CN100378084C - 2,5-diaryl substituting group-1,3,4-oxidazole derivative, its synthesis and use - Google Patents

2,5-diaryl substituting group-1,3,4-oxidazole derivative, its synthesis and use Download PDF

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CN100378084C
CN100378084C CNB200510041333XA CN200510041333A CN100378084C CN 100378084 C CN100378084 C CN 100378084C CN B200510041333X A CNB200510041333X A CN B200510041333XA CN 200510041333 A CN200510041333 A CN 200510041333A CN 100378084 C CN100378084 C CN 100378084C
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diaryl
oxadiazole
oxidazole
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CN1746163A (en
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徐洪耀
李村
光善仪
沈娟
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Anhui University
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Abstract

The present invention relates to a 2, 5-diaryl substituting group-1, 3, 4-oxidazole derivative, a synthetic method and application thereof. In the derivative, 1, 3, 4-oxidazole is connected with a 2, 5-diaryl substituting group. The chemical structural formula of the derivative is disclosed in the specification. In the formula, R stands for a saturated organic alkane group, and R' stands for an unsaturated aromatic hydrocarbon, alkyne or olefin group. The preparation method of the derivative comprises the following steps: bromo arylhalogen which contains 1, 3, 4-oxidazole structural units is synthesized by a bishydrazide cyclization method; through the catalyzing coupled action of Sonogashira palladium, the bromo arylhalogen reacts with different single substituting acetylene. Through the present invention, three kinds of novel 2, 5-diaryl substituting-1, 3, 4-oxidazole derivatives are synthesized. The thermal stability of the synthesized derivative is higher than that of PBD, and the yield of the synthetic method is high. The present invention relates to the synthesis of the novel derivative and relates to application of the derivative in the electron transport material field, the organic electroluminescent field, etc.

Description

2,5-diaryl substituting group-1,3,4-oxadiazole derivative and synthetic method thereof, purposes
Technical field
The present invention relates to chemosynthesis, specifically is a kind of novel 2,5-diaryl substituting group-1,3,4-oxadiazole derivative and synthetic method thereof, purposes.
Background technology
Since nineteen ninety Burroughes etc. had reported first polymer electroluminescent device, the research of organic/polymer electroluminescence had obtained significant progress, and the development of carrier transmission material efficiently also more and more is subject to people's attention.Present situation with regard to carrier transmission material research at present, the development of hole mobile material obviously is ahead of the research of electron transport material, and the development of electron transport material efficiently is considered to further improve the key of organic electroluminescence device performance, so the research of electron transport material has very important in theory and using value.2,5-diaryl substituting group-1,3,4-oxadiazole analog derivative are to use an electron-like transport material very widely, and the oxadiazole group in its structure has outstanding electrophilic performance, and is stable especially to oxygen and heat, and higher fluorescence quantum efficiency is arranged.
Figure C20051004133300041
2,5-diaryl substituting group-1,3, one of representative of 4-oxadiazole analog derivative is exactly the PBD (m.p.134 ℃) that has been widely used.But because small molecule material in use generally is prone to recrystallization phenomenon, and then have a strong impact on the luminous efficiency and the life-span of device, therefore how improving the film-forming properties of small molecule material and the thermostability of film is the emphasis of present small molecules electron transport material research.
Summary of the invention
The objective of the invention is small molecules electron transport material, for this analog derivative application in fields such as organic electroluminescence devices provides a kind of basic raw materials derivative for synthesizing new.In order to improve the thermostability of small molecule material, the present invention by increasing PBD rigidity and introduce hydrogen bond improve its thermostability synthesized three kinds with 2 of PBD similar, 5-diaryl substituting group-1,3,4-oxadiazole small molecules derivative.Concrete synthetic route is as follows:
Figure C20051004133300051
1,3,4-oxadiazole analog derivative synthetic, often adopting with the hydrazides is the synthetic route of intermediate product.At first, ester is changed into corresponding hydrazides, form bishydrazide with the acyl chlorides condensation then, the cyclization De that dewaters under the cyclizing agent effect then is Dao the oxadiazole derivative.The used raw material of this method is cheap and easy to get, and experimental implementation is simple, and productive rate is high and easily purify.The present invention just adopts this method to obtain the aryl bromide of Han oxadiazole group.Use (PPh3) 2PdCl2 as catalyzer then, by the effect of Sonogashira palladium catalytic coupling and different single replace alkyne reactions synthesized three kinds new 2,5-two replaces-1,3,4-oxadiazole micromolecular derivative.
Dewatering cyclization De oxadiazole ring by bishydrazide in this step, POCl 3Usually be cyclizing agent be again solvent, but this method generally all can use DMF instead as solvent with the generation of tarry matters, effectively avoided the generation of this phenomenon, productive rate brings up to 81% by original 70%.
In linked reaction, with (PPh 3) 2PdCl 2As catalyzer, under oxygen free condition, carry out Sonogshina palladium catalyzed coupling reaction.Because the divalence palladium is more stable in air, be convenient to store and operation, the catalytic activity of this class catalyzer is also than higher in addition.Adopt fragrant bromine as reactant, replace the very expensive fragrant iodine of price, will be reflected under the reflux state and carry out, obtain the product of high yield equally.
Because the synthetic aryl bromide is bad as solvabilities such as diethylamine, triethylamines in organic bases commonly used, productive rate is reduced.In order to improve productive rate, use THF as solvent, Et 3N can obtain higher productive rate (about 90%) as acid binding agent.
Above-mentioned synthetic obtain 2,5-diaryl substituting group-1,3,4-oxadiazole derivative is characterized in that in the derivative 1,3, the 4-oxadiazole is connected with 2, the 5-diaryl substituting group, chemical structural formula is:
R is saturated organic alkane group in the formula, and R ' is undersaturated aromatic hydrocarbons, alkynes or olefin group.
In the chemical structural formula 1,3, the 2-position of 4-oxadiazole is connected with replaced acetylene base phenyl, and the 5-position is connected with tert-butyl-phenyl.
The synthetic derivative has following several:
Derivative [1]
Figure C20051004133300062
Derivative [2]
Figure C20051004133300063
Derivative [3]
Figure C20051004133300064
The present invention has carried out ultimate analysis to the synthetic derivative, infrared spectroscopy, 1The sign of H nuclear magnetic resonance spectrometry.Three kinds of derivative thermal stabilities of the present invention all are higher than PBD, may be applied to fields such as organic electroluminescence device as electron transport material.
. the related data of table 1 synthesis of derivatives
Derivative Yield (%) Fusing point (℃) Ultimate analysis (%) experimental value (theoretical value)
[1] [2] [3] 91％ 92％ 87％ 150 161 194 C76.64(76.00)，H6.71(6.77)，N7.77(7.81) C82.51(82.28)，H5.86(5.88)，N7.40.(7.37) C75.88(75.49)，H6.06(6.08)，N 8.43(8.37)
Embodiment
Embodiment 1
To synthesizing of tertiary butyl substituted benzoyl hydrazides (compd A)
2g (10.4mmol) p-tert-butyl benzoic acid methyl esters is dissolved in the dehydrated alcohol of 10mL heat, dropwise adds hydrazine hydrate 2mL (34mmol) then under the agitation condition, drip off post-heating back flow reaction 24h.After reaction finishes reaction solution left standstill and be cooled to room temperature, add an amount of distilled water again in solution, the adularescent solid occurs at once, after having treated that a large amount of solids are separated out, suction filtration, the hydrazine hydrate that the water flush away is unnecessary, vacuum-drying then, getting 1.66g white plates solid is compd A.Productive rate 83%.
IR (KBr, v/cm -1): 3500～3100 (N-H); 3055 (Ar-H); 2960,2870 (CH 3); 1628 (C=O); 1563 (C=C); 1536 (N-H out-of-plane bendings); 857 (Ar-H para-orientation).
1H-NMR(300MHz，DMSO-d 6)(δ/ppm)：1.31(s，9H，C(CH 3) 3)；4.49(s，2H，NH 2)；7.45(d，2H，J＝8.3Hz，Ar-H)；7.75(d，2H，J＝8.3Hz，Ar-H)，9.69(s，1H，NH)。
Embodiment 2
Synthesizing of parabromobenzoyl chloride (compd B)
Add 1g (5.6mmol) parabromobenzoic acid in the 100mL round-bottomed flask, 1ml (13mmol) SOCl 2With the new dry toluene that steams of 20mL, reflux 5 hours, excessive SOCl is removed in underpressure distillation then 2And toluene solvant, obtaining yellowish needle-like solid after the cooling is compd B, parabromobenzoyl chloride.
Embodiment 3
N-is synthetic to benzoyl bromide-N-(to the tert.-butylbenzene formyl radical) hydrazine (Compound C)
Adding the anhydrous THF of 20mL in the bottle that parabromobenzoyl chloride (compd B) is housed dissolves it fully, under the condition of ice bath, the anhydrous THF of 10mL and the 1mL pyridine solution that will contain 1.08g (5.6mmol) hydrazides (compd A) dropwise add in the above-mentioned solution, drip off the back and under condition of ice bath, continue reaction 3 hours, reaction solution is poured in the 150mL frozen water then, the white powder precipitation appears, suction filtration obtains the white solid powder, use ethyl alcohol recrystallization, getting 1.4g white powder crystal is Compound C, productive rate 75%.
IR (KBr, v/cm -1): 3409,3283 (N-H); 3062,3026 (Ar-H); 2960,2867 (CH 3); 1677 (Br-Ar-C=O); 1642 ((CH 3) 3C-Ar-C=O); 1590 (C=C); 1544,1518 (N-H out-of-plane bendings); 847 (Ar-H para-orientation).
1H-NMR(300MHz，DMSO-d 6)(δ/ppm)：1.31(s，9H，C(CH 3) 3)；7.54(d，2H，J＝8.4Hz，Ar-H)；7.75(d，2H，J＝8.5Hz，Ar-H)；7.84～7.88(4H，Ar-H)；10.47(s，1H，NH)；10.60(s，1H，NH)。
Embodiment 4
2-is to bromo phenyl-5-(to tert-butyl-phenyl)-1,3,4-oxadiazole (Compound D) synthetic
With 1g (2.67mmol) Compound C, 20mlDMF and 10mL new system POCl 3Place the 50mL round-bottomed flask, at N 2Protection refluxed 16 hours down, and reaction is carefully poured reaction solution in the 50ml distilled water (under the condition of ice bath) after finishing, and uses 0.5mol/dm then -3NaOH solution removes the unnecessary POCl that neutralizes 3, then suction filtration obtains gray solid, uses ethanol/water=3: 1 (volume ratio) recrystallized product then, and getting 0.95g white powder crystal is Compound D, productive rate 73%.
IR (KBr, v/cm -1): 3085,3065 (Ar-H); 2960,2867 (CH 3); 1608 (C=C); 965 (C-O-C cyclic ethers); 836 (Ar-H para-orientation).
1H-NMR(300MHz，CDCl 3)(δ/ppm)：1.37(s，9H，C(CH 3) 3)；7.54(d，2H，J＝8.6Hz，Ar-H)；7.67(d，2H，J＝8.6Hz，Ar-H)；8.00(d，2H，J＝8.6Hz，Ar-H)；8.04(d，2H，J＝8.6Hz，Ar-H)。
Embodiment 5
2-[4-(3-methyl-3-hydroxyl-butynyl) phenyl]-5-(to tertiary butyl base)-1,3, the 4-oxadiazole } (derivative [1]) synthetic
Get 0.357g (1mmol) Compound D, 2.24mg Pd (OAc) 2(0.01mmol), 10.5mg (0.04mol) PPh 3, CuI 2mg (0.01mmol) places the 50mL three-necked bottle, uses biexhaust pipe extraction gas three times, makes reaction flask be in N 2Atmosphere, with 2-methyl-3-butyne-2-alcohol of microsyringe injection 3mmol, 20mL newly steams THF then, and 5mL newly steams triethylamine, stirring and refluxing reaction 8h.Reaction finishes back elimination amine salt, steams THF, and (use sherwood oil: the eluent of ethyl acetate=1: 1) product being purified, to obtain the off-white powder crystal be derivative [1], productive rate 91% to use column chromatography then.
IR (KBr, v/cm -1): 3350 (OH); 3064 (Ar-H); 2970,2869 (CH 3); 2225 (RC ≡ CR); 1611 (C=C); 962 (C-O-C cyclic ethers); 842 (Ar-H para-orientation).
1H-NMR(300MHz，CDCl 3)(δ/ppm)：1.37(s，9H，C(CH 3) 3)；1.65(s，6H，C(CH 3) 2)；1.94(s，1H，OH)；7.54～7.57(4H，a-H and b-H)；8.04～8.09(4H，c-Hand d-H)。
Embodiment 6
Synthesizing of [2-(4-phenylacetylene base phenyl)-5-(to tert-butyl-phenyl)-1,3,4-oxadiazole] (derivative [2])
Get 0.357g (1mmol) Compound D, 2.24mg Pd (OAc) 2(0.01mmol), 10.5mg (0.04mol) PPh 3, CuI 2mg (0.01mmol) places the 50mL three-necked bottle, uses biexhaust pipe extraction gas three times, makes reaction flask be in N 2Atmosphere, with the phenylacetylene of microsyringe injection 3mmol, 20mL newly steams THF then, and 5mL newly steams triethylamine, stirring and refluxing reaction 8h.Reaction finishes back elimination amine salt, steams THF, and (use sherwood oil: the eluent of ethyl acetate=1: 1) product being purified, to obtain the pale yellow powder crystal be derivative [2], productive rate 92% to use column chromatography then.
IR (KBr, v/cm -1): 3054 (Ar-H); 2960,2853 (CH 3); 2213 (RC ≡ CR); 1612 (C=C); 962 (C-O-C cyclic ethers); 839 (Ar-H para-orientation).
1H-NMR(300MHz，CDCl 3)(δ/ppm)：1.38(s，9H，C(CH 3) 3)；7.37～7.39(3H，f-H and g-H)；7.54～7.59(4H，a-H and b-H)；7.68(d，2H，J＝8.3Hz，e-H)；8.07(d，2H，J＝8.4Hz，c-H)；8.13(d，2H，J＝8.4Hz，d-H)。
Embodiment 7
2-[4-(3-hydroxypropyn base) phenyl]-5-(to tert-butyl-phenyl)-1,3, the 4-oxadiazole } (derivative [3]) synthetic
Get 0.357g (1mmol) Compound D, 2.24mg Pd (OAc) 2(0.01mmol), 10.5mg (0.04mol) PPh 3, CuI 2mg (0.01mmol) places the 50mL three-necked bottle, uses biexhaust pipe extraction gas three times, makes reaction flask be in N 2Atmosphere, with the propargyl alcohol of microsyringe injection 3mmol, 20mL newly steams THF then, and 5mL newly steams triethylamine, stirring and refluxing reaction 8h.Reaction finishes back elimination amine salt, steams THF, and (use sherwood oil: the eluent of ethyl acetate=1: 1) product being purified, to obtain the yellow powder crystal be derivative [3], productive rate 87% to use column chromatography then.
IR (KBr, v/cm -1): 3290 (OH); 3065,3050 (Ar-H); 2960,2871 (CH 3); 2930 (CH 2-); 1614 (C=C); 976 (C-O-C cyclic ethers); 847 (Ar-H para-orientation).
1H-NMR(300MHz，CDCl 3)(δ/ppm)：1.37(s，9H，C(CH 3) 3)；4.54(s，2H，CH 2)；7.55(d，2H，J＝8.6Hz，a-H)；7.58(d，2H，J＝8.6Hz，b-H)；8.06(d，2H，J＝8.5Hz，c-H)；8.09(d，2H，J＝8.5Hz，d-H)。

Claims (5)

1.2,5-diaryl substituting group-1,3,4-oxadiazole derivative is characterized in that derivative is following three kinds:
Derivative [1]
Figure C2005100413330002C1
Derivative [2]
Figure C2005100413330002C2
Derivative [3]
2. the synthetic method of derivative according to claim 1, it is characterized in that having synthesized and contain 1 with cyclization of 1,2-diaroylhydrazine, 3, the aryl bromide of 4-oxadiazole structural unit, synthesized 2,5-diaryl substituting group-1,3 by the effect of Sonogashira palladium catalytic coupling with different alkynes reactions then, 4-oxadiazole derivative, reaction scheme is as follows:
Figure C2005100413330002C4
3. the synthetic method of derivative according to claim 2 is characterized in that in this step, using DMF as solvent, POCl by bishydrazide dehydration cyclization De oxadiazole ring 3As cyclizing agent, under refluxad be dehydrated into ring; In linked reaction, use (PPh 3) 2PdCl 2As catalyzer, under oxygen free condition, carry out Sonogshina palladium catalyzed coupling reaction, and use aryl bromide as reactant, THF is as solvent Et 3N under refluxad reacts as acid binding agent.
4. the synthetic method of derivative according to claim 3 is characterized in that being dewatered cyclization De oxadiazole ring by bishydrazide in this step, and every 1g bishydrazide uses 10ml POCl 3, add 20ml DMF simultaneously as solvent; In the linked reaction, the ratio that wherein replaces alkynes and the amount of substance of aryl bromide is 3: 1.
5. the purposes of derivative according to claim 1 is characterized in that as electron transport material, in the use of organic electroluminescence device.
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CN100465168C (en) * 2006-09-15 2009-03-04 华东理工大学 Oxdiazole derivative and application thereof in electroluminescent material
US8486544B2 (en) 2009-08-28 2013-07-16 Industrial Technology Research Institute Quinoxaline derivatives and organic light-emitting diodes comprising the same
TWI402259B (en) 2009-08-28 2013-07-21 Ind Tech Res Inst Quinoxaline derivatives and organic light-emitting diodes comprising the same
CN106245053B (en) * 2016-08-26 2018-06-22 华南理工大学 By the method for -2 (3H) -one derivative of carbon dioxide, aryl hydrazine and paraformaldehyde electro synthesis 1,3,4- oxadiazoles
CN113072545B (en) * 2021-04-15 2022-08-26 天津孚信阳光科技有限公司 Compound with photochromic and fluorescent properties, and synthetic method and application thereof

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WO2003048280A1 (en) * 2001-11-30 2003-06-12 Uniroyal Chemical Company, Inc. 1,3,4-oxadiazole additives for lubricants
WO2004091502A2 (en) * 2003-04-11 2004-10-28 Ptc Therapeutics, Inc. 1,2,4-oxadiazole benzoic acid compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003048280A1 (en) * 2001-11-30 2003-06-12 Uniroyal Chemical Company, Inc. 1,3,4-oxadiazole additives for lubricants
WO2004091502A2 (en) * 2003-04-11 2004-10-28 Ptc Therapeutics, Inc. 1,2,4-oxadiazole benzoic acid compounds

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