CN1291977C - Polysubstituted quinazine derivative funcional material, and preparing method and thereof - Google Patents
Polysubstituted quinazine derivative funcional material, and preparing method and thereof Download PDFInfo
- Publication number
- CN1291977C CN1291977C CN 200310108055 CN200310108055A CN1291977C CN 1291977 C CN1291977 C CN 1291977C CN 200310108055 CN200310108055 CN 200310108055 CN 200310108055 A CN200310108055 A CN 200310108055A CN 1291977 C CN1291977 C CN 1291977C
- Authority
- CN
- China
- Prior art keywords
- amino
- dicyano
- quinoline derivative
- functional material
- methylphenyl
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机功能分子材料和有机电致发光材料技术领域，具体涉及4，5，7-三芳基取代的2-氨基-3，8-二氰基喹啉衍生物材料的制备及应用。本发明提出喹啉衍生物材料用芳香醛和各种1-芳基亚乙基丙二腈反应来制备。该类分子材料含有多个芳香取代基，并且氨基与氰基构成独特的“推-吸”电子结构，化合物的熔点在300℃以上，有很好的热稳定性，真空成膜后，薄膜能长久保持无定形状态。这类分子材料可以用做有机电致发光器件中的发光层，还可以作为发光层的掺杂材料，用于调制发光颜色。此外，这类有机分子还可作为有机合成中间体。The invention belongs to the technical field of organic functional molecular materials and organic electroluminescent materials, and specifically relates to the preparation and application of 4,5,7-triaryl-substituted 2-amino-3,8-dicyanoquinoline derivative materials. The present invention proposes quinoline derivative materials to be prepared by reacting aromatic aldehydes with various 1-arylethylene malononitriles. This type of molecular material contains multiple aromatic substituents, and the amino group and cyano group form a unique "push-suck" electronic structure. The melting point of the compound is above 300°C and has good thermal stability. After vacuum film formation, the film can Maintain an amorphous state for a long time. This type of molecular material can be used as a light-emitting layer in an organic electroluminescent device, and can also be used as a dopant material for the light-emitting layer to modulate the color of light emitted. In addition, such organic molecules can also be used as intermediates in organic synthesis.
Description
Technical field
The invention belongs to organic functional molecular material and electroluminescent organic material technical field, be specifically related to 4,5, the 2-amino-3 that the 7-triaryl replaces, 8-dicyano quinoline functional materials and preparation method thereof, and the application in organic electroluminescence device.
Technical background
Organic electroluminescent is big focus ([1] Tang C.W., Van Slyke S.A.Appl.Phys.Lett., 1987,51,913 in technique of display field, plane; [2] Muller C.D., Falcou A., Reckefuss N.et al..Nature, 2003,421,829.).Though red, green, blue is three kinds of basic colors in the panchromatic demonstration, also need some bright color and lusters (, sky blue etc.) to enrich the kind of color as light yellow.Modal Yellow luminous material is rubrene (Rubrene) ([3] Flora W.H., Hall H.K., Armstrong N.R.J.Phys.Chem.B, 2003,107 (5), 1142.), but costs an arm and a leg, and crystallization easily, therefore is unfavorable for practical application.
The present invention proposes and has prepared the quinoline that the novel polyaryl of a class replaces, and this quasi-molecule material can be used as electroluminescent organic material.The structure of this class organic compound is very unusual, but can be synthetic with very simple method, so easily mass-produced.
Summary of the invention
The objective of the invention is to propose class organic functional molecular material novel, easy practicability.
The organic functional molecular material that the present invention proposes is the quinoline functional materials that a kind of many virtues replace, and wherein contains a plurality of substituent quinolines, and substituting group comprises aromatic base, cyano group, amino etc.Particularly, the quinoline material adopts: 4,5, and the 2-amino-3 that the 7-triaryl replaces, 8-dicyano quinoline.This class organic materials has following chemical structural formula:
Ar wherein
1, Ar
2For aromatic base or itself contain substituent aromatic base.Ar
1And Ar
2Can be the same or different.Ar
1And Ar
2Permutation and combination can make up different compounds, be exemplified below:
(1) Ar
1And Ar
2Be phenyl, get compound (A), chemical structural formula is as follows:
Molecular formula is: C
29H
18N
4
Chinese is: 2-amino-3,8-dicyano-4,5,7-triphenyl quinoline
English name is: 2-amino-3,8-dicyano-4,5,7-triphenylquinoline.
(2) Ar
1Be phenyl, Ar
2Be the 2-naphthyl, get compound (B), chemical structural formula is shown below:
Molecular formula is: C
37H
22N
4
Chinese is: 2-amino-3,8-dicyano-4,7-two (2-naphthyl)-5-phenylquinoline
English name is: 2-amino-3,8-dicyano-4,7-di (2-Naphthyl)-5-phenylquinoline.
(3) Ar
1Be phenyl, Ar
2Be the 4-nitrophenyl, get compound (C), chemical structural formula is shown below:
Molecular formula is: C
29H
16N
6O
4
Chinese is: 2-amino-3,8-dicyano-4,7-two (4-nitrophenyl)-5-phenylquinoline
English name is: 2-amino-3,8-dicyano-4,7-di (4-nitrophenyl)-5-phenylquinoline.
(4) Ar
1Be phenyl, Ar
2Be the 4-aminomethyl phenyl, get compound (D), chemical structural formula is shown below:
Molecular formula is: C
31H
22N
4
Chinese is: 2-amino-3,8-dicyano-4,7-two (4-aminomethyl phenyl)-5-phenylquinoline
English name is: 2-amino-3,8-dicyano-4,7-di (4-methylphenyl)-5-phenylquinoline.
(5) Ar
1Be 4-nitrophenyl, Ar
2Be the 4-aminomethyl phenyl, get compound (E), chemical structural formula is shown below:
Molecular formula is: C
31H
21N
5O
2
Chinese is: 2-amino-3,8-dicyano-4,7-two (4-aminomethyl phenyl)-5-(4-nitro) phenylquinoline
English name is: 2-amino-3,8-dicyano-4,7-di (4-methylphenyl)-5-(4-nitrophenyl)-quinoline.
The invention allows for the preparation method of above-mentioned functions molecular material: react by aromatic aldehyde and 1-aryl ethylidene propane dinitrile and prepare 4,5, the 2-amino-3 that the 7-triaryl replaces, 8-dicyano quinoline.As catalyzer, alkali wherein can be mineral alkali (such as sodium hydroxide, potassium hydroxide etc.), also can adopt organic bases (such as pyridine, organic amine etc.) with alkali in this reaction.Reaction process is as follows:
Concrete steps are as follows: aromatic aldehyde, 1-aryl ethylidene propane dinitrile are dissolved in the ethanol, drip alkaline solution, stir under the room temperature 1～6 hour, (are generally 6-24 hour) more than 6 hours 50～80 ℃ of reactions then.In the above-mentioned steps, the consumption mol ratio of aromatic aldehyde and 1-aryl ethylidene propane dinitrile, alkali is respectively 0.5～1.2,0.9～1.2.With the reaction solution cooling, there is precipitation to separate out, filter, with DMF, ethanol or acetonitrile recrystallization.
In aforesaid method, if aromatic aldehyde is a phenyl aldehyde, 1-aryl ethylidene propane dinitrile is a 1-phenyl ethylidene propane dinitrile, obtains compound (A), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if aromatic aldehyde is a phenyl aldehyde, 1-aryl ethylidene propane dinitrile is 1-(2-naphthyl) ethylidene propane dinitrile, obtains compound (B), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if aromatic aldehyde is a phenyl aldehyde, 1-aryl ethylidene propane dinitrile is 1-(4-nitrophenyl) ethylidene propane dinitrile, obtains compound (C), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if aromatic aldehyde is a phenyl aldehyde, 1-aryl ethylidene propane dinitrile is 1-(4-aminomethyl phenyl) ethylidene propane dinitrile, obtains compound (D), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if aromatic aldehyde is the 4-nitrobenzaldehyde, 1-aryl ethylidene propane dinitrile is 1-(4-aminomethyl phenyl) ethylidene propane dinitrile, obtains compound (E), and its structural formula and molecular formula are equal to aforementioned.
By the resulting organic molecular compound of the present invention with quinoline structure of polyaryl replacement, amino and cyano group also constitutes unique " pushing away-inhale " electronic structure, constitutional features is relatively noveler, and the higher and difficult decomposition of such melting point compound has good thermostability; Behind the vacuum film formation, can keep metamict for a long time, therefore help the stable of device performance.
Synthetic polysubstituted quinoline reaction conditions is relatively harsher usually, generally also must polystep reaction.The organic molecule material structure that the present invention proposes is very special, but can finish with single step reaction, estimates to adopt similar approach can also prepare multiple derivative.The organic molecule material preparation cost that the present invention proposes is very low, and therefore mass production has actual application value easily.
The present invention also proposes the purposes of poly-substituted quinoline derivant material, and it can be used as a kind of electroluminescent material.Such as the luminescent layer and the modulation of the doping in the luminescent layer material that are used for being manufactured with organic electroluminescence devices.Be exemplified below:
In vacuum environment, use the organic electroluminescence device of vacuum evaporation coating membrane method preparation based on material (A):
(1)，ITO/HM(50nm)/(A)(60nm)/Alq
3(60nm)/Mg:Ag(50nm)；
(2)，ITO/HM(50nm)/(A)(5％):Alq
3(60nm)/Mg:Ag(50nm)；
Wherein, HM is a hole transmission layer, Alq
3Be oxine aluminium.In device (1), (A) be luminescent layer, Alq
3Be electron transfer layer, the bright gold-tinted of this device invention; In device (2), contain the Alq of 5% (A)
3As luminescent layer, be equivalent to modulate Alq with (A)
3As glow color, coloured light sent out light yellow by this device.Regulate (A) at Alq
3Content in the luminescent layer, the color of device changes along with the content of (A).In device (2), if do not contain (A), glow color is green.We also replace (A) with Rubrene, and study luminescent properties under the same process condition, find that luminosity is close, but the easier crystallization of Rubrene, and the stability of device is not good.Compound (A) is not easy crystallization because molecule itself lacks symmetry, and the stability of organic membrane is better, and device performance is also more stable.Other several organic molecule materials of the present invention's preparation also can be used as luminescent material and glow color modulation material.
The organic molecule material that the present invention proposes also has other multiple use, further makes up multiple functional molecule material such as can be used as organic synthesis intermediate.In addition, because therefore the amino and the electrophilic cyano group that contain a plurality of aromatic bases and push away electronics in the molecular structure also have other multiple functional property, comprise as molecule electronic material and fluorescent material etc.
Embodiment
The invention is further illustrated by the following examples
Embodiment 1,
1.68g (0.01mol) 1-phenyl ethylidene propane dinitrile, 1.06g (0.01mol) phenyl aldehyde and 20mL alcohol mixed solution stir the NaOH that drips 4mL 2M down again, stirring at room 6h, reflux 6h, cooling is filtered, the crude product ethyl alcohol recrystallization gets yellow solid.Productive rate 70%, m.p.299～300 ℃, UV-vis (solid) λ
Max: 336,408nm; IR (KBr) v:3452,3345,2216,1633,1560,1495,1414,1368cm
-1 1H NMR (DMSO-d
6, 500MHz) δ: 6.94～7.74 (m, 18H, ArH+NH
2);
13C NMR (DMSO-d
6, 500MHz) δ: 98.8,106.5,116.1,117.7,118.3,127.4,127.7,127.9,128.2,128.9,129.2,129.3,129.4,129.8,130.1,136.6,137.8,140.5,146.9,149.4,152.2,157.1,157.6.
Embodiment 2,
2.18g (0.01mol) 1-(2-naphthyl) ethylidene propane dinitrile, 1.06g (0.01mol) phenyl aldehyde and 20mL alcohol mixed solution, stir the NaOH that drips 4mL 2M down again, stirring at room 6h, reflux 6h, the crude product ethyl alcohol recrystallization is filtered in cooling, the yellow-green colour solid, productive rate: 61%; Mp＞300 ℃; UV-vis (solid, absorption) λ
Max346,408nm; IR (KBr) v3405,3333 (NH
2), 2220 (CN) cm
-1 1H NMR (500MHz, DMSO-d
6) δ 6.55-8.34 (22H, m, ArH+NH
2);
13C NMR (500MHz, DMSO-d
6) δ 98.9,106.7,116.1,117.9,118.7,126.6,126.7,126.8,127.0,127.2,127.3,127.5,127.6,127.7,127.8,128.1,128.3,128.4,128.7,128.9,129.1,129.6,130.3,132.2,132.7,133.1,133.4,134.0,135.3,140.5,147.0,149.5,152.4,157.2,157.4.MS (EI) m/z 522 (M, 100).
Embodiment 3,
2.13g (0.01mol) 1-(4-nitrophenyl) ethylidene propane dinitrile, 1.06g (0.01mol) phenyl aldehyde and 20mL alcohol mixed solution, stir the NaOH that drips 4mL 2M down again, stirring at room 6h, reflux 6h, the crude product ethyl alcohol recrystallization is filtered in cooling, yellow solid, productive rate: 60%; Mp＞300 ℃; UV-vis (solid, absorption) λ
Max340,411nm; IR (KBr) v3475,3357 (NH
2), 2219 (CN), 1348 (NO
2) cm
-1 1H NMR (500MHz, DMSO-d
6) δ 6.95-8.40 (16H, m, ArH+NH
2);
13C NMR (500MHz, DMSO-d
6) δ 95.5,99.3,106.9,115.5,117.2,118.7,122.9,124.2,127.7,128.0,130.2,130.7,131.1,131.9,140.0,143.3,144.0,146.7,147.4,148.4,151.9,155.5,157.0.MS (EI) m/z 512 (M, 100).
Embodiment 4,
1.80g (0.01mol) 1-(4-aminomethyl phenyl) ethylidene propane dinitrile, 1.06g (0.01mol) phenyl aldehyde and 20mL alcohol mixed solution, stir the NaOH that drips 4mL 2M down again, stirring at room 6h, reflux 6h, the crude product ethyl alcohol recrystallization is filtered in cooling, the yellow-green colour solid, productive rate: 69%; Mp＞300 ℃; UV-vis (solid, absorption) λ
Max344,404nm; IR (KBr) v3465,3347 (NH
2), 2208 (CN) cm
-1 1H NMR (500MHz, DMSO-d
6) δ 2.14 (3H, s, CH
3), 2.39 (3H, s, CH
3), 6.80-7.62 (16H, m, ArH+NH
2); 13C NMR (500MHz, DMSO-d
6) δ 21.1,21.3,98.5,106.3,116.1,117.8,118.3,126.8,127.6,128.1,128.5,129.3,129.7,130.0,133.6,134.9,138.3,139.6,140.6,146.8,149.3,152.3,157.2,157.6,160.1.MS (EI) m/z 450 (M, 100).
Embodiment 5,
1.80g (0.01mol) 1-(4-aminomethyl phenyl) ethylidene propane dinitrile, 1.51g (0.01mol) 4-nitrobenzaldehyde and 20mL alcohol mixed solution, stir the NaOH that drips 4mL 2M down again, stirring at room 6h, reflux 6h, the crude product ethyl alcohol recrystallization is filtered in cooling, yellow solid, productive rate: 56%; Mp＞300 ℃; UV-vis (solid, absorption) λ
Max340,410nm; IR (KBr) v3490,3317 (NH
2), 2215 (CN), 1343 (NO
2) cm
-1 1H NMR (500MHz, DMSO-d
6) δ 2.10 (3H, s, CH
3), 2.40 (3H, s, CH
3), 6.85-7.78 (15H, m, ArH+NH
2);
13C NMR (500MHz, DMSO-d
6) δ 20.9,21.3,98.6,107.3,115.9,117.6,118.3,122.5,127.8,128.7,129.4,129.8,130.4,131.2,133.5,134.7,139.1,139.8,144.2,146.0,147.4,149.4,152.1,157.1,157.2.MS (EI) m/z 495 (M, 100).
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108055 CN1291977C (en) | 2003-10-20 | 2003-10-20 | Polysubstituted quinazine derivative funcional material, and preparing method and thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108055 CN1291977C (en) | 2003-10-20 | 2003-10-20 | Polysubstituted quinazine derivative funcional material, and preparing method and thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1528748A CN1528748A (en) | 2004-09-15 |
| CN1291977C true CN1291977C (en) | 2006-12-27 |
Family
ID=34304622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310108055 Expired - Fee Related CN1291977C (en) | 2003-10-20 | 2003-10-20 | Polysubstituted quinazine derivative funcional material, and preparing method and thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1291977C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG10202103278TA (en) | 2013-10-14 | 2021-04-29 | Eisai R&D Man Co Ltd | Selectively substituted quinoline compounds |
| CN106892824B (en) * | 2015-12-19 | 2020-07-14 | 西安瑞联新材料股份有限公司 | arylamine-substituted anthracene derivative O L ED material preparation method |
-
2003
- 2003-10-20 CN CN 200310108055 patent/CN1291977C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1528748A (en) | 2004-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101139319B (en) | Substituted quinoline three polyindene derivatives and preparation method thereof | |
| US20070173657A1 (en) | Tetraphenylsilane-carbazole compound, its preparation method and its use as host material for dopants of organic light emitting diode | |
| CN101182412A (en) | Amide-type Ir metal-organic complex electroluminescent materials and their applications | |
| CN1407053A (en) | Blue light emitting compound and electroluminescert device with it as color display substance | |
| CN103805165A (en) | Benzanthracene organic electroluminescent material, and preparation method and application thereof | |
| CN113402561B (en) | High-color-purity platinum (II) complex luminescent material based on spirofluorene structure and application thereof | |
| CN1291977C (en) | Polysubstituted quinazine derivative funcional material, and preparing method and thereof | |
| WO2018014388A1 (en) | Light-emitting material, preparation method therefor, and organic light-emitting diode made of light-emitting material | |
| CN103992335B (en) | Aromatic amine derivative, and preparation method, use and organic electroluminescent device thereof | |
| CN1228414C (en) | Beta-diketone ligand and its europium coordination compound and europium coordinationi compound electroluminescence device | |
| WO2018014407A1 (en) | Light-emitting material, preparation method therefor, and organic light-emitting diode made of light-emitting material | |
| CN101307005B (en) | Ionic cathode buffer layer material and its preparation method and application | |
| CN118878565B (en) | A helical chiral multi-resonance thermally activated delayed luminescence material and its preparation method and application | |
| CN101144012A (en) | Anthracene electroluminescent material containing hole transport group and preparation method thereof | |
| US20050176952A1 (en) | Phenanthrene compounds | |
| CN1785943A (en) | Conjugate derivative material of 9-phenyl-9-pyrenyl fluorene substituted pyrene its preparation method and application | |
| US20220009857A1 (en) | Multi-Arm Monomolecular White Light-Emitting Materials, Preparation Method and Application Thereof | |
| WO2018014389A1 (en) | Light-emitting material, preparation method thereof and organic light-emitting diode using light-emitting material | |
| CN1236010C (en) | Red organic electroluminescent materials and method for preparing same | |
| CN103102299A (en) | Benzanthracene derivative and preparation method thereof and organic electroluminescence material prepared by same | |
| CN103159584B (en) | Bi-fluoranthene-containing organic semiconductor material, its preparation method and application | |
| CN107954985B (en) | Organic blue luminescent material and preparation method thereof | |
| CN107698584B (en) | Blue light material for organic light-emitting diode and synthetic method thereof | |
| CN116375762B (en) | A lanthanum-tin heterometallic oxygen-sulfur cluster compound and its preparation method and application | |
| CN103911145A (en) | Novel OLED electron transport material and application 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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061227 Termination date: 20091120 |