CN103865041A - Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof - Google Patents
Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof Download PDFInfo
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- 0 CC(*)(*)c(cc1)cc2c1c([s]c1c3c(I)c(*)c4c1SC1c(ccc(-c5c(*)c(*)c(-c(cc6)cc(N(*)C7=O)c6C7=C(c(c(N6*)c7)ccc7-c7c(*)c(*)c(*(*)*)[s]7)C6=O)[s]5)c5)c5SC41)c3[s]2 Chemical compound CC(*)(*)c(cc1)cc2c1c([s]c1c3c(I)c(*)c4c1SC1c(ccc(-c5c(*)c(*)c(-c(cc6)cc(N(*)C7=O)c6C7=C(c(c(N6*)c7)ccc7-c7c(*)c(*)c(*(*)*)[s]7)C6=O)[s]5)c5)c5SC41)c3[s]2 0.000 description 7
- ILZOPGQLWNHYHF-UHFFFAOYSA-N CCCCC(CC)c(c1c2SC3C(CCC(Br)=C4)=C4SC13)c(C(CC)CCCC)c1c2[s]c2c1[s]c1cc([Br]=C)ccc21 Chemical compound CCCCC(CC)c(c1c2SC3C(CCC(Br)=C4)=C4SC13)c(C(CC)CCCC)c1c2[s]c2c1[s]c1cc([Br]=C)ccc21 ILZOPGQLWNHYHF-UHFFFAOYSA-N 0.000 description 1
- YZOXLMXSNGEQGQ-UHFFFAOYSA-N COc(c(C1Sc2c3)c(c4c5c([s]c6c7ccc(Br)c6)c7[s]4)SC1c2ccc3Br)c5OC Chemical compound COc(c(C1Sc2c3)c(c4c5c([s]c6c7ccc(Br)c6)c7[s]4)SC1c2ccc3Br)c5OC YZOXLMXSNGEQGQ-UHFFFAOYSA-N 0.000 description 1
- FLIQQFGIWZQNEI-UHFFFAOYSA-N COc(c1c(c([s]2)c3cc2[Sn](C)(C)C)[s]c([Sn](C)(C)C)c1)c3OC Chemical compound COc(c1c(c([s]2)c3cc2[Sn](C)(C)C)[s]c([Sn](C)(C)C)c1)c3OC FLIQQFGIWZQNEI-UHFFFAOYSA-N 0.000 description 1
- FPLAGKILHLGJOL-UHFFFAOYSA-N COc(c1c(c2c3cc[s]2)[s]cc1)c3OC Chemical compound COc(c1c(c2c3cc[s]2)[s]cc1)c3OC FPLAGKILHLGJOL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene, and the structural formula is shown in the specification. In the structural formula, n is an integer between 1 to 60, R1 and R2 are H, C1-C0 alkyl or C1-C10 alkyloxy, R3 is C1-C16 alkyl, and R4 and R5 are H or C1-C16 alkyl. The above copolymer has the characteristics of wide light absorption scope, high carrier mobility, good solubility and the like, and is applicable to fields of organic solar cells, organic electroluminescence, organic field effect transistor and the like. Additionally, the invention also provided a preparation method of the conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene.
Description
Technical field
The present invention relates to organic semiconductor material technical field, particularly relate to a kind of conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene and its preparation method and application.
Background technology
Organic solar batteries is owing to having some incomparable advantages of inorganic solar cell, as with low cost, the advantage such as manufacture craft is simple, product weight is light, can large area flexible prepare and get more and more people's extensive concerning as the potential renewable energy source of a kind of tool.
People are devoted to solve the problem that organic solar batteries photoelectric transformation efficiency is low always, although having had, the performance of organic solar batteries steadily improves, its effciency of energy transfer has approached 10%, but the photoelectric transformation efficiency of organic solar batteries is than inorganic solar cell or much lower.Therefore, want to realize the commercialization of organic solar batteries, the organic semiconductor material of development of new is significant for the efficiency that improves organic solar batteries.
Organic semiconductor material of a great variety, wherein, conjugated polymers class organic semiconductor material, because of the progress on design and device fabrication, makes the photoelectric transformation efficiency of polymer solar battery obtain larger raising.One of challenge that polymer solar battery will face future is exactly the conjugated polymer material of synthesizing new, and conjugated polymer material need to possess following characteristics: (a) good solubility, be conducive to solvent processing, and realize suitability for industrialized production; (b) whole sunlight spectrum is had to wide and strong absorption; (c) high carrier mobility, is conducive to carrier transport.Wherein, how to widen the light abstraction width of conjugated polymer material, make its light abstraction width farthest cover whole sunlight spectrum most important to the photoelectric transformation efficiency of raising organic solar batteries.
Summary of the invention
Based on this, be necessary to provide wide conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene of a kind of light abstraction width and preparation method thereof.
Containing a conjugated polymers for bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene, structural formula is as follows:
Wherein, the natural number that n is 1 ~ 60; R
1and R
2for H, C
1~ C
10alkyl or C
1~ C
10alkoxyl group; R
3for C
1~ C
16alkyl; R
4and R
5for H or C
1~ C
16alkyl.
A preparation method who contains the conjugated polymers of bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene, concrete steps are as follows:
Under shielding gas atmosphere, the ratio that is 1:1 ~ 1.5:1 according to mol ratio by compd A and compd B is carried out return stirring reaction in catalyzer and organic solvent, obtains the described conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene,
Wherein, the structural formula of compd A is as follows:
The structural formula of compd B is as follows:
Structural formula containing the conjugated polymers of bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene is as follows:
Wherein, the natural number that n is 1 ~ 60; R
1and R
2for H, C
1~ C
10alkyl, C
1~ C
10alkoxyl group; R
3for C
1~ C
16alkyl; R
4and R
5for H, C
1~ C
16alkyl.
Above-mentioned preparation method's technique is simple, reaction is easy to control, be suitable for suitability for industrialized production, and the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene preparing can be applied in the fields such as organic solar batteries, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties and organic laser.
Brief description of the drawings
Fig. 1 is the structural representation of embodiment 8 organic solar batteries devices;
Fig. 2 is the structural representation of embodiment 9 organic electroluminescence devices;
Fig. 3 is the structural representation of embodiment 10 organic field effect tubes.
Embodiment
Below in conjunction with drawings and the specific embodiments, conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene and its preparation method and application is further detailed.
The conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene of one embodiment, structural formula is as follows:
Wherein, the natural number that n is 1 ~ 60; R
1and R
2for H, C
1~ C
10alkyl, C
1~ C
10alkoxyl group; R
3for C
1~ C
16alkyl; R
4and R
5for H, C
1~ C
16alkyl.
Dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene have lot of advantages as the structural unit of conjugated polymers, first, dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene have large rigidity conjugate planes, be a kind of electron rich give body unit, this large rigidity conjugate planes structure can be transmitted electronics effectively, and makes the conjugated polymers of its formation have good thermostability and environmental stability; Secondly, dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene have the one-dimentional structure that is similar to graphite, can effectively reduce the structural distortion that causes Dan Shuanjian locality in conjugated polymers, thus the Dan Shuanjian reducing on main chain replaces degree, can reduce significantly the bandwidth of polymkeric substance, and at dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] sulfur heteroatom introduced in two thiophene, can further reduce significantly dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] bandwidth of two thiophene, increase its photon absorbing intensity.Therefore the transfer of current carrier between the conjugated polymers molecular skeleton that is structural unit with dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene becomes easily, can greatly improve the mobility effect of current carrier.
Bioxindol is indigo a kind of isomers, in its structure, contain two strong electrophilic lactam groups, thereby make whole bioxindol height electron deficiency and have the characteristic of high electron affinity, therefore, bioxindol can be used as a kind of good acceptor with strong electron-withdrawing power; And bioxindol has stronger polar group and make the stacking ability of its interchain strong especially, be easy to form strong state of aggregation and make conjugated polymers there is higher carrier mobility; In addition, bioxindol unit has stronger modifiability, can utilize easy method in its structure, to introduce electron-donating group or electron-accepting group regulates its electrophilic performance, also can on its N atom, introduce the groups such as alkyl and improve its solvability.
And the conjugated polymers that contains bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene is except having bioxindol unit and dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] beyond the advantage that has separately of two thiophene units itself, it is in conjunction with also having specific effect: first, electron rich give body unit dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene and electron deficiency be subject to body unit bioxindol, by giving the interaction of acceptor this " push away-La electronics ", reduce the energy gap of conjugated polymers, not only can make its absorption band move to infrared and near infrared low energy wave band, widen the light abstraction width containing the conjugated polymers of bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene, but also can improve the mobility of current carrier, secondly, at dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] bioxindol introduced in the two thiophene-structures π-π non-binding effect intensity that can reverse to a certain extent conjugated polymers interchain is better than the phenomenon of intramolecular chemical bonding intensity, improved the solvability of conjugated polymers.Therefore there is the characteristics such as light abstraction width is wide, carrier mobility is high, solvability is good containing the conjugated polymers of bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene.
In addition, present embodiment also provides a kind of preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene, and concrete steps are as follows:
Under shielding gas atmosphere, the ratio that is 1:1 ~ 1.5:1 according to mol ratio by compd A and compd B is carried out return stirring reaction in catalyzer and organic solvent, obtains the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene.
The structural formula of compd A is:
the structural formula of compd B is:
wherein, R
1and R
2for H, C
1~ C
10alkyl, C
1~ C
10alkoxyl group; R
3for C
1~ C
16alkyl; R
4and R
5for H, C
1~ C
16alkyl.
In the present embodiment, shielding gas atmosphere can be N
2or Ar atmosphere.Catalyzer is organic palladium, as Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, be preferably Pd (PPh
3)
2cl
2.Be appreciated that catalyzer also can be organic palladium and organophosphorus ligand (as, P (o-Tol)
3or tricyclohexyl phosphine) mixture, as, the Pd that mol ratio is 1:2 ~ 1:20
2(dba)
3with P (o-Tol)
3mixture.The molar weight of catalyzer be compd A molar weight 0.01% ~ 5%.Organic solvent is DMF, toluene or tetrahydrofuran (THF).
In the present embodiment, organic solvent is DMF (DMF), toluene or tetrahydrofuran (THF) (THF).
In the present embodiment, also comprise the method that the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene that return stirring reaction is obtained carries out separation and purification, specifically comprise the steps:
The reaction solution of removing organic solvent is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, methanol wash, dry; Dried product is dissolved in chloroform solvent, and carries out chromatography by alumina column, then use chloroform drip washing, and collect leacheate; The leacheate of removing chloroform is added drop-wise in methyl alcohol and carries out sedimentation, and then suction filtration, carries out soxhlet extraction by the solid obtaining with acetone; The extracting solution of removing acetone is added drop-wise in methyl alcohol and carries out sedimentation, and then suction filtration, obtains the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene after purifying.
Above-mentioned preparation method's technique is simple, reaction is easy to control, be suitable for suitability for industrialized production, and the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene preparing can be applied in the fields such as organic solar batteries, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties and organic laser.
In the present embodiment, also comprise the preparation method of compd A, specifically comprise the steps:
The Compound C with following structural formula is provided:
Under lucifuge condition, the ratio that is 3:1 according to N-bromo-succinimide (NBS) and the mol ratio of Compound C joins NBS in the DMF solution of Compound C, under room temperature, stirring reaction is after 15 hours, by reaction solution successively through washing, organic solvent extraction, collect organic phase, dry filter after removing moisture, the solid rotary evaporation of collection to be to go out unnecessary organic solvent, then purifies and obtain described compd A through column chromatography for separation.
Compound C can be prepared as follows:
The Compound D with following structural formula is provided:
By Compound D and Vanadium Pentoxide in FLAKES, the ratio taking mol ratio as 1.5:1 ~ 2.0:1 joins in trifluoromethanesulfonic acid, stirring reaction 72 hours under room temperature, then reaction solution is poured into cancellation reaction in ice-water bath, the throw out obtaining is added in pyridine, is heated to 110 DEG C of back flow reaction 12 hours, afterwards reaction solution is cooled to room temperature, add organic solvent extraction, and with revolving steaming after anhydrous magnesium sulfate drying, purify through column chromatography analysis, obtain described Compound C.
Compound D can be prepared as follows:
Compd E and F are provided, and the structural formula of described compd E is as follows:
The structural formula of described compound F 17-hydroxy-corticosterone is as follows:
The ratio that is 1:2 ~ 1:2.5 according to the mol ratio of compd E and compound F 17-hydroxy-corticosterone joins compound F 17-hydroxy-corticosterone in compd E, and logical rare gas element bubbling is removed after 30 minutes and added rapidly above-mentioned catalyzer, is heated to 80 DEG C of stirring reactions 48 hours, obtains described Compound D.The consumption of catalyzer is 0.01% ~ 5% of compd E molar weight.
Compd E can adopt following steps preparation:
The compound G with following structural formula is provided:
Under shielding gas atmosphere; compound G is joined in tetrahydrofuran solution and by the solution obtaining and is cooled to-78 DEG C; then the ratio that is 2.2 ~ 2.5:1 according to the mol ratio of n-BuLi and compound G is slowly added to the hexane solution of n-BuLi in the tetrahydrofuran solution of compound G; stirring reaction 2 hours at-78 DEG C, then according to Me
3the mol ratio of SnCl and compound G is that the ratio of 2.2:1 ~ 2.5:1 is by Me
3snCl is added in reaction solution, and insulation reaction returned to room temperature after 0.5 hour, continues reaction 24 hours, obtains described compd E.
Wherein, shielding gas atmosphere is N
2or Ar atmosphere.
In addition, the above-mentioned conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene can be applied in the fields such as organic solar batteries, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties and organic laser.
Conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene and its preparation method and application is described below in conjunction with specific embodiment.
Embodiment 1
Preparation has the compound of following structural formula:
Specifically comprise the steps:
Step 1, prepare compd E 1:
In nitrogen atmosphere, by 2.36g (5mmol) 4, 5-bis-certain herbaceous plants with big flowers base benzos [2, 1-b:3, 4-b '] two thiophene (G1) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, stirring reaction 2h at-78 DEG C, add the trimethyltin chloride (12.5mmol) of 3.7mL, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-bis-certain herbaceous plants with big flowers base-2, 7-tin trimethyl benzo [2, 1-b:3, 4-b '] two thiophene (E1), mass spectrometric measurement data are MS (EI) m/z:796 (M+).
Step 2, preparation Compound D 1:
At N
2under atmosphere, respectively 1.22g (1.53mmol) compd E 1 and 0.74g (3.36mmol) compound F 17-hydroxy-corticosterone are joined in 30mL anhydrous dimethyl formamide (DMF), obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add 0.087g (0.075mmol) Pd (PPh rapidly
3)
4catalyzer, and at 80 DEG C, carry out coupling reaction 24 hours; After reaction finishes, excessive DMF is removed in underpressure distillation, obtains solid matter; Solid matter is dissolved in appropriate ethyl acetate, and with 10% the above-mentioned ethyl acetate solution of Potassium monofluoride (KF) solution washing; Separatory, collects the ethyl acetate layer on upper strata, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound D 1 after purifying through rotary evaporation, column chromatography; The Compound D 1 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:747 (M
+).
Step 3, preparation Compound C 1:
Respectively by 0.22g (0.3mmol) Compound D 1 and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES (P
2o
5) join 6mL trifluoromethanesulfonic acid (CF
3sO
3h) in, and under room temperature condition stirring reaction 72 hours; Then reaction mixture is poured into and in 100mL ice-water bath, carried out cancellation reaction; Filtration, collecting precipitation; Then the precipitation obtaining is collected in vacuum-drying, and is added in 30mL pyridine to precipitation after drying, heating reflux reaction 12 hours; Question response liquid is cooled to after room temperature, adds methylene dichloride to extract, collect and combined dichloromethane phase, and dry through anhydrous MgSOX; Filter, remove MgSO
4; Then obtain the Compound C 1 after purifying through rotary evaporation, column chromatography; The Compound C 1 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:683(M
+).
Step 4, prepare compd A 1:
Under lucifuge condition, respectively 2.31g (13.0mmol) N-bromo-succinimide (NBS) and 2.94g (4.31mmol) Compound C 1 are joined in 60mL DMF, and under the condition of room temperature stirring reaction 15 hours; Then reaction solution is poured into water, through washing, extracted with diethyl ether, and collect and merge ether phase; Above-mentioned ether is through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compd A 1 after purifying through rotary evaporation, column chromatography; The compd A 1 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:841 (M
+).
Step 5, prepare end product P1:
At N
2under atmosphere, respectively 1.68g (2.0mmol) compd A 1 and 2.84g (3.0mmol) compound B-11 (structural formula is as follows) are joined in 30mL dry toluene, obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add 46mg (0.04mmol) Pd (PPh rapidly
3)
4catalyzer, continues to pass into N
2bubbling is removed residual O for 1.0 hours
2; Be heated to 120 DEG C of back flow reaction 72 hours; After reaction finishes, excessive toluene is removed in underpressure distillation; Then remaining material is added drop-wise to and in methyl alcohol, carries out sedimentation; Suction filtration obtains solid matter, and the solid matter obtaining by methanol wash is also dry; Peroxidation aluminium post carries out chromatography; Then use chloroform drip washing alumina column, and collect leacheate; Remove the chloroform of collecting in the leacheate obtaining, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, the solid obtaining is carried out to soxhlet extraction 3 days with acetone; Collect extracting solution, then remove acetone in extracting solution, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, obtains the final product of embodiment 1 required preparation.Detection analytical results is: the average molecular of final product is 78120, molecular weight dispersion coefficient (M
w: M
n) be 2.1, wherein, detecting instrument is gel permeation chromatograph, and taking tetrahydrofuran (THF) as solvent.
Embodiment 2
Preparation has the compound of following structural formula:
Specifically comprise the steps:
Step 1, prepare compd E 2:
At N
2under atmosphere, 1.93g (5mmol) compound G2 is joined in 60mL anhydrous tetrahydro furan, the solution obtaining is cooled to-78 DEG C; In above-mentioned cooled solution, slowly adding 4.4mL concentration is the hexane solution of the n-Butyl Lithium (n-BuLi) of 2.5mol/L, and under the condition of-78 DEG C stirring reaction 2 hours; Then add the trimethyltin chloride (Me of 11mmol
3snCl), under the condition of-78 DEG C, continue stirring reaction 0.5 hour; Return to room temperature, under the condition of room temperature, then react 24 hours, obtain compd E 2; The compd E 2 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:712 (M
+).
Step 2, preparation Compound D 2:
At N
2under atmosphere, respectively 1.09g (1.53mmol) compd E 2 and 0.74g (3.36mmol) compound F 17-hydroxy-corticosterone are joined in 30mL anhydrous dimethyl formamide (DMF), obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add 0.107mg (0.000153mmol) Pd (PPh rapidly
3)
2cl
2catalyzer, and at 80 DEG C, carry out coupling reaction 48 hours; After reaction finishes, excessive DMF is removed in underpressure distillation, obtains solid matter; Solid matter is dissolved in appropriate ethyl acetate, and with 10% the above-mentioned ethyl acetate solution of Potassium monofluoride (KF) solution washing; Separatory, collects the ethyl acetate layer on upper strata, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound D 2 after purifying through rotary evaporation, column chromatography; The Compound D 2 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:663 (M
+).
Step 3, preparation Compound C 2:
Respectively by 0.27g (0.4mmol) Compound D 2 and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES (P
2o
5) join 6mL trifluoromethanesulfonic acid (CF
3sO
3h) in, and under room temperature condition stirring reaction 72 hours; Then reaction mixture is poured into and in 100mL ice-water bath, carried out cancellation reaction; Filtration, collecting precipitation; Then the precipitation obtaining is collected in vacuum-drying, and is added in 30mL pyridine to precipitation after drying, is heated to 110 DEG C of back flow reaction 12 hours; Question response liquid is cooled to after room temperature, adds methylene dichloride to extract, collect and combined dichloromethane phase, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound C 2 after purifying through rotary evaporation, column chromatography; The Compound C 2 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:599 (M
+).
Step 4, prepare compd A 2:
Under lucifuge condition, respectively 2.31g (13.0mmol) N-bromo-succinimide (NBS) and 2.46g (4.31mmol) Compound C 2 are joined in 60mL DMF, and under the condition of room temperature stirring reaction 15 hours; Then reaction solution is poured into water, through washing, extracted with diethyl ether, and collect and merge ether phase; Above-mentioned ether is through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compd A 2 after purifying through rotary evaporation, column chromatography; The compd A 2 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:757 (M
+).
Step 5, prepare end product P2:
At N
2under atmosphere, respectively by as follows to 1.51g (2.0mmol) compd A 2 and 2.64g (2.2mmol) compd B 2(structural formula) join in 30mL anhydrous tetrahydro furan, obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2; Then in mixing solutions, add 116mg (0.1mmol) Pd (PPh rapidly
3)
4catalyzer, continues to pass into N
2bubbling is removed residual O for 1.0 hours
2; Be heated to 60 DEG C of back flow reaction 48 hours; After reaction finishes, excessive tetrahydrofuran (THF) is removed in underpressure distillation; Then remaining material is added drop-wise to and in methyl alcohol, carries out sedimentation; Suction filtration obtains solid matter, and the solid matter obtaining by methanol wash is also dry; Peroxidation aluminium post carries out chromatography; Then use chloroform drip washing alumina column, and collect leacheate; Remove the chloroform of collecting in the leacheate obtaining, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, the solid obtaining is carried out to soxhlet extraction 3 days with acetone; Collect extracting solution, then remove acetone in extracting solution, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, obtains the final product of embodiment 2 required preparations; Detection analytical results is: the average molecular of final product is 44100, M
w: M
n=1.9, wherein, detecting instrument is gel permeation chromatograph, and taking tetrahydrofuran (THF) as solvent;
Embodiment 3
Preparation has the compound of following structural formula:
Specifically comprise the steps:
Step 1, prepare compd E 3:
At N
2under atmosphere, 1.09g (5mmol) compound G3 is joined in 60mL anhydrous tetrahydro furan, the solution obtaining is cooled to-78 DEG C; In above-mentioned cooled solution, slowly adding 4.5mL concentration is the hexane solution of the n-Butyl Lithium (n-BuLi) of 2.5mol/L, and under the condition of-78 DEG C stirring reaction 2 hours; Then add the trimethyltin chloride (Me of 11.25mmol
3snCl), under the condition of-78 DEG C, continue stirring reaction 0.5 hour; Return to room temperature, under the condition of room temperature, then react 24 hours, obtain compd E 3; The compd E 3 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:544 (M
+).
Step 2, prepare compound d3:
At N
2under atmosphere, respectively 0.83g (1.53mmol) compd E 3 and 0.74g (3.36mmol) compound F 17-hydroxy-corticosterone are joined in 30mL anhydrous tetrahydro furan (THF), obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add Pd rapidly
2(dba)
3(14mg, 0.015mmol) and P (o-Tol)
3the mixture of (9mg, 0.03mmol) is as catalyzer, and at 60 DEG C, carries out coupling reaction 24 hours; After reaction finishes, excessive THF is removed in underpressure distillation, obtains solid matter; Solid matter is dissolved in appropriate ethyl acetate, and with 10% the above-mentioned ethyl acetate solution of Potassium monofluoride (KF) solution washing; Separatory, collects the ethyl acetate layer on upper strata, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compound d3 after purifying through rotary evaporation, column chromatography; The compound d3 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:495 (M
+).
Step 3, preparation Compound C 3:
Respectively by 0.20g(0.4mmol) compound d3 and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES (P
2o
5) join 6mL trifluoromethanesulfonic acid (CF
3sO
3h) in, and under room temperature condition stirring reaction 72 hours; Then reaction mixture is poured into and in 100mL ice-water bath, carried out cancellation reaction; Filtration, collecting precipitation; Then the precipitation obtaining is collected in vacuum-drying, and is added in 30mL pyridine to precipitation after drying, is heated to 110 DEG C of back flow reaction 12 hours; Question response liquid is cooled to after room temperature, adds methylene dichloride to extract, collect and combined dichloromethane phase, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound C 3 after purifying through rotary evaporation, column chromatography; The Compound C 3 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:431 (M
+).
Step 4, prepare compound A-13:
Wherein, reaction process is as follows:
Under lucifuge condition, respectively 2.31g (13.0mmol) N-bromo-succinimide (NBS) and 1.86g (4.31mmol) Compound C 3 are joined in 60mL DMF, and under the condition of room temperature stirring reaction 15 hours; Then reaction solution is poured into water, through washing, extracted with diethyl ether, and collect and merge ether phase; Above-mentioned ether is through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compound A-13 after purifying through rotary evaporation, column chromatography; The compound A-13 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:588 (M
+).
Step 5, prepare end product P3:
At N
2under atmosphere, respectively by as follows to 1.18g (2.0mmol) compound A-13 and 2.7g (2.2mmol) compd B 3(structural formula) join in 30mL dry DMF, obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2; Then in mixing solutions, add 0.23mg (0.0002mmol) Pd (PPh rapidly
3)
4catalyzer, continues to pass into N
2bubbling is removed residual O for 1.0 hours
2; Be heated to 80 DEG C of back flow reaction 24 hours; After reaction finishes, excessive DMF is removed in underpressure distillation; Then remaining material is added drop-wise to and in methyl alcohol, carries out sedimentation; Suction filtration obtains solid matter, and the solid matter obtaining by methanol wash is also dry; Peroxidation aluminium post carries out chromatography; Then use chloroform drip washing alumina column, and collect leacheate; Remove the chloroform of collecting in the leacheate obtaining, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, the solid obtaining is carried out to soxhlet extraction 3 days with acetone; Collect extracting solution, then remove acetone in extracting solution, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, obtains the final product of embodiment 3 required preparations; Detection analytical results is: the average molecular of final product is 33250, M
w: M
n=2.1, wherein, detecting instrument is gel permeation chromatograph, and taking tetrahydrofuran (THF) as solvent.
Embodiment 4
Preparation has the compound of following structural formula:
Specifically comprise the steps:
Step 1, prepare compd E 4:
At N
2under atmosphere, 2.52g (5mmol) compound G4 is joined in 60mL anhydrous tetrahydro furan, the solution obtaining is cooled to-78 DEG C; In above-mentioned cooled solution, slowly adding 4.4mL concentration is the hexane solution of the n-Butyl Lithium (n-BuLi) of 2.5mol/L, and under the condition of-78 DEG C stirring reaction 2 hours; Then add the trimethyltin chloride (Me of 12mmol
3snCl), under the condition of-78 DEG C, continue stirring reaction 0.5 hour; Return to room temperature, under the condition of room temperature, then react 24 hours, obtain compd E 4; The compd E 4 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:712 (M
+).
Step 2, preparation Compound D 4:
At N
2under atmosphere, respectively 2.07g (2.5mmol) compd E 4 and 1.1g (5.0mmol) compound F 17-hydroxy-corticosterone are joined in 30mL anhydrous dimethyl formamide (DMF), obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add Pd rapidly
2(dba)
3(0.092g, 0.1mmol) and P (o-Tol)
3the mixture of (0.61g, 1.0mmol) is as catalyzer, and at 80 DEG C, carries out coupling reaction 24 hours; After reaction finishes, excessive DMF is removed in underpressure distillation, obtains solid matter; Solid matter is dissolved in appropriate ethyl acetate, and with 10% the above-mentioned ethyl acetate solution of Potassium monofluoride (KF) solution washing; Separatory, collects the ethyl acetate layer on upper strata, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound D 4 after purifying through rotary evaporation, column chromatography; The Compound D 4 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:779 (M
+).
Step 3, preparation Compound C 4:
Respectively by 0.35g (0.45mmol) Compound D 4 and 0.036g (0.25mmol) Vanadium Pentoxide in FLAKES (P
2o
5) join 6mL trifluoromethanesulfonic acid (CF
3sO
3h) in, and under room temperature condition stirring reaction 72 hours; Then reaction mixture is poured into and in 100mL ice-water bath, carried out cancellation reaction; Filtration, collecting precipitation; Then the precipitation obtaining is collected in vacuum-drying, and is added in 30mL pyridine to precipitation after drying, is heated to 110 DEG C of back flow reaction 12 hours; Question response liquid is cooled to after room temperature, adds methylene dichloride to extract, collect and combined dichloromethane phase, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound C 4 after purifying through rotary evaporation, column chromatography; The Compound C 4 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:715 (M
+).
Step 4, prepare compd A 4:
Under lucifuge condition, respectively 2.31g (13.0mmol) N-bromo-succinimide (NBS) and 4.08g (4.31mmol) Compound C 4 are joined in 60mL DMF, and under the condition of room temperature stirring reaction 15 hours; Then reaction solution is poured into water, through washing, extracted with diethyl ether, and collect and merge ether phase; Above-mentioned ether is through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compd A 4 after purifying through rotary evaporation, column chromatography; The compd A 4 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:873 (M
+).
Step 5, prepare end product P4:
At N
2under atmosphere, respectively by as follows to 1.75g (2.0mmol) compd A 4 and 3.27g (3.0mmol) compd B 4(structural formula) join in 30mL anhydrous tetrahydro furan, obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2; Then in mixing solutions, add Pd rapidly
2(dba)
3(0.092g, 0.1mmol) and P (o-Tol)
3the mixture of (0.61g, 2.0mmol), as catalyzer, continues to pass into N
2bubbling is removed residual O for 1.0 hours
2; Be heated to 60 DEG C of back flow reaction 48 hours; After reaction finishes, excessive tetrahydrofuran (THF) is removed in underpressure distillation; Then remaining material is added drop-wise to and in methyl alcohol, carries out sedimentation; Suction filtration obtains solid matter, and the solid matter obtaining by methanol wash is also dry; Peroxidation aluminium post carries out chromatography; Then use chloroform drip washing alumina column, and collect leacheate; Remove the chloroform of collecting in the leacheate obtaining, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, the solid obtaining is carried out to soxhlet extraction 3 days with acetone; Collect extracting solution, then remove acetone in extracting solution, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, obtains the final product of embodiment 4 required preparations; Detection analytical results is: the average molecular of final product is 29480, M
w: M
n=2.0, wherein, detecting instrument is gel permeation chromatograph, and taking tetrahydrofuran (THF) as solvent.
Embodiment 5
Preparation has the compound of following structural formula:
Specifically comprise the steps:
Step 1, prepare compd E 5:
At N
2under atmosphere, 2.52g (5mmol) compound G5 is joined in 60mL anhydrous tetrahydro furan, the solution obtaining is cooled to-78 DEG C; In above-mentioned cooled solution, slowly adding 4.4mL concentration is the hexane solution of the n-Butyl Lithium (n-BuLi) of 2.5mol/L, and under the condition of-78 DEG C stirring reaction 2 hours; Then add the trimethyltin chloride (Me of 12mmol
3snCl), under the condition of-78 DEG C, continue stirring reaction 0.5 hour; Return to room temperature, under the condition of room temperature, then react 24 hours, obtain compd E 5; The compd E 5 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:712 (M
+).
Step 2, preparation Compound D 5:
At N
2under atmosphere, respectively 2.07g (2.5mmol) compd E 5 and 1.1g (5.0mmol) compound F 17-hydroxy-corticosterone are joined in 30mL anhydrous dimethyl formamide (DMF), obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add Pd rapidly
2(dba)
3(0.092g, 0.1mmol) and P (o-Tol)
3the mixture of (0.61g, 1.0mmol) is as catalyzer, and at 80 DEG C, carries out coupling reaction 48 hours; After reaction finishes, excessive DMF is removed in underpressure distillation, obtains solid matter; Solid matter is dissolved in appropriate ethyl acetate, and with 10% the above-mentioned ethyl acetate solution of Potassium monofluoride (KF) solution washing; Separatory, collects the ethyl acetate layer on upper strata, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound D 5 after purifying through rotary evaporation, column chromatography; The Compound D 5 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:779 (M
+).
Step 3, preparation Compound C 5:
Respectively by 0.39g (0.5mmol) Compound D 5 and 0.036g (0.25mmol) Vanadium Pentoxide in FLAKES (P
2o
5) join 6mL trifluoromethanesulfonic acid (CF
3sO
3h) in, and under room temperature condition stirring reaction 72 hours; Then reaction mixture is poured into and in 100mL ice-water bath, carried out cancellation reaction; Filtration, collecting precipitation; Then the precipitation obtaining is collected in vacuum-drying, and is added in 30mL pyridine to precipitation after drying, is heated to 110 DEG C of back flow reaction 12 hours; Question response liquid is cooled to after room temperature, adds methylene dichloride to extract, collect and combined dichloromethane phase, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound C 5 after purifying through rotary evaporation, column chromatography; The Compound C 5 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:715 (M
+).
Step 4, prepare compound A-45:
Under lucifuge condition, respectively 2.31g (13.0mmol) N-bromo-succinimide (NBS) and 4.08g (4.31mmol) Compound C 5 are joined in 60mL DMF, and under the condition of room temperature stirring reaction 15 hours; Then reaction solution is poured into water, through washing, extracted with diethyl ether, and collect and merge ether phase; Above-mentioned ether is through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compound A-45 after purifying through rotary evaporation, column chromatography; The compound A-45 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:873 (M
+).
Step 5, prepare end product P5:
At N
2under atmosphere, respectively 1.75g (2.0mmol) compound A-45 and 2.4g (2.0mmol) compd B 2 are joined in 30mL anhydrous tetrahydro furan, obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2; Then in mixing solutions, add Pd rapidly
2(dba)
3(0.092g, 0.1mmol) and P (o-Tol)
3the mixture of (0.3g, 1mmol), as catalyzer, continues to pass into N
2bubbling is removed residual O for 1.0 hours
2; Be heated to 60 DEG C of back flow reaction 48 hours; After reaction finishes, excessive tetrahydrofuran (THF) is removed in underpressure distillation; Then remaining material is added drop-wise to and in methyl alcohol, carries out sedimentation; Suction filtration obtains solid matter, and the solid matter obtaining by methanol wash is also dry; Peroxidation aluminium post carries out chromatography; Then use chloroform drip washing alumina column, and collect leacheate; Remove the chloroform of collecting in the leacheate obtaining, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, the solid obtaining is carried out to soxhlet extraction 3 days with acetone; Collect extracting solution, then remove acetone in extracting solution, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, obtains the final product of embodiment 5 required preparations; Detection analytical results is: the average molecular of final product is 22110, M
w: M
n=2.0, wherein, detecting instrument is gel permeation chromatograph, and taking tetrahydrofuran (THF) as solvent.
Embodiment 6
Preparation has the compound of following structural formula:
Specifically comprise the steps:
Step 1, prepare compd E 6:
At N
2under atmosphere, 1.40g (5mmol) compound G6 is joined in 60mL anhydrous tetrahydro furan, the solution obtaining is cooled to-78 DEG C; In above-mentioned cooled solution, slowly adding 5mL concentration is the hexane solution of the n-Butyl Lithium (n-BuLi) of 2.5mol/L, and under the condition of-78 DEG C stirring reaction 2 hours; Then add the trimethyltin chloride (Me of 12.5mmol
3snCl), under the condition of-78 DEG C, continue stirring reaction 0.5 hour; Return to room temperature, under the condition of room temperature, then react 24 hours, obtain compd E 6; The compd E 6 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:576 (M
+).
Step 2, preparation Compound D 6:
At N
2under atmosphere, respectively 1.44g (2.5mmol) compd E 6 and 1.1g (5.0mmol) compound F 17-hydroxy-corticosterone are joined in 30mL anhydrous dimethyl formamide (DMF), obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add Pd rapidly
2(dba)
3(0.092g, 0.1mmol) and P (o-Tol)
3the mixture of (0.61g, 1.0mmol) is as catalyzer, and at 80 DEG C, carries out coupling reaction 48 hours; After reaction finishes, excessive DMF is removed in underpressure distillation, obtains solid matter; Solid matter is dissolved in appropriate ethyl acetate, and with 10% the above-mentioned ethyl acetate solution of Potassium monofluoride (KF) solution washing; Separatory, collects the ethyl acetate layer on upper strata, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound D 6 after purifying through rotary evaporation, column chromatography; The Compound D 6 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:527 (M
+).
Step 3, preparation Compound C 6:
Respectively by 0.26g (0.5mmol) Compound D 6 and 0.036g (0.25mmol) Vanadium Pentoxide in FLAKES (P
2o
5) join 6mL trifluoromethanesulfonic acid (CF
3sO
3h) in, and under room temperature condition stirring reaction 72 hours; Then reaction mixture is poured into and in 100mL ice-water bath, carried out cancellation reaction; Filtration, collecting precipitation; Then the precipitation obtaining is collected in vacuum-drying, and is added in 30mL pyridine to precipitation after drying, is heated to 110 DEG C of back flow reaction 12 hours; Question response liquid is cooled to after room temperature, adds methylene dichloride to extract, collect and combined dichloromethane phase, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound C 6 after purifying through rotary evaporation, column chromatography; The Compound C 6 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:463 (M
+).
Step 4, prepare compd A 6:
Under lucifuge condition, respectively 2.31g (13.0mmol) N-bromo-succinimide (NBS) and 2.0g (4.31mmol) Compound C 6 are joined in 60mL DMF, and under the condition of room temperature stirring reaction 15 hours; Then reaction solution is poured into water, through washing, extracted with diethyl ether, and collect and merge ether phase; Above-mentioned ether is through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compd A 6 after purifying through rotary evaporation, column chromatography; The compd A 6 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:620 (M
+).
Step 5, prepare end product P6:
At N
2under atmosphere, respectively 1.21g (2.0mmol) compd A 6 and 3.6g (3.0mmol) compd B 2 are joined in 30mL anhydrous tetrahydro furan, obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2; Then in mixing solutions, add Pd rapidly
2(dba)
3(0.092g, 0.1mmol) and P (o-Tol)
3the mixture of (0.06g, 0.2mmol), as catalyzer, continues to pass into N
2bubbling is removed residual O for 1.0 hours
2; Be heated to 60 DEG C of back flow reaction 48 hours; After reaction finishes, excessive tetrahydrofuran (THF) is removed in underpressure distillation; Then remaining material is added drop-wise to and in methyl alcohol, carries out sedimentation; Suction filtration obtains solid matter, and the solid matter obtaining by methanol wash is also dry; Peroxidation aluminium post carries out chromatography; Then use chloroform drip washing alumina column, and collect leacheate; Remove the chloroform of collecting in the leacheate obtaining, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, the solid obtaining is carried out to soxhlet extraction 3 days with acetone; Collect extracting solution, then remove acetone in extracting solution, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, obtains the final product of embodiment 6 required preparations; Detection analytical results is: the average molecular of final product is 13490, M
w: M
n=1.8, wherein, detecting instrument is gel permeation chromatograph, and taking tetrahydrofuran (THF) as solvent.
Embodiment 7
Preparation has the compound of following structural formula:
Specifically comprise the steps:
Step 1, prepare compd E 7:
At N
2under atmosphere, 0.95g (5mmol) compound G7 is joined in 60mL anhydrous tetrahydro furan, the solution obtaining is cooled to-78 DEG C; In above-mentioned cooled solution, slowly adding 5mL concentration is the hexane solution of the n-Butyl Lithium (n-BuLi) of 2.5mol/L, and under the condition of-78 DEG C stirring reaction 2 hours; Then add the trimethyltin chloride (Me of 12.5mmol
3snCl), under the condition of-78 DEG C, continue stirring reaction 0.5 hour; Return to room temperature, under the condition of room temperature, then react 24 hours, obtain compd E 7; The compd E 7 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:516 (M
+).
Step 2, preparation Compound D 7:
At N
2under atmosphere, respectively 1.03g (2.0mmol) compd E 6 and 1.1g (5.0mmol) compound F 17-hydroxy-corticosterone are joined in 30mL anhydrous dimethyl formamide (DMF), obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2, then in mixing solutions, add Pd rapidly
2(dba)
3(0.092g, 0.1mmol) and P (o-Tol)
3the mixture of (0.61g, 1.0mmol) is as catalyzer, and at 80 DEG C, carries out coupling reaction 48 hours; After reaction finishes, excessive DMF is removed in underpressure distillation, obtains solid matter; Solid matter is dissolved in appropriate ethyl acetate, and with 10% the above-mentioned ethyl acetate solution of Potassium monofluoride (KF) solution washing; Separatory, collects the ethyl acetate layer on upper strata, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound D 7 after purifying through rotary evaporation, column chromatography; The Compound D 7 that mass spectrometric detection obtains, detected result is: MS (EI) m/z:467 (M
+).
Step 3, preparation Compound C 7:
Respectively by 0.19g (0.4mmol) Compound D 7 and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES (P
2o
5) join 6mL trifluoromethanesulfonic acid (CF
3sO
3h) in, and under room temperature condition stirring reaction 72 hours; Then reaction mixture is poured into and in 100mL ice-water bath, carried out cancellation reaction; Filtration, collecting precipitation; Then the precipitation obtaining is collected in vacuum-drying, and is added in 30mL pyridine to precipitation after drying, is heated to 110 DEG C of back flow reaction 12 hours; Question response liquid is cooled to after room temperature, adds methylene dichloride to extract, collect and combined dichloromethane phase, and through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the Compound C 7 after purifying through rotary evaporation, column chromatography; The Compound C 7 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:403 (M
+).
Step 4, prepare compd A 7:
Under lucifuge condition, respectively 2.31g (13.0mmol) N-bromo-succinimide (NBS) and 1.74g (4.31mmol) Compound C 7 are joined in 60mL DMF, and under the condition of room temperature stirring reaction 15 hours; Then reaction solution is poured into water, through washing, extracted with diethyl ether, and collect and merge ether phase; Above-mentioned ether is through anhydrous MgSO
4dry; Filter, remove MgSO
4; Then obtain the compd A 7 after purifying through rotary evaporation, column chromatography; The compd A 7 that mass spectrometric detection obtains, detected result is: MS (MALDI) m/z:560 (M
+).
Step 5, prepare end product P7:
At N
2under atmosphere, respectively by as follows to 1.21g (2.0mmol) compd A 7 and 3.77g (3.0mmol) compd B 7(structural formula) join in 30mL dry toluene, obtain mixing solutions; In mixing solutions, pass into N
2bubbling is removed residual O for 0.5 hour
2; Then in mixing solutions, add Pd (PPh rapidly
3)
2cl
2(0.042g, 0.06mmol), as catalyzer, continues to pass into N
2bubbling is removed residual O for 1.0 hours
2; Be heated to 120 DEG C of back flow reaction 24 hours; After reaction finishes, excessive toluene is removed in underpressure distillation; Then remaining material is added drop-wise to and in methyl alcohol, carries out sedimentation; Suction filtration obtains solid matter, and the solid matter obtaining by methanol wash is also dry; Peroxidation aluminium post carries out chromatography; Then use chloroform drip washing alumina column, and collect leacheate; Remove the chloroform of collecting in the leacheate obtaining, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, the solid obtaining is carried out to soxhlet extraction 3 days with acetone; Collect extracting solution, then remove acetone in extracting solution, and remaining material is added drop-wise in methyl alcohol and carries out sedimentation, then suction filtration, obtains the final product of embodiment 7 required preparations; Detection analytical results is: the average molecular of final product is 1330, M
w: M
n=2.3, wherein, detecting instrument is gel permeation chromatograph, and taking tetrahydrofuran (THF) as solvent.
Embodiment 8
Taking the conjugated polymers for preparing in embodiment 5 as active layer material, prepare organic solar cell device.As shown in Figure 1, organic solar batteries device 100, comprises glass substrate 110, ITO conductive layer 120, poly-(3,4-Ethylenedioxy Thiophene) to its structure: poly-(styrene sulfonic acid) layer 130, active coating 140 and metal Al layer 150; Wherein, active coating 140 comprises electron donor material and electron acceptor material, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate, electron donor material is the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene preparing in embodiment.
The preparation process of above-mentioned organic solar batteries device is as follows: on the glass substrate of clean dried, be coated with ITO conductive layer, obtain ito glass, wherein, the square resistance of the ITO conductive layer being coated with is 10-20 ohm; Process the ito glass after ultrasonic cleaning with oxygen-Plasma, then coating poly-(3,4-Ethylenedioxy Thiophene) on ITO conductive layer: poly-(styrene sulfonic acid) layer; Then adopt spin coating technique at poly-(3,4-Ethylenedioxy Thiophene): on poly-(styrene sulfonic acid) layer, to apply active coating; And adopt vacuum evaporation technology evaporation metal Al layer on active coating, obtain above-mentioned organic solar batteries device.Above-mentioned organic solar batteries device, with after epoxy encapsulation, is placed under 110 DEG C of air tight conditions and is annealed 4 hours, then drop to room temperature.Due to device annealed after, the chemical structure of material is more regular in order, has improved transmission speed and the efficiency of current carrier, thereby has improved the photoelectric transformation efficiency of device.
By the I-E characteristic of Keithley236 current/voltage source-measuring system test component, the open circuit voltage that records organic solar batteries device is 0.53V, and packing factor is 41%, and short-circuit current density is 7.4mA/cm
2, energy conversion efficiency is 1.61%.
Embodiment 9
Taking the conjugated polymers for preparing in embodiment 2 as luminescent layer, be prepared with organic electroluminescence devices.Its structure as shown in Figure 2, organic electroluminescence device 200, comprise glass substrate 210, ITO conductive layer 220, luminescent layer 230, LiF buffer layer 240 and metal Al layer 250, wherein, the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene of luminescent layer 230 for preparing in embodiment.
The preparation process of above-mentioned organic electroluminescence device is as follows: on the glass substrate of clean dried, be coated with ITO conductive layer, obtain ito glass, wherein, ITO conductive layer is as the transparent anode of organic electroluminescence device, and the square resistance of the ITO conductive layer being coated with is 10-20 ohm; Adopt spin coating technique at ITO conductive layer coating luminescent layer; Adopt vacuum evaporation technology on luminescent layer, to be coated with LiF buffer layer; And adopt vacuum evaporation technology to be coated with metal Al layer as negative electrode on LiF buffer layer, obtain above-mentioned organic electroluminescence device.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400 Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 1.53cd/A, and high-high brightness is 1008cd/m
2.
Embodiment 10
Taking the conjugated polymers for preparing in embodiment 6 as organic semiconductor layer, be prepared with field effect transistors.As shown in Figure 3, organic field effect tube 300, comprises silicon chip 310, the SiO of doping to its structure
2insulation layer 320, octadecyl trichlorosilane alkane decorative layer 330, organic semiconductor layer 340, source electrode 350 and drain electrode 360, wherein, the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene of organic semiconductor layer 340 for preparing in embodiment.
The preparation process of above-mentioned organic field effect tube is as follows: on the silicon chip of the doping of clean dried, be coated with the SiO that thickness is 450nm
2insulation layer; Adopt spin coating technique at SiO
2on insulation layer, apply octadecyl trichlorosilane alkane decorative layer; Adopt spin coating technique to apply organic semiconductor layer on octadecyl trichlorosilane alkane decorative layer, and source electrode and drain electrode are set on organic semiconductor layer, obtain organic field effect tube.
By time of flight method (Time of Flight, TOF), 7.0 × 10
5vcm
-1electric field in the mean void mobility of the test organic field effect tube that contains polymer P 6 prepared by the embodiment of the present invention 6 be 1.9 × 10
-4cm
2/ Vs, shows that the polymkeric substance containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene prepared by the present invention has extraordinary hole transport performance.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. containing a conjugated polymers for bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene, structural formula is as follows:
Wherein, the natural number that n is 1 ~ 60;
R
1and R
2for H, C
1~ C
10alkyl or C
1~ C
10alkoxyl group;
R
3for C
1~ C
16alkyl;
R
4and R
5for H or C
1~ C
16alkyl.
2. a preparation method who contains the conjugated polymers of bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene, comprises the steps:
Compd A and compd B are provided, and the structure of described compd A is:
The structural formula of described compd B is:
Wherein, R
1and R
2for H, C
1~ C
10alkyl or C
1~ C
10alkoxyl group, R
3for C
1~ C
16alkyl, R
4and R
5for H or C
1~ C
16alkyl;
Under shielding gas atmosphere; the ratio that is 1:1 ~ 1.5:1 according to mol ratio by compd A and compd B is carried out return stirring reaction in catalyzer and organic solvent, obtains having the described conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene of following structural formula:
Wherein, the natural number that n is 1 ~ 60.
3. the preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 2, is characterized in that, described organic solvent is DMF, toluene or tetrahydrofuran (THF).
4. the preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 2, is characterized in that, the step of described separation and purification is:
The mixed solution reduction vaporization that obtains after reaction is removed to excessive solvent, then be added to and in methyl alcohol, carry out sedimentation, suction filtration, precipitate by methanol wash, unnecessary methyl alcohol is removed in collecting precipitation evaporation, and peroxidation aluminium column chromatography afterwards, uses chloroform drip washing, cross the methyl alcohol sedimentation of post after product, suction filtration, the solids of gained extracts three days by acetone Soxhlet, finally uses methyl alcohol sedimentation, suction filtration, under vacuum pump, taking out spends the night obtains the described conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene.
5. the preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 2, is characterized in that, described compd A adopts following steps preparation:
The Compound C with following structural formula is provided:
Under lucifuge condition, the ratio that is 3:1 according to the mol ratio of N-bromo-succinimide and Compound C joins N-bromo-succinimide the N of Compound C, in dinethylformamide solution, under room temperature, stirring reaction is after 15 hours, reaction solution, successively through washing, organic solvent extraction, is collected to organic phase, dry filter after removing moisture, the solid rotary evaporation of collecting to be to go out unnecessary organic solvent, then purifies and obtain described compd A through column chromatography for separation.
6. the preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 5, is characterized in that, described Compound C adopts following steps preparation:
The Compound D with following structural formula is provided:
By Compound D and Vanadium Pentoxide in FLAKES, the ratio taking mol ratio as 1.5:1 ~ 2.0:1 joins in trifluoromethanesulfonic acid, stirring reaction 72 hours under room temperature, then reaction solution is poured into cancellation reaction in ice-water bath, the throw out obtaining is added in pyridine, is heated to 110 DEG C of back flow reaction 12 hours, afterwards reaction solution is cooled to room temperature, add organic solvent extraction, and with revolving steaming after anhydrous magnesium sulfate drying, purify through column chromatography analysis, obtain described Compound C.
7. the preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 6, is characterized in that, described Compound D adopts following steps preparation:
Compd E and F are provided, and the structural formula of described compd E is as follows:
The structural formula of described compound F 17-hydroxy-corticosterone is as follows:
The ratio that is 1:2 ~ 1:2.5 according to the mol ratio of compd E and compound F 17-hydroxy-corticosterone joins compound F 17-hydroxy-corticosterone in compd E, and logical rare gas element bubbling is removed after 30 minutes and added rapidly catalyzer, is heated to 80 DEG C of stirring reactions 48 hours, obtains described Compound D.
8. the preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 7, is characterized in that, described catalyzer is Pd (PPh
3)
2cl
2, Pd (PPh
3)
4or Pd
2(dba)
3with P (o-Tol)
3mixture; In compd A and compd B reaction process, 0.01% ~ 5% of the molar weight that the consumption of described catalyzer is compd A; In the reaction process of compd E and compound F 17-hydroxy-corticosterone, 0.01% ~ 5% of the molar weight that the consumption of described catalyzer is compd E.
9. the preparation method of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 7, is characterized in that, described compd E adopts following steps preparation:
The compound G with following structural formula is provided:
Under shielding gas atmosphere; compound G is joined in tetrahydrofuran solution and by the solution obtaining and is cooled to-78 DEG C; then the ratio that is 2.2:1 ~ 2.5:1 according to the mol ratio of n-BuLi and compound G is slowly added to the hexane solution of n-BuLi in the tetrahydrofuran solution of compound G; stirring reaction 2 hours at-78 DEG C, then according to Me
3the mol ratio of SnCl and compound G is that the ratio of 2.2:1 ~ 2.5:1 is added to trimethyltin chloride in reaction solution, and insulation reaction returned to room temperature after 0.5 hour, continues reaction 24 hours, obtains described compd E.
10. the application of the conjugated polymers containing bioxindol-dibenzothiophene benzene 1,4-Dithiapentalene as claimed in claim 1 in polymer solar cell device, organic electroluminescence device, organic field effect tube, organic optical storage and organic laser.
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| CN105914298A (en) * | 2016-05-15 | 2016-08-31 | 吉林大学 | Polymer photovoltaic cell taking isoindigo derivative as cathode interface modification layer |
| CN106784314A (en) * | 2017-01-18 | 2017-05-31 | 南京邮电大学 | The preparation method of the OTFT with photo paper as substrate |
| CN115322338A (en) * | 2022-08-15 | 2022-11-11 | 东华大学 | Organic semiconductor material containing thiophene pyridine isoindigo structure and preparation method and application thereof |
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| CN102453228A (en) * | 2010-10-19 | 2012-05-16 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing fluorene, anthracene and benzodithiophene units, preparation method, and application thereof |
| CN102786666A (en) * | 2011-05-16 | 2012-11-21 | 海洋王照明科技股份有限公司 | Benzotriazolyl-containing copolymer, preparation method and organic electroluminescent devices thereof |
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| CN102786666A (en) * | 2011-05-16 | 2012-11-21 | 海洋王照明科技股份有限公司 | Benzotriazolyl-containing copolymer, preparation method and organic electroluminescent devices thereof |
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| CN105914298A (en) * | 2016-05-15 | 2016-08-31 | 吉林大学 | Polymer photovoltaic cell taking isoindigo derivative as cathode interface modification layer |
| CN105914298B (en) * | 2016-05-15 | 2018-12-25 | 吉林大学 | Using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer |
| CN106784314A (en) * | 2017-01-18 | 2017-05-31 | 南京邮电大学 | The preparation method of the OTFT with photo paper as substrate |
| CN115322338A (en) * | 2022-08-15 | 2022-11-11 | 东华大学 | Organic semiconductor material containing thiophene pyridine isoindigo structure and preparation method and application thereof |
| CN115322338B (en) * | 2022-08-15 | 2023-09-29 | 东华大学 | Organic semiconductor material containing thiophene pyridine isoindigo structure, and preparation method and application thereof |
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