CN106220553A - One class carbazole fluorene ethylene derivant and synthetic method thereof - Google Patents
One class carbazole fluorene ethylene derivant and synthetic method thereof Download PDFInfo
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- CN106220553A CN106220553A CN201610625422.7A CN201610625422A CN106220553A CN 106220553 A CN106220553 A CN 106220553A CN 201610625422 A CN201610625422 A CN 201610625422A CN 106220553 A CN106220553 A CN 106220553A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
- C08F38/04—Vinylacetylene
Abstract
Report a class carbazole fluorene ethylene derivant, and the typical synthetic route of this compounds in the present invention.The architectural feature of this compounds is, the atom N σ key connecting of 2 of fluorene group and carbazole group, and end fluorene group forms fluorene ethylene structure.The preparation method of double bond is toluene distillation evaporation.Due to the existence of double bond, this compounds can be prepared multiple conducting polymer by homopolymerization or copolymerization mode, thus had higher scientific research value and wide application prospect.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a class carbazole-fluorene ethylene derivant, and this compounds
Typical synthetic route.
Background technology
Conducting polymer is " to adulterate " make it be turned by insulator through chemistry or electrochemistry by having the macromolecule of gripping π-key altogether
Become a family macromolecule material of conductor.2000, American scientist A.G.McDiarmid and A.Heeger and Japan Science
Family's Hideki Shirakawa obtains Nobel chemistry Prize due to the initiative work in this field.
Conducting polymer is the new function material of a kind of function admirable, and rapid in 80-90 age progress, becomes
The research center of material science, promotes countries in the world scientist to be devoted to the practical of conducting polymer.Due to conducting polymer
Having pi-conjugated structure, therefore, it has fast response time (10-13And high nonlinear third order optical susceptibility (i=sec)
10-9——10-13Esu), can be used for information storage, frequency modulation, photoswitch and optical computer etc. technical.Meanwhile, there is high conductance
Conducting polymer can be used for electromagnetic shielding, the technical application such as antistatic, molecular wire.And there is leading of semiconducting behavior
Electricity macromolecule, can be used for opto-electronic device (transistor, rectifier tube), Organic Light Emitting Diode (organiclight emitting
Diode, OLED) and the aspect such as organic solar batteries.
In recent years, polyfluorene class material becomes one of the research emphasis in conducting polymer field.This kind of material has well
Heat stability, have a highest fluorescence quantum yield with in thin film in the solution, launch wavelength and be concentrated mainly on blue light range.
Their light stability and heat stability are better than PPV.Polyfluorene includes at least the plane of a rigidity in each repetitive
Double benzene ring structures.Compared with PPP, the substituted radical that fluorenes unit is 9 produces space obstacle, makes the rarer intermolecular phase interaction of polyfluorene
With.Polyfluorene has the liquid crystal property of uniqueness, and this is favourable for preparing polarizing optics.With the polyfluorene of octyl group at 170 DEG C
Enter liquid crystalline phase, enter homogeneous phase at 270～280 DEG C, and repeatedly can change between this is biphase.Polyfluorene is at room temperature made
The film become can be glassy state, it is also possible to be semi-crystalline.The electrically excited relaxation of polyfluorene is by TRFS (Time
Resolved Fluorescence Specroscopy) technical testing, for the ps order of magnitude.
In the nineties in early days, Yoshino et al. reports and carrys out the method for oxidised monomer with FeCl3 and obtain blue-fluorescence thing
Matter polyfluorene, similar method also apply be applicable to polythiophene.But the polyfluorene molecular weight obtained in this way relatively low (DP～
10), and it is difficult to remove the oxide of trace, but, or is made for device by this polyfluorene.
Later, Yamamoto reacts, i.e. the coupling reaction of nickel catalysis is also used for the polymerization of fluorenes, and has obtained a series of fluorenes
Homopolymerization and oligomer.This nickel catalyst system is more cheap than palladium, and the coupling reaction for two kinds of conjugation groups is relatively effective.
In recent years, Suzuki reaction is also used for the synthesis of polyfluorene.Very many dyestuffs can with fluorenes copolymerization, including benzene,
Naphthalene, anthracene, thiophene etc., due to the introducing of these dyestuffs, the luminescent properties of polyfluorene there has also been the biggest change, can realize from indigo plant
Light is to the transmitting of the shades of colour light of HONGGUANG.
The most also having synthesized some monodispersed oligomerisation fluorenes, the degree of polymerization, from 3 to 10, mainly investigates conjugation
The impact increasing alignment polyfluorene luminescent properties of system.
Carbazole (carbazole), has another name called 9-nitrogen (miscellaneous) fluorenes (dibenzopyrrole), and molecular formula is C12H9N, molecular weight
It is 167.20.Carbazole is important organic intermediate, in addition to the conventional use for dyestuff, medicine and pesticide synthesis, carbazole and
Its derivant is widely used in synthesizing photoelectric functional material.Such as utilize carbazole can prepare organic non linear optical material, have
Electroluminescent material, photorefractive material, difunctional system containing carbazole chromophore, containing the carbazole little molecular glass of Preset grating etc..
Ou Silang company Zeng Yongju 9-VCz (Fig. 1) adulterates with complex of iridium, and the final efficiency that obtains is the white of 20 lumen every watt
Color organic electroluminescence device, close to the efficiency of Commercial optical lamp, enters lighting field for organic electroluminescent LED and lays
Basis.
The most synthesized polyfluorene is mainly backbone chain type polyfluorene, although photoelectric properties are excellent, but there is also some shortcomings.
First, the dissolubility of backbone chain type polyfluorene is poor, it is difficult to processing film forming.In order to improve its processing characteristics, it has to introduce substantial amounts of
Alkyl chain, causes the vitrification point of material drastically to decline, and the heat stability of film is poor.Second, the molecular weight of backbone chain type polyfluorene
Relatively low, and be difficult to be improved by synthetic technology, therefore filming performance is poor.3rd, during the polymerization of backbone chain type polyfluorene, used
Metallic catalyst causes fluorenes nine to be oxidized to ketone sometimes, makes polyfluorene fluorescence spectrum red shift and broadens, and catalyst debris is likely to
Can enter in macromolecular chain.These defects being positioned on high polymer main chain are very difficult to remove, and ultimately result under the photoelectric properties of polyfluorene
Fall.
Summary of the invention
The problem existed for prior art, the present invention proposes a class carbazole-fluorene ethylene derivant, and this compounds
Typical synthetic route.
Compound involved by this patent, its chemical structural formula is:
Compound involved by this patent, its synthetic method is:
Step one, on 2 of fluorenes ring, introducing atomic iodine is as leaving group, obtains 2-iodine fluorenes；
Two hydrogen atom alkyl on gained 2-iodine fluorenes 9 in step one are replaced by step 2 with phase transfer catalysis process,
Obtain 2-iodo-9,9-dialkyl fluorene；
Step 3, introduces acetyl group with Friedel-crafts reaction on 7 of step 2 gained 2-iodo-9,9-dialkyl fluorene fluorenes ring
Group, obtains 2-iodo-9,9-dialkyl fluorene acetyl；
Step 4, under Hydro-Giene (Water Science)., potassium tert-butoxide and trans 1,2-cyclohexanediamine existence condition, by step 3 gained 2-
Iodo-9,9-dialkyl fluorene acetyl and carbazole coupling, obtain 2-carbazyl-9,9-dialkyl fluorene acetyl；
Step 5, with gained 2-carbazyl-9 in sodium borohydride reduction step 4, on 7,9-dialkyl fluorene acetyl fluorenes ring
Acetyl group, obtains intermediate product 2-carbazyl-9,9-dialkyl fluorene ethanol；
Step 6, in boiling toluene, makes 2-carbazyl-9 with p-methyl benzenesulfonic acid for catalyst, and 9-dialkyl fluorene ethanol takes off
Water, it is thus achieved that 2-carbazyl-9,9-dialkyl fluorene ethylene；
Step 7, on 2,7 of fluorenes ring, introducing atomic iodine are as leaving group, obtain 2,7-diiodo-fluorenes；
Step 7 gained 2, two hydrogen atom alkyl on 7-diiodo-fluorenes 9 are taken by step 8 with phase transfer catalysis process
In generation, obtain 2,7-bis-iodo-9,9-dialkyl fluorene；
Step 9, under Hydro-Giene (Water Science)., potassium tert-butoxide and trans 1,2-cyclohexanediamine existence condition, by step 8 gained 2,
7-bis-iodo-9,9-dialkyl fluorene and carbazole coupling, obtain 2-iodo-7-carbazyl-9,9-dialkyl fluorene；
Step 10, with Sonogashira coupling method by gained 2-iodo-9 in step 3,2,9-dialkyl fluorene acetyl fluorenes ring
On atomic iodine be changed into acetenyl, obtain 2-acetenyl-9,9-dialkyl fluorene acetyl；
Step 11, with sodium borohydride reduction step 10 gained 2-acetenyl-9, on 7,9-dialkyl fluorene acetyl fluorenes ring
Acetyl group, obtains intermediate product 2-acetenyl-9,9-dialkyl fluorene ethanol；
Step 12, with Sonogashira coupling method by step 11 gained 2-acetenyl-9,9-dialkyl fluorene ethanol with
Step 9 gained 2-iodo-7-carbazyl-9,9-dialkyl fluorene coupling, obtain 2-(2-acetenyl-7-carbazyl-9,9-dialkyl group
Fluorenes)-9,9-dialkyl fluorene ethanol；
Step 13, in boiling toluene, makes 2-(2-acetenyl-7-carbazyl-9,9-with p-methyl benzenesulfonic acid for catalyst
Dialkyl fluorene)-9,9-dialkyl fluorene ethanol dehydration, it is thus achieved that 2-(2-acetenyl-7-carbazyl-9,9-dialkyl fluorene)-9,9-bis-
Alkyl fluorene ethylene.
Compound involved by this patent, 2 of fluorenes are connected with σ key with the nitrogen-atoms in carbazole group, and are formed big
Conjugated structure.
Organic compound described in this patent, is characterized in that the number of fluorene group is 1-2.Those skilled in the art
Member, can utilize the synthetic route described in this patent according to actual needs, improves the number of fluorene group further.Work as existence
During multiple fluorene group, use Sonogashira method coupling between fluorene group, and between group, form three bond structures.Coupling catalyst
For zero valent palladium catalyst, promoter is Hydro-Giene (Water Science)..Reaction is carried out in the solution less than 50 DEG C.
Synthetic route described by this patent, is to select atomic iodine as the leaving group of Sonogashira coupling reaction.
Synthetic route described by this patent, is to form 2-iodo-fluorenes acetyl class formation as intermediate.
9 hydrogen atoms of fluorenes are all replaced by the organic compound described by this patent, steady to improve the chemistry of fluorene group
Qualitative, improve dissolubility and the processing characteristics of compound simultaneously.In this patent, preferred substituted monomer is bromination of n-butane, used
Substitution technique is phase transfer catalysis process, and this method has that conversion ratio is high, simple to operate, agents useful for same is cheap, particularly suitable
The advantages such as industrialized production.Used catalyst is tetrabutyl ammonium bromide, and reaction is carried out in 50% sodium hydrate aqueous solution.
Compound involved by this patent, is characterized in that end fluorenes forms fluorene ethylene structure, the wherein preparation method of double bond
Use secondary alcohol evaporation, it is characterized in that using fluorenes second Monomer of acyls as intermediate, with sodium borohydride, acetyl group is reduced to
Secondary alcohol, then in the toluene of boiling, dehydration forms fluorene ethylene structure.From the technical point of view, secondary alcohol dehydration is can be converse
Should, course of reaction also can generate by-product ether type monomer, for obtaining high conversion, it is necessary at any time, rapidly by reaction system
Moisture remove.This patent uses a kind of toluene distillation evaporation, method particularly includes: reaction is entered under toluene boiling temperature
OK, moisture is constantly taken out of by the toluene steamed, and makes chemical equilibrium move to the direction forming double bond rapidly.The method response speed
Hurry up, the response time is less than 1 hour；Productivity is high, and double bond production rate is 50%-85%；The toluene steamed can follow after simple dehydration
Ring uses, and i.e. protects environment, has saved again cost, therefore has good industrial applications prospect.
Compared with prior art, the invention have the advantages that: the organic compound described in this patent, its essence
It is a kind of imitative 9-VCz structure, and by the introducing of fluorene group, expands conjugation volume, make the fluorescence emission of material
There is red shift in spectrum, near ultraviolet band gradually goes to blue wave band, improves fluorescence quantum efficiency further simultaneously.According to this patent
Described in technology path, synthesis similar structures compound, to change physical and mechanical properties and the photoelectric properties of material, right
For those skilled in the art, it is feasible.The compound of this class formation all polymerization or with other vinyl list
After body combined polymerization, it is possible to form the multiple polymeric material with different photoelectric properties, molecular structure, molecular weight etc. of theory unlimited
Material, thus there is the highest theoretical research and practical value.
Accompanying drawing explanation
Fig. 1 is poly-9-VCz structure chart；
Fig. 2 is 2-carbazyl-9, the synthetic route of 9-dibutyl fluorene ethylene；
Fig. 3 is the synthetic route chart of 2-(2-acetenyl-7-carbazyl-9,9-dibutyl fluorenes)-9,9-dibutyl fluorene ethylene.
Detailed description of the invention
Compound involved by this patent, its chemical structural formula is:
Compound involved by this patent, its synthetic method is:
Step one, on 2 of fluorenes ring, introducing atomic iodine is as leaving group, obtains 2-iodine fluorenes；
Two hydrogen atom alkyl on gained 2-iodine fluorenes 9 in step one are replaced by step 2 with phase transfer catalysis process,
Obtain 2-iodo-9,9-dialkyl fluorene；
Step 3, introduces acetyl group with Friedel-crafts reaction on 7 of step 2 gained 2-iodo-9,9-dialkyl fluorene fluorenes ring
Group, obtains 2-iodo-9,9-dialkyl fluorene acetyl；
Step 4, under Hydro-Giene (Water Science)., potassium tert-butoxide and trans 1,2-cyclohexanediamine existence condition, by step 3 gained 2-
Iodo-9,9-dialkyl fluorene acetyl and carbazole coupling, obtain 2-carbazyl-9,9-dialkyl fluorene acetyl；
Step 5, with gained 2-carbazyl-9 in sodium borohydride reduction step 4, on 7,9-dialkyl fluorene acetyl fluorenes ring
Acetyl group, obtains intermediate product 2-carbazyl-9,9-dialkyl fluorene ethanol；
Step 6, in boiling toluene, makes 2-carbazyl-9 with p-methyl benzenesulfonic acid for catalyst, and 9-dialkyl fluorene ethanol takes off
Water, it is thus achieved that 2-carbazyl-9,9-dialkyl fluorene ethylene；
Step 7, on 2,7 of fluorenes ring, introducing atomic iodine are as leaving group, obtain 2,7-diiodo-fluorenes；
Step 7 gained 2, two hydrogen atom alkyl on 7-diiodo-fluorenes 9 are taken by step 8 with phase transfer catalysis process
In generation, obtain 2,7-bis-iodo-9,9-dialkyl fluorene；
Step 9, under Hydro-Giene (Water Science)., potassium tert-butoxide and trans 1,2-cyclohexanediamine existence condition, by step 8 gained 2,
7-bis-iodo-9,9-dialkyl fluorene and carbazole coupling, obtain 2-iodo-7-carbazyl-9,9-dialkyl fluorene；
Step 10, with Sonogashira coupling method by gained 2-iodo-9 in step 3,2,9-dialkyl fluorene acetyl fluorenes ring
On atomic iodine be changed into acetenyl, obtain 2-acetenyl-9,9-dialkyl fluorene acetyl；
Step 11, with sodium borohydride reduction step 10 gained 2-acetenyl-9, on 7,9-dialkyl fluorene acetyl fluorenes ring
Acetyl group, obtains intermediate product 2-acetenyl-9,9-dialkyl fluorene ethanol；
Step 12, with Sonogashira coupling method by step 11 gained 2-acetenyl-9,9-dialkyl fluorene ethanol with
Step 9 gained 2-iodo-7-carbazyl-9,9-dialkyl fluorene coupling, obtain 2-(2-acetenyl-7-carbazyl-9,9-dialkyl group
Fluorenes)-9,9-dialkyl fluorene ethanol；
Step 13, in boiling toluene, makes 2-(2-acetenyl-7-carbazyl-9,9-with p-methyl benzenesulfonic acid for catalyst
Dialkyl fluorene)-9,9-dialkyl fluorene ethanol dehydration, it is thus achieved that 2-(2-acetenyl-7-carbazyl-9,9-dialkyl fluorene)-9,9-bis-
Alkyl fluorene ethylene.
Embodiment 1:2-iodo-9, the synthesis of 9-dibutyl fluorenes
1.46g 2-iodine fluorenes, 2 milliliters of n-bromide butane, 0.5 milliliter of DMSO, 0.03g tetra-is added in 25 milliliters of round-bottomed flasks
Butylammonium bromide, 50%NaOH solution 2 milliliters.80 DEG C are reacted 6 hours.After reaction terminates, add 10 milliliters of water, 10 milliliters of oil
Ether, vibrate separatory, takes upper strata petroleum ether phase, and aqueous phase extracts once with 10 milliliters of petroleum ether again.With petroleum ether for flowing phase, use color
Spectrum post separates.Vacuum drying oven 50 DEG C drying, product is light green solid.Productivity 80%.1H NMR(ppm)(400MHz CDCl3):
7.65-7.24(m,7H).1.95-1.90(m,4H).1.10-1.04(m,4H).0.68-0.54(m,10H).
Embodiment 2:2-iodo-9, the synthesis of 9-dibutyl fluorenes acetyl
0.73g aluminum trichloride (anhydrous) adds in 20 milliliters of dichloromethane, and stirring, after ice bath cools down 10 minutes, is slowly dropped into
Acetic anhydride makes mixture bleach.After sufficiently cool, it is dividedly in some parts 1.01g 9,9-dibutyl fluorenes, reacts 12 hours.Mixture
Pour in 50 milliliters of frozen water, separatory, washs aqueous phases 2 times with 50 milliliters of dichloromethane, merges oil phase, be spin-dried for solvent, through column chromatography
Purification obtains 0.95g faint yellow solid.Productivity 85%.Eluant is petroleum ether: dichloromethane=5:1.1H NMR(ppm)
(400MHz CDCl3):7.96-7.94(d,2H).7.74-7.69(m.3H).7.51-7.49(d.1H).2.67(s.3H)
.2.04-1.92(m.4H).1.10-1.O4(m.4H).0.68-0.65(m.6H).0.57-0.51(m.4H).
Embodiment 3:2-carbazyl-9, the synthesis of 9-dibutyl fluorenes acetyl
4.46g is to iodine butyl fluorenes acetyl, 1.68g carbazole, 0.5g Hydro-Giene (Water Science)., 2.97g trans 1,2-cyclohexanediamine, 3.0g
Potassium tert-butoxide, 50 milliliters of dioxane are placed in 100 milliliters of there-necked flasks, be warming up to 110 DEG C, react 12 hours under nitrogen protection.
Product is poured in 200 ml deionized water.Separatory, is spin-dried for.Pillar layer separation.Eluent petroleum ether: ethyl acetate=5:1.Produce
Rate 60%.1H NMR(ppm)(400MHz CDCl3):8.83-8.82(d.1H).8.24-8.23(d.1H).8.09-8.08
(m.1H).7.94-7.92(d.1H).7.79-7.78(t.1H).7.52-7.39(m.9H).2.75(s.3H).2.04-2.00
(m.4H).1.15-1.11(m.4H).0.75-0.70(m.10H).
Embodiment 4:2-carbazyl-9, the synthesis of 9-dibutyl fluorenes ethanol
4.85g 2-carbazyl-9,9-dibutyl fluorenes acetyl, 0.038g sodium borohydride add in 20 milliliters of dehydrated alcohol, room
The lower stirring of temperature 6 hours.Mixture is poured in 50 ml deionized water, extracts Organic substance with dichloromethane, and anhydrous magnesium sulfate is dried.
With petroleum ether: ethyl acetate=2:1 purifies for flowing phase, pillar layer separation.Productivity 90%.1H NMR(ppm)(400MHz,
CDCl3):8.19-8.17(d.2H).7.90-7.88(d.1H).7.75-7.74(d.1H).7.54-7.52(m.2H).7.46-
7.39(m.6H).7.32-7.29(m.2H).5.04-5.02(m.1H).2.05-1.98(m.4H).1.89-1.88(d.1H)
.1.59-1.55(m.3H).1.15-1.07(m.4H).0.75-0.65(m.10H).
Embodiment 5:2-carbazyl-9, the synthesis of 9-dibutyl fluorene ethylene
Equipped with still head, condensing tube 250 milliliters of there-necked flasks in add 100 milliliters of toluene and 4.87g 2-carbazole
Base-9,9-dibutyl fluorenes ethanol, oil bath adds the boiling of thermic toluene, starts timing after toluene condenses in distilling head.Keep first
Benzene steams 10 minutes continuously, is subsequently adding 20 milligrams of p-methyl benzenesulfonic acid.After half an hour, reactant mixture is poured in frozen water, point
Liquid, with 50 milliliters of toluene washing aqueous phases once.It is spin-dried for organic facies, with petroleum ether: dichloromethane=2:1 is for flowing phase, column chromatography
Separating-purifying.Productivity 50%.1H NMR(ppm)(400MHz,CDCl3):8.18-8.16(d.2H).7.89-7.87(d.2H)
.7.73-7.71(d.1H).7.54-7.52(t.2H).7.47-7.40(m.6H).7.32-7.28(m.2H).6.88-6.80
(m.1H).5.87-5.83(d.1H).5.32-5.29(d.2H).2.03-1.99(m.4H).1.16-1.09(m.4H).0.75-
0.71(m.10H).
Embodiment 6:2-(2-methyl-3-butyne-2-alcohol)-9, the synthesis of 9-dibutyl fluorenes acetyl
50 milliliters of there-necked flasks add 2.23g 2-iodo-9,9-dibutyl fluorenes acetyl, 2 milliliters of 2-methyl-3-butynyl-2-
Alcohol, 25 milliliters of oxolanes, 5 milliliters of triethylamines.After argon deoxygenation, adding 0.12g tetra-triphenylphosphine palladium, 0.06g iodate is sub-
Copper.Under argon shield, 45 DEG C are reacted 6 hours.After reaction terminates, mixture is poured in beaker, adds 3g ammonium chloride, 20 milliliters of water
With 20 milliliters of dichloromethane, vibrate separatory, takes organic facies, is dried with anhydrous magnesium sulfate.With petroleum ether: ethyl acetate 2:1 is for stream
Dynamic phase, pillar layer separation purifies.Productivity 80%.1H NMR(ppm)(400MHz CDCl3):7.97-7.95(m.2H).7.74-
7.68(m.2H).7.44-7.43(d.2H).2.67(s.3H).2.07-1.93(m.4H).1.67(s.6H).1.11-1.02
(m.4H).0.67-0.63(m.6H).0.53-0.47(m.4H).
Embodiment 7:2-(2-methyl-3-butyne-2-alcohol)-9, the synthesis of 9-dibutyl-fluorenes ethanol
4.02g 2-(2-methyl-3-butyne-2-alcohol)-9,9-dibutyl-fluorenes acetyl, 0.038g sodium borohydride add 20 millis
Rise in dehydrated alcohol, stir 6 hours under room temperature.Mixture is poured in 50 ml deionized water, extracts Organic substance with dichloromethane,
Anhydrous magnesium sulfate is dried.With petroleum ether: ethyl acetate=2:1 purifies for flowing phase, pillar layer separation.Productivity 95%.1H NMR
(ppm)(400MHz CDCl3):7.62-7.59(m.2H).7.40-7.38(d.2H).7.34-7.26(d.2H).4.99-4.98
(d.2H).1.97-1.93(t.4H).1.66(s.6H).1.09-1.02(m.4H).0.68-0.62(m.6H).0.60-0.50
(m.4H).
Embodiment 8:2-acetenyl-9, the synthesis of 9-dibutyl-fluorenes ethanol
2.02g 2-(2-methyl-3-butyne-2-alcohol)-9,9-bis-is added in equipped with 50 milliliters of there-necked flasks of condensing tube
Butyl-fluorenes ethanol, 0.4g powdered potassium hydroxide and 25 milliliters of isopropanols, react 15 hours at 80 DEG C.Mixture pours 50 milliliters into
In deionized water, extracting Organic substance with dichloromethane, anhydrous magnesium sulfate is dried organic facies.With petroleum ether: ethyl acetate=5:1 is
Flowing phase, pillar layer separation purifies.Productivity 60%.1H NMR(ppm)(400MHz CDCl3):7.66-7.63(t.2H).7.48-
7.46(d.2H).7.35-7.33(t.2H).5.01-4.96(m.1H).3.14(s.1H).1.66(s.6H).1.97-1.93
(m.4H).1.11-1.02(m.4H).0.68-0.50(m.10H).
Embodiment 9:2, the synthesis of 7-bis-iodo-9,9-dibutyl fluorenes
Addition 2.09g 2,7-diiodo-fluorenes in 25 milliliters of round-bottomed flasks, 2 milliliters of n-bromide butane, 0.5 milliliter of DMSO,
0.03g tetrabutyl ammonium bromide, 50%NaOH solution 2 milliliters.80 DEG C are reacted 6 hours.After reaction terminates, add 10 milliliters of water, 10
Milliliter petroleum ether, vibrate separatory, takes upper strata petroleum ether phase, and aqueous phase extracts once with 10 milliliters of petroleum ether again.With petroleum ether for stream
Dynamic phase, separates by chromatographic column.Vacuum drying oven 50 DEG C drying, product is light yellow solid.Productivity 76%.1H NMR(ppm)
(400MHz CDCl3):7.66-7.25(m.6H).1.91-1.87(m.4H).1.11-1.05(m.4H).0.70-0.66
(t.6H).0.57-0.53(m.4H).
The synthesis of embodiment 10:2-iodo-7-carbazyl-9,9-dibutyl fluorenes
50 milliliters of there-necked flasks add 2.65g 2,7-bis-iodo-9,9-dibutyl fluorenes, 0.84g carbazole, 20mg iodate Asia
Copper, 0.3g trans 1,2-cyclohexanediamine, 1.5g potassium tert-butoxide and 25 milliliters of dioxane.Being warming up to 110 DEG C, nitrogen protection is lower anti-
Answer 12 hours.Mixture is poured into water, and adds 50 milliliters of dichloromethane, separatory.Aqueous phase washed once with 50 milliliters of dichloromethane.
Merge organic facies.Anhydrous magnesium sulfate is dried.With petroleum ether: dichloromethane=5:1 is for flowing phase, pillar layer separation.Productivity 52%
。1H NMR(ppm)(400MHz CDCl3):8.17-8.16(d.2H).7.88-7.87(d.1H).7.72-7.71(d.2H)
.7.55-7.51(m.3H).7.45-7.37(m.4H).7.31-7.30(d.2H).2.02-1.93(m.4H).1.17-1.11
(m.4H).0.75-0.73(d.10H).
The synthesis 50 of embodiment 11:2-(2-acetenyl-7-carbazyl-9,9-dibutyl fluorenes)-9,9-dibutyl fluorenes ethanol
Milliliter there-necked flask adds iodo-7 carbazyl-9 of 2.85g 2-, 9-dibutyl fluorenes, 2,1.74g 2-acetenyl-9,9-dibutyl-
Fluorenes ethanol, 25 milliliters of oxolanes, 5 milliliters of triethylamines.After argon deoxygenation, add 0.12g tetra-triphenylphosphine palladium, 0.06g iodine
Change cuprous.Under argon shield, 45 DEG C are reacted 6 hours.After reaction terminates, mixture is poured in beaker, adds 3g ammonium chloride, 20 millis
Rising water and 20 milliliters of dichloromethane, vibrate separatory, takes organic facies, is dried with anhydrous magnesium sulfate.With petroleum ether: ethyl acetate 5:1
For flowing phase, pillar layer separation purifies.Productivity 72%.1H NMR(ppm)(400MHz CDCl3):8.19-8.17(d.2H)
.7.92-7.90(d.1H).7.78-7.76(d.1H).7.70-7.55(m.8H).7.47-7.42(m.4H).7.37-7.29
(m.4H).5.02-4.99(m.1H).2.06-1.98(m.8H).1.88-1.87(d.1H).1.57-1.55(m.3H).1.17-
1.06(m.8H).0.76-0.56(m.20H).
The synthesis of embodiment 12:2-(2-acetenyl-7-carbazyl-9,9-dibutyl fluorenes)-9,9-dibutyl fluorene ethylene exists
Equipped with still head, condensing tube 250 milliliters of there-necked flasks in add 100 milliliters of toluene and 3.94g 2-(2-acetenyl-7-carbazole
Base-9,9-dibutyl fluorenes)-9,9-dibutyl fluorenes ethanol, oil bath adds the boiling of thermic toluene, opens after toluene condenses in distilling head
Beginning timing.Keep toluene to steam continuously 10 minutes, be subsequently adding 20 milligrams of p-methyl benzenesulfonic acid.After half an hour, reactant mixture is fallen
Enter in frozen water, separatory, with 50 milliliters of toluene washing aqueous phases once.It is spin-dried for organic facies, with petroleum ether: dichloromethane=5:1 is for stream
Dynamic phase, pillar layer separation purifies.Productivity 77%.1H NMR(ppm)(400MHz CDCl3):8.19-8.17(d.2H).7.92-
7.90(d.1H).7.78-7.76(d.1H).7.69-7.55(m.8H).7.47-7.38(m.6H).7.33-7.29(m.2H)
.6.85-6.78(m.1H).5.85-5.84(d.1H).5.30-5.27(d.1H).2.06-1.98(m.8H).1.17-1.06
(m.8H).0.76-0.59(m.20H).m/z 770.46.Found 770.47。
Claims (9)
1. a class carbazole fluorene ethylene derivant, it is characterised in that its molecular structure is:
A class carbazole fluorene ethylene derivant the most according to claim 1, it is characterised in that its synthetic method is:
Step one, on 2 of fluorenes ring, introducing atomic iodine is as leaving group, obtains 2-iodine fluorenes；
Two hydrogen atom alkyl on gained 2-iodine fluorenes 9 in step one are replaced with phase transfer catalysis process, obtain by step 2
2-iodo-9,9-dialkyl fluorene；
Step 3, introduces acetyl group with Friedel-crafts reaction on 7 of step 2 gained 2-iodo-9,9-dialkyl fluorene fluorenes ring,
To 2-iodo-9,9-dialkyl fluorene acetyl；
Step 4, under Hydro-Giene (Water Science)., potassium tert-butoxide and trans 1,2-cyclohexanediamine existence condition, by iodo-for step 3 gained 2-
9,9-dialkyl fluorene acetyl and carbazole coupling, obtain 2-carbazyl-9,9-dialkyl fluorene acetyl；
Step 5, with gained 2-carbazyl-9 in sodium borohydride reduction step 4, the acetyl on 7,9-dialkyl fluorene acetyl fluorenes ring
Base, obtains intermediate product 2-carbazyl-9,9-dialkyl fluorene ethanol；
Step 6, in boiling toluene, makes 2-carbazyl-9 with p-methyl benzenesulfonic acid for catalyst, 9-dialkyl fluorene ethanol dehydration,
Obtain 2-carbazyl-9,9-dialkyl fluorene ethylene；
Step 7, on 2,7 of fluorenes ring, introducing atomic iodine are as leaving group, obtain 2,7-diiodo-fluorenes；
Step 8, replaces step 7 gained 2, the alkyl of two hydrogen atoms on 7-diiodo-fluorenes 9 with phase transfer catalysis process,
To 2,7-bis-iodo-9,9-dialkyl fluorene；
Step 9, under Hydro-Giene (Water Science)., potassium tert-butoxide and trans 1,2-cyclohexanediamine existence condition, by step 8 gained 2,7-bis-
Iodo-9,9-dialkyl fluorene and carbazole coupling, obtain 2-iodo-7-carbazyl-9,9-dialkyl fluorene；
Step 10, with Sonogashira coupling method by gained 2-iodo-9 in step 3, on 2,9-dialkyl fluorene acetyl fluorenes ring
Atomic iodine is changed into acetenyl, obtains 2-acetenyl-9,9-dialkyl fluorene acetyl；
Step 11, with sodium borohydride reduction step 10 gained 2-acetenyl-9, the acetyl on 7,9-dialkyl fluorene acetyl fluorenes ring
Base, obtains intermediate product 2-acetenyl-9,9-dialkyl fluorene ethanol；
Step 12, with Sonogashira coupling method by step 11 gained 2-acetenyl-9,9-dialkyl fluorene ethanol and step
Nine gained 2-iodo-7-carbazyl-9,9-dialkyl fluorene coupling, obtain 2-(2-acetenyl-7-carbazyl-9,9-dialkyl fluorene)-
9,9-dialkyl fluorene ethanol；
Step 13, in boiling toluene, makes 2-(2-acetenyl-7-carbazyl-9,9-dioxane with p-methyl benzenesulfonic acid for catalyst
Base fluorenes)-9,9-dialkyl fluorene ethanol dehydration, it is thus achieved that 2-(2-acetenyl-7-carbazyl-9,9-dialkyl fluorene)-9,9-dialkyl group
Fluorene ethylene.
A class carbazole fluorene ethylene derivant the most according to claim 1, it is characterised in that 2 of fluorenes and carbazole group
In nitrogen-atoms be connected with σ key, and form big conjugated structure.
A class carbazole fluorene ethylene derivant the most according to claim 2, it is characterised in that select atomic iodine conduct
The leaving group of Sonogashira coupling reaction；Coupling catalyst is zero valent palladium catalyst, and promoter is Hydro-Giene (Water Science)., instead
Should carry out in the solution less than 50 DEG C.
A class carbazole fluorene ethylene derivant the most according to claim 2, it is characterised in that it is iodo-that course of reaction forms 2-
Fluorenes acetyl class formation is as intermediate.
A class carbazole fluorene ethylene derivant the most according to claim 2, it is characterised in that to fluorenes 9 in course of reaction
Hydrogen atom is replaced, and to improve the chemical stability of fluorene group, improves dissolubility and the processing characteristics of compound simultaneously.
A class carbazole fluorene ethylene derivant the most according to claim 2, it is characterised in that preferably substituted monomer is bromine
For normal butane, substitution technique used is phase transfer catalysis process；Used catalyst is tetrabutyl ammonium bromide, and reaction is in 50% hydroxide
Sodium water solution is carried out.
A class carbazole fluorene ethylene derivant the most according to claim 2, it is characterised in that end fluorenes forms fluorene ethylene knot
Structure, wherein the preparation method of double bond uses secondary alcohol evaporation, is specially and uses fluorenes second Monomer of acyls as intermediate, uses hydroboration
Acetyl group is reduced to secondary alcohol by sodium, and then in the toluene of boiling, dehydration forms fluorene ethylene structure.
A class carbazole fluorene ethylene derivant the most according to claim 2, it is characterised in that use toluene distillation dehydration
Method, is specially reaction and carries out under toluene boiling temperature, and moisture is constantly taken out of by the toluene steamed, and makes chemical equilibrium rapidly to shape
The direction becoming double bond is moved.
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