CN108675938B - Novel method for preparing N-N-butylacrylamide - Google Patents
Novel method for preparing N-N-butylacrylamide Download PDFInfo
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- CN108675938B CN108675938B CN201810694413.2A CN201810694413A CN108675938B CN 108675938 B CN108675938 B CN 108675938B CN 201810694413 A CN201810694413 A CN 201810694413A CN 108675938 B CN108675938 B CN 108675938B
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- reaction
- butyl
- butylacrylamide
- preparing
- fluorine
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- 238000000034 method Methods 0.000 title claims abstract description 18
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract 3
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 21
- KISFVPPZJYBXKY-UHFFFAOYSA-N N-butylbutanethioamide Chemical compound C(CCC)NC(CCC)=S KISFVPPZJYBXKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical class F* 0.000 claims 3
- 238000004821 distillation Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000012363 selectfluor Substances 0.000 abstract 1
- -1 tetrafluoroborate Chemical compound 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of fine chemical engineering, and discloses a novel method for preparing N-N-butylacrylamide. The method comprises the following specific steps: the N-N-butyl-3-methylthiopropanamide as a starting material and an additive Selectfluor (1-chloromethyl-4-fluoro-1, 4-diazabicyclooctane bis (tetrafluoroborate)) are stirred and react for 8 hours at 100 ℃ in an organic solvent 1, 4-dioxane to obtain the N-N-butyl acrylamide. The invention has the following characteristics: the N-N-butyl acrylamide can be obtained by directly heating and stirring fluorine as an additive. Compared with the prior art, the method does not need to use toxic, easily-corroded and easily-volatilized acyl chloride as a raw material, is simple to operate and has small influence on the environment.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a novel method for preparing N-N-butylacrylamide.
Background
N-N-butylacrylamide is a very important chemical raw material and is widely applied to the synthesis of various drug intermediates and fine chemicals. There are many methods for synthesizing acrylamide compounds, and the most common method for preparing acrylamide is to synthesize acrylamide derivatives by using acryloyl chloride and corresponding amines as starting materials, but the reaction process usually requires the use of the more harmful acryloyl chloride as a raw material. Meanwhile, toxic and harmful hydrogen chloride gas is generated in the reaction process, and the technical characteristics of environment friendliness at present are not met.
The traditional synthesis method of N-N-butylacrylamide comprises the following steps:
it can be seen from the above that the starting material of the reaction needs to use acryloyl chloride, which is a highly corrosive organic chemical, and has strong burning, and the acryloyl chloride itself is easily decomposed, and has the characteristics of easy volatilization, flammability, etc., and can release equivalent amount of toxic and harmful hydrogen chloride gas in the reaction process. Therefore, it is necessary to develop a synthetic method which is low in toxicity, environment-friendly and simple in operation.
Disclosure of Invention
The invention provides a novel method for preparing N-N-butyl acrylamide by a synthetic method without using acryloyl chloride aiming at the defects in the synthetic process of the N-N-butyl acrylamide.
The reaction steps for synthesizing the N-N-butyl acrylamide comprise: sequentially adding N-butyl-3-methylthiopropionamide and 1-chloromethyl-4-fluoro-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroborate) into a reaction solvent 1, 4-dioxane, violently stirring for 6-10h at 80-120 ℃, washing with water after the reaction is finished, extracting, and distilling the filtrate under reduced pressure to obtain the N-N-butylacrylamide.
In the present invention, the solvent may be 1, 4-dioxane, acetonitrile or a mixed system of 1, 4-dioxane and acetonitrile, and 1, 4-dioxane is preferred.
In the invention, the dosage molar ratio of the N-butyl-3-methylthiopropionamide to the chloromethyl-4-fluoro-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroborate) is 1: 1.
The reaction temperature in the present invention is 80 to 120 ℃, preferably 100 ℃.
The reaction time in the present invention is 6 to 10 hours, preferably 8 hours.
Detailed Description
The following examples will help illustrate the invention, but do not limit its scope.
Specific example 1:
in a 100mL round-bottom flask were added N-butyl-3-methylthiopropionamide (20mmol,3.51g), 1-chloromethyl-4-fluoro-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroborate) salt (20mmol,3.55g), and 20mL of 1, 4-dioxane in this order, the reaction temperature was controlled at 100 ℃, and the reaction was stirred vigorously for 8 h. After the reaction, the reaction system was cooled to room temperature, washed with water, extracted, and the filtrate was distilled under reduced pressure to collect the main fraction, thereby obtaining N-butylacrylamide (2.42g, 95%).
The reaction involves the following equation:
specific example 2:
in a 100mL round-bottom flask were added N-butyl-3-methylthiopropionamide (20mmol,3.51g), 1-chloromethyl-4-fluoro-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroborate) salt (20mmol,7.10g), and 20mL of N, N-dimethylformamide in that order, the reaction temperature was controlled at 80 ℃, and the reaction was stirred vigorously for 8 h. After the reaction was completed, the reaction system was cooled to room temperature, washed with water, extracted, and the filtrate was distilled under reduced pressure to collect the main fraction, thereby obtaining N-N-butylacrylamide (2.29g, 90%).
The above specific reaction embodiments are intended to guide those skilled in the art how to implement and reproduce the processes of the present invention. The foregoing detailed description has simplified or eliminated some of the conventional technical operations in order to facilitate the process of the present invention. Those skilled in the art will appreciate variations from this aspect that fall within the scope of the invention.
Claims (6)
1. The method for preparing the N-N-butyl acrylamide comprises the following steps: adding N-butyl-3-methylthiopropionamide and fluorine salt into an organic solvent and heating to obtain the N-N-butylacrylamide, wherein the fluorine salt used in the reaction is 1-chloromethyl-4-fluorine-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroborate) salt.
2. The method according to claim 1, further comprising water washing, extraction, and distillation of the filtrate under reduced pressure after the reaction, and collecting the main fraction.
3. The method of claim 1, wherein: the reaction temperature is 100 DEGoC。
4. The method of claim 1, wherein: the reaction time was 8 h.
5. The method of claim 1, wherein: the addition amount of the N-butyl-3-methylthiopropanamide and the fluorine salt is in accordance with the standard of a molar ratio of 1: 1.
6. The method of claim 1, wherein: the organic solvent used in the reaction is 1, 4-dioxane.
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| CN201810694413.2A CN108675938B (en) | 2018-06-29 | 2018-06-29 | Novel method for preparing N-N-butylacrylamide |
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| CN201810694413.2A CN108675938B (en) | 2018-06-29 | 2018-06-29 | Novel method for preparing N-N-butylacrylamide |
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| CN108675938B true CN108675938B (en) | 2019-12-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110563599B (en) * | 2019-09-02 | 2022-03-22 | 常州大学 | Method for preparing 3-methoxy-N-phenylpropionamide |
| CN113402412B (en) * | 2021-06-10 | 2023-02-14 | 温州大学 | (E) Method for synthesizing (E) -beta-fluoroacrylamide derivative |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837539A (en) * | 2015-01-15 | 2016-08-10 | 复旦大学 | Synthesis method of 2-position aryl substituted benzofuran ring 3-position fluoro |
| CN107445856A (en) * | 2017-09-19 | 2017-12-08 | 辽宁三洋新材料科技有限公司 | A kind of synthesis technique of N N-isopropylacrylamides |
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- 2018-06-29 CN CN201810694413.2A patent/CN108675938B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837539A (en) * | 2015-01-15 | 2016-08-10 | 复旦大学 | Synthesis method of 2-position aryl substituted benzofuran ring 3-position fluoro |
| CN107445856A (en) * | 2017-09-19 | 2017-12-08 | 辽宁三洋新材料科技有限公司 | A kind of synthesis technique of N N-isopropylacrylamides |
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