CN113135865B - Method for preparing N-phenyl-3- (benzotriazole-1-yl) propionamide - Google Patents
Method for preparing N-phenyl-3- (benzotriazole-1-yl) propionamide Download PDFInfo
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- CN113135865B CN113135865B CN202110354970.1A CN202110354970A CN113135865B CN 113135865 B CN113135865 B CN 113135865B CN 202110354970 A CN202110354970 A CN 202110354970A CN 113135865 B CN113135865 B CN 113135865B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention relates to the technical field of fine chemical engineering, and discloses a method for preparing N-phenyl- (3-benzotriazole) propionamide. The method comprises the following specific steps: 3-methylthio-N-phenyl propionamide and benzotriazole are used as raw materials, iodobenzene acetate and potassium carbonate are used as additives, and the reaction is carried out in acetonitrile at 120 ℃ for 12 hours to obtain the target product N-phenyl- (3-benzotriazole) propionamide. The method is simple and convenient to operate and mild in reaction, the 3-methylthio-N-phenylpropionamide and the benzotriazole are used as reaction raw materials, the target product N-alkyl benzotriazole derivative is synthesized in a green and efficient mode, and the potential application value is achieved.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a method for preparing N-phenyl-3- (benzotriazole-1-yl) propionamide.
Background
N-phenyl-3- (benzotriazole-1-yl) propionamide belongs to N-alkyl benzotriazole derivatives, is an important fine chemical intermediate, is mainly used for vapor phase corrosion inhibitors, water treatment corrosion and scale inhibitors, coating additives, foaming inhibitors and the like, can also be used as antistatic and ultraviolet resistant additives and the like, and has wide application in the aspects of medicines, pesticides, high polymer materials, dyes and the like. Because the N-alkyl benzotriazole derivatives have various biological activities, the synthesis and activity research of the N-alkyl benzotriazole derivatives are more and more concerned, and therefore, the research and development of the N-alkyl benzotriazole derivatives have important significance.
At present, the synthesis of N-phenyl-3- (benzotriazole-1-yl) propionamide is not reported by related documents, but a synthesis method of 3-benzotriazole propionamide which is an analogue of the N-phenyl-3- (benzotriazole-1-yl) propionamide is reported, and acrylamide and benzotriazole are used as raw materials, and Triton B is used as an important additive to synthesize a target product, namely 3-benzotriazole propionamide. Acrylamide is a highly toxic chemical, and can cause poisoning, produce central nervous system disorder and liver injury, corrode the skin and stimulate eyes when being inhaled by vapor or absorbed through skin, so that the research on other chemicals for replacing acrylamide to synthesize a target compound has important synthetic significance.
According to the method, benzotriazole and 3-methylthio-N-phenyl propionamide are used as raw materials, iodobenzene acetate is used as an additive, a target product N-phenyl-3- (benzotriazole-1-yl) propionamide is synthesized in one step through C-S bond breakage and C-N bond construction, the reaction mode is not reported, in addition, the use of acrylamide derivatives is avoided, and the method accords with the characteristics of environmental protection.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-efficiency and green synthesis method of N-phenyl-3- (benzotriazole-1-yl) propionamide.
The invention relates to a method for synthesizing N-phenyl-3- (benzotriazole-1-yl) propionamide, which comprises the following steps: sequentially adding 3-methylthio-N-phenyl propionamide, benzotriazole, iodobenzene acetate and potassium carbonate into a sealed tube containing a reaction solvent, violently stirring and reacting for a period of time at the reaction temperature of 120 ℃, and after the reaction is finished, sequentially concentrating the reaction liquid and carrying out column chromatography separation to obtain the N-phenyl-3- (benzotriazole-1-yl) propionamide.
Further, the reaction solvent of the system of the present invention is acetonitrile.
Further, the concentration of the N-phenyl-3- (benzotriazole-1-yl) propionamide in the reaction solvent is 0.05 to 0.2 mol/L, preferably 0.1 mol/L.
Furthermore, the molar ratio of the 3-methylthio-N-phenylpropionamide to the benzotriazole to the iodobenzene acetate to the potassium carbonate is 1: 2: 1: 3.
the reaction temperature in the present invention is 120 ℃.
Further, the reaction time in the invention is 6-24 hours, preferably 12 hours.
Compared with the prior art, the invention has the beneficial effects that: the method is characterized in that 3-methylthio-N-phenyl propionamide and benzotriazole are used as raw materials, iodobenzene acetate and potassium carbonate are used as additives, and the N-phenyl-3- (benzotriazole-1-yl) propionamide is efficiently synthesized by a one-step method.
Detailed Description
The following examples will help illustrate the invention, but do not limit its scope.
Specific example 1: the synthesis method comprises the following steps: acetonitrile (10mL), 3-methylthio-N-phenylpropionamide (1mmol,0.195g), benzotriazole (2mmol,0.238g), iodobenzene acetate (1mmol,0.322g), and potassium carbonate (3mmol,0.414g) were added in this order to a 50mL sealed tube, the reaction temperature was controlled at 120 ℃ and the reaction was stirred vigorously for 12 hours. After the reaction is finished, reaction liquid is sequentially concentrated and separated by column chromatography, and the N-phenyl-3- (benzotriazole-1-yl) propionamide (0.186g, 70%) is obtained. The reaction involves the following equation:
specific example 2: comparative experiment: acetonitrile (10mL), 3-methylthio-N-phenylpropionamide (1mmol,0.195g), benzotriazole (2mmol,0.238g), and potassium carbonate (3mmol,0.414g) were added sequentially in a 50mL sealed tube, the reaction temperature was controlled at 120 degrees Celsius, and the reaction was stirred vigorously for 12 hours. After the reaction is finished, the reaction liquid is concentrated and separated by column chromatography in turn, and then the N-phenyl-3- (benzotriazole-1-yl) propionamide (0.027g, 10%) is obtained. The reaction involves the following equation:
specific example 3: comparative experiment: acetonitrile (10mL), 3-methylthio-N-phenylpropionamide (1mmol,0.195g), benzotriazole (2mmol,0.238g), and iodobenzene acetate (1mmol,0.322g) were added sequentially in a 50mL sealed tube, the reaction temperature was controlled at 120 ℃ and the reaction was stirred vigorously for 12 hours. After the reaction, the reaction solution is concentrated and separated by column chromatography in turn to obtain the N-phenyl-3- (benzotriazole-1-yl) propionamide (0.016g, 6%). The reaction involves the following equation:
specific example 4: the synthesis method comprises the following steps: acetonitrile (10mL), 3-methylthio-N-phenylpropionamide (1mmol,0.195g), benzotriazole (2mmol,0.238g), iodobenzene acetate (1mmol,0.322g) and various bases (3mmol) were added sequentially to a 50mL stopcock, except that: sodium carbonate, sodium hydroxide, cesium carbonate, sodium bicarbonate or triethylamine, the reaction temperature was controlled at 120 degrees celsius, and the reaction was vigorously stirred for 12 hours. After the reaction is finished, the reaction solution is concentrated and separated by column chromatography in turn, and the specific conditions are as follows:
(1) when sodium carbonate is used, N-phenyl-3- (benzotriazole-1-yl) propionamide (0.04g, 15%) can be obtained;
(2) when sodium hydroxide is used, N-phenyl-3- (benzotriazole-1-yl) propionamide (0.013g, 5%) can be obtained; (3) when cesium carbonate is used, N-phenyl-3- (benzotriazol-1-yl) propionamide (0.128g, 48%) is obtained;
(4) when sodium bicarbonate is used, the N-phenyl-3- (benzotriazole-1-yl) propionamide cannot be separated;
(5) when triethylamine is used, N-phenyl-3- (benzotriazol-1-yl) propanamide cannot be isolated.
Specific example 5: compared with the example 1, the one-step method is changed into the two-step method for reaction, namely, acetonitrile, 3-methylthio-N-phenylpropionamide and iodobenzene acetate are added for reaction, then the reacted intermediate is reacted with potassium carbonate and benzotriazole, the reaction temperature is the same, and the yield of the obtained N-phenyl-3- (benzotriazole-1-yl) propionamide is far lower than that of the example 1.
The nuclear magnetic data and the mass spectrum data of the target product N-phenyl-3- (benzotriazole-1-yl) propionamide are as follows:
1H NMR(300MHz,CDCl3)δ8.63(br,1H),7.90(d,J＝8.4Hz,1H),7.63(d,J＝8.4Hz,1H),7.44–7.39(m,3H),7.34–7.16(m,4H),7.01(t,J＝7.4Hz,1H),4.94(t,J＝6.6Hz,2H),3.18(t,J＝6.6Hz,2H).
13C NMR(75MHz,CDCl3)δ168.09,145.54,137.81,133.36,128.96,127.74,124.48,124.38,120.08,119.43,110.11,44.02,37.14.
LCMS(ESI,m/z):267.0[M+H]+.
the foregoing describes alternative embodiments of the invention to teach those skilled in the art how to make and reproduce the invention. Some conventional technical aspects have been simplified and omitted for the purpose of teaching the inventive arrangements. Those skilled in the art will appreciate variations from this aspect that fall within the scope of the invention.
Claims (8)
1. A method for preparing N-phenyl-3- (benzotriazole-1-yl) propionamide is characterized in that: adding 3-methylthio-N-phenyl propionamide (I), benzotriazole (II), iodobenzene acetate and potassium carbonate into a sealed tube containing a reaction solvent for reaction, and after the reaction is finished, sequentially concentrating and carrying out column chromatography separation on a reaction solution to obtain a target product N-phenyl-3- (benzotriazole-1-yl) propionamide (III);
（Ⅰ） （Ⅱ） （Ⅲ）。
2. the method for preparing N-phenyl-3- (benzotriazol-1-yl) propanamide according to claim 1, wherein: the reaction solvent is acetonitrile.
3. The process for preparing N-phenyl-3- (benzotriazol-1-yl) propanamide according to claim 1, wherein: the reaction temperature was 120 ℃.
4. The process for preparing N-phenyl-3- (benzotriazol-1-yl) propanamide according to claim 1, wherein: the reaction time is 6-24 hours.
5. The method for preparing N-phenyl-3- (benzotriazol-1-yl) propanamide according to claim 4, wherein: the reaction time was 12 hours.
6. The process for preparing N-phenyl-3- (benzotriazol-1-yl) propanamide according to claim 1, wherein: the concentration of the 3-methylthio-N-phenylpropionamide in the reaction solvent is 0.05 to 0.2 mol/l.
7. The method for preparing N-phenyl-3- (benzotriazol-1-yl) propanamide according to claim 6, wherein: the concentration of 3-methylthio-N-phenylpropionamide in the reaction solvent was 0.1 mol/l.
8. The process for preparing N-phenyl-3- (benzotriazol-1-yl) propanamide according to claim 1, wherein: the molar ratio of the 3-methylthio-N-phenylpropionamide, the benzotriazole, the iodobenzene acetate and the potassium carbonate is 1: 2: 1: 3.
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