CN103601741B - A kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative and synthetic method thereof - Google Patents

A kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative and synthetic method thereof Download PDF

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CN103601741B
CN103601741B CN201310425254.3A CN201310425254A CN103601741B CN 103601741 B CN103601741 B CN 103601741B CN 201310425254 A CN201310425254 A CN 201310425254A CN 103601741 B CN103601741 B CN 103601741B
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dialkyl group
thiophene
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thieno
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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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Wuhan Institute of Technology
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Abstract

The invention provides a kind of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative, this derivative is 5,8-dialkyl group two thieno-diazosulfide, and its preparation method is: prepare 5 successively, 5 ˊ-dialkyl group-3,3 ˊ-two bithiophene, 2,7-dialkyl benzene 1,4-Dithiapentalenes-4,5-diketone, 2,7-dialkyl benzene 1,4-Dithiapentalene-4,5-dione dioximes, 2,7-dialkyl group-4,5-dihydrobenzene 1,4-Dithiapentalene-2,5-diamines, then by SOCl 2dropwise join 2,7-dialkyl group-4,5-dihydrobenzene 1,4-Dithiapentalene-2,5-diamines, triethylamine and CH 2cl 2mixture in, under normal temperature reaction prepare 5,8-dialkyl group two thieno-diazosulfide.This analog derivative has good plane regularity, thermostability, to good environmental adaptability, is easy to process film forming, can be used as the intermediate of organic solar battery material synthesis.

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 applying wider at present, 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 application at present, but itself have make trouble, high in cost of production shortcoming, based on this, there is easy manufacture, the organic solar batteries of 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, thus obtain lower band gap, widen and 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 a kind of 2,1,3-diazosulfide of synthesis 1,4-Dithiapentalene derivative.Introduce alkyl or alkoxyl group in No. 2 positions of thienyl group and be conducive to improving 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-[2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles, its structural formula is:
In formula, R represents hydrogen atom, substituted or unsubstituted C 1-20alkyl.
A kind of synthetic method of 2,1,3-diazosulfide 1,4-Dithiapentalene derivative, specifically comprises the following steps:
The preparation of (1) 5,5'-dialkyl group-3,3'-bis-bithiophene: get 3 bromo thiophene, add ether, after being cooled to-78 DEG C, drip n-Butyl Lithium, keep the condition 0.25 ~ 0.5h of-78 DEG C, then be warming up to-55 DEG C, after adding cupric chloride,-55 DEG C keep 1 ~ 2h, then ambient temperature overnight, after carrying out purification processes, obtains 5 to reaction solution, 5'-dialkyl group-3,3'-bis-bithiophene;
(2) 2,7-dialkyl group benzo [1,2-b:4,3-b']-two thiophene-4, the preparation of 5-diketone: 1,2-methylene dichloride and oxalyl chloride are joined 5,5'-dialkyl group-3, in 3'-bis-bithiophene, be heated to 40 ~ 45 DEG C, reflux 4 ~ 6 days, add oxalyl chloride again, reflux 4 ~ 6 days, reaction solution is down to room temperature, after carrying out purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b']-two 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']-two thiophene-4,5-diketone and sodium carbonate joins in the mixing solutions of pyridine and ethanol, is heated to 80 ~ 90 DEG C, drip the ethanolic soln of azanol again, reflux 4 ~ 6h, is down to room temperature by reaction solution, after carrying out purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioximes;
(4) 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] preparation of two thiophene-2,5-diamines: tindichloride is dissolved in concentrated hydrochloric acid, joins 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioximes ethanolic soln in, after 10 ~ 15min, be heated to 80 ~ 85 DEG C, backflow 3 ~ 5h, is down to room temperature by reaction solution, after carrying out 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-[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-2,5-diamines, triethylamine and methylene dichloride mixture in; react 1 ~ 2h under normal temperature, reheat to 40 ~ 45 DEG C, backflow 5 ~ 6h; add water stopped reaction, after carrying out purification processes, obtains purer 5 to reaction solution; 8-dialkyl group two thieno-[2', 3':3,4; 3'', 2'':5,6] benzo [1,2-c] [1,2,5] thiadiazoles.
In such scheme, step (1) described 3 bromo thiophene: cupric chloride: the mole ratio of n-Butyl Lithium is 1:1:1 ~ 1:1.05:1.1.
In such scheme, described 5,5'-dialkyl group-3,3'-bis-bithiophenes of step (2): the mole ratio of oxalyl chloride is 1:2.5 ~ 1:3; Described oxalyl chloride adds at twice, and it is identical in quality that first time and second time add.
In such scheme, the volume ratio of step (3) described pyridine and ethanol is 1:4, described 2,7-dialkyl group benzo [1,2-b:4,3-b']-two thiophene-4,5-diketone: azanol: the mole ratio of sodium carbonate is 1:1:1 ~ 1:1.2:1.5.
In such scheme, step (4) described tindichloride: the mole ratio of 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime is 8:1 ~ 12:1.
In such scheme, step (5) described thionyl chloride: 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 step (5) described reaction solution is: reaction solution is stirred 0.5 ~ 1h, separatory after leaving standstill, oil reservoir saturated common salt water washing, and uses anhydrous MgSO 4drying, then use column chromatography, namely obtain final product after drying.
In the present invention, the synthetic route of described 2,1,3-diazosulfide 1,4-Dithiapentalene derivatives is as follows:
Beneficial effect of the present invention: 2,1,3-diazosulfide 1,4-Dithiapentalene derivatives of the present invention's synthesis have comparatively regular two dimensional structure, Heat stability is good, to good environmental adaptability, is easy to processing film forming and optimization; Preparation method of the present invention is simple, and 2,1,3-diazosulfide 1,4-Dithiapentalene derivatives of synthesis can be used as the intermediate of a class organic solar battery material synthesis, have wide application prospect.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 3,3'-bis-bithiophene.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of benzo [1,2-b:4,3-b'] two thiophene-2,5-diketone.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of 4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2,5-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 thiophene of 5--2-base) thieno-[2', 3':3,4,3', 2':5,6] benzo [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 thiophene of 5--2-base) thieno-[2', 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2, the 5] thiadiazoles of 5,8-.
Fig. 8 is two (4-octyl thiophene-2-base) thieno-[2', the 3':3 of 5,8-, 4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles and two (2-ethyl hexyl oxy) benzo [1 of 4,8-, 2-b:4,5-b'] the nucleus magnetic hydrogen spectrum figure of conjugated polymers of two thiophene.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, 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 synthesis comprises the steps:
The synthesis of (1) 3,3'-bis-bithiophene (compound 2):
10g (61.35mmol) three bromothiophene is added in the single port bottle of 200ml, nitrogen replacement three times, add the ether 80ml through drying treatment again, be cooled to-78 DEG C, slowly drip the n-Buli(n-Butyl Lithium of 2.4mol/L) 26.25ml (63mmol),-78 DEG C keep 15min, after rise to-55 DEG C, add 8.336gCuCl 2keep this temperature 1h, ambient temperature overnight, then add a large amount of shrends and to go out reaction; Reaction solution dichloromethane extraction, uses anhydrous MgSO afterwards 4drying, column chromatography for separation (sherwood oil) obtains white solid 3.76g, productive rate 73.9%.Hydrogen nuclear magnetic resonance spectrum analysis is carried out to described white solid, 1hNMR (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 figure, white solid is 3,3'-bis-bithiophene.
(2) synthesis of benzo [1,2-b:4,3-b']-two thiophene-4,5-diketone (compound 3):
In the two-mouth bottle of 100ml, adding 0.83g (5mmol) step, (compound 2 that (1) synthesizes, then add 50ml1,2-ethylene dichloride and 0.365g oxalyl chloride (6.54mmol), after being heated to 42 DEG C, refluxes 5 days; Add 0.365g oxalyl chloride (6.54mmol) again, continue backflow 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%.Hydrogen nuclear magnetic resonance spectrum analysis is carried out to described red solid, 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, and from figure, this solid is benzo [1,2-b:4,3-b']-two thiophene-4,5-diketone.
(3) synthesis of benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime (compound 4):
Compound 3,477mg (4.5mmol) Na that 660mg (3mmol) step (2) is synthesized is added in the single port bottle of 100ml 2cO 3, 10ml pyridine and 40ml ethanol, be heated to 80 DEG C of backflows, then by NH 2oHHCl (730mg, 3.5mmol) is dissolved in ethanol and is added drop-wise to the 5h that to reflux after in reaction flask; Reacted rear cool to room temperature, underpressure distillation stirs 3h except adding 60ml water after desolventizing and being heated to 80 DEG C, filtration after completing with a large amount of water washings, vacuum-drying obtains red powder 576mg, productive rate 76.7%.Hydrogen nuclear magnetic resonance spectrum analysis is carried out to red powder, 1hNMR (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 figure, this solid is benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioximes.
The synthesis of (4) 4,5-dihydrobenzo [1,2-b:4,3-b'] two thiophene-2,5-diamines (compound 5):
By SnCl 22H 2o (5.226g, 23mmol) be dissolved in 10ml concentrated hydrochloric acid, compound 4 (0.576g step (3) being housed and synthesizing is added drop-wise in 0 DEG C, 2.3mmol) with in the 100ml reaction flask of 40ml ethanol, 10min post-heating to 81 DEG C back flow reaction 3h, be cooled to 0 DEG C of filtration again, with a large amount of saturated NaHCO 3solution rinses, and drying obtains Beige powder 0.224g, productive rate 44.3%.Hydrogen nuclear magnetic resonance spectrum analysis is carried out to Beige powder, 1hNMR (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 figure, 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] synthesis of benzo [1,2-c] [1,2,5] thiadiazoles:
At 0 DEG C, by SOCl 2(0.357g, 3mmol) is slowly added drop-wise to the compound 5 (0.22g, 1mmol) containing (4) in steps and synthesize, triethylamine (0.304g, 3mmol) and 10mlCH 2cl 225ml reaction flask in, react after 1h at normal temperatures and reheat to 42 DEG C, backflow 5h; Add 10ml shrend to go out reaction, stir half an hour, separatory, the washing of oil reservoir saturated brine also uses anhydrous MgSO 4drying, then use column chromatography (CH 2cl 2/ sherwood oil=1:3) obtain yellow solid 99.1mg, productive rate 45.4%.Hydrogen nuclear magnetic resonance spectrum analysis is carried out to yellow solid, 1hNMR (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, and from figure, 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 prepares 5 further, two (the bromo-4-octyl thiophene of 5--2-base) thieno-[2', 3':3,4,3', the 2':5 of 8-, 6] benzo [1,2-c] [1,2,5] thiadiazoles, concrete synthesis step is as follows:
The synthesis of (1) 5,8-dibromo two thieno-[2', 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles: at 0 DEG C, by Br 2(322mg, 2mmol) is dissolved in 10mlCHCl 3, be slowly added drop-wise to containing two thieno-s [2', 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles (124mg, 0.5mmol), 10mlCHCl 3and 10mlCH 3in the 100ml reaction flask of COOH.Be heated to 65 DEG C, back flow reaction 12h, then cool to room temperature, in reaction solution, drip Na 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-[2', 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles;
(2) 5, two (4-octyl thiophene-2-base) thieno-[2' of 8-, 3':3, 4, 3', 2':5, 6] benzo [1, 2-c] [1, 2, 5] synthesis of thiadiazoles: get 5 of above-mentioned synthesis, 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-base) tin (765mg, 1.575mmol) be added in 100mL reaction flask with 40mLDMF, inflated with nitrogen 30min is in order to remove air, add four (triphenyl phosphorus) palladium (35mg again, 0.03mmol), be heated to 160 DEG C, backflow 48h, cool to room temperature, by reaction solution underpressure distillation except desolventizing, add 50ml ethyl acetate again and with a large amount of water washings, then anhydrous MgSO is used 4drying, 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 thiophene-2-base) thieno-[2', 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2, the 5] thiadiazoles of 5,8-,
The synthesis of two (the bromo-4-octyl thiophene of 5--2-base) thieno-[2', 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2, the 5] thiadiazoles of (3) 5,8-:
At room temperature, NBS (55mg, 0.308mmol) is slowly added to and contains in the 100ml reaction flask of compound 3 (89mg, 0.14mmol) and the 30mL tetrahydrofuran (THF) (THF) (2) in steps synthesized, stir 12h, add saturated NaHCO 3the aqueous solution, with dichloromethane extraction, then uses anhydrous MgSO 4drying, column chromatography for separation (CH 2cl 2/ sherwood oil=1:10) obtain yellow solid 79mg, productive rate is 71.0%.Hydrogen nuclear magnetic resonance spectrum analysis is carried out to described yellow solid, 1hNMR (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 149.2,142.7,140.4,136.4,135.7,126.7,126.3,118.4,110.5,40.0,33.9,32.5,28.8,25.7,23.1,14.2,10.9.Hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 6, carbon-13 nmr spectra figure is shown in Fig. 7, and from Fig. 6, Fig. 7, this solid is two (the bromo-4-octyl thiophene of the 5--2-base) thieno-[2' of 5,8-, 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles.
Utilize 5,8-of above-mentioned synthesis two (the bromo-4-octyl thiophene of 5--2-base) thieno-[2', 3':3,4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles and 2, two (2-ethyl hexyl oxy) benzo [1, the 2-b:4 of 6-two (tin trimethyl)-4,8-, 5-b'] the following conjugated polymers of two thiophene synthesis, concrete building-up process is as follows:
The synthesis of (1) 4,8-two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene:
The synthesis of this material is with benzo [1,2-b:4,5-b'] two thiophene-4,8-diketone for raw material, and route is as follows, can refer to document (YLiang, DFeng, YWu, STTsai, GLi, CRay, LYu.J.Am.Chem.Soc., 2009,131,7792.) synthesis.
In formula, Et represents 2-ethylhexyl.
The synthesis of (2) 2,6-two (tin trimethyl)-4,8-two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene:
4 are added in 50ml flask, two (2-ethyl hexyl oxy) benzo [1 of 8-, 2-b:4,5-b'] two thiophene (628mg, 1.4mmol) and 20mlTHF solution cool to-78 DEG C, slowly drip the THF solution of 3.5ml n-Butyl Lithium, wherein the molar weight of n-Butyl Lithium is 3.5mmol, normal-temperature reaction 0.5h is risen to after-78 DEG C of stirring reaction 0.5h, be cooled to the hexane solution adding 4.2ml trimethyltin chloride after-78 DEG C fast again, wherein the molar weight of trimethyltin chloride is 4.2mmol, rises to room temperature reaction 12h.After reaction terminates, add a large amount of water and use n-hexane extraction, extraction liquid anhydrous Na 2sO 4drying, except after desolventizing in Virahol recrystallization obtain colourless acicular crystal 867mg, productive rate is 80.2%.This clear crystal is 2,6-two (tin trimethyl)-4,8-two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene.
Two (4-octyl thiophene-2-base) thieno-[2', 3':3,4, the 3' of (3) 5,8-, 2':5,6] benzo [1,2-c] [1,2,5] synthesis of the conjugated polymers of thiadiazoles and 4,8-two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene:
Two (the bromo-4-octyl thiophene of 5--2-base) thieno-[2', the 3':3 of 5,8-is added in 25ml reaction flask, 4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles (278mg, 0.35mmol), 2, two (2-ethyl hexyl oxy) benzo [1, the 2-b:4 of 6-two (tin trimethyl)-4,8-, 5-b'] two thiophene (270mg, 0.35mmol) and through exquisite dry toluene 8ml.Under liquid nitrogen freezing, vacuumize, logical nitrogen circulation three times; return to room temperature, add catalyzer four (triphenyl phosphorus) palladium (12mg, 0.01mmol) under nitrogen protection fast; the molar weight of described catalyzer is two (the bromo-4-octyl thiophene of 5--2-base) 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 DEG C of reactions of lucifuge condition 48 hours, be cooled to room temperature, add 50mL methyl alcohol and stir 2 hours, will filter and the dry solid obtained by column chromatography (80-100 object silica gel, use chloroform give eluent) purifying, revolve and steam most of chloroform, more dropwise drip in methyl alcohol, leave standstill, filter, vacuum-drying, obtains red solid 281mg, productive rate 74.4%.Hydrogen nuclear magnetic resonance spectrum analysis is carried out to described red solid, 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 thiophene-2-base) 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 8-two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b'] two thiophene, the number-average molecular weight of this conjugated polymers is 34230, molecular weight distribution (M w/ M n) be 1.63, n be 32.
Utilize above-mentioned 5,8-two (4-octyl thiophene-2-base) thieno-[2', 3':3 prepared, 4,3', 2':5,6] benzo [1,2-c] [1,2,5] thiadiazoles and two (2-ethyl hexyl oxy) benzo [1 of 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 61time 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 only for the example done clearly is described, and the restriction not 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 the need to also giving all embodiments.And therefore amplified apparent change or variation are still within the protection domain of the invention.

Claims (7)

1. a diazosulfide 1,4-Dithiapentalene derivative, is characterized in that described derivative is 5,8-dialkyl group two thieno-[2', 3':3,4; 3 ", 2 ": 5,6] benzo [1,2-c] [1,2,5] thiadiazoles, its structural formula is:
In formula, R represents hydrogen atom or unsubstituted C 1-20alkyl.
2. the synthetic method of derivative described in claim 1, is characterized in that comprising the steps:
The preparation of (1) 5,5'-dialkyl group-3,3'-bis-bithiophene: get 3 bromo thiophene, add ether, be cooled to-78 DEG C, after dropping n-Butyl Lithium is complete,-78 DEG C keep 0.25 ~ 0.5h, then are warming up to-55 DEG C, after adding cupric chloride,-55 DEG C keep 1 ~ 2h, ambient temperature overnight, after carrying out purification processes, obtains 5 to reaction solution, 5'-dialkyl group-3,3'-bis-bithiophene;
(2) 2,7-dialkyl group benzo [1,2-b:4,3-b']-two thiophene-4, the preparation of 5-diketone: 1,2-methylene dichloride and oxalyl chloride are joined 5,5'-dialkyl group-3, in 3'-bis-bithiophene, be heated to 40 ~ 45 DEG C, reflux 4 ~ 6 days, add oxalyl chloride again, continue backflow 4 ~ 6 days, reaction solution is down to room temperature, after carrying out purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b']-two thiophene-4,5-diketone; 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, and it is identical in quality that first time and second time add;
(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']-two thiophene-4,5-diketone and sodium carbonate joins in the mixing solutions of pyridine and ethanol, is heated to 80 ~ 90 DEG C, drip the ethanolic soln of azanol again, reflux 4 ~ 6h, is down to room temperature by reaction solution, after carrying out purification processes, obtain 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioximes;
(4) 2,7-dialkyl group-4,5-dihydrobenzo [1,2-b:4,3-b'] preparation of two thiophene-2,5-diamines: tindichloride is dissolved in concentrated hydrochloric acid, joins 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioximes ethanolic soln in, 10 ~ 15min post-heating to 80 ~ 85 DEG C, backflow 3 ~ 5h, is down to room temperature by reaction solution, after carrying out 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-[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-2,5-diamines, triethylamine and methylene dichloride mixture in, react 1 ~ 2h under normal temperature, reheat to 40 ~ 50 DEG C, backflow 5 ~ 6h, add water stopped reaction, after carrying out purification processes, obtains 5 to reaction solution, 8-dialkyl group two thieno-[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 step (1) described 3 bromo thiophene: 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 the volume ratio of step (3) described pyridine and ethanol is 1:4, described 2,7-dialkyl group benzo [1,2-b:4,3-b']-two thiophene-4,5-diketone: azanol: the mole ratio of sodium carbonate is 1:1:1 ~ 1:1.2:1.5.
5. method according to claim 2, is characterized in that step (4) described tindichloride: the mole ratio of 2,7-dialkyl group benzo [1,2-b:4,3-b'] two thiophene-4,5-dione dioxime is 8:1 ~ 12:1.
6. method according to claim 2, is characterized in that step (5) described thionyl chloride: 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.
7. method according to claim 2, is characterized in that the purification processes of step (5) described reaction solution is: reaction solution is stirred 0.5 ~ 1h, separatory after leaving standstill, oil reservoir saturated common salt water washing, and uses anhydrous MgSO 4drying, then use column chromatography, namely obtain product after drying.
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