CN108250124A - A kind of method of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction - Google Patents
A kind of method of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction Download PDFInfo
- Publication number
- CN108250124A CN108250124A CN201810192892.8A CN201810192892A CN108250124A CN 108250124 A CN108250124 A CN 108250124A CN 201810192892 A CN201810192892 A CN 201810192892A CN 108250124 A CN108250124 A CN 108250124A
- Authority
- CN
- China
- Prior art keywords
- carbazyl
- benzazole compounds
- microporous polymer
- photocatalysis
- formylation reaction
- 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.)
- Granted
Links
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
Abstract
The invention discloses a kind of methods of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction; this method is in oxygen-containing atmosphere and water/organic mixed solvent system; Benzazole compounds carry out formylation reaction with methyl aminated compounds under salt compounded of iodine and carbazyl conjugation microporous polymer (CMPs) catalytic action and illumination condition, obtain 3 formaldehyde Benzazole compounds；This method reaction condition is mild, can implement under room temperature and illumination condition, and target product can be obtained with highly selective high yield, and reaction belongs to heterogeneous catalytic reaction, and catalyst can realize recycling and recycle, and be conducive to industrialized production.
Description
Technical field
It is more particularly to a kind of to be gathered using carbazoles conjugation micropore the present invention relates to a kind of Benzazole compounds formylation reaction
The method that object (CMPs) is used for the efficient formylation reaction of catalyzing indole class compound as photochemical catalyst is closed, belongs to catalysis material
Expect application field.
Background technology
It is well known that with economic continuous development, the energy it is increasingly exhausted, look for the green novel energy source of sustainable development
Energy situation to change present sternness has become the target that countries in the world section scholar payes attention to the most.In existing many new energy
In, solar energy because its rich reserves, range of exposures be wide on earth and receives significant attention the advantages of cleanliness without any pollution.
3- formyl indole Compound Compounds are a kind of important chemical intermediates, are widely used in field of medicaments,
So the formylated synthesis for indoles plays an important roll.At present, mainly have about the formylated of Benzazole compounds
Gattermann-Koch, Vilsmeier-Haack and Reimer-Tiemann reaction etc., but use strong acid in these reactions
Highly basic and the industrial residue of generation limit it and are widely applied.The seminars such as Su have used metal rhodium and copper catalysis to aoxidize aldehyde
The synthesis of base, but the recycling of expensive metal price and metal limits its light reaction；Although some seminars with
Organic molecule Rose Bengal catalyzing indole aldehyde radicals, under the open energy saving light irradiations of system 14W, are urged by solvent of acetonitrile
Change indoles aldehyde radical, obtain preferable catalytic effect and selectivity, but this catalyst is not easily recycled recycling, and catalytic process needs
It heats.
Conjugation microporous polymer is a kind of material with extended conjugation system, has high-specific surface area, regulatable hole
The advantages such as structure, good thermal stability and chemical stability, while for the limitation of homogeneous catalyst, organic porous polymer
As different-phase catalyst significant advantage is embodied in terms of post processing, recycling and reuse.And polyalcohol catalyst can
With recycling, pollution etc. will not be generated to environment.But yet there are no can be used as photocatalyst applications in indoles
It closes object and carries out formylated relevant report.
Invention content
For the Benzazole compounds reported in the prior art process for hydroformylation there are the defects of, the purpose of the present invention is
It is to provide and a kind of utilizes carbazyl conjugation microporous polymer as major catalyst for the conversion of photocatalysis Benzazole compounds height
The method of rate and highly selective generation 3- formaldehyde Benzazole compounds, this method reaction condition is mild, is polymerize using Porous-Organic
Object replaces noble metal catalyst of the prior art, and significant advantage is embodied in terms of post processing, recycling and reuse.
In order to realize above-mentioned technical purpose, the present invention provides a kind of carbazyls to be conjugated microporous polymer photocatalysis indoles
The method of compound formylation reaction, this method are the Benzazole compounds in oxygen-containing atmosphere and water/organic mixed solvent system
Progress formylated is anti-under salt compounded of iodine and carbazyl conjugation microporous polymer catalytic action and illumination condition with methyl aminated compounds
Should, obtain 3- formaldehyde Benzazole compounds；
The Benzazole compounds have 1 structure of formula：
The 3- indolecarboxaldehydes class compound has 2 structure of formula：
Wherein, R, R1And R2For small molecule substituent group.
Preferred scheme, R1Selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester group, cyano or nitro.R1More preferably for hydrogen or
Alkyl.Alkyl such as C1~C5Alkyl.
Preferred scheme, R2Selected from alkyl, benzyl or phenyl, R2More preferably it is alkyl.Alkyl such as C1~C5Alkyl.
Preferred scheme, R are selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester group, cyano or nitro.R more preferably for hydrogen or
Alkyl.Alkyl such as C1~C5Alkyl.
The Benzazole compounds of the present invention are during the formylation reaction of 3 is carried out, R, R1And R2Influence phase to reaction
To smaller, theoretically R, R1And R2Various conventional small molecule substituent groups can realize indoles chemical combination in the selection scope of the invention
The formylation reaction of object.
Preferred scheme, the carbazyl conjugation microporous polymer have following molecular structure unit：(CMP-CSU1)、(CMP-CSU2)、(CMP-CSU2)、
(CMP-CSU4) or(CMP-CSU5)。
The existing document synthesis of synthesized reference of the carbazyl conjugation microporous polymer of the present invention, such as document：(Journal
of the American Chemical Society,134(14),6084-6087；2012)；(Morin,J.F.；Leclerc,
M.；Ades,D.；Siove,A.Macromol.Rapid Commun.2005,26(10),761-778.)；(Blouin,N.；
Leclerc, M.Acc.Chem.Res.2008,41 (9), 1110-1119.), mainly exist using carbazyl small molecule as raw material
FeCl3The lower generation coupling polymerization of catalysis obtains.
Preferred scheme, the water/organic mixed solvent system press 1 by water and organic solvent:4~6 compositions.
Preferred scheme, the organic solvent are at least one of acetonitrile, DMF, THF, DMSO, DCM, MeOH, EtOH.
Preferred scheme, the temperature of the formylation reaction is room temperature, and the reaction time is 30~60h.More preferably react
Time is 48h.
The mass ratio of preferred scheme, carbazyl conjugation microporous polymer and Benzazole compounds is 1:4~7；It is optimal
It is selected as 1:6.
The molar ratio of preferred scheme, methyl aminated compounds and Benzazole compounds is 3~5:1；More preferably it is 4:1.
The molar ratio of preferred scheme, Benzazole compounds and salt compounded of iodine is 1:3~5.
More preferably scheme, the methyl aminated compounds are tetramethylethylenediamine.
More preferably scheme, the salt compounded of iodine are potassium iodide.
Benzazole compounds are substrate in technical scheme of the present invention, and tetramethylethylenediamine mainly provides formoxyl carbon source,
Carbazyl is conjugated microporous polymer as major catalyst, and potassium iodide is as co-catalyst, and oxygen is as oxidant, water/organic solvent
As mixed solvent, light source mainly carries out at ambient temperature as energy source, reaction.
Compared with the prior art, the advantageous effect that technical scheme of the present invention is brought：
1) technical scheme of the present invention is provided for the first time using Benzazole compounds and tetramethylethylenediamine as reaction raw materials, in iodine
Change the method that formylation reaction is carried out under potassium/carbazyl conjugation microporous polymer catalytic action and illumination condition, it can be with high selection
Property, high yield obtain 3- formaldehyde Benzazole compounds target products；
2) technical scheme of the present invention reaction condition is mild, can be realized in room temperature and illumination condition；
3) technical scheme of the present invention is had using carbazyl conjugation microporous polymer/potassium iodide as composite catalyst system
There is the characteristics of high catalytic efficiency, more than 90% target product yield can be obtained, and carbazyl conjugation microporous polymer has
The features such as large specific surface area chemical stabilization and high thermal stability, and as different-phase catalyst, convenient for detaching and recycling, and have
There is the advantage of reuse.
Description of the drawings
【Fig. 1】It is the nucleus magnetic hydrogen spectrum figure of 1- methyl -3- aldehyde radical indoles in embodiment 1；
【Fig. 2】It is the nucleus magnetic hydrogen spectrum figure of 1,4- dimethyl -3- aldehyde radical indoles in embodiment 1；
【Fig. 3】It is the nucleus magnetic hydrogen spectrum figure of 1,2- dimethyl -3- aldehyde radical indoles in embodiment 1.
Specific embodiment
Following embodiment is intended to be described in further detail present disclosure rather than limit the claims in the present invention
Protection domain.
Embodiment 1
The synthetic method of the 3- formaldehyde Benzazole compounds of the present invention, synthetic route are as follows：
Specific examples below is specifically described by taking compound 1 respectively 1a, 1b and 1c as an example：
Weigh Compound 1 (1mmol) is dissolved in the water and 20mg that 5mL acetonitriles are dissolved in 1mL with KI (664mg, 4mmol)
CMP-CSU1 is added in the reaction bulb of 25mL, the 2 of 300 microlitres is added with liquid-transfering gun, in the condition for being continuously passed through oxygen
Under, LED light continuous illumination 48h.It is spin-dried for solvent, chromatography is to get to corresponding product 3a (yield 90%), 3b (yields
66%), 3c (yield 72%).
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of product 3a：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 product 3b nucleus magnetic hydrogen spectrum figures: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 product 3b nucleus magnetic hydrogen spectrum figures: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).
Embodiment 2
CMP-CSU1 is replaced using CMP-CSU2 as different from Example 1；Obtain corresponding product 3a (yield 67%), 3b
(yield 54%), 3c (yield 64%).
Embodiment 3
CMP-CSU1 is replaced using CMP-CSU3 as different from Example 1；Obtain corresponding product 3a (yield 43%), 3b
(yield 50%), 3c (yield 48%).
Embodiment 4
CMP-CSU1 is replaced using CMP-CSU4 as different from Example 1；Obtain corresponding product 3a (yield 61%), 3b
(yield 67%), 3c (yield 64%).
Embodiment 5
CMP-CSU1 is replaced using CMP-CSU5 as different from Example 1；Obtain corresponding product 3a (yield 67%), 3b
(yield 70%), 3c (yield 72%).
The application of feasibility analysis that a series of synthesis of carbazoles conjugation microporous polymer listed above and monomer carry out
Example only illustrates the present invention, the present invention is specifically described by embodiment, embodiment is served only for the present invention
It is further described rather than limiting the scope of the present invention, person skilled in art can make according to the present invention
Go out some nonessential modifications and adaptations.
Claims (9)
- A kind of 1. method of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction, it is characterised in that： In oxygen-containing atmosphere and water/organic mixed solvent system, Benzazole compounds are with methyl aminated compounds in salt compounded of iodine and carbazyl Formylation reaction is carried out under conjugation microporous polymer catalytic action and illumination condition, obtains 3- formaldehyde Benzazole compounds；The Benzazole compounds have 1 structure of formula：The 3- indolecarboxaldehydes class compound has 2 structure of formula：Wherein, R, R1And R2For small molecule substituent group.
- 2. a kind of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction according to claim 1 Method, it is characterised in that：R1Selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester group, cyano or nitro；R2Selected from alkyl, benzyl or phenyl；R is selected from hydrogen, alkyl, halogen, phenyl, benzyl, ester group, cyano or nitro.
- 3. a kind of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction according to claim 2 Method, it is characterised in that：R1Selected from hydrogen or alkyl；R2Selected from alkyl；R is selected from hydrogen or alkyl.
- 4. a kind of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction according to claim 1 Method, it is characterised in that：The carbazyl conjugation microporous polymer has following molecular structure unit：
- 5. a kind of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction according to claim 1 Method, it is characterised in that：The water/organic mixed solvent system presses 1 by water and organic solvent:4~6 compositions.
- 6. a kind of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction according to claim 5 Method, it is characterised in that：The organic solvent is at least one of acetonitrile, DMF, THF, DMSO, DCM, MeOH, EtOH.
- 7. microporous polymer photocatalysis Benzazole compounds are conjugated according to a kind of carbazyl of claim 1~6 any one of them The method of formylation reaction, it is characterised in that：The temperature of the formylation reaction is room temperature, and the reaction time is 30~60h.
- 8. microporous polymer photocatalysis Benzazole compounds are conjugated according to a kind of carbazyl of claim 1~6 any one of them The method of formylation reaction, it is characterised in that：It is 1 that carbazyl, which is conjugated microporous polymer and the mass ratio of Benzazole compounds,:4~7；The molar ratio of methyl aminated compounds and Benzazole compounds is 3~5:1.The molar ratio of Benzazole compounds and salt compounded of iodine is 1:3~5.
- 9. a kind of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction according to claim 8 Method, it is characterised in that：The methyl aminated compounds is tetramethylethylenediamine；The salt compounded of iodine 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 true CN108250124A (en) | 2018-07-06 |
| CN108250124B 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942570A (en) * | 2019-03-11 | 2019-06-28 | 中南大学 | A kind of conjugation microporous polymer based on phenthazine, preparation method and efficient catalytic 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 |
| CN114591476A (en) * | 2022-03-15 | 2022-06-07 | 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
| 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 |
-
2018
- 2018-03-09 CN CN201810192892.8A patent/CN108250124B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
| 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 |
|---|
| LIN LU,ET AL: "Iodine-catalyzed C3-formylation of indoles via C-N bond cleavage of tertiary amines under aerobic conditions", 《TETRAHEDRON》 * |
| NICOLAS BLOUIN，ET AL: "Poly(2,7-carbazole)s: Structure-Property Relationships", 《ACCOUNTS OF CHEMICAL RESEARCH》 * |
| QI CHEN,ET AL: "Microporous Polycarbazole with High Specific Surface Area for Gas Storage and Separation", 《J. AM. CHEM. SOC.》 * |
| YIBIN YE,ET AL: "Synthesis of 2 ‑ (Tri fl uoromethyl)indoles via Domino Trifluoromethylation/Cyclization of 2‑Alkynylanilines", 《ORG. LETT.》 * |
| 彭毅，等: "共轭微孔聚合物及其复合材料的制备及应用", 《化学通报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942570A (en) * | 2019-03-11 | 2019-06-28 | 中南大学 | A kind of conjugation microporous polymer based on phenthazine, preparation method and efficient catalytic 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 |
| CN114591476A (en) * | 2022-03-15 | 2022-06-07 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108250124B (en) | 2020-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Selective C–F bond carboxylation of gem-difluoroalkenes with CO 2 by photoredox/palladium dual catalysis | |
| Xu et al. | Visible-light-induced trifluoromethylation of N-aryl acrylamides: a convenient and effective method to synthesize CF (3)-containing oxindoles bearing a quaternary carbon center. | |
| CN108250124A (en) | A kind of method of carbazyl conjugation microporous polymer photocatalysis Benzazole compounds formylation reaction | |
| Li et al. | An Amine‐, Copper‐and Phosphine‐Free Sonogashira Coupling Reaction Catalyzed by Immobilization of Palladium in Organic–Inorganic Hybrid Materials | |
| Zhu et al. | Nickel-catalyzed sonogashira C (sp)–C (sp2) coupling through visible-light sensitization | |
| Midya et al. | Metal-free radical trifluoromethylation of β-nitroalkenes through visible-light photoredox catalysis | |
| Bakherad et al. | Solvent-free Heck and copper-free Sonogashira cross-coupling reactions catalyzed by a polystyrene-anchored Pd (II) phenyldithiocarbazate complex | |
| CN104761488A (en) | Three-dimensional bipyridine functionalized covalent organic frame material synthesis method | |
| Likhar et al. | Highly Efficient and Reusable Polyaniline‐Supported Palladium Catalysts for Open‐Air Oxidative Heck Reactions under Base‐and Ligand‐Free Conditions | |
| 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 | |
| Wu et al. | Gold-catalyzed generation of azafulvenium from an enyne sulfonamide: rapid access to fully substituted pyrroles | |
| Liu et al. | Formal β‐C− H Arylation of Aldehydes and Ketones by Cooperative Nickel and Photoredox Catalysis | |
| Zhang et al. | Visible-Light-Induced Cascade Cyclization of N-Propargyl Aromatic Amines and Acyl Oxime Esters: Rapid Access to 3-Acylated Quinolines | |
| Niknam et al. | Synthesis of some new 1, 4-distyrylbenzenes using immobilized palladium nanoparticles on silica functionalized morpholine as a recyclable catalyst | |
| Mohammadkhanni et al. | Palladium supported SBA-functionalizd 1, 2-dicarboxylic acid: The first Pd-based heterogeneous synthesis of fluorenones | |
| Hao et al. | A phosphine-free heterogeneous formylation of aryl halides catalyzed by a thioether-functionalized MCM-41-immobilized palladium complex | |
| Guo et al. | Synthesis of quinoline derivatives from anilines and aldehydes catalyzed by Cp2ZrCl2 and recyclable Cp2ZrCl2/MCM-41 system | |
| Liu et al. | Dehydroxyalkylative halogenation of C (aryl)–C bonds of aryl alcohols | |
| CN109867614B (en) | 4, 4-dialkyl sulfide-1-phenyl-3-butylene-1-ketone derivative and synthetic method thereof | |
| Mingzhong et al. | Silica-supported poly-γ-methylselenopropylsiloxane palladium complex: An efficient catalyst for Heck carbonylation of aryl halides | |
| Liu et al. | A powerful azomethine ylide route mediated by TiO 2 photocatalysis for the preparation of polysubstituted imidazolidines | |
| Li et al. | Direct Deoxygenative Intramolecular Acylation of Biarylcarboxylic Acids | |
| CN111484436A (en) | Method for introducing isopentenyl group to C3 position of indole | |
| Xu et al. | A facile synthesis of terminal arylacetylenes via Sonogashira coupling reactions catalyzed by MCM-41-supported mercapto palladium (0) complex |
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 |