CN102079693B - Method for preparing polymerizable beta-diketone ligand - Google Patents
Method for preparing polymerizable beta-diketone ligand Download PDFInfo
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- CN102079693B CN102079693B CN200910154337.7A CN200910154337A CN102079693B CN 102079693 B CN102079693 B CN 102079693B CN 200910154337 A CN200910154337 A CN 200910154337A CN 102079693 B CN102079693 B CN 102079693B
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Abstract
The invention discloses a method for preparing a polymerizable beta-diketone ligand. The polymerizable beta-diketone ligand has a structural formula, wherein R1 and R2 are trifluoromethyl or C1-C10 alkyl. The preparation method comprises the following steps of: reacting 4-halomethyl styrene with an excessive amount of beta-diketone at 20 to 100 DEG C for 0.5 to 100h by taking polyethylene glycol, KOH and KI as catalysts, and purifying the product to obtain the polymerizable beta-diketone ligand. In the reaction, the excessive amount of beta-diketone serves as a solvent, and other solvents are not required to be added. The method ensures high yield and short time, and is simple and convenient.
Description
Technical field
The invention belongs to organic compound and organic electroluminescent field, be specifically related to a kind of preparation method of polymerisable beta-diketonate ligand.
Background technology
Organic electroluminescence device is as flat panel display of new generation, have that cut-in voltage is low, fast response time, active illuminating, the advantage such as visual angle is wide, radiationless, thermal adaptability is good and anti-seismic performance is good, therefore in full color demonstration field, have broad application prospects.Organic electroluminescence device can be divided into small molecules organic electroluminescence device and polymer organic electroluminescence device according to the difference of its material.In use, easily there is the problems such as thin layer crystallization, thereby affect device lifetime in small molecules organic electroluminescence device.The problem existing in order to solve small molecules organic electroluminescence device, best bet is the synthetic luminescence polymer of design.Because polymer organic electroluminescence device can be made by methods such as spin coating, spray ink Printings, technique is simple, cost is low, good mechanical property, makes it more and more receive people's concern simultaneously.
Beta-diketon is the organic ligand of the high specific absorbance of a class, the title complex that beta-diketon and osmium, iridium, platinum and rare earth form because of have excellent luminescent properties be always people's study hotspot (Nature, 2009,459,234-239).In order to obtain luminescence polymer, a kind of terms of settlement is to prepare electroluminescent coordination compound monomer by polymerisable beta-diketonate ligand and osmium, iridium, platinum or rare earth coordination, and then aggregates into required polymkeric substance.Yet seldom, and productive rate is not high for this type of polymerisable beta-diketonate ligand preparation method's report at present, and by product is many, and method is complicated.
Summary of the invention
The defect or the deficiency that for above-mentioned prior art, exist, the object of the invention is to, and the preparation method of easy, the practical polymerisable beta-diketonate ligand of a kind of method is provided.
In order to realize above-mentioned task, the present invention takes following technical solution:
A preparation method for polymerisable beta-diketonate ligand, described polymerisable beta-diketonate ligand structural formula is as follows:
R wherein
1, R
2for trifluoromethyl or C
1-10alkyl; It is characterized in that:
Concrete steps: separately do not add other solvent, under the effect of catalyzer, 4-halogeno-toluene ethene and excessive beta-diketon are heated to after 20-100 ℃, reaction 0.5-100h, product is purified again obtains polymerisable beta-diketonate ligand.
As preferably, described catalyzer is the mixture of polyoxyethylene glycol, KOH and KI.
As preferably, described 4-halogeno-toluene ethene is 4-1-chloro-4-methyl-benzene, 4-brooethyl vinylbenzene or 4-iodomethyl vinylbenzene.
As preferably, described beta-diketon structural formula is as follows:
R wherein
1, R
2for trifluoromethyl or C
1-10alkyl.
As preferably, the present invention makes solvent with excessive beta-diketon, does not separately add other solvent.
As preferably, the mol ratio of 4-halogeno-toluene ethene, beta-diketon, polyoxyethylene glycol, KOH and KI is 1: 1-100: 0-1: 0.1-10: 0-1.
As preferably, described purifying comprises the following steps: first reaction solution is poured into water, separates organic phase and be washed to neutrality, then use second alcohol and water (V
ethanol: V
water=1: mixed solvent washing 1).
Compared with prior art, the invention has the advantages that: the present invention makes solvent with excessive beta-diketonate ligand, the mixture as catalyst of polyoxyethylene glycol, KOH and KI reacts, and reaction yield is high, and the time is short, and method is easy.
Accompanying drawing explanation
Fig. 1 is the mass spectrum of the 4-vinyl benzene methyl methyl ethyl diketone of embodiment 1.
Embodiment
The present invention is described in further detail for the embodiment providing below in conjunction with accompanying drawing and contriver.
According to the preparation method of polymerisable beta-diketonate ligand of the present invention, contriver provides following examples, it should be noted that, these embodiment are mainly used in those skilled in the art's a further understanding of the present invention, the invention is not restricted to these embodiment.
Embodiment 1:
Reaction scheme is as follows:
In 100mL there-necked flask, add successively 40mL (0.39mol) methyl ethyl diketone, 1mL polyoxyethylene glycol-600,0.83g (0.005mol) KI, 4.61g (0.08mol) KOH, and constantly stir, be heated to after 50 ℃, more slowly drip the mixture of 8mL (about 0.05mol) 4-1-chloro-4-methyl-benzene and 8mL (0.08mol) methyl ethyl diketone, reaction 4h.After completion of the reaction reaction solution is poured in 150mL water, separated organic phase and be washed to neutrality, then use second alcohol and water (V
ethanol: V
water=1: mixed solvent 1) washs to obtain oily liquids product, productive rate 87%.
Products therefrom mass spectrum as shown in Figure 1.
Infrared spectra (KBr, cm
-1): 3006 (ph-H), 1701 (C=O), 1608,1407,1358 (CO-CH
3), 991 (C=C-H), 909 (C=C-H), 823 (ph-H).
Ultimate analysis: C
14h
16o
2calculated value: C, 77.75; H, 7.46; Measured value: C, 77.55; H, 7.11.
The compound that the above-mentioned reaction of above data acknowledgement obtains is 4-vinyl benzene methyl methyl ethyl diketone, and its structural formula is as follows:
Embodiment 2:
Reaction scheme is as follows:
Other are with examples of implementation 1, and beta-diketon is 2,2,6,6-tetramethyl--3, and 5-heptadione has been prepared polymerisable beta-diketonate ligand 2,2,6,6-tetramethyl--4-(4-vinyl benzene methyl)-3, and 5-heptadione, other and examples of implementation 1 are similar.Productive rate is 83%.
Embodiment 3:
Reaction scheme is as follows:
Other are with examples of implementation 1, and beta-diketon is 1,1,1,5,5,5-hexafluoro-2,4-diacetylmethane, 4-halogeno-toluene ethene is 4-brooethyl vinylbenzene, prepared polymerisable beta-diketonate ligand 3-(4-vinyl benzene methyl)-1,1,1,5,5,5-hexafluoro-2,4-diacetylmethane, other and examples of implementation 1 are similar.Productive rate is 89%.
Embodiment 4:
Reaction scheme is as follows:
Other are with examples of implementation 1, and beta-diketon is 3,5-heptadione, 4-halogeno-toluene ethene is 4-brooethyl vinylbenzene, and both mol ratios are 1: 5, has prepared polymerisable beta-diketonate ligand 4-(4-vinyl benzene methyl)-3,5-heptadione, other and examples of implementation 1 are similar.Productive rate is 86%.
Embodiment 5:
Other mol ratios with examples of implementation Isosorbide-5-Nitrae-1-chloro-4-methyl-benzene and methyl ethyl diketone are 1: 100, have prepared polymerisable beta-diketonate ligand 4-vinyl benzene methyl methyl ethyl diketone, and other and examples of implementation 1 are similar.Productive rate is 91%.
Embodiment 6:
Other are with examples of implementation 1, and the reaction times is 40h, have prepared polymerisable beta-diketonate ligand 4-vinyl benzene methyl methyl ethyl diketone, and other and examples of implementation 1 are similar.Productive rate is 89%.
Embodiment 7:
Other are with examples of implementation 4, and temperature of reaction is 35 ℃, have prepared polymerisable beta-diketonate ligand 4-(4-vinyl benzene methyl)-3,5-heptadione, and other and examples of implementation 4 are similar.Productive rate is 68%.
Embodiment 8:
Other do not add KI with examples of implementation 4, have prepared polymerisable beta-diketonate ligand 4-(4-vinyl benzene methyl)-3,5-heptadione, and other and examples of implementation 4 are similar.Productive rate is 75%.
Embodiment 9:
Other do not add polyoxyethylene glycol-600 with examples of implementation 4, have prepared polymerisable beta-diketonate ligand 4-(4-vinyl benzene methyl)-3,5-heptadione, and other and examples of implementation 4 are similar.Productive rate is 65%.
Claims (4)
1. a preparation method for polymerisable beta-diketonate ligand, described polymerisable beta-diketonate ligand structural formula is as follows:
R wherein
1, R
2for trifluoromethyl or C
1-10alkyl;
It is characterized in that: under the effect of catalyzer, 4-halogeno-toluene ethene and excessive beta-diketon are heated to after 20-100 ℃, reaction 0.5-100h, product is purified again obtains polymerisable beta-diketonate ligand;
Described catalyzer is the mixture of polyoxyethylene glycol, KOH and KI;
With excessive beta-diketon, make solvent, separately do not add other solvent.
2. the preparation method of polymerisable beta-diketonate ligand as claimed in claim 1, is characterized in that, described 4-halogeno-toluene ethene is 4-1-chloro-4-methyl-benzene, 4-brooethyl vinylbenzene or 4-iodomethyl vinylbenzene.
3. the preparation method of polymerisable beta-diketonate ligand as claimed in claim 1, is characterized in that, described beta-diketon structural formula is as follows:
R wherein
1, R
2for trifluoromethyl or C
1-10alkyl.
4. the preparation method of polymerisable beta-diketonate ligand as claimed in claim 1, is characterized in that, described purifying comprises the following steps: first reaction solution is poured into water, separates organic phase and be washed to neutrality, then use second alcohol and water V
ethanol: V
waterthe mixed solvent washing of=1:1.
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Citations (1)
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|---|---|---|---|---|
| US20050145830A1 (en) * | 2003-06-26 | 2005-07-07 | Jsr Corporation | Phosphors and process for production thereof, luminescent compositions, and organic electroluminescent devices and processes for production thereof |
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| US20050145830A1 (en) * | 2003-06-26 | 2005-07-07 | Jsr Corporation | Phosphors and process for production thereof, luminescent compositions, and organic electroluminescent devices and processes for production thereof |
Non-Patent Citations (6)
| Title |
|---|
| "Living Radical Polymerization of Bipolar Transport Materials for Highly Efficient Light Emitting Diodes";Lan Deng et al.;《Chem. Mater.》;20051222;第18卷(第2期);第386-395页 * |
| Antiviral Activity of Some β-Diketones.4.Benzyl Diketones.In Vitro Activity against Both RNA and DNA Virues;G.D.Diana et al.;《Journal of Medicinal Chemistry》;19781231;第21卷(第9期);第889-894页 * |
| G.D.Diana et al..Antiviral Activity of Some β-Diketones.4.Benzyl Diketones.In Vitro Activity against Both RNA and DNA Virues.《Journal of Medicinal Chemistry》.1978,第21卷(第9期),第889-894页. |
| Lan Deng et al.."Living Radical Polymerization of Bipolar Transport Materials for Highly Efficient Light Emitting Diodes".《Chem. Mater.》.2005,第18卷(第2期),Page 386-395和supporting information s11. |
| 以四碳不饱和酸为原料成对电合成1,2-二醇类化合物;顾登平等;《精细化工》;20010430;第18卷(第4期);第208-211页 * |
| 顾登平等.以四碳不饱和酸为原料成对电合成1 2-二醇类化合物.《精细化工》.2001 |
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