CN102766084A - Vertically asymmetrical methyl spirobifluorene compound - Google Patents
Vertically asymmetrical methyl spirobifluorene compound Download PDFInfo
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- CN102766084A CN102766084A CN2011104593271A CN201110459327A CN102766084A CN 102766084 A CN102766084 A CN 102766084A CN 2011104593271 A CN2011104593271 A CN 2011104593271A CN 201110459327 A CN201110459327 A CN 201110459327A CN 102766084 A CN102766084 A CN 102766084A
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Abstract
The invention relates to a vertically asymmetrical methyl spirobifluorene compound. The structural formula of the product provided by the invention is as shown in the formula (I), wherein R1 can be various electron-withdrawing and electro-donating groups such as various alkyl groups, substituted aryl group, substituted heterocyclic radical group, substituted alkylene group, substituted amino group, chlorine, bromine, iodine and the like, but is not methyl. Cheap and easily available 4,4'-dimethyl biphenyl is used as a raw material and undergoes bromination and reaction with 2,7-diX(X represents substituent)fluorenone, and the Xsubstituent on the fluorine ring is changed into various function groups so as to obtain the compound (I). The vertically asymmetrical methyl spirobifluorene compound provided by the invention has advantages of low product cost, simple synthetic route and high yield, is easy for industrial production, has a special spiro-conjugation effect, good dissolvability and high thermal stability, and can be widely applied in fields of organic electroluminesence display, organic non-linear materials, fluorescent probe and the like.
Description
Technical field
The present invention relates to one type of spiral shell two fluorene compound, specifically, is one type of " on-down " asymmetrical type methylspiro two fluorene compound.
Background technology
9,9 '-spiral shell, two fluorenes have just been synthesized as far back as nineteen thirty Clarkson and Gomberg etc.Salbeck in 1997 etc. are used in the electroluminescent material aspect with spiral shell two fluorenes, thereby have caused spiral shell two fluorenes extensively carrying out at the organic photoelectric functional material area research.Because spiral shell two fluorenes are three-dimensional orthogonal intersection space structure, can avoid chromophoric tightly packed in the molecule, improve the thermostability and the solubility property of material; And pass through sp
3The spiral shell carbon atom of hydridization can be realized the control of molecular conjugation length again 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 extends to fields such as organic solar batteries, organic non-linear optical properties and fluorescent probe from initial electroluminescent.
The classical way of at present synthetic spiral shell two fluorenes generally is to utilize the Grignard reagent of 2-bromo biphenyl and Fluorenone reaction to obtain, and the 2-bromo biphenyl generally is to utilize adjacent dibromobenzene to make through linked reaction, costs an arm and a leg.During spiral shell two is fluorene structured 2,2 ', 7,7 ' position has good reactive behavior; Through substitution reaction 2,2 '-two R-9 that are easy to get, 9 '-spiral shell two fluorenes (R representes substituting group) or 2,2 '-two R-7; 7 '-two R '-9,9 '-spiral shell two fluorenes (R, R ' expression substituting group can be identical or different).And " on-down " and asymmetrical type spiral shell two fluorene compounds 2,7-two R-2 ', 7 '-two R '-9,9 '-spiral shell two fluorenes or 2-R-2 '-R '-9,9 '-spiral shell two fluorenes (R, R ' expression substituting group, and inequality), because the difficulty on synthetic, bibliographical information is less.
The present invention from cheaply be easy to get 4,4 '-dimethyl diphenyl sets out, and obtained 2,7-dimethyl--2 ', 7 '-two X-9,9 '-(X can be H to spiral shell two fluorenes, can be the R in the claim 1
1But be not methyl).Through the substituent functional group of X is changed, prepared in a large number " on-down " asymmetrical type methylspiro two fluorene compounds.This synthetic route has been widened the synthesis path of " on-down " asymmetrical type spiral shell two fluorene compounds.
Spiral shell two fluorene compounds are used widely in the organic electroluminescent field, have formed suitable article and patent.Bibliographical information is arranged the different fluorenes rings of spiral shell two fluorenes connect respectively hole mobile material and electron transport material " on-down " 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 the fluorescent probe aspect but rarely has report.
Summary of the invention
The object of the invention is to propose one type of " on-down " asymmetrical type methylspiro two fluorene compound.
Another object of the present invention is to propose the preparation method of one type of " on-down " asymmetrical type methylspiro two fluorene compound.
Another purpose of the present invention is to propose a kind of " on-down " asymmetrical type methylspiro two fluorene compounds as application luminous or the laser diode device material.
A purpose more of the present invention is to propose the application as second order or third-order non-linear material of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds.
Of the present invention also have a purpose, is to propose the application of the biological or chemiluminescence probe of the conduct of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds.
For realizing above-mentioned purpose, technical solution of the present invention is:
A kind of " on-down " asymmetrical type methylspiro two fluorene compounds with following general formula (I):
In the formula:
R
1For:
(1) C
2-C
5Branched-chain alkyl or straight chained alkyl, Cl, Br, I, NH
2Or
Wherein m, n are separately integer, the *-CH of 0-8
2Br, *-CHO, *-CN or-Ar, wherein Ar can be selected from structure unit or the unitary verivate of structure:
(2) or the structure unit:
Wherein:
R
2, R
3, R
4, R
5For hydrogen or have straight chain, side chain or cyclic alkyl or the oxyalkyl chain of 1-22 carbon atom, and can be identical or different;
(3) or the structure unit:
Wherein:
R
6For
Wherein:
R
7, R
8For hydrogen, contain 1-10 carbon atom branched-chain or straight-chain alkyl, contain the aryl of 6-15 carbon atom, and can be identical or different;
R
9For hydrogen or have straight chain, side chain or cyclic alkyl or the oxyalkyl chain of 1-22 carbon atom;
R
10Be CH
2, O, S or NR ', R ' is the side chain or the straight-chain paraffin of hydrogen, a 1-12 carbon.
(4) or structural unit:
Wherein:
R
11, R
12Be H, *-NO
2, *-CN, *-COOH,
Wherein R ' be hydrogen, a 1-12 carbon side chain or straight chained alkyl,
R wherein " be the side chain or the straight chained alkyl of hydrogen, a 1-12 carbon, R
11With R
12Can be identical or different, collateral condition is that both are not H simultaneously;
(5) or structural unit:
R
13, R
14For hydrogen or have straight chained alkyl, branched-chain alkyl or cyclic alkyl, oxyalkyl chain or the aryl of 1-22 carbon atom, R
13, R
14Can be identical or different, M is S, O, CH
2, or NR " ', wherein R " ' be the side chain or the straight chained alkyl of hydrogen, a 1-12 carbon;
(6) or structural unit:
R
15, R
16For hydrogen or have straight chained alkyl, branched-chain alkyl or cyclic alkyl, oxyalkyl chain or the aryl of 1-22 carbon atom, R
15With R
16Can be identical or different.
The preparation method of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds is characterized in that may further comprise the steps:
(1), produces 4,4 '-dimethyl--2-bromo biphenyl
With 4,4 '-dimethyl diphenyl, iodine and exsiccant methylene dichloride join in single neck flask successively, in ice-water bath, stir 30min after, with the slow dropping liquid bromine of constant pressure funnel; After being added dropwise to complete, continue reaction 5h; Stopped reaction adds the saturated sodium sulfite aqueous solution in flask, be stirred to brown taking off; Separatory, collected organic layer, water layer merge organic layer with dichloromethane extraction 3 times, use anhydrous sodium sulfate drying; Suction filtration, removing desolvates promptly gets 4,4 '-dimethyl-2-bromo biphenyl;
(2), produce 2,7-dimethyl--2 ', 7 '-two X-9,9 '-spiral shell, two fluorenes, wherein X can be H, can be the R in (I) formula
1Perhaps R
2, but be not methyl.
Under the nitrogen protection, 4,4 '-dimethyl--2-bromo biphenyl is in anhydrous tetrahydro furan, and the following and exsiccant magnesium rod reaction 0.5-1h of catalysis of iodine processes Grignard reagent; The Grignard reagent for preparing slowly is added drop-wise to is equipped with 2, in the anhydrous tetrahydrofuran solution of 7-two X-9-Fluorenones, backflow 14-20h obtains corresponding fluorenol; Remove the THF in the reaction soln, add acetate and hydrochloric acid, backflow 3-6h has solid to separate out, and is cooled to room temperature, filters, and gets thick product, uses normal hexane and absolute ethanol washing respectively, promptly obtains 2,7-dimethyl--2 ', 7 '-two X-9,9 '-spiral shell, two fluorenes;
(3), produce 2,7-dimethyl--2 ', 7 '-two Y-9,9 '-spiral shell, two fluorenes, wherein Y can be
Deng the R described in (I)
1, but be not methyl, wherein comprise following preparation method:
(a), when Y is
, preparation method is:
Under nitrogen protection, in the exsiccant list neck flask that is connected to reflux condensing tube, add 2 successively, 7-dimethyl--2 ', 7 '-two bromo-9; 9 '-spiral shell, two fluorenes, carbazole, or derivatives thereof, salt of wormwood; Activated copper powder, 18-is preced with-6 ethers, the new orthodichlorobenzene that steams that reinjects, back flow reaction 36h.After reaction finished, underpressure distillation removed and desolvates, and column chromatography promptly gets 2,7-dimethyl--2 ', 7 '-two carbazyls-9,9 '-spiral shell, two fluorenes;
(b), when Y is
, preparation method is:
Under nitrogen protection, successively with 2,7-dimethyl--2 ', 7 '-two bromo-9,9 '-spiral shell, two fluorenes, 4-boric acid triphenylamine, or derivatives thereof, palladium, triphenylphosphine and Anhydrous potassium carbonate join in single neck flask, the anhydrous tetrahydro furan that reinjects, back flow reaction 36h.Stopped reaction is cooled to room temperature, adds silica gel, carries out column chromatography, promptly gets 2,7-dimethyl--2 ', 7 '-two (triphenylamine)-9,9 '-spiral shell, two fluorenes;
The preparation method of " on-down " asymmetrical type methylspiro two fluorene compounds that the present invention relates to can also adopt following technical measures to come further to realize.
Aforesaid method, wherein in the step (1), 4, the mol ratio of 4 '-dimethyl diphenyl and liquid bromine is 1: 1.2, temperature of reaction is 0～5 ℃.
Aforesaid method, wherein in the step (2), 4,4 '-dimethyl--2-bromo biphenyl, magnesium rod and 2, the mol ratio of 7-two X-9-Fluorenones is 1: 1.2: 0.8; During the final step dehydration cyclization, need original solvents tetrahydrofurane is removed, to improve productive rate; The concentrated hydrochloric acid massfraction that is added is 30%～37%, and itself and glacial acetic acid volume ratio are 1: 10～15.
Aforesaid method, wherein in the step (3a), 2,7-dimethyl--2 ', 7 '-two bromo-9,9 '-spiral shell, two fluorenes, carbazole, the mol ratio of or derivatives thereof, salt of wormwood, activated copper powder, 18-hat-6 ethers is 1: 3: 8: 5: 0.25.
Aforesaid method, wherein in the step (3b), 2,7-dimethyl--2 ', 7 '-two bromo-9, the mol ratio of 9 '-spiral shell, two fluorenes, 4-boric acid triphenylamine, palladium, triphenylphosphine and Anhydrous potassium carbonate is 1: 2.2: 0.2: 0.2: 10.
The application of the luminous or laser diode device material of the conduct of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds; Wherein the structure of LED device is transparent anode/hole mobile material/luminescent material/electronics injecting material/negative electrode, wherein adopts " on-down " asymmetrical type methylspiro two fluorene compounds as hole mobile material.
The application of the luminous or laser diode device material of the conduct of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds; Wherein the structure of LED device is transparent anode/hole mobile material/luminescent material/electronics injecting material/negative electrode, wherein adopts the material of main part of " on-down " asymmetrical type methylspiro two fluorene compounds as luminescent material or white light and phosphorescence.
The application of the luminous or laser diode device material of the conduct of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds; Wherein the structure of LED device is transparent anode/hole mobile material/luminescent material/electronics injecting material/negative electrode, wherein adopts " on-down " asymmetrical type methylspiro two fluorene compounds as electron transport material.
The application as second order or third-order non-linear material of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds.
The application of the biological or chemiluminescence probe of the conduct of a kind of " on-down " asymmetrical type methylspiro two fluorene compounds.
Main points of the present invention are: with 4,4 '-dimethyl diphenyl is a raw material, through bromination, grignard reaction, with Fluorenone or 2; 7-two replaces Fluorenone and is dehydrated into reactions such as ring, obtains 2,7-dimethyl--2 '; 7 '-two X-9,9 '-(X can be H to spiral shell two fluorenes, can be the R in the claim 1
1, but be not methyl).By 2,7-dimethyl--2 ', 7 '-two X-9,9 '-spiral shell two fluorenes, through being transformed, the substituent functional group of X can make compound (I), and reaction formula is following:
Y can be in the formula
Etc. the described R of claim 1
1, but be not methyl.
Compared with prior art, beneficial effect of the present invention is:
(1) adopt cheaply 4, that 4 '-dimethyl--2-bromo biphenyl substitutes is present 9,9 '-spiral shell two fluorenes prepare the expensive 2-bromo biphenyl that generally uses in the process.4,4 '-dimethyl--2-bromo biphenyl is to be that raw material makes through coupling and bromination reaction with the para-bromo toluene.
(2) through changing X group on the fluorenes ring into various functional groups, widened the synthesis path of " on-down " asymmetrical type spiral shell two fluorene compounds.
(3) will " on-down " asymmetrical type methylspiro two fluorene compounds as organic non-linear optical properties.
(4) will " on-down " asymmetrical type methylspiro two fluorene compounds as pH probe and fluorescent probe.
The invention has the advantages that:
1. utilize be simple and easy to raw material, the reaction through common has prepared " on-down " asymmetrical type methylspiro two fluorene compounds.That this method has is with low cost, synthetic route is simple, productive rate is high and characteristics such as easy suitability for industrialized production.
2. this compound method provides a kind of important approach and thinking for synthetic " on-down " asymmetrical type spiral shell two fluorene compounds.
3. institute's synthetic " on-down " asymmetrical type methylspiro two fluorene compounds have special electronic structure and photoelectric properties; It is the important materials in organic photoelectrical material field; Will " on-down " asymmetrical type methylspiro two fluorene compounds as organic non-linear optical properties; PH probe and fluorescent probe etc. have greatly been widened the range of application of spiral shell two fluorene compounds.
4. institute's synthetic " on-down " asymmetrical type methylspiro two fluorene compounds have special spiral shell conjugative effect, good solubility and light transmission, higher thermostability.
Description of drawings
Fig. 1 is 2,7-dimethyl--2 ', 7 '-two (triphen amidos)-9,9 '-spiral shell, two fluorenes
1H NMR;
Fig. 2 is 2,7-dimethyl--2 ', 7 '-two bromo-9, the extinction spectrum figure of 9 '-spiral shell, two fluorenes;
Fig. 3 is 2,7-dimethyl--2 ', 7 '-two bromo-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-dimethyl--2 ', 7 '-two carbazoles-9, the preparation of 9 '-spiral shell, two fluorenes may further comprise the steps:
(1) 4, the preparation of 4 '-dimethyl diphenyl
Adopt cheaply be easy to get 4; 4 '-dimethyl diphenyl is a raw material; Under nitrogen protection; Take by weighing 3g (125mmol) exsiccant magnesium powder successively, 0.2g (1.2mmol) iron trichloride takes by weighing 11g (64.3mmol) para-bromo toluene in 50ml exsiccant constant pressure funnel again in 100ml exsiccant three-necked flask.In three-necked flask, inject anhydrous 60ml THF, at room temperature vigorous stirring.The para-bromo toluene of earlier quick Dropwise 5 % after reaction causes, slowly drips again.After being added dropwise to complete, continuation reaction 30min, stopped reaction is cooled to room temperature, and suction filtration gets black filtrating, removes and desolvates, and gets the black mashed prod.Add 50ml methylene dichloride and 30ml water successively, a large amount of flosss appear in high vibration in the solution.In solution, slowly drip dilute hydrochloric acid solution and constantly concussion, disappear until floss.Separatory, collected organic layer, water layer merge organic layer with dichloromethane extraction 3 times (10ml * 3), add anhydrous sodium sulfate drying.Cross and filter yellow liquid, remove desolvate yellow mashed prod, add absolute ethyl alcohol, separate out a large amount of water white transparency needle-like solids immediately, suction filtration, 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 by weighing 4 of 1.2g (6.6mmol), 4 '-dimethyl diphenyl injects 8ml exsiccant methylene dichloride in the single neck flask of 50ml; Add iodine; After in ice-water bath, stirring 30min, 0.41ml (7.92mmol) liquid bromine is injected in the 50ml constant pressure funnel, slowly drips.After being added dropwise to complete, continue reaction 3h.Stopped reaction adds the saturated sodium sulfite aqueous solution in flask, be stirred to brown taking off.Use the separating funnel separatory, collected organic layer, water layer is with washed with dichloromethane 3 times (5ml * 3).In organic layer, add anhydrous sodium sulfate drying.Suction filtration, the exsiccant yellow solution, remove after desolvating the 1.61g brown oil, promptly 4,4 '-dimethyl--2-bromo biphenyl, productive rate 94%.
(3) 2,7-dimethyl--2 ', 7 '-two bromo-9,9 '-spiral shell, two fluorenes synthetic
Under the nitrogen protection, in the 100ml three-necked flask, add 4 of 1.70g (6.5mmol) successively, 4 '-dimethyl--2-bromo biphenyl, iodine, 0.19g (7.9mmol) exsiccant magnesium rod, the 10ml anhydrous tetrahydro furan reinjects.Oil bath refluxes, and after reaction caused, solution colour became faint yellowly by brown, and viscosity obviously increases.After treating that most of magnesium powder disappears, Grignard reagent slowly is added drop-wise to is dissolved with 1.7g (5.0mmol) 2, in the tetrahydrofuran solution of 7-two bromo-9-Fluorenones, continue back flow reaction 14h.Stopped reaction is removed the solvent in the flask, gets faint yellow mashed prod, in flask, adds 8ml glacial acetic acid and 0.6ml hydrochloric acid (10mol/L) successively, continues back flow reaction 4h.Stopped reaction, solution is cooled to room temperature, separates out a large amount of solids, suction filtration gets pale solid, with washing with alcohol 2 times, 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-dimethyl--2 ', 7 '-two carbazoles-9,9 '-spiral shell, two fluorenes synthetic
Under nitrogen protection, in the single neck flask of the exsiccant 10ml that is connected to reflux condensing tube, add 1.2g (2.4mmol) 2 successively, 7-dimethyl--2 '; 7 '-two bromo-9,9 '-spiral shell, two fluorenes, 1.2g (7.2mmol) carbazole; 2.65g (19.2mmol) salt of wormwood, 0.77g (12mmol) activated copper powder, 0.16g (0.6mmol) 18-is preced with-6 ethers; The new orthodichlorobenzene that steams of the 3ml that reinjects, back flow reaction 36h.Behind the stopped reaction, underpressure distillation removes and to desolvate, column chromatography (sherwood oil: ETHYLE ACETATE=80: 1), white solid 0.42g, promptly 2,7-dimethyl--2 ', 7 '-two carbazoles-9,9 '-spiral shell, two fluorenes, productive rate 26%.
1H?NMR(400MHz，CDCl
3，δppm)：2.2(s，6H)，6.5(s，2H)，6.9(s，2H)，7.1(d，4H)，7.2(t，4H)，7.3(t，4H)，7.5(s，2H)，7.8(d，2H)，8.1(d，4H)，8.2(d，2H)，8.3(d，2H)
Embodiment 2
2,7-dimethyl--2 ', 7 '-two (triphen amidos)-9, the preparation of 9 '-spiral shell, two fluorenes:
(1) 2,7-dimethyl--2 ', 7 '-two bromo-9, the preparation of 9 '-spiral shell, two fluorenes
With among the embodiment 12,7-dimethyl--2 ', 7 '-two bromo-9, the preparation of 9 '-spiral shell, two fluorenes
(2) 2,7-dimethyl--2 ', 7 '-two (triphen amidos)-9,9 '-spiral shell, two fluorenes synthetic
Under nitrogen protection, successively with 100mg (0.2mmol) 2,7-dimethyl--2 '; 7 '-two bromo-9; 9 '-spiral shell, two fluorenes, 126mg (0.44mmol) 4-boric acid triphenylamine, 9mg (0.04mmol) palladium, 11mg (0.04mmol) triphenylphosphine and 276mg (2mmol) Anhydrous potassium carbonate join in the single neck flask of 100ml; The 25ml anhydrous tetrahydro furan that reinjects, back flow reaction 36h.Stopped reaction is cooled to room temperature, adds 300-400 order silica gel, carries out column chromatography, gets title product 85mg, productive rate 51.6%.。
1H?NMR(400MHz，CDCl
3，δppm)：2.2(s，6H)，6.5(s，2H)，6.95(s，2H)，6.99(t，8H)，7.02(t，8H)，7.04(d，2H)，7.2(t，8H)，7.3(d，4H)，7.48(d，2H)，7.52(d，2H)，7.88(d，2H)
Embodiment 3
The photoluminescence spectra of " on-down " asymmetrical type methylspiro two fluorene compounds is measured (with 2,7-dimethyl--2 ', 7 '-two bromo-, 9,9 '-spiral shell, two fluorenes are example)
With 2,7-dimethyl--2 ', 7 '-two bromo-9,9 '-spiral shell, two fluorenes are mixed with 1 * 10 in the solvent of opposed polarity
-5The solution of M carries out absorption spectrum and emission spectrometry at ultraviolet-visual spectrometer and XRF respectively.Uv absorption spectrum is seen accompanying drawing 2, and fluorescence emission spectrum is seen accompanying drawing 3.Can see obviously that from Fig. 2 the maximum absorption spectrum of compound ends in 330nm about 285nm.Can see obviously that from Fig. 3 the emission maximum spectrum of compound is about 360nm.
Above embodiment only supplies to explain the present invention's usefulness, but not limitation of the present invention, the technician in relevant technologies field under the situation that does not break away 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 each claim.
Claims (8)
1. one kind " on-down " asymmetrical type methylspiro two fluorene compounds, have following general formula (I):
In the formula:
R
1For:
(1) C
2-C
5Branched-chain alkyl or straight chained alkyl, Cl, Br, I, NH
2Or
Wherein m, n are separately integer, the *-CH of 0-8
2Br, *-CHO, *-CN or-Ar, wherein Ar is for being selected from the unitary verivate of structure unit or structure:
(2) or the structure unit:
Wherein:
R
2, R
3, R
4, R
5For hydrogen or have straight chain, side chain or cyclic alkyl or the oxyalkyl chain of 1-22 carbon atom, and can be identical or different;
(3) or the structure unit:
Wherein:
R
6For
Wherein:
R
7, R
8For hydrogen, contain 1-10 carbon atom branched-chain or straight-chain alkyl, contain the aryl of 6-15 carbon atom, and can be identical or different;
R
9For hydrogen or have straight chain, side chain or cyclic alkyl or the oxyalkyl chain of 1-22 carbon atom;
R
10Be CH
2, O, S or NR ', R ' is the side chain or the straight-chain paraffin of hydrogen, a 1-12 carbon;
(4) or structural unit:
Wherein:
R
11, R
12Be H, *-NO
2, *-CN, *-COOH,
Wherein R ' be hydrogen, a 1-12 carbon side chain or straight chained alkyl,
R wherein " be the side chain or the straight chained alkyl of hydrogen, a 1-12 carbon, R
11With R
12Be identical or different substituting groups, collateral condition is that both are not H simultaneously;
(5) or structural unit:
R
13, R
14For hydrogen or have straight chained alkyl, branched-chain alkyl or cyclic alkyl, oxyalkyl chain or the aryl of 1-22 carbon atom, R
13With R
14Can be identical or different, M is S, O, CH
2, or NR " ', wherein R " ' be the side chain or the straight chained alkyl of hydrogen, a 1-12 carbon;
(6) or structural unit:
R
15, R
16For hydrogen or have straight chained alkyl, branched-chain alkyl or cyclic alkyl, oxyalkyl chain or the aryl of 1-22 carbon atom, R
15With R
16Can be identical or different.
2. the preparation method of claim 1 said a kind of " on-down " asymmetrical type methylspiro two fluorene compounds is characterized in that may further comprise the steps:
(1), produces 4,4 '-dimethyl--2-bromo biphenyl
With 4,4 '-dimethyl diphenyl, iodine and exsiccant methylene dichloride join in single neck flask successively, in ice-water bath, stir 30min after, with the slow dropping liquid bromine of constant pressure funnel; After being added dropwise to complete, continue reaction 5h; Stopped reaction adds the saturated sodium sulfite aqueous solution in flask, be stirred to brown taking off; Separatory, collected organic layer, water layer merge organic layer with dichloromethane extraction 3 times, use anhydrous sodium sulfate drying; Suction filtration, removing desolvates promptly gets 4,4 '-dimethyl--2-bromo biphenyl;
(2), produce 2,7-dimethyl--2 ', 7 '-two X-9,9 '-spiral shell, two fluorenes, wherein X is H or (I) R in the formula
1Or R
2, but be not methyl;
Under the nitrogen protection, 4,4 '-dimethyl--2-bromo biphenyl is in anhydrous tetrahydro furan, and the following and exsiccant magnesium rod reaction 0.5-1h of catalysis of iodine processes Grignard reagent; The Grignard reagent for preparing slowly is added drop-wise to is equipped with 2, in the anhydrous tetrahydrochysene furan solution of 7-two X-9-Fluorenones, backflow 14-20h obtains corresponding fluorenol; Remove the THF in the reaction soln, add acetate and hydrochloric acid, backflow 3-6h has solid to separate out, and is cooled to room temperature, filters, and gets thick product, uses normal hexane and absolute ethanol washing respectively, promptly obtains 2,7-dimethyl--2 ', 7 '-two X-9,9 '-spiral shell, two fluorenes;
(3), produce 2,7-dimethyl--2 ', 7 '-two Y-9,9 '-spiral shell, two fluorenes, wherein Y is
Deng the R described in (I)
1, but be not methyl, wherein comprise following preparation method:
(a), when Y is
, preparation method is:
Under nitrogen protection, in the exsiccant list neck flask that is connected to reflux condensing tube, add 2 successively, 7-dimethyl--2 ', 7 '-two bromo-9,9 '-spiral shell, two fluorenes; Carbazole, or derivatives thereof, salt of wormwood, activated copper powder, 18-is preced with-6 ethers; The orthodichlorobenzene that reinjects and newly steam, back flow reaction 36h, after reaction finished, underpressure distillation removed and desolvates; Column chromatography promptly gets 2,7-dimethyl--2 ', 7 '-two carbazyls-9,9 '-spiral shell, two fluorenes;
(b), when Y is
, preparation method is:
Under nitrogen protection, successively with 2,7-dimethyl--2 ', 7 '-two bromo-9,9 '-spiral shell, two fluorenes, 4-boric acid triphenylamine, palladium, triphenylphosphine and Anhydrous potassium carbonate join in single neck flask, the anhydrous tetrahydro furan that reinjects, back flow reaction 36h; Stopped reaction is cooled to room temperature, adds silica gel, carries out column chromatography, promptly gets 2,7-dimethyl--2 ', 7 '-two (triphenylamine)-9,9 '-spiral shell, two fluorenes.
3. the preparation method of " on-down " according to claim 2 asymmetrical type methylspiro two fluorene compounds, it is characterized in that: wherein in the step (1), the mol ratio of 4,4 '-dimethyl diphenyl and liquid bromine is 1: 1.2, temperature of reaction is 0～5 ℃.
4. the preparation method of " on-down " according to claim 2 asymmetrical type methylspiro two fluorene compounds is characterized in that: wherein in the step (2), and 4,4 '-dimethyl--2-bromo biphenyl, magnesium rod and 2, the mol ratio of 7-two X-9-Fluorenones is 1: 1.2: 0.8; During the final step dehydration cyclization, need original solvents tetrahydrofurane is removed, to improve productive rate; The concentrated hydrochloric acid massfraction that is added is 30～37%, and itself and glacial acetic acid volume ratio are 1: 15.
5. the preparation method of " on-down " according to claim 2 asymmetrical type methylspiro two fluorene compounds; It is characterized in that: wherein in the step (3a); 2,7-dimethyl--2 ', 7 '-two bromo-9; 9 '-spiral shell, two fluorenes, carbazole, the mol ratio of or derivatives thereof, salt of wormwood, activated copper powder, 18-hat-6 ethers is 1: 3: 8: 5: 0.25;
In the step (3b), 2,7-dimethyl--2 ', 7 '-two bromo-9, the mol ratio of 9 '-spiral shell, two fluorenes, 4-boric acid triphenylamine, palladium, triphenylphosphine and Anhydrous potassium carbonate is 1: 2.2: 0.2: 0.2: 10.
6. the application of the luminous or laser diode device material of the conduct of claim 1 said a kind of " on-down " asymmetrical type methylspiro two fluorene compounds.
7. the application as second order or third-order non-linear material of claim 1 said a kind of " on-down " asymmetrical type methylspiro two fluorene compounds.
8. the application of the biological or chemiluminescence probe of the conduct of claim 1 said a kind of " on-down " asymmetrical type methylspiro two fluorene compounds.
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