CN111269141B - Method for synthesizing imine by catalyzing alcohol-amine with NNN cobalt complex - Google Patents
Method for synthesizing imine by catalyzing alcohol-amine with NNN cobalt complex Download PDFInfo
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- CN111269141B CN111269141B CN202010160234.8A CN202010160234A CN111269141B CN 111269141 B CN111269141 B CN 111269141B CN 202010160234 A CN202010160234 A CN 202010160234A CN 111269141 B CN111269141 B CN 111269141B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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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
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Abstract
The invention discloses a method for synthesizing imine by catalyzing alcohol-amine with NNN cobalt complex, which comprises the following steps: under nitrogen atmosphere and at 75-85 deg.C, under alkaline condition, using organic solvent as solvent and NNN cobalt complex (LCoCl) 2 ) The arylamine and the aryl methanol are reacted for 40 to 55 hours to obtain the imine as a catalyst. The preparation method disclosed by the invention has the characteristics of high yield, few byproducts, environmental friendliness and the like, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a novel preparation technology of imine.
Background
Imines are important organic intermediates and ligands, and have important applications in medicine, particularly anticancer and anti-inflammatory drugs. Previous imine syntheses were prepared by the dehydrocondensation of aldehydes and primary amines, but since aldehydes are malodorous and unstable, alternative methods of preparation need to be developed. For example, by the oxidative coupling of primary amines or the dehydrooxidation of secondary amines, although good results are obtained in the preparation of symmetrical imine compounds, asymmetric imines are not good enough, and two types of primary amines with large differences in activity are generally selected, and a good yield can be obtained under the condition that one substrate is excessive, and the substrate range is narrow.
The research of the literature can find that the reaction of taking amine and alcohol as raw materials by hydrogen is a green, efficient and atom-economical method for synthesizing imine. The byproducts of the reaction are water and hydrogen, and the atom economy is high, thereby conforming to the basic concept of green chemistry. However, the hydrogen-borrowing reaction of most homogeneous catalytic systems needs to be completed under the catalytic action of transition noble metals ruthenium and iridium, and many reactions often have secondary alkylation, so that the selectivity of the product is difficult to control. Although some cheap metals can catalyze the reaction, the problems of poor catalytic performance and the like exist.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing imine by catalyzing alcohol-amine with an NNN cobalt complex, which has the advantages of high yield, less side reaction and environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing imine by catalyzing alcohol-amine with NNN cobalt complex comprises the following steps:
in nitrogen atmosphere at 75-85 deg.c, organic solvent is used as solventUnder alkaline conditions, with NNN cobalt complex (LCoCl) 2 ) The arylamine and the aryl methanol are reacted for 40 to 55 hours to obtain the imine as a catalyst.
Preferably, in the above method for catalyzing alcohol-amine synthesis of an imine, the aromatic amine is 2-methoxyaniline, 3-chloroaniline, 3-methylaniline, 4-fluoroaniline, 4-chloroaniline, 4-dimethylaminoaniline, 4-methylaniline, 4-methoxyaniline, or aniline.
Preferably, in the above method for catalyzing alcohol-amine synthesis of an imine, the aryl carbinol is 3, 4-dimethoxybenzyl alcohol, 4-methoxybenzyl alcohol, 3-methylbenzyl alcohol, 2-methylbenzyl alcohol or benzyl alcohol.
Preferably, in the above method for catalyzing alcohol-amine synthesis of imine, the basic condition means addition of potassium tert-butoxide.
Preferably, in the above method for catalyzing alcohol-amine synthesis of imine, the reaction time is 48 hours.
Preferably, in the above method for catalyzing alcohol-amine synthesis of imine, the reaction temperature is 80 ℃.
Preferably, in the above method for catalyzing alcohol-amine synthesis of imine, the organic solvent is toluene.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention researches the reaction between aniline with different substituents as a substrate and benzyl alcohol and also researches the reaction effect between benzyl alcohol with different substituents as the substrate and aniline. The invention finds that the substrate with the benzene ring connected with the halogen can obtain the product with higher yield, and the halogen can be well reserved. The aniline substrate with the electron-donating group connected to the 4-position can obtain better yield; the yield of the aniline substrate having the electron-withdrawing group attached to the 4-position was slightly decreased, but a yield on an intermediate level was also obtained. Meta-substituted substrates give better yields. The yield of ortho-substituted substrates is significantly reduced due to steric effects. The aniline substrate with the 4-position connected with the electron-donating group can obtain better yield; the yield of the aniline substrate having the electron-withdrawing group attached to the 4-position was slightly decreased, but a yield on an intermediate level was also obtained. The substituent on the benzyl alcohol in the reaction has no influence of steric hindrance, the yield of the benzene ring para-position, meta-position and ortho-position connected methyl substrates is increased in sequence, and the yield of the ortho-position methyl benzyl alcohol is equivalent. The best substrates obtained are therefore aniline and benzyl alcohol.
2. The invention also researches the influence of reaction time, reaction temperature, catalyst, alkaline environment and reaction time on the reaction yield, thereby obtaining the optimal imine preparation method which has the characteristics of high yield, few byproducts, environmental protection and the like and has wide application prospect.
Detailed Description
Example 1: preparation of imines
The reaction equation is:
5% of LCoCl in a toluene solvent at 80 ℃ under a nitrogen atmosphere and under the condition of 1.2 equivalents of potassium tert-butoxide 2 The aniline and benzyl alcohol are catalyzed to react for 48 hours to obtain imine, and the yield is 94%.
Comparative example 1:
on the basis of example 1, the catalyst was changed to 5% CoCl 2 Otherwise, the reaction was hardly reacted, which indicates that the ligand has an important influence on the reaction.
Comparative example 2:
on the basis of example 1, the toluene solvent is changed to DMF or THF or CH 3 CN, otherwise unchanged, the resulting reaction produced only a small amount of product.
Comparative example 3:
the reaction time was shortened to 36 hours on the basis of example 1, but otherwise the reaction yield was only 86%.
Comparative example 4:
based on example 1, 100mg of 4A molecular sieve was added without adding 1.2 equivalents of potassium tert-butoxide, and the reaction yield was only 8% without changing the others.
Example 2: preparation of imines
The reaction equation is as follows:
5% of LCoCl in a nitrogen atmosphere, a toluene solvent at 75 ℃ and 1.2 equivalents of potassium tert-butoxide 2 Catalyzing 4-anisidine to react with benzyl alcohol, and reacting for 48 hours to obtain imine, wherein the yield is 83%.
Example 3: preparation of imines
The reaction equation is:
5% of LCoCl in a toluene solvent at 80 ℃ under a nitrogen atmosphere and under the condition of 1.2 equivalents of potassium tert-butoxide 2 Catalyzing 4-methylaniline to react with benzyl alcohol, and reacting for 48 hours to obtain imine, wherein the yield is 83%.
Example 4: preparation of imines
The reaction equation is as follows:
5% of LCoCl in a nitrogen atmosphere, a toluene solvent at 80 ℃ and 1.2 equivalents of potassium tert-butoxide 2 Catalyzing 4-dimethylamino aniline to react with benzyl alcohol, and reacting for 48 hours to obtain imine, wherein the yield is 82%.
Example 5: preparation of imines
The reaction equation is:
5% of LCoCl in a toluene solvent at 80 ℃ under a nitrogen atmosphere and under the condition of 1.2 equivalents of potassium tert-butoxide 2 4-chloroaniline is catalyzed to react with benzyl alcohol, imine is obtained after 48 hours of reaction, and the yield is 95%.
Example 6: preparation of imines
The reaction equation is:
5% of LCoCl in a toluene solvent at 80 ℃ under a nitrogen atmosphere and under the condition of 1.2 equivalents of potassium tert-butoxide 2 Catalyzing 4-fluoroaniline to react with benzyl alcohol, and obtaining imine after 55 hours of reaction, wherein the yield is 89%.
Example 7: preparation of imines
The reaction equation is:
5% of LCoCl in a toluene solvent at 80 ℃ under a nitrogen atmosphere and under the condition of 1.2 equivalents of potassium tert-butoxide 2 3-methylaniline is catalyzed to react with benzyl alcohol, imine is obtained after 48 hours of reaction, and the yield is 90%.
Example 8: preparation of imines
The reaction equation is:
5% of LCoCl in a toluene solvent at 80 ℃ under a nitrogen atmosphere and under the condition of 1.2 equivalents of potassium tert-butoxide 2 Catalyzing 3-chloroaniline to react with benzyl alcohol, and reacting for 48 hours to obtain imine, wherein the yield is 95%.
Example 9: preparation of imines
The reaction equation is as follows:
5% of LCoCl in a nitrogen atmosphere, a toluene solvent at 80 ℃ and 1.2 equivalents of potassium tert-butoxide 2 Catalyzing 2-anisidine to react with benzyl alcohol, and reacting for 48 hours to obtain imine, wherein the yield is 89%.
Example 10: preparation of imines
The reaction equation is as follows:
5% of LCoCl in a nitrogen atmosphere, a toluene solvent at 80 ℃ and 1.2 equivalents of potassium tert-butoxide 2 The aniline and 2-methyl benzyl alcohol react for 48 hours to obtain imine, and the yield is 96%.
Example 11: preparation of imines
The reaction equation is:
5% of LCoCl in a toluene solvent at 80 ℃ under a nitrogen atmosphere and under the condition of 1.2 equivalents of potassium tert-butoxide 2 The catalytic aniline reacts with 4-methoxy benzyl alcohol for 48 hours to obtain imine, and the yield is 88%.
Example 12: preparation of imines
The reaction equation is as follows:
5% of LCoCl in a nitrogen atmosphere, a toluene solvent at 80 ℃ and 1.2 equivalents of potassium tert-butoxide 2 The catalytic aniline reacts with 3, 4-dimethoxy benzyl alcohol for 48 hours to obtain imine, and the yield is 99%.
Example 13: preparation of imines
The reaction equation is as follows:
5% of LCoCl in a nitrogen atmosphere, a toluene solvent at 80 ℃ and 1.2 equivalents of potassium tert-butoxide 2 The catalytic aniline reacts with 3-methyl benzyl alcohol for 48 hours to obtain imine, and the yield is 90%.
Claims (3)
1. A method for synthesizing imine by catalyzing alcohol-amine with NNN cobalt complex is characterized by comprising the following steps:
reacting arylamine and aryl methanol at 75-85 deg.C in nitrogen atmosphere and under alkaline condition with toluene as solvent and NNN cobalt complex as catalyst for 40-55 hr to obtain imine;
the arylamine is 2-methoxyaniline, 3-chloroaniline, 3-methylaniline, 4-fluoroaniline, 4-chloroaniline, 4-dimethylaminoaniline, 4-methylaniline, 4-methoxyaniline or aniline;
the aryl methanol is 3, 4-dimethoxy benzyl alcohol, 4-methoxy benzyl alcohol, 3-methyl benzyl alcohol, 2-methyl benzyl alcohol or benzyl alcohol;
the alkaline condition refers to adding potassium tert-butoxide.
2. The method for catalyzing the synthesis of an imine from an alcohol-amine of claim 1, wherein the reaction time is 48 hours.
3. The method for catalyzing alcohol-amine synthesis of an imine of claim 1, wherein the reaction temperature is 80 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710325A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for one step synthesis of imine through catalyzing alcohol and amine by supported manganese oxide |
| CN105712899A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for synthesizing imine at one step by means of catalyzing alcohol and amine by aid of supported cobalt compounds |
| CN108084050A (en) * | 2017-12-22 | 2018-05-29 | 安徽工业大学 | A kind of aluminium phosphate molecular sieve is catalyzed imines synthetic method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710325A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for one step synthesis of imine through catalyzing alcohol and amine by supported manganese oxide |
| CN105712899A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for synthesizing imine at one step by means of catalyzing alcohol and amine by aid of supported cobalt compounds |
| CN108084050A (en) * | 2017-12-22 | 2018-05-29 | 安徽工业大学 | A kind of aluminium phosphate molecular sieve is catalyzed imines synthetic method |
Non-Patent Citations (8)
| Title |
|---|
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| Cobalt-Catalyzed Acceptorless Alcohol Dehydrogenation: Synthesis of Imines from Alcohols and Amines;Guoqi Zhang and Susan K. Hanson;《ORGANIC LETTERS》;20130111;第15卷(第3期);第650-653页 * |
| Direct access to N -alkylated amines and imines via acceptorless dehydrogenative coupling catalyzed by a cobalt (II)-NNN pincer complex;Siba P. Midya et al.;《Catal. Sci. Technol.》;20180622;第8卷;第3469-3473页 * |
| Direct synthesis of imines from primary alcohols and amines using an active ruthenium(II) NNN–pincer complex;Elangovan Sindhuja, Rengan Ramesh;《Tetrahedron Letters》;20140814;第55卷;第5504-5507页 * |
| First used of Alkylbenzimidazole-Cobalt(II) complexes as a catalyst for the N-Alkylation of amines with alcohols under solvent-free medium;Neslihan Sahin et al.;《Journal of Organometallic Chemistry》;20200421;第918卷;第1-7页 * |
| In Situ Generated Cobalt Catalyst for the Dehydrogenative Coupling of Alcohols and Amines into Imines;Fabrizio Bottaro and Robert Madsen;《ChemCatChem》;20190508;第11卷;第2707-2712页 * |
| Solvent-free synthesis of imines via N-alkylation of aromatic amines with alcohols over Co2+-exchanged zeolites;Y.-W. Sun et al.;《Catalysis Communications》;20131018;第43卷;第213-217页 * |
| Switchable Imine and Amine Synthesis Catalyzed by a Well-Defined Cobalt Complex;Keshav Paudel et al.;《Organometallics》;20210115;第40卷;第418-426页 * |
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