CN102863391B - Compound containing 4-N-substituted phenyl-benzimidazole and preparation method thereof - Google Patents
Compound containing 4-N-substituted phenyl-benzimidazole and preparation method thereof Download PDFInfo
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- CN102863391B CN102863391B CN201210355100.7A CN201210355100A CN102863391B CN 102863391 B CN102863391 B CN 102863391B CN 201210355100 A CN201210355100 A CN 201210355100A CN 102863391 B CN102863391 B CN 102863391B
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Abstract
The invention discloses a compound containing 4-N-substituted phenyl-benzimidazole. The compound containing 4-N-substituted phenyl-benzimidazole is an SPF 4-N--substituted phenyl-benzimidazole compound and a 4-N-substituted phenyl-benzimidazole pyrene compound. The compound containing 4-N-substituted phenyl-benzimidazole synthesizes N-substituted phenyl-benzimidazole boronic acid pinacol ester with a pair of bromine phenyl-benzimidazole and bis-diboron as raw materials; and the compound is subjected to suzuki reaction with 2, 2', 7, 7'-tetrabromo-9, 9'-SPF or tetrabromo pyrene. The two-step reaction is simple, targeted product is easy to obtain, and the material has advantages in terms of synthesis and purification and has application prospect in the field of electroluminescence.
Description
Technical field
The present invention relates to Based on Organic Electrophosphorescence (PhOLED) field of material preparation, be specifically related to the compound of a kind of spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound and N-substituted-phenyl benzoglyoxaline pyrene, and preparation method thereof.
Background technology
Electroluminescent organic material and device are current international research hot fields.At present, the commercialization of many electroluminescent organic materials, part organic display device is also used widely in mobile phone, indicating meter etc.But realize big area full-color EL display and white-light illuminating, stable red, green and blue three primary colours must be had.But only have at present ruddiness and filter reasonablely can reach luminous efficiency required for commercial applications and life-span, the stability and the luminous efficiency that improve blue light material remain challenging problem instantly.
With regard to blue emitting material, what generally use at present has TBADN, DPVBi and some derivatives etc. containing fluorenyl.These materials can be used for doping, also can directly use as main body luminescent layer.But these materials also exist that efficiency is not high, stability is bad at present, life-span long etc. problem.Therefore study novel blue light material to be significant for realizing white-light illuminating.
Benzoglyoxaline is a kind of heterogeneous ring compound containing two nitrogen-atoms, and benzimidizole derivatives and metal complexes always are study hotspot.Benzimidazoles compound has good fluorescence radiation character, and high thermostability simultaneously also can transmission electronic effectively.As a kind of blue light material of classics, spiral shell two fluorenes (SPF) is because having large conjugated system and distinctive spiral shell conjugative effect, mutual bridging on the 9-position of fluorenes unit, solves the shortcoming of the poor stability that compound of fluorene class not exclusively causes because of replacement on 9-position; Its good vertical geometry skeleton, more effectively can suppress the nonradiative transition process in strong intermolecular interaction and luminescence process, and be subject to the special concern of people simultaneously.Be introduced into and have in the molecule of electroluminescence characters, have very large using value to the aspect such as thermostability and spectrum stability improving compound.At first, Krewuder etc. once reported the polymeric system containing spiral shell two fluorenes, but poorly soluble due to it, did not carry out further research.Spiral shell two fluorenes to be incorporated in polymkeric substance and to do electroluminescent material research by yellow dimension afterwards, causes the extensive concern of colleague.Pyrene is a kind of large-area condensed-nuclei aromatics, has very strong π-electron delocalized energy and higher fluorescence quantum efficiency, sends out light dark blue.
Summary of the invention
Technical problem to be solved by this invention: a kind of the spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound and the N-substituted-phenyl benzoglyoxaline pyrene compound that have using value in organic electroluminescence device are provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: containing four-N-substituted-phenyl benzimidazoles compounds be: the compound of spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound, N-substituted-phenyl benzoglyoxaline pyrene;
Described spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound (I), its structural formula is:
The compound (II) of described N-substituted-phenyl benzoglyoxaline pyrene, its structural formula is:
Second technical problem to be solved by this invention is: provide a kind of has the spiral shell two fluorenes N-substituted-phenyl benzimidazole compound of using value and the preparation method of N-substituted-phenyl benzoglyoxaline pyrene compound in organic electroluminescence device.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: the preparation method of a kind of spiral shell two fluorenes-N-substituted-phenyl benzoglyoxaline organic compound and N-substituted-phenyl benzoglyoxaline pyrene organic compound, the steps include:
1), under nitrogen protection, two glutaryl two boron, [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl is added successively
2), dimethyl sulfoxide (DMSO) (DMSO), ultrasonic degas process, under nitrogen protection, stirring at normal temperature 30 ± 5min, then add bromophenyl benzoglyoxaline, be heated to 80 ± 5 DEG C, reaction 24 ± 2h, TLC detect and react completely to bromophenyl benzoglyoxaline, and reaction terminates, remove solvent, column chromatography, purify and obtain N-substituted-phenyl benzoglyoxaline boric acid that ester (a) frequently;
Described couple of glutaryl two boron, [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl
2) and be 11 ± 0.01:0.1 ± 0.01:10 ± 0.01 to the mass ratio of bromophenyl benzoglyoxaline; Described dimethyl sulfoxide (DMSO) consumption adds 300 ± 10mL metering with 10g to bromophenyl benzoglyoxaline;
Reaction equation is:
2) under nitrogen protection; step 1) gained N-substituted-phenyl benzoglyoxaline boric acid that ester (a), 2,2' is frequently added successively, 7 in reactor; bromo-9,9'-spiral shell two fluorenes (b) of 7'-tetra-or tetrabromo pyrene (c), tetrakis triphenylphosphine palladium (Pd (PPh
3)
4), the wet chemical of 2 ± 0.01mol/L, toluene, be heated to 105 ± 5 DEG C, reaction 96 ± 2h, TLC detect, bromo-9,9'-spiral shell two fluorenes (b) of 2,2', 7,7'-tetra-or tetrabromo pyrene (c) react completely, reaction terminate; Remove solvent, column chromatography, purification obtain spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound (I) or N-substituted-phenyl benzoglyoxaline pyrene compound (II);
N-substituted-phenyl benzoglyoxaline boric acid is that ester (a) frequently, and bromo-9,9'-spiral shell two fluorenes (b) or tetrabromos pyrene (c) of 2,2', 7,7'-tetra-, with tetrakis triphenylphosphine palladium (Pd (PPh
3)
4) mass ratio be 8 ± 0.01:1:0.04 ± 0.0001; With 2,2' of 1g, 7,7'-tetra-bromo-9,9'-spiral shell two fluorenes (b) or tetrabromo pyrene (c) meter, need wet chemical 3 ± 0.1ml, the toluene 50 ± 1ml of 2 ± 0.01mol/L.
Described spiral shell two fluorenes-N-substituted-phenyl benzoglyoxaline organic compound synthetic route:
The synthetic route of described N-substituted-phenyl benzoglyoxaline pyrene compound is:
The present invention by with to bromophenyl benzoglyoxaline and two glutaryl two boron for Material synthesis N-substituted-phenyl benzoglyoxaline boric acid that ester frequently; And then carrying out SUZUKI reaction with bromo-9,9'-spiral shell two fluorenes of 2,2', 7,7'-tetra-or tetrabromo pyrene, two-step reaction is simple, and be easy to get target product; This material has advantage in synthesis and purifying, has important application prospect in electroluminescent field.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Embodiment 1:
The preparation of spiral shell two fluorenes-N-substituted-phenyl benzoglyoxaline organic compounds (I):
Step 1: synthetic intermediate a:N-substituted-phenyl benzoglyoxaline boric acid is that ester frequently
In the 500mL there-necked flask that stirring, gas access equipment are housed, and pass into nitrogen protection, add two glutaryl two boron of 2.79g successively, [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl
2) 0.073g, 105ml dimethyl sulfoxide (DMSO) (DMSO), degassed process, nitrogen protection stirring at normal temperature 30min, then add 3.49g to bromophenyl benzoglyoxaline, be heated to 80 DEG C, reaction 24h.Remove solvent, the ethyl acetate/petroleum ether with 1/10 is as eluent, and post separation crossed by 100-200 object silica gel, purifying obtains corresponding intermediate (a).
1H NMR(CDCl
3,400MHz,ppm)δ:7.90(d,1H,J=8.4Hz),7.73(d,1H,J=8.0Hz),7.56(d,1H,J=8.0Hz),7.51–7.44(m,3H),7.36–7.24(m,5H),1.33(s,12H)。EI-MS(m/z):396(M
+)。
Step 2: in the 500mL there-necked flask that stirring, gas access equipment are housed, and pass into nitrogen protection, adds the compound a 3.17g of synthesis in step 1,2,2', 7,7'-tetra-bromo-9,9'-spiral shell two fluorenes 0.55g, Pd (PPh successively
3)
4the solution of potassium carbonate 3ml of 0.047g, 2M, 50ml toluene, is heated to 105 DEG C, reaction 96h.Remove solvent, the dichloromethane/ethyl acetate with 1/1 is as eluent, and post separation crossed by 200-300 object silica gel, purifying obtains corresponding product (I).
1H NMR(CDCl
3,400MHz,ppm)δ:8.83(d,4H,J=8.4Hz),8.76(d,4H,J=8.4Hz),8.71(d,4H,J=8.4Hz),8.47(s,2H),7.99(d,8H,J=8.2Hz)7.81(d,4H,J=8.0Hz),7.61-7.58(m,15H),7.51–7.44(m,4H),7.36–7.24(m,13H)。MALDI-TOF MS(m/z):1275.3(M
+)。
Embodiment 2:
The preparation of N-substituted-phenyl benzoglyoxaline pyrene organic compounds (II):
Step 1: synthetic intermediate a:N-substituted-phenyl benzoglyoxaline boric acid is that ester frequently
In the 500mL there-necked flask that stirring, gas access equipment are housed, and pass into nitrogen protection, add two glutaryl two boron of 2.79g successively, [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride (Pd (dppf) Cl
2) 0.073g, 105ml dimethyl sulfoxide (DMSO) (DMSO), degassed process, nitrogen protection stirring at normal temperature 30min, then add 3.49g to bromophenyl benzoglyoxaline, be heated to 80 DEG C, reaction 24h.Remove solvent, the ethyl acetate/petroleum ether with 1/10 is as eluent, and post separation crossed by 100-200 object silica gel, purifying obtains corresponding intermediate (a).
1H NMR(CDCl
3,400MHz,ppm)δ:7.90(d,1H,J=8.4Hz),7.73(d,1H,J=8.0Hz),7.56(d,1H,J=8.0Hz),7.51–7.44(m,3H),7.36-7.24(m,5H),1.33(s,12H)。EI-MS(m/z):396(M
+)。
Step 2: in the 500mL there-necked flask that stirring, gas access equipment are housed, and pass into nitrogen protection, adds the compound a 3.17g of synthesis in step 1, tetrabromo pyrene 0.52g, Pd (PPh successively
3)
4the solution of potassium carbonate 3ml of 0.047g, 2M, 50ml toluene, is heated to 105 DEG C, reaction 96h.Remove solvent, the dichloromethane/ethyl acetate with 1/1 is as eluent, and post separation crossed by 200-300 object silica gel, purifying obtains corresponding product (II).
1H NMR(CDCl
3,400MHz,ppm)δ:8.88(d,4H,J=8.4Hz),8.14-8.09(m,12H),7.61-7.54(m,32H),7.42–7.30(m,16H)。MALDI-TOF MS(m/z):1389.6(M
+)。
Claims (1)
1. the preparation method of the compound of spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound and N-substituted-phenyl benzoglyoxaline pyrene, the steps include:
1) under nitrogen protection, add two glutaryl two boron, [1 successively, two (diphenylphosphine) ferrocene of 1'-] palladium chloride, dimethyl sulfoxide (DMSO), ultrasonic degas process, under nitrogen protection, stirring at normal temperature 30 ± 5min, add 2-(4-bromophenyl)-1-phenyl-1H-benzoglyoxaline again, be heated to 80 ± 5 DEG C, reaction 24 ± 2h, TLC detect 2-(4-bromophenyl)-1-phenyl-1H-benzoglyoxaline and react completely, and reaction terminates, remove solvent, column chromatography, purify and obtain N-substituted-phenyl benzoglyoxaline boric acid that ester (a) frequently;
The mass ratio of described pair of glutaryl two boron, [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride and 2-(4-bromophenyl)-1-phenyl-1H-benzoglyoxaline is 11 ± 0.01:0.1 ± 0.01:10 ± 0.01; Described dimethyl sulfoxide (DMSO) consumption adds 300 ± 10mL metering with 10g2-(4-bromophenyl)-1-phenyl-1H-benzoglyoxaline;
Reaction equation is:
2) under nitrogen protection, step 1 is added successively in reactor) gained N-substituted-phenyl benzoglyoxaline boric acid that ester (a), 2 frequently, 2', 7,7'-tetra-bromo-9,9'-spiral shell two fluorenes (b) or tetrabromo pyrene (c), tetrakis triphenylphosphine palladium, the wet chemical of 2 ± 0.01mol/L, toluene, be heated to 105 ± 5 DEG C, reaction 96 ± 2h, TLC detect, 2,2', 7,7'-tetra-bromo-9,9'-spiral shell two fluorenes (b) or tetrabromo pyrene (c) react completely, and reaction terminates; Remove solvent, column chromatography, purification obtain spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound (I) or N-substituted-phenyl benzoglyoxaline pyrene compound (II);
N-substituted-phenyl benzoglyoxaline boric acid is that ester (a) frequently, 2,2', 7, bromo-9,9'-spiral shell two fluorenes (b) or tetrabromos pyrene (c) of 7'-tetra-are 8 ± 0.01:1:0.04 ± 0.0001 with the mass ratio of tetrakis triphenylphosphine palladium; With 2,2' of 1g, 7,7'-tetra-bromo-9,9'-spiral shell two fluorenes (b) or tetrabromo pyrene (c) meter, need wet chemical 3 ± 0.1ml, the toluene 50 ± 1ml of 2 ± 0.01mol/L;
Spiral shell two fluorenes-N-substituted-phenyl benzimidazole compound, its structural formula is for shown in (I):
The compound of N-substituted-phenyl benzoglyoxaline pyrene, its structural formula is for shown in (II):
Reaction equation is:
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| CN103289675B (en) * | 2013-01-24 | 2017-06-06 | 西安交通大学 | Fluorine substitution fluorenes Blue-light emitting host material of 9,9 ' spiral shell two and its preparation method and application |
| CN104370823A (en) * | 2014-10-22 | 2015-02-25 | 上海大学 | Fluorenbenzimidazole derivatives and preparation method thereof |
| CN107011268B (en) * | 2017-05-27 | 2019-07-23 | 中国矿业大学 | The 1,3,6,8- tetra- of bipolarity D- π-A configuration replaces pyrenyl material and preparation method and application |
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| CN101989647A (en) * | 2009-08-05 | 2011-03-23 | 财团法人山形县产业技术振兴机构 | Organic electroluminescence element |
| CN102276514A (en) * | 2011-01-20 | 2011-12-14 | 华中科技大学 | Fluorene-bridged blue phosphorescent main body material and preparation method and application thereof |
| CN102576814A (en) * | 2010-08-05 | 2012-07-11 | 出光兴产株式会社 | Organic electroluminescent element |
| CN102659846A (en) * | 2012-03-30 | 2012-09-12 | 中国科学院宁波材料技术与工程研究所 | N-substituted phenylbenzimidazole trivalent-iridium organometallic complex and its preparation method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101989647A (en) * | 2009-08-05 | 2011-03-23 | 财团法人山形县产业技术振兴机构 | Organic electroluminescence element |
| CN102576814A (en) * | 2010-08-05 | 2012-07-11 | 出光兴产株式会社 | Organic electroluminescent element |
| CN102276514A (en) * | 2011-01-20 | 2011-12-14 | 华中科技大学 | Fluorene-bridged blue phosphorescent main body material and preparation method and application thereof |
| CN102659846A (en) * | 2012-03-30 | 2012-09-12 | 中国科学院宁波材料技术与工程研究所 | N-substituted phenylbenzimidazole trivalent-iridium organometallic complex and its preparation method and use |
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