CN101747227A - Novel compound containing styryl and azobenzene and preparation method and application thereof - Google Patents
Novel compound containing styryl and azobenzene and preparation method and application thereof Download PDFInfo
- Publication number
- CN101747227A CN101747227A CN200810204115A CN200810204115A CN101747227A CN 101747227 A CN101747227 A CN 101747227A CN 200810204115 A CN200810204115 A CN 200810204115A CN 200810204115 A CN200810204115 A CN 200810204115A CN 101747227 A CN101747227 A CN 101747227A
- Authority
- CN
- China
- Prior art keywords
- reaction
- styryl
- azobenzene
- group
- new
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a novel compound containing styryl and azobenzene and a preparation method and application thereof, which relates to the technical field of the compound synthesis and preparation. The basic constitutional formula of the novel compound containing the styryl and azobenzene: the constitutional formula contains azonbenzene radical and styryl radical, and R1 and R2 in the chemical constitutional formula is alkyl radical or alkoxy group; the compound can be prepared through a series of reactions such as diazotization reaction, coupling reaction, and the like; since the azonbenzene radical is of a favorable photochromism radical, and high polymer can be obtained through the free polymerization of styryl, the compound has promising application prospect on the aspects of non-linear optical material, photoresponse, storage element and the like; and the attached diagram is the hydrogen spectrogram of the novel compound containing the styryl and the azobenzene (R1= -OCH3, and R2= -C4H9), which proves the successful synthesis of the target compound.
Description
[technical field]
The present invention relates to the synthetic and preparing technical field of compound, be specifically related to a kind of new styryl azobenzene compound and its production and application that contains.
[background technology]
In recent years, the synthetic and preparation of nitrogen benzide functional compound has obtained significant progress, and this mainly is to have features such as good optics, thermal property and photic cis-trans isomerism because contain the azobenzene derivatives of chromophore.Because azo-compound has the character of photic cis-trans isomerism, is the important photochromic compound of a class, has huge application potential aspect the storage media that can wipe re-write optical disk.On the other hand, though the research of organic non linear optical material at present mainly concentrates on the organic compound of electron donor-acceptor structure and intramolecular charge transfer, but azo-compound has good photoelectric properties, it is the good nonlinear optics chromophore of a class, this is owing to contain the cause that the material of azo-compound has characteristics such as photic isomery and molecule reorientation, this will cause that absorbed and refractive isotropy and anisotropy change, produce optical non-linear effect, thereby the material that contains azo-compound is had broad application prospects in the nonlinear optical material field, and it has obtained developing by leaps and bounds in recent years.
[summary of the invention]
The objective of the invention is to by synthetic a kind of new compound that contains the styryl nitrogen benzide of molecular designing, for the application of this compounds in fields such as nonlinear optical material, photoresponse and memory devices provides a kind of new functional compound material; Second purpose of the present invention is, for described new compound provides a kind of preparation method; The 3rd purpose of the present invention is, for described new compound proposes new purposes.
For achieving the above object, the technical scheme taked of the present invention is:
A kind of new styryl azobenzene compound that contains, its basic structure formula is:
Contain azobenzene group and styrene group in the described structural formula.
Described azobenzene group is a photochromic group, has features such as optics, thermal property and photic cis-trans isomerism.
Described styrene group can obtain superpolymer by free crowd.
R in the described chemical structural formula
1And R
2Be alkyl (C
nH
2n+1) or alkoxyl group (OC
nH
2n+1).
R in the described chemical structural formula
1And R
2Number n=1～12 of methylene radical.
For realizing above-mentioned second purpose, the technical scheme that the present invention takes is:
A kind of new preparation method who contains the styryl azobenzene compound synthesizes preparation by the breath reaction of loving and respect one's elder brother diazotization reaction, linked reaction, esterification and Wei, and the chemical structural formula of its reaction process is:
Its concrete reaction process is:
(1) before linked reaction, be R with para-orienting group earlier
1Aniline under acidic conditions, carry out diazotization reaction with Sodium Nitrite, form diazonium salt;
Diazonium salt solution carries out linked reaction with the m-methyl phenol sodium that m-methyl phenol and sodium hydroxide reaction generate again;
The temperature of diazotization reaction and linked reaction is controlled at 0～5 ℃; R
1Substituting group is alkyl (C
nH
2n+1) or alkoxyl group (OC
nH
2n+1), n=1～12 wherein;
(2) adopt N, N-dicyclohexylcarbodiimide (DCC) is a dewatering agent, N, N-Dimethylamino pyridine (DMAP) is a catalyzer, and solvent is an anhydrous solvent, as methylene dichloride, trichloromethane, tetrahydrofuran (THF), N, aprotic solvent such as dinethylformamide or methyl-sulphoxide carries out esterification;
(3) adopt N-bromosuccinimide (NBS) to carry out the bromination substitution reaction, because bromo-succinimide can make the reaction quantification as brominated reagent;
(4) adopt phosphorus ylide, with triphenyl phosphorus (PPh
3) be raw material and tetracol phenixin (CCl
4) to carry out ylide salt synthetic for solvent, this helps the carrying out that react and productive rate height;
(5) with formalin raw material, the breath that under alkaline environment, carries out loving and respect one's elder brother Wei reaction; The regulation and control of alkaline environment can be used KOH, NaOH, KHCO
3Control with solution such as ammoniacal liquor.
In the chemical structural formula of reaction process, R
1Substituting group is alkyl (C
nH
2n+1) or alkoxyl group (OC
nH
2n+1), n=1～12 wherein.
For realizing above-mentioned the 3rd purpose, the technical scheme that the present invention takes is:
A kind of new styryl azobenzene compound that contains is characterized in that the application in nonlinear optical material, photoresponse and memory device field.
Positively effect of the present invention is:
Preparation in accordance with the present invention obtains a kind of new styryl azobenzene compound that contains, its styryl can obtain superpolymer by free crowd; The superpolymer derivative that is obtained, or it is blended into the material that forms in the superpolymer base, can be widely used in fields such as nonlinear optical material, photoresponse and memory device.
[description of drawings]
Accompanying drawing 1 is a kind of new styryl azobenzene compound (R that contains
1=-OCH
3, R
2=-OC
4H
9) infrared spectrogram;
Accompanying drawing 2 is a kind of new styryl azobenzene compound (R that contains
1=-OCH
3, R
2=-OC
4H
9) hydrogen spectrum nucleus magnetic resonance figure.
[embodiment]
By the following examples a kind of new preparation method who contains the styryl azobenzene compound of the present invention is specifically described or is described further; its purpose is to understand technical connotation of the present invention better, but protection scope of the present invention is not limited to following practical range.
With R
1=-OCH
3And R
2=-OC
4H
9For example illustrates a kind of new preparation process that contains the styryl azobenzene compound:
(1) in the 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, adds 20.0g P-nethoxyaniline, 100mL concentrated hydrochloric acid and 150.0mL water, fully stirring and dissolving;
Afterwards, under 0～5 ℃ of temperature, in this solution, drip the solution of forming by 14.0g Sodium Nitrite and 50.0mL water, stirring reaction while dripping;
After waiting to dropwise, in this solution, drip the solution of forming by 18.0g m-cresol, 30.0g sodium hydroxide and 100.0mL water again, the stirring reaction while dripping, temperature of reaction remains on 0～5 ℃;
After reaction finished, suction filtration, water washed 3 times at least, make ethanol and water mixed liquid recrystallization, obtain product (intermediates) behind 50 ℃ of vacuum-drying 24hr, and yield is 90%.
(2) in the 250mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, the product 14.5g, the 10.0g that add step (1) gained at room temperature are stirred to abundant dissolving to butoxy benzoic acid and 100mL exsiccant methylene dichloride;
Afterwards, drip the solution of forming by 27.0gDCC, 2.0gDMAP and 100mL methylene dichloride;
After dropwising, at room temperature continue stirring reaction 24hr, afterwards, filter and remove throw out, be spin-dried for methylene dichloride, separate with silica column, eluent is a methylene dichloride: sherwood oil=4: 1 (volume ratio), and dry 24hr under 50 ℃ of vacuum conditions, product (intermediates) yield is 85%.
(3) in the 250mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (2) products therefrom 15.5g, 10.0gNBS, 0.5g dibenzoyl peroxide and 150mL exsiccant tetrachloromethane, stirring reaction 4hr under 90 ℃ of conditions;
Afterwards, remove by filter throw out, be spin-dried for tetrachloromethane, use toluene: the mixed solution recrystallization of sherwood oil=1: 4 (volume ratio), dry 24hr under 50 ℃ of vacuum conditions, product (intermediates) yield is 90%.
(4) in the 100mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (3) products therefrom 5.0g, 7.0gPPh
3With 40mL formalin, stirring reaction 5hr;
Afterwards, be spin-dried for acetone,, obtain product with the anhydrous diethyl ether precipitation again with exsiccant methylene dichloride dissolved product, dry 24hr under 40 ℃ of vacuum conditions apace, product (intermediates) yield is 95%.
(5) in the 100mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (4) products therefrom 6.5g, 40mL tetrahydrofuran (THF) and 40mL formalin, room temperature condition stirs fully dissolving down;
Afterwards, drip by 5.0gKHCO
3With the solution that 30mL water is formed, after dropwising, room temperature condition continues stirring reaction 24hr down;
Afterwards, be spin-dried for solvent, methylene dichloride dissolving, washing, anhydrous MgSO
4Dry, filter, be spin-dried for methylene dichloride, separate with silica column, eluent is a methylene dichloride, dry 24hr under 50 ℃ of vacuum conditions, product (the finished product) yield is 80%.
Accompanying drawing 1 the new styryl azobenzene compound (R that contains for obtaining in implementing
1=-OCH
3, R
2=-OC
4H
9) infrared spectrogram, its charateristic avsorption band (1734cm
-1, 1602cm
-1And 1505cm
-1) proved and contain ester group and phenyl ring base in the compound.
Accompanying drawing 2 the new styryl azobenzene compound (R that contains for obtaining in implementing
1=-OCH
3, R
2=-OC
4H
9) the hydrogen spectrogram, its success that has proved target compound is synthetic.
Preparation in accordance with the present invention obtains the new styryl azobenzene compound that contains is because its styryl can obtain superpolymer by free crowd; And the superpolymer derivative, or with the derivative blended material that forms in the superpolymer base of superpolymer, contain the nitrogen benzide chromophore of characteristics such as photic isomery and molecule reorientation in such material, can be widely used in fields such as nonlinear optical material, photoresponse and memory device.
Claims (9)
1. new styryl azobenzene compound that contains is characterized in that its basic structure formula is:
2. the new styryl azobenzene compound that contains according to claim 1 is characterized in that, contains azobenzene group and styrene group in the described structural formula.
3. the new styryl azobenzene compound that contains according to claim 2 is characterized in that described azobenzene group is a photochromic group, has optics, thermal property and photic cis-trans isomerism feature.
4. the new styryl azobenzene compound that contains according to claim 2 is characterized in that described styrene group can obtain superpolymer by free crowd.
5. the new styryl azobenzene compound that contains according to claim 1 is characterized in that R in the described chemical structural formula
1And R
2Be alkyl (C
nH
2n+1) or alkoxyl group (OC
nH
2n+1).
6. the new styryl azobenzene compound that contains according to claim 5 is characterized in that R in the described chemical structural formula
1And R
2Number n=1～12 of methylene radical.
7. a new preparation method who contains the styryl azobenzene compound as claimed in claim 1 synthesizes preparation by the breath reaction of loving and respect one's elder brother diazotization reaction, linked reaction, esterification and Wei, and the chemical structural formula of its reaction process is:
Its concrete reaction process is:
(1) before linked reaction, be R with para-orienting group earlier
1Aniline under acidic conditions, carry out diazotization reaction with Sodium Nitrite, form diazonium salt; Diazonium salt solution carries out linked reaction with the m-methyl phenol sodium that m-methyl phenol and sodium hydroxide reaction generate again; The temperature of diazotization reaction and linked reaction is controlled at 0～5 ℃; R
1Substituting group is alkyl (C
nH
2n+1) or alkoxyl group (OC
nH
2n+1), n=1～12 wherein;
(2) adopt N, N-dicyclohexylcarbodiimide (DCC) is a dewatering agent, N, N-Dimethylamino pyridine (DMAP) is a catalyzer, and solvent is an anhydrous solvent, as methylene dichloride, trichloromethane, tetrahydrofuran (THF), N, aprotic solvent such as dinethylformamide or methyl-sulphoxide carries out esterification;
(3) adopt N-bromosuccinimide (NBS) to carry out the bromination substitution reaction, because bromo-succinimide can make the reaction quantification as brominated reagent;
(4) adopt phosphorus ylide, with triphenyl phosphorus (PPh
3) be raw material and tetracol phenixin (CCl
4) synthesize for solvent carries out ylide salt;
(5) with formalin raw material, the breath that under alkaline environment, carries out loving and respect one's elder brother Wei reaction, the regulation and control of alkaline environment can be used KOH, NaOH, KHCO
3Control with ammoniacal liquor.
8. the new preparation method who contains the styryl azobenzene compound according to claim 7 is characterized in that, in the chemical structural formula of reaction process, and R
1Substituting group is alkyl (C
nH2
N+1) or alkoxyl group (OC
nH
2n+1), n=1～12 wherein.
9. the new styryl azobenzene compound that contains as claimed in claim 1 is characterized in that the application in nonlinear optical material, photoresponse and memory device field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102041157A CN101747227B (en) | 2008-12-05 | 2008-12-05 | Novel compound containing styryl and azobenzene and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102041157A CN101747227B (en) | 2008-12-05 | 2008-12-05 | Novel compound containing styryl and azobenzene and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101747227A true CN101747227A (en) | 2010-06-23 |
| CN101747227B CN101747227B (en) | 2012-11-14 |
Family
ID=42474917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102041157A Expired - Fee Related CN101747227B (en) | 2008-12-05 | 2008-12-05 | Novel compound containing styryl and azobenzene and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101747227B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127222A (en) * | 2010-11-18 | 2011-07-20 | 华东师范大学 | Novel azobenzene polypeptide, and preparation method and application thereof |
| CN103086362A (en) * | 2012-12-11 | 2013-05-08 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
| CN104829771A (en) * | 2015-05-14 | 2015-08-12 | 苏州大学 | Polymer containing cyclic azobenzene-dinaphthalene structure on side chain as well as preparation method and application of polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61171463A (en) * | 1985-01-25 | 1986-08-02 | Shin Etsu Chem Co Ltd | Acrylic acid ester compound containing azo bond |
| JPS61212549A (en) * | 1985-03-15 | 1986-09-20 | Shin Etsu Chem Co Ltd | 2-methyl-4'-substituted-4-(4"-methoxycinnamic acid)azobenzene and production thereof |
-
2008
- 2008-12-05 CN CN2008102041157A patent/CN101747227B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61171463A (en) * | 1985-01-25 | 1986-08-02 | Shin Etsu Chem Co Ltd | Acrylic acid ester compound containing azo bond |
| JPS61212549A (en) * | 1985-03-15 | 1986-09-20 | Shin Etsu Chem Co Ltd | 2-methyl-4'-substituted-4-(4"-methoxycinnamic acid)azobenzene and production thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王建营等: "光致变色聚合物研究进展", 《化 学 进 展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127222A (en) * | 2010-11-18 | 2011-07-20 | 华东师范大学 | Novel azobenzene polypeptide, and preparation method and application thereof |
| CN102127222B (en) * | 2010-11-18 | 2013-10-30 | 华东师范大学 | Azobenzene polypeptide, and preparation method and application thereof |
| CN103086362A (en) * | 2012-12-11 | 2013-05-08 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
| CN103086362B (en) * | 2012-12-11 | 2014-10-15 | 武汉工程大学 | Preparation method for electroactive aniline oligomer-modified graphene |
| CN104829771A (en) * | 2015-05-14 | 2015-08-12 | 苏州大学 | Polymer containing cyclic azobenzene-dinaphthalene structure on side chain as well as preparation method and application of polymer |
| CN104829771B (en) * | 2015-05-14 | 2017-08-01 | 苏州大学 | A kind of side chain contains polymer of ring-type azobenzene binaphthyl structure and its production and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101747227B (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101845005B (en) | Side substitution aromatic ester diphenol, preparation method and preparation method of mesomorphic epoxy monomer | |
| CN105925004B (en) | A kind of fluorine boron pyrrolizine fluorescent dye and its synthetic method | |
| CN101943862A (en) | Sulfonium salt photo-acid generator using stilbene as main body and preparation method thereof | |
| CN101747227B (en) | Novel compound containing styryl and azobenzene and preparation method and application thereof | |
| CN102141731A (en) | Toluylene-containing meta-substituted sulfonium salt photoproduction acid agent and preparation method thereof | |
| CN103193967B (en) | A kind of preparation method of hyperbranched azobenzene polymer and application thereof | |
| CN102051184B (en) | Symmetrical discotic liquid crystal molecule taking pyrene as rigid core and preparation method thereof | |
| CN108997391B (en) | Preparation method of trimeric indenyl BODIPY-fullerene star-shaped compound | |
| CN101885687A (en) | Novel styryl-containing azobenzene compound and preparation method thereof | |
| CN113512023B (en) | Crosslinking agent containing double-dynamic imine bond, self-repairing polymer and preparation method of self-repairing polymer | |
| CN102898287B (en) | Novel two fluoro second two ethers liquid crystal and compositions thereof | |
| CN111718724B (en) | Reactive azobenzene main side chain liquid crystal compound and preparation method and application thereof | |
| CN105732417A (en) | Method for preparing initiating agent monomer containing azobenzene structure | |
| CN102746853B (en) | Triazole bending rodlike liquid crystal compound and preparation method thereof | |
| CN102516980B (en) | Salophen type bis-Schiff base photochromic material and its preparation method | |
| CN108503669A (en) | A kind of efficient diarylethene light-operated switch molecule and preparation method thereof | |
| Wang et al. | Synthesis of novel nonlinear optical chromophore containing bis (trifluoromethyl) benzene as an isolated group | |
| CN108892969B (en) | 3, 5-position non-aryl substituted R-azaBODIPY fluorescent dye and preparation method thereof | |
| CN111004146A (en) | Liquid azophenyl molecular solar thermal fuel and synthesis method and application thereof | |
| CN113999218B (en) | Flavonol compound, preparation method and application thereof in detection of biological mercaptan | |
| CN112920160B (en) | Degradable monomer based on cyclic acetal structure, and synthesis method and application thereof | |
| CN109320708A (en) | A kind of chiral liquid crystal polymer and preparation method thereof that shines | |
| CN102660001A (en) | Synthesis method of conjugated polymer gelling agent polyphenylene ethynylene and preparation method of gel of the conjugated polymer gelata polyphenylene ethynylene | |
| CN103193755A (en) | Spirofluorene xanthene phenol compound and preparation method thereof | |
| CN111233698A (en) | Polymerizable asymmetric azobenzene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20100623 Assignee: Shanghai Ruinian Fine Chemical Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2013310000016 Denomination of invention: Novel compound containing styryl and azobenzene and preparation method and application thereof Granted publication date: 20121114 License type: Exclusive License Record date: 20130314 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121114 Termination date: 20131205 |