CN103304568B - Trimerization Benzazole compounds and its production and use - Google Patents
Trimerization Benzazole compounds and its production and use Download PDFInfo
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- 0 C*CC=C(C#N)C#N Chemical compound C*CC=C(C#N)C#N 0.000 description 7
- UYYDRUUJLZSHAW-UHFFFAOYSA-N CC(C)C(C)=[P]1(CC1)(c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound CC(C)C(C)=[P]1(CC1)(c1ccccc1)(c1ccccc1)c1ccccc1 UYYDRUUJLZSHAW-UHFFFAOYSA-N 0.000 description 1
- FRFFJLWBOPOCBG-UHFFFAOYSA-N CCCCC(C1)C2NSN=C2C(C)=[N]1(C)=C Chemical compound CCCCC(C1)C2NSN=C2C(C)=[N]1(C)=C FRFFJLWBOPOCBG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to trimerization Benzazole compounds and its production and use, structure is such as formula shown in I, and in formula, the definition of R, X as used in the description.Trimerization Benzazole compounds of the present invention has the mother nucleus structure unit of solubility pi-conjugated greatly and conjugated electrons to body and/or acceptor push-pull configuration side chain, is a class low band gap micromolecular compound, has broad application prospects in solar cell device.
Description
Technical field
The invention belongs to 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, there is chemical structure diversity, can volume to volume big area produce, flexible, the advantages such as frivolous and relative inexpensiveness, be one of advanced subject of the richest vigour and vitality of current novel solar battery research field, there is important development and application prospect.
Current organic solar batteries many employings conjugated polymers, but conjugated polymers is difficult to purifying, device poor repeatability, relative to conjugated polymers, organic small molecule material has the molecular structure more determined, be easy to modify and purify and high repeatability and other advantages, therefore, become one of the study hotspot in organic solar batteries field in recent years.
How to pass through the microvisual model state of regulation activity layer, while making to form being separated of nanoscale to body and acceptor (PCBM), ensureing to the high efficiency charge of body phase (hole) transmission, is the important key issue improving 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 formula, R is H or C
1-12alkyl; The structure of X is such as formula shown in II or formula III:
In formula, R
1for H or C
1-12alkyl;
D is selected from the group of lower group:
In formula, R
2for C
1-12alkyl.
A
1for substituted or unsubstituted 8 yuan to 10 yuan assorted fragrant bicyclic ring systems, substituted or unsubstituted 12 yuan to 14 yuan assorted fragrant three ring ring systems,
Wherein, described replacement refers to that the substituting group that one or more H in group is selected from lower group replaced :-COOC
1-12alkyl, C
1-12alkyl, C
1-12alkoxyl group, fluorine atom or trifluoromethyl;
A
2for being selected from the group of lower group:
In formula, R
3for C
1-12alkyl.
In another preference, A is substituted or unsubstituted 8 yuan to 9 yuan assorted fragrant bicyclic ring systems, substituted or unsubstituted 12 yuan of assorted fragrant three ring ring systems;
Wherein, described " replacement " refers to that the substituting group that one or more H in group is selected from lower group replaced :-COOC
1-12alkyl, C
1-12alkyl, C
1-12alkoxyl group, fluorine atom or trifluoromethyl.
In another preference, R is C
2-10alkyl, preferably C
6-8alkyl, is more preferably C
6or C
8alkyl.
In another preference, R
1for C
2-10alkyl, is preferably C
6-8alkyl, is more preferably C
6or C
8alkyl.
In another preference, R
2for C
2-8alkyl, is preferably C
2-8alkyl.
In another preference, R
3for C
2-8alkyl.Be preferably C
2, C
6, C
8alkyl.
In another preference, A
1for being selected from the group of lower group:
In 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
6respective is independently H, fluorine atom or trifluoromethyl.
In another preference, Z is S atom.
In another preference, A
1for being selected from the group of lower group:
In formula, R
7for C
1-12alkyl.
In another preference, R
7for C
4-10alkyl, is preferably C
6-8alkyl, is more preferably C
6or C
8alkyl.
In another preference, A
1for being selected from the group of lower group:
In another preference, A
2for being selected from the group of lower group:
In another preference, described X is selected from the group of lower group:
A second aspect of the present invention provides the preparation method of the type I compound described in a kind of first aspect present invention, and described method comprises step:
(1) in the presence of a catalyst, formula IV compound is carried out boron esterification, thus forms formula V compound,
(2) in the presence of a catalyst, formula V compound and formula VI compound are carried out Suzuki linked reaction, thus form type I compound,
In formula, R, X as first aspect present invention define; L is I or Br.
In another preference, described reaction is carried out under rare gas element existence condition.
In another preference, described reaction is carried out in confined conditions.
In another preference, the temperature of reaction of described reaction is 80 ~ 120 DEG C.
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, described reaction alkali there is situation under carry out.
In another preference, described catalyzer is selected from:
(a) palladium catalyst;
The combination of (b) 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 type I compound described in a kind of first aspect present invention, 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 type I compound described in first aspect present invention.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and 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 the current density voltage curve of the solar cell device prepared for donor material with compound TAT-hTBT.
Embodiment
Contriver is through extensive and deep research, develop a class trimerization Benzazole compounds first, this compounds is with trimerization indoles for mother nucleus structure, and the α position to thiphene ring modifies the small molecules that the class obtained has hub-and-spoke configuration by conjugated electrons to body and/or conjugated electrons acceptor groups.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.Complete the present invention on this basis.
As used herein, " compound shown in formula I ", " type I compound " are used interchangeably, and all refer to that structural formula is the compound of formula I.
group definition
Term " C
1-12alkyl " refer to the straight or branched alkyl with 1-12 carbon atom, such as 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 the straight or branched alkoxyl group with 1-12 carbon atom, such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy or similar group.
Term " heteroaryl " refers to the loop systems of aromatic monocyclic shape of ring hetero atom being selected from oxygen, nitrogen, sulphur containing at least one, or in the ring wherein existed, at least one is aromatic series and polycyclic loop systems containing at least one ring hetero atom.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 shape, and/or the ring of non-aromatic is mixed the group of monocyclic heteroaryl group ring that alkyl ring condenses.
Term " ring " or " ring system " refer to carbocyclic ring or heterocycle.
Term " heterocycle " finger-type becomes at least one atom in the atom of described heterocyclic skeleton not to be carbon, 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 " finger ring system is the ring system of heterocycle.
At least one ring in term " hetero-aromatic ring ring system " finger ring system is the system of aromatic ring.
As used herein, term " 8 yuan to 10 yuan assorted fragrant bicyclic ring systems " and " 12 yuan to 14 yuan assorted fragrant 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 of following structure is comprised:
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, pyrydinothiadiazole base, pyrido triazol radical, thieno-thiadiazolyl group, thienopyrazine base, thieno-triazol radical, thienothiophene base, 2,5-dihydro-pyrrole-1,4-diketo, thiophene-[3,4-c]-pyrroles-4,6-diketo, thiadiazoles benzo thiadiazolyl group etc.
As used herein, " conjugated electrons is to body " refers to the group that can form conjugatedπbond system, and this group can to adjacent atom donates electrons.The heteroaryl of the electron rich of 5-14 unit is mainly comprised in the present invention.
As used herein, " conjugated electrons acceptor " refers to the group that can form conjugatedπbond system, and this group is connected with electron-withdrawing 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
0c
1-20alkyl, C
2-20thiazolinyl, C
2-20alkynyl, C
6-14aryl, or C
3-14cycloalkyl.
Various unsubstituted heteroaryl can be described to electron rich (or π-excessive) or electron deficiency (or π-deficiency).This classification is based on the average electron density on each annular atoms compared with the carbon atom of benzene.The example of electron rich system comprises and has heteroatomic 5 yuan of heteroaryls, as furans, pyrroles and thiophene; Or the group that plural 5 yuan of heteroaryls connect; Or there are plural 5 yuan of heteroaryl-condensed groups together, as bithiophene, thienothiophene.
The heteroaromatic ring of mixing can belong to a certain kind according to the one or more heteroatomic type in this ring, quantity and position.
Term " halogen " or " halogen atom " refer to fluorine atom, chlorine atom, bromine atoms or atomic iodine.
As used herein, " mobility " refers to and represents the charged particle mobile amount by the speed of this material under the influence of electric fields.This parameter depends on the framework of device, and fieldtron or space-charge current limliting method of masurement can be used 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 of the power being converted to electric energy by the light absorbed.Can being calculated divided by the surface-area of the input light irradiance under 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 synthesis process well known by persons skilled in the art to prepare.In a class preferred embodiment of the present invention, the preparation method of compound comprises step: in the presence of a catalyst, and formula IV compound is carried out boron esterification, thus forms formula V compound.
(2) in the presence of a catalyst, formula V compound and formula VI compound are carried out Suzuki linked reaction, thus form type I compound.
In formula, the definition of R, X is the same; L is I or Br.
Catalyzer can adopt the conventional catalyst used in linked reaction, is preferably palladium catalyst or uses for 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
2; Wherein, M is acetate, trifluoracetic acid root, trifluoromethanesulfonic acid root, pivalate or halide-ions.
Part is not particularly limited, and can select according to the palladium catalyst used in concrete reaction.The preferred part of one class comprises the phosphorus part such as triphenyl phosphorus, tri-tert phosphorus.
Formula V does not specifically limit with the mol ratio of formula VI compound, the mol ratio >=3:1 of usual formula VI compound and formula V compound.Preferably 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 DEG C, and the reaction times is generally 2 ~ 24 hours.Reaction product is carried out process purifying by ordinary method known in the art and is obtained.
Reaction can be deposited at alkali and be carried out in case, alkali used 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]-5-in ninth of the ten Heavenly Stems alkene (DBN), Potassium ethanoate, salt of wormwood, saleratus, sodium carbonate, 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 to synthesize.The preferred synthetic route of one class is shown below:
In formula, the definition of R, L is the same.
Formula VI compound can adopt ordinary method well-known to those skilled in the art to synthesize.The preferred synthetic route of one class is shown below:
In formula, R, A
1, D definition the same.
Or be shown below:
The purposes of trimerization Benzazole compounds
Traditional organic solar batteries device architecture comprises: glass coating, ITO layer and PEDOT, PEDOT comprise: PSS composite bed, active coating and metal electrode layer.
Trimerization Benzazole compounds of the present invention can be used for preparing donor material in described active coating, and in described active coating, acceptor material is PC
61bM or PC
71bM.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 large π plane system, there is strong π-π and interact between molecule, and easy self-assembly forms the ordered structure of nanoscale, improves the carrier mobility of molecule in crystal or film.
(2) compound of the present invention is compared with existing conjugated polymers, has structure and determines, synthesis is simple, is easy to purify, the advantages such as solvability is good.
(3) compound of the present invention can be used for the material preparing solar cell device, has and absorbs preferably and lower energy gap width, have broad application prospects in solar cell device.
The above-mentioned feature that the present invention mentions, or the feature that embodiment is mentioned can arbitrary combination.All features that this case specification sheets discloses can with any composition forms and use, each feature disclosed in specification sheets, anyly can be provided alternative characteristics that is identical, impartial or similar object and replace.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and number calculate by weight.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the same meaning be familiar with.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Implementation column 1:
The synthesis of TAT-hTBT, the structure of this compound is:
The preparation method of TAT-hTBT comprises the steps (1) ~ (11):
(1) synthesis of 1-hexyl-2-indolone:
Under nitrogen protection; 2-indolone (2.66g is added in 100mL two mouthfuls of flasks; 20mmol), bromo normal hexane (4.2mL; 30mmol), N; dinethylformamide (40mL) and salt of wormwood (13.82g; 100mmol), 80 DEG C of reactions 20 hours are heated to.React rear cool to room temperature, added water, with petroleum ether extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation removing organic solvent.Mixture sherwood oil: ethyl acetate (V:V:=6:1) carries out silica gel column chromatography separation for eluent, obtains brown-red oil 1 (1.65g, productive rate 38%).
1HNMR(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) synthesis of the bromo-2-indolone of 1-hexyl-5-:
Get 1-hexyl-2-indolone (6.52g, 30mmol) and be dissolved in acetonitrile (100), then add N-bromo-succinimide (5.87g, 33mmol) under room temperature in batches, add rear continuation reaction 2 days.React rear rotary evaporation removing acetonitrile, add methylene dichloride, organic phases washed with water three times, anhydrous sodium sulfate drying, filter, rotary evaporation except desolventizing, with sherwood oil: ethyl acetate (V:V:=6:1) carries out silica gel column chromatography separation for eluent, obtain faint yellow solid 2 (7.20g, 81%).
1HNMR(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).
13CNMR(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) synthesis of compound 3:
Getting the bromo-2-indolone (3.60g, 15mmol) of 1-hexyl-5-joins in phosphorus oxychloride (25mL), back flow reaction 6 hours.React rear cool to room temperature, be poured in a large amount of frozen water, filtered.Crude product sherwood oil: ethyl acetate (V:V:=6:1) carries out silica gel column chromatography separation for eluent, obtains white solid 3 (1.10g, 33%).
1HNMR(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).
13CNMR(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) synthesis of compound 4:
Compound 3 (417mg, 0.5mmol), duplex tetramethyl ethylene ketone boric acid ester (762mg, 6mmol), Potassium ethanoate (491mg, 5mmol) and Pd (dppf) Cl is added in 100mL round-bottomed flask
2(18mg, 0.025mmol), takes out logical nitrogen three times, adds anhydrous and oxygen-free Isosorbide-5-Nitrae-dioxane (20mL), the lower 85 DEG C of reactions of nitrogen protection 48 hours.Reacted rear cool to room temperature, added water, dichloromethane extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: ethyl acetate (V:V=10:1) carries out silica gel column chromatography separation for eluent, obtains white solid 4 (370mg, productive rate 76%).
1HNMR(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) synthesis of 4-hexyl-2-thienyl-tri-n-butyl tin:
Under nitrogen protection; 3-hexyl thiophene (20.20g is added in 500mLSchlenk bottle; 120mmol) with anhydrous and oxygen-free tetrahydrofuran (THF) (200mL), be cooled to-78 DEG C, in this solution, slowly drip the hexane solution (45.8mL of n-Butyl Lithium; 2.4M); after adding ,-78 DEG C are continued stirring reaction 1 hour, then add tributyltin chloride (35.3mL, 130mmol); holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add shrend to go out reaction, petroleum ether extraction, merge organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, the light yellow oil 5 of rotary evaporation removing organic solvent, crude product, without further purification, is directly used as next step and synthesizes.
The synthesis of (6) 4,7-bis-(4-hexyl-2-thienyl)-benzo [c] [1,2,5] thiadiazoles:
4 are added in 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) removing oxygen, back flow reaction 24 hours under nitrogen protection.Reacted rear cool to room temperature, added water, dichloromethane extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=8:1) carries out silica gel column chromatography separation for eluent, obtains orange solids 6 (4.67g, productive rate 99%).
1HNMR(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).
13CNMR(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) synthesis of compound 7:
Get 4,7-bis-(4-hexyl-2-thienyl)-benzo [c] [1,2,5] thiadiazoles (5.62g, 12mmol) be dissolved in chloroform (300mL), then add N-bromo-succinimide (2.14g, 12mmol) under room temperature in batches, add rear continuation reaction 2 days.Wash three times after having reacted with water, anhydrous sodium sulfate drying, filter, rotary evaporation except desolventizing, with sherwood oil: chloroform (V:V:=8:1) carries out silica gel column chromatography separation for eluent, obtains Orange red solid 7 (5.20g, 79%).
1HNMR(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).
13CNMR(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) synthesis of 5-hexyl-2-thienyl-tri-n-butyl tin:
Under nitrogen protection; 2-hexyl thiophene (20.20g is added in 500mLSchlenk bottle; 120mmol) with anhydrous and oxygen-free tetrahydrofuran (THF) (200mL), be cooled to-78 DEG C, in this solution, slowly drip the hexane solution (45.8mL of n-Butyl Lithium; 2.4M); after adding ,-78 DEG C are continued stirring reaction 1 hour, then add tributyltin chloride (35.3mL, 130mmol); holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add shrend to go out reaction, petroleum ether extraction, merge organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, the light yellow oil 7 of rotary evaporation removing organic solvent, crude product, without further purification, is directly used as next step and synthesizes.
(9) synthesis of compound 9:
Compound 7 (2.19g is added in 100mL round-bottomed flask; 4mmol), 5-hexyl-2-thienyl-tri-n-butyl tin (2.74g; 6mmol) He four triphenyl phosphorus palladium (12mg; 0.01mmol); take out logical nitrogen three times; add the toluene (40mL) removing oxygen, back flow reaction 24 hours under nitrogen protection.Reacted rear cool to room temperature, added water, dichloromethane extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=5:1) carries out silica gel column chromatography separation for eluent, obtains red solid 9 (2.28g, productive rate 90%).
1HNMR(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) synthesis of compound 10:
Get compound 9 (2.28g, 3.6mmol) and be dissolved in chloroform (100mL), then add N-bromo-succinimide (0.64g, 3.6mmol) under room temperature in batches, add rear continuation reaction 1 day.Wash three times after having reacted with water, anhydrous sodium sulfate drying, filter, rotary evaporation except desolventizing, with sherwood oil: chloroform (V:V:=8:1) carries out silica gel column chromatography separation for eluent, obtains red solid 10 (2.30g, 90%).
1HNMR(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) synthesis of compound TAT-hTBT:
Compound 4 (195mg is added in 50mL round-bottomed flask; 0.2mmol), compound 10 (857mg; 1.2mmol), salt of wormwood (2.76g; 20mmol) He four triphenyl phosphorus palladium (10mg; 0.008mmol); take out logical nitrogen three times, add the toluene (20mL) and water (10mL) that removed oxygen, back flow reaction 3 days under nitrogen protection.Reacted rear cool to room temperature, chloroform extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=4:1) carries out silica gel column chromatography separation for eluent, obtains black solid TAT-hTBT (447mg, productive rate 90%).
1HNMR(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).
13CNMR(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.forC150H184N9S12[M+H]
+:2495.1；found,2495.2.
Implementation column 2:
The synthesis of TAT-hTBTT, the structure of this compound is:
The preparation method of TAT-hTBTT comprises the steps (1) ~ (11):
(1) synthesis of 1-hexyl-2-indolone:
Step (1) in its building-up process detailed in Example 1.
(2) synthesis of the bromo-2-indolone of 1-hexyl-5-:
Step (2) in its building-up process detailed in Example 1.
(3) synthesis of compound 3:
Step (3) in its building-up process detailed in Example 1.
(4) synthesis of compound 4:
Step (4) in its building-up process detailed in Example 1.
(5) synthesis of 4-hexyl-2-thienyl-tri-n-butyl tin:
Step (5) in its building-up process detailed in Example 1.
The synthesis of (6) 4,7-bis-(4-hexyl-2-thienyl)-benzo [c] [1,2,5] thiadiazoles:
Step (6) in its building-up process detailed in Example 1.
(7) synthesis of compound 7:
Step (7) in its building-up process detailed in Example 1.
(8) synthesis of compound 11:
Under nitrogen protection; 5-hexyl-2,2 '-thiophene (2.27g, 9.1mmol) and anhydrous and oxygen-free tetrahydrofuran (THF) (50mL) is added in 500mLSchlenk bottle; be cooled to-78 DEG C; in this solution, slowly drip the hexane solution (10mL, 2.4M) of n-Butyl Lithium, after adding ,-78 DEG C are continued stirring reaction 1 hour; then tributyltin chloride (3mL is added; 11.0mmol), holding temperature continues reaction 1 hour, and system rises to stirred overnight at room temperature.Add shrend to go out reaction, petroleum ether extraction, merge organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, the light yellow oil 11 of rotary evaporation removing organic solvent, crude product, without further purification, is directly used as next step and synthesizes.
(9) synthesis of compound 12:
Compound 7 (2.19g is added in 100mL round-bottomed flask; 4.0mmol), compound 11 (2.37g; 4.4mmol) He four triphenyl phosphorus palladium (12mg; 0.01mmol); take out logical nitrogen three times; add the toluene (20mL) removing oxygen, back flow reaction 24 hours under nitrogen protection.Reacted rear cool to room temperature, added water, dichloromethane extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=5:1) carries out silica gel column chromatography separation for eluent, obtains red solid 12 (2.80g, productive rate 98%).
1HNMR(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) synthesis of compound 13:
Get compound 12 (2.87g, 4.0mmol) and be dissolved in chloroform (50mL), then add N-bromo-succinimide (0.64g, 3.6mmol) under room temperature in batches, add rear continuation reaction 1 day.Wash three times after having reacted with water, anhydrous sodium sulfate drying, filter, rotary evaporation except desolventizing, with sherwood oil: chloroform (V:V:=3:1) carries out silica gel column chromatography separation for eluent, obtains dark red solid 13 (2.70g, 85%).
1HNMR(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) synthesis of compound TAT-hTBTT:
Compound 4 (195mg is added in 50mL round-bottomed flask; 0.2mmol), compound 13 (955mg; 1.2mmol), salt of wormwood (2.76g; 20mmol) He four triphenyl phosphorus palladium (10mg; 0.008mmol); take out logical nitrogen three times, add the toluene (30mL) and water (10mL) that removed oxygen, back flow reaction 3 days under nitrogen protection.Reacted rear cool to room temperature, chloroform extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=5:1) carries out silica gel column chromatography separation for eluent, obtains black solid TAT-hTBTT (450mg, productive rate 82%).
1HNMR(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).
13CNMR(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.forC162H190N9S15[M+H]
+:2741.1；found,2742.5.
Implementation column 3:
The synthesis of TAT-oDPP, the structure of this compound is:
The preparation method of TAT-oDPP comprises the steps (1) ~ (10):
(1) synthesis of 1-hexyl-2-indolone:
Step (1) in its building-up process detailed in Example 1.
(2) synthesis of the bromo-2-indolone of 1-hexyl-5-:
Step (2) in its building-up process detailed in Example 1.
(3) synthesis of compound 3:
Step (3) in its building-up process detailed in Example 1.
(4) synthesis of compound 4:
Step (4) in its building-up process detailed in Example 1.
(5) synthesis of compound 15:
Compound 14 (purchased from slope and Ji Guang scientific & technical corporation) (1.50g is added in 100mL flask, 5.0mmol), Anhydrous potassium carbonate (3.46g, 25.0mmol) and N, dinethylformamide (50mL), be heated to 120 DEG C of reactions and add n-octane bromide (2.2mL, 12.5mmol) after 1 hour, maintain 130 DEG C of reactions 12 hours.Reacted rear cool to room temperature, be poured in large water gaging, filter, filter cake sherwood oil: chloroform (V:V=1:1) carries out silica gel column chromatography separation for eluent, obtains red brown solid 15 (0.60g, 23%).
1HNMR(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).
13CNMR(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) synthesis of compound 16:
Get compound 15 (1.12g, 2.1mmol) and be dissolved in chloroform (50mL), then add N-bromo-succinimide (0.37g, 2.1mmol) under room temperature in batches, add rear continuation reaction 1 day.Wash three times after having reacted with water, anhydrous sodium sulfate drying, filter, rotary evaporation except desolventizing, with sherwood oil: chloroform (V:V:=1:1) carries out silica gel column chromatography separation for eluent, obtains dark red solid 16 (1.07g, 84%).
1HNMR(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).
13CNMR(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) synthesis of 5-hexyl-2-thienyl-tri-n-butyl tin:
Step (8) in its building-up process detailed in Example 1.
(8) synthesis of compound 17:
Compound 16 (302mg is added in 25mL round-bottomed flask; 0.5mmol), 5-hexyl-2-thienyl-tri-n-butyl tin (457mg; 1.0mmol) He four triphenyl phosphorus palladium (1mg; 0.001mmol); take out logical nitrogen three times; add the toluene (10mL) removing oxygen, back flow reaction 12 hours under nitrogen protection.Reacted rear cool to room temperature, added water, dichloromethane extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=1:1) carries out silica gel column chromatography separation for eluent, obtains brown solid 17 (280mg, productive rate 81%).
1HNMR(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).
13CNMR(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) synthesis of compound 18:
Get compound 17 (1.11g, 1.6mmol) and be dissolved in chloroform (50mL), then add N-bromo-succinimide (0.31g, 1.7mmol) under room temperature in batches, add rear continuation reaction 1 day.Wash three times after having reacted with water, anhydrous sodium sulfate drying, filter, rotary evaporation except desolventizing, with sherwood oil: chloroform (V:V:=1:1) carries out silica gel column chromatography separation for eluent, obtains brown solid 18 (1.07g, 87%).
1HNMR(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).
13CNMR(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) synthesis of compound TAT-oDPP:
Compound 4 (98mg is added in 50mL round-bottomed flask; 0.1mmol), compound 18 (371mg; 0.6mmol), salt of wormwood (1.38g; 10.0mmol) He four triphenyl phosphorus palladium (5mg; 0.004mmol); take out logical nitrogen three times, add the toluene (15mL) and water (5mL) that removed oxygen, back flow reaction 3 days under nitrogen protection.Reacted rear cool to room temperature, chloroform extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=1:2) carries out silica gel column chromatography separation for eluent, obtains black solid TAT-oDPP (197mg, productive rate 74%).
1HNMR(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).
13CNMR(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.forC162H208N9O6S9[M+H]
+:2663.4；found,2663.6.
Implementation column 4:
The synthesis of TAT-DCV, the structure of this compound is:
The preparation method of TAT-DCV comprises the steps (1) ~ (9):
(1) synthesis of 1-hexyl-2-indolone:
Step (1) in its building-up process detailed in Example 1.
(2) synthesis of the bromo-2-indolone of 1-hexyl-5-:
Step (2) in its building-up process detailed in Example 1.
(3) synthesis of compound 3:
Step (3) in its building-up process detailed in Example 1.
(4) synthesis of compound 4:
Step (4) in its building-up process detailed in Example 1.
(5) synthesis of compound 19:
Under nitrogen protection; 3-hexyl thiophene (1.68g is added in 100mLSchlenk bottle; 10mmol) with anhydrous and oxygen-free tetrahydrofuran (THF) (40mL), be cooled to-78 DEG C, in this solution, slowly drip the hexane solution (4.6mL of n-Butyl Lithium; 2.4M); after adding ,-78 DEG C are continued stirring reaction 1 hour, then add 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, merge organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation removing organic solvent.Crude product sherwood oil is that eluent carries out silica gel column chromatography separation, obtains pale yellow oil 19 (1.54g, productive rate 92%).
1HNMR(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) synthesis of compound 20:
Get compound 19 (3.35g, 10mmol) and be dissolved in DMF (20mL), N-bromo-succinimide (0.31g, 1.7mmol) be dissolved in DMF (40mL), then the latter be slowly added drop-wise in the former.Drip rear continuation reaction 8 hours, add large water gaging, petroleum ether extraction after having reacted, dry, filter, rotary evaporation, except desolventizing, is that eluent carries out silica gel column chromatography separation with sherwood oil, obtains pale yellow oil 20 (3.94g, 80%).
(7) synthesis of compound 21:
Under nitrogen protection; add compound 20 (4.45g, 9.0mmol) and anhydrous and oxygen-free tetrahydrofuran (THF) (100mL) in 250mLSchlenk bottle, be cooled to-78 DEG C; hexane solution (the 3.8mL of n-Butyl Lithium is slowly dripped in this solution; 2.4M), after adding ,-78 DEG C are continued stirring reaction 1 hour, then add anhydrous N; 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, merge organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation removing organic solvent.Crude product sherwood oil: chloroform (V:V=5:1) carries out silica gel column chromatography separation for eluent, obtains yellow oil 21 (3.02g, productive rate 76%).
1HNMR(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).
13CNMR(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) synthesis of compound 22:
Get compound 21 (1.69g, 3.8mmol) He the third two eyeball (0.51g, 7.6mmol) is dissolved in anhydrous chloroform (50mL), adds a small amount of triethylamine (0.1mL), then room temperature reaction 8 hours, react after washing, dry, filter, rotary evaporation is except desolventizing, be that eluent carries out silica gel column chromatography separation with sherwood oil, obtain yellow-brown solid 22 (1.69g, 91%).
1HNMR(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).
13CNMR(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) synthesis of compound TAT-DCV:
Compound 4 (98mg is added in 50mL round-bottomed flask; 0.1mmol), compound 22 (294mg; 0.6mmol), salt of wormwood (1.38g; 10.0mmol) He four triphenyl phosphorus palladium (5mg; 0.004mmol); take out logical nitrogen three times, add the toluene (15mL) and water (5mL) that removed oxygen, back flow reaction 3 days under nitrogen protection.Reacted rear cool to room temperature, chloroform extraction, merged organic phase, use saturated aqueous common salt and washing successively, anhydrous sodium sulfate drying, filter, rotary evaporation goes out organic solvent.Solid sherwood oil: chloroform (V:V=1:2) carries out silica gel column chromatography separation for eluent, obtains red brown solid TAT-DCV (80mg, productive rate 44%).
1HNMR(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).
13CNMR(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.forC114H135N9S6[M]
+:1821.9；found,1821.9.
Embodiment 5: uv-visible absorption spectra is tested
Compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and TAT-DCV uv-visible absorption spectra test in chlorobenzene solution:
The uv-visible absorption spectra of above-claimed cpd carries out on spectrophotometry instrument, and wherein solution absorption spectra solvent for use is chlorobenzene, and concentration is 10
-5mol/L; The solution getting each compound of 2mL joins in quartz colorimetric utensil, puts in mapadaUV-3300 type spectrophotometry instrument, after Calibration Base Line and blank, at the absorption spectrum of 200-1000nm scope build-in test solution.Test result display (as shown in Figure 1), compound solution described in the application all has good absorption in visible region, meets the basic extinction requirement of organic solar batteries donor material.The absorption spectrum of compound solution is by branch chain strongly affecting to receptor structure simultaneously.
The film absorption spectrum test of compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and TAT-DCV:
Film absorption spectrum is with the spin coating preparation on silica glass of the chlorobenzene solution of above-claimed cpd.Get the quartz plate made and scribble compound film, put in mapadaUV-3300 type spectrophotometry instrument, after Calibration Base Line and blank, at the absorption spectrum of 200-1000nm scope build-in test film.Test result display (as shown in Figure 2), compound film described in the application all has good absorption in visible region, meets the basic extinction requirement of organic solar batteries donor material.Be compared to the absorption spectrum in compound solution, the absorption spectrum of compound film has red shift in various degree, and this illustrates that compound there occurs gathering in the film.
Embodiment 6: cyclic voltammetry is tested
Cyclic voltammetry test is carried out to compound TAT-hTBT, TAT-hTBTT, TAT-oDPP and TAT-DCV:
Highest occupied molecular orbital (HOMO) energy level of molecule and the energy level of lowest unoccupied molecular orbital (LUMO) can be calculated by the redox potential of cyclic voltammetry test molecule.Carry out the test of electrochemical properties with electrochemical workstation in the present embodiment, 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), interior mark is done with ferrocene, dried methylene dichloride or acetonitrile are 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), and calculate HOMO and the lumo energy of molecule, 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 from table 1, the compound prepared by embodiment 1-4 has lower energy gap width, and lumo energy is all higher than PCBM (3.7-4.2eV), and lumo energy is suitable, can form active coating as donor material and the common acceptor material PCBM that obtains.
Embodiment 7:
The preparation of the solar cell device being donor material with compound TAT-hTBT:
Device architecture is ITO/PEDOT:PSS/TAT-hTBT:PC
71bM/Ca/Al.Concrete preparation process is: first ito glass is carried out pre-treatment, first cleans ito glass with clean-out system, washes from the beginning, and deionization is washed, and then ito glass is used successively each about 20 minutes of acetone, isopropanol solvent ultrasonic cleaning, dries up after taking-up with nitrogen.Then use UvOzone pre-treatment 20 minutes, process rear spin coating PEDOT:PSS (BaytronPVPAl4083) (rotating speed 4000rpm, 60 seconds time) as anode modification layer, 140 DEG C of dryings are after 10 minutes, by TAT-hTBT:PC
71chlorobenzene solution (5mg:15mg) spin coating (rotating speed 1000rpm, 60 seconds time) of BM is surperficial as active coating at PEDOT:PSS, and then evaporation Ca (20nm) and metal electrode Al (160nm).Under standard sunlight (AM1.5G) radiation condition, device performance is tested.
The current density voltage curve of device as shown in Figure 4.The body heterojunction solar cell device of the solution-treated utilizing compound TAT-hTBT to prepare for donor material, open circuit voltage is up to 0.92V, and short-circuit current reaches 8.19mA/cm
2, packing factor is 33%, and energy conversion efficiency is 2.46%.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that 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 limited range equally.
Claims (10)
1. the compound shown in formula I, its structure is as follows:
In formula, R is H or C
1-12alkyl; The structure of X is such as formula shown in II or formula III:
In formula, R
1for H or C
1-12alkyl;
D is selected from the group of lower group:
In formula, R
2for C
1-12alkyl;
A
1for substituted or unsubstituted 8 yuan to 10 yuan assorted fragrant bicyclic ring systems, and for being selected from the group of lower group:
In formula,
Y is CR
6;
R
4for C
1-12alkyl;
R
5, R
6respective is independently H;
Wherein, described replacement refers to that the substituting group that one or more H in group is selected from lower group replaced :-COOC
1-12alkyl, C
1-12alkyl, C
1-12alkoxyl group, fluorine atom or trifluoromethyl;
A
2for being selected from the group of lower group:
2. compound as claimed in claim 1, is characterized in that, A
1for being selected from the group of lower group:
in formula, Y and R
5as claim 1 define.
3. compound as claimed in claim 1, is characterized in that, A
1for being selected from the group of lower group:
4. compound as claimed in claim 1, is characterized in that, described X is selected from the group of lower group:
5. a preparation method for type I compound according to claim 1, is characterized in that, described method comprises step:
(1) in the presence of a catalyst, formula IV compound is carried out boron esterification, thus forms formula V compound,
(2) in the presence of a catalyst, formula V compound and formula VI compound are carried out Suzuki linked reaction, thus form type I compound,
In formula, R, X are as defined in claim 1; L is I or Br.
6. method as claimed in claim 5, it is characterized in that, described catalyzer is selected from:
(a) palladium catalyst;
The combination of (b) palladium catalyst and part.
7. method as claimed in claim 6, it is characterized in that, described palladium catalyst is selected from: 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.
8. method as claimed in claim 6, it is characterized in that, described part is selected from: triphenyl phosphorus, trimethylphenyl phosphorus, tri-tert phosphorus.
9. a purposes for type I compound according to claim 1, is characterized in that, for the preparation of solar cell device.
10. a solar cell device, is characterized in that, described device comprises type I compound according to claim 1.
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| WO2007015414A1 (en) * | 2005-08-01 | 2007-02-08 | Ihara Chemical Industry Co., Ltd. | OXADIAZOLE-SUBSTITUTED Sym-TRIINDOLE DERIVATIVE AND ORGANIC EL ELEMENT EMPLOYING THE SAME |
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