CN102633610B - 'Vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on fluorene loop and preparation method and application thereof - Google Patents
'Vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on fluorene loop and preparation method and application thereof Download PDFInfo
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- CN102633610B CN102633610B CN201110459231.5A CN201110459231A CN102633610B CN 102633610 B CN102633610 B CN 102633610B CN 201110459231 A CN201110459231 A CN 201110459231A CN 102633610 B CN102633610 B CN 102633610B
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Abstract
The invention relates to a 'vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on a fluorene loop. A structural formula of the compound is (I) shown in the source text, wherein R1 and R2 in the formula can be various electron withdrawing and donating groups such as alkyl, substituted aryl, substituted heterocyclic radical, substituted alkylene, substituted amino, chlorine, bromine, iodine and the like, and the R1 and R2 are different. 4,4'-dimethyl diphenyl which is cheap and easy to obtain is used as a raw material to be bromized and reacted with fluorenone or 2,7-substituted fluorenone to covert the methyl on the fluorine loop into various fluctional groups and the like to obtain the compound (I). The 'vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on the fluorene loop is low in cost, simple in synthetic route, high in yield and easy in industrial production, has special spiral conjugation effect, high dissolubility and high heat stability, and is widely applicable to fields of organic luminous display, organic nonlinear materials, fluorescent probes and the like.
Description
Technical field
The present invention relates to class spiral shell two fluorene compounds, specifically, is that a class comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes and its preparation method and application.
Background technology
As far back as nineteen thirty Clarkson and Gomberg etc., 9,9 '-spiral shell, two fluorenes have just been synthesized.Salbeck in 1997 etc. are used in electroluminescent material aspect by spiral shell two fluorenes, thereby have caused spiral shell two fluorenes extensively carrying out at organic photoelectric functional material area research.Because spiral shell two fluorenes are three-dimensional orthogonal intersection space structure, can avoid chromophoric tightly packed in molecule, improve thermostability and the solubility property of material; And pass through sp
3the spiral shell carbon atom of hydridization can be realized again the control of molecular conjugation length or produce special spiral shell conjugative effect.In recent years, spiral shell two fluorenes have become " star molecule " of field of photovoltaic materials, and its research field, from initial electroluminescent, extends to the fields such as organic solar batteries, organic non-linear optical properties and fluorescent probe.
The classical way of at present synthetic spiral shell two fluorenes is generally to utilize the Grignard reagent of 2-bromo biphenyl to react and obtain with Fluorenone, and 2-bromo biphenyl is generally to utilize o-dibromobenzene to make by linked reaction, expensive.During spiral shell two is fluorene structured 2,2 ', 7,7 ' position has good reactive behavior, by substitution reaction 2,2 '-bis-R-9 that are easy to get, 9 '-spiral shell, two fluorenes (R represents substituting group) or 2,2 '-bis-R-7,7 '-bis-R '-9,9 '-spiral shell, two fluorenes (R, R ' expression substituting group, can be identical or different).And " previous-next " asymmetrical type spiral shell two fluorene compounds 2,7-bis-R-2 ', 7 '-bis-R '-9,9 '-spiral shell, two fluorenes or 2-R-2 '-R '-9,9 '-spiral shell, two fluorenes (R, R ' expression substituting group, and not identical), due to the difficulty on synthetic, bibliographical information is less.
The present invention sets out from 4, the 4 '-dimethyl diphenyl being cheaply easy to get, obtained 2,7-dimethyl-2 ', 7 '-bis-X-9, (X can be H to 9 '-spiral shell, two fluorenes, can be the R in claim 1
1or R
2but be not methyl).Because the methyl of 2,7 can change brooethyl into again, aldehyde radical, the various functional groups such as carboxyl, have widened the synthesis path of " previous-next " asymmetrical type spiral shell two fluorene compounds, and have prepared thus a large amount of " previous-next " asymmetrical type spiral shell two fluorene compounds.
Spiral shell two fluorene compounds are used widely in organic electroluminescent field, have formed suitable article and patent.Have bibliographical information the different fluorenes rings of spiral shell two fluorenes connect respectively hole mobile material and electron transport material " previous-next " asymmetrical type spiral shell two fluorene compounds (referring to Tobat P.I.Saragi etc., Chem.Rev.2007,107,1011-1065).Yet, spiral shell two fluorene compounds are applied to organic non-linear optical properties and fluorescent probe aspect but rarely has report.
Summary of the invention
Object of the present invention, is to propose a class and comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes.
Another object of the present invention, is to propose the preparation method that a class comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes.
Another object of the present invention, is to propose the application that a class comes from the luminous or laser diode device material of the conduct of " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes.
A further object of the present invention, is to propose the application as second order or third-order non-linear material that a class comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes.
An object in addition of the present invention, is to propose a class and comes from the conduct biology of " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes or the application of Chemical Luminescent Probes.
For achieving the above object, technical solution of the present invention is:
One class comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes, and has following general formula (I):
In formula:
R
1, R
2be separately:
(1) C
1-C
5branched-chain alkyl or straight chained alkyl, Cl, Br, I, NH
2or
integer, *-CH that wherein m, n are 0-8
2br, *-CHO, *-CN or-Ar, wherein Ar can be selected from the derivative of following structural unit or following structural unit:
Or following structural unit (2):
Wherein:
R
3, R
4, R
5, R
6for hydrogen or there is straight chain, side chain or cyclic alkyl or the oxyalkyl chain of 1-22 carbon atom, and can be identical or different;
Or following structural unit (3):
Wherein:
R
7for
*-OR
10or
Wherein:
R
8, R
9for hydrogen, containing the branched-chain or straight-chain alkyl of 1-10 carbon atom, contain the aryl of 6-15 carbon atom, can be identical or different;
R
10for hydrogen or there is straight chain, side chain or cyclic alkyl or the oxyalkyl chain of 1-22 carbon atom;
R
11for CH
2, O, S or NR ', R ' is side chain or the straight chained alkyl of hydrogen, a 1-12 carbon.
Or structural unit (4):
Wherein:
R
12, R
13for H, *-NO
2, *-CN, *-COOH,
wherein R ' be the side chain of hydrogen, a 1-12 carbon or straight chained alkyl,
r wherein " be side chain or the straight chained alkyl of hydrogen, a 1-12 carbon, R
12with R
13can be identical or different, collateral condition is H while being both differences;
Or structural unit (5):
R
14, R
15for hydrogen or there is straight chained alkyl, branched-chain alkyl or cyclic alkyl, oxyalkyl chain or the aryl of 1-22 carbon atom, R
14with R
15can be identical or different, M is S, O, CH
2, or NR " ', wherein R " ' be side chain or the straight chained alkyl of hydrogen, a 1-12 carbon;
Or structural unit (6):
R
16, R
17for hydrogen or there is straight chained alkyl, branched-chain alkyl or cyclic alkyl, oxyalkyl chain or the aryl of 1-22 carbon atom, R
16with R
17can be identical or different.
One class comes from the preparation method of " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes, and it is characterized in that comprising the following steps:
(1), produce 4,4 '-dimethyl-2-bromo biphenyl
By 4,4 '-dimethyl diphenyl, a small amount of iodine and dry methylene dichloride join in single neck flask, stir after 30min in ice-water bath, with constant pressure funnel, slowly drip bromine successively; After being added dropwise to complete, continue reaction 5h; Stopped reaction adds the saturated sodium sulfite aqueous solution in flask, is stirred to brown taking off; Separatory, collected organic layer, water layer dichloromethane extraction 3 times, merge organic layer, with anhydrous sodium sulfate drying; Suction filtration, except desolventizing obtains 4,4 '-dimethyl-2-bromo biphenyl;
(2), produce 2,7-dimethyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, wherein X can be H, can be the R in (I) formula
1or R
2, but be not methyl.
Under nitrogen protection, 4,4 '-dimethyl-2-bromo biphenyl, in anhydrous tetrahydro furan, reacts 0.5-1h with dry magnesium rod under catalysis of iodine, makes Grignard reagent; The Grignard reagent preparing is slowly added drop-wise in the anhydrous tetrahydrofuran solution that 2,7-, bis-X-9-Fluorenones are housed, backflow 14-20h, obtains corresponding fluorenol; Remove the tetrahydrofuran (THF) in reaction soln, add acetic acid and hydrochloric acid, backflow 3-6h, has solid to separate out, and is cooled to room temperature, filters, and obtains thick product, uses respectively normal hexane and absolute ethanol washing, obtains 2,7-dimethyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes; (3), produce 2,7-, bis-bromomethyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, wherein X can be H, can be the R in (I) formula
1or R
2, but be not methyl.
Under nitrogen protection, to being connected in the dry three-necked flask of reflux condensing tube, add successively 2,7-dimethyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, N-bromo-succinimide (NBS) and dibenzoyl peroxide (BP0), the dry tetracol phenixin that reinjects, back flow reaction 12-18h; Stopped reaction, is cooled to room temperature, in reaction solution, adds silica gel, and column chromatography obtains 2,7-, bis-bromomethyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes;
(4), produce 2,7-diformyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, wherein X can be H, can be the R in (I) formula
1or R
2, but be not methyl.
Under nitrogen protection, to being connected in single neck flask of reflux condensing tube, add successively 2,7-, bis-bromomethyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, sodium bicarbonate, the appropriate methyl-sulphoxide that reinjects, at 110 ℃ of reaction 12-18h; Stopped reaction, is cooled to room temperature, adds frozen water, separates out a large amount of solids, filters, and gained solid is carried out to column chromatography, obtains 2,7-diformyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes;
(5), produce 2,7-, bis-Y-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, wherein X can be H, can be the R in (I) formula
1or R
2, but be not methyl; Y can be *-CN,
deng the R in (I) formula
1or R
2group, wherein comprises following preparation method:
(a), when Y is *-CN, preparation method is:
Under nitrogen protection, to being connected in single neck flask of reflux condensing tube, add successively 2,7-diformyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, oxammonium hydrochloride, the new N-Methyl pyrrolidone (NMP) steaming that reinjects, at 115 ℃ of reaction 12-20h.Stopped reaction, is cooled to room temperature, adds frozen water, separates out a large amount of solids, filters, and gained solid is carried out to column chromatography, obtains 2,7-dinitrile-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes;
(b), when Y is
time, preparation method is:
Successively by 2,7-diformyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes,
toluene, alkaline aluminium sesquioxide join in single neck flask, back flow reaction 12-24h; After reaction finishes, underpressure distillation, removes toluene; Remaining solid is carried out to column chromatography, obtain 2,7-disubstituted olefin base-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes;
(c), when Y is
time, preparation method is:
Take successively 2,7-diformyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, O-Phenylene Diamine, or ortho-aminophenol, or adjacent mercaptoaniline, or derivatives thereof and brometo de amonio, in round-bottomed flask, inject appropriate methyl alcohol, at room temperature stirring reaction 30-50h; Stopped reaction, except desolventizing, then water successively, ethyl acetate, sherwood oil mixed solvent and washing with alcohol, obtain 2,7-, bis-nitrogen heterocycles-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes.
The preparation method that the class the present invention relates to comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes can also be further achieved by the following technical measures.
Aforesaid method, wherein in step (1), 4, the mol ratio of 4 '-dimethyl diphenyl and bromine is 1: 1.2, temperature of reaction is 0～5 ℃.
Aforesaid method, wherein in step (2), 4, the mol ratio of 4 '-dimethyl-2-bromo biphenyl, magnesium rod and 2,7-, bis-X-9-Fluorenones is 1: 1.2: 0.8; During final step dehydration cyclization, original solvents tetrahydrofurane need to be removed, to improve productive rate; The concentrated hydrochloric acid massfraction adding is 37%, and itself and glacial acetic acid volume ratio are 1: 15.
Aforesaid method, wherein in step (3), 2,7-dimethyl-2 ', 7 '-bis-X-9, the mol ratio of 9 '-spiral shell, two fluorenes, N-bromo-succinimide, dibenzoyl peroxide is 1: 2.2: 0.2.
Aforesaid method, wherein in step (4), 2,7-, bis-bromomethyl-2 ', 7 '-bis-X-9, the mol ratio of 9 '-spiral shell, two fluorenes and sodium bicarbonate is 1: 30.
Aforesaid method, wherein in step (5a), 2,7-diformyl-2 ', 7 '-bis-X-9, the mol ratio of 9 '-spiral shell, two fluorenes and oxammonium hydrochloride is 1: 20.
Aforesaid method, wherein in step (5b) 2,7-diformyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes,
with the mol ratio of alkaline aluminium sesquioxide be 1: 10: 40.
Aforesaid method, wherein in step (5c), 2,7-diformyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, O-Phenylene Diamine, or ortho-aminophenol, or adjacent mercaptoaniline, the mol ratio of or derivatives thereof and brometo de amonio is 1: 2: 10.
The application of the luminous or laser diode device material of a kind of conduct that comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that methyl on fluorenes ring changes, wherein the structure of LED device is transparent anode/hole mobile material/luminescent material/electron injection material/negative electrode, wherein adopts " previous-next " asymmetrical type spiral shell two fluorene compounds that come from methyl transformation on fluorenes ring as hole mobile material.
The application of the luminous or laser diode device material of a kind of conduct that comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that methyl on fluorenes ring changes, wherein the structure of LED device is transparent anode/hole mobile material/luminescent material/electron injection material/negative electrode, wherein adopts and comes from " previous-next " asymmetrical type spiral shell two fluorene compounds of methyl transformation on fluorenes ring as the material of main part of luminescent material or white light and phosphorescence.
The application of the luminous or laser diode device material of a kind of conduct that comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that methyl on fluorenes ring changes, wherein the structure of LED device is transparent anode/hole mobile material/luminescent material/electron injection material/negative electrode, wherein adopts " previous-next " asymmetrical type spiral shell two fluorene compounds that come from methyl transformation on fluorenes ring as electron transport material.
A kind of application as second order or third-order non-linear material that comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes.
A kind ofly come from the conduct biology of " previous-next " asymmetrical type spiral shell two fluorene compounds that methyl on fluorenes ring changes or the application of Chemical Luminescent Probes.
Main points of the present invention are: with 4,4 '-dimethyl diphenyl is raw material, through bromination, grignard reaction, with Fluorenone or 2,7-bis-replaces Fluorenones and is dehydrated into the reactions such as ring, obtain 2,7-dimethyl-2 ', 7 '-bis-X-9, (X can be H to 9 '-spiral shell, two fluorenes, can be the R in claim 1
1or R
2, but be not methyl).By 2,7-dimethyl-2 ', 7 '-bis-X-9,9 '-spiral shell, two fluorenes, the functional group by methyl on fluorenes ring transforms can make compound (I), chemical equation is as follows:
In formula Y can be *-CN,
etc. the R described in claim 1
1or R
2group.
Compared with prior art, beneficial effect of the present invention is:
(1) adopt 4,4 cheap '-dimethyl-2-bromo biphenyl to substitute the expensive 2-bromo biphenyl generally using in current 9,9 '-spiral shell, two fluorenes preparation process.4,4 '-dimethyl-2-bromo biphenyl is to take para-bromo toluene by coupling and bromination reaction, to make as raw material.
(2) by methyl being changed into the various functional groups such as brooethyl, aldehyde radical, carboxyl, widened the synthesis path of " previous-next " asymmetrical type spiral shell two fluorene compounds.
(3) " previous-next " asymmetrical type spiral shell two fluorene compounds are used as to organic non-linear optical properties.
(4) " previous-next " asymmetrical type spiral shell two fluorene compounds are used as to pH probe and fluorescent probe.
The invention has the advantages that:
1. utilize raw material simple and easy to get, by common reaction, prepared " previous-next " asymmetrical type spiral shell two fluorene compounds.That this method has is with low cost, synthetic route is simple, productive rate is high and the feature such as easy suitability for industrialized production.
2. this synthetic method provides a kind of important approach and thinking for synthesizing " previous-next " asymmetrical type spiral shell two fluorene compounds.
3. " previous-next " asymmetrical type spiral shell two fluorene compounds of synthesized have special electronic structure and photoelectric properties, it is the important materials in organic photoelectrical material field, " previous-next " asymmetrical type spiral shell two fluorene compounds are used as to organic non-linear optical properties, pH probe and fluorescent probe etc., widened the range of application of spiral shell two fluorene compounds.
4. " previous-next " asymmetrical type spiral shell two fluorene compounds of synthesized have special spiral shell conjugative effect, good solubility and light transmission, higher thermostability.
Accompanying drawing explanation
Fig. 1 is 2,7-dimethyl-2 ', and 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes
1h NMR;
Fig. 2 is 2,7-, bis-bromomethyl-2 ', and 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes
1h NMR;
Fig. 3 is 2,7-diformyl-2 ', and 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes
1h NMR;
Fig. 4 is 2,7-dinitrile-2 ', 7 '-bis-carbazole-9,9 '-spiral shell, two fluorenes
1h NMR;
Fig. 5 is 2,7-dinitrile-2 ', 7 '-bis-carbazole-9, the extinction spectrum figure of 9 '-spiral shell, two fluorenes;
Fig. 6 is 2,7-dinitrile-2 ', 7 '-bis-carbazole-9, the fluorescence spectrum figure of 9 '-spiral shell, two fluorenes.
Embodiment
Below in conjunction with embodiment and accompanying drawing thereof, the present invention is illustrated further.
Embodiment 1
2,7-diformyl-2 ', 7 '-bis-is bromo-9, and the preparation method of 9 '-spiral shell, two fluorenes, comprises the following steps:
(1) 4, the preparation of 4 '-dimethyl diphenyl
Adopt be cheaply easy to get 4; 4 '-dimethyl diphenyl is raw material; under nitrogen protection; take successively the magnesium powder that 3g (125mmol) is dry; 0.2g (1.2mmol) iron trichloride, in the dry three-necked flask of 100ml, then takes 11g (64.3mmol) para-bromo toluene in the dry constant pressure funnel of 50ml.In three-necked flask, inject anhydrous 60ml tetrahydrofuran (THF), at room temperature vigorous stirring.First drip fast 5% para-bromo toluene, after reaction causes, more slowly drip.After being added dropwise to complete, continue reaction 30min, stopped reaction, is cooled to room temperature, and suction filtration obtains black filtrate, except desolventizing, obtains black mashed prod.Adding successively 50ml methylene dichloride and 30ml water,, there are a large amount of flosss in high vibration in solution.In solution, slowly drip dilute hydrochloric acid solution constantly concussion, until floss disappears.Separatory, collected organic layer, dichloromethane extraction 3 times (10ml * 3) for water layer, merges organic layer, adds appropriate anhydrous sodium sulfate drying.Filter to obtain yellow liquid, except desolventizing obtains yellow mashed prod, add a small amount of dehydrated alcohol, separate out immediately a large amount of water white transparency needle-like solids, suction filtration, obtains 3.6g 4,4-dimethyl diphenyl, productive rate 61.3%.Surveying its fusing point is 120～122 ℃.
(2) 4,4 '-dimethyl-2-bromo biphenyl synthetic
Take 4 of 1.2g (6.6mmol), 4 '-dimethyl diphenyl, in the mono-neck flask of 50ml, injects the dry methylene dichloride of 8ml, add a small amount of iodine, in ice-water bath, stir after 30min, 0.41ml (7.92mmol) bromine is injected in 50ml constant pressure funnel, slowly drip.After being added dropwise to complete, continue reaction 3h.Stopped reaction adds a small amount of saturated sodium sulfite aqueous solution in flask, is stirred to brown taking off.Use separating funnel separatory, collected organic layer, washed with dichloromethane 3 times (5ml * 3) for water layer.In organic layer, add a small amount of anhydrous sodium sulfate drying.Suction filtration, obtains dry yellow solution, except after desolventizing 1.61g brown oil, 4,4 '-dimethyl-2-bromo biphenyl, productive rate 94%.
(3) 2,7-dimethyl-2 ', 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes synthetic
Under nitrogen protection, in 100ml three-necked flask, add 4 of 1.70g (6.5mmol) successively, 4 '-dimethyl-2-bromo biphenyl, a small amount of iodine, the dry magnesium rod of 0.19g (7.9mmol), 10ml anhydrous tetrahydro furan reinjects.Oil bath refluxes, and after reaction causes, solution colour becomes faint yellowly from brown, and viscosity obviously increases.After most of magnesium powder disappears, Grignard reagent is slowly added drop-wise to and is dissolved with 1.7g (5.0mmol) 2, in the tetrahydrofuran solution of 7-bis-bromo-9-Fluorenones, continue back flow reaction 14h.Stopped reaction, removes the solvent in flask, obtains faint yellow mashed prod, in flask, adds successively 8ml glacial acetic acid and 0.6ml concentrated hydrochloric acid (10mol/L), continues back flow reaction 4h.Stopped reaction, solution is cooled to room temperature, separates out a large amount of solids, and suction filtration obtains pale solid, uses washing with alcohol 2 times, obtains white solid 1.5g, productive rate 46.3%.
1H?NMR(400MHz，CDCl
3，δppm)：2.2(s，6H)，6.5(s，2H)，6.8(d，2H)，7.2(d，2H)，7.5(d，2H)，7.7(d，4H)
(4) 2,7-, bis-bromomethyl-2 ', 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes synthetic
Under nitrogen protection; to being connected in the dry 100ml three-necked flask of reflux condensing tube, add successively 2g (4mmol) 2; 7-dimethyl-2 '; 7 '-bis-bromo-9; 9 '-spiral shell, two fluorenes; 1.5g (8.43mmol) NBS, 0.20g (0.82mmol) dibenzoyl peroxide (BP0), 10mlCCl reinjects
4, back flow reaction 12h.After stopped reaction, be cooled to room temperature, in reaction solution, add appropriate silica gel, carry out column chromatography (developping agent is sherwood oil), obtain white solid 1.7g, 2,7-bis-bromomethyl-2 ', 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes, productive rate 65%.A large amount of solids, suction filtration obtains pale solid, uses washing with alcohol 2 times, obtains white solid 1.5g, productive rate 46.3%.
1H?NMR(400MHz，CDCl
3，δppm)：4.4(s，4H)，6.7(s，2H)，6.8(d，2H)，7.4(d，2H)，7.5(d，2H)，7.7(d，2H)，7.8(d，2H)
(5) 2,7-diformyls-2 ', 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes synthetic
Under nitrogen protection; in the mono-neck flask of the dry 20ml that is connected to reflux condensing tube, add successively 0.4g (0.606mmol) 2; 7-bis-bromomethyl-2 '; 7 '-bis-bromo-9; 9 '-spiral shell, two fluorenes; 1.5g (18mmol) sodium bicarbonate and magneton, the 5mlDMS0 that reinjects reacts 12h at 110 ℃.After stopped reaction, be cooled to room temperature, add about 10ml frozen water, separate out a large amount of solids, filter to obtain white solid.By white solid carry out column chromatography (developping agent is sherwood oil: ethyl acetate=10: 1), obtain faint yellow solid 0.131g, 2,7-diformyl-2 ', 7 '-bis-is bromo-9,9 '-spiral shell, two fluorenes, productive rate 41%.
1H?NMR(400MHz，CDCl
3，δppm)：6.9(s，2H)，7.3(s，2H)，7.6(d，2H)，7.7(d，2H)，8.0(d，2H)，8.1(d，2H)，9.9(s，2H)
Embodiment 2
2,7-dinitrile-2 ', 7 '-bis-carbazole-9, the preparation of 9 '-spiral shell, two fluorenes, comprises the following steps:
Under nitrogen protection; in the mono-neck flask of the dry 10ml that is connected to reflux condensing tube, add successively 10mg (0.014mmol) 2; 7-diformyl-2 '; 7 '-bis-carbazole-9; 9 '-spiral shell, two fluorenes; 20mg (0.29mmol) oxammonium hydrochloride, the new N-Methyl pyrrolidone (NMP) steaming of the 2ml that reinjects reacts 12h at 115 ℃.After stopped reaction, be cooled to room temperature, add about 5ml frozen water, separate out a large amount of solids, filter to obtain yellow solid, (developping agent is sherwood oil to column chromatography: ethyl acetate=15: 1), obtain faint yellow solid 8mg, 2,7-dinitrile-2 ', 7 '-bis-carbazole-9,9 '-spiral shell, two fluorenes, productive rate 80%.
1H?NMR(400MHz，CDCl
3，δppm)：6.8(s，2H)，7.1(d，4H)，7.2(t，4H)，7.3(t，4H)，7.5(s，2H)，7.8(d，2H)，7.9(d，2H)，8.1(d，4H)，8.3(d，2H)，8.5(d，2H)
Embodiment 3
Come from the photoluminescence spectra measuring method (with 2,7-dinitrile-2 ', 7 '-bis-carbazole-9,9 '-spiral shell, two fluorenes are example) of " previous-next " asymmetrical type spiral shell two fluorene compounds that methyl on fluorenes ring changes
Product is mixed with to 1 * 10 in the solvent of opposed polarity
-5the solution of M, carries out absorption spectrum and emission spectrometry at ultraviolet-visual spectrometer and fluorescence spectrophotometer respectively.Ultra-violet absorption spectrum is shown in accompanying drawing 5, and fluorescence emission spectrum is shown in accompanying drawing 6.From Fig. 5, can obviously see, the absorption spectrum of compound, in 325nm left and right, ends in 370nm, meets the practical requirement of the nonlinear material transparency completely.From Fig. 6, can obviously see, the emission maximum spectrum of compound is in 410nm left and right, and emission peak increases and red shift with solvent polarity.During this explanation excited state there is obvious transfer in intramolecular electric charge, and spiral shell conjugative effect has obtained sufficient embodiment in " previous-next " asymmetrical type spiral shell two fluorene compounds.
Embodiment 4
Come from the testing method (with 2,7-dinitrile-2 ', 7 '-bis-carbazyl-9,9 '-spiral shell, two fluorenes are example) of " previous-next " asymmetrical type spiral shell two fluorene compound second nonlinear performances that methyl on fluorenes ring changes
Utilize the molten variable color method that causes, second eyeball (37.5D) and toluene (2.4D) that the difference in dielectric constant of take is larger are solvent, record the molten variable color equation that causes of substitution after related data, calculate 2,7-dinitrile-2 ', 7 '-bis-carbazole-9,9, the β of-spiral shell two fluorenes
cTμ
gbe 1574.And 2,7-dinitrile-2,, 7 ,-bis-carbazyl-9,9, the fusing point of-spiral shell two fluorenes is greater than 250 ℃.As can be seen here, " previous-next " asymmetrical type spiral shell two fluorene compounds with D-π-A structure, there is larger second-order nonlinear polarizability, and light transmission and thermostability all very good, be expected to solve current second nonlinear material " non-linear-light transmission-thermostability " contradiction.Can predict, this class material is more and more wider in the application meeting in non-linear field.
Above embodiment is used for illustrative purposes only, but not limitation of the present invention, person skilled in the relevant technique, without departing from the spirit and scope of the present invention, can also make various conversion or variation.Therefore, all technical schemes that are equal to also should belong to category of the present invention, should be limited by each claim.
Claims (4)
1. come from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes, there is following logical formula I:
In formula:
R
1for, R
2for
r wherein
5, R
6for hydrogen.
2. the application of the luminous or laser diode device material of a kind of conduct that comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that methyl on fluorenes ring changes described in claim 1.
3. a kind of application as second order or third-order non-linear material that comes from " previous-next " asymmetrical type spiral shell two fluorene compounds that on fluorenes ring, methyl changes described in claim 1.
4. a kind ofly described in claim 1 come from the conduct biology of " previous-next " asymmetrical type spiral shell two fluorene compounds that methyl on fluorenes ring changes or the application of Chemical Luminescent Probes.
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| CN103589419B (en) * | 2013-09-17 | 2015-05-20 | 吉林奥来德光电材料股份有限公司 | Spirobifluorene organic electroluminescence material and preparation method thereof |
| CN105622442A (en) * | 2016-02-23 | 2016-06-01 | 中节能万润股份有限公司 | Tert-butyl spirobifluorene compound and preparation method and application thereof |
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