CN108250124B - Method for catalyzing formylation reaction of indole compounds by using carbazolyl conjugated microporous polymer - Google Patents
Method for catalyzing formylation reaction of indole compounds by using carbazolyl conjugated microporous polymer Download PDFInfo
- Publication number
- CN108250124B CN108250124B CN201810192892.8A CN201810192892A CN108250124B CN 108250124 B CN108250124 B CN 108250124B CN 201810192892 A CN201810192892 A CN 201810192892A CN 108250124 B CN108250124 B CN 108250124B
- Authority
- CN
- China
- Prior art keywords
- carbazolyl
- conjugated microporous
- microporous polymer
- indole
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing formylation reaction of indole compounds by carbazolyl conjugated microporous polymers, which comprises the following steps of carrying out formylation reaction on the indole compounds and methylamine compounds under the catalysis of iodide and carbazolyl Conjugated Microporous Polymers (CMPs) and the illumination condition in an oxygen-containing atmosphere and a water/organic mixed solvent system to obtain 3-formaldehyde indole compounds; the method has mild reaction conditions, can be implemented at room temperature and under the illumination condition, can obtain the target product with high selectivity and high yield, belongs to heterogeneous catalytic reaction, can realize the recovery and the recycling of the catalyst, and is beneficial to industrial production.
Description
Technical Field
The invention relates to a formylation reaction of indole compounds, in particular to a method for catalyzing high-efficiency formylation reaction of indole compounds by using carbazole Conjugated Microporous Polymers (CMPs) as a photocatalyst, belonging to the field of application of catalytic functional materials.
Background
As is well known, with the continuous development of economy and the gradual depletion of energy, the change of the current severe energy situation by searching for green new energy which can be continuously developed becomes the most important target of all national scholars in the world. Among the existing new energy sources, solar energy is receiving attention because of its advantages of abundant reserves, wide irradiation range, cleanness and no pollution on the earth.
The 3-formyl indole compound is an important chemical intermediate, is widely applied to the field of medicine, and has an important effect on the synthesis of formylation of indoles. At present, the formylation of indole compounds mainly comprises Gattermann-Koch, Vilsmeier-Haack and Reimer-Tiemann reactions, etc., but the use of strong acid and alkali in the reactions and the generated industrial waste residue limit the wide application of the indole compounds. Su et al, however, have limited their photoreaction due to expensive metal price and recycling of metals; although some subject groups use small organic molecule Rose Bengal to catalyze the hydroformylation of indole, under the irradiation of an open system 14W energy-saving lamp, acetonitrile is used as a solvent to catalyze the hydroformylation of indole, so as to obtain better catalytic effect and selectivity, the catalyst is not easy to recycle, and the catalytic process needs heating.
The conjugated microporous polymer is a material with an expanded conjugated system, has the advantages of high specific surface area, adjustable pore structure, good thermal stability, chemical stability and the like, and shows remarkable advantages in the aspects of post-treatment, recovery and repeated use of the organic porous polymer as a heterogeneous catalyst aiming at the limitation of the homogeneous catalyst. And the polymer catalyst can be repeatedly used, and does not produce pollution to the environment and the like. However, no report about the application of the photocatalyst in formylation of indole compounds is available at present.
Disclosure of Invention
Aiming at the defects of the formylation method of the indole compounds reported in the prior art, the invention aims to provide the method for generating the 3-formaldehyde indole compounds by using the carbazolyl conjugated microporous polymer as the main catalyst for photocatalysis of the indole compounds with high conversion rate and high selectivity, the method has mild reaction conditions, adopts the organic porous polymer to replace the noble metal catalyst in the prior art, and has obvious advantages in post-treatment, recovery and reuse.
In order to realize the technical purpose, the invention provides a method for carrying out a formylation reaction on an indole compound by a carbazolyl conjugated microporous polymer photocatalysis, which comprises the steps of carrying out the formylation reaction on the indole compound and a methylamine compound under the catalysis of an iodonium salt and the carbazolyl conjugated microporous polymer and under the condition of illumination in an oxygen-containing atmosphere and a water/organic mixed solvent system to obtain a 3-formaldehyde indole compound;
the indole compound has a structure shown in formula 1:
the 3-indole formaldehyde compound has a structure shown in a formula 2:
wherein, R, R1And R2Is a small molecule substituent group.
Preferred embodiment, R1Selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester, cyano or nitro. R1More preferably hydrogen or alkyl. Alkyl radicals such as C1～C5Alkyl group of (1).
Preferred embodiment, R2Selected from alkyl, benzyl or phenyl, R2More preferably an alkyl group. Alkyl radicals such as C1～C5Alkyl group of (1).
In a preferred embodiment, R is selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester, cyano or nitro. R is more preferably hydrogen or alkyl. Alkyl radicals such as C1～C5Alkyl group of (1).
R, R during the formylation reaction of the indole compound of the invention at the 3-position1And R2The effect on the reaction is relatively small, in theory R, R1And R2Various conventional small molecule substituents within the scope of the invention can be selected to achieve formylation of indole compounds.
In a preferred embodiment, the carbazolyl conjugated microporous polymer has the following molecular structural units:
(CMP-CSU1)、
(CMP-CSU2)、
(CMP-CSU2)、
(CMP-CSU4) or
(CMP-CSU5)。
The synthesis of the carbazolyl conjugated microporous polymer is synthesized by referring to the prior literature, such as the following documents: (journal of the American Chemical Society,134(14), 6084-; (Morin, J.F.; Leclerc, M.; Ades, D.; Simove, A.Macromol. Rapid Commun.2005,26(10), 761-778.); (Blouin, N.; Leclerc, M.Acc.chem.Res.2008,41 (9); 1110-1119.), mainly carbazolyl micromolecules are used as raw materials in FeCl3The catalyst is catalyzed to generate coupling polymerization to obtain the catalyst.
In a preferred scheme, the water/organic mixed solvent system consists of water and an organic solvent according to a ratio of 1: 4-6.
In a preferred embodiment, the organic solvent is at least one of acetonitrile, DMF, THF, DMSO, DCM, MeOH, EtOH.
In a preferable scheme, the formylation reaction temperature is room temperature, and the reaction time is 30-60 h. The reaction time is preferably 48 hours.
In the preferable scheme, the mass ratio of the carbazolyl conjugated microporous polymer to the indole compound is 1: 4-7; most preferably 1: 6.
In a preferable scheme, the molar ratio of the methylamine compound to the indole compound is 3-5: 1; more preferably 4: 1.
In a preferable scheme, the mol ratio of the indole compound to the iodide salt is 1: 3-5.
In a more preferred embodiment, the methylamine-type compound is tetramethylethylenediamine.
In a more preferred embodiment, the iodide salt is potassium iodide.
According to the technical scheme, an indole compound is used as a substrate, tetramethylethylenediamine mainly provides a formyl carbon source, a carbazolyl conjugated microporous polymer is used as a main catalyst, potassium iodide is used as a cocatalyst, oxygen is used as an oxidant, water/organic solvent is used as a mixed solvent, a light source is used as an energy source, and the reaction is mainly carried out at room temperature.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the technical scheme of the invention provides a method for formylation reaction by taking indole compounds and tetramethylethylenediamine as reaction raw materials under the catalysis of potassium iodide/carbazolyl conjugated microporous polymers and under the condition of illumination for the first time, and the target product of the 3-formaldehyde indole compounds can be obtained with high selectivity and high yield;
2) the technical scheme of the invention has mild reaction conditions, and can be realized at room temperature and under illumination conditions;
3) the technical scheme of the invention adopts the carbazolyl conjugated microporous polymer/potassium iodide as a composite catalytic system, has the characteristic of high catalytic efficiency, can obtain more than 90% of yield of a target product, has the characteristics of large specific surface area, high chemical stability, high thermal stability and the like, is used as a heterogeneous catalyst, is convenient to separate and recover, and has the advantage of repeated use.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1-methyl-3-formylindole in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 1, 4-dimethyl-3-formylindole in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 1, 2-dimethyl-3-formylindole in example 1.
Detailed Description
The following examples are intended to illustrate the present invention in further detail, but are not intended to limit the scope of the claims.
Example 1
The synthetic method of the 3-formaldehyde indole compound comprises the following synthetic route:
the following specific examples are specifically illustrated by taking compound 1 as 1a, 1b and 1c, respectively:
compound 1(1mmol) was weighed out and dissolved in 5mL acetonitrile, KI (664mg,4mmol) in 1mL water and 20mg CMP-CSU1, and added to a 25mL reaction flask, and 300. mu.L of 2 was added using a pipette, and the LED lamp was continuously illuminated for 48h with oxygen continuously. The solvent was dried by rotary chromatography to obtain the corresponding products 3a (90% yield), 3b (66% yield), and 3c (72% yield).
FIG. 1 is a nuclear magnetic hydrogen spectrum of product 3 a:1H NMR Analysis:1H NMR(400MHz,CDCl3):δ10.00(s,1H),8.32-8.30(d,1H),7.69(s,1H),7.39-7.32(3H),3.89(s,3H).
FIG. 2 is a nuclear magnetic hydrogen spectrum of product 3 b:1H NMR Analysis:1H NMR(400MHz,CDCl3):δ10.16(s,1H),7.84(s,1H),7.27-7.07(3H),3.88(s,3H),2.86(s,3H).
FIG. 3 is a nuclear magnetic hydrogen spectrum of product 3 b:1H NMR Analysis:1H NMR(400MHz,CDCl3):δ9.76(s,1H),8.47-8.46(d,1H),7.59(s,3H),7.47-7.37(3H),3.71(s,3H).
example 2
Different from example 1, CMP-CSU1 was replaced with CMP-CSU 2; the corresponding products 3a (67% yield), 3b (54% yield), 3c (64% yield) were obtained.
Example 3
Different from example 1, CMP-CSU1 was replaced with CMP-CSU 3; the corresponding products 3a (43% yield), 3b (50% yield), 3c (48% yield) were obtained.
Example 4
Different from example 1, CMP-CSU1 was replaced with CMP-CSU 4; the corresponding products 3a (61% yield), 3b (67% yield), 3c (64% yield) were obtained.
Example 5
Different from example 1, CMP-CSU1 was replaced with CMP-CSU 5; the corresponding products 3a (67% yield), 3b (70% yield), 3c (72% yield) were obtained.
The present invention is described in detail by way of examples, which are provided for further illustration and are not intended to limit the scope of the invention, and many insubstantial modifications and adaptations of the invention may be made by those skilled in the art.
Claims (7)
1. A method for catalyzing formylation reaction of indole compounds by carbazolyl conjugated microporous polymers is characterized in that: in an oxygen-containing atmosphere and a water/organic mixed solvent system, performing formylation reaction on an indole compound and a methylamine compound under the catalysis of an iodonium salt and a carbazolyl conjugated microporous polymer and under the condition of illumination to obtain a 3-formaldehyde indole compound;
the indole compound has a structure shown in formula 1:
the 3-indole formaldehyde compound has a structure shown in a formula 2:
wherein the content of the first and second substances,
R1selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester, cyano or nitro;
R2selected from alkyl, benzyl or phenyl;
r is selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester group, cyano or nitro;
the carbazolyl conjugated microporous polymer has the following molecular structural units:
2. the method for the carbazolyl conjugated microporous polymer photocatalytic indole compound formylation reaction according to claim 1, wherein:
R1selected from hydrogen or alkyl;
R2selected from alkyl groups;
r is selected from hydrogen or alkyl.
3. The method for the carbazolyl conjugated microporous polymer photocatalytic indole compound formylation reaction according to claim 1, wherein: the water/organic mixed solvent system is composed of water and an organic solvent in a ratio of 1: 4-6.
4. The method for the carbazolyl conjugated microporous polymer photocatalytic indole compound formylation reaction according to claim 3, wherein: the organic solvent is at least one of acetonitrile, DMF, THF, DMSO, DCM, MeOH, and EtOH.
5. The method for the carbazolyl conjugated microporous polymer photocatalytic indole compound formylation reaction according to any one of claims 1 to 4, wherein: the formylation reaction temperature is room temperature, and the reaction time is 30-60 h.
6. The method for the carbazolyl conjugated microporous polymer photocatalytic indole compound formylation reaction according to any one of claims 1 to 4, wherein:
the mass ratio of the carbazolyl conjugated microporous polymer to the indole compound is 1: 4-7;
the molar ratio of the methylamine compound to the indole compound is 3-5: 1.
The mol ratio of the indole compound to the iodide salt is 1: 3-5.
7. The method for the carbazolyl conjugated microporous polymer photocatalytic indole compound formylation reaction according to claim 6, wherein:
the methyl amine compound is tetramethyl ethylene diamine;
the iodine salt is potassium iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810192892.8A CN108250124B (en) | 2018-03-09 | 2018-03-09 | Method for catalyzing formylation reaction of indole compounds by using carbazolyl conjugated microporous polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810192892.8A CN108250124B (en) | 2018-03-09 | 2018-03-09 | Method for catalyzing formylation reaction of indole compounds by using carbazolyl conjugated microporous polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108250124A CN108250124A (en) | 2018-07-06 |
| CN108250124B true CN108250124B (en) | 2020-04-28 |
Family
ID=62745851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810192892.8A Active CN108250124B (en) | 2018-03-09 | 2018-03-09 | Method for catalyzing formylation reaction of indole compounds by using carbazolyl conjugated microporous polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108250124B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942570B (en) * | 2019-03-11 | 2020-08-04 | 中南大学 | Conjugated microporous polymer based on phenothiazine, preparation method and high-efficiency catalysis application |
| CN113817532A (en) * | 2021-10-29 | 2021-12-21 | 无锡奇比特润滑油有限公司 | Piezofluorescence color-changing lubricating oil and preparation process thereof |
| CN114591476B (en) * | 2022-03-15 | 2023-04-07 | 浙江大学 | Covalent organic framework material based on indanone framework and preparation method and application thereof |
| CN114591248A (en) * | 2022-04-24 | 2022-06-07 | 湖南工程学院 | Method for preparing benzimidazole compound by using carbazolyl conjugated microporous polymer photocatalysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922903A (en) * | 2014-04-01 | 2014-07-16 | 湖南大学 | Method for catalytically oxidizing alkane and cycloparaffin by use of conjugated polymetalloporphyrin |
| CN107698742A (en) * | 2017-06-14 | 2018-02-16 | 中南大学 | Benzene thiophene diketo conjugation microporous polymer prepares and its photocatalytic applications |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304779B (en) * | 2012-03-15 | 2016-01-20 | 国家纳米科学中心 | A kind of polycarbazole polymkeric substance and its preparation method and application |
-
2018
- 2018-03-09 CN CN201810192892.8A patent/CN108250124B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922903A (en) * | 2014-04-01 | 2014-07-16 | 湖南大学 | Method for catalytically oxidizing alkane and cycloparaffin by use of conjugated polymetalloporphyrin |
| CN107698742A (en) * | 2017-06-14 | 2018-02-16 | 中南大学 | Benzene thiophene diketo conjugation microporous polymer prepares and its photocatalytic applications |
Non-Patent Citations (5)
| Title |
|---|
| Iodine-catalyzed C3-formylation of indoles via C-N bond cleavage of tertiary amines under aerobic conditions;Lin Lu,et al;《Tetrahedron》;20141202;第71卷;第3637-3641页 * |
| Microporous Polycarbazole with High Specific Surface Area for Gas Storage and Separation;Qi Chen,et al;《J. Am. Chem. Soc.》;20120328;第134卷;第6084-6087页 * |
| Poly(2,7-carbazole)s: Structure-Property Relationships;NICOLAS BLOUIN，et al;《ACCOUNTS OF CHEMICAL RESEARCH》;20080726;第41卷(第9期);第1110-1119页 * |
| Yibin Ye,et al.Synthesis of 2 ‑(Tri fluoromethyl)indoles via Domino Trifluoromethylation/Cyclization of 2‑Alkynylanilines.《Org. Lett.》.2018,第20卷第1676-1679页. * |
| 共轭微孔聚合物及其复合材料的制备及应用;彭毅，等;《化学通报》;20161231;第79卷(第8期);第699-706,713页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108250124A (en) | 2018-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108250124B (en) | Method for catalyzing formylation reaction of indole compounds by using carbazolyl conjugated microporous polymer | |
| Yan et al. | Construction of C (sp2)− C (sp3) Bond between Quinoxalin‐2 (1H)‐ones and N‐Hydroxyphthalimide Esters via Photocatalytic Decarboxylative Coupling | |
| Ju et al. | Synthesis of oxindoles via visible light photoredox catalysis | |
| Ni et al. | Sunlight-promoted cyclization versus decarboxylation in the reaction of alkynoates with N-iodosuccinimide: easy access to 3-iodocoumarins | |
| An et al. | FeCl 3-Catalyzed synthesis of pyrrolo [1, 2-a] quinoxaline derivatives from 1-(2-aminophenyl) pyrroles through annulation and cleavage of cyclic ethers | |
| Zhang et al. | Insight into the catalytic properties and applications of metal–organic frameworks in the cyanosilylation of aldehydes | |
| Jensen et al. | Bicyclization of unsaturated hydrazones mediated by zirconocene complexes. A new annulation strategy based on the reductive cocyclization of azomethine linkages with carbon-carbon multiple bonds | |
| He et al. | Combining enzyme and photoredox catalysis for aminoalkylation of indoles via a relay catalysis strategy in one pot | |
| CN112044450B (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
| Wu et al. | Palladium-catalyzed dearomative cyclization by a norbornene-mediated sequence: a route to spiroindolenine derivatives | |
| CN107011145A (en) | A kind of method that utilization visible light catalytic prepares the derovatives of alkene 1,4 of 2 iodine penta 2 | |
| CN113548998B (en) | N- (2-aryl formaldehyde) -1-aminoindole derivative and synthesis method and application thereof | |
| Liu et al. | Solvent‐free Synthesis of Alkylaminophenols via Petasis Boronic Mannich Reaction in One Pot without Catalysts | |
| Zhao et al. | Highly enantioselective construction of strained spiro [2, 3] hexanes through a michael addition/ring expansion/cyclization cascade | |
| Ling et al. | Recyclable and reusable n-Bu 4 NBF 4/PEG-400/H 2 O system for electrochemical C-3 formylation of indoles with Me 3 N as a carbonyl source | |
| Qiao et al. | Switchable aroylation and diaroylation of allyl sulfones with aldehydes enabled by decatungstate photocatalysis | |
| Liu et al. | Difluoroborate-based conjugated organic polymer: a high-performance heterogeneous photocatalyst for oxidative coupling reactions | |
| CN109908957B (en) | Coordination type zirconium phosphotungstate catalyst and application thereof in catalytic hydrogenation of furfural | |
| Hu et al. | Rh (iii)-Catalyzed spiroannulation of ketimines with cyclopropenones via sequential C–H/C–C bond activation | |
| Gao et al. | Asymmetric Michael Addition/Intramolecular Cyclization Catalyzed by Bifunctional Tertiary Amine-Squaramides: Construction of Chiral 2-Amino-4 H-chromene-3-Carbonitrile Derivatives. | |
| You et al. | An Eosin Y Encapsulated Cu (I) Covalent Metal Organic Framework for Efficient Photocatalytic Sonogashira Cross-Coupling Reaction | |
| Guo et al. | Cu/Pd-Catalyzed chemoselective synthesis of C-3 dicarbonyl indoles and bis (indolyl) alkanes from aldehydes and indoles | |
| Bäckvall et al. | Palladium-catalyzed cis-and trans-annulations to 1, 3-cyclohexadiene and 1, 3-cycloheptadiene1 | |
| CN110183317B (en) | Method for generating cyclopentenones through furfuryl alcohol cyclization conversion | |
| Halimehjani et al. | Catalyst-free Friedel–Crafts alkylation of naphthols with nitrostyrenes in the presence of water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |