CN101125829B

CN101125829B - Vinylbiphenyl compounds

Info

Publication number: CN101125829B
Application number: CN2007101641525A
Authority: CN
Inventors: 别国军; 薛云娜; 刘波; 柴生勇
Original assignee: Xian Modern Chemistry Research Institute
Current assignee: Xian Modern Chemistry Research Institute
Priority date: 2007-10-08
Filing date: 2007-10-08
Publication date: 2010-08-04
Anticipated expiration: 2027-10-08
Also published as: CN101125829A

Abstract

The invention discloses a vinyl -biphenyl luminescent compound, a structural formula of which is that: wherein, R1 in the formula is hydrogen atom or phenyl. The compound of the invention is fundamentally applicable to an organic electroluminescent display, and the compound can be used alone as a luminescent layer or used as adopant for producing the luminescent layer.

Description

Vinylbiphenyl compounds

Technical field

The present invention is a kind of Vinylbiphenyl compounds, belongs to the organic electroluminescent field, is mainly used in ORGANIC ELECTROLUMINESCENCE DISPLAYS.

Background technology

To organism apply that voltage imports electric current and luminous phenomenon organic electroluminescent (OEL), this organism is called electroluminescent organic material, adopts the display device of this material making to claim display of organic electroluminescence (OLED).Luminescent material thin-film is added in the plate electrode intermediate fabrication and becomes panel display screen.

Luminescent material used in the display of organic electroluminescence is divided into polymer and small molecule material by type; Divide multiple materials such as blue light, green glow, ruddiness, gold-tinted, orange light by glow color, but based on three kinds of blue lights, green glow, ruddiness.The distyryl compounds has luminescent properties preferably, as two (diphenylethyllene) biphenyl (being called for short DPVBi) of reporting among the US5516577, and structure such as figure below:

Its blue light excellent performance, but its fusing point is lower, and fusing point is about 204 ℃, has limited its use.The biphenyl analog derivative that proposes in the above-mentioned patent has good luminous property, but because its structure stacked form is restricted, makes that its fusing point is lower, has limited its application in organic electroluminescent.

Summary of the invention

Technical problem to be solved by this invention provides the higher Vinylbiphenyl luminophor of a kind of fusing point, it can be used alone as luminescent layer, it is luminous also to can be used as adulterate body making luminescent layer, has expanded the kind that can prepare the organic compound of organic electroluminescence device.

Design of the present invention: to achieve these goals, select for use N-methylpyrrole vinyl biphenyl as backbone structure.Itself has aromaticity pyrrole ring, can form big π key and be easy to emitting fluorescence with the Vinylbiphenyl structure; On the other hand, utilize the polarization of hydrogen on the five-membered ring α position and form hydrogen bond, the association between the compound molecule is strengthened, improved the fusing point and the thermostability of compound greatly.

Vinylbiphenyl luminophor structural formula general formula of the present invention is as follows:

R wherein ₁Be hydrogen atom or phenyl.

The preferred compound of the present invention, its structural formula is as follows:

Another preferred Vinylbiphenyl luminophor of the present invention, its structural formula is as follows:

The present invention can also synthesize a series of derivative, and its structural formula is as follows:

R ₁, R ₂Can be identical or different, can be hydrogen atom, can be the alkyl that contains 1-6 carbon atom, can be contain alkyl that the aryl of 7-20 carbon atom replaces, can be the aryl, the cyclohexyl that contain 4-18 carbon atom, can be the alkoxyl group that contains the aryloxy of 6-18 carbon atom and contain 1-6 carbon atom.

R ₃Can be one or more substituting groups, comprise the alkyl of hydrogen, cyano group, halogenic substituent, nitro, amido, a 1-6 C, the aroyl of the aralkyl of the alkoxyl group of 1-6 carbon, a 7-8 carbon, the ester acyl group of a 1-3 carbon, a 7-10 carbon etc.

And, R ₁, R ₂In said aryl, cyclohexyl, aryloxy can have various R ₃Substituting group.

Advantage of the present invention is as follows:

The compound of the present invention's design has big π bond structure, and its conjugated degree is strengthened, and has improved the fusing point of this compound, and its thermostability is improved.

Embodiment

Embodiment 1:9, two [2-(2-(N-methylpyrrole base)-the vinyl)] biphenyl (NMPVBi) of 10-synthetic

1.1 the present invention implements with reference to following synthetic route

1.2 9, two [2-(2-(N-methylpyrrole base)-the vinyl)] biphenyl (NMPVBi) of 10-synthetic

1.2.1 it is raw-material synthetic

4,4 '-two (diethoxy phosphonium mesitoyl methyl) used biphenyl reference literature [functional materials, 2004,5 (35): 595-597] disclosed method of this invention is synthesized.N-methylpyrrole aldehyde reference literature [J Am Chem Soc, 1953,75 (1): 989] disclosed method is synthetic.

1.2.2 product is synthetic

In the 250ml four-hole bottle, add 4,4 '-two (diethoxy phosphonium mesitoyl methyl) biphenyl 9g (0.02mol), KOH 4g (0.071mol), THF60ml refluxes and stirs 30min.5ml (0.044mol) N-methylpyrrole aldehyde with 20ml THF dilution, is slowly splashed in the system.Drip about 30min.Behind the backflow 2h, stopped reaction, cooling is poured in the frozen water, stirs, and separates out solid.Filter, get solid, use methanol wash 3 times, obtain yellow solid 5.8g, i.e. product NMPVBi.Productive rate: 80%.At 210 ℃, 1 * 10 ^-3The Pa distillation is elevated product 3.0g.Fusing point: 260.86 ℃ (DSC method); It is 314 ℃ that TGA analyzes weightless 5% o'clock temperature.

Structure is identified:

Ultimate analysis: C ₂₆H ₂₄N ₂

Theoretical value: C 85.68%, H 6.64%, and N 7.69%;

Measured value: C 85.48%, H 6.70%, and N 7.72%.

Infrared spectra (KBr, cm ^-1): 3092,3023 (=CH), 2924 (CH ₃), 1623 (C=C), 1492,1481,1473 (Ar), 1423 (C-H), 1317,1308,1283,1241 (pyrroles), 1007,1000 (=C-H), 965,950,854,808,778 (C-H).

Magnetic resonance spectroscopy ( ¹H-NMR, CDCl ₃, 500MHz): δ 7.539 (d, 4H, J=13); δ 7.501 (d, 4H, J=9); δ 7.011 (d, 2H, J=16); δ 6.652 (s, 2H); δ 6.513 (s, 2H); δ 6.166 (s, 2H); δ 3.719 (s, 6H ,-CH ₃).

Confirm that the resulting material of above-mentioned reaction is 9, two [2-(2-(N-methylpyrrole base)-the vinyl)] biphenyl (NMPVBi) of 10-.

1.3 optical performance test

NMPVBi is dissolved in methylene dichloride, is mixed with dilute solution and measures its uv-visible absorption spectra and fluorescence spectrum.Uv-visible absorption spectra uses UNICO UV-2102PCS type ultraviolet-visible pectrophotometer to measure; Fluorescence spectrum 970CRT type fluorescent spectrophotometer assay.

The absorption spectrum peak wavelength is 386nm; Fluorescence spectrum emission peak peak wavelength is 470nm.

Embodiment 2:9, two [2-(2,2-(N-methylpyrrole base)-the phenyl vinyl)] biphenyl (NMPPVBi) of 10-synthetic

2.1 the present invention implements with reference to following synthetic route

2.2 9, two [2-(2,2-(N-methylpyrrole base)-the phenyl vinyl)] biphenyl (NMPPVBi) of 10-synthetic

2.2.1 it is raw-material synthetic

4,4 '-two (diethoxy phosphonium mesitoyl methyl) used biphenyl reference literature [functional materials, 2004,5 (35): 595-597] disclosed method of this invention is synthesized.N-methylpyrrole benzophenone reference literature [Organic syntheses Col] .Vol.2,520; Vol.12,62] disclosed method is synthetic.

2.2.2 product is synthetic

In the 250ml four-hole bottle, add 4,4 '-two (diethoxy phosphonium mesitoyl methyl) biphenyl 11.3g (0.025mol), 10.2g (0.55mol) N-methylpyrrole benzophenone, NaH 3.6g (0.15mol), THF 100ml stirs temperature rising reflux.Behind the backflow 3h, stopped reaction, cooling is poured in the frozen water, stirs, and separates out solid.Filter, solid, with methanol wash 3 times, obtain yellow solid 12g, i.e. product NMPPVBi, productive rate: 93%.Separate refined product at silica gel chromatographic column.Fusing point: 210 ℃ (DSC method); It is 308 ℃ that TGA analyzes weightless 5% o'clock temperature.

Structure is identified:

Ultimate analysis: C ₃₈H ₃₂N ₂

Theoretical value: C 88.34%, H 6.24%, and N 5.42%;

Measured value: C 88.25%, H 6.32%, and N 5.49%.

Infrared spectra (KBr, cm ^-1): 3052,3021 (=C-H); 2942 (CH ₃); 1632,1597 (C=C); 1575,1546; 1494,1444,1430 (Ar); 1244,1203,1176 (pyrroles); 1072,1029,1003 (=C-H); 880,815,765 (=C-H).

Magnetic resonance spectroscopy ( ¹H-NMR, CDCl ₃, 500MHz): δ 7.46 (d, 4H, biphenyl); δ 7.422 (d, 4H, biphenyl); δ 7.349 (m, 4H, benzene); δ 7.291 (m, 4H, benzene); δ 7.098 (t, 2H, benzene); δ 7.027 (m, 2H, pyrroles); δ 6.847 (s, 2H, alkene); δ 6.766 (m, 2H, pyrroles); δ 6.361 (t, 2H, pyrroles); δ 3.197 (s, 6H, CH ₃).

Confirm that the resulting material of above-mentioned reaction is 9, two [2-(2,2-(N-methylpyrrole base)-the phenyl vinyl)] biphenyl (NMPPVBi) of 10-.

2.3 optical performance test

NMPPVBi is dissolved in methylene dichloride, is mixed with dilute solution and measures its uv-visible absorption spectra and fluorescence spectrum.Uv-visible absorption spectra uses UNICO UV-2102PCS type ultraviolet-visible pectrophotometer to measure; Fluorescence spectrum 970CRT type fluorescent spectrophotometer assay.

The absorption spectrum peak wavelength is 366nm; The fluorescence spectrum peak wavelength is 488nm.

Claims

1. Vinylbiphenyl compounds, the structural formula general formula is as follows:

R wherein ₁Be to be all hydrogen atom or phenyl.

2. Vinylbiphenyl compounds according to claim 1 is characterized in that structural formula is as follows:

3. Vinylbiphenyl compounds according to claim 1 is characterized in that structural formula is as follows: