CN117964512B - Synthesis method of N, N-dimethyl-3-methoxy propionamide - Google Patents
Synthesis method of N, N-dimethyl-3-methoxy propionamide Download PDFInfo
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- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 71
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 29
- ZEVPZBDCQLTDHD-UHFFFAOYSA-N 3-hydroxy-n,n-dimethylpropanamide Chemical compound CN(C)C(=O)CCO ZEVPZBDCQLTDHD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 9
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 9
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021576 Iron(III) bromide Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 description 18
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- SFPQDYSOPQHZAQ-UHFFFAOYSA-N 2-methoxypropanenitrile Chemical compound COC(C)C#N SFPQDYSOPQHZAQ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HTNUUDFQRYBJPH-UHFFFAOYSA-N 3-methoxypropanehydrazide Chemical compound COCCC(=O)NN HTNUUDFQRYBJPH-UHFFFAOYSA-N 0.000 description 2
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 2
- YSIKHBWUBSFBRZ-UHFFFAOYSA-N 3-methoxypropanoic acid Chemical compound COCCC(O)=O YSIKHBWUBSFBRZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- -1 sodium alkoxide Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ICPWFHKNYYRBSZ-UHFFFAOYSA-N 2-methoxypropanoic acid Chemical compound COC(C)C(O)=O ICPWFHKNYYRBSZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthetic method of N, N-dimethyl-3-methoxy propionamide, which comprises the following steps: under the action of a Lewis acid catalyst, N, N-dimethylformamide and ethylene glycol are subjected to alkylation reaction to obtain N, N-dimethyl-3-hydroxy-propionamide, and the N, N-dimethyl-3-hydroxy-propionamide and methanol are subjected to methoxy reaction to generate N, N-dimethyl-3-methoxy-propionamide. The invention provides a novel method for synthesizing N, N-dimethyl-3-methoxy propionamide by taking N, N-dimethyl formamide and ethylene glycol as raw materials and Lewis acid as a catalyst, which has the advantages of low raw material toxicity, wide sources and easy transportation, and is suitable for industrial production. In addition, the process flow is simple, the reaction yield is high, and the yield can reach 86.3 percent.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of N, N-dimethyl-3-methoxy propionamide.
Background
N, N-dimethyl-3-methoxypropionamide is a colorless transparent liquid having amide functional groups and methoxy groups, is an important organic solvent, and can be used as a solvent, an intermediate, and a catalyst due to its good solubility and reactivity. Can be mixed with various solvents, and can dissolve polymer polyamide to a high degree; the modified polyvinyl pyrrolidone has the characteristics of high solubility, high permeability, high fluidity, low viscosity, low surface tension and the like, has no irritation to skin, is safe and environment-friendly, can well replace the traditional solvent N-methylpyrrolidone, and is widely applied to industries such as electronics, medicines, pesticides, pigments, cleaning agents, insulating materials and the like. In the safety solvent market which is in competition for continuous refinement, high volatility and low toxicity become important chips for solvent competition besides solubility, so the market prospect of the product is wide. The current synthesis method of N, N-dimethyl-3-methoxy propionamide mainly comprises the following steps:
In patent CN 106966923, acrylonitrile, anhydrous methanol and metal alkoxide are added into a reactor for reaction, and unreacted anhydrous methanol is recovered to obtain 3-methoxy propionitrile; adding an acid catalyst and water into 3-methoxypropionitrile, heating for hydrolysis reaction, and filtering to obtain 3-methoxypropionic acid; adding 3-methoxy propionic acid and dimethylamine into a closed reactor, and heating to react to obtain 3-methoxy-N, N-dimethyl propionamide. The method takes acrylonitrile as an initial raw material, the acrylonitrile is alkoxylated to obtain methoxy propionitrile, then the methoxy propionitrile is hydrolyzed to obtain methoxy propionic acid, and then the methoxy propionitrile reacts with acid and alkali to form salt and is dehydrated to obtain a target product. However, the method uses raw materials such as acrylonitrile, dimethylamine and the like, has certain toxicity, and meanwhile, the reaction is under a high pressure condition, so that the reaction condition is harsh, and the industrial operation is not facilitated.
Patent CN116924909 discloses that the 3-methoxypropionate is obtained by michael addition reaction of acrylic acid ester and methanol as raw materials in the presence of an alkaline catalyst, and the 3-methoxypropionate and dimethylamine are used as raw materials, and diethylene glycol is used as a solvent to be synthesized under the catalysis of sodium alkoxide. The method still uses dimethylamine with low boiling point as raw material, and has great limitation.
The related technology for synthesizing N, N-dimethyl-3-methoxy propionamide is not mature enough at present, and a route suitable for industrial production is lacking, so the prior technology needs to be further developed.
Disclosure of Invention
Aiming at various defects in the prior art, in order to solve the problems, a synthesis method of N, N-dimethyl-3-methoxy propionamide is provided, and the following technical scheme is provided:
A synthetic method of N, N-dimethyl-3-methoxy propionamide comprises the following steps: under the action of a Lewis acid catalyst, N, N-dimethylformamide and ethylene glycol are subjected to alkylation reaction to obtain N, N-dimethyl-3-hydroxy-propionamide, and the N, N-dimethyl-3-hydroxy-propionamide and methanol are subjected to methoxy reaction to generate N, N-dimethyl-3-methoxy-propionamide.
Further, in the alkylation reaction process, the ethylene glycol is dropwise added to the N, N-dimethylformamide for 5-6 hours.
Further, after the ethylene glycol is added dropwise, the reaction is continued for 0.5 to 1.5 hours to obtain the N, N-dimethyl-3-hydroxy-propionamide.
Further, the reaction temperature of the alkylation reaction is 150-190 ℃.
Further, the reaction mole ratio of N, N-dimethylformamide to ethylene glycol is 1: (1.05-1.2).
Further, in the methoxy reaction process, methanol is added dropwise into N, N-dimethyl-3-hydroxy-propionamide for 2-3h.
Further, the reaction temperature of the methoxy reaction is 60-120 ℃.
Further, the molar usage ratio of the N, N-dimethylformamide to the methanol is 1: (1.0-2.0).
Further, the Lewis acid catalyst is AlCl 3、BF3、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2, a molecular sieve containing Lewis acid or zeolite containing Lewis acid, and the addition amount of the Lewis acid catalyst is 0.5-5 wt% of N, N-dimethylformamide.
Further, by-product water is generated in the alkylation reaction process, and is removed by normal pressure rectification.
The beneficial effects are that:
1. the invention selects N, N-dimethylformamide and ethylene glycol as raw materials, has low toxicity, wide sources and easy transportation, and is suitable for industrial production.
2. In the invention, the amino group of the N, N-dimethylformamide does not react in the reaction process, but the acyl carbon and alcohol are subjected to alkylation reaction, lewis acid and electron-rich center of the N, N-dimethylformamide are coordinated to form a complex, so that carbon atoms of an amide bond are activated, and the reaction is promoted.
3. The invention has simple process flow, no need of separation and purification after the reaction in the first step is finished, and the N, N-dimethyl-3-methoxy propionamide is directly generated in situ by dropwise adding methanol in the second step, so that the reaction yield is high and can reach 86.3 percent.
Drawings
FIG. 1 is a schematic illustration of the reaction mechanism of the present invention.
Detailed Description
In order to make the technical solution of the present application better understood by those skilled in the art, the technical solution of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and based on the embodiments of the present application, other similar embodiments obtained by those skilled in the art without making creative efforts should fall within the protection scope of the present application.
According to an embodiment of the invention, there is provided a synthesis method of N, N-dimethyl-3-methoxypropionamide, the synthesis method comprising: under the action of a Lewis acid catalyst, N, N-dimethylformamide and ethylene glycol are subjected to alkylation reaction to obtain N, N-dimethyl-3-hydroxy-propionamide, and the N, N-dimethyl-3-hydroxy-propionamide and methanol are subjected to methoxy reaction to generate N, N-dimethyl-3-methoxy-propionamide. The invention discloses a novel method for synthesizing N, N-dimethyl-3-methoxy propionamide, which takes N, N-Dimethylformamide (DMF) and ethylene glycol as raw materials and takes Lewis acid as a catalyst, has low toxicity, wide sources and easy transportation, and is suitable for industrial production. In addition, the process flow is simple, the reaction yield is high, and the yield can reach 86.3 percent. The specific reaction mechanism is shown in FIG. 1.
The alkylation reaction temperature is controlled at 150-190 ℃, ethylene glycol is dripped at a constant speed, the temperature is slowly raised, and the dripping time is 5-6h. The dripping time is strictly controlled in the reaction process, and too fast dripping time can lead to the self-polymerization of part of ethylene glycol, and simultaneously the water generated by the reaction is timely removed through evaporation by controlling the reaction temperature, thereby being beneficial to promoting the reaction. The second dehydration to ether reaction also requires controlling the dropping speed of methanol, which is beneficial to controlling the occurrence of side reaction.
After the reaction is finished, the N, N-dimethyl-3-methoxy propionamide with the content of more than 99 percent is obtained by purification through post-treatment operations such as filtration, rectification and the like.
The catalyst remained at the bottom of the rectifying still after filtering and rectifying can be recycled after being recovered.
Hereinafter, N-dimethylformamide is abbreviated as DMF.
Example 1
1L of a reaction kettle with magnetic stirring and a rectifying column is prepared, 292.4g of DMF and 1.5g of AlCl 3 are added into the reaction container, then the temperature is raised to 150 ℃, 273.1g of ethylene glycol is slowly added dropwise, the generated water is distilled off by slowly raising the temperature in the dropwise adding process, the dropwise adding time is controlled to be 5h, and the temperature is raised to 190 ℃ after the dropwise adding is finished, and the temperature is kept for 1h, so that the N, N-dimethyl-3-hydroxy-propionamide solution is obtained. And (3) after the heat preservation is finished, the temperature is reduced to 60 ℃, 192.2g of methanol is continuously added into the reaction liquid in a dropwise manner for 2 hours, the temperature is slowly increased to 110 ℃ after the dropwise addition is finished, the heat preservation is carried out for 2 hours, the residual quantity of the N, N-dimethyl-3-hydroxy-propionamide is detected to be less than or equal to 0.5% through sampling, the heat preservation is stopped, the reaction liquid is subjected to rectification treatment, and the content of the N, N-dimethyl-3-methoxy-propionamide 433.5g is 99.2%, and the yield is 82.1%.
Example 2
Preparing a 1L reaction kettle with a magnetic stirring and rectifying column, adding 292.4g of DMF and 6.0g of ZSM-5 type molecular sieve into the reaction container, then heating to 180 ℃, slowly dropwise adding 273.1g of glycol, slowly heating in the dropwise adding process, evaporating out the generated water, controlling the dropwise adding time to be 6h, heating to 190 ℃ after the dropwise adding is finished, and preserving the heat for 1h to obtain the N, N-dimethyl-3-hydroxy-propionamide solution. And (3) after the heat preservation is finished, the temperature is reduced to 60 ℃, 192.2g of methanol is continuously added into the reaction liquid in a dropwise manner for 3 hours, the temperature is slowly increased to 110 ℃ after the dropwise addition is finished, the heat preservation is carried out for 2 hours, the residual quantity of the N, N-dimethyl-3-hydroxy-propionamide is detected to be less than or equal to 0.5% through sampling, the heat preservation is stopped, the reaction liquid is subjected to rectification treatment, and the content of the N, N-dimethyl-3-methoxy-propionamide 455.3g is 99.4%, and the yield is 86.3%.
Example 3
1L of a reaction kettle with magnetic stirring and a rectifying column is prepared, 292.4g of DMF and 10.0g of platinum mordenite are added into the reaction container, then the temperature is raised to 150 ℃, 273.1g of ethylene glycol is slowly added dropwise, the generated water is distilled off by slowly raising the temperature in the dropwise adding process, the dropwise adding time is controlled to be 5h, and the temperature is raised to 190 ℃ after the dropwise adding is finished, and the temperature is kept for 1h, so that the N, N-dimethyl-3-hydroxy-propionamide solution is obtained. And (3) after the heat preservation is finished, the temperature is reduced to 60 ℃, 192.2g of methanol is continuously added into the reaction liquid in a dropwise manner for 3 hours, the temperature is slowly increased to 110 ℃ after the dropwise addition is finished, the heat preservation is carried out for 2 hours, the residual quantity of the N, N-dimethyl-3-hydroxy-propionamide is detected to be less than or equal to 0.5% through sampling, the heat preservation is stopped, the reaction liquid is subjected to rectification treatment, and 432.3g of N, N-dimethyl-3-methoxy-propionamide is obtained, the content is 99.1%, and the yield is 81.7%.
Example 4
1L of a reaction kettle with magnetic stirring and a rectifying column is prepared, 292.4g of DMF and 6g of ZnCl 2 are added into the reaction container, then the temperature is raised to 150 ℃, 273.1g of ethylene glycol is slowly added dropwise, the generated water is distilled off by slowly raising the temperature in the dropwise adding process, the dropwise adding time is controlled to be 6h, and the temperature is raised to 190 ℃ after the dropwise adding is finished, and the temperature is kept for 1h, so that the N, N-dimethyl-3-hydroxy-propionamide solution is obtained. And (3) after the heat preservation is finished, the temperature is reduced to 60 ℃, 192.2g of methanol is continuously added into the reaction liquid in a dropwise manner for 2 hours, the temperature is slowly increased to 120 ℃ after the dropwise addition is finished, the heat preservation is carried out for 3 hours, the residual quantity of the N, N-dimethyl-3-hydroxy-propionamide is detected to be less than or equal to 0.5% through sampling, the heat preservation is stopped, the reaction liquid is subjected to rectification treatment, and the N, N-dimethyl-3-methoxy-propionamide 380.3g with the content of 99.0% and the yield of 71.8% are obtained.
Example 5
Preparing a 1L reaction kettle with a magnetic stirring and rectifying column, adding 292.4g of DMF and 10.4g of recovered platinum mordenite into the reaction container, then heating to 150 ℃, slowly dropwise adding 273.1g of ethylene glycol, slowly heating in the dropwise adding process, evaporating out the generated water, controlling the dropwise adding time to be 6h, heating to 190 ℃ after the dropwise adding is finished, and preserving the heat for 1h to obtain the N, N-dimethyl-3-hydroxy-propionamide solution. And after the heat preservation is finished, the temperature is reduced to 60 ℃, 192.2g of methanol is continuously added into the reaction liquid in a dropwise manner for 2 hours, the temperature is slowly increased to 110 ℃ after the dropwise addition is finished, the heat preservation is carried out for 3 hours, the residual quantity of the N, N-dimethyl-3-hydroxy-propionamide is detected to be less than or equal to 0.5% by sampling, the heat preservation is stopped, the reaction liquid is subjected to rectification treatment, and the N, N-dimethyl-3-methoxy-propionamide 389.1g with the content of 99.2% and the yield of 73.6% are obtained.
Comparative example 1
1L of a reaction kettle with magnetic stirring and a rectifying column is prepared, 292.4g of DMF and 6.0g of ZSM-5 type molecular sieve are added into the reaction container, then the temperature is raised to 180 ℃, 273.1g of ethylene glycol is dropwise added, the dropwise adding process is slowly heated, the generated water is distilled off, the dropwise adding time is controlled to be 2h, and the temperature is raised to 190 ℃ after the dropwise adding is finished, and the temperature is kept for 1h, so that the N, N-dimethyl-3-hydroxy-propionamide solution is obtained. And after the heat preservation is finished, the temperature is reduced to 60 ℃, 192.2g of methanol is continuously added into the reaction liquid in a dropwise manner for 1h, the temperature is slowly increased to 110 ℃ after the dropwise addition is finished, the heat preservation is carried out for 2h, the residual quantity of the N, N-dimethyl-3-hydroxy-propionamide is detected to be less than or equal to 0.5% by sampling, the heat preservation is stopped, the reaction liquid is subjected to rectification treatment, and 151.8g of N, N-dimethyl-3-methoxy-propionamide is obtained, the content is 92.6%, and the yield is 26.8%.
Comparative example 2
1L of a reaction kettle with magnetic stirring is prepared, 292.4g of DMF and 6.0g of ZSM-5 molecular sieve are added into the reaction container, then the temperature is raised to 180 ℃, ethylene glycol is slowly added dropwise, the gas phase is condensed in the dropping process and then is totally refluxed, the generated water is not distilled out, the dropping time is controlled to be 6 hours, the temperature is raised to 190 ℃ after the dropping is finished and is kept for 1 hour, the N, N-dimethyl-3-hydroxy-propionamide solution is obtained, the conversion rate of the sampling detection raw materials is 4.3%, and the content of N, N-dimethyl-3-hydroxy-propionamide is very low.
As can be seen from the above examples 1-5, the present invention provides a novel synthesis method of N, N-dimethyl-3-methoxy propionamide, the yield can reach 86.3%, wherein the catalyst is Lewis acid, and the electrophilic center of the Lewis acid containing electron defects and DMF is coordinated to form a complex, so that the carbon atom of the amide bond is activated, and the reaction is promoted. The whole reaction process is divided into two parts, namely alkylation and etherification, and the target product N, N-dimethyl-3-methoxy propionamide is generated by in-situ catalysis of a catalyst. The whole process is simple to operate, the intermediate process does not need to be purified, is similar to a one-pot method for direct synthesis, and is very suitable for industrial production. In addition, the ZSM-5 type molecular sieve has larger specific surface area and more outstanding catalytic effect.
Comparative example 1 compared with example 2, since the dropping time for dropping ethylene glycol in comparative example 1 was shortened and the dropping speed was thereby accelerated, the self-polymerization of a part of ethylene glycol was caused, and the generation of side reaction could not be controlled.
Comparative example 2 compared with example 2, since the water generated by the reaction was not removed in time by evaporation in comparative example 2, the progress of the reaction was hindered, and finally the yield of N, N-dimethyl-3-methoxypropionamide was greatly reduced.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. A method for synthesizing N, N-dimethyl-3-methoxy propionamide, which is characterized by comprising the following steps: under the action of a Lewis acid catalyst, carrying out alkylation reaction on N, N-dimethylformamide and ethylene glycol to obtain N, N-dimethyl-3-hydroxy-propionamide, and carrying out methoxy reaction on the N, N-dimethyl-3-hydroxy-propionamide and methanol to generate N, N-dimethyl-3-methoxy-propionamide;
In the alkylation reaction process, dropwise adding ethylene glycol into N, N-dimethylformamide for 5-6 hours;
In the methoxy reaction process, dropwise adding methanol into N, N-dimethyl-3-hydroxy propionamide for 2-3h;
byproduct water is generated in the alkylation reaction process, and is removed by normal pressure rectification.
2. The method for synthesizing N, N-dimethyl-3-methoxypropionamide according to claim 1, wherein the N, N-dimethyl-3-hydroxypropyl amid is obtained after the reaction is continued for 0.5 to 1.5 hours after the addition of ethylene glycol is completed.
3. The method for synthesizing N, N-dimethyl-3-methoxypropionamide according to claim 1, wherein the reaction temperature of the alkylation reaction is 150 to 190 ℃.
4. The method for synthesizing N, N-dimethyl-3-methoxypropionamide according to claim 1, wherein the reaction molar ratio of N, N-dimethylformamide to ethylene glycol is 1: (1.05-1.2).
5. The method for synthesizing N, N-dimethyl-3-methoxypropionamide according to claim 1, wherein the reaction temperature of the methoxy reaction is 60 to 120 ℃.
6. The method for synthesizing N, N-dimethyl-3-methoxypropionamide according to claim 1, wherein the molar ratio of N, N-dimethylformamide to methanol is 1: (1.0-2.0).
7. The method for synthesizing N, N-dimethyl-3-methoxypropionamide according to claim 1, wherein the Lewis acid catalyst is AlCl 3、BF3、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2, a molecular sieve containing Lewis acid or a zeolite containing Lewis acid, and the addition amount of the Lewis acid catalyst is 0.5wt% to 5wt% of N, N-dimethylformamide.
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