CN104030974A - Aryl-substituted terpyridyl compounds, and preparation method and application thereof - Google Patents

Aryl-substituted terpyridyl compounds, and preparation method and application thereof Download PDF

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CN104030974A
CN104030974A CN201410287370.8A CN201410287370A CN104030974A CN 104030974 A CN104030974 A CN 104030974A CN 201410287370 A CN201410287370 A CN 201410287370A CN 104030974 A CN104030974 A CN 104030974A
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terpyridyl
aryl
reaction
formula
compounds
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朱红军
刘宇剑
刘睿
郭军
朱晓林
黄海
金晓东
李炜
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Nanjing Tech University
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Abstract

The invention provides aryl-substituted terpyridyl compounds, and a preparation method and application thereof. According to the method, 2-bromophenyl-2,2':6'2''-terpyridyl (II) and aryl borate used as raw materials react under reflux for 18-24 hours in an ultrasonic-degassed mixed solvent system composed of toluene and water in a ratio of 4:1 by using tetra(triphenylphosphine)palladium as a catalyst and potassium carbonate as an alkali. The compounds are suitable for developing and preparing organic luminescent materials and fluorescent materials.

Description

A kind of terpyridyl compounds replacing containing aryl and its preparation method and application
Technical field
The present invention relates to a kind of terpyridyl compounds, preparation method and application in electroluminescent as photoelectric material thereof replacing containing aryl.
Technical background
Terpyridyl compounds has σ electron donation and π is subject to electronic capability, can form stable title complex with various metals.In addition, terpyridyl compounds and other Compound Phase ratios, have unique magnetic, optical physics and electrochemical properties.Terpyridyl structure is modified, the optical physics of regulating compound and electrochemical properties easily, therefore utilize these characteristics can design the functionalization material of a lot of novelties, for (Synth.Met. such as opto-electronic device, information storage, molecular switch, molecule machine and solar cells, 2004,146,11-15; J.Am.Chem.Soc., 2004,126,4958-4971; Chem.Mat., 2010,22,6384-6492).
Terpyridyl be the earliest by in 1796, on Sythesis magazine, report.Take 2-acetylpyridine and substituted aroma aldehyde is raw material; under the effect of alkali; a part 2-acetylpyridine and aromatic aldehyde generation aldol condensation, generate alpha, beta-unsaturated ketone; the 2-acetylpyridine of another molecule produces the intermediate containing carbanion under the effect of alkali; carry out the Isosorbide-5-Nitrae-addition of beta-unsaturated carbonyl compounds with alpha, beta-unsaturated ketone; reaction produces 1,5-diketone.1,5-diketone, under the effect of amine, forms Isosorbide-5-Nitrae-dihydropyridine ring, then under heating condition, there is oxydehydrogenation in Isosorbide-5-Nitrae-dihydropyridine ring, forms a pyridine ring with aromaticity, finally obtain terpyridyl compounds (Synthesis, 1976,1,1-24).Afterwards the people such as Newkome in 1972, reported hydrazonium salt pyrolysis method synthesize terpyridyl compounds (J.Org.Chem., 1972,37,1329-1336), but its severe reaction conditions, raw material is complicated, route is comparatively loaded down with trivial details.
The structure of terpyridyl compounds mainly can be passed through Stille linked reaction, Ulmann linked reaction and Suzuki linked reaction etc. and modify (Angew.Chem.Int.Ed.2004,43,4704-4734; Angew. Chem.Int.Ed.2009,48,6954-6971).
Stille linked reaction is the cross-coupling reaction that organo-tin compound and the halohydrocarbon (or triflate) that does not contain β-hydrogen occur under palladium catalysis.Be first to be found in 20 century 70s by people such as Stille, this reaction is generally carried out under anhydrous and oxygen-free condition, conventionally has larger toxicity, thereby limited its application but common are machine tin compound in experiment.
Ulmann linked reaction is that halogenated aromatic compound is total to reacting of heat generation biaryl compound with copper powder, and this reaction is found in 1901 by Germanization scholar Ulmann, but this reaction mostly needs higher temperature of reaction.Because its reaction conditions is not too gentle, thereby limited its application.
Suzuki linked reaction is that aryl boric acid or boric acid ester and halogenated aryl hydrocarbon or alkene, under the catalysis of palladium complex, cross-coupling reaction occurs, this reaction is first to be reported in 1979 by Japanization scholar Suzuki chapter, purposes in organic synthesis is (Chem.Rev. very extensively, 1995,95,2457-2483).In addition, Suzuki linked reaction is very good to the tolerance of functional group, reactant can with-CHO ,-COCH 3, ,-CN ,-NO 2deng functional group, react and unaffected.In this reaction, conventional catalyzer has Pd (PPh 3) 4with Pd (dppf) Cl 2deng; Alkali also has a lot of selections, and conventional have sodium carbonate, cesium carbonate, salt of wormwood, a Quilonum Retard etc.The optimal selection of reacting middle catalyst and alkali, because of reaction substrate difference difference.
Have bibliographical information, terpyridyl compounds aspect electroluminescent, have better performance (ACS Appl.Mat.Interfaces, 2012,4,2877-2880).The object of this invention is to provide a kind of novel terpyridyl compounds replacing containing aryl, and optimum preparation method and the application aspect photoelectric material.
Summary of the invention
The object of the present invention is to provide a kind of terpyridyl compounds, preparation method and application in electroluminescent as photoelectric material thereof replacing containing aryl.
The technical solution used in the present invention is:
Suc as formula the terpyridyl compounds replacing containing aryl shown in I
R in formula I 1be selected from:
R wherein 2for the alkyl of H, carbonatoms 1 to 12, the aromatic base of carbonatoms 7 to 12.
The present invention also provides the described preparation method suc as formula the terpyridyl compounds replacing containing aryl shown in I, and described method is:
Compound shown in compound shown in formula II and formula III carries out Suzuki linked reaction under nitrogen protection, take tetrakis triphenylphosphine palladium as catalyzer, toluene in ultrasonic degasification: water=4: in 1 mixed solvent, under alkaline condition, back flow reaction 18-24h, reaction finishes rear reaction solution aftertreatment and obtains compound shown in formula I; Compound shown in described formula II is 1: 1.5 with the ratio of the amount of substance of compound shown in formula III;
R in formula III 1be selected from:
R wherein 2for the alkyl of H, carbonatoms 1 to 12, the aromatic base of carbonatoms 7 to 12.
The amount of substance consumption of described catalyzer tetrakis triphenylphosphine palladium be generally compound shown in formula II amount of substance 5%.
Described alkaline condition, adds conventional bases such as salt of wormwood, sodium carbonate or sodium hydroxide etc., and the pH value that keeps reaction solution is alkalescence.Described reaction solution post-treating method is: after reaction finishes, reaction solution adds the shrend reaction of going out, add methylene dichloride dilution, filter out insolubles, filtrate anhydrous magnesium sulfate drying, except desolventizing, obtain compound crude product shown in formula I, the crude product of compound shown in formula I be take sherwood oil: methylene dichloride=5: 1 mixing solutions is eluent, through column chromatography for separation, purify, and obtain pure compounds shown in formula I.
Shown in described formula II, compound can prepare conventionally by the following method: in the methanol solution of 4-bromobenzaldehyde, add successively 2-acetylpyridine, sodium hydroxide and strong aqua, and heating reflux reaction 72～80h, then cool to room temperature, obtains gray precipitate thing.Filter, filter cake is the dry compound shown in formula II, the NH in described 4-bromobenzaldehyde, 2-acetylpyridine, sodium hydroxide and strong aqua of obtaining after water, methanol wash successively 3h 2the ratio of the amount of substance of O is 1: 2: 1～2: 70～100.
Described reaction formula is as follows.
This is to well known to a person skilled in the art preparation method.
Shown in described formula III, compound can prepare conventionally by the following method: compound shown in formula IV and connection pinacol borate are with [1, 1 '-bis-(diphenylphosphine) ferrocene] palladium chloride is catalyzer, take Potassium ethanoate as alkali, take methyl-sulphoxide under solvent condition, heating reflux reaction 8～10h, then add toluene extraction, getting organic layer washes with water rear dry, after removal of solvent under reduced pressure, obtain crude product shown in formula V, take sherwood oil: ethyl acetate=4: 1 mixing solutions is eluent, through column chromatography, purify, obtain compound pure products shown in formula V, compound shown in described formula IV, connection pinacol borate, [1, 1 '-bis-(diphenylphosphine) ferrocene] palladium chloride, the ratio of the amount of substance of Potassium ethanoate is 1: 1～1.1: 0.005～0.01: 2～4.
Described reaction formula is as follows:
R in formula IV 1be selected from:
R wherein 2for the alkyl of H, carbonatoms 1 to 12, the aromatic base of carbonatoms 7 to 12.
This is to well known to a person skilled in the art preparation method.
The invention provides the terpyridyl compounds replacing containing aryl shown in formula I by test, have luminescent properties, can be used as luminescent material, and it is simple to have reaction conditions, raw material is easy to get, and productive rate is compared with advantages of higher.
Accompanying drawing explanation
The uv-visible absorption spectra (1 * 10 of the normalized compound VI-XI of Fig. 1 in dichloromethane solution -5m)
The fluorescence emission spectrum (1 * 10 of the normalized compound VI-XI of Fig. 2 in dichloromethane solution -7m)
The fluorescence emission spectrum (1 * 10 of the normalized compound VI-XI of Fig. 3 in different solvents -7m)
Embodiment
Below in conjunction with specific examples, the present invention is further elaborated, but protection scope of the present invention is not limited to this.
Agents useful for same in following preparation example, is commercial reagent:
Embodiment 1:2-bromophenyl-2,2 ': 6 ' 2 " preparation of-terpyridyl (II)
To being equipped with in the round-bottomed flask of 200mL methyl alcohol, add successively 4-bromobenzaldehyde (2.0g, 10.80mmol), 2-acetylpyridine (4.4g; 21.6mmol), sodium hydroxide (0.44g; 10.80mmol) and the strong aqua (28%) of 60mL, be heated to 70 ℃, backflow 72h.After cool to room temperature, obtain gray precipitate thing, filter, filter cake washes with water successively, and methyl alcohol is washed, and is dried and obtains 2-bromophenyl-2,2 ': 6 ' 2 "-terpyridyl (3.8g, 89%). 1H?NMR(CDCl 3，400MHz)：δppm7.36-7.40(m，3H)，7.48(t，J＝8.0Hz，2H)，7.67(d，J＝8.0Hz，2H)，7.74(d，J＝8.0Hz，2H)，7.87-7.91(m，2H)，8.00(d，J＝8.0Hz，2H)，8.68(d，J＝8.0Hz，2H)，8.73-8.76(m，2H)，8.80(s，2H).
Embodiment 2: compound shown in formula VI synthetic:
Under nitrogen protection, by II (388mg, 1mmol), salt of wormwood (552mg; 4.0mmol), tetrakis triphenylphosphine palladium (46mg, 0.04mmol), naphthalene boronic acids ester (1.75g; 7.0mmol) all join in Shrek pipe, vacuumize, use nitrogen replacement three times.At N 2under the atmosphere of protection, get 10mL through the toluene of ultrasonic degasification: water=4: 1 mixed solvent, be expelled in Shrek pipe, be heated to subsequently reflux, more than reaction 20h.TLC follows the tracks of, shows residual without raw material, reaction end.Close heating unit, question response system is down to room temperature, with the dilution of 20mL methylene dichloride, and with saturated common salt water washing 3 times, filters out insolubles, collects organic phase.Use anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, obtains thick product again.With sherwood oil: methylene dichloride=1: 1 mixed solvent is eluent, utilize 200-300 object aluminum oxide to carry out column chromatography, separation obtains white solid 0.36g, and productive rate is 83.5%, and fusing point is 220-221 ℃. 1H?NMR(CDCl 3，400MHz)：δppm7.36-7.40(m，3H)，7.48(t，J＝8.0Hz，2H)，7.57(d，J＝8.0Hz，2H)，7.67(d，J＝8.0Hz，2H)，7.74(d，J＝8.0Hz，2H)，7.87-7.94(m，4H)，8.00(d，J＝8.0Hz，2H)，8.68(d，J＝8.0Hz，2H)，8.73-8.76(m，2H)，8.80(s，2H).TOF-MS(ES +)calcd.for?C 27H 19N 3[M+1] +：453.1，found453.3.
Get 10mg sample and put into the sample cavity of Japanese shore pine Quantaurus-Tau C11367-1 type fluorescence lifetime system, the fluorescence lifetime that records this product is 2.64ns.
Embodiment 3: compound shown in formula VII synthetic:
Under nitrogen protection, by method in embodiment 2 is synthetic, obtain compound VI I, product is white solid, and productive rate is 85.0%, and fusing point is 229-231 ℃. 1H?NMR(CDCl 3，400MHz)：δppm7.01(d，J＝2.0Hz，2H)，7.34-7.38(m，2H)，7.62(dd，J＝2.0Hz，2H)，7.7(d，J＝8.0Hz，2H)，7.85-7.90(m，2H)，7.95-8.03(m，4H)，8.69(d，J＝8.0Hz，2H)，8.73-8.77(m，3H)，8.80(s，2H).TOF-MS(ES +)calcd.for?C 28H 21N 3O[M+1] +：462.2，found462.1.
The fluorescence lifetime of this product is 2.15ns, and testing method is with embodiment 2.
Embodiment 4: the preparation of compound shown in formula III
Wherein, R 1for substituted carbazole base, structure is as follows:
Wherein, R 2for the carbonatoms alkyl chain that is 6.
N-bromo-succinimide bromo: at ambient temperature, carbazole (15.0g, 89.88mmol) is dissolved in 150mL DMF, then adds N-bromo-succinimide (15.9g, 90mmol), reaction is stirred and spent the night.Reaction solution is extracted with ethyl acetate 3 times, merges organic layer, with saturated common salt water washing 3 times, then uses anhydrous magnesium sulfate drying organic phase, removal of solvent under reduced pressure.The thick product ethyl alcohol recrystallization obtaining, obtains faint yellow solid 11.5g.Productive rate is 66.8%.
Alkyl chain replaces: at ambient temperature, by the carbazole (4.10g of bromo, 16.66mmol) join in dimethyl sulfoxide (DMSO) (80mL), being stirred to solid all dissolves, add successively again bromohexane (2.49mL, 17.49mmol), potassium hydroxide (7.46g, 133.28mmol) and potassiumiodide (0.28g, 1.67mmol), more than mix and blend 24h.Then with saturated aqueous common salt, fully wash, then use dichloromethane extraction, isolate organic phase, anhydrous magnesium sulfate drying, obtains thick product.Using sherwood oil as eluent, and column chromatography obtains pale yellow oily liquid body 5.0g, and productive rate is 90.9%. 1H?NMR(CDCl 3，400MHz)：δppm0.85(s，3H)，1.24(s，12H)，1.25-1.52(m，8H)，4.15(m，2H)，7.57(m，2H)，7.67-7.73(m，5H).
Embodiment 5: compound shown in formula VIII synthetic:
By the carbon of the bromo obtaining six chain substituted carbazoles (1.5g, 4.53mmol), [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride (116mg, 0.038mmol), Potassium ethanoate (1.35g, 13.8mmol) be placed in 100mL round-bottomed flask with two valeryl two boron (1.2g, 4.83mmol), add the methyl-sulphoxide of 20mL, at 95 ℃, react after 8h, add the extraction of 100mL toluene, get organic layer, water is dried after washing away methyl-sulphoxide, except desolventizing, obtain thick product.Thick product is purified with column chromatography, take sherwood oil: methylene dichloride=4: 1 is eluent, obtains pure products, productive rate is 75%. 1H?NMR(CDCl 3，400MHz)：δppm0.85(s，4H)，1.25-1.52(m，7H)，1.92-1.95(m，2H)，4.35(s，2H)，7.33(s，1H)，7.45-7.57(m，3H)，8.34(d，J＝8.0Hz，1H)，8.45(s，1H，J＝8.0Hz)，9.10(s，1H).
The fluorescence lifetime of this product is 2.08ns, and testing method is with embodiment 2.
Embodiment 6: compound shown in formula IX synthetic:
Alkyl chain replaces: synthetic method replaces with the alkyl chain in embodiment 4.Through aftertreatment, obtain pale yellow oily liquid body, productive rate is 86.9%.
N-bromo-succinimide bromo: synthetic method is with the bromo in embodiment 4.Through aftertreatment, obtain yellow oily liquid, productive rate is 84.2%.
The synthetic method of bromo carbochain fluorenes boric acid is with embodiment 4.The thick product obtaining is purified by column chromatography for separation, and eluent is sherwood oil, obtains colourless oil liquid 6.8g, and productive rate is 50.4%. 1H?NMR(CDCl 3，400MHz)：δppm?0.57(s，4H)，0.72-0.76(m，6H)，0.88-1.26(m，12H)，1.38(s，12H)，1.98(d，4H)，7.29(m，3H)，7.70(m，1H)，7.79(s，1H)，7.81(d，1H).
Under nitrogen protection, by method in embodiment 2 is synthetic, obtain Compound I X, product is white solid, and productive rate is 80%, and fusing point is 110-111 ℃. 1H?NMR(CDCl 3，400MHz)：δppm?0.76-0.80(m，6H，CH 3)，1.07-1.44(m，16H，CH 2)，1.95-2.05(m，4H，CH 2)，7.34-7.38(m，5H)，7.64-7.71(m，2H)，7.72-7.81(m，4H)，7.85-7.95(m，2H)，8.04-8.06(m，2H)，8.69-8.74(m，2H)，8.75-8.80(dd，2H)，8.83(s，2H).TOF-MS(ES +)calcd.for?C 46H 47N 3[M+1] +：642.4，found?642.1.
The fluorescence lifetime of this product is 2.45ns, and testing method is with embodiment 2.
Embodiment 7: compound shown in formula X synthetic:
Under nitrogen protection, by method in embodiment 2 is synthetic, obtain compounds X, product is white solid, and productive rate is 82%, and fusing point is 217-218 ℃. 1H?NMR(CDCl 3，400MHz)：δppm7.04-7.08(m，2H)，7.15-7.19(m，6H)，7.27-7.31(m，4H)，7.35-7.38(m，2H)，7.56(d，J＝8.0Hz，2H)，7.71(d，J＝8.0Hz，2H)，7.87-7.91(m，2H)，7.98(d，J＝8.0Hz，2H)，8.68(d，J＝8.0Hz，2H)，8.74-8.76(m，2H)，8.80(s，2H).TOF-MS(ES +)calcd.for?C 39H 28N 4[M+1] +：553.3，found?553.8.
The fluorescence lifetime of this product is 3.15ns, and testing method is with embodiment 2.
Embodiment 8: compound shown in formula XI synthetic:
Under nitrogen protection, by method in embodiment 2 is synthetic, obtain compounds X I, product is white solid, and productive rate is 84%, and fusing point is 198-199 ℃. 1H?NMR(CDCl 3，400MHz)：δppm?7.12-7.14(m，5H)，7.16-7.19(m，6H)，7.27-7.31(m，4H)，7.35-7.38(m，2H)，8.68(d，J＝8.0Hz，2H)，8.74-8.76(m，2H)，8.80(s，2H).TOF-MS(ES +)calcd.for?C 39H 28N 4[M+1] +：478.5，found?478.8.
The fluorescence lifetime of this product is 2.45ns, and testing method is with embodiment 2.
Although with preferred embodiment in detail the present invention has been described in detail, yet it is not intended to limit the present invention.Any those skilled in the art, without departing from the spirit and scope of the present invention, should make various modifications and change.Therefore protection scope of the present invention should be considered as appending claims limited range.

Claims (3)

1. the terpyridyl compounds replacing containing aryl, its general structure is:
R wherein 1be selected from:
R wherein 2for H, the alkyl of carbonatoms 1 to 12, the aromatic base of carbonatoms 7 to 12.
2. the synthetic method of the terpyridyl compounds replacing containing aryl as claimed in claim 1, it is characterized in that: 2-bromophenyl-2,2 ': 6 ' 2 "-terpyridyl (II) and aryl-boric acid ester are at the toluene through ultrasonic degasification: water=4: in 1 mixed solvent system; tetrakis triphenylphosphine palladium is catalyzer; salt of wormwood is alkali; back flow reaction 18-24h, obtains target compound.
3. the terpyridyl compounds replacing containing aryl, as an application for luminescent material, can be used as fluorescent material and is manufactured with the luminescent layer in OLED.
CN201410287370.8A 2014-06-23 2014-06-23 Aryl-substituted terpyridyl compounds, and preparation method and application thereof Pending CN104030974A (en)

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CN112062752B (en) * 2020-09-08 2021-09-14 吉林大学 Organic fluorescent molecule and preparation method thereof, fluorescent sensor and application thereof, and standard fluorescent card
CN113512000A (en) * 2021-04-29 2021-10-19 河南阿尔法医药科技有限公司 Method for large-scale production of 4 '-bromo-2, 2', 6 ', 2' -terpyridine

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