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
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- 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
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- dicyano
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Abstract
The present invention relates to the preparation and the application of 4, 5, 7-triaryl substituted 2-amino-3, 8-dicyano quinoline derivative materials, which belongs to the technical field of organic functional molecule materials and organic electroluminescent materials. The present invention proposes that the quinoline derivative materials are prepared by the reaction of aromatic aldehyde and different kinds of 1-aryl ethylidene malononitrile. The kind of molecule materials contain a plurality of aromatic substituents, and a unique 'push-suction' electronic structure is formed from an amino group and a cyano group. The melting point of a compound is more than 300 DEG C, and the compound has very good thermostability. An amorphous state can be kept for long by a thin membrane after the membrane is formed in vacuum. The kind of molecule materials can be used as a luminescent layer in an organic electroluminescent device, and can also be used as doping materials of the luminescent layer for regulating luminescent colors. In addition, the kind of organic molecules can also be used as an organic synthetic intermediate compound.
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)
1. a poly-substituted quinoline derivative functional materials is characterized in that molecular material for containing a plurality of substituent quinolines, and substituting group comprises aromatic base, cyano group and amino, and its chemical structural formula is as follows::
Ar wherein
1, Ar
2Be aromatic base.
2. poly-substituted quinoline derivative functional materials according to claim 1 is characterized in that Ar
1, Ar
2Be phenyl, its Chinese name is called: 2-amino-3, and 8-dicyano-4,5,7-triphenyl quinoline, English name is: 2-amino-3,8-dicyano-4,5,7-triphenylquinoline, molecular formula is: C
29H
18N
4, chemical structural formula is shown below:
3. poly-substituted quinoline derivative functional materials according to claim 1 is characterized in that Ar
1Be phenyl, Ar
2Be the 2-naphthyl, its Chinese name is called: 2-amino-3, and 8-dicyano-4,7-two (2-naphthyl)-5-phenylquinoline, English name is: 2-amino-3,8-dicyano-4,7-di (2-Naphthyl)-5-phenylquinoline, molecular formula is: C
37H
22N
4, chemical structural formula is shown below:
4. poly-substituted quinoline derivative functional materials according to claim 1 is characterized in that Ar
1Be phenyl, Ar
2Be the 4-nitrophenyl, its Chinese name is called: 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, molecular formula is: C
29H
16N
6O
4, chemical structural formula is shown below:
5. poly-substituted quinoline derivative functional materials according to claim 1 is characterized in that Ar
1Be phenyl, Ar
2Be the 4-aminomethyl phenyl, its Chinese name is called: 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, molecular formula is: C
31H
22N
4, chemical structural formula is shown below:
6. poly-substituted quinoline derivative functional materials according to claim 1 is characterized in that Ar
1Be 4-nitrophenyl, Ar
2Be the 4-aminomethyl phenyl, its Chinese name is called: 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, molecular formula is: C
31H
21N
5O
2, chemical structural formula is shown below:
7. the preparation method as the described poly-substituted quinoline derivative of claim 1-6 functional materials is characterized in that this material is obtained by aromatic aldehyde and 1-aryl ethylidene propane dinitrile prepared in reaction, and adopts alkali as catalyzer.
8. the preparation method of poly-substituted quinoline derivative functional materials according to claim 7, it is characterized in that reaction solution at room temperature stirred 1～6 hour, react more than 6 hours at 50～80 ℃ 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.
9. the preparation method of poly-substituted quinoline derivative functional materials according to claim 8 is characterized in that: phenyl aldehyde and the reaction of 1-phenyl ethylidene propane dinitrile obtain compound (A); The reaction of phenyl aldehyde and 1-(2-naphthyl) ethylidene propane dinitrile obtains compound (B); The reaction of phenyl aldehyde and 1-(4-nitrophenyl) ethylidene propane dinitrile obtains compound (C); The reaction of phenyl aldehyde and 1-(4-aminomethyl phenyl) ethylidene propane dinitrile obtains compound (D); The reaction of 4-nitrobenzaldehyde and 1-(4-aminomethyl phenyl) ethylidene propane dinitrile obtains compound (E).
10. application as the described poly-substituted quinoline derivative of claim 1～6 functional materials is characterized in that as a kind of electroluminescent material, is used for being manufactured with the luminescent layer of organic electroluminescence devices and is used as color modulation material in the luminescent layer.
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| 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 |
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