CN102516284A - Silole substituted compound containing terpyridine and preparation method and application thereof - Google Patents
Silole substituted compound containing terpyridine and preparation method and application thereof Download PDFInfo
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- CN102516284A CN102516284A CN2011103892990A CN201110389299A CN102516284A CN 102516284 A CN102516284 A CN 102516284A CN 2011103892990 A CN2011103892990 A CN 2011103892990A CN 201110389299 A CN201110389299 A CN 201110389299A CN 102516284 A CN102516284 A CN 102516284A
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- FMBKAKNECDCJMS-UHFFFAOYSA-N CCCCCC[Si+](CCCCCC)(C(c(cc1)ccc1-c(cc1)ccc1-c1cc(-c2ccccn2)nc(-c2ncccc2)c1)=C1c2ccccc2)C(c(cc2)ccc2-c(cc2)ccc2-c2cc(-c3ccccn3)nc(-c3ncccc3)c2)=C1c1ccccc1 Chemical compound CCCCCC[Si+](CCCCCC)(C(c(cc1)ccc1-c(cc1)ccc1-c1cc(-c2ccccn2)nc(-c2ncccc2)c1)=C1c2ccccc2)C(c(cc2)ccc2-c(cc2)ccc2-c2cc(-c3ccccn3)nc(-c3ncccc3)c2)=C1c1ccccc1 FMBKAKNECDCJMS-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a silole substituted compound represented by general formula V, containing terpyridine and identical in bilateral substitution, and discloses a preparation method of the silole substituted compound containing the terpyridine and identical in the bilateral substitution and application of the silole substituted compound serving as a luminescent material.
Description
Technical field
The bilateral identical replacement thiophene that the present invention relates to contain ter cycloheptapyridine is coughed up compounds and as the application of photovaltaic material in electroluminescent.The invention still further relates to the bilateral identical replacement thiophene that contains ter cycloheptapyridine and cough up the preparation method of compounds.
Background technology
Thiophene is coughed up the novel unique electronic structure that has and has been given its good electron avidity and electronic mobility; Make it wide application prospect arranged in the photoelectron material field; It can be used as the electron transport material in the organic electroluminescence device (OLED), also can be used as luminescent material.Since the nineties in last century, coughed up and verivate synthetic round thiophene, and they are as the application of photovaltaic material etc., the investigator has done many work.
And ter cycloheptapyridine is compared magnetic, optical physics and the electrochemical properties with uniqueness as important supramolecular structure unit with other title complexs.If distich three pyridine ligand structures are modified; Title complex be can regulate and control easily and optical physics and electrochemical properties put into; Therefore utilize these characteristics can design the functionalization material of a lot of novelties, be used for opto-electronic device, information storage, molecular switch, molecule machine and solar cell etc.
Researching and analysing in recent years show, and thiophene coughs up-and the ter cycloheptapyridine title complex has good pl-and electroluminescent properties.So the purpose of this invention is to provide a kind of novel photovaltaic material, study its concrete luminous efficiency, for photoelectric field provides the novel material of the photoelectric functional with using value prospect.
Summary of the invention
The object of the present invention is to provide a kind of bilateral identical replacement thiophene that contains ter cycloheptapyridine to cough up compounds.
Another object of the present invention is to provide a kind of bilateral identical replacement thiophene that contains ter cycloheptapyridine to cough up the preparation method of compounds.
Another purpose of the present invention is to provide a kind of bilateral identical replacement thiophene that contains ter cycloheptapyridine to cough up the application of compounds as luminescent material.
The technical scheme that the present invention adopts is:
The bilateral identical replacement thiophene that contains ter cycloheptapyridine suc as formula shown in the V is coughed up compounds:
R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6; Preferred R
1, R
2Independent separately is methyl or phenyl.
R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl; Be preferably any one or two or more combinations in hydrogen, methyl, ethyl or the phenyl.
R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl; Be preferably any one or two or more combinations in hydrogen, methyl, ethyl or the phenyl.
Among the formula V, the R of different positions
3Represent identical group, the R of different positions
4Represent identical group.
Further, the bilateral identical replacement thiophene that contains ter cycloheptapyridine according to the invention is coughed up compounds and most preferably is compound shown in following formula IX, formula XI or the formula XII.
The present invention also provides said and coughs up the preparation method of compounds suc as formula the bilateral identical replacement thiophene that contains ter cycloheptapyridine shown in the V, and said method is:
Compound shown in compound shown in the formula I and the formula III carries out the Suzuki linked reaction under nitrogen protection; With four-(triphenyl phosphorus) palladiums is catalyzer; In the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9, back flow reaction 72～100 hours, and reaction finishes the reaction solution aftertreatment and obtains compound shown in the formula V; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III;
In formula I or the formula III, R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6;
Among the formula I, R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;
In the formula III, R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;
Among the formula I, the R of different positions
3Represent identical group; In the formula III, the R of different positions
4Represent identical group.
The amount of substance consumption of said catalyzer four-(triphenyl phosphorus) palladium be generally compound shown in the formula I amount of substance 10%.
It is 7～9 that said adding alkaline matter keeps reacting liquid pH value, adds bases commonly used for example salt of wormwood, yellow soda ash or sodium hydroxide etc. usually, and the pH value that keeps reaction solution is that alkalescence gets final product.Said reaction solution post-treating method is: after reaction finished, reaction solution added water quencher reaction, filters, and gets filter cake and dissolves with THF, with adding Et behind the KOH solution washing
2The O extraction is got the organic layer steaming and is desolventized, and obtains compound crude mixture shown in the formula V; Crude mixture is through column chromatography for separation shown in the formula V; With sherwood oil and 4: 1 mixing solutionss of ETHYLE ACETATE volume ratio is eluent, and the gained elutriant steams and desolventizes, and makes the pure article of compound shown in the formula V.
In the said method, normally THF and water are with the mixing of volume ratio 1: 0.3～0.8 for the mixed solvent of said THF and water, and the TV consumption of the mixed solvent of said THF and water is counted 30～100mL/g with the quality of compound shown in the formula I.
Compound shown in the formula I according to the invention can prepare by following method:
Under the nitrogen protection, metallic lithium and naphthalene are dissolved in the THF, and reaction dripped the compound shown in the formula vi after 4 hours under the room temperature, reacted 10 minutes～1 hour, was cooled to-10 ℃ then, added ZnCl
2-TMEDA complex compound and THF reacted after 1～2 hour, added 4-bromo-iodobenzene and catalyst P dCl
2(PPh
3)
2Reacted 12 hours down at 30 ℃, reaction finishes afterreaction liquid and adds 1N hydrochloric acid quencher reaction, adding anhydrous diethyl ether extraction behind water, the saturated NaCl solution washing successively; Get the organic layer drying; Obtaining crude product and cross the silicagel column purification, is eluent with the sherwood oil, and elutriant steams to desolventize and promptly gets compound shown in the formula I; Compound shown in said metallic lithium, naphthalene, the formula vi, ZnCl
2The ratio of the amount of substance of-TMEDA complex compound, 4-bromo-iodobenzene is 1: 1～1.1: 0.25: 1: 0.5.Said catalyst P dCl
2(PPh
3)
2The amount of substance consumption be generally the compound shown in the formula vi amount of substance 2～5%.
Among the formula vi, R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl, and, the R of different positions
3Represent identical group.
Total consumption of said THF is counted 2～4mL/mmol with the amount of substance of naphthalene, and wherein, the consumption that is used for the THF of dissolution of metals lithium and naphthalene is counted 1～2mL/mmol with the amount of substance of naphthalene, with ZnCl
2-TMEDA complex compound adds the consumption of the THF of reaction solution together and counts 1～2mL/mmol with the amount of substance of naphthalene.
This is to well known to a person skilled in the art the preparation method.
The said compound of said formula III can prepare by following method usually: compound shown in the formula II and two valeryl two boron are with Pd (dppf) Cl
2Being catalyzer, adding Potassium ethanoate, is solvent with DMSO; Heating reflux reaction 8～10 hours adds extracted in toluene then, gets organic layer and uses the water washing after drying; Obtain crude product shown in the formula III after removing solvent under reduced pressure, crude product shown in the formula III is crossed silicagel column and is purified, and is eluent with sherwood oil and 4: 1 mixing solutions of ETHYLE ACETATE volume ratio; Elutriant steams to desolventize and obtains the pure products of compound shown in the formula III, compound shown in the said formula II, two valeryl two boron, Pd (dppf) Cl
2, Potassium ethanoate the ratio of amount of substance be 1: 1～1.1: 0.005～0.02: 2～4.
Said reaction formula is following:
Among the formula II, R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl, and, the R of different positions
4Represent identical group.
This is to well known to a person skilled in the art the preparation method.
Compound shown in the said formula II can prepare by following method:
In the methanol solution of 4-bromobenzaldehyde; Pyridine compounds and their, NaOH and strong aqua shown in the adding formula A; Heating reflux reaction 72～80 hours, cool to room temperature obtains yellow mercury oxide and filters then; Filter cake water, methanol wash after drying successively obtains compound shown in the formula II, NH in pyridine compounds and their, NaOH, the strong aqua shown in said 4-bromobenzaldehyde, the formula A
3H
2The ratio of the amount of substance of O is 1: 2: 1～2: 70～100.
Said reaction formula is following:
Among the formula A, R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl.
This is to well known to a person skilled in the art the preparation method.
Most preferred, preparation method according to the invention carries out according to the following steps:
Compound shown in compound shown in the formula I and the formula III carries out the suzuki linked reaction under nitrogen protection, be catalyzer with four-(triphenyl phosphorus) palladiums, in the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9; Back flow reaction 72～100 hours, reaction finish reaction solution and add water quencher reaction, filter; Get filter cake and dissolve, with adding Et behind the KOH solution washing with THF
2The O extraction is got the organic layer steaming and is desolventized, and obtains compound bullion shown in the formula V; The bullion of compound shown in the formula V is through column chromatography for separation; With sherwood oil and 4: 1 mixing solutionss of ETHYLE ACETATE volume ratio is eluent, and the gained elutriant steams and desolventizes, and makes the pure article of compound shown in IV and the formula V; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III; The amount of substance consumption of said four-(triphenyl phosphorus) palladiums be compound shown in the formula I amount of substance 10%.
The bilateral identical replacement thiophene that contains ter cycloheptapyridine provided by the invention is coughed up compounds and is had luminescent properties, can use as luminescent material.Further, need in the organic electronic devices of luminescent material can be applicable to.
The present invention also provides a kind of and coughs up compounds suc as formula the asymmetric replacement thiophene that contains ter cycloheptapyridine shown in the IV:
Among the formula IV, R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6; Preferred R
1, R
2Independent separately is methyl or phenyl.
R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl; Be preferably any one or two or more combinations in hydrogen, methyl, ethyl or the phenyl.
R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl; Be preferably any one or two or more combinations in hydrogen, methyl, ethyl or the phenyl.
Among the formula IV, the R of different positions
3Represent identical group, the R of different positions
4Represent identical group.
The asymmetric replacement thiophene that contains ter cycloheptapyridine shown in the said formula IV is coughed up compounds and most preferably is compound shown in following formula VIII or the formula X:
The said preparation method who coughs up compounds suc as formula the asymmetric replacement thiophene that contains ter cycloheptapyridine shown in the IV is:
Compound shown in compound shown in the formula I and the formula III carries out the Suzuki linked reaction under nitrogen protection; With four-(triphenyl phosphorus) palladiums is catalyzer; In the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9, back flow reaction 10～15 hours, and reaction finishes the reaction solution aftertreatment and obtains compound shown in the formula IV; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III;
In formula I or the formula III, R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6;
Among the formula I, R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;
In the formula III, R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;
Among the formula I, the R of different positions
3Represent identical group; In the formula III, the R of different positions
4Represent identical group.
The amount of substance consumption of said catalyzer four-(triphenyl phosphorus) palladium be generally compound shown in the formula I amount of substance 10%.
Said reaction solution post-treating method is: after reaction finished, reaction solution added water quencher reaction, filters, and gets filter cake and dissolves with THF, with adding Et behind the KOH solution washing
2The O extraction is got the organic layer steaming and is desolventized, and obtains compound crude mixture shown in the formula IV; Crude mixture is through column chromatography for separation shown in the formula IV; With sherwood oil and 4: 1 mixing solutionss of ETHYLE ACETATE volume ratio is eluent, and the gained elutriant steams and desolventizes, and makes the pure article of compound shown in the formula IV.
In the said method, normally THF and water are with the mixing of volume ratio 1: 0.3～0.8 for the mixed solvent of said THF and water, and the TV consumption of the mixed solvent of said THF and water is counted 30～100mL/g with the quality of compound shown in the formula I.
Saidly cough up compounds suc as formula the asymmetric replacement thiophene that contains ter cycloheptapyridine shown in the IV and have luminescent properties, can use as luminescent material.Further, need in the organic electronic devices of luminescent material can be applicable to.
The present invention provides formula V and two kinds of new compounds of formula IV,, through test, have the good optical performance, and it is simple to have a reaction conditions, raw material is easy to get, and productive rate is higher, and it is stable to generate compound, deposits advantages such as simple.
Embodiment
Below in conjunction with specific examples the present invention is done further elaboration, but protection scope of the present invention is not limited thereto.
Agents useful for same in the following preparation example is the commercial reagent:
Embodiment 1:
| R 1 | R 2 | R 3 | R 4 | Compound | Fusing point |
| Methyl | Hexyl | - | - | VI | 80℃ |
1-methyl-2-hexyl-3,4-phenylbenzene-2, the preparation that 5-dibromo thiophene is coughed up
Under the nitrogen protection, to the lithium grain (83mg, 12mmol) and naphthalene (1.54g adds THF (12mL) preparation naphthyl lithium solution in mixture 12.1mmol), after 4 hours, slowly add tolane ylmethyl hexyl silane (991mg, 3.0mmol)), and the time was above 10 minutes.Reactant is cooled to-10 ℃, adds ZnCl
2-TMEDA (3.0g, 12mmol) and THF (20ml).React after one hour, add the 4-bromo-iodobenzene (1.7g, 6mmol) and PdCl
2(PPh
3)
2(70mg 0.1mmol), reacted 12 hours down at 30 ℃.Add 10mL HCl (1N) quencher reaction, washing, saturated NaCl solution is washed, and the organic layer drying is got in the extraction of 50ml anhydrous diethyl ether.Obtain crude product and cross the silicagel column purification, sherwood oil is an eluent, and elutriant steams to desolventize and promptly gets compound 3.1g shown in the formula VI, yield 71.8%.
Get the product of 0.2g amount, at vacuum 3*10
-4Under the Pa, smear into unitary film, put into SSP3110LED photoelectric parameter integration test machine again, detect its high-high brightness, obtaining the product high-high brightness is 600cd/cm
2
1HNMR(400MHz，CDCl3)，dZ7.26(d，4H，Ph-H)，7.03(m，6H，Ph-H)，6.80(m，8H，Ph-H)，0.47(s，3H，-CH
3-)，0.96(m，2H，-CH
2-)，0.92(m，8H，-CH
2-)，1.30(s，3H，-CH
3-).
Embodiment 2:
2,2 ': 6 ' 2 "-and ter cycloheptapyridine-4 '-phenyl-4,4,5,5-tetramethyl--1,3,2-dioxane pentaborane
| R 1 | R 2 | R 3 | R 4 | Compound | Fusing point |
| - | - | - | H | VII | - |
In the round-bottomed flask of 500ml, (1.0g, in methyl alcohol 5.40mmol) (120ml) solution, (2.2g, 10.80mmol), (0.22g 5.4mmol) with 30ml strong aqua (28%), is heated to 70 ℃ and refluxed 72 hours NaOH to add the 2-acetylpyridine to the 4-bromobenzaldehyde.Behind the cool to room temperature, obtain yellow mercury oxide and filter, get filter cake successively with washing, methyl alcohol is washed, and drying obtains 2-bromophenyl-2, and 2 ': 6 ' 2 "-ter cycloheptapyridine (1.8g, 86%).With 2-bromophenyl-2,2 ': 6 ' 2 "-(1.8g, 4.6mmol), (116mg; 0.038mmol), (1.35g, 13.8mmol) (1.2g 4.83mmol) places the 25ml round-bottomed flask to KOAc to Pd (dppf) Cl2 to ter cycloheptapyridine; add 10ml DMSO, after 8 hours, adds the 50ml extracted in toluene; get organic layer water (3*100mL) flush away DMSO after drying, spin off solvent, obtain crude product 85 ℃ of refluxed with two valeryl two boron.Crude product is crossed silicagel column and is purified, with petrol ether/ethyl acetate (v/v=4: be eluent 1), obtain compound shown in the pure products formula VII (0.84g, yield 42%).1H?NMR(400MHz，CDCl3)8.76(s，2H，H3)，8.75(dm，2H，J?4.8，0.9，H6)，8.66(d，2H，J?7.8，H3)，7.98(d，2H，J?8.4，Hphenyl)，7.93(d，2H，J8.4，Hphenyl)，7.86(td，2H，J?7.8，1.5，H4)，7.34(ddd，2H，J?7.5，6.3，1.2Hz，H5)，1.39(s，12H)
Embodiment 3:
| R 1 | R 2 | R 3 | R 4 | Compound | Fusing point |
| Methyl | Methyl | Hydrogen | H | VIII | 380℃ |
1,1-dimethyl--3,4-phenylbenzene-2-(2,2 ': 6 ' 2 "-ter cycloheptapyridine) preparation that phenyl-5-bromophenyl thiophene is coughed up
At N
2Under the protection, 1,1-dimethyl--3,4-phenylbenzene-2,5-dibromo phenyl thiophene are coughed up (0.23g; 0.4mmol), 2,2 ': 6 ' 2 "-ter cycloheptapyridine-4 '-phenyl-4,4; 5,5-tetramethyl--1,3,2-dioxane pentaborane VII (0.52g; 1.2mmol), and salt of wormwood (0.16g, 1.2mmol), catalyst P d (PPh
3)
40.04mmol, in 10ml THF and 5ml water solvent, be heated to 70 ℃ of back flow reaction 12 hours.After reaction finished, elder generation filtered with 10ml water quencher reaction, and filter cake dissolves with the 20ml oxolane.KOH solvent wash with 5%, 30mlEt
2O extraction is got organic layer and is steamed and desolventize, obtain crude product and cross silicagel column and purify, be eluent with sherwood oil and ETHYLE ACETATE (volume ratio 4: 1), the steaming of gained elutriant desolventize product (0.11g, yield 35%) shown in the formula VIII.
The product high-high brightness is 620cd/cm
2Testing method is with embodiment 1.
1HNMR(400MHz，CDCl
3)，8.68-8.78(m，6H)，7.96-7.98(d，J＝8.4Hz，2H)，7.87-7.91(m，2H)，7.69-7.71(d，J＝8.4Hz，2H)，7.45-7.47(d，J＝8.4Hz，2H)，7.35-7.38(m，2H)，7.24-7.26(d，J＝8Hz，2H)，7.02-7.07(m，8H)，6.80-6.87(m，6H)，0.52(s，6H).
Wherein 1,1-dimethyl--3,4-phenylbenzene-2,5-dibromo phenyl thiophene are coughed up by following method preparation:
Under the nitrogen protection, to the lithium grain (83mg, 12mmol) and naphthalene (1.54g adds THF (12mL) preparation naphthyl lithium solution in mixture 12.1mmol), after 4 hours, slowly add tolane base dimethylsilane (800mg, 3.0mmol)), and the time was above 10 minutes.Reactant is cooled to-10 ℃, adds ZnCl
2-TMEDA (3.0g, 12mmol) and THF (20ml).React after one hour, add the 4-bromo-iodobenzene (1.7g, 6mmol) and PdCl
2(PPh3) 2 (70mg, 0.1mmol), 30 ℃ of reactions 12 hours down.Add 10ml HCl (1N) quencher reaction, washing, saturated NaCl solution is washed, and the organic layer drying is got in the extraction of 50ml anhydrous diethyl ether.Obtain crude product and cross the post purification, sherwood oil is an eluent, and elutriant steams to desolventize and promptly gets 1,1-dimethyl--3, and 4-phenylbenzene-2,5-dibromo phenyl thiophene is coughed up 0.90g.
Embodiment 4:
| R 1 | R 2 | R 3 | R 4 | Compound | Fusing point |
| Methyl | Methyl | Hydrogen | Hydrogen | IX | 450℃ |
1,1-dimethyl--3,4-phenylbenzene-2, the preparation that 5-two (2,2 ': 6 ' 2 "-ter cycloheptapyridine) phenyl thiophene is coughed up
At N
2Protection down, by embodiment 3 methods make 1,1-dimethyl--3,4-phenylbenzene-2; 5-dibromo phenyl thiophene cough up (0.23g, 0.4mmol), 2,2 ': 6 ' 2 "-ter cycloheptapyridine-4 '-phenyl-4; 4,5,5-tetramethyl--1,3; 2-dioxane pentaborane (0.52g, 1.2mmol), salt of wormwood 0.1g, catalyst P d (PPh
3)
40.04mmol, in 10ml THF and 5ml water solvent, be heated to 70 ℃ of back flow reaction 72 hours, after reaction finishes, add 10ml water quencher reaction earlier, filter, filter cake dissolves with the 20ml THF.KOH solvent wash with 5%, 30ml Et
2O extraction is got organic layer and is steamed and desolventize, obtain crude product and purify with column chromatography, be eluent with sherwood oil and ETHYLE ACETATE (volume ratio 4: 1), the steaming of gained elutriant desolventize product (0.19g, yield 45%) shown in the formula IX.
The product high-high brightness is 650cd/cm
2Testing method is with embodiment 1.
1HNMR(400MHz，CDCl
3)，8.71-8.75(m，8H)，8.64-8.66(d，J＝8Hz，4H)，7.93-7.95(d，J＝8Hz，5H)，7.82-7.86(t，J＝6.8Hz，5H)，7.67-7.69(d，J＝8Hz，5H)，7.45-7.47(d，J＝7.6Hz，4H)，7.30-7.33(t，J＝5.2Hz，5H)，7.07(s，7H)，6.91(m，3H)，0.59(s，6H).
Embodiment 5:
| R 1 | R 2 | R 3 | R 4 | Compound | Fusing point |
| Methyl | Hexyl | Hydrogen | Hydrogen | X | 450℃ |
At N
2Protection down, by 1-methyl-2 hexyl-3 that embodiment 1 method makes, 4-phenylbenzene-2,5-dibromo phenyl thiophene cough up (0.35g, 0.4mmol); 2,2 ': 6 ' 2 "-and ter cycloheptapyridine-4 '-phenyl-4,4,5,5-tetramethyl--1; 3,2-dioxane pentaborane (0.52g, 1.2mmol), catalyst P d (PPh
3)
40.04mmol, salt of wormwood 0.1g, in 10ml THF and 5ml water solvent, back flow reaction 12 hours.After reaction finished, elder generation filtered with 10ml water quencher reaction, and filter cake dissolves with the 20ml oxolane.KOH solvent wash with 5%, 30ml Et
2O extraction is got organic layer and is steamed and desolventize, obtain crude product and purify with column chromatography, be eluent with sherwood oil and ETHYLE ACETATE (volume ratio 4: 1), the steaming of gained elutriant desolventize product (0.14g, yield 40%) shown in the formula X.
The product high-high brightness is 640cd/cm
2, testing method is with embodiment 1.
1HNMR(400MHz，CDCl
3)，8.68-8.78(m，6H)，7.96-7.98(d，J＝8.4Hz，2H)，7.87-7.91(m，2H)，7.69-7.71(d，J＝8.4Hz，2H)，7.45-7.47(d，J＝8.4Hz，2H)，7.35-7.38(m，2H)，7.24-7.26(d，J＝8Hz，2H)，7.02-7.07(m，8H)，6.80-6.87(m，6H)，1.42-1.21(m，8H)，1.09-0.99(m，2H)，0.86-0.83(t，J＝6.8Hz，3H)，0.50(s，3H)..
Embodiment 6:
| R 1 | R 2 | R 3 | R 4 | Compound | Fusing point |
| Methyl | Hexyl | Hydrogen | Hydrogen | XI | 430℃ |
At N
2Protection down, by 1-methyl-2 hexyl-3 that embodiment 2 methods make, 4-phenylbenzene-2,5-dibromo phenyl thiophene cough up (0.26g, 0.4mmol); 2,2 ': 6 ' 2 "-and ter cycloheptapyridine-4 '-phenyl-4,4,5,5-tetramethyl--1; 3,2-dioxane pentaborane (0.52g, 1.2mmol), catalyst P d (PPh
3)
40.04mmol, salt of wormwood 0.1g, in 10ml THF and 5ml water solvent, back flow reaction 72 hours.After reaction finished, elder generation filtered with 10ml water quencher reaction, and filter cake dissolves with the 20ml oxolane.KOH solvent wash with 5%, 30ml Et
2O extraction is got organic layer and is steamed and desolventize, obtain crude product and cross post and purify, be eluent with sherwood oil and ETHYLE ACETATE (volume ratio 4: 1), the steaming of gained elutriant desolventize product (0.22g, yield 50%) shown in the formula XI.
The product high-high brightness is 660cd/cm
2, testing method is with embodiment 1.
1HNMR(400MHz，CDCl
3)，8.71-8.75(m，8H)，8.64-8.66(d，J＝8Hz，4H)，7.93-7.95(d，J＝8Hz，5H)，7.82-7.86(t，J＝6.8Hz，5H)，7.67-7.69(d，J＝8Hz，5H)，7.45-7.47(d，J＝7.6Hz，4H)，7.30-7.33(t，J＝5.2Hz，5H)，7.07(s，7H)，6.91(m，3H)，1.42-1.21(m，8H)，1.09-0.99(m，2H)，0.86-0.83(t，J＝6.8Hz，3H)，0.50(s，3H)..
Embodiment 7:
| R 1 | R 2 | R 3 | R 4 | Compound | Fusing point |
| Hexyl | Hexyl | Hydrogen | Hydrogen | XII | 450℃ |
At N
2Protection down, 1,1-dihexyl-3,4-phenylbenzene-2,5-dibromo phenyl thiophene cough up (0.28g, 0.4mmol), 2,2 ': 6 ' 2 "-ter cycloheptapyridine-4 '-phenyl-4,4,5,5-tetramethyl--1,3,2-dioxane pentaborane (0.52g, 1.2mmol), catalyst P d (PPh
3)
40.04mmol, salt of wormwood 0.1g, in 10ml THF and 5ml water solvent, back flow reaction 72 hours.After reaction finished, elder generation filtered with 10ml water quencher reaction, and filter cake dissolves with the 20ml oxolane.KOH solvent wash with 5%, 30ml Et
2O extraction is got organic layer and is steamed and desolventize, obtain crude product and purify through column chromatography, be eluent with sherwood oil and ETHYLE ACETATE (volume ratio 4: 1), the steaming of gained elutriant desolventize product (0.21g, 46%) shown in the formula XII.
The product high-high brightness is 680cd/cm
2, testing method is with embodiment 1.
1HNMR(400MHz，CDCl
3)，8.71-8.75(m，8H)，8.64-8.66(d，J＝8Hz，4H)，7.93-7.95(d，J＝8Hz，5H)，7.82-7.86(t，J＝6.8Hz，5H)，7.67-7.69(d，J＝8Hz，5H)，7.45-7.47(d，J＝7.6Hz，4H)，7.30-7.33(t，J＝5.2Hz，5H)，7.07(s，7H)，6.91(m，3H)，1.42-1.21(m，16H)，1.09-0.99(m，4H)，0.86-0.83(t，J＝6.8Hz，6H).
Wherein 1,1-dihexyl-3,4-phenylbenzene-2,5-dibromo phenyl thiophene are coughed up by following method preparation:
Under the nitrogen protection, to the lithium grain (83mg, 12mmol) and naphthalene (1.54g adds THF (12mL) preparation naphthyl lithium solution in mixture 12.1mmol), after 4 hours, slowly add tolane base dihexyl silane (900mg, 3.0mmol)), and the time was above 10 minutes.Reactant is cooled to-10 ℃, adds ZnCl
2-TMEDA (3.0g, 12mmol) and THF (20ml).React after one hour, add the 4-bromo-iodobenzene (1.7g, 6mmol) and PdCl
2(PPh
3)
2(70mg 0.1mmol), reacted 12 hours down at 30 ℃.Add 10ml HCl (1N) quencher reaction, washing, saturated NaCl solution is washed, and the organic layer drying is got in the extraction of 50ml anhydrous diethyl ether.Obtain crude product and cross the post purification, sherwood oil is an eluent, and elutriant steams to desolventize and promptly gets 1,1-dihexyl-3, and 4-phenylbenzene-2,5-dibromo phenyl thiophene is coughed up 0.91g.
Claims (10)
1. cough up compounds suc as formula the bilateral identical replacement thiophene that contains ter cycloheptapyridine shown in the V:
Among the formula V, R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6; R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;
R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;
Among the formula V, the R of different positions
3Represent identical group, the R of different positions
4Represent identical group.
2. compound as claimed in claim 1 is characterized in that said R
1Be methyl or phenyl; R
2Be methyl or phenyl; R
3Be any one or the two or more combinations in hydrogen, methyl, ethyl or the phenyl; R
4Be any one or the two or more combinations in hydrogen, methyl, ethyl or the phenyl.
3. the preparation method of compound as claimed in claim 1 is characterized in that said method is:
Compound shown in compound shown in the formula I and the formula III carries out the Suzuki linked reaction under nitrogen protection; With four-(triphenyl phosphorus) palladiums is catalyzer; In the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9 salt of wormwood, back flow reaction 72～100 hours, and reaction finishes the reaction solution aftertreatment and obtains compound shown in the formula V; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III;
In formula I or the formula III, R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6;
Among the formula I, R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;
In the formula III, R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;
Among the formula I, the R of different positions
3Represent identical group; In the formula III, the R of different positions
4Represent identical group.
4. method as claimed in claim 3 is characterized in that said reaction solution post-treating method is: after reaction finished, reaction solution added water quencher reaction, filters, and gets filter cake and dissolves with THF, with adding Et behind the KOH solution washing
2The O extraction is got the organic layer steaming and is desolventized, and obtains compound bullion shown in the formula V; The bullion of compound shown in the formula V is through column chromatography for separation; With sherwood oil and 4: 1 mixing solutionss of ETHYLE ACETATE volume ratio is eluent, and the gained elutriant steams and desolventizes, and makes the pure article of compound shown in the formula V.
5. method as claimed in claim 3 is characterized in that compound prepares by following method shown in the said formula I:
Under the nitrogen protection, metallic lithium and naphthalene are dissolved in the THF, and reaction dripped the compound shown in the formula vi after 4 hours under the room temperature, reacted 10 minutes～1 hour, was cooled to-10 ℃ then, added ZnCl
2-TMEDA complex compound and THF reacted after 1～2 hour, added 4-bromo-iodobenzene and catalyst P dCl
2(PPh
3)
2Reacted 12 hours down at 30 ℃, reaction finishes afterreaction liquid and adds 1N hydrochloric acid quencher reaction, adding anhydrous diethyl ether extraction behind water, the saturated NaCl solution washing successively; Get the organic layer drying; Obtaining crude product and cross the post purification, is eluent with the sherwood oil, and elutriant steams to desolventize and promptly gets compound shown in the formula I; Compound shown in said metallic lithium, naphthalene, the formula vi, ZnCl
2The ratio of the amount of substance of-TMEDA complex compound, 4-bromo-iodobenzene is 1: 1～1.1: 0.25: 1: 0.5;
Among the formula vi, R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl, and, the R of different positions
3Represent identical group.
6. method as claimed in claim 3 is characterized in that the step of said method is:
Compound shown in compound shown in the formula I and the formula III carries out the suzuki linked reaction under nitrogen protection, be catalyzer with four-(triphenyl phosphorus) palladiums, in the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9; Back flow reaction 72～100 hours, reaction finish reaction solution and add water quencher reaction, filter; Get filter cake and dissolve, with adding Et behind the KOH solution washing with THF
2The O extraction is got the organic layer steaming and is desolventized, and obtains compound bullion shown in the formula V; The bullion of compound shown in the formula V is through column chromatography for separation; With sherwood oil and 4: 1 mixing solutions of ETHYLE ACETATE volume ratio is eluent, and the gained elutriant steams and desolventizes, and makes the pure article of compound shown in the formula V; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III; The amount of substance consumption of said four-(triphenyl phosphorus) palladiums be compound shown in the formula I amount of substance 10%.
7. the bilateral identical replacement thiophene that contains ter cycloheptapyridine as claimed in claim 1 is coughed up the application of compounds as luminescent material.
8. cough up compounds suc as formula the asymmetric replacement thiophene that contains ter cycloheptapyridine shown in the IV:
Among the formula IV, R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6; R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;
R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;
Among the formula IV, the R of different positions
3Represent identical group, the R of different positions
4Represent identical group.
9. the preparation method of compound as claimed in claim 8 is characterized in that said method is:
Compound shown in compound shown in the formula I and the formula III carries out the Suzuki linked reaction under nitrogen protection; With four-(triphenyl phosphorus) palladiums is catalyzer; In the mixed solvent of THF and water; Adding alkaline matter maintenance reacting liquid pH value is 7～9, back flow reaction 10～15 hours, and reaction finishes the reaction solution aftertreatment and obtains compound shown in the formula IV; Compound shown in the said formula I is 1: 3 with the ratio of the amount of substance of compound shown in the formula III;
In formula I or the formula III, R
1, R
2Independent separately is the alkyl of hydrogen, C1～C10, naphthenic base or the phenyl of C3～C6;
Among the formula I, R
3Be the naphthenic base of the alkyl of hydrogen, C1～C10, C3～C6 or any one or two or more combinations in the phenyl;
In the formula III, R
4Be the naphthenic base of the alkyl of hydrogen, C1～C6, C3～C6 or any one or two or more combinations in the phenyl;
Among the formula I, the R of different positions
3Represent identical group; In the formula III, the R of different positions
4Represent identical group.
10. the asymmetric replacement thiophene that contains ter cycloheptapyridine as claimed in claim 8 is coughed up the application of compounds as luminescent material.
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