CN110407781A - 双（芳基乙烯基）苯胺类有机染料及其制备方法 - Google Patents
双（芳基乙烯基）苯胺类有机染料及其制备方法 Download PDFInfo
- Publication number
- CN110407781A CN110407781A CN201910676410.0A CN201910676410A CN110407781A CN 110407781 A CN110407781 A CN 110407781A CN 201910676410 A CN201910676410 A CN 201910676410A CN 110407781 A CN110407781 A CN 110407781A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- bis
- base
- vinyl
- furans
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000975 dye Substances 0.000 title claims abstract description 30
- 125000003609 aryl vinyl group Chemical group 0.000 title claims abstract description 24
- 150000001448 anilines Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 60
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 150000002240 furans Chemical class 0.000 claims description 33
- 229920002554 vinyl polymer Polymers 0.000 claims description 29
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 208000032825 Ring chromosome 2 syndrome Diseases 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 229930192474 thiophene Natural products 0.000 claims description 10
- -1 (4- bromophenyl) azepine diyl Chemical group 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 150000003935 benzaldehydes Chemical class 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 2
- 238000010541 McMurry coupling reaction Methods 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- 206010070834 Sensitisation Diseases 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000008313 sensitization Effects 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- HWBOSRMGKRNJAO-UHFFFAOYSA-N [N]C1=CC=C(Br)C=C1 Chemical compound [N]C1=CC=C(Br)C=C1 HWBOSRMGKRNJAO-UHFFFAOYSA-N 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 125000002541 furyl group Chemical group 0.000 abstract description 4
- 125000001544 thienyl group Chemical group 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 241001169121 Gabriella Species 0.000 description 1
- 101100437915 Populus deltoides BSPA gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明公开了一种双(芳基乙烯基)苯胺类有机染料及其制备方法。所述的双(芳基乙烯基)苯胺类有机染料的化学结构通式为式中，AR为电子供体，所述的AR基选自或本发明的双(芳基乙烯基)苯胺类有机染料中，呋喃基和噻吩基作为良好的供电子基团，以其作为敏化剂制成的DSSCS的能量转换效率最高可达6.01％。
Description
技术领域
本发明属于染料敏化太阳能电池(DSSCS)敏化剂技术领域，涉及一种双(芳基乙烯基)苯胺类有机染料及其制备方法。
背景技术
太阳能以其环保、可再生、能量蕴藏大等优势，作为新能源显示出巨大的优越性。自从瑞士洛桑联邦理工学院的M.研究团队于1991年开发出染料敏化太阳能电池以来，DSSCS领域开展了大量的研究。DSSCS是一种模拟光合作用的太阳能电池，与传统的太阳电池相比，具有以下优势：(1)分子结构易于修改，显示效率可以预测；(2)性能优异，具有较大的紫外-可见吸收光范围；(3)易于制备，生产工艺简单，易于大规模工业化生产；(4)生产成本较低，价格低廉；(5)低毒性，对环境友好。
作为电池的重要组成部分，DSSCS敏化剂能够有效地吸收太阳光，并由此产生激发电子，然后注入到二氧化钛等半导体的导带中。因此染料敏化剂的光电性能对染料敏化太阳能电池的光电转换效率有着至关重要的影响。目前现有的DSSCS有机染料合成路线长，目标产物的产率非常低，很难达到理想中的能量转换效率(η)。
文献1报道了一系列新的偶氮苯桥联无金属有机染料，使用其制成的DSSCS能量转换效率最高仅为4.78％(Kuo Yuan Chiu,Thai Thi Ha Tran.A new series ofazobenzene-bridged metal-free organic dyes andapplication on DSSC[J].Dyes andPigments,2017,(146):512-519)。
文献2报道了一系列硅二醇类有机染料的分子设计方法，其合成条件相对苛刻，且使用其制成的DSSCS能量转换效率最高仅为4.3％(Gabriella BarozzinoConsiglio,FabioPedna.Assessment of new gem-silanediols as suitable sensitizers for dye-sensitizedsolar cells[J].Journal of Organometallic Chemistry 2013,(723):198-206)。
发明内容
本发明的目的在于提供一种双(芳基乙烯基)苯胺类有机染料及其制备方法。
实现本发明目的的技术方案如下：
双(芳基乙烯基)苯胺类有机染料，化学结构通式(FWD)如下所示：
式中，AR为电子供体，所述的AR基选自
具体地，在本发明具体实施方式中，所述的双(芳基乙烯基)苯胺类有机染料为(E)-3-(5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸(FWD7)，结构式为或(E)-3-(5-(4-(双(4-((E)-2-(噻吩-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸(化合物FWD8)，结构式为
本发明还提供上述双(芳基乙烯基)苯胺类有机染料的制备方法，包括如下步骤：
步骤1，氮气保护下，将锌粉加入四氢呋喃(THF)中，-5～0℃下逐滴加入TiCl4，60～80℃下回流，将4,4'–((4-溴苯基)氮杂二基)二苯甲醛与2-芳醛(ARCHO)和THF加入上述混合物中，60～90℃下回流，经McMurry偶联反应，制备4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺(化合物1)，合成路线如下：
步骤2，氮气保护下，在1,4-二氧六环和水存在下，将4-溴-N,N-双(4-(E)-2-(芳环-2-基)乙烯基)苯基)苯胺(化合物1)和2-甲酰基呋喃-5-硼酸、催化剂四(三苯基膦)钯、碳酸钾混合，90～110℃下回流，发生Suzuki偶联反应制备5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛(化合物2)，合成路线如下：
步骤3，氮气保护下，在甲苯和冰醋酸存在下，将5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛、氰基乙酸和醋酸铵混合，95～115℃下回流，经Knoevenagel反应制备目标产物(E)-3-(5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸(化合物FWD)，合成路线如下：
进一步地，步骤1中，所述的4,4'-((4-溴苯基)氮杂二基)二苯甲醛与2-芳醛、TiCl4、锌粉的摩尔比为1:4:12.5:25。
进一步地，步骤1中，所述的反应时间为4～6h。
进一步地，步骤1中，所述的4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺为4-溴-N,N-双(4-(E)-2-(呋喃-2-基)乙烯基)苯基)苯胺或4-溴-N,N-双(4-(E)-2-(噻吩-2-基)乙烯基)苯基)苯胺。
进一步地，步骤2中，所述的4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺和2-甲酰基呋喃-5-硼酸、四(三苯基膦)钯、碳酸钾的摩尔比为1:1.2:0.05:11.5。
进一步地，步骤2中，所述的催化剂四(三苯基膦)钯的摩尔量是4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺的5％。
进一步地，步骤2中，所述的5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛为5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛或5-(4-(双(4-((E)-2-(噻吩-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛。
进一步地，步骤2中，所述的反应时间为12～16h。
进一步地，步骤3中，所述的5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛与氰基乙酸以及醋酸铵的摩尔比为1:2:2.4。
进一步地，步骤3中，所述的反应时间为4～8h。
进一步地，步骤3中，目标产物通过以下步骤进行后处理：反应完全后，向反应物中加入水，用CH2Cl2萃取，有机相用饱和NaCl溶液洗涤，有机层用无水Na2SO4干燥并旋转蒸发，CH2Cl2/CH3OH作洗脱剂，柱层析得到双(芳基乙烯基)苯胺类有机染料。
与现有技术相比，本发明具有以下优点：
本发明合成路线短，生产成本较低，价格低廉，能合成较高产率的目标产物。本发明用呋喃基或噻吩基取代双(芳基乙烯基)苯胺(BSPA)的苯基，测试结果显示呋喃基和噻吩基均为良好的供电子基团，且噻吩基的能量转换效率更高，以其作为敏化剂制成的DSSCS的能量转换效率高达6.01％。
附图说明
图1为基于双(芳基乙烯基)苯胺类染料的DSSCs的J-V曲线。
具体实施方式
下面结合实施例和附图对本发明作进一步详述。
本实施例的染料的合成路线如下：
实施例1
4-溴-N,N-双(4-(E)-2-(呋喃-2-基)乙烯基)苯基)苯胺(化合物1a)的合成：向烧瓶中加入Zn(975mg，15mmol)和THF(40mL)，然后在-5～0℃逐滴加入TiCl4(0.82mL，7.5mmol)，并将混合物在室温下搅拌30分钟。然后将混合物回流2.5小时并再次冷却至-5～0℃。将2-糠醛(0.2mL，2.4mmol)与4,4'–((4-溴苯基)氮杂二基)二苯甲醛(226.8mg，0.6mmol)和THF(13mL)加入混合物中，并将混合物再次回流4小时后用10％NaHCO3水溶液)淬灭反应。过滤后，滤液用二氯甲烷萃取。收集有机相并用无水硫酸钠干燥。使用旋转蒸发器蒸发有机溶剂。通过柱色谱(SiO 2；洗脱液，PE/CH2Cl2＝7：1)纯化后，得到1a，为浅黄色粉末(99.2mg，32.6％)。Mp:154.4～156.1℃.1H NMR(500MHz,CDCl3)δ(ppm):7.35-7.40(m,8H),7.04(d,J＝8.0Hz,4H),6.97-7.00(m,4H),6.81(d,J＝16.0Hz,2H),6.42(m,2H),6.33(d,J＝3.0Hz,2H)；13C NMR(126MHz,CDCl3)δ(ppm):153.35,146.32,141.93,132.27,132.03,127.29,126.37,125.71,124.09,115.51,115.42,111.61,108.17.
5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛(化合物2a)的合成：向烧瓶中加入1a(289.8mg，0.57mmol)，2-甲酰基呋喃-5-硼酸(95.70mg，0.68mmol)，Pd(PPh 3)4(32.9mg，0.029mmol)，K 2CO3(943.4mg，6.83mmol)。)，1,4-二氧六环(5.5mL)和水0.8mL)，将混合物在99℃搅拌过夜。冷却至室温后，过滤反应混合物。然后将滤液倒入水中并用二氯甲烷萃取3次。收集有机相并用无水硫酸钠干燥。使用旋转蒸发器蒸发有机溶剂。通过柱色谱(SiO2；洗脱液，PE/CH2Cl2＝1：1)纯化后，得到2a，为橙色粉末(120.2mg，40.3％)。Mp:87.4～89.1℃.1H NMR(500MHz,CDCl3)δ(ppm):9.61(s,1H),7.69(d,J＝8.5Hz,2H),7.38-7.40(m,6H),7.31(d,J＝3.5Hz,1H),7.14(d,J＝9.0Hz,2H),7.10(d,J＝8.5Hz,4H),7.00(d,J＝16.0Hz,2H),6.83(d,J＝16.5Hz,2H),6.74(d,J＝3.5Hz,1H),6.42-6.43(m,2H),6.34(d,J＝3.5Hz,2H)；13C NMR(126MHz,CDCl3)δ(ppm):176.81,159.62,153.33,151.67,148.59,145.98,142.02,132.70,127.37,126.44,126.30,124.90,122.95,122.75,115.74,111.64,108.32,106.65。
(E)-3-(5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸(化合物FWD7)的合成：向烧瓶中加入2a(94.3mg，0.18mmol)，氰基乙酸(29.0mg，0.34mmol)，CH3COONH4(33.3mg，0.43mmol)，乙酸(4.8mL)和甲苯(6mL)，并且混合物回流5小时。冷却后，将混合物用二氯甲烷萃取3次。收集有机相并用无水硫酸钠干燥。使用旋转蒸发器蒸发有机溶剂。通过柱色谱(SiO2；洗脱液，CH2Cl2/CH3OH＝25：1)纯化后，得到FWD7，为红色粉末(97.7mg，91.9％)。Mp:159.8～161.2℃.1H NMR(500MHz,DMSO-d6)δ(ppm):8.00(s,1H),7.82(d,J＝8.5Hz,2H),7.68(s,2H),7.55(d,J＝8.0Hz,4H),7.50(d,J＝3.5Hz,1H),7.23(d,J＝3.5Hz,1H),7.03-7.10(m,8H),6.97(d,J＝16.5Hz,2H),6.53-6.54(m,4H)；13C NMR(126MHz,CDCl3)δ(ppm):168.11,160.94,153.35,148.96,147.35,145.78,142.03,138.47,132.95,127.41,126.76,126.32,125.14,122.61,122.04,115.86,111.64,108.36,94.95.HRMS(ESI–)m/z:calcd for[M–COOH]–C37H25N2O3 –:545.1871,found:545.1862。
实施例2
4-溴-N,N-双(4-(E)-2-(噻吩-2-基)乙烯基)苯基)苯胺(化合物1b)的合成：向烧瓶中加入Zn(1033mg，16mmol)和THF(29mL)，然后在-5～0℃逐滴加入TiCl4(0.84mL，8mmol)并将混合物在室温下搅拌30分钟。分钟。然后将混合物回流2.5小时并再次冷却至-5～0℃。将2-噻吩甲醛(0.25mL，2.7mmol)，4,4'–((4-溴苯基)氮杂二基)二苯甲醛(200.0mg，0.53mmol)和THF(10mL)加入混合物中，并将混合物再次回流用于4小时用10％NaHCO3水溶液淬灭反应。过滤后，滤液用二氯甲烷萃取。收集有机相并用无水硫酸钠干燥。使用旋转蒸发器蒸发有机溶剂。用柱色谱(SiO2；洗脱液，PE/CH2Cl2＝7：1)纯化后，得到浅黄色粉末状的1b(72.3mg，25.3％)。Mp:185.8～187.6℃.1H NMR(500MHz,CDCl3)δ(ppm):7.35-7.37(m,6H),7.18(d,J＝5.0Hz,2H),7.15(d,J＝16.0Hz,2H),7.04-7.05(m,6H),6.99-7.01(m,4H),6.88(d,J＝3.0Hz,2H)；13C NMR(126MHz,CDCl3)δ(ppm):146.40,143.07,132.32,132.05,127.60,127.30,125.74,124.16,124.05,120.73,115.60。
5-(4-(双(4-((E)-2-(噻吩-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛(化合物2b)的合成：向烧瓶中加入1b(380.0mg，0.72mmol)，2-甲酰基呋喃-5-硼酸(119.21mg，0.86mmol)，Pd(PPh 3)4(41.0mg，0.036mmol)，K2CO3(1175mg，8.5mmol)。1,4-二氧六环(6.8mL)和水(1.0mL)，将混合物在99℃搅拌过夜。冷却至室温后，过滤反应混合物。然后将滤液倒入水中并用二氯甲烷萃取3次。收集有机相并用无水硫酸钠干燥。使用旋转蒸发器蒸发有机溶剂。通过柱色谱(SiO2；洗脱液，PE/CH2Cl2＝1：1)纯化后，得到2b，为橙色粉末(131.6mg，32.9％)。.Mp:93.1～94.6℃.1H NMR(500MHz,CDCl3)δ(ppm):9.61(s,1H),7.69(d,J＝9.0Hz,2H),7.39(d,J＝8.5Hz,4H),7.31(d,J＝3.5Hz,1H),7.18-7.19(m,3H),7.13-7.15(m,3H),7.10(d,J＝8.5Hz,4H),7.06(d,J＝3.0Hz,2H),7.00-7.01(m,2H),6.90(d,J＝16.0Hz,2H),6.74(d,J＝4.0Hz,1H)；13C NMR(126MHz,CDCl3)δ(ppm):176.78,159.59,151.71,148.57,146.01,142.99,132.65,127.59,127.53,127.37,126.46,125.84,124.92,124.16,122.99,122.82,121.03,106.66.
(E)-3-(5-(4-(双(4-((E)-2-(噻吩-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸(化合物FWD8)的合成：向烧瓶中加入2b(130.2mg，0.23mmol)，氰基乙酸(37.8mg，0.45mmol)，CH3COONH4(43.3mg，0.56mmol)，乙酸(6.4mL)和甲苯(8mL)，并且混合物回流5小时。冷却后，将混合物用二氯甲烷萃取3次。收集有机相并用无水硫酸钠干燥。使用旋转蒸发器蒸发有机溶剂。用柱色谱(SiO2；洗脱液，CH2Cl2/CH3OH＝25：1)纯化后，得到FWD8，为红色粉末(129.1mg，88.7％)。Mp:170.9～172.8℃.1H NMR(500MHz,DMSO-d6)δ(ppm):7.94(s,1H),7.82(d,J＝8.5Hz,2H),7.56(d,J＝8.5Hz,4H),7.45(d,J＝5.0Hz,2H),7.43(d,J＝3.5Hz,1H),7.38(d,J＝16.0Hz,2H),7.20(m,3H),7.05-7.10(m,8H),6.93(d,J＝16.5Hz,2H)；13C NMR(126MHz,DMSO-d6)δ(ppm):163.93,147.87,147.60,145.51,142.54,132.47,128.02,127.71,127.07,126.51,126.30,125.10,124.71,122.75,121.21,108.83.HRMS(ESI–)m/z:calcd for[M–COOH]–C37H25N2OS2 –:577.1414,found:577.1418。
FWD7与FWD8染料的光电性能
表1为染料FWD7和FWD8的DSSCs的光伏性能参数
图1为FWD7和FWD8的CV曲线，曲线2和3为FWD7，曲线1和4为FWD8。从图1和表1可以看出，基于染料FWD7和FWD8的DSSCs的电流短路密度(Jsc)分别为9.88mA/cm-2，11.59mA/cm-2，开路电压(Voc)则分别为0.69V，0.75V，填充因子(FF)为0.72、0.72。通过计算得到这两种染料的能量转换效率分别为4.89％、6.01％。与FWD7相比，FWD8显示出更强的响应，导致其具有更高的JSC值，因此具有更高的η值。
综上所述，呋喃基和噻吩基作为优异的电子供体，在同样的合成方法及测试环境下，以2-呋喃基与2-噻吩基(上述AR基团)作为电子供体合成双(芳基乙烯基)苯胺类有机染料，其作为敏化剂制成的DSSCS可以得到相近甚至更高的光电转化效率。
Claims (10)
1.双(芳基乙烯基)苯胺类有机染料，化学结构通式如下所示：
式中，AR为电子供体，所述的AR基选自
2.根据权利要求1所述的双(芳基乙烯基)苯胺类有机染料，其特征在于，所述的双(芳基乙烯基)苯胺类有机染料敏化剂为(E)-3-(5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸或(E)-3-(5-(4-(双(4-((E)-2-(噻吩-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸。
3.根据权利要求1或2所述的双(芳基乙烯基)苯胺类有机染料的制备方法，其特征在于，包括如下步骤：
步骤1，氮气保护下，将锌粉加入THF中，-5～0℃下逐滴加入TiCl4，60～80℃下回流，将4,4'–((4-溴苯基)氮杂二基)二苯甲醛与2-芳醛和THF加入上述混合物中，60～90℃下回流，经McMurry偶联反应，制备4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺，合成路线如下：
步骤2，氮气保护下，在1,4-二氧六环和水存在下，将4-溴-N,N-双(4-(E)-2-(芳环-2-基)乙烯基)苯基)苯胺和2-甲酰基呋喃-5-硼酸、催化剂四(三苯基膦)钯、碳酸钾混合，90～110℃下回流，发生Suzuki偶联反应制备5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛，合成路线如下：
步骤3，氮气保护下，在甲苯和冰醋酸存在下，将5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛、氰基乙酸和醋酸铵混合，95～115℃下回流，经Knoevenagel反应制备目标产物(E)-3-(5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-基)-2-氰基丙烯酸，合成路线如下：
4.根据权利要求3所述的制备方法，其特征在于，步骤1中，所述的4,4'-((4-溴苯基)氮杂二基)二苯甲醛与2-芳醛、TiCl4、锌粉的摩尔比为1:4:12.5:25；所述的反应时间为4～6h。
5.根据权利要求3所述的制备方法，其特征在于，步骤1中，所述的4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺为4-溴-N,N-双(4-(E)-2-(呋喃-2-基)乙烯基)苯基)苯胺或4-溴-N,N-双(4-(E)-2-(噻吩-2-基)乙烯基)苯基)苯胺。
6.根据权利要求3所述的制备方法，其特征在于，步骤2中，所述的4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺和2-甲酰基呋喃-5-硼酸、四(三苯基膦)钯、碳酸钾的摩尔比为1:1.2:0.05:11.5；所述的催化剂四(三苯基膦)钯的摩尔量是4-溴-N,N-双(4-(E)-2-(芳基乙烯基)苯基)苯胺的5％；所述的反应时间为12～16h。
7.根据权利要求3所述的制备方法，其特征在于，步骤2中，所述的5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛为5-(4-(双(4-((E)-2-(呋喃-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛或5-(4-(双(4-((E)-2-(噻吩-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛。
8.根据权利要求3所述的制备方法，其特征在于，步骤3中，所述的5-(4-(双(4-((E)-2-(芳环-2-基)乙烯基)苯基)氨基)苯基)呋喃-2-甲醛与氰基乙酸以及醋酸铵的摩尔比为1:2:2.4；所述的反应时间为4～8h。
9.根据权利要求3所述的制备方法，其特征在于，步骤3中，目标产物通过以下步骤进行后处理：反应完全后，向反应物中加入水，用CH2Cl2萃取，有机相用饱和NaCl溶液洗涤，有机层用无水Na2SO4干燥并旋转蒸发，CH2Cl2/CH3OH作洗脱剂，柱层析得到双(芳基乙烯基)苯胺类有机染料。
10.根据权利要求1或2所述的双(芳基乙烯基)苯胺类有机染料在制备染料敏化太阳能电池中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910676410.0A CN110407781A (zh) | 2019-07-25 | 2019-07-25 | 双（芳基乙烯基）苯胺类有机染料及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910676410.0A CN110407781A (zh) | 2019-07-25 | 2019-07-25 | 双（芳基乙烯基）苯胺类有机染料及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110407781A true CN110407781A (zh) | 2019-11-05 |
Family
ID=68363134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910676410.0A Pending CN110407781A (zh) | 2019-07-25 | 2019-07-25 | 双（芳基乙烯基）苯胺类有机染料及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110407781A (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003903A (zh) * | 2010-06-29 | 2013-03-27 | 迪纳莫公司 | 高效率染料敏化太阳能电池 |
| CN106831748A (zh) * | 2016-12-14 | 2017-06-13 | 浙江工业大学上虞研究院有限公司 | 三芳胺类化合物及其制备方法、在制备太阳能电池上的应用 |
-
2019
- 2019-07-25 CN CN201910676410.0A patent/CN110407781A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003903A (zh) * | 2010-06-29 | 2013-03-27 | 迪纳莫公司 | 高效率染料敏化太阳能电池 |
| CN106831748A (zh) * | 2016-12-14 | 2017-06-13 | 浙江工业大学上虞研究院有限公司 | 三芳胺类化合物及其制备方法、在制备太阳能电池上的应用 |
Non-Patent Citations (4)
| Title |
|---|
| BONNIER, CATHERINE 等: "The effect of donor-modification in organic light-harvesting motifs: triphenylamine donors appended with polymerizable thienyl subunits", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| HEIRTZLER, FENTON R. 等: "Cyclophanes. XL. On the preparation of conjugated polyenes with [2.2.2]paracyclophanyl end groups", 《LIEBIGS ANNALEN》 * |
| MATEUSZ WIELOPOLSKI 等: "Position-Dependent Extension of π ‑ Conjugation in D‑ π‑ A Dye Sensitizers and the Impact on the Charge-Transfer Properties", 《THE JOURNAL OF PHYSICAL CHEMISTRY》 * |
| YING, XINTONG 等: "Low-cost, high-efficiency, and efficiency predictable small molecule organic dyes with bis(4-styryl)phenyl amino donor for dye-sensitized solar cells", 《SOLAR RRL》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109666033B (zh) | 基于九并稠杂环类共轭小分子及其制备方法与应用 | |
| CN107652304B (zh) | 一种稠环非富勒烯受体材料及其制备方法与应用 | |
| CN101525334B (zh) | 一种有机太阳能电池材料及其制备 | |
| CN105949814B (zh) | 一类吩噻嗪衍生物、制备方法及其在染料敏化太阳能电池中的应用 | |
| CN103130812B (zh) | 一种吲哚并[3,2,1-jk]咔唑衍生物及其制备方法和应用 | |
| CN109694464A (zh) | 一种n型有机半导体材料及其制备方法和应用 | |
| CN106188506A (zh) | 一类含8‑羟基喹啉衍生物合Cu(II)的聚合金属配合物染料敏化剂及其制备方法 | |
| CN110606856A (zh) | 基于3-烷基并噻吩的七并稠杂环类共轭小分子及其制备方法与应用 | |
| KR20200026162A (ko) | 유기 반도전성 물질 및 이의 합성 및 이러한 물질을 갖는 유기 반도전성 부품 | |
| CN109517142B (zh) | 基于三茚并五元芳杂环的星型d-a结构共轭分子及其制备方法和应用 | |
| CN110423486A (zh) | 三苯胺类有机染料及其合成方法 | |
| CN103304568B (zh) | 三聚吲哚类化合物及其制备方法和用途 | |
| CN106008929A (zh) | 一种含邻苯二胺衍生物合Cd(Ⅱ)的聚合配合物染料敏化剂及其制备方法 | |
| CN111138389B (zh) | 以呋喃衍生物为π桥的脱氢枞酸三芳胺基D-π-A型化合物及其合成方法 | |
| CN108503669A (zh) | 一种高效二芳基乙烯光控开关分子及其制备方法 | |
| CN110407781A (zh) | 双（芳基乙烯基）苯胺类有机染料及其制备方法 | |
| CN106565753B (zh) | 一种富勒烯衍生物、制备方法和应用 | |
| CN106810898B (zh) | 吡咯二硫酮修饰的三苯胺类有机染料敏化剂及其应用 | |
| CN107446373B (zh) | 用于染料敏化太阳能电池的小分子有机染料 | |
| CN108503654A (zh) | 噻吩并吡咯二酮修饰的硫脲三苯胺类染料敏化剂 | |
| CN101676259A (zh) | 镍催化的溴代芳烃与二芳胺偶联反应合成三芳胺的方法 | |
| CN103834190A (zh) | 含苯并噻二唑-氰基苯丙烯酸受体的有机染料及在染料敏化太阳电池中的应用 | |
| CN103601741B (zh) | 一种2,1,3-苯并噻二唑并二噻吩衍生物及其合成方法 | |
| CN102924463B (zh) | 多锚自组装卟啉及其合成方法 | |
| CN105037167A (zh) | 一种n,n-二芳基-2-溴-6-萘胺的合成方法及其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191105 |