CN109942483A - A kind of purpurine ion monomer and the preparation method and application thereof - Google Patents
A kind of purpurine ion monomer and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109942483A CN109942483A CN201910260476.1A CN201910260476A CN109942483A CN 109942483 A CN109942483 A CN 109942483A CN 201910260476 A CN201910260476 A CN 201910260476A CN 109942483 A CN109942483 A CN 109942483A
- Authority
- CN
- China
- Prior art keywords
- purpurine
- preparation
- ion monomer
- formula
- zincke
- 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.)
- Pending
Links
Abstract
The structural formula of a kind of purpurine ion monomer and the preparation method and application thereof, the purpurine ion monomer is shown below, and is replaced contraposition aniline to react in organic solvent through Zincke with R functional group by purpurine base Zincke salt VL-Br and is made.According to the demand of practical application, it can design and prepare a variety of purpurine ion monomers replaced with specific function group.Preparation method of the invention, required reaction condition is mild, the reaction time is short, and device therefor is simple, is suitable for scale application.Purpurine ion monomer of the invention can be used for preparing purpurine Quito ionic porogen polymer material, enrich the type of the purpurine ionic comonomer of multifunction.
Description
Technical field
The present invention relates to the preparation and application of compound, and in particular to a kind of purpurine ion monomer and preparation method thereof with answer
With.
Background technique
Purpurine (viologen) be 1,1'- it is disubstituted-laudatory title of 4,4'- bipyridine salt, can be by nothing when it is reduced
Discoloration purple, then image is referred to as purpurine.Tool is there are two N cationic species in purpurine structure, in different oxidation state or
Person's reduction-state can provide electronics and receive electronics, reversible redox reaction can occur, and along with the change of color
Change.Recently, purpurine structure is introduced into porous polymer by people, and it is porous to be prepared for a series of functional purpurine base ionics
Organic polymer, and applied in multiple fields (ACS Appl.Mater.Interfaces, 2019,11,6705-
6716)。
Currently, the preparation method about purpurine ion monomer depends on Menschutkin reaction, i.e. 4,4'- joins pyrrole
The quaternization reaction occurred between pyridine and two substitution halogenated alkanes.However, purpurine ion monomer made from this method, usual band
Flexible alkyl chain, rigidity is not strong enough, covalently has machine frame in the ionic that synthesis ionic porous polymer is especially ordered into
It is very restricted when frame material, it is more difficult to the porous framework structure of synthesizing high specific surface area.In recent years, pyrrole is joined by 4,4'-
Pyridine Zincke salt is reacted with the aniline that R group replaces by Zincke, and rigid purpurine ion monomer can be prepared
(J.Phys.Chem.B, 2012,116,2842-2849).Up to the present, may be used as polymerization reaction, to prepare ionic porous
The ionic comonomer type of organic polymer is still insufficient, and especially ion monomer anion is more single, as cl anion.
Therefore, the type that the purpurine ionic comonomer of abundant multifunction how is reacted by Zincke, regardless of being studied in material foundation
Or significance is suffered from application field.
Summary of the invention
Inventor has developed the preparation method of a kind of purpurine base ion monomer by lot of experiments, and designs synthesis
A variety of purpurine ion monomers that can be used for preparing purpurine Quito ionic porogen polymer material.
Specifically, structural formula is shown below the present invention provides a kind of purpurine ion monomer:
Wherein, R is amido, aldehyde radical, carboxyl, cyano, bromo, iodo, nitro or pinacol borate base.
The present invention also provides the preparation methods of above-mentioned a kind of purpurine ion monomer, by Zincke salt shown in formula 1 and 2 institute of formula
Show that compound is dissolved in organic solvent, reacts to obtain the purpurine ion monomer through Zincke
Wherein, R is amido, aldehyde radical, carboxyl, cyano, bromo, iodo, nitro or pinacol borate base.
Further, the preparation method specifically includes the following steps:
S1: weighing compound shown in Zincke salt shown in a certain amount of formula 1 and formula 2, and the container for filling organic solvent is added
In, stirring makes it completely dissolved, obtains homogeneous solution.
S2: homogeneous solution is transferred in reaction vessel, and heating stirring is reacted；
S3: after reaction, filtering, wash, dry, obtained solid, that is, purpurine ion monomer.
Further, in the step S1, the molar ratio of compound shown in Zincke salt shown in formula 1 and formula 2 is 1:2.
Further, the organic solvent in the step S1 is acetonitrile or ethyl alcohol.
Further, 80-100 DEG C of reaction temperature in the step S2, reaction time 24-48h.
The present invention also provides above-mentioned a kind of purpurine ion monomers in preparation purpurine Quito ionic porogen polymer material
Using.
Compared with prior art, beneficial effects of the present invention:
The aniline and 4 that the present invention is replaced using R group contraposition, 4'- bipyridyl Zincke salt are reacted by Zincke and are prepared
A kind of novel purpurine ion monomer can design the purpurine ion replaced with specific function group according to the demand of practical application
Monomer；
Preparation method of the invention, required reaction condition is mild, the reaction time is short, and device therefor is simple, is suitable for scale
Using；
A kind of purpurine ion monomer of the invention can be used for preparing purpurine Quito ionic porogen polymer material, enrich more function
The type of the purpurine ionic comonomer of energyization.
Specific embodiment:
Novel purpurine ionic compound of the present invention and detailed preparation method are illustrated below with reference to example.
But the example implemented only is described preferred embodiment of the invention, and it is not intended to limit the concept and scope of the present invention.
Under the premise of not departing from mentality of designing of the present invention, professional and technical personnel in the art change R group in novel compound
Become and to the various change that R group carries out on position on phenyl ring, all belongs to the scope of protection of the present invention.
Embodiment 1: the preparation of purpurine base Zincke salt VL-Br
It weighs 4,4'- bipyridyl (10mmol, 1.56g) and the bromo- 2,4- dinitrobenzene (20mmol, 4.94g) of 1- is placed at
In reaction flask, 100mL solvent acetonitrile is added, stirring is completely dissolved raw material.Then, by above-mentioned solution in 90 DEG C of return stirrings
72h.After reaction, the solid product of generation is finally obtained into yellow solid, as by simple filtration, washing and drying
Purpurine base Zincke salt VL-Br, yield 90%.It is characterized as below:
1H NMR (400MHz, D2O): δ 9.41~9.42 (CH, 4H), 9.33~9.34 (CH, 2H), 8.86~8.89
(CH, 6H) and 8.24~8.26ppm (CH, 2H) .13C NMR (100MHz, D2O): δ 152.58,149.81,146.80,
142.77,138.19,131.11,130.70,127.54and 122.77ppm. elemental analysis: measured value: C, 40.85；H,
2.51；N, 12.83wt%. theoretical value C22H14O8N6Br2 (M.W.650.19): C, 40.64；H,2.17；N, 12.93wt%..
Embodiment 2: the preparation of the purpurine ion monomer of anilino- functionalization
The preparation of the purpurine ion monomer of anilino- functionalization: firstly, weighing Zincke salt VL-Br (10mmol, 6.50g)
It is placed in reaction flask with p-phenylenediamine (20mmol, 2.16g), 200mL etoh solvent is added, stirring divides raw material uniformly
It dissipates, the heating reflux reaction 48h at 80 DEG C.After reaction, add 50mL water to stir a few hours, filtered with common funnel, filtrate
For dark-brown, 10g active carbon is added after filtering and stirs 2h, refilters, filtrate lighter.Filtrate low pressure is rotated and is removed
Water obtains dark brown solid, then is washed for several times with tetrahydrofuran (THF).It is finally dry in vacuum drying oven, it is solid to obtain dark-brown
Body product V-NH2-Br.
Embodiment 3: the preparation of the purpurine ion monomer of benzonitrile functionalization
The preparation of the purpurine ion monomer of benzonitrile functionalization: firstly, weighing Zincke salt VL-Br (10mmol, 6.50g)
It is placed in reaction flask with to amido cyanophenyl (20mmol, 2.36g), 200mL etoh solvent is added, stirring divides raw material uniformly
It dissipates, the heating reflux reaction 48h at 80 DEG C.After reaction, add 50mL water to stir a few hours, filtered with common funnel, filtrate
For light brown, filtrate low pressure is rotated and removes water, obtains light tan solid, then washed for several times with tetrahydrofuran (THF).Finally exist
It is dry in vacuum drying oven, obtain light tan solid product V-CN-Br.
Embodiment 4: the preparation of the purpurine ion monomer of bromobenzene functionalization
The preparation of the purpurine ion monomer of bromobenzene functionalization: firstly, weigh Zincke salt VL-Br (10mmol, 6.50g) and
Para-bromoaniline (20mmol, 3.44g) is placed in reaction flask, and 200mL etoh solvent is added, and stirring keeps raw material evenly dispersed,
The heating reflux reaction 48h at 80 DEG C.Reaction terminates, and generates yellow solid and brown solution, isolates solid by filtering, uses
Ethyl alcohol sufficiently washs.It is finally dry in vacuum drying oven, obtain light tan solid product V-Br-Br.
Embodiment 5: the purpurine ion monomer V-NO of nitrobenzene functionalization2The preparation of-Br
The use of paranitroanilinum and VL-Br is raw material, the purple of nitrobenzene functionalization can be prepared by Zincke reaction
Smart ion monomer V-NO2- Br, specific preparation method is the same as embodiment 2~4.
Embodiment 6: the preparation of the purpurine ion monomer V-CHO-Br of benzaldehyde functionalization
The use of 4-aminobenzoic acid and VL-Br is raw material, benzaldehyde functionalization can be prepared by Zincke reaction
Purpurine ion monomer V-COOH-Br, specific preparation method is the same as embodiment 2~4.
Embodiment 7: the preparation of the purpurine ion monomer V-COOH-Br of benzoic acid functionalization
The use of 4- aminobenzaldehyde and VL-Br is raw material, benzaldehyde functionalization can be prepared by Zincke reaction
Purpurine ion monomer V-CHO-Br, specific preparation method is the same as embodiment 2~4
Embodiment 8: the preparation of the purpurine ion monomer V-I-Br of iodobenzene functionalization
The use of paraiodoaniline and VL-Br is raw material, by Zincke reaction can prepare the purpurine of iodobenzene functionalization from
Sub- monomer V-I-Br, specific preparation method is the same as embodiment 2~4.
Embodiment 9: the preparation of the purpurine ion monomer V-Bpin-Br of phenyl boric acid pinacol ester functionalization
The use of 4- aminobenzene pinacol borate and VL-Br is raw material, phenyl boric acid can be prepared by Zincke reaction
The purpurine ion monomer V-Bpin-Br of pinacol ester functionalization, specific preparation method is the same as embodiment 2~4.
Claims (7)
1. a kind of purpurine ion monomer, it is characterized in that, structural formula is shown below:
Wherein, R is amido, aldehyde radical, carboxyl, cyano, bromo, iodo, nitro or pinacol borate base.
2. the preparation method of one kind purpurine ion monomer described in claim 1, which is characterized in that by Zincke salt shown in formula 1 with
Compound shown in formula 2 is dissolved in organic solvent, reacts to obtain the purpurine ion monomer through Zincke
Wherein, R is amido, aldehyde radical, carboxyl, cyano, bromo, iodo, nitro or pinacol borate base.
3. preparation method according to claim 2, which is characterized in that itself specifically includes the following steps:
S1: weighing compound shown in Zincke salt shown in a certain amount of formula 1 and formula 2, is added in the container for filling organic solvent, stirs
It mixes, makes it completely dissolved, obtain homogeneous solution.
S2: homogeneous solution is transferred in reaction vessel, and heating stirring is reacted；
S3: after reaction, filtering, wash, dry, obtained solid, that is, purpurine ion monomer.
4. preparation method according to claim 3, which is characterized in that in the step S1, Zincke salt and formula shown in formula 1
The molar ratio of compound shown in 2 is 1:2.
5. preparation method according to claim 3, which is characterized in that the organic solvent in the step S1 is acetonitrile or second
Alcohol.
6. preparation method according to claim 3, which is characterized in that 80-100 DEG C of reaction temperature in the step S2,
Reaction time 24-48h.
7. application of one kind purpurine ion monomer described in claim 1 in preparation purpurine Quito ionic porogen polymer material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910260476.1A CN109942483A (en) | 2019-04-02 | 2019-04-02 | A kind of purpurine ion monomer and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910260476.1A CN109942483A (en) | 2019-04-02 | 2019-04-02 | A kind of purpurine ion monomer and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109942483A true CN109942483A (en) | 2019-06-28 |
Family
ID=67013424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910260476.1A Pending CN109942483A (en) | 2019-04-02 | 2019-04-02 | A kind of purpurine ion monomer and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109942483A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978516A (en) * | 2020-07-27 | 2020-11-24 | 大连理工大学 | Preparation and catalytic application of donor-acceptor type ion porous polymer |
| CN114349960A (en) * | 2021-12-21 | 2022-04-15 | 常州大学 | Preparation method of ionic chiral covalent organic framework material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411084A (en) * | 1977-06-28 | 1979-01-26 | Dainippon Toryo Co Ltd | Electrochromic composition and diffusion type electrochromic display element |
| JPS54151581A (en) * | 1978-05-22 | 1979-11-28 | Dainippon Toryo Co Ltd | Electrochromic composition and disperse type electrochromic display element |
| US4693564A (en) * | 1984-10-31 | 1987-09-15 | Sony Corporation | Electrochromic display device |
-
2019
- 2019-04-02 CN CN201910260476.1A patent/CN109942483A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411084A (en) * | 1977-06-28 | 1979-01-26 | Dainippon Toryo Co Ltd | Electrochromic composition and diffusion type electrochromic display element |
| JPS54151581A (en) * | 1978-05-22 | 1979-11-28 | Dainippon Toryo Co Ltd | Electrochromic composition and disperse type electrochromic display element |
| US4693564A (en) * | 1984-10-31 | 1987-09-15 | Sony Corporation | Electrochromic display device |
Non-Patent Citations (2)
| Title |
|---|
| DAVID R.ROSSEINSKY ET AL: "Solid-state Conductivities of CPQ [1,1"-Bis(p-cyanophenyl)-4,4"-bipyridilium]Salts, Redox-state Mixtures and a New Intervalence Adduct", 《J.CHEM.SOC.FARADAY TRANS.》 * |
| KLIMISHA, G. P. ET AL: "N,N"-diaryl-4,4"-dipyridinium dibromides", 《KHIMIYA GETEROTSIKLICHESKIKH SOEDINENII》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978516A (en) * | 2020-07-27 | 2020-11-24 | 大连理工大学 | Preparation and catalytic application of donor-acceptor type ion porous polymer |
| CN111978516B (en) * | 2020-07-27 | 2022-05-10 | 大连理工大学 | Preparation and catalytic application of donor-acceptor type ion porous polymer |
| CN114349960A (en) * | 2021-12-21 | 2022-04-15 | 常州大学 | Preparation method of ionic chiral covalent organic framework material |
| CN114349960B (en) * | 2021-12-21 | 2023-09-19 | 常州大学 | Preparation method of ionic chiral covalent organic framework material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yue et al. | Synthesis of self-doped conducting polyaniline | |
| CN109942483A (en) | A kind of purpurine ion monomer and the preparation method and application thereof | |
| Pratihar et al. | Tetradentate amido azo Schiff base Cu (II), Ni (II) and Pd (II) complexes: Synthesis, characterization, spectral properties, and applications to catalysis in C–C coupling and oxidation reaction | |
| Leng et al. | A novel heteropolyanion-based amino-containing cross-linked ionic copolymer catalyst for epoxidation of alkenes with H2O2 | |
| CN101307065A (en) | N-heterocyclic dicarbene metal complex connected with ether chain, method for preparing same and use | |
| JP5813561B2 (en) | Color material and method for producing the same | |
| Chen et al. | Two pairs of 1: 2 nickel (II) and copper (II) metal-complex dyes showing the same trans configuration and azo–hydrazone transformation but different thermal properties | |
| CN106831830B (en) | A kind of supermolecule cage complex and its preparation method and application | |
| CN108558919A (en) | A kind of cadmium metal organic coordination compound and preparation method thereof | |
| CN102993206B (en) | Method for synthesising tetraphenylporphyrin metal complex via one-step process | |
| CN101914042A (en) | Preparation method of nicarbazin midbody 4,4'- binitro sym-diphenylurea | |
| CN107129597A (en) | A kind of uvioresistant composite of hydrotalcite confinement synthesis Schiff base molecule, preparation method and application | |
| CN108822130B (en) | Benzimidazole cyclophane and preparation method and application thereof | |
| Yang et al. | Synthesis, structure and characterization of binuclear copper (I) complexes | |
| CN110551291A (en) | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof | |
| CN105418491B (en) | A kind of 1 (4 pyridine radicals) 4 (4 ＇ pyridine radicals vinyl) benzene and its production and use | |
| CN108929674A (en) | A kind of preparation method of composition metal organic framework materials MOF-5 | |
| CN113058653B (en) | Catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile and preparation method thereof | |
| CN113321789B (en) | Four polymeric metal complex dye sensitizers containing pyrrole derivatives, and preparation method and application thereof | |
| CN108993599A (en) | A kind of functionalized order mesoporous organosilicon Pd catalyst of N- heterocycle carbine and preparation method thereof | |
| CN103073919A (en) | Solvent yellow 33 | |
| WO2014061143A1 (en) | Coloring material and method for producing same | |
| CN104628753B (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
| CN102827169A (en) | Novel porphyrin ligand and metal complex, preparation method and application for novel porphyrin ligand | |
| CN112079831A (en) | Quinacridone-thiophene derivative and preparation method and application thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190628 |
|
| WD01 | Invention patent application deemed withdrawn after publication |