the intermediate liquid is cooled, the intermediate liquid is sent back to the reaction kettle, primary alcohol is added into the reaction kettle for stirring and mixing, and then the intermediate liquid is heated to generate ester liquid; mixing ammonia water and copper sulfate into the ester liquid, standing, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent. In the present invention, the yield of carboxylic acid amide is indirectly increased by increasing the yield of raw materials such as carboxylic acid, carboxylic ester and the like.
Description
Technical Field
The invention relates to the technical field of compound preparation, in particular to a preparation process of compound acetamide.
Background
Carboxylic acid amides, also known as carboxamides, are carboxylic acid derivatives, which are compounds in which the hydroxyl group of the carboxyl group in the carboxylic acid molecule is substituted by an amino group or a hydrocarbylamino group (-NHR or-NR 2); it can also be considered as a compound in which hydrogen on nitrogen atoms in ammonia or amine molecules is substituted with acyl groups.
The novel process for preparing hydroxyamic acid derivatives of the formula I via the corresponding novel carboxylic acid esters, as described in CN1117487A, involves a process for preparing carboxamides by aryl, protected hydroxy, protected amino, amido, succinimidyl, 2, 3-dihydro-1, 3-dioxo-1H-benzo [ d, e ] isoquinolin-2-yl, protected carboxy, carbamoyl, carboxy-lower alkanoylamino, pyrrolidino or morpholino optionally replacing the R1 group of H, protected amino, amido or lower alkyl and optionally replacing the R2 group of lower alkyl by protected carboxy, mono-or di (lower alkyl) carbamoyl or morpholino, but suffers from the problem of lower yields of carboxamides, which cannot be used for mass production of carboxamides.
In order to improve the yield of carboxylic acid amide compounds so as to facilitate large-scale production, a preparation process of a compound acetamide is provided.
Disclosure of Invention
The invention aims to provide a preparation process of a compound acetamide, which aims to solve the problems in the background technology.
In order to achieve the above object, the present invention provides a process for preparing acetamide, comprising the steps of:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, and adding a catalyst into the reaction kettle to azeotropically generate azeotropic liquid;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating the azeotropic liquid at normal pressure to generate intermediate liquid;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing, and heating to generate ester liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent.
As a further improvement of the technical scheme, in the S1, the catalyst is tetramethyl piperidine oxide and chromium oxide, wherein the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4.
As a further improvement of the technical scheme, in the S1, the temperature during azeotropic distillation is 85-95 ℃.
As a further improvement of the technical scheme, in the S2, the ratio of the added amount of the N, N-dimethylformamide to the added amount of the thionyl chloride is 0.25-0.40.
As a further improvement of the technical scheme, in the step S3, the amount of the primary alcohol added is 0.45-0.85 of the weight of the intermediate liquid.
As a further improvement of the technical scheme, in the step S3, the stirring rotating speed is 70-100rpm/min.
As a further improvement of the technical scheme, in the step S4, the standing time is 3-8h.
As a further improvement of the present technical solution, in S4, the organic solvent is tetrahydrofuran.
In the invention, tetramethyl piperidine oxide and chromium oxide are used as catalysts, molecular surface activities of pyridine oxygen free radicals and chromium oxide are used for carrying out polarization on hydrocarbon bonds to dehydrogenate, and H-separated by adsorption are used for realizing dehydrogenation and oxygenation, promoting the conversion of water and ethanol into carboxylic acid, improving the conversion rate of the carboxylic acid, and then the carboxylic acid is reacted with thionyl chloride to be converted into acyl chloride, improving the reaction activity and then reacted with alcohols to generate carboxylic acid ester, so that the reversible reaction can be avoided, the reaction rate of generating the carboxylic acid ester is improved, the carboxylic acid ester is subjected to urethane exchange with ammonia water under the catalysis of copper sulfate, and the amino group in the ammonia water replaces an ester group originally connected to an acyclic carbon atom on a carbon frame of the carboxylic acid ester, thereby generating carboxylic acid amide.
Compared with the prior art, the invention has the beneficial effects that:
in the preparation process of the compound acetamide, hydrocarbon bonds are polarized by pyridine oxygen free radicals and chromium trioxide to be dehydrogenated, water and ethanol are promoted to be converted into carboxylic acid, the conversion rate of the carboxylic acid is improved, the carboxylic acid is reacted with thionyl chloride to be converted into acyl chloride, the carboxylic acid is reacted with alcohols to generate carboxylic acid ester after the reaction activity is improved, the occurrence of reversible reaction can be avoided, the reaction rate of generating the carboxylic acid ester is improved, the carboxylic acid ester is subjected to urethane exchange with ammonia water under the catalysis of copper sulfate, and the amino group in the ammonia water replaces ester groups originally connected to acyclic carbon atoms on a carbon frame of the carboxylic acid ester, so that the carboxylic acid amide is generated.
Drawings
FIG. 1 is a schematic overall flow chart of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the present invention aims to provide a process for preparing acetamide, which comprises the following steps:
s1, adding enough deionized water and ethanol into a reaction kettle to stir, adding a catalyst into the reaction kettle to carry out azeotropy in a temperature range of 85-95 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4, the pyridine oxygen free radical in the tetramethyl piperidine oxide is stable nitrogen oxygen free radical, the pyridine oxygen free radical can be used as a catalyst for promoting water and ethanol to be converted into carboxylic acid in the oxidation process, and the chromium oxide polarizes hydrocarbon bonds to dehydrogenate due to the molecular surface activity of the chromium oxide and adsorbs separated H-, so that dehydrogenation and oxygenation are converted into carboxyl, and the conversion rate in the reaction process can be improved through azeotropy;
s2, taking out azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, heating to 30-50 ℃ under normal pressure to generate intermediate liquid, wherein the reaction condition for preparing acyl chloride from thionyl chloride is mild, the acyl chloride can react at room temperature or slightly heated, the ratio of the added N, N-dimethylformamide to the added thionyl chloride is 0.25-0.40, and the thionyl chloride is combined with the N, N-dimethylformamide and then combined with carboxylic acid under the catalysis of the N, N-dimethylformamide to generate acyl chloride;
s3, after the intermediate liquid is cooled, the intermediate liquid is sent back to the reaction kettle, primary alcohol is added into the reaction kettle, stirred and mixed uniformly at the rotating speed of 70-100rpm/min, and then heated to generate ester liquid, the primary alcohol is fully contacted with acyl chloride in the intermediate liquid in a stirring manner to improve the yield of carboxylic ester, wherein the added primary alcohol is 0.45-0.85 of the weight of the intermediate liquid, and the direct esterification reaction of the carboxylic acid and the alcohol is reversible, and the reaction rate is extremely slow, so that the yield of the carboxylic ester is lower, and the carboxylic ester is generated by converting carboxylic acid into acyl chloride firstly, improving the reaction activity and then reacting with the alcohol, so that the occurrence of reversible reaction can be avoided, and the reaction rate is improved;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 3-8 hours, wherein long-time standing is favorable for the amino group in the ammonia water to exchange with ester groups of carboxylic acid ester, the amino group replaces ester groups originally connected to acyclic carbon atoms on a carbon frame of the carboxylic acid ester, so that carboxylic acid amide is generated, saturated sodium carbonate is adopted to wash out carboxylic acid, and the carboxylic acid amide is extracted by using an organic solvent after the ester liquid is acidified, wherein the organic solvent is tetrahydrofuran, and the tetrahydrofuran can dissolve all organic compounds except polyethylene, polypropylene and fluororesin, so that the organic solvent can be used for extracting the carboxylic acid amide.
In the invention, tetramethyl piperidine oxide and chromium oxide are used as catalysts, molecular surface activities of pyridine oxygen free radicals and chromium oxide are used for carrying out polarization on hydrocarbon bonds to dehydrogenate, and H-separated by adsorption are used for realizing dehydrogenation and oxygenation, promoting the conversion of water and ethanol into carboxylic acid, improving the conversion rate of the carboxylic acid, and then the carboxylic acid is reacted with thionyl chloride to be converted into acyl chloride, improving the reaction activity and then reacted with alcohols to generate carboxylic acid ester, so that the reversible reaction can be avoided, the reaction rate of generating the carboxylic acid ester is improved, the carboxylic acid ester is subjected to urethane exchange with ammonia water under the catalysis of copper sulfate, and the amino group in the ammonia water replaces an ester group originally connected to an acyclic carbon atom on a carbon frame of the carboxylic acid ester, thereby generating carboxylic acid amide.
The preparation method of the carboxylic acid amide compound provided by the invention is further described by the following specific examples according to the difference of technological parameters in the preparation process.
Example 1
S1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 85 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 30 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.25;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the rotating speed of 70rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.45 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 3 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Example 2
S1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 90 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 40 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.30;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the speed of 85rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.65 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 6 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Example 3
S1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 95 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 50 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.40;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the rotating speed of 100rpm/min, and heating to generate ester liquid, wherein the adding amount of the primary alcohol is 0.85 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 8 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Example 4
S1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 90 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 45 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.30;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the rotating speed of 80rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.80 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 4 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Table 1 comparative process parameters in examples 1-4
Comparative example 1
The comparative example was prepared by the method of example 1, the azeotropic temperature was set to 80℃and the rest was unchanged, and the specific procedure was as follows:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 80 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 30 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.25;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the rotating speed of 70rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.45 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 3 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Comparative example 2
The preparation method of the comparative example 1 is adopted, the azeotropic temperature is set to be 100 ℃, the rest is unchanged, the specific steps are similar to those of the comparative example 1, and the comparative example is not repeated.
Table 2 comparative process parameters comparative examples 1-2
Comparative example 3
The preparation method of example 2 was adopted in this comparative example, the heating temperature was set to 25 ℃, and the rest was unchanged, and the specific steps were as follows:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 90 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 25 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.30;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the speed of 85rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.65 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 6 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Comparative example 4
The preparation method of example 2 is adopted in this comparative example, the heating temperature is set to 80 ℃, the rest is unchanged, the specific steps are similar to those of comparative example 3, and the detailed description of this comparative example is omitted.
Table 3 comparative process parameters comparative examples 3-4
Comparative example 5
This comparative example was prepared by the method of example 3, and the ratio of the amount of added N, N-dimethylformamide to the amount of thionyl chloride was set to 0.15, the remainder being unchanged, and the specific procedure was as follows:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 95 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 50 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.15;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the rotating speed of 100rpm/min, and heating to generate ester liquid, wherein the adding amount of the primary alcohol is 0.85 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 8 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Comparative example 6
The comparative example was prepared by the method of example 3, the ratio of the amount of added N, N-dimethylformamide to the amount of thionyl chloride was set to 0.50, the remainder was unchanged, and the specific procedure was similar to comparative example 5, and the comparative example was not repeated.
Table 4 comparative process parameters comparative examples 5-6
Comparative example 7
The preparation method of example 4 was adopted in this comparative example, the stirring rotation speed was set to 50rpm/min, and the rest was unchanged, and the specific steps were as follows:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 90 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 45 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.30;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the rotating speed of 50rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.80 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 4 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Comparative example 8
The preparation method of example 4 is adopted in the comparative example, the stirring rotation speed is set to 120rpm/min, the rest is unchanged, the specific steps are similar to those of comparative example 7, and the comparative example is not repeated.
Table 5 comparative process parameters comparative examples 7-8
Comparative example 9
The comparative example uses the preparation method of example 1, the amount of primary alcohol added is set to be 0.30 of the weight of the intermediate liquid, and the rest is unchanged, and the specific steps are as follows:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 85 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 30 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.25;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the rotating speed of 70rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.30 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 3 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Comparative example 10
The preparation method of the comparative example 1 is adopted, the amount of primary alcohol added is set to be 0.90 of the weight of the intermediate liquid, the rest is unchanged, the specific steps are similar to those of the comparative example 9, and the comparative example is not repeated.
Table 6 comparative process parameters comparative examples 9-10
Comparative example 11
The preparation method of example 2 is adopted in the comparative example, the standing time is set to be 2 hours, and the rest is unchanged, and the specific steps are as follows:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, adding a catalyst into the reaction kettle, and carrying out azeotropy in a temperature range of 90 ℃ to generate azeotropic liquid, wherein the catalyst is tetramethyl piperidine oxide and chromium oxide, and the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating to 40 ℃ under normal pressure to generate intermediate liquid, wherein the ratio of the added N, N-dimethylformamide to the amount of the added thionyl chloride is 0.30;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing at the speed of 85rpm/min, and heating to generate ester liquid, wherein the amount of the added primary alcohol is 0.65 of the weight of the intermediate liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing for 2 hours, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting carboxylic acid amide by using an organic solvent, wherein the organic solvent is tetrahydrofuran.
Comparative example 12
The preparation method of example 2 is adopted in this comparative example, the standing time is set to 10h, the rest is unchanged, the specific steps are similar to those of comparative example 11, and the detailed description of this comparative example is omitted.
Table 7 comparative process parameters comparative examples 11-12
Test examples
The preparation was carried out according to the preparation process of one of the compound acetamides provided in examples 1 to 4 and comparative examples 1 to 12, respectively, and the yield of the carboxylic acid amide was measured and calculated after completion of the preparation, the yield calculation formula was carboxylic acid amide yield/(total amount of ethanol charged-total amount of ethanol remaining), and the data was filled in Table 8.
Table 8 comparison of the yields of carboxylic acid amides of examples and comparative examples
As can be seen from table 8, the process for preparing a compound acetamide according to the present invention has a higher yield of carboxylic acid amide than that of the comparative example, and the process for preparing a compound acetamide according to the present invention has a lower yield of carboxylic acid amide than that of the comparative example, which is advantageous for mass industrial production of carboxylic acid amide.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A process for the preparation of a compound acetamide, comprising the steps of:
s1, adding enough deionized water and ethanol into a reaction kettle, stirring, and adding a catalyst into the reaction kettle to azeotropically generate azeotropic liquid;
s2, taking out the azeotropic liquid, adding N, N-dimethylformamide and thionyl chloride into the azeotropic liquid, and heating the azeotropic liquid at normal pressure to generate intermediate liquid;
s3, after the intermediate liquid is cooled, sending the intermediate liquid back to the reaction kettle, adding primary alcohol into the reaction kettle, stirring and uniformly mixing, and heating to generate ester liquid;
s4, mixing ammonia water and copper sulfate into the ester liquid, standing, eluting carboxylic acid by using saturated sodium carbonate, acidifying the ester liquid, and extracting acetamide by using an organic solvent;
in the S1, the catalyst is tetramethyl piperidine oxide and chromium oxide, wherein the weight ratio of the tetramethyl piperidine oxide to the chromium oxide is 1:4;
in the step S1, the temperature during azeotropic distillation is 85-95 ℃;
in the step S2, the heating temperature is 30-50 ℃.
2. The process for preparing the compound acetamide of claim 1, wherein: in the S2, the ratio of the added amount of the N, N-dimethylformamide to the added amount of the thionyl chloride is 0.25-0.40.
3. The process for preparing the compound acetamide of claim 1, wherein: in the step S3, the amount of the primary alcohol added is 0.45-0.85 of the weight of the intermediate liquid.
4. The process for preparing the compound acetamide of claim 1, wherein: in the step S3, the stirring rotation speed is 70-100rpm/min.
5. The process for preparing the compound acetamide of claim 1, wherein: in the step S4, standing time is 3-8h.
6. The process for preparing the compound acetamide of claim 1, wherein: in the step S4, the organic solvent is tetrahydrofuran.
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