CN103304568A - Tripolyindole compound, and preparation method and use thereof - Google Patents
Tripolyindole compound, and preparation method and use thereof Download PDFInfo
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- CN103304568A CN103304568A CN2013102729740A CN201310272974A CN103304568A CN 103304568 A CN103304568 A CN 103304568A CN 2013102729740 A CN2013102729740 A CN 2013102729740A CN 201310272974 A CN201310272974 A CN 201310272974A CN 103304568 A CN103304568 A CN 103304568A
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- 0 ***OC(c([s]c1c(*)[s]c([*+])c11)c1F)O Chemical compound ***OC(c([s]c1c(*)[s]c([*+])c11)c1F)O 0.000 description 13
- AUYDLKLOWMXLLR-UHFFFAOYSA-N CC(B1OC(C)(C)C(C)(C)O1)CB1OC(C)(C)C(C)(C)O1 Chemical compound CC(B1OC(C)(C)C(C)(C)O1)CB1OC(C)(C)C(C)(C)O1 AUYDLKLOWMXLLR-UHFFFAOYSA-N 0.000 description 1
- QYPGBFDCDQQHOF-UHFFFAOYSA-N CCc1ccc(C)c2n[s]nc12 Chemical compound CCc1ccc(C)c2n[s]nc12 QYPGBFDCDQQHOF-UHFFFAOYSA-N 0.000 description 1
- YIUHGBNJJRTMIE-UHFFFAOYSA-N O=C(C1=C(c2ccc[s]2)N2)NC(c3ccc[s]3)=C1C2=O Chemical compound O=C(C1=C(c2ccc[s]2)N2)NC(c3ccc[s]3)=C1C2=O YIUHGBNJJRTMIE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a tripolyindole compound, and a preparation method and use thereof. The tripolyindole compound is shown in formula I, wherein R and X are defined in the specification. The tripolyindole compound provided by the invention comprises a large-pi conjugate soluble parent nucleus structural unit, and push-pull structural side chains of a conjugate electron donor and/or a receptor, and is a low-energy gap small molecular compound; and the compound has wide application prospect in solar battery devices.
Description
Technical field
The invention belongs to the solar cell material technical field, be specifically related to a kind of trimerization Benzazole compounds and its production and use.
Background technology
Organic solar batteries is a kind of novel solar cell, has the chemical structure diversity, but the volume to volume big area is produced, flexible, frivolous relative advantage such as cheap with cost, be current novel solar battery research field one of the advanced subject of rich vigour and vitality, have important development and application prospect.
Organic solar batteries adopts conjugated polymers more at present, yet conjugated polymers is difficult to purifying, the device poor repeatability, with respect to conjugated polymers, organic small molecule material has more definite molecular structure, be easy to modification and purification and high repeatability and other advantages, therefore, become one of the research focus in organic solar batteries field in recent years.
How by the microvisual model attitude of regulation activity layer, make when forming being separated of nanoscale to body with acceptor (PCBM), guarantee to give high efficiency charge (hole) transmission of body phase, be the important key issue of raising organic molecule solar cell.
Summary of the invention
The object of the present invention is to provide a kind of trimerization Benzazole compounds and its production and use.
A first aspect of the present invention provides the compound shown in a kind of formula I, and its structure is as follows:
In the formula, R is H or C
1-12Alkyl; The structure of X is suc as formula shown in II or the formula III:
In the formula, R
1Be H or C
1-12Alkyl;
D is the group that is selected from down group:
In the formula, R
2Be C
1-12Alkyl.
A
1For replacing or unsubstituted 8 yuan to 10 yuan assorted fragrant bicyclic ring systems, replacement or unsubstituted 12 yuan to 14 yuan assorted virtue three ring ring systems,
Wherein, described replacement refers to that the substituting group that one or more H in the group are selected from down group replaces :-COOC
1-12Alkyl, C
1-12Alkyl, C
1-12Alkoxyl group, fluorine atom or trifluoromethyl;
A
2For being selected from down the group of group:
In the formula, R
3Be C
1-12Alkyl.
In another preference, A is for replacing or unsubstituted 8 yuan to 9 yuan assorted fragrant bicyclic ring systems, replacement or unsubstituted 12 yuan of assorted virtue three ring ring systems;
Wherein, described " replacement " refer to that the substituting group that one or more H in the group are selected from down group replaces :-COOC
1-12Alkyl, C
1-12Alkyl, C
1-12Alkoxyl group, fluorine atom or trifluoromethyl.
In another preference, R is C
2-10Alkyl, be preferably C
6-8Alkyl, more preferably C
6Or C
8Alkyl.
In another preference, R
1Be C
2-10Alkyl is preferably C
6-8Alkyl, more preferably C
6Or C
8Alkyl.
In another preference, R
2Be C
2-8Alkyl is preferably C
2-8Alkyl.
In another preference, R
3Be C
2-8Alkyl.Be preferably C
2, C
6, C
8Alkyl.
In another preference, A
1For being selected from down the group of group:
In the formula, Z is O or S;
Y is N or CR
6
R
4For-COOC
1-12Alkyl, C
1-12Alkyl or C
1-12Alkoxyl group;
R
5, R
6Independent separately is H, fluorine atom or trifluoromethyl.
In another preference, Z is the S atom.
In another preference, A
1For being selected from down the group of group:
In the formula, R
7Be C
1-12Alkyl.
In another preference, R
7Be C
4-10Alkyl is preferably C
6-8Alkyl, more preferably C
6Or C
8Alkyl.
In another preference, A
1For being selected from down the group of group:
In another preference, A
2For being selected from down the group of group:
In another preference, described X is the group that is selected from down group:
A second aspect of the present invention provides the preparation method of the described formula I of a kind of first aspect present invention compound, and described method comprises step:
(1) in the presence of catalyzer, formula IV compound is carried out the boron esterification, thereby form formula V compound,
(2) in the presence of catalyzer, formula V compound and formula VI compound are carried out the Suzuki linked reaction, thereby form formula I compound,
In the formula, R, X are as defined in claim 1; L is I or Br.
In another preference, described being reflected under the rare gas element existence condition carried out.
In another preference, described reaction is carried out in confined conditions.
In another preference, the temperature of reaction of described reaction is 80～120 ℃.
In another preference, the reaction times of described reaction is 2～24 hours.
In another preference, described preparation method also comprises the step of aftertreatment.
In another preference, describedly be reflected at existing under the situation of alkali and carry out.
In another preference, described catalyzer is selected from:
(a) palladium catalyst;
(b) combination of palladium catalyst and part.
In another preference, described palladium catalyst comprises: PdM
2, Pd (MeCN)
2Cl
2, Pd (PhCN)
2Cl
2, Pd (dppf) Cl
2, Pd (dppe) Cl
2, Pd (dppb) Cl
2, Pd (dppp) Cl
2, Pd (dppm) Cl
2, Pd (PPh
3)
2Cl
2, Pd (PPh
3)
4, Pd
2(dba)
3(η
3-C
3H
5)
2Pd
2Cl
2
Wherein, M is acetate, trifluoracetic acid root, trifluoromethanesulfonic acid root, pivalate or halide-ions.
In another preference, described part comprises: triphenyl phosphorus, trimethylphenyl phosphorus, tri-tert phosphorus.
A third aspect of the present invention provides the purposes of the described formula I of a kind of first aspect present invention compound, and described compound is for the preparation of solar cell device.
A fourth aspect of the present invention provides a kind of solar cell device, and described device comprises the described formula I of first aspect present invention compound.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can making up mutually between specifically described each technical characterictic in below (eg embodiment), thus constitute new or optimized technical scheme.As space is limited, this tired stating no longer one by one.
Description of drawings
Fig. 1 is compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and the TAT-DCV uv-visible absorption spectra figure in chlorobenzene solution.
Fig. 2 is the uv-visible absorption spectra figure of the film of compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and TAT-DCV.
Fig. 3 is the cyclic voltammetry curve of compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and TAT-DCV.
Fig. 4 is for compound TAT-hTBT being the current density-voltage curve of the solar cell device of donor material preparation.
Embodiment
The contriver is through extensive and deep research, developed a class trimerization Benzazole compounds first, this compounds is to be mother nucleus structure with the trimerization indoles, and the small molecules that a class that obtains has hub-and-spoke configuration is modified in the α position of thiphene ring for body and/or conjugated electrons acceptor groups by conjugated electrons.The easy self-assembly of this compounds forms the ordered structure of nanoscale, and has good carrier mobility in crystal or film, therefore has broad application prospects in solar cell device.Finished the present invention on this basis.
As used herein, " compound shown in the formula I ", " formula I compound " are used interchangeably, and refer to that all structural formula is the compound of formula I.
Group definition
Term " C
1-12Alkyl " refer to have the straight or branched alkyl of 1-12 carbon atom, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl or similar group.
Term " C
1-12Alkoxyl group " refer to have the straight or branched alkoxyl group of 1-12 carbon atom, for example methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy or similar group.
Term " heteroaryl " refers to contain the loop systems of the aromatic series monocycle shape of at least one ring hetero atom that is selected from oxygen, nitrogen, sulphur, or at least one is aromatic series and the polycyclic loop systems that contains at least one ring hetero atom in the ring that wherein exists.The polycyclic heteroaryl comprises those and has the group that two or more condense heteroaryl ring together, and those have at least one and the ring of one or more aromatic carbon ring shape, the ring of non-aromatic carbocyclic ring shape, and/or the group of the monocycle shape heteroaryl ring that condenses of the assorted alkyl ring of the ring of non-aromatic.
Term " ring " or " ring system " refer to carbocyclic ring or heterocycle.
Term " heterocycle " finger-type becomes that at least one atom is not carbon in the atom of described heterocycle skeleton, is nitrogen, oxygen or sulphur.Usually, heterocycle comprises and is no more than 4 nitrogen, is no more than 2 oxygen and/or is no more than 2 sulphur.Except as otherwise noted, heterocycle can be saturated, part is undersaturated or complete undersaturated ring.
Term " ring system " refers to two or more rings and condensed ring together.
At least one ring in term " heterocycle ring system " the finger ring system is the ring system of heterocycle.
At least one ring in term " hetero-aromatic ring ring system " the finger ring system is the system of aromatic ring.
As used herein, term " 8 yuan to 10 yuan assorted fragrant bicyclic rings are " and " 12 yuan to 14 yuan assorted virtue three ring ring systems " comprise 6 yuan-5 yuan, 6 yuan-6 yuan, 5 yuan-5 yuan or 5 yuan of-6 yuan of bicyclic heteroaryls, or 5 yuan-6 yuan-5 yuan or 6 yuan of-6 yuan of-6 yuan of tricyclic heteroaryls, preferably, the compound that comprises following structure:
Wherein, T is O, S, NH, N-C
1-12Alkyl or N-COOC
1-12Alkyl.T' is S.Such heteroaryl comprises: benzotriazole base, diazosulfide base, pyrido thiadiazolyl group, pyrido triazol radical, thieno-thiadiazolyl group, thieno-pyrazinyl, thieno-triazol radical, thienothiophene base, 2,5-dihydro-pyrroles-1,4-diketo, thiophene-[3,4-c]-pyrroles-4,6-diketo, thiadiazoles and benzo thiadiazolyl group etc.
As used herein, " conjugated electrons is given body " refers to form the group of conjugated system, and this group can be to the adjacent atom donates electrons.The heteroaryl that mainly comprises the electron rich of 5-14 unit among the present invention.
As used herein, " conjugated electrons acceptor " refers to form the group of conjugated system, is connected with electron-withdrawing group on this group, the electronics of adjacent atom can be pulled to oneself.The example of electron-withdrawing group includes but not limited to: halogen ,-NO
2,-CN ,-NC ,-COOH ,-COR
0,-COOR
0,-CONHR
0,-CON (R
0)
2, C
1-20Alkylhalide group, C
6-14Aryl, and the electron deficiency heteroaryl of 5-14 unit.Wherein, R
0Be C
1-20Alkyl, C
2-20Thiazolinyl, C
2-20Alkynyl, C
6-14Aryl, or C
3-14Cycloalkyl.
Various unsubstituted heteroaryls can be described to electron rich (or π-excessive) or electron deficiency (or π-deficiency).This classification is based on the average electron density of comparing with the carbon atom of benzene on each annular atoms.The example of electron rich system comprises having heteroatomic 5 yuan of heteroaryls, as furans, pyrroles and thiophene; Or the group of plural 5 yuan of heteroaryls connection; Or have plural 5 yuan of heteroaryl-condensed groups together, as bithiophene, thienothiophene.
The heteroaromatic ring that mixes can belong to a certain kind according to one or more heteroatomic type, quantity and the position in this ring.
Term " halogen " or " halogen atom " refer to fluorine atom, chlorine atom, bromine atoms or iodine atom.
As used herein, " mobility " refers to represent that charged particle moves through the amount of the speed of this material under electric field effects.This parameter depends on the framework of device, can use fieldtron or space-electric charge current limliting method of masurement to measure.
As used herein, packing factor is the ratio (representing with percentage) of actual obtainable peak power and theoretical(horse)power.
As used herein, the effciency of energy transfer of solar cell is the percentage that is converted to the power of electric energy by the light that absorbs.Can being calculated divided by the surface-area of the input light irradiance under the standard test condition and solar cell by maximum power value of solar cell.
The preparation method of trimerization Benzazole compounds
Trimerization Benzazole compounds of the present invention can adopt conventional synthetic method preparation well known by persons skilled in the art.In a class preferred embodiment of the present invention, the preparation method of compound comprises step: in the presence of catalyzer, formula IV compound is carried out the boron esterification, thereby form formula V compound.
(2) in the presence of catalyzer, formula V compound and formula VI compound are carried out the Suzuki linked reaction, thereby form formula I compound.
In the formula, the definition of R, X is the same; L is I or Br.
Catalyzer can adopt employed conventional catalyst in the linked reaction, preferably is palladium catalyst or is the use of palladium catalyst and ligand combination.
Palladium catalyst includes but not limited to: PdM
2, Pd (MeCN)
2Cl
2, Pd (PhCN)
2Cl
2, Pd (dppf) Cl
2, Pd (dppe) Cl
2, Pd (dppb) Cl
2, Pd (dppp) Cl
2, Pd (dppm) Cl
2, Pd (PPh
3)
2Cl
2, Pd (PPh
3)
4, Pd
2(dba)
3(η
3-C
3H
5)
2Pd
2Cl
2Wherein, M is acetate, trifluoracetic acid root, trifluoromethanesulfonic acid root, pivalate or halide-ions.
Part is not particularly limited, and can select according to employed palladium catalyst in the concrete reaction.The preferred part of one class comprises phosphorus parts such as triphenyl phosphorus, tri-tert phosphorus.
The not specific restriction of the mol ratio of formula V and formula VI compound, the mol ratio 〉=3:1 of formula VI compound and formula V compound gets final product usually.Preferable mol ratio is 3:1-10:1.
Reaction is preferably carried out under airtight and rare gas element existence condition.Temperature of reaction is preferably 80～120 ℃, and the reaction times is generally 2～24 hours.Reaction product can be handled purifying by ordinary method known in the art and obtain.
Reaction can be carried out under the situation that alkali exists, used alkali comprises (but being not limited to): triethylamine, diisopropyl ethyl amine, diethylamine, piperidines, piperazine, morpholine, N-methylmorpholine, triethylene diamine (DABOC), 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene (DBN), Potassium ethanoate, salt of wormwood, saleratus, yellow soda ash, sodium bicarbonate, cesium carbonate, sodium phosphate, potassiumphosphate, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, or its combination.
Formula IV compound can adopt ordinary method well-known to those skilled in the art synthetic.The preferred synthetic route of one class is shown below:
In the formula, the definition of R, L is the same.
Formula VI compound can adopt ordinary method well-known to those skilled in the art synthetic.The preferred synthetic route of one class is shown below:
In the formula, R, A
1, D definition the same.
Perhaps be shown below:
The purposes of trimerization Benzazole compounds
Traditional organic solar batteries device architecture comprises: glass coating, ITO layer and PEDOT, PEDOT comprises: PSS composite bed, active coating and metal electrode layer.
Trimerization Benzazole compounds of the present invention can be used for preparing donor material in the described active coating, and acceptor material is PC in the described active coating
61BM or PC
71BM.The organic solar batteries device can adopt the preparation method of this area routine to make.
Compared with prior art, the present invention has following major advantage:
(1) compound of the present invention has big π plane system, exists strong π-π between the molecule and interacts, and self-assembly forms the ordered structure of nanoscale easily, improves the carrier mobility of molecule in crystal or film.
Advantages such as (2) compound of the present invention is compared with existing conjugated polymers, has structure and determines, and is synthetic simple, is easy to purify, and solvability is good.
(3) compound of the present invention can be used for preparing the material of solar cell device, has to absorb preferably and lower energy gap width, has broad application prospects in solar cell device.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can arbitrary combination.All features that this case specification sheets discloses can with any composition forms and usefulness, each feature that discloses in the specification sheets, the alternative characteristics that can anyly be provided identical, impartial or similar purpose replaces.Therefore except special instruction is arranged, the feature that discloses only is the general example of equalization or similar features.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
Unless otherwise defined, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
Implementation column 1:
TAT-hTBT's is synthetic, and the structure of this compound is:
The preparation method of TAT-hTBT comprises the steps (1)～(11):
(1) 1-hexyl-2-indolone is synthetic:
Under the nitrogen protection, add in two mouthfuls of flasks of 100mL the 2-indolone (2.66g, 20mmol), (4.2mL, 30mmol), N, (13.82g 100mmol), is heated to 80 ℃ and reacted 20 hours the bromo normal hexane for dinethylformamide (40mL) and salt of wormwood.Reacted the back cool to room temperature, added water, used petroleum ether extraction, merged organic phase, used saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying filters, and rotary evaporation is removed organic solvent.The mixture sherwood oil: ethyl acetate (V:V:=6:1) is separated for eluent carries out silica gel column chromatography, obtains sorrel oily matter 1(1.65g, productive rate 38%).
1H NMR(400MHz,CDCl
3),δ(ppm):7.26(t,J=8.0Hz,1H),7.23(d,J=8.0Hz,1H),7.02(t,J=8.0Hz,1H),6.82(d,J=8.0Hz,1H),3.69(t,J=8.0Hz,2H),3.51(s,2H),1.66(m,2H),1.30(m,6H),0.88(t,J=6.0Hz,3H).
(2) 1-hexyl-5-bromo-2-indolone is synthetic:
(6.52g 30mmol) is dissolved in acetonitrile (100), and add the N-bromo-succinimide then under the room temperature (5.87g 33mmol), adds the back and continues reaction 2 days in batches to get 1-hexyl-2-indolone.Reacted the back rotary evaporation and removed acetonitrile, added methylene dichloride, the organic phase water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying filters the rotary evaporation desolventizing, use sherwood oil: ethyl acetate (V:V:=6:1) is separated for eluent carries out silica gel column chromatography, obtains faint yellow solid 2(7.20g, 81%).
1H NMR(400MHz,CDCl
3),δ(ppm):7.39(d,J=8.0Hz,1H),7.36(s,1H),6.70(d,J=8.0Hz,1H),3.66(t,J=8.0Hz,2H),3.51(s,2H),1.61(m,2H),1.29(m,6H),0.87(t,J=8.0Hz,3H).
13C NMR(100MHz,CDCl
3),δ(ppm):174.2,143.7,130.6,127.6,126.7,114.6,109.6,40.2,35.6,31.4,27.3,26.6,22.5,14.0.
(3) compound 3 is synthetic:
(3.60g 15mmol) joins in the phosphorus oxychloride (25mL) back flow reaction 6 hours to get 1-hexyl-5-bromo-2-indolone.Reacted the back cool to room temperature, be poured in a large amount of frozen water, filtered.The crude product sherwood oil: ethyl acetate (V:V:=6:1) is separated for eluent carries out silica gel column chromatography, obtains white solid 3(1.10g, 33%).
1H NMR(400MHz,CDCl
3),δ(ppm):8.24(d,J=1.6Hz,3H),7.53(dd,J=8.4Hz,3H),7.44(d,J=8.4Hz,1.8Hz,3H),4.62(t,J=8.0Hz,6H),1.98(m,6H),1.29(m,18H),0.84(t,J=7.0Hz,9H).
13C NMR(100MHz,CDCl
3),δ(ppm):139.1,138.8,125.4,124.2,123.6,113.0,111.5,101.6,46.9,31.6,30.2,26.3,22.6,14.0.
(4) compound 4 is synthetic:
Add compound 3(417mg in the 100mL round-bottomed flask, 0.5mmol), duplex tetramethyl ethylene ketone boric acid ester (762mg, 6mmol), Potassium ethanoate (491mg, 5mmol) and Pd(dppf) Cl
2(18mg 0.025mmol), takes out logical nitrogen three times, adds anhydrous and oxygen-free 1,4-dioxane (20mL), the following 85 ℃ of reactions of nitrogen protection 48 hours.Reacted the back cool to room temperature, added water, dichloromethane extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: ethyl acetate (V:V=10:1) is separated for eluent carries out silica gel column chromatography, obtains white solid 4(370mg, productive rate 76%).
1H NMR(400MHz,CDCl
3),δ(ppm):8.81(s,3H),7.92(d,J=8.0Hz,3H),7.64(d,J=8.0Hz,3H),5.00(t,J=8.0Hz,6H),2.05(m,6H),1.44(m,6H),1.42(s,36H),1.28(m,12H),0.81(t,J=7.2Hz,9H).
(5) 4-hexyl-2-thienyl-tri-n-butyl tin is synthetic:
Under the nitrogen protection; add 3-hexyl thiophene (20.20g in the 500mL Schlenk bottle; 120mmol) and anhydrous and oxygen-free tetrahydrofuran (THF) (200mL), be cooled to-78 ℃, slowly drip the hexane solution (45.8mL of n-Butyl Lithium in this solution; 2.4M); add-78 ℃ of backs and continued stirring reactions 1 hour, add then tributyltin chloride (35.3mL, 130mmol); holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add water the cancellation reaction, petroleum ether extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation is removed the light yellow oil 5 of organic solvent, and crude product is without further purification, and is directly synthetic as next step.
Synthesizing of (6) 4,7-two (4-hexyl-2-thienyl)-benzo [c] [1,2,5] thiadiazoles:
Add 4 in the 100mL round-bottomed flask; 7-dibromo benzo [c] [1; 2; 5] thiadiazoles (2.94g, 10mmol), 4-hexyl-2-thienyl-tri-n-butyl tin (11.43g, 25mmol) and four triphenyl phosphorus palladium (12mg; 0.01mmol); take out logical nitrogen three times, add the toluene (50mL) that removed oxygen, back flow reaction is 24 hours under the nitrogen protection.Reacted the back cool to room temperature, added water, dichloromethane extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=8:1) separates for eluent carries out silica gel column chromatography, obtains orange solids 6(4.67g, productive rate 99%).
1H NMR(400MHz,CDCl
3),δ(ppm):7.98(d,J=1.2Hz,2H),7.82(s,2H),7.04(d,J=1.2Hz,2H),2.70(t,J=7.2Hz,4H),1.71(m,4H),1.33(m,12H),0.89(t,J=5.6Hz,6H).
13C NMR(100MHz,CDCl
3),δ(ppm):152.6,144.3,139.0,129.0,126.0,125.4,121.5,31.8,30.7,30.5,29.1,22.7,14.1.
(7) compound 7 is synthetic:
(5.62g 12mmol) is dissolved in chloroform (300mL), and add the N-bromo-succinimide then under the room temperature (2.14g 12mmol), adds the back and continues reaction 2 days in batches to get 4,7-two (4-hexyl-2-thienyl)-benzo [c] [1,2,5] thiadiazoles.Reacted the back water and given a baby a bath on the third day after its birth time, anhydrous sodium sulfate drying filters, and sherwood oil use in the rotary evaporation desolventizing: chloroform (V:V:=8:1) obtains orange red solid 7(5.20g, 79% for eluent carries out the silica gel column chromatography separation).
1H NMR(400MHz,CDCl
3),δ(ppm):7.98(d,J=1.2Hz,1H),7.81-7.73(m,3H),7.04(s,1H),2.69(t,J=7.6Hz,2H),2.64(t,J=7.6Hz,2H),1.70(m,4H),1.35(m,12H),0.90(m,6H).
13C NMR(100MHz,CDCl
3),δ(ppm):152.5,152.4,144.4,143.0,138.9,138.7,127.9,126.4,125.4,125.0,121.7,111.3,31.7,31.6,30.6,30.5,29.8,29.7,29.1,29.0,22.6,14.1.
(8) 5-hexyl-2-thienyl-tri-n-butyl tin is synthetic:
Under the nitrogen protection; add 2-hexyl thiophene (20.20g in the 500mL Schlenk bottle; 120mmol) and anhydrous and oxygen-free tetrahydrofuran (THF) (200mL), be cooled to-78 ℃, slowly drip the hexane solution (45.8mL of n-Butyl Lithium in this solution; 2.4M); add-78 ℃ of backs and continued stirring reactions 1 hour, add then tributyltin chloride (35.3mL, 130mmol); holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add water the cancellation reaction, petroleum ether extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation is removed the light yellow oil 7 of organic solvent, and crude product is without further purification, and is directly synthetic as next step.
(9) compound 9 is synthetic:
Add compound 7(2.19g in the 100mL round-bottomed flask; 4mmol), 5-hexyl-2-thienyl-tri-n-butyl tin (2.74g; 6mmol) with four triphenyl phosphorus palladium (12mg; 0.01mmol); take out logical nitrogen three times; add the toluene (40mL) that removed oxygen, back flow reaction is 24 hours under the nitrogen protection.Reacted the back cool to room temperature, added water, dichloromethane extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=5:1) separates for eluent carries out silica gel column chromatography, obtains red solid 9(2.28g, productive rate 90%).
1H NMR(400MHz,CDCl
3),δ(ppm):7.98(d,J=1.6Hz,2H),7.81(m,2H),7.04(d,J=3.2Hz,2H),6.76(d,J=3.6Hz,1H),2.74(m,4H),2.70(t,J=7.6Hz,2H),1.71(m,6H),1.34(m,18H),0.91(m,9H).
(10) compound 10 is synthetic:
Get compound 9(2.28g, 3.6mmol) be dissolved in chloroform (100mL), add the N-bromo-succinimide then under the room temperature (0.64g 3.6mmol), adds the back and continues reaction 1 day in batches.Reacted the back water and given a baby a bath on the third day after its birth time, anhydrous sodium sulfate drying filters, and sherwood oil use in the rotary evaporation desolventizing: chloroform (V:V:=8:1) obtains red solid 10(2.30g, 90% for eluent carries out the silica gel column chromatography separation).
1H NMR(400MHz,CDCl
3),δ(ppm):7.98(s,1H),7.80-7.73(m,3H),7.06(d,J=3.6Hz,1H),6.78(d,J=3.6Hz,1H),2.86(m,4H),2.65(t,J=7.6Hz,2H),1.71(m,6H),1.26(m,18H),0.92(m,9H).
(11) compound TAT-hTBT's is synthetic:
Add compound 4(195mg in the 50mL round-bottomed flask; 0.2mmol), compound 10(857mg; 1.2mmol), salt of wormwood (2.76g; 20mmol) with four triphenyl phosphorus palladium (10mg; 0.008mmol); take out logical nitrogen three times, add the toluene (20mL) and the water (10mL) that removed oxygen, back flow reaction is 3 days under the nitrogen protection.Reacted the back cool to room temperature, chloroform extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=4:1) separates for eluent carries out silica gel column chromatography, obtains black solid TAT-hTBT(447mg, productive rate 90%).
1H NMR(400MHz,CDCl
3),δ(ppm):8.42(s,3H),8.15(s,3H),7.97(s,3H),7.74(d,J=7.6Hz,3H),7.66(d,J=7.6Hz,3H),7.59(d,J=8.4Hz,3H),7.52(d,J=8.4Hz,3H),7.10(d,J=3.6Hz,3H),6.81(d,J=3.6Hz,3H),4.75(br,6H),2.89(m,18H),1.97-1.68(m,24H),1.57-0.81(m,99H),0.61(t,J=6.8Hz,9H).
13C NMR(100MHz,CDCl
3),δ(ppm):152.5,146.4,141.5,140.3,139.8,139.2,138.9,136.6,136.5,133.6,132.8,130.5,130.2,125.8,125.7,125.6,125.0,124.9,124.6,124.5,124.0,123.4,122.8,110.4,103.2,100.0,58.5,47.0,31.8,31.7,31.6,31.5,31.2,30.7,30.2,30.0,29.5,29.2,28.9,26.5,22.7,22.6,22.5,18.4,14.2,14.1,13.9.MS(m/z):calcd.for C150H184N9S12[M+H]
+:2495.1;found,2495.2.
Implementation column 2:
TAT-hTBTT's is synthetic, and the structure of this compound is:
The preparation method of TAT-hTBTT comprises the steps (1)～(11):
(1) 1-hexyl-2-indolone is synthetic:
Its building-up process sees the step (1) among the embodiment 1 for details.
(2) 1-hexyl-5-bromo-2-indolone is synthetic:
Its building-up process sees the step (2) among the embodiment 1 for details.
(3) compound 3 is synthetic:
Its building-up process sees the step (3) among the embodiment 1 for details.
(4) compound 4 is synthetic:
Its building-up process sees the step (4) among the embodiment 1 for details.
(5) 4-hexyl-2-thienyl-tri-n-butyl tin is synthetic:
Its building-up process sees the step (5) among the embodiment 1 for details.
Synthesizing of (6) 4,7-two (4-hexyl-2-thienyl)-benzo [c] [1,2,5] thiadiazoles:
Its building-up process sees the step (6) among the embodiment 1 for details.
(7) compound 7 is synthetic:
Its building-up process sees the step (7) among the embodiment 1 for details.
(8) compound 11 is synthetic:
Under the nitrogen protection; add 5-hexyl-2 in the 500mL Schlenk bottle, (2.27g is 9.1mmol) with anhydrous and oxygen-free tetrahydrofuran (THF) (50mL) for 2 '-thiophene; be cooled to-78 ℃; (10mL 2.4M), adds the back and continued stirring reactions 1 hour for-78 ℃ slowly to drip the hexane solution of n-Butyl Lithium in this solution; add tributyltin chloride (3mL then; 11.0mmol), holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add water the cancellation reaction, petroleum ether extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation is removed the light yellow oil 11 of organic solvent, and crude product is without further purification, and is directly synthetic as next step.
(9) compound 12 is synthetic:
Add compound 7(2.19g in the 100mL round-bottomed flask, 4.0mmol), compound 11(2.37g, 4.4mmol) and four triphenyl phosphorus palladium (12mg; 0.01mmol); take out logical nitrogen three times, add the toluene (20mL) that removed oxygen, back flow reaction is 24 hours under the nitrogen protection.Reacted the back cool to room temperature, added water, dichloromethane extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=5:1) separates for eluent carries out silica gel column chromatography, obtains red solid 12(2.80g, productive rate 98%).
1H NMR(400MHz,CDCl
3),δ(ppm):7.99(d,J=1.2Hz,1H),7.98(s,1H),7.83(d,J=1.6Hz,2H),7.12(d,J=4.0Hz,1H),7.08(d,J=4.0Hz,1H),7.05(d,J=0.8Hz,1H),7.02(d,J=3.6Hz,1H),6.71(d,J=3.6Hz,1H),2.86(t,J=8.0Hz,2H),2.81(t,J=7.6Hz,2H),2.70(t,J=7.6Hz,2H),1.71(m,6H),1.34(m,18H),0.91(m,9H).
(10) compound 13 is synthetic:
Get compound 12(2.87g, 4.0mmol) be dissolved in chloroform (50mL), add the N-bromo-succinimide then under the room temperature (0.64g 3.6mmol), adds the back and continues reaction 1 day in batches.Reacted the back water and given a baby a bath on the third day after its birth time, anhydrous sodium sulfate drying filters, and sherwood oil use in the rotary evaporation desolventizing: chloroform (V:V:=3:1) obtains garnet solid 13(2.70g, 85% for eluent carries out the silica gel column chromatography separation).
1H NMR(400MHz,CDCl
3),δ(ppm):7.98(s,1H),7.83-7.76(m,3H),7.12(d,J=4.0Hz,1H),7.08(d,J=3.6Hz,1H),7.02(d,J=3.6Hz,1H),6.71(d,J=3.6Hz,1H),2.86(t,J=7.6Hz,2H),2.81(t,J=7.6Hz,2H),2.64(t,J=7.6Hz,2H),1.71(m,6H),1.34(m,18H),0.92(m,9H).
(11) compound TAT-hTBTT's is synthetic:
Add compound 4(195mg in the 50mL round-bottomed flask; 0.2mmol), compound 13(955mg; 1.2mmol), salt of wormwood (2.76g; 20mmol) with four triphenyl phosphorus palladium (10mg; 0.008mmol); take out logical nitrogen three times, add the toluene (30mL) and the water (10mL) that removed oxygen, back flow reaction is 3 days under the nitrogen protection.Reacted the back cool to room temperature, chloroform extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=5:1) separates for eluent carries out silica gel column chromatography, obtains black solid TAT-hTBTT(450mg, productive rate 82%).
1H NMR(400MHz,CDCl
3),δ(ppm):8.37(s,3H),8.11(s,3H),7.92(s,3H),7.72(dd,J=7.6Hz,3.2Hz,3H),7.62(dd,J=7.6Hz,3.2Hz,3H),7.55(d,J=8.4Hz,3H),7.50(d,J=8.4Hz,3H),7.12(d,J=4.0Hz,3H),7.08(d,J=4.0Hz,3H),7.03(d,J=3.6Hz,3H),6.71(d,J=3.2Hz,3H),4.73(br,6H),2.88(m,18H),1.88-1.69(m,24H),1.47-0.90(m,90H),0.84(t,J=6.8Hz,9H),0.59(t,J=7.2Hz,9H).
13C NMR(100MHz,CDCl
3),δ(ppm):152.5,152.4,145.6,141.5,140.4,140.3,139.2,139.0,137.8,136.9,136.6,134.5,134.4,132.1,130.5,130.3,126.4,125.8,125.7,125.0,124.9,124.7,124.5,124.1,123.4,123.3,122.7,110.4,103.2,47.1,31.8,31.7,31.6,31.2,30.6,30.2,30.0,29.7,29.4,29.2,28.8,26.5,22.7,22.6,22.5,22.4,14.2,14.1,13.9.MS(m/z):calcd.for C162H190N9S15[M+H]
+:2741.1;found,2742.5.
Implementation column 3:
TAT-oDPP's is synthetic, and the structure of this compound is:
The preparation method of TAT-oDPP comprises the steps (1)～(10):
(1) 1-hexyl-2-indolone is synthetic:
Its building-up process sees the step (1) among the embodiment 1 for details.
(2) 1-hexyl-5-bromo-2-indolone is synthetic:
Its building-up process sees the step (2) among the embodiment 1 for details.
(3) compound 3 is synthetic:
Its building-up process sees the step (3) among the embodiment 1 for details.
(4) compound 4 is synthetic:
Its building-up process sees the step (4) among the embodiment 1 for details.
(5) compound 15 is synthetic:
In the 100mL flask, add compound 14(available from slope and machine light scientific ﹠ technical corporation) (1.50g, 5.0mmol), Anhydrous potassium carbonate (3.46g, 25.0mmol) and N, dinethylformamide (50mL), being heated to 120 ℃ of reactions adds n-octane bromide after 1 hour (2.2mL 12.5mmol), keeps 130 ℃ of reactions 12 hours.Reacted the back cool to room temperature, be poured in the big water gaging, filtered the filter cake sherwood oil: chloroform (V:V=1:1) separates for eluent carries out silica gel column chromatography, obtains sorrel solid 15(0.60g, 23%).
1H NMR(400MHz,CDCl
3),δ(ppm):8.95(dd,J=4.0Hz,1.2Hz,2H),7.66(dd,J=4.8Hz,1.2Hz,2H),7.32(dd,J=4.8Hz,4.0Hz,2H),4.09(t,J=8.0Hz,4H),1.78(m,4H),1.45(m,4H),1.30(m,16H),0.89(t,J=6.8Hz,6H).
13C NMR(100MHz,CDCl
3),δ(ppm):161.4,140.0,135.2,130.6,129.8,128.6,107.7,42.2,31.8,29.2,26.9,22.6,14.1.
(6) compound 16 is synthetic:
Get compound 15(1.12g, 2.1mmol) be dissolved in chloroform (50mL), add the N-bromo-succinimide then under the room temperature (0.37g 2.1mmol), adds the back and continues reaction 1 day in batches.Reacted the back water and given a baby a bath on the third day after its birth time, anhydrous sodium sulfate drying filters, and sherwood oil use in the rotary evaporation desolventizing: chloroform (V:V:=1:1) obtains garnet solid 16(1.07g, 84% for eluent carries out the silica gel column chromatography separation).
1H NMR(400MHz,CDCl
3),δ(ppm):8.93(dd,J=4.0Hz,1.2Hz,1H),8.66(d,J=4.4Hz,1H),7.66(dd,J=5.2Hz,1.2Hz,1H),7.29(dd,J=5.2Hz,4.0Hz,1H),7.23(d,J=4.0Hz,1H),4.06(t,J=8.0Hz,2H),3.99(t,J=8.0Hz,2H),1.72(m,4H),1.39(m,4H),1.27(m,16H),0.87(m,6H).
13C NMR(100MHz,CDCl
3),δ(ppm):161.3,161.1,140.5,138.6,135.5,135.0,131.6,131.2,130.9,129.7,128.7,118.7,108.0,107.6,42.3,42.2,31.7,29.1,26.9,26.8,22.6,14.0.
(7) 5-hexyl-2-thienyl-tri-n-butyl tin is synthetic:
Its building-up process sees the step (8) among the embodiment 1 for details.
(8) compound 17 is synthetic:
Add compound 16(302mg in the 25mL round-bottomed flask; 0.5mmol), 5-hexyl-2-thienyl-tri-n-butyl tin (457mg; 1.0mmol) and four triphenyl phosphorus palladium (1mg; 0.001mmol); take out logical nitrogen three times; add the toluene (10mL) that removed oxygen, back flow reaction is 12 hours under the nitrogen protection.Reacted the back cool to room temperature, added water, dichloromethane extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=1:1) separates for eluent carries out silica gel column chromatography, obtains brown solid 17(280mg, productive rate 81%).
1H NMR(400MHz,CDCl
3),δ(ppm):8.94(d,J=4.0Hz,1H),8.90(d,J=4.0Hz,1H),7.62(d,J=5.2Hz,1H),7.28(d,J=4.0Hz,1H),7.24(d,J=4.0Hz,1H),7.15(d,J=3.6Hz,1H),6.74(d,J=3.6Hz,1H),4.08(t,J=8.0Hz,4H),4.08(t,J=8.0Hz,4H),2.82(t,J=7.6Hz,2H),1.72(m,4H),1.39(m,4H),1.27(m,16H),0.87(m,6H).
13C NMR(100MHz,CDCl
3),δ(ppm):161.4,161.2,147.9,143.8,139.9,139.1,136.8,134.9,133.5,130.3,129.9,128.5,127.3,125.3,125.1,124.2,108.0,107.7,42.3,31.8,31.5,31.5,30.0,29.2,28.7,26.9,22.6,22.5,14.0.
(9) compound 18 is synthetic:
Get compound 17(1.11g, 1.6mmol) be dissolved in chloroform (50mL), add the N-bromo-succinimide then under the room temperature (0.31g 1.7mmol), adds the back and continues reaction 1 day in batches.Reacted the back water and given a baby a bath on the third day after its birth time, anhydrous sodium sulfate drying filters, and sherwood oil use in the rotary evaporation desolventizing: chloroform (V:V:=1:1) obtains brown solid 18(1.07g, 87% for eluent carries out the silica gel column chromatography separation).
1H NMR(400MHz,CDCl
3),δ(ppm):8.95(d,J=4.4Hz,1H),8.64(d,J=4.4Hz,1H),7.24(d,J=4.0Hz,1H),7.22(d,J=4.0Hz,1H),7.16(d,J=3.6Hz,1H),6.74(d,J=3.6Hz,1H),4.06(t,J=7.6Hz,2H),4.00(t,J=8.0Hz,2H),2.82(t,J=7.6Hz,2H),1.72(m,6H),1.40-1.28(m,28H),0.87(m,9H).
13C NMR(100MHz,CDCl
3),δ(ppm):161.2,160.7,148.0,144.1,140.1,137.4,137.2,134.8,133.4,131.4,131.3,127.2,125.3,125.2,124.1,118.3,108.1,107.4,42.3,31.8,31.7,31.5,31.4,30.0,29.2,28.8,26.9,26.8,22.6,22.5,14.1,14.0.
(10) compound TAT-oDPP's is synthetic:
Add compound 4(98mg in the 50mL round-bottomed flask; 0.1mmol), compound 18(371mg; 0.6mmol), salt of wormwood (1.38g; 10.0mmol) and four triphenyl phosphorus palladium (5mg; 0.004mmol); take out logical nitrogen three times, add the toluene (15mL) and the water (5mL) that removed oxygen, back flow reaction is 3 days under the nitrogen protection.Reacted the back cool to room temperature, chloroform extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=1:2) separates for eluent carries out silica gel column chromatography, obtains black solid TAT-oDPP(197mg, productive rate 74%).
1H NMR(400MHz,CDCl
3),δ(ppm):9.16(d,J=4.0Hz,3H),8.91(d,J=4.0Hz,3H),8.11(s,3H),7.58(d,J=8.0Hz,3H),7.43(d,J=8.4Hz,3H),7.34(d,J=4.0Hz,3H),7.06(d,J=4.0Hz,3H),7.01(d,J=2.4Hz,3H),6.65(d,J=3.6Hz,3H),4.57(br,6H),4.08(br,12H),2.76(t,J=7.6Hz,6H),1.78(m,18H),1.68(m,6H),1.50(m,12H),1.33(m,66H),1.08(m,18H),0.91(m,27H),0.67(t,J=6.8Hz,9H).
13C NMR(100MHz,CDCl
3),δ(ppm):160.9,151.3,147.4,143.0,141.2,139.0,138.8,138.4,137.2,136.6,133.8,127.9,127.6,125.2,125.1,124.7,123.9,123.3,123.1,121.6,119.0,110.8,107.7,107.5,103.4,46.8,42.3,31.9,31.8,31.6,31.5,31.4,30.3,29.5,29.3,28.9,27.2,27.0,26.3,22.7,22.6,22.4,14.1,14.0,13.8.MS(m/z):calcd.for C162H208N9O6S9[M+H]
+:2663.4;found,2663.6.
Implementation column 4:
TAT-DCV's is synthetic, and the structure of this compound is:
The preparation method of TAT-DCV comprises the steps (1)～(9):
(1) 1-hexyl-2-indolone is synthetic:
Its building-up process sees the step (1) among the embodiment 1 for details.
(2) 1-hexyl-5-bromo-2-indolone is synthetic:
Its building-up process sees the step (2) among the embodiment 1 for details.
(3) compound 3 is synthetic:
Its building-up process sees the step (3) among the embodiment 1 for details.
(4) compound 4 is synthetic:
Its building-up process sees the step (4) among the embodiment 1 for details.
(5) compound 19 is synthetic:
Under the nitrogen protection; add 3-hexyl thiophene (1.68g in the 100mL Schlenk bottle; 10mmol) and anhydrous and oxygen-free tetrahydrofuran (THF) (40mL), be cooled to-78 ℃, slowly drip the hexane solution (4.6mL of n-Butyl Lithium in this solution; 2.4M); add-78 ℃ of backs and continued stirring reactions 1 hour, add then anhydrous cupric chloride (2.69g, 20mmol); holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add dilute hydrochloric acid cancellation reaction, petroleum ether extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation is removed organic solvent.The crude product sherwood oil is that eluent carries out the silica gel column chromatography separation, obtains faint yellow oily thing 19(1.54g, productive rate 92%).
1H NMR(400MHz,CDCl
3),δ(ppm):7.00(s,2H),6.78(s,2H),2.58(t,J=8.0Hz,4H),1.63(m,4H),1.35(m,12H),0.90(t,J=6.8Hz,6H).
(6) compound 20 is synthetic:
Get compound 19(3.35g, 10mmol) be dissolved in N, dinethylformamide (20mL), (0.31g 1.7mmol) is dissolved in N to the N-bromo-succinimide, and dinethylformamide (40mL) slowly is added drop-wise to the latter among the former then.Drip back continuation reaction 8 hours, reacted the back and added big water gaging, petroleum ether extraction, drying is filtered, the rotary evaporation desolventizing is that eluent carries out the silica gel column chromatography separation with sherwood oil, obtains faint yellow oily thing 20(3.94g, 80%).
(7) compound 21 is synthetic:
Under the nitrogen protection; add compound 20(4.45g in the 250mL Schlenk bottle, 9.0mmol) with anhydrous and oxygen-free tetrahydrofuran (THF) (100mL), be cooled to-78 ℃; slowly drip the hexane solution (3.8mL of n-Butyl Lithium in this solution; 2.4M), add the back and continued stirring reaction 1 hour for-78 ℃, add anhydrous N then; dinethylformamide (0.99g; 13.5mmol), holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add dilute hydrochloric acid cancellation reaction, petroleum ether extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation is removed organic solvent.The crude product sherwood oil: chloroform (V:V=5:1) separates for eluent carries out silica gel column chromatography, obtains yellow oil 21(3.02g, productive rate 76%).
1H NMR(400MHz,CDCl
3),δ(ppm):7.81(s,1H),7.11(s,1H),7.01(s,1H),2.71(t,J=8.0Hz,2H),2.55(t,J=8.0Hz,2H),1.60(m,4H),1.31(m,12H),0.90(m,6H).
13C NMR(100MHz,CDCl
3),δ(ppm):181.5,153.8,145.2,143.6,135.9,135.6,126.6,126.3,110.7,31.6,31.5,31.3,29.6,29.5,29.0,28.8,28.5,22.6,22.5,14.1,14.0.
(8) compound 22 is synthetic:
Get compound 21(1.69g, 3.8mmol) and the third two eyeballs (0.51g 7.6mmol) is dissolved in anhydrous chloroform (50mL), adds a small amount of triethylamine (0.1mL), room temperature reaction is 8 hours then, reacted after washing, drying is filtered, the rotary evaporation desolventizing, be that eluent carries out silica gel column chromatography and separates with sherwood oil, obtain pale brown look solid 22(1.69g, 91%).
1H NMR(400MHz,CDCl
3),δ(ppm):10.00(s,1H),7.03(s,1H),6.98(s,1H),2.93(t,J=7.6Hz,2H),2.56(t,J=7.6Hz,2H),1.70(m,2H),1.60(m,2H),1.34(m,12H),0.91(m,6H).
13C NMR(100MHz,CDCl
3),δ(ppm):157.2,147.6,146.8,144.2,134.6,128.6,128.0,125.7,114.9,113.8,112.6,74.4,31.5,31.4,31.2,29.6,29.2,29.0,28.9,22.6,22.5,14.1,14.0.
(9) compound TAT-DCV's is synthetic:
Add compound 4(98mg in the 50mL round-bottomed flask; 0.1mmol), compound 22(294mg; 0.6mmol), salt of wormwood (1.38g; 10.0mmol) and four triphenyl phosphorus palladium (5mg; 0.004mmol); take out logical nitrogen three times, add the toluene (15mL) and the water (5mL) that removed oxygen, back flow reaction is 3 days under the nitrogen protection.Reacted the back cool to room temperature, chloroform extraction merges organic phase, uses saturated aqueous common salt and washing successively, and anhydrous sodium sulfate drying filters, and rotary evaporation goes out organic solvent.The solid sherwood oil: chloroform (V:V=1:2) separates for eluent carries out silica gel column chromatography, obtains reddish-brown solid TAT-DCV(80mg, productive rate 44%).
1H NMR(400MHz,CDCl
3),δ(ppm):8.34(s,3H),7.84(s,3H),7.70(d,J=8.4Hz,3H),7.56(d,J=8.0Hz,3H),7.43(s,3H),7.15(s,3H),4.93(t,J=7.6Hz,6H),2.78(m,12H),2.06(m,6H),1.66(m,12H),1.38-1.08(m,54H),0.95(t,J=6.8Hz,9H),0.85(t,J=6.8Hz,9H),0.71(t,J=7.2Hz,9H).
13C NMR(100MHz,CDCl
3),δ(ppm):157.4,148.5,147.5,143.4,140.9,140.4,139.4,132.6,132.3,130.9,129.9,128.8,128.3,125.3,125.2,124.5,123.5,122.6,115.3,114.1,110.6,103.3,73.2,65.6,47.4,31.6,31.5,31.3,30.9,30.6,30.2,29.7,29.3,29.2,29.1,28.9,26.6,22.6,19.2,14.1,13.9,13.7.MS(m/z):calcd.for C114H135N9S6[M]
+:1821.9;found,1821.9.
Embodiment 5: the uv-visible absorption spectra test
Compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and the TAT-DCV uv-visible absorption spectra test in chlorobenzene solution:
The uv-visible absorption spectra of above-claimed cpd carries out at the ultraviolet-visible spectrophotometer, and wherein solution absorption spectrum solvent for use is chlorobenzene, and concentration is 10
-5Mol/L; The solution of getting each compound of 2mL joins in the quartz colorimetric utensil, puts in the mapada UV-3300 type ultraviolet-visible spectrophotometer, after Calibration Base Line and the blank, at the absorption spectrum of 200-1000nm scope build-in test solution.Test result shows (as shown in Figure 1), and the described compound solution of the application all has absorption preferably at visible region, satisfies the basic extinction requirement of organic solar batteries donor material.The absorption spectrum of compound solution is subjected to a chain to give influencing strongly of receptor structure simultaneously.
The film absorption spectrum test of compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and TAT-DCV:
Film absorption spectrum is with chlorobenzene solution spin coating preparation on silica glass of above-claimed cpd.Get and make the quartz plate that scribbles compound film, put in the mapada UV-3300 type ultraviolet-visible spectrophotometer, after Calibration Base Line and the blank, at the absorption spectrum of 200-1000nm scope build-in test film.Test result shows (as shown in Figure 2), and the described compound film of the application all has absorption preferably at visible region, satisfies the basic extinction requirement of organic solar batteries donor material.Be compared to the absorption spectrum in the compound solution, the absorption spectrum of compound film has red shift in various degree, and gathering has taken place in film this explanation compound.
Embodiment 6: the cyclic voltammetry test
Compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and TAT-DCV are carried out the cyclic voltammetry test:
Can calculate highest occupied molecular orbital (HOMO) energy level of molecule and the energy level of lowest unoccupied molecular orbital (LUMO) by the redox potential of cyclic voltammetry test molecule.Carry out the test of electrochemical properties in the present embodiment with electrochemical workstation, electrolyzer is that (glass-carbon electrode is working electrode to three-electrode system, glass silk electrode is supporting electrode, silver/silver chloride electrode is reference electrode), do interior mark with ferrocene, dry methylene dichloride or the acetonitrile of crossing is solvent, and the tetrabutyl ammonium hexafluorophosphate of 0.1mol/L is supporting electrolyte, and sweep velocity is 50mV/S.Under argon shield, scanning obtains cyclic voltammetry curve (as shown in Figure 3), calculates HOMO and the lumo energy of molecule, and calculation result is as shown in table 1:
Table 1
| Compound | HOMO(eV) | LUMO（eV） | E g(eV) |
| TAT-hTBT | -5.16 | -3.06 | 2.1 |
| TAT-hTBTT | -5.00 | -3.06 | 1.94 |
| TAT-oDPP | -4.89 | -3.49 | 1.4 |
| TAT-DCV | -5.20 | -3.18 | 2.02 |
Can find out that from table 1 the prepared compound of embodiment 1-4 has lower energy gap width, lumo energy all is higher than PCBM(3.7-4.2eV), lumo energy is suitable, can be as donor material and common that acceptor material PCBM forms active coating.
Embodiment 7:
Be the preparation of the solar cell device of donor material with compound TAT-hTBT:
Device architecture is ITO/PEDOT:PSS/TAT-hTBT:PC
71BM/Ca/Al.Concrete preparation process is: at first ito glass carried out pre-treatment, cleans ito glass with clean-out system earlier, and washing from the beginning, acetone, isopropanol solvent ultrasonic cleaning each about 20 minutes are used ito glass in the deionization washing then successively, take out the back and dry up with nitrogen.Use Uv Ozone pre-treatment 20 minutes then, handle back spin coating PEDOT:PSS(Baytron P VP Al4083) (rotating speed 4000rpm, 60 seconds time), as the anode modification layer, 140 ℃ of dryings were after 10 minutes, with TAT-hTBT:PC
71The chlorobenzene solution of BM (5mg:15mg) spin coating (rotating speed 1000rpm, 60 seconds time) on the PEDOT:PSS surface as active coating, and then evaporation Ca(20nm) and metal electrode Al(160nm).Under standard sunlight (AM1.5G) radiation condition, device performance is tested.
Current density-the voltage curve of device as shown in Figure 4.Utilize compound TAT-hTBT to be the body heterojunction solar cell device of the solution-treated of donor material preparation, open circuit voltage is up to 0.92V, and short-circuit current reaches 8.19mA/cm
2, packing factor is 33%, energy conversion efficiency is 2.46%.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. the compound shown in the formula I, its structure is as follows:
In the formula, R is H or C
1-12Alkyl; The structure of X is suc as formula shown in II or the formula III:
In the formula, R
1Be H or C
1-12Alkyl;
D is the group that is selected from down group:
In the formula, R
2Be C
1-12Alkyl;
A
1For replacing or unsubstituted 8 yuan to 10 yuan assorted fragrant bicyclic ring systems, replacement or unsubstituted 12 yuan to 14 yuan assorted virtue three ring ring systems,
Wherein, described replacement refers to that the substituting group that one or more H in the group are selected from down group replaces :-COOC
1-12Alkyl, C
1-12Alkyl, C
1-12Alkoxyl group, fluorine atom or trifluoromethyl;
A
2For being selected from down the group of group:
In the formula, R
3Be C
1-12Alkyl.
2. compound as claimed in claim 1 is characterized in that, A
1For being selected from down the group of group:
In the formula, Z is O or S;
Y is N or CR
6
R
4For-COOC
1-12Alkyl, C
1-12Alkyl or C
1-12Alkoxyl group;
R
5, R
6Independent separately is H, fluorine atom or trifluoromethyl.
3. compound as claimed in claim 1 is characterized in that, A
1For being selected from down the group of group:
In the formula, R
7Be C
1-12Alkyl.
4. compound as claimed in claim 1 is characterized in that, A
1For being selected from down the group of group:
5. compound as claimed in claim 1 is characterized in that, A
2For being selected from down the group of group:
6. compound as claimed in claim 1 is characterized in that, described X is the group that is selected from down group:
7. the preparation method of the described formula I of claim 1 compound is characterized in that described method comprises step:
(1) in the presence of catalyzer, formula IV compound is carried out the boron esterification, thereby form formula V compound,
(2) in the presence of catalyzer, formula V compound and formula VI compound are carried out the Suzuki linked reaction, thereby form formula I compound,
In the formula, R, X are as defined in claim 1; L is I or Br.
8. method as claimed in claim 7 is characterized in that, described catalyzer is selected from:
(a) palladium catalyst;
(b) combination of palladium catalyst and part.
9. the purposes of the described formula I of claim 1 compound is characterized in that, for the preparation of solar cell device.
10. a solar cell device is characterized in that, described device comprises the described formula I of claim 1 compound.
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