CN113929610A - Method for catalyzing nitrogen heterocycle aerobic dehydrogenation based on ionic liquid porous carbon material - Google Patents
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- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/74—Quinazolines; Hydrogenated quinazolines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms of the hetero ring
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Abstract
The invention discloses a method for catalyzing aerobic dehydrogenation of nitrogen heterocycles based on an ionic liquid porous carbon material, which is applicable to the field of organic synthesis, wherein a heterogeneous catalysis system takes the nitrogen heterocycles and derivatives thereof as substrates, carbon materials as catalysts, water or ethanol as solvents, air or oxygen spheres as oxygen sources, and the heterogeneous catalysis system can react at 0-80 ℃ under normal pressure to realize oxidative dehydrogenation of the nitrogen heterocycles and synthesize target products of pharmaceutical intermediates such as indole, quinoline, isoquinoline, quinazoline, quinoxaline, benzothiazole, hansfoot and derivatives thereof. The invention uses the ionic liquid as the precursor to prepare the non-metallic catalyst, has no activating agent and no other additives in the reaction process, and has industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for catalyzing nitrogen heterocycle aerobic dehydrogenation based on an ionic liquid porous carbon material.
Background
Aromatic nitrogen heterocycles are widely available in natural organic compounds, and are widely applied to the fields of biomedicine, pesticide, catalyst ligand, material and the like. Therefore, the research on the synthetic method of the aromatic nitrogen heterocycle has important significance. Among the many methods for the synthesis of aromatic nitrogen heterocycles, the synthesis of aromatic nitrogen heterocycles by oxidative dehydrogenation of nitrogen heterocycles is an important strategy. At present, stoichiometric oxidant (HgO-I) is mostly needed in the method for synthesizing aromatic nitrogen heterocycles by nitrogen heterocycle oxidative dehydrogenation2、MnO2DDQ, hydrogen peroxide, elemental sulfur and 2-iodoxybenzoic acid) or metal (such as ruthenium, iridium, rhodium, palladium, iron, cobalt and zinc) as a catalyst, which brings about the disadvantages of difficult purification, more auxiliary agents, more wastes, increased cost and the like. Therefore, it is very important to develop a high-efficiency, economic and green catalyst for the conversion from the basic research or practical application prospectThe significance of (1).
Disclosure of Invention
The invention aims to provide a method for catalyzing nitrogen heterocycle aerobic dehydrogenation based on an ionic liquid porous carbon material, which realizes efficient, economic and green oxidative dehydrogenation of nitrogen heterocycle compounds and simultaneously produces a medical intermediate.
In order to achieve the purpose, the invention adopts the technical scheme that: an aerobic dehydrogenation method for nitrogen heterocycles based on ionic liquid porous carbon material catalysis is characterized in that nitrogen heterocycles or derivatives thereof are used as substrates, porous carbon materials are used as catalysts, water or absolute ethyl alcohol is used as a solvent, air or oxygen is used as an oxidant, and the nitrogen heterocycles are reacted for 0-48 hours at a temperature of 0-80 ℃ under a certain pressure to obtain a dehydrogenated nitrogen heterocycle product, wherein the reaction general formula is as follows:
wherein R is1,R2Is phenyl or substituted phenyl; the substituent on the phenyl is hydroxyl, C1-C10 alkyl, alkoxy, amino, nitro, halogen or phenyl, and the number of the substituent is 1-5.
Preferably, the substrate is: 1,2,3, 4-tetrahydroquinoline, 1,2,3, 4-tetrahydroisoquinoline, indoline, 1,2,3, 4-tetrahydroquinazoline, 1,2,3, 4-tetrahydroquinoxaline, 1, 2-dihydrobenzothiazole, or diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate.
Preferably, the carbon material is added in a mass fraction of 0 to 100% relative to the substrate.
Preferably, the pressure is 0.1 to 1 MPa.
Preferably, the catalyst is obtained by taking polyion liquid as a precursor and carbonizing the polyion liquid under the protection of inert gas at 600-1000 ℃.
The metal-free catalyst is simple, efficient and stable in preparation, the catalytic process conditions are mild, and the efficient, economic and green synthesis of the aromatic nitrogen heterocycle can be realized.
The synthesis steps of the precursor of the catalyst adopt a formula (I) or (II):
wherein n is 1000-200 ten thousand; x-Is Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -Or C2H5COO-。
Preferably, the specific synthesis steps of the formula (II) are as follows:
s1, dissolving N-vinylimidazole and bromoacetonitrile in methanol, stirring at room temperature for 5-7h, settling in ether, and vacuum drying for more than 24h to obtain an ionic liquid monomer CMVImBr;
s2, carrying out anion exchange on the product obtained in the step S1 and lithium bistrifluoromethanesulfonylimide to obtain an ionic liquid monomer CMVImNtf 2;
s3, dissolving the obtained ionic liquid monomer and an initiator azobisisobutyronitrile into a DMSO solution, protecting with inert gas, and carrying out cross-linking polymerization at 75 ℃ for more than 24 hours;
s4, precipitating in excessive tetrahydrofuran, washing a product by using ethanol, and drying in vacuum at 60 ℃ for more than 12h to obtain the polyion liquid.
Compared with the prior art, the invention has the beneficial effects that:
1. the method is applicable to the field of organic synthesis, the heterogeneous catalytic system takes nitrogen heterocycles or derivatives thereof as a substrate, carbon materials as a catalyst, water or ethanol as a solvent, air or an oxygen ball as an oxygen source, and the heterogeneous catalytic system can react at 0-80 ℃ under normal pressure to realize the oxidative dehydrogenation of the nitrogen heterocycles, and simultaneously synthesize target products of pharmaceutical intermediates such as indole, quinoline, isoquinoline, quinazoline, quinoxaline, benzothiazole, hans' ester and derivatives thereof, so that a new way is provided for the synthesis of the pharmaceutical intermediates;
2. the catalyst is obtained by calcining polyion liquid in an inert gas atmosphere, is simple, efficient and stable in preparation, has mild catalytic reaction conditions, and can realize efficient, economic and green synthesis of aromatic nitrogen heterocycles;
3. the invention uses the polyion liquid as a precursor to prepare the nonmetal catalyst, has no activating agent or other additives in the reaction process, and has industrial application prospect.
Detailed Description
The following embodiments are helpful for understanding the present invention, but are not limited to the present invention.
An aerobic dehydrogenation method based on ionic liquid porous carbon material catalysis nitrogen heterocycle is characterized in that nitrogen heterocycle or derivatives thereof are used as a substrate, a porous carbon material is used as a catalyst, water or absolute ethyl alcohol is used as a solvent, air or oxygen is used as an oxidant, and the nitrogen heterocycle reacts at a temperature of 0-80 ℃ for 0-48 hours under a certain pressure to obtain a dehydrogenated nitrogen heterocycle product;
wherein, the precursor of the catalyst is synthesized by adopting the steps of formula (I) or (II):
wherein n is 1000-200 ten thousand; x-Is Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -Or C2H5COO-；
The specific synthesis steps of the formula (II) are as follows: dissolving N-vinylimidazole (6.21g,66mmol) and bromoacetonitrile (7.2g,60mmol) in 5mL of methanol, stirring at room temperature for 6 hours, then settling in 100mL of diethyl ether, and drying the obtained product in a vacuum drying oven at room temperature overnight to obtain an ionic liquid monomer 1-cyanomethyl-3-vinylimidazolium bromide (CMVImBr); carrying out anion exchange with lithium bistrifluoromethanesulfonylimide (LiNTF2) to obtain an ionic liquid monomer (I);
then, dissolving the obtained ionic liquid monomer (I) (10g) and an initiator azobisisobutyronitrile (0.2g) in 100mL of DMSO solution, carrying out crosslinking polymerization at 75 ℃ for 24 hours under the protection of inert gas, settling in excessive tetrahydrofuran after the reaction is finished, washing the product with ethanol, and carrying out vacuum drying at 60 ℃ overnight to obtain the polyion liquid (II).
Example 1
Preparation of the catalyst: carbonizing the polyion liquid (II) in a tube furnace at 800 ℃ for 2 hours in nitrogen atmosphere, and naturally cooling to room temperature to obtain the required catalyst.
0.5mmol of indoline, 40mg of catalyst, 2mL of ethanol and an oxygen ball are added into a Schlenk reaction tube as oxygen sources, then the mixture is stirred and reacted for 24 hours at the temperature of 60 ℃, and a silica gel chromatographic column is used for separating and purifying the product to obtain the target product (10a) of the indole, wherein the yield is 96%.
Derivatives (1a-1i) give the corresponding products (2a-2i) under the same conditions, with the following examples of substrate extensions:
example 2
0.5mmol of 1,2,3, 4-tetrahydroquinoxaline and 40mg of catalyst (the preparation method of the catalyst is as in example 1) are added into a Schlenk reaction tube, 2mL of ethanol and an oxygen ball are used as oxygen sources, then the mixture is stirred and reacted for 24 hours at 60 ℃, and a silica gel chromatographic column is used for separating and purifying products to obtain the target product of the quinoxaline, wherein the yield is 71%.
Derivatives (3a-3b) give the corresponding products (4a-4b) under the same conditions, with the following examples of substrate extensions:
example 3
0.5mmol of 1, 2-dihydrobenzothiazole, 40mg of catalyst (the preparation method of the catalyst is as in example 1), 2mL of ethanol and an oxygen ball are added into a Schlenk reaction tube, then the mixture is stirred and reacted for 24 hours at 60 ℃, and a silica gel chromatographic column separates and purifies the product to obtain the target product of the benzothiazole, wherein the yield is 90%.
Derivatives (5a-5d) give the corresponding products (6a-6d) under the same conditions, with the following examples of substrate extension:
example 4
0.5mmol of diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate, 40mg of a catalyst (the catalyst preparation method is as in example 1), 2mL of ethanol, and an oxygen balloon as an oxygen source were added to a Schlenk reaction tube, and then the mixture was stirred and reacted at 60 ℃ for 24 hours, and the product was separated and purified by a silica gel chromatography column to obtain the target product of diethyl 2, 6-dimethyl-3, 5-pyridinedicarboxylate with a yield of 95%.
Derivatives (7a-7e) give the corresponding products (8a-8e) under the same conditions, with the following examples of substrate extensions:
example 5
Preparation of the catalyst: carbonizing the ionic liquid (I) in a tube furnace at 800 ℃ for 2 hours in nitrogen atmosphere, and naturally cooling to room temperature to obtain the required catalyst.
Adding 0.5mmol of 1,2,3, 4-tetrahydroquinoline, 40mg of catalyst, 2mL of ethanol and an oxygen ball serving as an oxygen source into a Schlenk reaction tube, stirring and reacting at 60 ℃ for 24 hours, and separating and purifying a product by using a silica gel chromatographic column to obtain a target product of quinoline with the yield of 85%.
Derivatives (9a-9k) give the corresponding products (10a-10k) under the same conditions, with the following examples of substrate extension:
example 6
0.5mmol of 1,2,3, 4-tetrahydroisoquinoline and 40mg of catalyst (the preparation method of the catalyst is as in example 5) are added into a Schlenk reaction tube, 2mL of ethanol and an oxygen ball are used as oxygen sources, then the mixture is stirred and reacted for 24 hours at 60 ℃, and a silica gel chromatographic column is used for separating and purifying the product to obtain the target product of the isoquinoline, wherein the yield is 90%.
Derivatives (11a-11d) give the corresponding products (12a-12d) under the same conditions, with the following examples of substrate extension:
example 7
0.5mmol of 1,2,3, 4-tetrahydroquinazoline and 40mg of catalyst (the preparation method of the catalyst is as in example 5) are added into a Schlenk reaction tube, 2mL of ethanol and an oxygen ball are used as oxygen sources, then the mixture is stirred and reacted for 24 hours at 60 ℃, and a silica gel chromatographic column is used for separating and purifying the product to obtain the target product of the quinazoline, wherein the yield is 87%.
Derivatives (13a-13e) give the corresponding products (14a-14e) under the same conditions, with the following examples of substrate extensions:
Claims (7)
1. a method for catalyzing nitrogen heterocycle aerobic dehydrogenation based on an ionic liquid porous carbon material is characterized by comprising the following steps: the method comprises the steps of taking nitrogen heterocycles or derivatives thereof as a substrate, taking a porous carbon material as a catalyst, taking water or absolute ethyl alcohol as a solvent, taking air or oxygen as an oxidant, and reacting at a temperature of 0-80 ℃ for 0-48 hours under a certain pressure to obtain a dehydrogenated nitrogen heterocycle product.
2. The method for catalyzing the aerobic dehydrogenation of the nitrogen heterocycle based on the ionic liquid porous carbon material as claimed in claim 1, characterized in that: the substrate is: 1,2,3, 4-tetrahydroquinoline, 1,2,3, 4-tetrahydroisoquinoline, indoline, 1,2,3, 4-tetrahydroquinazoline, 1,2,3, 4-tetrahydroquinoxaline, 1, 2-dihydrobenzothiazole, or diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate.
3. A method for catalyzing the aerobic dehydrogenation of nitrogen heterocycles based on an ionic liquid porous carbon material according to claim 1 or 2, characterized in that: adding the carbon material in an amount of 0-100% by mass relative to the mass fraction of the substrate.
4. The method for catalyzing the aerobic dehydrogenation of the nitrogen heterocycle based on the ionic liquid porous carbon material as claimed in claim 3, is characterized in that: the pressure is 0.1 to 1 MPa.
5. The method for catalyzing the aerobic dehydrogenation of the nitrogen heterocycle based on the ionic liquid porous carbon material as claimed in claim 1,2 or 4, wherein: the catalyst is obtained by taking ionic liquid as a precursor and carbonizing the ionic liquid under the protection of inert gas at 600-1000 ℃.
6. The method for catalyzing the aerobic dehydrogenation of the nitrogen heterocycle based on the ionic liquid porous carbon material as claimed in claim 5, wherein: the precursor of the catalyst is synthesized by adopting the steps of formula (I) or (II):
wherein n is 1000-200 ten thousand; x-Is Cl-、Br-、I-、BF4 -、PF6 -、NTf2、TFSI-、H2PO4、NO3 -Or C2H5COO-。
7. The method for catalyzing the aerobic dehydrogenation of the nitrogen heterocycle based on the ionic liquid porous carbon material as claimed in claim 6, wherein: the specific synthesis steps of the formula (II) are as follows:
s1, dissolving N-vinylimidazole and bromoacetonitrile in methanol, stirring at room temperature for 5-7h, settling in ether, and vacuum drying for more than 24h to obtain an ionic liquid monomer CMVImBr;
s2, carrying out anion exchange on the product obtained in the step S1 and lithium bistrifluoromethanesulfonylimide to obtain an ionic liquid monomer CMVImNtf 2;
s3, dissolving the obtained ionic liquid monomer and an initiator azobisisobutyronitrile into a DMSO solution, protecting with inert gas, and carrying out cross-linking polymerization at 75 ℃ for more than 24 hours;
s4, precipitating in excessive tetrahydrofuran, washing a product by using ethanol, and drying in vacuum at 60 ℃ for more than 12h to obtain the polyion liquid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111365197.5A CN113929610A (en) | 2021-11-17 | 2021-11-17 | Method for catalyzing nitrogen heterocycle aerobic dehydrogenation based on ionic liquid porous carbon material |
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| CN202111365197.5A CN113929610A (en) | 2021-11-17 | 2021-11-17 | Method for catalyzing nitrogen heterocycle aerobic dehydrogenation based on ionic liquid porous carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116272943A (en) * | 2023-03-24 | 2023-06-23 | 遵义医科大学 | Carbon-based nonmetallic catalyst and preparation method and application thereof |
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| CN104876207A (en) * | 2015-04-13 | 2015-09-02 | 华南理工大学 | Method for preparing nitrogen-doped carbon material of multistage porous structure based on CaCl2 catalyzed thermal cracking of bagasse |
| CN106831563A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | A kind of method that carbon-nitrogen material catalysis nitrogen heterocyclic ring oxidative dehydrogenation prepares quinoline |
| CN108707110A (en) * | 2018-07-03 | 2018-10-26 | 宝鸡文理学院 | The method that the catalysis nitrogen heterocyclic ring oxidative dehydrogenation of biology base carbon material prepares quinoline, indole derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116272943A (en) * | 2023-03-24 | 2023-06-23 | 遵义医科大学 | Carbon-based nonmetallic catalyst and preparation method and application thereof |
| CN116272943B (en) * | 2023-03-24 | 2024-06-11 | 遵义医科大学 | Carbon-based nonmetallic catalyst and preparation method and application thereof |
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