CN112724025A - Preparation method of N-benzyl benzylamine - Google Patents
Preparation method of N-benzyl benzylamine Download PDFInfo
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- CN112724025A CN112724025A CN202110024816.8A CN202110024816A CN112724025A CN 112724025 A CN112724025 A CN 112724025A CN 202110024816 A CN202110024816 A CN 202110024816A CN 112724025 A CN112724025 A CN 112724025A
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- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- WGQKYBSKWIADBV-UHFFFAOYSA-O benzylaminium Chemical compound [NH3+]CC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-O 0.000 claims abstract description 16
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 14
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
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- 238000003756 stirring Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical group [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
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- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 description 1
- 101710086378 Bradykinin-potentiating and C-type natriuretic peptides Proteins 0.000 description 1
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- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
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- 229960004699 valsartan Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/46—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acids or esters thereof in presence of 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of N-benzyl benzylamine, which is characterized by comprising the following steps: the polyoxometallate is used as a catalyst and is put into a reaction container, an organic solvent, benzylammonium and benzoic acid are sequentially added into the container, finally, an additive is added, heating and stirring reaction are carried out, and separation is carried out to obtain the N-benzyl benzylamine. After the reaction is finished, the catalyst can be recycled, the system after the reaction is finished is directly filtered, the polyoxometallate can be directly filtered out, the polyoxometallate is recycled after treatment, and the recycled polyacid is reused for preparing the N-benzyl benzylamine. Compared with the prior art, the method has the advantages that the N-benzyl benzylamine can be prepared by reacting the benzylammonium with the benzoic acid, the method has high activity and high selectivity, the reaction condition is mild, green and environment-friendly, the catalyst can be recycled, and the method has great industrial production potential.
Description
Technical Field
The invention relates to the technical field of catalysis, and particularly relates to a preparation method of N-benzyl benzylamine.
Background
The amine and the derivatives thereof widely exist in basic and commercially important molecules, are important structural units of a plurality of bioactive molecules, and widely exist in chemical drugs, natural products and functional materials, so that the development of a simple and efficient method for constructing the C-N bond is always the focus of attention in the industry and academia. There are many methods to date by which carbon-nitrogen bonds can be constructed, such as N-alkylation, Ullmann coupling, Buchwald-Hartwig coupling, Goldberg coupling reactions, and hydroamination.
The C-N bond is one of the most important structural motifs in nature, is present in natural products, proteins and therapeutic drugs, and has important significance in organic chemistry and biochemistry. In addition, it is counted that about 25% of the drugs on the global market contain at least one C-N group, including some drugs having important biological activities such as antitumor, antiviral, antihypertensive, lipid-lowering, etc., for example, Valsartan (which can effectively inhibit angiotensin-II receptor), Atorvastatin (which is the most effective cholesterol-lowering drug sold worldwide), Lisinopril (which is an effective angiotensin converting enzyme inhibitor), dialezem (which can be used as a calcium channel blocker to treat angina and hypertension), etc., and thus the development of a green, effective and inexpensive method for forming C-N bond has become an important research issue.
The traditional method has high toxicity of C-N bond reagent, and some reactions can also generate stoichiometric metal salt waste or waste acid to aggravate the problems of environmental pollution and the like. In the last two decades, metal organic catalysts have made great progress in selective oxidation and coupling reaction, but in the catalytic oxidation process, the metal organic catalysts have the problems of metal residue, difficult recycling, environmental unfriendliness and the like, so that the metal organic catalysts are difficult to reach the industrial level.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the method for preparing the N-benzyl benzylamine, which can prepare the N-benzyl benzylamine by reacting the benzylammonium with the benzoic acid, has the advantages of high activity and high selectivity, mild, green and environment-friendly reaction conditions, recyclable catalyst and great industrial production potential.
The purpose of the invention can be realized by the following technical scheme:
the inventors have appreciated that polyoxometallate is a very advantageous catalyst with unique redox properties, strong durability to oxidizing agents and environmental compatibility. Polyoxometallate (polyacid) is a novel high-efficiency multifunctional catalyst, has acid catalytic performance, redox catalytic performance and good stability, can be used for homogeneous reaction, heterogeneous reaction and even phase transfer catalyst, is a green and environment-friendly catalyst with a very promising prospect, and is widely applied to the fields of catalysis, analysis, medicine, electrochemistry, photochemistry, petrochemical industry and the like. Has the advantages of high activity, high selectivity, high stability and recycling, and then the following specific scheme is proposed:
a preparation method of N-benzyl benzylamine comprises the following steps: the method comprises the following steps of putting polyoxometallate serving as a catalyst into a reaction container, sequentially adding an organic solvent, benzylammonium and benzoic acid into the container, finally adding an additive, heating, stirring, reacting, and separating to obtain the N-benzyl benzylamine, wherein the reaction formula is as follows:
after the reaction is finished, the catalyst can be recycled, the system after the reaction is finished is directly filtered, the polyoxometallate can be directly filtered out, the polyoxometallate is recycled after treatment, and the recycled polyacid is reused for preparing the N-benzyl benzylamine.
Further, the polyoxometallate is Keggin type, Dawson type, Silverton type, Waugh type, Lindquist type or Anderson type.
Furthermore, the catalyst is Anderson type polyoxometallate taking Fe, Al, Cr, Ni, Mn, Cu or Co as the center.
Further, the amount of the catalyst added is 0.1 to 2.0 mol%, where mol% is compared to that of benzylammonium, e.g. 1mmol of benzylammonium and 1mmol of benzoic acid are added in an amount of 0.001 to 0.02mmol of catalyst.
Further, the amount of the catalyst added was 0.5 mol%.
Further, the additive is phenylsilane, and the amount of the phenylsilane is 2.0 to 6.0 equivalents. Equivalent means an amount corresponding to a particular or trivial value, where equivalent is relative to the amount of benzylammonium species, e.g. 1mmol of benzylammonium and 1mmol of benzoic acid requires the addition of 2-6mmol of phenylsilane.
Further, the amount of said phenylsilane was 3.0 equivalents.
Further, the organic solvent is N, N-dimethylformamide, toluene, 1, 4-dioxane or benzene, preferably toluene.
Further, the heating temperature is 80-120 ℃, and the reaction time is 12-48 h.
Further, the heating temperature is 120 ℃, and the reaction time is 18 h.
Further, when toluene is used as the solvent, the temperature is most effective at 120 ℃.
Compared with the prior art, the method has the characteristics of simple preparation, high product yield, no three wastes, low production cost and the like, and is an environment-friendly method for preparing the N-benzyl benzylamine with high atom economy. The catalyst is a novel catalyst, namely polyoxometallate (polyacid), can be recycled for multiple times after simple treatment, does not need to add acid in the reaction process, and is very beneficial to industrial production, so the method has potential application prospect.
Drawings
FIG. 1 is the NMR spectrum of N-benzylbenzylamine obtained by the present invention13C NMR(CDCl3)；
FIG. 2 is the NMR spectrum of N-benzylbenzylamine obtained by the present invention1H NMR(CDCl3)。
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. For further details of the present invention, several embodiments are given below, which mainly take the example of the Anderson-type polyoxometalate catalyst with different metal atoms as the center. However, the present invention is not limited to these examples.
Example 1
0.1072g of benzylammonium, 0.1222g of benzoic acid, 0.1-2.0 mol% of Anderson type polyoxometallate taking Ni as a central metal, 2.0-6.0equiv of phenyl silane and 2.0-6.0mL of solvent toluene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled to be 80-120 ℃, the reaction is stopped after 18 hours of heat preservation reaction, the reaction is cooled to room temperature, a sample is prepared and is subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 96%. And performing nuclear magnetic test after separation and purification, and verifying that the product is N-benzyl benzylamine by using the obtained hydrogen spectrum and carbon spectrum data.
Example 2
0.1072g of benzylammonium, 0.1222g of benzoic acid, 0.1-2.0 mol% of Anderson type polyoxometallate taking Al as a central metal, 2.0-6.0equiv of phenyl silane and 2.0-6.0mL of solvent toluene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled to be 80-120 ℃, the reaction is stopped after 18 hours of heat preservation reaction, the reaction is cooled to room temperature, a sample is prepared and is subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 83%. And performing nuclear magnetic test after separation and purification, and verifying that the product is N-benzyl benzylamine by using the obtained hydrogen spectrum and carbon spectrum data.
Example 3
0.1072g of benzylammonium, 0.1222g of benzoic acid, 0.1-2.0 mol% of Anderson type polyoxometallate taking Cr as a central metal, 2.0-6.0equiv of phenyl silane and 2.0-6.0mL of solvent toluene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled to be 80-120 ℃, the reaction is stopped after 18 hours of heat preservation reaction, the reaction is cooled to room temperature, a sample is prepared and is subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 91%. And performing nuclear magnetic test after separation and purification, and verifying that the product is N-benzyl benzylamine by using the obtained hydrogen spectrum and carbon spectrum data.
Example 4
0.1072g of benzylammonium, 0.1222g of benzoic acid, 0.1-2.0 mol% of Anderson type polyoxometallate taking Fe as a central metal, 2.0-6.0equiv of phenyl silane and 2.0-6.0mL of solvent toluene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled to be 80-120 ℃, the reaction is stopped after 18 hours of heat preservation reaction, the reaction is cooled to room temperature, a sample is prepared and is subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 86%. And performing nuclear magnetic test after separation and purification, and verifying that the product is N-benzyl benzylamine by using the obtained hydrogen spectrum and carbon spectrum data.
Example 5
0.1072g of benzylammonium, 0.1222g of benzoic acid, 0.1-2.0 mol% of Anderson type polyoxometallate taking Mn as a central metal, 2.0-6.0equiv of phenyl silane and 2.0-6.0mL of solvent toluene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled to be 80-120 ℃, the reaction is stopped after 18 hours of heat preservation reaction, the reaction is cooled to room temperature, a sample is prepared and is subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 92%. And performing nuclear magnetic test after separation and purification, and verifying that the product is N-benzyl benzylamine by using the obtained hydrogen spectrum and carbon spectrum data.
Example 6
0.1072g of benzylammonium, 0.1222g of benzoic acid, 0.1-2.0 mol% of Anderson type polyoxometallate taking Co as a central metal, 2.0-6.0equiv of phenyl silane and 2.0-6.0mL of solvent toluene are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled to be 80-120 ℃, the reaction is stopped after 18 hours of heat preservation reaction, the reaction is cooled to room temperature, a sample is prepared and is subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 91%. And performing nuclear magnetic test after separation and purification, and verifying that the product is N-benzyl benzylamine by using the obtained hydrogen spectrum and carbon spectrum data.
Example 7
0.1072g of benzylammonium, 0.1222g of benzoic acid, 0.1-2.0 mol% of Anderson type polyoxometallate taking Cu as a central metal, 2.0-6.0equiv of phenyl silane and 2.0-6.0L of toluene solvent are put into a dry reaction tube, an air ball is sleeved on the reaction tube, the reaction temperature is controlled to be 80-120 ℃, the reaction is stopped after 18 hours of heat preservation reaction, the reaction is cooled to room temperature, a sample is prepared and is subjected to GC-MS detection, and the GC-MS result shows that the conversion rate of a reaction substrate is 80%. And performing nuclear magnetic test after separation and purification, and verifying that the product is N-benzyl benzylamine by using the obtained hydrogen spectrum and carbon spectrum data. And (4) treating and recycling the catalyst after reaction.
Example 8
The reaction procedure is the same as example 1, but the difference is that the catalyst is recovered and used for the 1 st time, the GC-MS analysis shows that the conversion rate of the reaction substrate is more than 94%, the product is obtained by separation and purification, and the nuclear magnetism is confirmed to be N-benzyl benzylamine.
Example 9
The reaction procedure is the same as example 1, but the difference is that the catalyst is recovered and used for the 2 nd time, the GC-MS analysis shows that the conversion rate of the reaction substrate is more than 93%, the product is obtained by separation and purification, and the nuclear magnetism is confirmed to be N-benzyl benzylamine.
Example 10
The reaction procedure was the same as in example 1, except that the catalyst was recovered and used 3 rd time, the conversion of the reaction substrate was 92% by GC-MS analysis, and the product was isolated and purified and confirmed to be N-benzylbenzylamine by nuclear magnetic resonance.
Example 11
The reaction procedure was the same as in example 1, except that the catalyst was used 4 th time after recovery, the conversion of the reaction substrate was 90% by GC-MS analysis, and the product was isolated and purified and confirmed to be N-benzylbenzylamine by nuclear magnetic resonance.
Example 12
The reaction procedure was the same as in example 1, except that 4.8g (0.5 mol%) of 4-butylammonium bromide was added to the reaction, the conversion of the reaction substrate was less than 90% by GC-MS analysis, the catalyst solid was obtained by filtration, washed and dried, collected for reuse, and the filtrate was separated and purified to obtain a pale yellow product which was confirmed to be N-benzylbenzylamine by nuclear magnetic resonance.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of N-benzyl benzylamine is characterized by comprising the following steps: the polyoxometallate is used as a catalyst and is put into a reaction container, an organic solvent, benzylammonium and benzoic acid are sequentially added into the container, finally, an additive is added, heating and stirring reaction are carried out, and separation is carried out to obtain the N-benzyl benzylamine.
2. The method of claim 1, wherein the polyoxometallate is Keggin, Dawson, Silverton, Waugh, Lindquist or Anderson.
3. The method of claim 1, wherein the catalyst is an Anderson polyoxometalate centered on Fe, Al, Cr, Ni, Mn, Cu, or Co.
4. The method of claim 1, wherein the catalyst is added in an amount of 0.1 to 2.0 mol%.
5. The method of claim 4, wherein the catalyst is added in an amount of 0.5 mol%.
6. The method of claim 1, wherein the additive is phenylsilane, and the amount of phenylsilane is 2.0 to 6.0 equivalents.
7. The method of claim 6, wherein the amount of phenylsilane is 3.0 equivalents.
8. The method of claim 1, wherein the organic solvent comprises N, N-dimethylformamide, toluene, 1, 4-dioxane, or benzene.
9. The method for preparing N-benzylbenzylamine according to claim 1, wherein the heating temperature is 80-120 ℃, and the reaction time is 12-48 h.
10. The method for preparing N-benzylbenzylamine according to claim 1, wherein the heating temperature is 120 ℃, and the reaction time is 18 h.
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| CN115073258A (en) * | 2022-02-21 | 2022-09-20 | 上海应用技术大学 | Polyacid catalytic preparation method of biphenyl |
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| CN111807970A (en) * | 2020-06-28 | 2020-10-23 | 上海应用技术大学 | Method for preparing N-benzylaniline by catalytic oxidation of aniline with polyoxometallate |
| CN111825575A (en) * | 2019-04-23 | 2020-10-27 | 临沂斯科瑞聚氨酯材料有限公司 | Method for efficiently preparing toluene diisocyanate compound by polyoxometallate |
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| CN111825575A (en) * | 2019-04-23 | 2020-10-27 | 临沂斯科瑞聚氨酯材料有限公司 | Method for efficiently preparing toluene diisocyanate compound by polyoxometallate |
| CN111807970A (en) * | 2020-06-28 | 2020-10-23 | 上海应用技术大学 | Method for preparing N-benzylaniline by catalytic oxidation of aniline with polyoxometallate |
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| CN115073258A (en) * | 2022-02-21 | 2022-09-20 | 上海应用技术大学 | Polyacid catalytic preparation method of biphenyl |
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