CN103819415A - Large-conjugation fluoreno pyrazine derivative and preparation method thereof - Google Patents

Large-conjugation fluoreno pyrazine derivative and preparation method thereof Download PDF

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CN103819415A
CN103819415A CN201310682018.XA CN201310682018A CN103819415A CN 103819415 A CN103819415 A CN 103819415A CN 201310682018 A CN201310682018 A CN 201310682018A CN 103819415 A CN103819415 A CN 103819415A
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fluorenes
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pyrazines derivatives
toluene
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林海霞
郝增帅
崔永梅
顾泽彬
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a large-conjugation fluoreno pyrazine derivative and a preparation method of the large-conjugation fluoreno pyrazine derivative. For the fluoreno pyrazine derivative of large conjugated molecules, a condensation reaction is carried out directly on raw material 2, 3-diamino-9, 9'-dialkyl fluorene and the Suzuki reaction or the Sonagashira reaction is carried out on halogenated 2, 3-diamino-9, 9'-dialkyl fluorene to obtain a series of the large conjugated molecules containing fluoreno pyrazine structures. Alkyls at the molecule periphery help to overcome solubility reduction due to high plane rigid structures of the molecules and improve dissolution processing properties of material molecules. Meanwhile, conjugation of Pi electrons on skeletons of the molecules is further strengthened, so that an energy gap of the molecules is reduced, and certain effect on overcoming defects such as poor chemical stabilities of traditional organic molecule materials is realized, as a result, the large-conjugation fluoreno pyrazine derivative can be widely applied to fields of organic semiconductor materials, nonlinear optical materials, biological and chemical sensors, and solar cells and the like.

Description

The fluorenes of large conjugation pyrazines derivatives and preparation method thereof
Technical field
The present invention relates to the fluorenes of the large conjugation of a class pyrazines derivatives and preparation method thereof, belong to organic photoelectrical material field, can be used as the directions such as organic semiconductor material, nonlinear optical material, biochemical sensor and solar cell.
Background technology
Since 21st century, along with the high speed development of information industry, the mankind have marched toward the era of knowledge-driven economy.Transmission, processing, storage and the demonstration of information become developing direction and the target of information science and technology.In 2000, the polyacetylene of organic conductive material obtained after Nobel chemistry Prize, and electroluminescent organic material obtains develop rapidly, and performance is more superior, and the novel material that the life-span is longer, be easy to make device continues to bring out.
Organic electroluminescence device have low dc voltage driving, active illuminating, the color full volumetric that can match with unicircuit little, without angle limitations, flexible folding, the advantage such as operating temperature range is large, manufacture craft is simple, material range of choice is wide, be expected to become in the near future full color flat-panel display device of new generation.
In various electroluminescent organic materials, compound of fluorene class or polymkeric substance have higher light and thermally stable ' property, when solid-state, its fluorescence quantum efficiency is up to 60-80%, band-gap energy is greater than 2.90 eV, be the blue light material of excellent property, be acknowledged as a kind of electroluminescent organic material of tool some commercial potential.Now relevant research utilizes 2 of fluorenes, 7 and 9 s' modifiability mostly, introduces different groups and obtains a series of derivatives, to improve photoelectric property and to improve application performance.
At present fluorenes class luminescent material 2,3 optionally and a heterocycle, by increasing conjugation to improve its luminous efficiency, improve the luminescent chromaticity of material and also well do not realize.Thisly first optionally introduce functional group at 2,3 and 7, be incorporated to six-ring by condensation, metal linked reaction then occurs will exert an influence to its photoelectric property and solubility property.Therefore design has very important value with synthetic new fluorenes heterocyclic compound.
Summary of the invention
The object of the invention is a synthetic class using the fluorene structured novel organic photoelectrical material of gripping greatly altogether as parent.Not only 2,3 at intermediate fluorenes are incorporated to new pyrazine ring, have improved the conjugated degree of molecule, and by the aromatic ring of metal pair the United Nations General Assembly, have improved molecule photoelectric properties, will apply to some extent in organic photoelectrical material field.
The present invention addresses the above problem adopted technical scheme:
The fluorenes of large conjugation a pyrazines derivatives, is characterized in that this derivative is one of following general structure:
a.
Figure DEST_PATH_RE-59187DEST_PATH_IMAGE001
b.
Figure DEST_PATH_RE-471713DEST_PATH_IMAGE002
c.
Figure DEST_PATH_RE-234133DEST_PATH_IMAGE003
Wherein: R 1=hydrogen or C 6~ C 12straight chained alkyl, R 2=hydrogen, chlorine, bromine, iodine.
A kind of method of fluorenes the pyrazines derivatives of preparing above-mentioned large conjugation, the concrete steps that it is characterized in that the method are: by 2, 3-diamino-9, 9 '-dialkyl group fluorene derivatives and dibenzoyl or luxuriant and rich with fragrance a kind of jade or 4, 5-dicarbapentaborane pyrene and highly basic, 1:1 ~ 1.1:0.5 ~ 1 joins in organic solvent in molar ratio, the consumption of solvent and the ratio of raw material are 15 ~ 25 mL:1g, under the protection of nitrogen, be heated to back flow reaction 2 ~ 24 hours, after cooling, add ethyl acetate and water extraction, get after organic phase is dried and be spin-dried for, obtain fluorenes the pyrazines derivatives of large conjugation through column chromatography for separation, described 2,3-diamino-9, the structural formula of 9 '-dialkyl group fluorene derivatives is:
Figure DEST_PATH_DEST_PATH_IMAGE002AA
.
Above-mentioned highly basic can be: salt of wormwood, potassium hydroxide, hydrolith, sodium carbonate, sodium hydroxide, sodium methylate, sodium ethylate or sodium hydride.
Above-mentioned organic solvent can be: 1,4-dioxane, acetonitrile, DMF, methyl-sulphoxide, N-Methyl pyrrolidone, quinoline, imidazoles, acetic acid, propionic acid, butyric acid, ethylene glycol monomethyl ether, glycol dimethyl ether, chlorobenzene, orthodichlorobenzene, toluene, tetramethylene sulfone, methyl alcohol or ethanol.
The fluorenes of large conjugation a pyrazines derivatives, is characterized in that this derivative is one of following general structure:
a.
Figure DEST_PATH_DEST_PATH_IMAGE004A
；
b.
Figure DEST_PATH_DEST_PATH_IMAGE006A
；
c.
Figure DEST_PATH_DEST_PATH_IMAGE008A
；
Wherein: R 1=hydrogen or C 6~ C 12straight chained alkyl, R 3=benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorenes, pyrazine, pyrroles, pyrazoles, oxazole, thiazole, thiophene, carbazole, pyrimidine, piperidines, purine, quinoline, isoquinoline 99.9, quinoxaline, quinazoline, benzanthrene, benzophenanthrene, pentanoic, triphenylamine, cumarone, benzoxazole, benzoisoxazole, mono-substituted phenyl ring, polysubstituted phenyl ring.
Prepare a method for fluorenes the pyrazines derivatives of above-mentioned large conjugation, it is characterized in that the concrete steps of the method are:
A. by dibenzoyl, luxuriant and rich with fragrance a kind of jade or 4,5-dicarbapentaborane pyrene and 2,3-diamino-7-halo-9,9 '-dialkyl group fluorenes and highly basic are by (1～1.1): 1:(0.5～1) mol ratio be dissolved in organic solvent, the consumption of organic solvent and the ratio of raw material are 15～25 mL:1g; Under inert atmosphere protection, back flow reaction 2～24 hours, adds ethyl acetate and water extraction after cooling, gets organic phase and is spin-dried for after dry, obtains fluorenes the pyrazines derivatives of halo through separation and purification, and its structural formula is respectively:
Figure DEST_PATH_RE-415716DEST_PATH_IMAGE004
,
Figure DEST_PATH_RE-808651DEST_PATH_IMAGE005
or
Figure DEST_PATH_RE-708474DEST_PATH_IMAGE006
; Described 2,3-diamino-7-halo-9, the structural formula of 9 '-dialkyl group fluorenes is:
Figure DEST_PATH_RE-274584DEST_PATH_IMAGE007
, R 3' be chlorine, bromine or iodine;
B. by the fluorenes of the halo of step a gained pyrazines derivatives, aryl boric acid, palladium catalyst and alkali, 1:1.2 ~ 2.0:0.05 ~ 0.1:2 ~ 2.5 join in solvent in molar ratio, the consumption of solvent and the ratio of raw material are 15 ~ 25 mL:1g, under nitrogen protection, be heated to 60 ~ 90 ℃, react 12 ~ 36 hours, after TLC plate monitoring reaction finishes, be cooled to room temperature, after being extracted with ethyl acetate, organic phase is spin-dried for, obtains fluorenes the pyrazines derivatives of large conjugation through column chromatography for separation;
Above-mentioned aryl boric acid structural formula is:
Figure DEST_PATH_RE-497624DEST_PATH_IMAGE008
, wherein Ar is benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorenes, pyrazine, pyrroles, pyrazoles, oxazole, thiazole, thiophene, carbazole, pyrimidine, piperidines, purine, quinoline, isoquinoline 99.9, quinoxaline, quinazoline, benzanthrene, benzophenanthrene, pentanoic, triphenylamine, cumarone, benzoxazole, benzoisoxazole, mono-substituted phenyl ring, polysubstituted phenyl ring.
Above-mentioned palladium catalyst is: PdCl 2, Pd (OAc) 2, Pd (PPh 3) 4, Pd (PPh 3) 2cl 2or Pd (dppf) Cl 2.
Above-mentioned alkali is: salt of wormwood, potassiumphosphate, Potassium monofluoride, sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium ethylate, sodium tert-butoxide, cesium fluoride, cesium carbonate, Quilonum Retard or hydrated barta.
Above-mentioned organic solvent is: dioxane/water, toluene/water, toluene and methanol, toluene/ethanol, toluene/tetrahydrofuran (THF), toluene/ethanol/water, acetonitrile/water, DMF/water, tetrahydrofuran (THF) or methyl-sulphoxide.
The fluorenes of large conjugation a pyrazines derivatives, is characterized in that this derivative is one of following general structure:
a.
Figure DEST_PATH_DEST_PATH_IMAGE010A
；
b.
Figure DEST_PATH_DEST_PATH_IMAGE012A
；
c.
Wherein: R 1=hydrogen or C 6~ C 12straight chained alkyl, R 4=the benzene, naphthalene, anthracene, pyrene, fluorenes, the triphenylamine that contain end-group alkyne.
Prepare a method for fluorenes the pyrazines derivatives of above-mentioned large conjugation, it is characterized in that the concrete steps of the method are:
A. by dibenzoyl, luxuriant and rich with fragrance a kind of jade or 4,5-dicarbapentaborane pyrene and 2,3-diamino-7-halo-9,9 '-dialkyl group fluorenes and highly basic are by (1～1.1): 1:(0.5～1) mol ratio be dissolved in organic solvent, the consumption of organic solvent and the ratio of raw material are 15～25 mL:1g; Under inert atmosphere protection, back flow reaction 2～24 hours, adds ethyl acetate and water extraction after cooling, gets organic phase and is spin-dried for after dry, obtains fluorenes the pyrazines derivatives of halo through separation and purification, and its structural formula is respectively:
,
Figure DEST_PATH_RE-615119DEST_PATH_IMAGE005
or
Figure DEST_PATH_RE-708977DEST_PATH_IMAGE006
; Described 2,3-diamino-7-halo-9, the structural formula of 9 '-dialkyl group fluorenes is:
Figure DEST_PATH_RE-506031DEST_PATH_IMAGE007
, R 3' be chlorine, bromine or iodine;
B. by the fluorenes of the halo of step a gained pyrazines derivatives, end group aryne compounds, palladium catalyst and cuprous iodide, 1:1.2:0.05:0.1 joins in solvent in molar ratio, the consumption of solvent and the ratio of raw material are 15 ~ 25 mL:1g, under nitrogen protection, be heated to reflux, react 20 ~ 36 hours, after TLC plate monitoring reaction finishes, be cooled to room temperature, after being extracted with ethyl acetate, organic phase is spin-dried for, obtains fluorenes the pyrazines derivatives of large conjugation through column chromatography for separation;
The fluorenes of above-mentioned halo pyrazines derivatives: above-mentioned end group aryne compounds structural formula: , wherein Ar is benzene, naphthalene, anthracene, pyrene, fluorenes, triphenylamine.
12. methods according to claim 11, is characterized in that the described palladium catalyst of stating is: PdCl 2, Pd (OAc) 2, Pd (PPh 3) 4, Pd (PPh 3) 2cl 2or Pd (dppf) Cl 2.
Above-mentioned organic solvent is: toluene, ether, triethylamine, tributylamine, tetrahydrofuran (THF), Diisopropylamine, DMF, N,N-dimethylacetamide or toluene/triethylamine.。
The invention has the beneficial effects as follows: a class is by raw material 2 containing fluorenes the pyrazines derivatives of large conjugated molecule, 3-diamino-9, directly there is condensation reaction in 9 '-dialkyl group base fluorenes, and by 2 of halogen replacement, 3-diamino-9,9 '-dialkyl group base fluorenes generation Suzuki reacts or Sonagashira reacts and then obtain A, B and tri-serial compounds of C.The alkyl of molecule periphery contributes to overcome the solvability causing due to the high plane rigid structure of molecule to be reduced, and improves the dissolving processing characteristics of material molecule.Simultaneously because the conjugation of π-electron on the skeleton of this quasi-molecule is further strengthened, not only can subtract micromolecular energy gap, and can play a role to overcoming the shortcomings such as the poor chemical stability of traditional organic small molecule material, can be widely used in the fields such as organic semiconductor material, nonlinear optical material, biochemical sensor and solar cell.
Embodiment
embodiment 1
1g 2; 3-diamino-9; 9 '-di-n-octyl fluorenes; the salt of wormwood of the dibenzoyl of 1 times of molar weight and 0.5 times of molar weight joins in 15mL glacial acetic acid, under the protection of nitrogen, and back flow reaction 5 hours; after cooling, add 50mL ethyl acetate; 20mL washing twice, 20mL saturated sodium bicarbonate solution is washed after twice, gets organic phase and is spin-dried for through column chromatographic isolation and purification and obtains 1g colourless oil liquid. 1H NMR (500M，CDCl 3)： δ(ppm) 8.44 (s，1H)，8.11(s，1H)，7.96-7.92(m，1H)，7.60-7.56(m，4H)，7.47-7.43(m，3H)，7.40-7.35(m，6H)，2.18-2.06(m，4H)，1.22-1.02(m，20H)，0.81(t， J=7Hz，6H)，0.73-0.66(m，4H)。HR-MS(ESI， m/z)： [ M+H] + calcd for C 43H 50N 2，595.4054；found，595.4043。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 385nm, and maximum emission wavelength is 408nm, fluorescence quantum yield Φ=0.54.Test condition: Shimadzu RF-5301 type spectrophotofluorometer, excites slit and transmitting slit to be 3nm, with CH 2cl 2for solvent is mixed with 1.0 × 10 -6the dilute solution of mol/L is measured fluorescence spectrum under 25 ℃ of conditions of room temperature; Measure fluorescence quantum yield take the sulphuric acid soln (Φ=0.55) of the 0.1N of Quinine Sulphate Di HC as reference.
embodiment 2
1g 2,3-diamino-9,9 '-di-n-octyl fluorenes; the salt of wormwood of the phenanthrenequione of 1 times of molar weight and 0.5 times of molar weight joins in 15mL glacial acetic acid, under the protection of nitrogen, and back flow reaction 2 hours; after cooling rear suction filtration, re-crystallizing in ethyl acetate obtains 1g yellow powder shape solid.Mp=98-101℃。 1H NMR(500M，CDCl 3)： δ(ppm) 9.49-9.42(m，2H)，8.61(d， J=7.5Hz，2H)，8.58(s，1H)，8.26(s，1H)，8.05-8.01(m，1H)，7.84-7.76(m，4H)，7.51-7.45(m，3H)，2.26-2.11(m，4H)，1.22-1.02(m，20H)，0.80(t， J=7Hz，6H)，0.77-0.70(m，4H)。HR-MS(ESI， m/z)： [ M+H] + calcd for C 43H 48N 2，593.3897；found，593.3923。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 389nm, and maximum emission wavelength is 429nm, fluorescence quantum yield Φ=0.51, and test condition is identical with embodiment 1.
embodiment 3
1g2,3-diamino-9,9 '-di-n-octyl fluorenes; 1 times of molar weight 4, the salt of wormwood of 5-dicarbapentaborane pyrene and 0.5 times of molar weight joins in 15mL glacial acetic acid, under the protection of nitrogen; back flow reaction 2 hours, after cooling rear suction filtration, re-crystallizing in ethyl acetate obtains 1g yellow-green colour pulverulent solids.Mp=101-104℃。 1H NMR(500M，CDCl 3)： δ(ppm) 9.60-9.54(m，2H)，8.59(s，1H)，8.28(s，1H)，8.27-8.24(m，2H)，8.11-8.06(m，2H)，8.04-8.01(m，3H)，7.50-7.45(m，3H)，2.25-2.11(m，4H)，1.18-1.02(m，20H)，0.79-0.71(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 45H 48N 2，617.3897；found，617.3893。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 451nm, and maximum emission wavelength is 473nm, fluorescence quantum yield Φ=0.42, and test condition is identical with embodiment 1.
embodiment 4
1g2; 3-diamino-7-bromine 9; 9 '-di-n-octyl fluorenes; the salt of wormwood of the dibenzoyl of 1 times of molar weight and 0.5 times of molar weight joins in 15mL glacial acetic acid, under the protection of nitrogen, and back flow reaction 5 hours; after cooling, add 50mL ethyl acetate; 20mL washing twice, 20mL saturated sodium bicarbonate solution is washed after twice, gets organic phase and is spin-dried for through column chromatographic isolation and purification and obtains 1g colourless oil liquid. 1H NMR(500M，CDCl 3)： δ(ppm) 8.39 (s，1H)，8.07(s，1H)，7.76(d， J=7.7Hz，1H)，7.56-7.53(m，6H)，7.37-7.34(m，6H)，2.14-2.08(m，2H)，2.06-1.99(m，2H)，1.16-1.00(m，20H)，0.79(t， J=7.1Hz，6H)，0.70-0.62(m，4H)。
embodiment 5
1g2,3-diamino-7-bromine 9,9 '-di-n-octyl fluorenes; the salt of wormwood of the phenanthrenequione of 1 times of molar weight and 0.5 times of molar weight joins in 15mL glacial acetic acid; under the protection of nitrogen, back flow reaction 2 hours, after cooling rear suction filtration, re-crystallizing in ethyl acetate obtains 1g yellow powder shape solid.Mp=157-159℃。 1H NMR(500M，CDCl 3)：δ(ppm) 9.43-9.37(m，2H)，8.57(d， J=8.0Hz，2H)，8.52 (s，1H)，8.21(s，1H)，7.80(d， J=8.0Hz，1H)，7.81-7.73(m，4H)，7.60-7.56(m，2H)，2.22-2.15(m，2H)，2.11-2.05(m，2H)，1.18-1.02(m，20H)，0.77(t， J=7.0Hz，6H)，0.74-0.67(m，4H)。
embodiment 6
1g2,3-diamino-7-bromine 9,9 '-di-n-octyl fluorenes; 1 times of molar weight 4, the salt of wormwood of 5-dicarbapentaborane pyrene and 0.5 times of molar weight joins in 15mL glacial acetic acid, under the protection of nitrogen; back flow reaction 2 hours, after cooling rear suction filtration, re-crystallizing in ethyl acetate obtains yellow-green colour pulverulent solids.Mp=194-196℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.50-9.45(m，2H)，8.53(s，1H)，8.26 (s，1H)，8.25-8.22(m，2H)，8.08-8.03(m，2H)，7.99(s，2H)，7.84(d， J=8.4Hz，1H)，7.60-7.57(m，2H)，2.26-2.18(m，2H)，2.14-2.07(m，2H)，1.18-1.04(m，20H)，0.79-0.72(m，10H)。
embodiment 7
By 200mg bromo fluorenes pyrazine compound, the phenylo boric acid of 1.2 times of molar weights, 2 times of molar weight salt of wormwood and 0.05 times of molar weight dual-triphenylphosphine palladium chloride; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 12 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 180mg colourless oil liquid through column chromatography for separation. 1H NMR (500M，CDCl 3)： δ(ppm) 8.45(s，1H)，8.11(s，1H)，7.98(d，J = 7.5Hz，1H)，7.73-7.67(m，3H)，7.63(m，1H)，7.59-7.56(m，4H)，7.52-7.48(m，2H)，7.42-7.35(m，7H)，2.20-2.09 (m，4H)，1.19-1.03(m，20H)，0.81-0.71(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 49H 54N 2，671.4367；found，671.4334。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 394nm, and maximum emission wavelength is 422nm, fluorescence quantum yield Φ=0.65, and test condition is identical with embodiment 1.
embodiment 8
By 200mg bromo fluorenes pyrazine compound, the naphthalene boronic acids of 1.2 times of molar weights, 2 times of molar weight salt of wormwood and 0.05 times of molar weight dual-triphenylphosphine palladium chloride; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 12 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 150mg colourless oil liquid through column chromatography for separation. 1H NMR (500M，CDCl 3)： δ(ppm) 8.49(s，1H)，8.13(s，1H)，8.03(d， J=7.6Hz，1H)，7.98-7.94(m，2H)，7.91(d， J=8.3Hz，1H)，7.61-7.51(m，9H)，7.48-7.43(m，1H)，7.40-7.34(m，6H)，2.20-2.07(m，4H)，1.21-1.03(m，20H)，0.85-0.76(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 53H 56N 2，721.4523；found，721.4522。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 391nm, and maximum emission wavelength is 428nm, fluorescence quantum yield Φ=0.55, and test condition is identical with embodiment 1.
embodiment 9
By 200mg bromo fluorenes pyrazine compound, the 9-anthracene boric acid of 1.5 times of molar weights, 2.5 times of molar weight salt of wormwood and 0.1 times of molar weight dual-triphenylphosphine palladium chloride; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 24 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 120mg colourless oil liquid through column chromatography for separation.Mp= 85- 87℃。 1H NMR (500M，CDCl 3)：δ(ppm) 8.55-8.53(m，2H)，8.14 (s，1H)，8.12(d， J=7.7Hz，1H)，8.09(d， J=8.6Hz，1H)，7.77-7.73(m，2H)，7.61-7.57(m，4H)，7.52-7.47(m，4H)，7.39-7.34(m，8H)，2.20-2.04(m，4H)，1.19-1.06(m，20H)，0.89-0.76(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 57H 58N 2，771.4680；found，771.4681。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 392nm, and maximum emission wavelength is 497nm, fluorescence quantum yield Φ=0.67, and test condition is identical with embodiment 1.
embodiment 10
By 200mg bromo fluorenes pyrazine compound, the 2-pyrene boric acid of 2 times of molar weights, the salt of wormwood of 2.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.1 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 24 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains the light yellow oily liquid of 137mg through column chromatography for separation.Mp=98- 100℃。 1H NMR (500M，CDCl 3)：δ(ppm) 8.54 (s，1H)，8.30-8.22(m，3H)，8.21-8.16 (m，2H)，8.15-8.09 (m，4H)，8.07-8.02(m，2H)，7.72(d， J=7.9Hz，1H)，7.69 (s，1H)，7.62-7.57(m，4H)，7.41-7.36 (m，6H)，2.24-2.12 (m，4H)，1.22-1.08(m，20H)，0.93-0.78(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 59H 60N 2，797.4836；found，797.4750。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 396nm, and maximum emission wavelength is 483nm, fluorescence quantum yield Φ=0.49, and test condition is identical with embodiment 1.
embodiment 11
By 200mg bromo fluorenes pyrazine compound, the triphenylamine boric acid of 2 times of molar weights, the salt of wormwood of 2.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.1 times of molar weight; join in the mixed solvent of toluene (15mL) and water (1.5mL); under nitrogen protection; at 90 ℃, react 36 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 110mg yellow powder shape solid through column chromatography for separation.Mp=112-114℃。 1H NMR(500M，CDCl 3)：δ(ppm) 8.41 (s，1H)，8.09 (s，1H)，7.94(d， J=7.8Hz，1H)，7.67-7.64(m，1H)，7.60-7.54(m，7H)，7.38-7.33(m，6H)，7.31-7.27(m，4H)，7.20-7.15(m，6H)，7.08-7.04(m，2H)，2.18-2.07(m，4H)，1.18-1.01(m，20H)，0.80-0.68(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 61H 63N 3，838.5102；found，838.5109。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 408nm, and maximum emission wavelength is 561nm, fluorescence quantum yield Φ=0.10, and test condition is identical with embodiment 1. embodiment 12
By 200mg bromo fluorenes pyrazine compound, the phenylo boric acid of 1.2 times of molar weights, the salt of wormwood of 1.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 12 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 184mg yellow powder shape solid through column chromatography for separation.Mp=119 -121℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.50-9.44(m，2H)，8.64-8.59(m，3H)，8.27(s，1H)，8.08(d，J = 7.5Hz，1H)，7.86-7.78(m，4H)，7.77-7.72 (m，3H)，7.67 (s，1H)，7.56-7.52 (m，2H)，7.46-7.42(m，1H)，2.30-2.15(m，4H)，1.21-1.03(m，20H)，0.82-0.75 (m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 49H 52N 2，669.4210；found，669.4202。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 428nm, and maximum emission wavelength is 447nm, fluorescence quantum yield Φ=0.71, and test condition is identical with embodiment 1.
embodiment 13
By 200mg bromo fluorenes pyrazine compound, the naphthalene boronic acids of 1.2 times of molar weights, the salt of wormwood of 1.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 12 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 174mg yellow powder shape solid through column chromatography for separation.Mp=129 -131℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.48-9.41(m，2H)，8.62 (s，1H)，8.56(d， J=7.7Hz，2H)，8.30(s，1H)，8.12(d， J=7.6Hz，1H)，8.08-7.92(m，3H)，7.81-7.74(m，4H)，7.64-7.54(m，5H)，7.51-7.47(m，1H)，2.30-2.15(m，4H)，1.21-1.08(m，20H)，0.92-0.84(m，4H)，0.79(t， J=7.0Hz，6H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 53H 54N 2，719.4367；found，719.4405。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 425nm, and maximum emission wavelength is 453nm, fluorescence quantum yield Φ=0.63, and test condition is identical with embodiment 1.
embodiment 14
By 200mg bromo fluorenes pyrazine compound, the 9-anthracene boric acid of 2 times of molar weights, the salt of wormwood of 2.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.08 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 24 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 107mg yellow powder shape solid through column chromatography for separation.Mp= 189-191℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.50-9.43(m，2H)，8.68(s，1H)，8.60-8.55(m，3H)，8.32(s，1H)，8.22(d， J=7.6Hz，1H)，8.10(d， J=8.9Hz，2H)，7.82-7.76(m，6H)，7.57-7.49(m，4H)，7.52-7.47(m，4H)，7.42-7.37(m，2H)，2.30-2.12(m，4H)，1.21-1.08(m，20H)，0.97-0.87(m，4H)，0.78(t， J=7.0Hz，6H)。HR-MS(ESI， m/z)： [ M+H] + calcd for C 57H 56N 2，769.4523；found，769.4567。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 425nm, and maximum emission wavelength is 542nm, fluorescence quantum yield Φ=0.69, and test condition is identical with embodiment 1.
embodiment 15
By 200mg bromo fluorenes pyrazine compound, the 2-pyrene boric acid of 1.5 times of molar weights, the salt of wormwood of 2.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 24 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 171mg yellow powder shape solid through column chromatography for separation.Mp= 129-130℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.49-9.43(m，2H)，8.66 (s，1H)，8.61-8.57(m，2H)，8.32-8.25(m，3H)，8.25-8.17(m，3H)，8.15-8.10(m，3H)，8.08-8.049(m，2H)，7.83-7.74(m，5H)，7.72 (s，1H)，2.31-2.18(m，4H)，1.21-1.09(m，20H)，0.97-0.85(m，4H)，0.78(t， J=7.0Hz，6H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 59H 58N 2，795.4680；found，795.4615。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 429nm, and maximum emission wavelength is 524nm, fluorescence quantum yield Φ=0.55, and test condition is identical with embodiment 1.
embodiment 16
By 200mg bromo fluorenes pyrazine compound, the triphenylamine pinacol borate of 1.5 times of molar weights, the salt of wormwood of 2.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.1 times of molar weight; join in the mixed solvent of toluene (15mL) and water (1.5mL); under nitrogen protection; at 90 ℃, react 24 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 160mg yellow powder shape solid through column chromatography for separation.Mp=101-103℃。 1H NMR(500M，CDCl 3)：δ(ppm) 9.46-9.41(m，2H)，8.58(d， J=7.5Hz，2H)，8.55 (s，1H)，8.24 (s，1H)，8.03(d， J=7.9Hz，1H)，7.82-7.74(m，4H)，7.70-7.67(m，1H)，7.64-7.60(m，3H)，7.33-7.28(m，4H)，7.23-7.17(m，6H)，7.09-7.05(m，2H)，2.27-2.13(m，4H)，1.18-1.01(m，20H)，0.81-0.73(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 61H 61N 3，836.4945；found，836.4964。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 438nm, and maximum emission wavelength is 642nm, fluorescence quantum yield Φ=0.21, and test condition is identical with embodiment 1.
embodiment 17
By 200mg bromo fluorenes pyrazine compound, the phenylo boric acid of 1.2 times of molar weights, the salt of wormwood of 1.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 12 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 188mg yellow powder shape solid through column chromatography for separation.Mp= 97-99℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.70-9.58 (m，2H)，8.66-8.61 (m，1H)，8.36-8.26 (m，3H)，8.19-8.04 (m，5H)，7.80-7.72(m，3H)，7.68 (s，1H)，7.58-7.52 (m，2H)，7.47-7.41 (m，1H)，2.30-2.15 (m，4H)，1.20-1.03 (m，20H)，0.86-0.75 (m， 10H)。HR-MS(ESI， m/z)： [ M+H] + calcd for C 51H 52N 2，743.4367；found，743.4373。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 456nm, and maximum emission wavelength is 474nm, fluorescence quantum yield Φ=0.55, and test condition is identical with embodiment 1.
embodiment 18
By 200mg bromo fluorenes pyrazine compound, the naphthalene boronic acids of 1.2 times of molar weights, the salt of wormwood of 1.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 12 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 178mg yellow powder shape solid through column chromatography for separation.Mp= 99-101℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.49-9.45(m，2H)，8.62 (s，1H)， 8.36(s，1H)，8.16-8.13(m，3H)，8.06(d， J=8.5Hz，1H)，8.02-7.98(m，3H)，7.97-7.93(m，1H)，7.91 (s，2H)，7.66-7.55(m，5H)，7.54-7.49(m，1H)，2.36-2.20(m，4H)，1.24-1.13(m，20H)，1.01-0.94(m，4H)，0.81(t， J=7.0Hz，6H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 55H 54N 2，743.4367；found，743.4373。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 455nm, and maximum emission wavelength is 476nm, fluorescence quantum yield Φ=0.53, and test condition is identical with embodiment 1.
embodiment 19
By 200mg bromo fluorenes pyrazine compound, the 9-anthracene boric acid of 1.5 times of molar weights, the salt of wormwood of 2 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.1 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 30 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 98mg yellow powder shape solid through column chromatography for separation.Mp= 91-93℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.66-9.59(m，2H)，8.72(s，1H)，8.56(s，1H)，8.36(s，1H)，8.30-8.27(m，2H)，8.24(d， J=7.6Hz，1H)，8.13-8.08(m，4H)，8.05(s，2H)，7.80(d， J=8.9Hz，2H)，7.58-7.54(m，2H)，7.53-7.48(m，2H)，7.41-7.37(m，2H)，2.31-2.24(m，2H)，2.20-2.13(m，2H)，1.17-1.08(m，20H)，0.96-0.86(m，4H)，0.77(t， J=7.1Hz，6H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 59H 56N 2，793.4523；found，793.4510。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 456nm, and maximum emission wavelength is 477nm, fluorescence quantum yield Φ=0.60, and test condition is identical with embodiment 1.
embodiment 20
By 200mg bromo fluorenes pyrazine compound, the 2-pyrene boric acid of 1.5 times of molar weights, the salt of wormwood of 2 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.08 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 12 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 180mg yellow powder shape solid through column chromatography for separation.Mp= 115-117℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.66-9.60(m，2H)，8.71(s，1H)，8.38(s，1H)，8.32-8.28(m，4H)，8.26-8.20(m，3H)，8.17-8.11(m，5H)，8.10-8.05(m，4H)，7.80-7.74(m，2H)，7.83-7.74(m，5H)，7.72 (s，1H)，2.36-2.22(m，4H)，1.24-1.12(m，20H)，1.01-0.93(m，4H)，0.80(t， J=7.0Hz，6H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 61H 58N 2，819.4680；found，819.4587。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 458nm, and maximum emission wavelength is 478nm, fluorescence quantum yield Φ=0.40, and test condition is identical with embodiment 1.
embodiment 21
By 200mg bromo fluorenes pyrazine compound, the triphenylamine boric acid of 1.5 times of molar weights, the salt of wormwood of 2.5 times of molar weights and the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight; join in the mixed solvent of toluene (9mL) and water (1mL); under nitrogen protection; at 90 ℃, react 24 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 210mg yellow powder shape solid through column chromatography for separation.Mp= 130-131℃。 1H NMR (500M，CDCl 3)：δ(ppm) 9.61-9.56(m，2H)，8.58(s，1H)，8.29(s，1H)，8.28-8.24 (m，2H)，8.12-8.07(m，2H），8.06-8.02(m，3H)，7.71-7.68(m，1H)，7.65-7.61(m，3H)，7.33-7.28(m，4H)，7.23-7.17(m，6H)，7.09-7.05(m，2H)，2.29-2.16(m，4H)，1.17-1.04(m，20H)，0.83-0.73(m，10H)。HR-MS(ESI， m/z)： [ M+H] + calcd for C 63H 61N 3，860.4945；found，860.4949。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 464nm, and maximum emission wavelength is 640nm, fluorescence quantum yield Φ=0.14, and test condition is identical with embodiment 1.
embodiment 22
By 200mg bromo fluorenes pyrazine compound, the phenylacetylene of 1.2 times of molar weights, the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight and the cuprous iodide of 0.1 times of molar weight; join in the triethylamine that 15mL heavily steamed; under nitrogen protection; back flow reaction 24 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 159mg yellow powder shape solid through column chromatography for separation. 1H NMR(500M，CDCl 3)： δ(ppm) 8.42(s，1H)，8.09(s，1H)，7.88(d， J=7.9Hz，1H)，7.62-7.54 (m，8H)，7.40-7.33(m，3H)，2.17-2.04(m，4H)，1.19-1.02(m，20H)，0.789 (t， J=7.1Hz，6H)，0.73-0.64 (m，4H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 51H 54N 2， 695.4367；found，695.4368。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 398nm, and maximum emission wavelength is 423nm, fluorescence quantum yield Φ=0.58, and test condition is identical with embodiment 1.
embodiment 23
By 200mg bromo fluorenes pyrazine compound, the phenylacetylene of 1.2 times of molar weights, the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight and the cuprous iodide of 0.1 times of molar weight; join in the triethylamine that 15mL heavily steamed; under nitrogen protection; back flow reaction 20 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 155mg yellow powder shape solid through column chromatography for separation.Mp=89-92℃。 1H NMR(500M，CDCl 3)：δ(ppm) 9.38-9.35(m，2H)，8.51-8.47(m，3H)，8.25(s，1H)，7.95(d， J=7.9Hz，1H)，7.74-7.70(m，4H)，7.67-7.63(m，4H)，7.43-7.37(m，3H)，2.26-2.14(m，4H)，1.20-1.05(m，20H)，0.82-0.75(m，10H)。HR-MS(ESI，m/z)： [M+H]+ calcd for C 51H 52N 2，693.4210；found，693.4226。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 431nm, and maximum emission wavelength is 447nm, fluorescence quantum yield Φ=0.58, and test condition is identical with embodiment 1.
embodiment 24
By 200mg bromo fluorenes pyrazine compound, the phenylacetylene of 1.2 times of molar weights, the dual-triphenylphosphine palladium chloride of 0.05 times of molar weight and the cuprous iodide of 0.1 times of molar weight; join in the triethylamine that 15mL heavily steamed; under nitrogen protection; back flow reaction 25 hours; stopped reaction is cooled to room temperature, is extracted with ethyl acetate rear concentrated organic phase and obtains 172mg yellow powder shape solid through column chromatography for separation.Mp=138-141℃。 1H NMR(500M，CDCl 3)：δ(ppm) 9.56-9.52(m，2H)，8.55(s，1H)，8.28(s，1H)，8.26-8.22(m，2H)，8.09-8.05(m，2H)，8.01-7.96(m，3H)，7.66-7.61(m，4H)，7.42-7.37(m，3H)，2.29-2.16(m，4H)，1.19-1.04(m，20H)，0.81-0.73(m，10H)。HR-MS(ESI， m/z)：[ M+H] + calcd for C 53H 52N 2，717.4210；found，717.4196。
Excitation spectrum and the emmission spectrum of this compound that utilized fluorescent spectrophotometer assay, determines that maximum excitation wavelength is 459nm, and maximum emission wavelength is 474nm, fluorescence quantum yield Φ=0.42, and test condition is identical with embodiment 1.

Claims (13)

1. the fluorenes of large conjugation a pyrazines derivatives, is characterized in that this derivative is one of following general structure:
a.
Figure 801953DEST_PATH_IMAGE002
b.
Figure DEST_PATH_IMAGE004A
c.
Figure DEST_PATH_IMAGE006A
Wherein: R 1=hydrogen or C 6~ C 12straight chained alkyl, R 2=hydrogen, chlorine, bromine, iodine.
2. prepare the method for fluorenes the pyrazines derivatives of large conjugation according to claim 1 for one kind, the concrete steps that it is characterized in that the method are: by 2, 3-diamino-9, 9 '-dialkyl group fluorene derivatives and dibenzoyl or luxuriant and rich with fragrance a kind of jade or 4, 5-dicarbapentaborane pyrene and highly basic, 1:1 ~ 1.1:0.5 ~ 1 joins in organic solvent in molar ratio, the consumption of solvent and the ratio of raw material are 15 ~ 25 mL:1g, under the protection of nitrogen, be heated to back flow reaction 2 ~ 24 hours, after cooling, add ethyl acetate and water extraction, get after organic phase is dried and be spin-dried for, obtain fluorenes the pyrazines derivatives of large conjugation through column chromatography for separation, described 2,3-diamino-9, the structural formula of 9 '-dialkyl group fluorene derivatives is:
Figure DEST_PATH_IMAGE008
.
3. method according to claim 2, is characterized in that described highly basic is: salt of wormwood, potassium hydroxide, hydrolith, sodium carbonate, sodium hydroxide, sodium methylate, sodium ethylate or sodium hydride.
4. method according to claim 2, it is characterized in that described organic solvent is: 1,4-dioxane, acetonitrile, DMF, methyl-sulphoxide, N-Methyl pyrrolidone, quinoline, imidazoles, acetic acid, propionic acid, butyric acid, ethylene glycol monomethyl ether, glycol dimethyl ether, chlorobenzene, orthodichlorobenzene, toluene, tetramethylene sulfone, methyl alcohol or ethanol.
5. the fluorenes of large conjugation a pyrazines derivatives, is characterized in that this derivative is one of following general structure:
a.
Figure DEST_PATH_IMAGE010
b.
Figure DEST_PATH_IMAGE012
c.
Wherein: R 1=hydrogen or C 6~ C 12straight chained alkyl, R 3=benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorenes, pyrazine, pyrroles, pyrazoles, oxazole, thiazole, thiophene, carbazole, pyrimidine, piperidines, purine, quinoline, isoquinoline 99.9, quinoxaline, quinazoline, benzanthrene, benzophenanthrene, pentanoic, triphenylamine, cumarone, benzoxazole, benzoisoxazole, mono-substituted phenyl ring, polysubstituted phenyl ring.
6. prepare a method for fluorenes the pyrazines derivatives of large conjugation according to claim 5, it is characterized in that the concrete steps of the method are:
A. by dibenzoyl, luxuriant and rich with fragrance a kind of jade or 4,5-dicarbapentaborane pyrene and 2,3-diamino-7-halo-9,9 '-dialkyl group fluorenes and highly basic are by (1～1.1): 1:(0.5～1) mol ratio be dissolved in organic solvent, the consumption of organic solvent and the ratio of raw material are 15～25 mL:1g; Under inert atmosphere protection, back flow reaction 2～24 hours, adds ethyl acetate and water extraction after cooling, gets organic phase and is spin-dried for after dry, obtains fluorenes the pyrazines derivatives of halo through separation and purification, and its structural formula is respectively:
Figure DEST_PATH_IMAGE016
,
Figure DEST_PATH_IMAGE018
or
Figure DEST_PATH_IMAGE020
; Described 2,3-diamino-7-halo-9, the structural formula of 9 '-dialkyl group fluorenes is:
Figure DEST_PATH_IMAGE022
, R 3' be chlorine, bromine or iodine;
B. by the fluorenes of the halo of step a gained pyrazines derivatives, aryl boric acid, palladium catalyst and alkali, 1:1.2 ~ 2.0:0.05 ~ 0.1:2 ~ 2.5 join in solvent in molar ratio, the consumption of solvent and the ratio of raw material are 15 ~ 25 mL:1g, under nitrogen protection, be heated to 60 ~ 90 ℃, react 12 ~ 36 hours, after TLC plate monitoring reaction finishes, be cooled to room temperature, after being extracted with ethyl acetate, organic phase is spin-dried for, obtains fluorenes the pyrazines derivatives of large conjugation through column chromatography for separation;
Above-mentioned aryl boric acid structural formula is:
Figure DEST_PATH_IMAGE024
, wherein Ar is benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorenes, pyrazine, pyrroles, pyrazoles, oxazole, thiazole, thiophene, carbazole, pyrimidine, piperidines, purine, quinoline, isoquinoline 99.9, quinoxaline, quinazoline, benzanthrene, benzophenanthrene, pentanoic, triphenylamine, cumarone, benzoxazole, benzoisoxazole, mono-substituted phenyl ring, polysubstituted phenyl ring.
7. method according to claim 6, is characterized in that described palladium catalyst is: PdCl 2, Pd (OAc) 2, Pd (PPh 3) 4, Pd (PPh 3) 2cl 2or Pd (dppf) Cl 2.
8. tired main officer of Tibet according to claim 6, is characterized in that described alkali is: salt of wormwood, potassiumphosphate, Potassium monofluoride, sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium ethylate, sodium tert-butoxide, cesium fluoride, cesium carbonate, Quilonum Retard or hydrated barta.
9. method according to claim 6, it is characterized in that described organic solvent is: dioxane/water, toluene/water, toluene and methanol, toluene/ethanol, toluene/tetrahydrofuran (THF), toluene/ethanol/water, acetonitrile/water, DMF/water, tetrahydrofuran (THF) or methyl-sulphoxide.
10. the fluorenes of large conjugation a pyrazines derivatives, is characterized in that this derivative is one of following general structure:
a.
Figure DEST_PATH_IMAGE026
b.
c.
Figure DEST_PATH_IMAGE030
Wherein: R 1=hydrogen or C 6~ C 12straight chained alkyl, R 4=the benzene, naphthalene, anthracene, pyrene, fluorenes, the triphenylamine that contain end-group alkyne.
Prepare the method for fluorenes the pyrazines derivatives of large conjugation according to claim 10 for 11. 1 kinds, it is characterized in that the concrete steps of the method are:
A. by dibenzoyl, luxuriant and rich with fragrance a kind of jade or 4,5-dicarbapentaborane pyrene and 2,3-diamino-7-halo-9,9 '-dialkyl group fluorenes and highly basic are by (1～1.1): 1:(0.5～1) mol ratio be dissolved in organic solvent, the consumption of organic solvent and the ratio of raw material are 15～25 mL:1g; Under inert atmosphere protection, back flow reaction 2～24 hours, adds ethyl acetate and water extraction after cooling, gets organic phase and is spin-dried for after dry, obtains fluorenes the pyrazines derivatives of halo through separation and purification, and its structural formula is respectively:
Figure 342262DEST_PATH_IMAGE016
,
Figure 121999DEST_PATH_IMAGE018
or
Figure 83920DEST_PATH_IMAGE020
; Described 2,3-diamino-7-halo-9, the structural formula of 9 '-dialkyl group fluorenes is: , R 3' be chlorine, bromine or iodine;
B. by the fluorenes of the halo of step a gained pyrazines derivatives, end group aryne compounds, palladium catalyst and cuprous iodide, 1:1.2:0.05:0.1 joins in solvent in molar ratio, the consumption of solvent and the ratio of raw material are 15 ~ 25 mL:1g, under nitrogen protection, be heated to reflux, react 20 ~ 36 hours, after TLC plate monitoring reaction finishes, be cooled to room temperature, after being extracted with ethyl acetate, organic phase is spin-dried for, obtains fluorenes the pyrazines derivatives of large conjugation through column chromatography for separation;
The fluorenes of above-mentioned halo pyrazines derivatives: above-mentioned end group aryne compounds structural formula:
Figure DEST_PATH_IMAGE032
, wherein Ar is benzene, naphthalene, anthracene, pyrene, fluorenes, triphenylamine.
12. methods according to claim 11, is characterized in that the described palladium catalyst of stating is: PdCl 2, Pd (OAc) 2, Pd (PPh 3) 4, Pd (PPh 3) 2cl 2or Pd (dppf) Cl 2.
13. methods according to claim 11, is characterized in that described organic solvent is: toluene, ether, triethylamine, tributylamine, tetrahydrofuran (THF), Diisopropylamine, DMF, N,N-dimethylacetamide or toluene/triethylamine.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418515A (en) * 2015-12-09 2016-03-23 上海大学 Fluorine and imidazole derivative and preparation method thereof
KR20160076356A (en) * 2014-12-22 2016-06-30 주식회사 두산 Organic compound and organic electroluminescent device using the same
CN106632319A (en) * 2016-11-17 2017-05-10 赵明根 2-(pyrene-1-yl)-1,8-naphthyridine and synthetic method thereof
CN107200830A (en) * 2017-05-25 2017-09-26 南方医科大学 A kind of ionization containing organic radical polymerization fluorenes and its preparation method and application
CN108864042A (en) * 2018-07-26 2018-11-23 上海天马有机发光显示技术有限公司 A kind of azepine condensed ring and indene compound and organic light-emitting display device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302219A (en) * 2008-07-02 2008-11-12 大连理工大学 Fluorene derivative containing large conjugated molecule and preparation thereof
CN101747209A (en) * 2009-12-22 2010-06-23 上海大学 2, 3-diamino-9, 9'-dialkyl substituted fluorene and preparation method thereof
CN102146077A (en) * 2011-01-13 2011-08-10 上海大学 Fluoreneimidazole derivatives and preparation method thereof
EP2657226A1 (en) * 2010-12-20 2013-10-30 Ocean's King Lighting Science&Technology Co., Ltd. Organic semiconductor material, preparation methods and uses thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101302219A (en) * 2008-07-02 2008-11-12 大连理工大学 Fluorene derivative containing large conjugated molecule and preparation thereof
CN101747209A (en) * 2009-12-22 2010-06-23 上海大学 2, 3-diamino-9, 9'-dialkyl substituted fluorene and preparation method thereof
EP2657226A1 (en) * 2010-12-20 2013-10-30 Ocean's King Lighting Science&Technology Co., Ltd. Organic semiconductor material, preparation methods and uses thereof
CN102146077A (en) * 2011-01-13 2011-08-10 上海大学 Fluoreneimidazole derivatives and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
胡跃飞，等: "《现代有机反应-金属催化反应》", 31 December 2008, article "薗頭反应", pages: 257-267 *

Cited By (9)

* Cited by examiner, † Cited by third party
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KR20160076356A (en) * 2014-12-22 2016-06-30 주식회사 두산 Organic compound and organic electroluminescent device using the same
KR102263233B1 (en) * 2014-12-22 2021-06-10 솔루스첨단소재 주식회사 Organic compound and organic electroluminescent device using the same
CN105418515A (en) * 2015-12-09 2016-03-23 上海大学 Fluorine and imidazole derivative and preparation method thereof
CN106632319A (en) * 2016-11-17 2017-05-10 赵明根 2-(pyrene-1-yl)-1,8-naphthyridine and synthetic method thereof
CN106632319B (en) * 2016-11-17 2019-01-25 赵明根 A kind of 2- (pyrene -1- base) -1,8- naphthyridines and its synthetic method
CN107200830A (en) * 2017-05-25 2017-09-26 南方医科大学 A kind of ionization containing organic radical polymerization fluorenes and its preparation method and application
CN107200830B (en) * 2017-05-25 2018-12-25 南方医科大学 A kind of ionization containing organic radical polymerization fluorenes and its preparation method and application
CN108864042A (en) * 2018-07-26 2018-11-23 上海天马有机发光显示技术有限公司 A kind of azepine condensed ring and indene compound and organic light-emitting display device
US11183643B2 (en) 2018-07-26 2021-11-23 Shanghai Tianma AM-OLED Co., Ltd. Nitrogen heterocycle fused ring-indene compound and organic light-emitting display device

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