CN103601741A - 2,1,3-benzothiadiazoledithiophene derivatives and synthetic method thereof - Google Patents

2,1,3-benzothiadiazoledithiophene derivatives and synthetic method thereof Download PDF

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CN103601741A
CN103601741A CN201310425254.3A CN201310425254A CN103601741A CN 103601741 A CN103601741 A CN 103601741A CN 201310425254 A CN201310425254 A CN 201310425254A CN 103601741 A CN103601741 A CN 103601741A
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thiophene
dialkyl group
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刘治田
胡双强
柳斌
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Hubei Polymeric Polymer Material Co., Ltd.
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Abstract

The invention discloses 2,1,3-benzothiadiazoledithiophene derivatives. The derivatives relate to 5,8-dialkylbisthiophene benzothiadiazole. A preparation method includes preparing in sequence 5,5'-dialkyl-3,3'-bithiophene, 2,7-dialkylbenzodithiophene-4,5-diketone, 2,7-dialkylbenzodithiophene-4,5-dione dioxime, 2,7-dialkyl-4,5-dihydrobenzodithiophene-2,5-diamine, adding dropwise SOCl2 into a mixture of the 2,7-dialkyl-4,5-dihydrobenzodithiophene-2,5-diamine, triethylamine and CH2Cl2, and reacting at room temperature to obtain the 5,8-dialkylbisthiophene benzothiadiazole. The derivatives have good plane regularity, heat stability and good environment adaptability. The derivatives are liable to be processed to membrane, and can be used as intermediates in synthesis for organic solar energy battery materials.

Description

A kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative and synthetic method thereof
Technical field
The present invention relates to the heterogeneous ring compound of carbon containing, hydrogen, nitrogen, sulphur, specifically belong to a kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative and synthetic method thereof.
Background technology
Since entering 21 century, along with the scarcity day by day of petroleum resources, new resource is badly in need of being developed.The resources such as tidal energy, wind energy, water energy, sun power, nuclear energy, low calorie are the energy of applying at present extensivelyr, and wherein sun power becomes the wherein the most promising energy with its cleanliness without any pollution, steady sources, the advantage such as inexhaustible.
Solar cell is an importance of Application of Solar Energy.Silicon solar cell is the solar cell the most widely of applying at present, but itself have make trouble, high in cost of production shortcoming, based on this, the organic solar batteries with easy manufacture, low cost and other advantages becomes one of comparatively popular solar cell in the world today.
Organic solar batteries based on diazosulfide is the more of research at present.Diazosulfide group has certain rigid planar structure and good carrier transmission characteristics, simultaneously can form donor-receiver (D-A) conjugated structure with electron-donating group, thereby obtain compared with low band gap, widen with the spectral absorption of strongthener and be widely used in building high efficiency organic solar battery material.
Summary of the invention
Object of the present invention is intended to synthetic a kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative.In No. 2 positions of thienyl group, introduce alkyl or alkoxyl group is conducive to improve its solvability in organic solvent, this analog derivative has comparatively regular two dimensional structure, Heat stability is good, and preparation method is comparatively simple.
For solving the problems of the technologies described above, the present invention takes following technical scheme:
A kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative, is 5,8-dialkyl group, two thieno-s [2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles, its structural formula is:
Figure BDA0000383606790000011
In formula, R represents hydrogen atom, replacement or unsubstituted C 1-20alkyl.
A kind of 2,1, the synthetic method of 3-diazosulfide 1,4-Dithiapentalene derivative, specifically comprises the following steps:
(1) 5,5'-dialkyl group-3, the preparation of 3'-bis-bithiophenes: get 3 bromo thiophene, add ether, be cooled to after-78 ℃, drip n-Butyl Lithium, keep the condition 0.25～0.5h of-78 ℃, then be warming up to-55 ℃, add after cupric chloride,-55 ℃ keep 1～2h, then normal temperature spends the night, and reaction solution is carried out, after purification processes, obtaining 5,5'-dialkyl group-3,3'-bis-bithiophenes;
(2) 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4, the preparation of 5-diketone: 1,2-methylene dichloride and oxalyl chloride are joined to 5,5'-dialkyl group-3, in 3'-bis-bithiophenes, be heated to 40～45 ℃, reflux 4～6 days, add again oxalyl chloride, reflux 4～6 days, reaction solution is down to room temperature, carry out after purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone;
(3) 2,7-dialkyl group benzo [1,2-b:4,3-b'], two thiophene-4, the preparation of 5-dione dioxime: by 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone and sodium carbonate join in the mixing solutions of pyridine and ethanol, are heated to 80～90 ℃, drip the ethanolic soln of azanol, reflux 4～6h, is down to room temperature by reaction solution again, carry out after purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime;
(4) 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2, the preparation of 5-diamines: tindichloride is dissolved in concentrated hydrochloric acid, joins 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4, in the ethanolic soln of 5-dione dioxime, after 10～15min, be heated to 80～85 ℃, the 3～5h that refluxes, is down to room temperature by reaction solution, carries out after purification processes, obtain 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2,5-diamines;
(5) 5,8-dialkyl group, two thieno-s [2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1; 2,5] preparation of thiadiazoles: thionyl chloride is added drop-wise to 2,7-dialkyl group-4,5-dihydrobenzo [1; 2-b:4,3-b'] two thiophene-2, in the mixture of 5-diamines, triethylamine and methylene dichloride; under normal temperature, react 1～2h, reheat to 40～45 ℃, 5～6h refluxes; add water stopped reaction, reaction solution is carried out after purification processes, obtain purer 5; 8-dialkyl group two thieno-s [2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles.
In such scheme, the described 3 bromo thiophene of step (1): cupric chloride: the mole ratio of n-Butyl Lithium is 1:1:1～1:1.05:1.1.
In such scheme, step (2) is described 5,5'-dialkyl group-3,3'-bis-bithiophenes: the mole ratio of oxalyl chloride is 1:2.5～1:3; Described oxalyl chloride adds at twice, for the first time with add for the second time identical in quality.
In such scheme, the volume ratio of the described pyridine of step (3) and ethanol is 1:4, described 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone: azanol: the mole ratio of sodium carbonate is 1:1:1～1:1.2:1.5.
In such scheme, the described tindichloride of step (4): 2,7-dialkyl group benzo [1,2-b:4,3-b'], two thiophene-4, the mole ratio of 5-dione dioxime is 8:1～12:1.
In such scheme, the described thionyl chloride of step (5): 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2,5-diamines: the mole ratio of triethylamine is 3:1:3.
In such scheme, the purification processes of the described reaction solution of step (5) is: reaction solution is stirred to 0.5～1h, and standing rear separatory, oil reservoir saturated common salt water washing, and use anhydrous MgSO 4dry, then use column chromatography, after being dried, obtain final product.
In the present invention, described 2,1, the synthetic route of 3-diazosulfide 1,4-Dithiapentalene derivative is as follows:
Figure BDA0000383606790000031
Beneficial effect of the present invention: the present invention synthesize 2,1,3-diazosulfide 1,4-Dithiapentalene derivative has comparatively regular two dimensional structure, Heat stability is good, to good environmental adaptability, is easy to process film forming and optimization; Preparation method of the present invention is simple, synthetic 2,1, and 3-diazosulfide 1,4-Dithiapentalene derivative can be used as the synthetic intermediate of a class organic solar battery material, has wide application prospect.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 3,3'-, bis-bithiophenes.
Fig. 2 is benzo [1,2-b:4,3-b'] two thiophene-2, the hydrogen nuclear magnetic resonance spectrogram of 5-diketone.
Fig. 3 is benzo [1,2-b:4,3-b'] two thiophene-4, the hydrogen nuclear magnetic resonance spectrogram of 5-dione dioxime.
Fig. 4 is 4,5-dihydrobenzo [1,2-b:4,3-b'], two thiophene-2, the hydrogen nuclear magnetic resonance spectrogram of 5-diamines.
Fig. 5 is two thieno-s [2', 3':3,4; 3'', 2'':5,6] the hydrogen nuclear magnetic resonance spectrogram of benzo [1,2-c] [1,2,5] thiadiazoles.
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2, the 5] thiadiazoles of 5,8-.
Fig. 7 is the carbon-13 nmr spectra figure of two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2, the 5] thiadiazoles of 5,8-.
Fig. 8 is two (4-octyl group thiophene-2-yl) thieno-[2', 3':3,4, the 3' of 5,8-, 2':5,6] benzo [1,2-c] [1,2,5] the nucleus magnetic hydrogen spectrum figure of the conjugated polymers of two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene of thiadiazoles and 4,8-.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to example below.
Embodiment 1
A kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative, its synthetic comprising the steps:
Synthesizing of (1) 3,3'-, bis-bithiophenes (compound 2):
In the single port bottle of 200ml, add 10g (61.35mmol) three bromothiophenes, nitrogen replacement three times, add again the ether 80ml through drying treatment, be cooled to-78 ℃, slowly drip the n-Buli(n-Butyl Lithium of 2.4mol/L) 26.25ml (63mmol),-78 ℃ keep 15min, after rise to-55 ℃, add 8.336g CuCl 2keep this temperature 1h, normal temperature spends the night, then adds a large amount of shrends reaction of going out; Reaction solution dichloromethane extraction, uses anhydrous MgSO afterwards 4dry, column chromatography for separation (sherwood oil) obtains white solid 3.76g, productive rate 73.9%.Described white solid is carried out to hydrogen nuclear magnetic resonance spectrum analysis, 1h NMR (600MHz, CDCl3): δ 7.38 (s, dd, J=1.46Hz, J=2.79Hz, 2H), 7.35 (dd, J=2.90Hz, J=5.05Hz, 2H), 7.34 (dd, J=1.49Hz, J=5.03Hz, 2H), hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 1, from scheming, white solid is 3,3'-, bis-bithiophenes.
(2) benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone (compound 3) synthetic:
In the two-mouth bottle of 100ml, add 0.83g (5mmol) step (compound 2 that (1) is synthetic, then add 50ml1,2-ethylene dichloride and 0.365g oxalyl chloride (6.54mmol), be heated to after 42 ℃, refluxes 5 days; Add again 0.365g oxalyl chloride (6.54mmol), continue to reflux 5 days; Be cooled to ambient temperature overnight, filter, with a large amount of washings, finally use 100ml washing with alcohol, obtain red solid 0.366g, productive rate 30.6%.Described red solid is carried out to hydrogen nuclear magnetic resonance spectrum analysis, 1hNMR (600MHz, CDCl 3): δ ppm7.82 (d, J=4.97Hz, 2H), 7.29 (d, J=4.97Hz, 2H), hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 2, from scheming, this solid is benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone.
(3) benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime (compound 4) synthetic:
In the single port bottle of 100ml, add the synthetic compound 3 of 660mg (3mmol) step (2), 477mg (4.5mmol) Na 2cO 3, 10ml pyridine and 40ml ethanol, be heated to 80 ℃ of backflows, then by NH 2backflow 5h after OHHCl (730mg, 3.5mmol) is dissolved in and is added drop-wise in reaction flask in ethanol; Reacted rear cool to room temperature, underpressure distillation is stirred 3h except adding 60ml water after desolventizing and being heated to 80 ℃, filtration with a large amount of water washings after completing, and vacuum-drying obtains red powder 576mg, productive rate 76.7%.Red powder is carried out to hydrogen nuclear magnetic resonance spectrum analysis, 1h NMR (600MHz, d-DMSO): δ 12.89 (s, 2H), 7.82 (d, J=6.0Hz, 2H), 7.62 (d, J=6.0Hz, 2H), hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 3, from scheming, this solid is benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime.
(4) 4,5-dihydrobenzos [1,2-b:4,3-b'] two thiophene-2,5-diamines (compound 5) synthetic:
By SnCl 22H 2o (5.226g, 23mmol) be dissolved in 10ml concentrated hydrochloric acid, in 0 ℃, be added drop-wise to the synthetic compound 4 (0.576g of step (3) are housed, 2.3mmol) and in the 100ml reaction flask of 40ml ethanol, 10min post-heating to 81 ℃ back flow reaction 3h, be cooled to again 0 ℃ of filtration, with a large amount of saturated NaHCO 3solution rinses, dry beige powder 0.224g, the productive rate 44.3% of obtaining.Beige powder is carried out to hydrogen nuclear magnetic resonance spectrum analysis, 1h NMR (600MHz, CDCl 3): δ 7.62 (d, J=5.4Hz, 2H), 7.33 (d, J=5.4Hz, 2H), 3.65 (s, 2H), hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 4, from scheming, this solid is 4,5-dihydrobenzo [1,2-b:4,3-b'], two thiophene-2,5-diamines.
(5) two thieno-[2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles synthetic:
At 0 ℃, by SOCl 2(0.357g, 3mmol) is slowly added drop-wise to and contains (4) synthetic compound 5 (0.22g, 1mmol) in steps, triethylamine (0.304g, 3mmol) and 10ml CH 2cl 225ml reaction flask in, reheat to 42 ℃ backflow 5h after reacting at normal temperatures 1h; Add the 10ml shrend reaction of going out, stir half an hour, separatory, oil reservoir washs and uses anhydrous MgSO with saturated brine 4dry, then use column chromatography (CH 2cl 2/ sherwood oil=1:3) obtain yellow solid 99.1mg, productive rate 45.4%.Yellow solid is carried out to hydrogen nuclear magnetic resonance spectrum analysis, 1h NMR (600MHz, CDCl 3): δ 7.74 (d, J=5.42H), 7.71 (d, J=5.4Hz, 2H), hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 5, from scheming, this solid is two thieno-s [2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles.
Two thieno-s [2', 3':3,4 that utilize the present embodiment to prepare; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles further prepares two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2, the 5] thiadiazoles of 5,8-, and concrete synthesis step is as follows:
Synthesizing of (1) 5,8-dibromo, two thieno-s [2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2,5] thiadiazoles: at 0 ℃, by Br 2(322mg, 2mmol) is dissolved in 10ml CHCl 3, be slowly added drop-wise to and contain two thieno-s [2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2,5] thiadiazoles (124mg, 0.5mmol), 10ml CHCl 3with 10ml CH 3in the 100ml reaction flask of COOH.Be heated to 65 ℃, back flow reaction 12h, then cool to room temperature drip Na in reaction solution 2s 2o 3after the aqueous solution, separatory, the saturated NaHCO of organic phase 3washing, then use anhydrous MgSO 4dry, filtration, vacuum-drying, obtains yellow solid 164.4mg with dimethyl formamide (DMF) recrystallization, and productive rate is 81.1%, and this solid is 5,8-dibromo, two thieno-s [2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2,5] thiadiazoles;
(2) 5, two (the 4-octyl group thiophene-2-yl) thieno-[2' of 8-, 3':3, 4, 3', 2':5, 6] benzo [1, 2-c] [1, 2, 5] thiadiazoles is synthetic: get above-mentioned synthetic 5, 8-dibromo two thieno-[2', 3':3, 4, 3', 2':5, 6] benzo [1, 2-c] [1, 2, 5] thiadiazoles (245mg, 0.603mmol), tributyl (4-ethylhexyl thiophene-2-yl) tin (765mg, 1.575mmol) be added in 100mL reaction flask with 40mL DMF, inflated with nitrogen 30min is in order to remove air, add again four (triphenyl phosphorus) palladium (35mg, 0.03mmol), be heated to 160 ℃, backflow 48h, cool to room temperature, reaction solution underpressure distillation is removed to desolventizing, add again 50ml ethyl acetate also with a large amount of water washings, then use anhydrous MgSO 4dry, column chromatography for separation (CH 2cl 2/ sherwood oil=1:10) obtain yellow solid 308mg, productive rate 80.2%, this solid is two (4-octyl group thiophene-2-yl) thieno-[2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2, the 5] thiadiazoles of 5,8-,
Synthesizing of two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2, the 5] thiadiazoles of (3) 5,8-:
At room temperature, NBS (55mg, 0.308mmol) is slowly added in the 100ml reaction flask containing (2) in steps synthetic compound 3 (89mg, 0.14mmol) and 30mL tetrahydrofuran (THF) (THF), stirring 12h, adds saturated NaHCO 3the aqueous solution, with dichloromethane extraction, then uses anhydrous MgSO 4dry, column chromatography for separation (CH 2cl 2/ sherwood oil=1:10) obtain yellow solid 79mg, productive rate is 71.0%.Described yellow solid is carried out to hydrogen nuclear magnetic resonance spectrum analysis, 1h NMR (600MHz, CDCl 3): δ 7.50 (s, 2H), 7.02 (s, 2H), 2.52 (d, J=0.6Hz, 4H) .1.65-1.68 (m, 2H), 1.30-1.40 (m, 8H), 0.91-0.94 (m, 6H), carbon-13 nmr spectra analysis, 13cNMR (150MHz, CDCl 3): δ 149.2,142.7, and 140.4,136.4,135.7,126.7,126.3,118.4,110.5,40.0,33.9,32.5,28.8,25.7,23.1,14.2,10.9.Hydrogen nuclear magnetic resonance spectrogram is shown in that Fig. 6, carbon-13 nmr spectra figure are shown in Fig. 7, and from Fig. 6, Fig. 7, this solid is two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2, the 5] thiadiazoles of 5,8-.
Utilize above-mentioned synthetic 5, two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', the 3':3 of 8-, 4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles and 2, two (tin trimethyl)-4 of 6-, two (2-ethyl hexyl oxy) benzo [1, the 2-b:4 of 8-, 5-b'] the synthetic following conjugated polymers of two thiophene, concrete building-up process is as follows:
Synthesizing of two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene of (1) 4,8-:
Synthesizing with benzo [1,2-b:4,5-b'] two thiophene-4 of this material, 8-diketone is raw material, and route is as follows, can synthesize by reference literature (Y Liang, D Feng, Y Wu, ST Tsai, G Li, C Ray, L Yu.J.Am.Chem.Soc., 2009,131,7792.).
Figure BDA0000383606790000071
In formula, Et represents 2-ethylhexyl.
Two (tin trimethyl)-4 of (2) 2,6-, two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene of 8-synthetic:
In 50ml flask, add 4, two (2-ethyl hexyl oxy) benzos [1 of 8-, 2-b:4,5-b'] two thiophene (628mg, 1.4mmol) and 20ml THF solution cool to-78 ℃, slowly drip the THF solution of 3.5ml n-Butyl Lithium, wherein the molar weight of n-Butyl Lithium is 3.5mmol, after-78 ℃ of stirring reaction 0.5h, rise to normal-temperature reaction 0.5h, be cooled to again the hexane solution that adds fast 4.2ml trimethyltin chloride after-78 ℃, wherein the molar weight of trimethyltin chloride is 4.2mmol, rises to room temperature reaction 12h.After reaction finishes, add a large amount of water and use n-hexane extraction, extraction liquid anhydrous Na 2sO 4dry, except after desolventizing in Virahol recrystallization obtain colourless acicular crystal 867mg, productive rate is 80.2%.This clear crystal is two (tin trimethyl)-4 of 2,6-, two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene of 8-.
Synthesizing of the conjugated polymers of two (4-octyl group thiophene-2-yl) thieno-[2', 3':3,4,3', 2':5,6] benzos [1,2-c] [1,2, the 5] thiadiazoles of (3) 5,8-and two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene of 4,8-:
In 25ml reaction flask, add two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', the 3':3 of 5,8-, 4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles (278mg, 0.35mmol), 2, two (tin trimethyl)-4 of 6-, two (2-ethyl hexyl oxy) benzo [1, the 2-b:4 of 8-, 5-b'] two thiophene (270mg, 0.35mmol) and the exquisite dry toluene 8ml of process.Under liquid nitrogen freezing, vacuumize logical nitrogen circulation three times; return to room temperature, under nitrogen protection, add fast catalyzer four (triphenyl phosphorus) palladium (12mg, 0.01mmol); the molar weight of described catalyzer is two (the bromo-4-octyl group thiophene-2-of 5-yl) thieno-[2', the 3':3 of 5,8-; 4,3', 2':5; 6] benzo [1; 2-c] [1,2,5] thiadiazoles molar weight 3%.The lower 110 ℃ of reactions of lucifuge condition 48 hours, be cooled to room temperature, add 50mL methyl alcohol and stir 2 hours, by filtering and be dried the solid obtaining, pass through column chromatography (80-100 object silica gel, use chloroform give eluent) purifying, revolve and steam most of chloroform, more dropwise drip in methyl alcohol, standing, filter, vacuum-drying, obtains red solid 281mg, productive rate 74.4%.Described red solid is carried out to hydrogen nuclear magnetic resonance spectrum analysis, 1hNMR (600MHz, CDCl 3): δ 7.28 (br, 4H), 7.10 (br, 2H), 4.13 (br, 2H), 2.83 (br, 4H), 2.5-0.7 (br, 60H).Hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 8, and as can be seen from Figure 8, this solid is 5, two (4-octyl group thiophene-2-yl) thieno-[2', 3':3,4 of 8-, 3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles and 4, the conjugated polymers of two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene of 8-, the number-average molecular weight of this conjugated polymers is 34230, molecular weight distribution (M w/ M n) be that 1.63, n is 32.
Utilize above-mentioned prepare 5, two (4-octyl group thiophene-2-yl) thieno-[2', the 3':3 of 8-, 4,3', 2':5,6] benzo [1,2-c] [1,2,5] two (2-ethyl hexyl oxy) benzos [1 of thiadiazoles and 4,8-, 2-b:4,5-b'] to have prepared structure be ITO/PEDOT:PSS/copolymers:PC for the conjugated polymers of two thiophene 61the device of BM/Al, works as PC 61during BM/copolymers=1/1 (w/w), every important parameter of device is followed successively by: short-circuit current J sc=4.01mA/cm 2, packing factor FF=0.45, open circuit voltage V oc=0.80V, conversion of solar energy PCE=1.45%.Above-mentioned data show, such 2,1,3-diazosulfide 1,4-Dithiapentalene bromo derivative is the organic solar battery material that a class is potential very much.
Obviously, above-described embodiment is to be only the example that clearly explanation is done, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.And the apparent variation of therefore amplifying or change are still within the protection domain in the invention.

Claims (8)

1. one kind 2,1,3-diazosulfide 1,4-Dithiapentalene derivative, is characterized in that described derivative is 5,8-dialkyl group, two thieno-s [2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles, its structural formula is:
Figure FDA0000383606780000011
In formula, R represents hydrogen atom, replacement or unsubstituted C 1-20alkyl.
2. the synthetic method of derivative described in claim 1, is characterized in that comprising the steps:
(1) 5,5'-dialkyl group-3, the preparation of 3'-bis-bithiophenes: get 3 bromo thiophene, add ether, be cooled to-78 ℃, after dropping n-Butyl Lithium is complete,-78 ℃ keep 0.25～0.5h, then are warming up to-55 ℃, add after cupric chloride,-55 ℃ keep 1～2h, normal temperature spends the night, and reaction solution is carried out, after purification processes, obtaining 5,5'-dialkyl group-3,3'-bis-bithiophenes;
(2) 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4, the preparation of 5-diketone: 1,2-methylene dichloride and oxalyl chloride are joined to 5,5'-dialkyl group-3, in 3'-bis-bithiophenes, be heated to 40～45 ℃, reflux 4～6 days, add again oxalyl chloride, continue to reflux 4～6 days, reaction solution is down to room temperature, carry out after purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone;
(3) 2,7-dialkyl group benzo [1,2-b:4,3-b'], two thiophene-4, the preparation of 5-dione dioxime: by 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone and sodium carbonate join in the mixing solutions of pyridine and ethanol, are heated to 80～90 ℃, drip the ethanolic soln of azanol, reflux 4～6h, is down to room temperature by reaction solution again, carry out after purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime;
(4) 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2, the preparation of 5-diamines: tindichloride is dissolved in concentrated hydrochloric acid, joins 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4, in the ethanolic soln of 5-dione dioxime, 10～15min post-heating to 80～85 ℃, backflow 3～5h, is down to room temperature by reaction solution, carries out after purification processes, obtain 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2,5-diamines;
(5) 5,8-dialkyl group, two thieno-s [2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1; 2,5] preparation of thiadiazoles: thionyl chloride is added drop-wise to 2,7-dialkyl group-4,5-dihydrobenzo [1; 2-b:4,3-b'] two thiophene-2, in the mixture of 5-diamines, triethylamine and methylene dichloride; under normal temperature, react 1～2h, reheat to 40～50 ℃, 5～6h refluxes; add water stopped reaction, reaction solution is carried out, after purification processes, obtaining 5; 8-dialkyl group two thieno-s [2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles.
3. method according to claim 2, is characterized in that the described 3 bromo thiophene of step (1): n-Butyl Lithium: the mole ratio of cupric chloride is 1:1:1～1:1.05:1.1.
4. method according to claim 2, is characterized in that step (2) is described 5,5'-dialkyl group-3,3'-bis-bithiophenes: the mole ratio of oxalyl chloride is 1:2.5～1:3; Described oxalyl chloride adds at twice, for the first time with add for the second time identical in quality.
5. method according to claim 2, the volume ratio that it is characterized in that the described pyridine of step (3) and ethanol is 1:4, described 2,7-dialkyl group benzo [1,2-b:4,3-b']-bis-thiophene-4,5-diketone: azanol: the mole ratio of sodium carbonate is 1:1:1～1:1.2:1.5.
6. method according to claim 2, is characterized in that the described tindichloride of step (4): 2,7-dialkyl group benzo [1,2-b:4,3-b'], two thiophene-4, the mole ratio of 5-dione dioxime is 8:1～12:1.
7. method according to claim 2, is characterized in that the described thionyl chloride of step (5): 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2,5-diamines: the mole ratio of triethylamine is 3:1:3.
8. method according to claim 2, is characterized in that the purification processes of the described reaction solution of step (5) is: reaction solution is stirred to 0.5～1h, and standing rear separatory, oil reservoir saturated common salt water washing, and use anhydrous MgSO 4dry, then use column chromatography, after being dried, obtain product.
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CN113105477A (en) * 2020-01-13 2021-07-13 北京大学深圳研究生院 Sulfur atom fused ring electron acceptor material and preparation method and application thereof
CN113105477B (en) * 2020-01-13 2022-07-12 北京大学深圳研究生院 Sulfur atom fused ring electron acceptor material and preparation method and application thereof

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