CN116217560A - N, N-diethylaminocoumarin compound and preparation method and application thereof - Google Patents
N, N-diethylaminocoumarin compound and preparation method and application thereof Download PDFInfo
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- -1 N, N-diethylaminocoumarin compound Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003480 eluent Substances 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 4
- 206010070834 Sensitisation Diseases 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract description 2
- SMBSZJBWYCGCJP-UHFFFAOYSA-N 3-(diethylamino)chromen-2-one Chemical compound C1=CC=C2OC(=O)C(N(CC)CC)=CC2=C1 SMBSZJBWYCGCJP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 229930192474 thiophene Natural products 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 3
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 2
- JUWYQISLQJRRNT-UHFFFAOYSA-N (5-formylfuran-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)O1 JUWYQISLQJRRNT-UHFFFAOYSA-N 0.000 description 2
- DEQOVKFWRPOPQP-UHFFFAOYSA-N (5-formylthiophen-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)S1 DEQOVKFWRPOPQP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 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 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- H01G9/2063—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution comprising a mixture of two or more dyes
-
- 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
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/02—Coumarine dyes
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses an N, N-diethylaminocoumarin compound, a preparation method and application thereof, wherein the molecular structure of the N, N-diethylaminocoumarin compound is shown as a formula (C-4), a formula (C-5) or a formula (C-6);
Description
Technical Field
The invention relates to an N, N-diethylaminocoumarin compound, a preparation method and application thereof.
Background
Dye-sensitized solar cells (Dye-sensitized solar cells, DSSCs) have received attention because of their low production cost, simple manufacturing process, and the like. The dye sensitizer is used as a key component of the DSSCs, plays roles in absorbing light and generating electrons, and determines the photoelectric performance of the DSSCs.
Currently, single dye has a weak light capturing capability and the highest photoelectric conversion efficiency of single dye-based DSSCs has been difficult to break through. To overcome these problems, more and more researchers have focused on co-sensitization. The organic dye and the metallic dye are co-sensitized, so that the spectrum absorption range can be widened, the molar extinction coefficient can be improved, and the ideal dye co-sensitization effect is that the absorption spectrum of the two dyes can reach full-color absorption complementation, and the light capturing capacity of the dye can be improved, so that the photoelectric performance of DSSCs is improved.
Disclosure of Invention
The invention aims to provide an N, N-diethylaminocoumarin compound, a preparation method and application thereof, wherein the N, N-diethylaminocoumarin compound can be used as a dye sensitizer to be co-sensitized with a classical metal sensitizer Z907, and the assembled dye-sensitized solar cell has good photoelectric conversion efficiency, so that a new applicable substance is added for screening the dye sensitizer.
The invention discloses an N, N-diethylaminocoumarin compound, which comprises three compounds with the following structures, wherein the molecular structures of the three compounds are shown as a formula (C-4), a formula (C-5) or a formula (C-6);
the invention also discloses a preparation method of the N, N-diethylaminocoumarin compound, which specifically comprises the following steps: dissolving a compound shown in a formula (II-1), a formula (II-2) or a formula (II-3) and cyanoacetic acid in a solvent, adding an alkaline substance, heating, refluxing and stirring under the protection of nitrogen atmosphere, concentrating a reaction solution after the reaction is finished to remove the solvent, dissolving the obtained concentrate in an eluent, separating and purifying the eluent by column chromatography silica gel, collecting the eluent, and steaming the eluent to obtain a target product;
the structural formulas of the compounds represented by the formula (II-1), the formula (II-2) and the formula (II-3) are as follows:
further, the invention also discloses a heating reflux stirring reaction time of 8-12h.
Furthermore, the invention also discloses a mixed solvent consisting of chloroform and acetonitrile, wherein the volume ratio of the chloroform to the acetonitrile is 1:1-3, and is preferably 1:2.
Furthermore, the invention also discloses a mixed solvent of dichloromethane and methanol as an eluent, wherein the volume ratio of the dichloromethane to the methanol is 10-30:1, and preferably 20:1.
Furthermore, the invention also discloses a compound shown in the formula (II-1), the formula (II-2) or the formula (II-3), wherein the molar ratio of the cyanoacetic acid to the alkaline substance is 1:2-4:8-12, preferably 1:3:10.
Furthermore, the invention also discloses that the alkaline substance is piperidine.
Further, the invention also discloses a ratio of the amount of the substance of the compound shown in the formula (II-1), the formula (II-2) or the formula (II-3) to the volume of the solvent is 1:30-60, the unit of the amount of the substance is mmol, and the unit of the volume is mL.
Further, the invention also discloses a synthesis method of the compound shown in the formula (II-1), the formula (II-2) or the formula (II-3), which comprises the following steps:
adding 3- (5-bromo-thiophene-2-yl) -7-N, N-diethylaminocoumarin, tetraphenylphosphine palladium and potassium carbonate into a Schlenk tube, adding any one of 5-formyl-2-thiopheneboronic acid, 5-formyl-2-furanboronic acid and 4-formylphenylboronic acid into the Schlenk tube, adding tetrahydrofuran and water under the protection of nitrogen, heating and refluxing for reaction, cooling to room temperature after the reaction is finished, pouring the reaction solution into water, extracting with dichloromethane, washing with saturated saline water, drying an organic phase with anhydrous sodium sulfate, and spin-drying the solvent; the residue was purified by column chromatography to give a compound represented by the formula (II-1), the formula (II-2) or the formula (II-3).
Further, the invention also discloses a method for synthesizing the compound shown in the formula (II-1), the formula (II-2) or the formula (II-3), wherein the eluent is petroleum ether and methylene dichloride with the volume ratio of 1:1, and the column chromatography separation process comprises the following steps: separating and purifying the concentrate by column chromatography silica gel after dissolving the concentrate in the eluent, collecting the eluent, evaporating the eluent, and drying to obtain a solid powder product.
Furthermore, the invention also discloses application of the N, N-diethylaminocoumarin compound in dye sensitizers.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects: according to the invention, the N, N-diethylaminocoumarin compound is synthesized by taking N, N-diethylaminocoumarin as a donor, thiophene, furan and benzene ring of bithiophene as bridge bonds and cyanoacetic acid as a receptor, and can be used as a dye sensitizer to be sensitized together with a classical metal sensitizer Z907, and the dye-sensitized solar cell assembled by the compound as the dye sensitizer and the Z907 has good photoelectric conversion efficiency, so that a new applicable substance is added for screening the dye sensitizer.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1 synthesis of a compound of formula (C-4):
1) Synthesis of Compound represented by the formula (II-1)
3- (5-bromo-thiophen-2-yl) -7-N, N-diethylaminocoumarin (0.8 mmol), 5-formyl-2-thiopheneboronic acid (1.6 mmol), tetraphenylphosphine palladium (0.04 mmol) and potassium carbonate (4.0 mmol) were weighed into a Schlenk tube, tetrahydrofuran (12 mL) and water (2 mL) were added under nitrogen protection, and the mixture was heated to reflux and reacted for 12 hours. After the reaction solution was cooled, it was poured into water, extracted with methylene chloride several times, and the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and dried with a solvent by spin-drying. The residue was purified by column chromatography to give red solid II-10.14g in 42.7% yield.
Wherein the eluent is petroleum ether and methylene dichloride with the volume ratio of 1:1, and the column chromatography separation process comprises the following steps: the concentrate is dissolved in an eluent and then separated and purified by column chromatography on silica gel, the eluent is collected and distilled off, and the solid powder product is obtained by drying, the steps of examples 2 and 3 are equivalent.
A compound represented by the formula (II-1): melting point: 209-211 ℃. 1 H NMR(500MHz,CDCl 3 )δ9.87(s,1H),7.96(s,1H),7.69(d,J＝3.9Hz,1H),7.57(d,J＝4.0Hz,1H),7.40-7.35(m,2H),7.31(d,J＝3.9Hz,1H),6.65(dd,J＝8.8,2.4Hz,1H),6.56(d,J＝2.2Hz,1H),3.46(q,J＝7.0Hz,4H),1.25(t,J＝7.0Hz,6H).HRMS(ESI)m/z calcd for C 22 H 20 NO 3 S 2 + (M+H) + 410.0885,found410.0881.
2) Synthesis of Compound of formula (C-4):
to the Schlemk tube were added compound II-1 (0.3 mmol) and cyanoacetic acid (0.6 mmol), chloroform (3 mL) and acetonitrile (6 mL) were added under nitrogen protection, and piperidine (0.24 mL) was slowly added dropwise, and the mixture was heated under reflux for 12h. After the reaction was completed, the solvent was removed. The residue was purified by column chromatography (V DCM :V MeOH =20:1) to afford C-40.07g as a dark red solid in 48.9% yield.
A compound represented by the formula (C-4): melting point: 60-63 ℃. 1 H NMR(500MHz,DMSO)δ8.54(s,1H),7.96(s,1H),7.79(d,J＝4.1Hz,1H),7.63(d,J＝4.0Hz,1H),7.55(d,J＝9.0Hz,1H),7.49(d,J＝3.8Hz,1H),7.14(d,J＝3.8Hz,1H),6.80(dd,J＝9.0,2.4Hz,1H),6.63(d,J＝2.3Hz,1H),3.47(q,J＝7.0Hz,4H),1.15(t,J＝7.0Hz,6H).HRMS(ESI)m/z calcd for C 25 H 21 N 2 O 4 S 2 + (M+H) + 477.0943,found 477.0939.
Example 2 synthesis of a compound of formula (C-5):
1) Synthesis of Compound represented by the formula (II-2)
3- (5-bromo-thiophen-2-yl) -7-N, N-diethylaminocoumarin (0.8 mmol), 5-formyl-2-furanboronic acid (1.6 mmol), tetrakis triphenylphosphine palladium (0.04 mmol) and potassium carbonate (4.0 mmol) were weighed into a Schlenk tube, tetrahydrofuran (12 mL) and water (2 mL) were added under nitrogen protection, and the mixture was heated to reflux at elevated temperature and reacted for 12h. After the reaction solution was cooled, it was poured into water, extracted with methylene chloride several times, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was dried by spin-drying. The residue was purified by column chromatography (V PE :V DCM =1:1) to give red solid II-20.18g in 57.2% yield.
A compound represented by the formula (II-2): melting point: 150-153 ℃. 1 H NMR(500MHz,DMSO)δ9.56(s,1H),8.55(s,1H),7.77(d,J＝4.1Hz,1H),7.68(d,J＝4.1Hz,1H),7.65(d,J＝3.8Hz,1H),7.53(d,J＝9.0Hz,1H),7.10(d,J＝3.7Hz,1H),6.80(dd,J＝9.0,2.4Hz,1H),6.61(d,J＝2.3Hz,1H),3.47(q,J＝7.0Hz,4H),1.15(t,J＝7.0Hz,6H).HRMS(ESI)m/z calcd for C 22 H 20 NO 4 S + (M+H) + 394.1113,found 394.1114.
2) Synthesis of Compound represented by the formula (C-5)
Compound II-2 (0.3 mmol) and cyanoacetic acid (0.9 mmol) were added to the Schlenk tube, and a mixed solution of chloroform (5 mL) and acetonitrile (10 mL) was added under nitrogen protection, followed by dropwise addition of 0.3mL piperidine slowly, and the reaction was heated under reflux for 10h. Spin-drying and dissolving after the reaction is finishedAnd (3) an agent. The residue was purified by column chromatography (V DCM :V MeOH =20:1) to afford C-50.10g as a dark red solid in 72.5% yield.
A compound represented by the formula (C-5): melting point: 225-227 ℃. 1 H NMR(500MHz,DMSO)δ8.48(s,1H),7.73(d,J＝4.0Hz,1H),7.68(s,1H),7.54(d,J＝9.0Hz,1H),7.52(d,J＝4.0Hz,1H),7.20(d,J＝3.7Hz,1H),6.99(d,J＝3.7Hz,1H),6.78(dd,J＝9.0,2.3Hz,1H),6.60(d,J＝2.1Hz,1H),3.45(q,J＝7.0Hz,4H),1.14(t,J＝7.0Hz,6H).HRMS(ESI)m/z calcd for C 25 H 21 N 2 O 5 S + (M+H) + 461.1171,found 461.1167.
Example 3 Synthesis of Compound of formula (C-6):
1) Synthesis of Compound represented by the formula (II-3)
3- (5-bromo-thiophen-2 yl) -7-N, N-diethylaminocoumarin (0.8 mmol), 4-formylphenylboronic acid (1.6 mmol), tetraphenylphosphine palladium (0.04 mmol) and potassium carbonate (4.0 mmol) were weighed into a Schlenk tube, tetrahydrofuran (10 mL) and water (2 mL) were added under nitrogen protection, and the mixture was heated to reflux at elevated temperature and reacted for 12h. After the reaction solution was cooled, it was poured into water, extracted with methylene chloride several times, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was dried by spin-drying. The residue was purified by column chromatography (V PE :V DCM =1:1) to yield orange-red solid II-30.17g in 52.7% yield.
A compound represented by the formula (II-3): melting point: 153-155 ℃. 1 H NMR(500MHz,CDCl 3 )δ10.01(s,1H),7.95(s,1H),7.89(d,J＝7.5Hz,2H),7.81(d,J＝8.3Hz,2H),7.66(d,J＝4.0Hz,1H),7.47(t,J＝5.6Hz,1H),7.36(d,J＝8.8Hz,1H),6.67(d,J＝8.6Hz,1H),6.58(d,J＝1.5Hz,1H),3.46(q,J＝7.1Hz,4H),1.25(t,J＝7.3Hz,6H).HRMS(ESI)m/z calcd for C 24 H 22 NO 3 S + (M+H) + 404.1320,found404.1317.
2) Synthesis of Compound represented by the formula (C-6)
Compound II-3 (0.3 mmol) and cyanoacetic acid (0.12 mmol) were weighed, chloroform (6 mL) and acetonitrile (12 mL) were then added under nitrogen protection, piperidine (0.36 mL) was slowly added dropwise, and the mixture was heated to 80℃for reaction for 8h. After the reaction solution was cooled, the solvent was removed. The residue was purified by column chromatography (V DCM :V MeOH =20:1) to give red solid C-60.08g in 56.6% yield.
A compound represented by the formula (C-6): melting point: 208-211 ℃. 1 H NMR(500MHz,DMSO)δ8.51(s,1H),8.27(s,1H),8.08(d,J＝8.6Hz,2H),7.89(d,J＝8.5Hz,2H),7.80-7.75(m,2H),7.55(d,J＝9.0Hz,1H),6.81(dd,J＝9.0,2.4Hz,1H),6.63(d,J＝2.3Hz,1H),3.48(q,J＝7.0Hz,4H),1.16(t,J＝7.0Hz,6H).HRMS(ESI)m/z calcd for C 27 H 23 N 2 O 4 S + (M+H) + 471.1379,found471.1382.
Example 4 use of n, n-diethylaminocoumarin-based compounds as dye sensitizers:
when used as a dye sensitizer, the application comprises the steps of:
dissolving N, N-diethylaminocoumarin compound and dye Z907 in CH 3 Cl-CH 3 In OH mixed solvent to obtain mixed solution of N, N-diethylaminocoumarin compound and Z907 (concentration of N, N-diethylaminocoumarin compound is 2×10) -4 mol·L -1 The method comprises the steps of carrying out a first treatment on the surface of the Z907 concentration is 3×10 -4 mol·L -1 ) The method comprises the steps of carrying out a first treatment on the surface of the The CH is 3 Cl-CH 3 CH in OH mixed solvent 3 Cl and CH 3 The volume ratio of OH was 10:1.
Double-layer TiO prepared by screen printing 2 Nanoparticle films as photoelectrodes: first, a layer of TiO with the thickness of 12 mu m and the thickness of 20nm is printed on the conductive glass FTO 2 Calcining the particles in a muffle furnace at 450 ℃ for 30min, cooling the calcined film to room temperature, and immersing the calcined film in 0.04 mol.L -1 TiCl of (2) 4 The aqueous solution was pretreated for 30min at 70℃and the film was then removed from TiCl 4 Taking out the water solution, washing with water and ethanol respectively, and drying with electric hair drier. Calcining again at 450 ℃ for 30min in a muffle furnace to obtain the double-layer TiO 2 Nanoparticle film photoelectrodes.
Double-layer TiO obtained by calcining 2 Cooling the nanoparticle film photoelectrode to 80 ℃, immersing the nanoparticle film photoelectrode in the mixed solution of the N, N-diethylaminocoumarin compound and the Z907, and sensitizing the nanoparticle film photoelectrode at room temperature for 24 hours to obtain TiO loaded with the N, N-diethylaminocoumarin compound and the Z907 compound 2 An electrode.
Preparation of a platinum counter electrode: screen printing method is adopted to print H 2 PtCl 6 Printing aqueous solution on FTO conductive glass, H 2 PtCl 6 Wetting the surface of the FTO conductive glass with the aqueous solution, drying, and sintering for 20min at 400 ℃ in a muffle furnace to obtain the platinum counter electrode.
The prepared double-layer TiO is prepared 2 The nanoparticle membrane photoelectrode and the platinum counter electrode are assembled into a sandwich structure, and electrolyte (containing 0.07mmol/L I) is dripped into the edge of the sandwich structure - The electrolyte is from Yingkou epirelief new energy science and technology Co., ltd.), is introduced into the cell by capillary permeation principle, and is assembled to form the dye sensitized solar cell, the dye sensitized solar cell is manufactured at a power of 100mW/cm 2 Under the light intensity irradiation, the current-voltage curve of the DSSC obtained by assembling the N, N-diethylaminocoumarin compound and the Z907 is measured, and the performance parameter results are shown in table 1:
TABLE 1 DSSC Performance parameters obtained by assembling N, N-diethylaminocoumarin Compounds
As can be seen from table 1: the dye-sensitized solar cell assembled by the N, N-diethylaminocoumarin compound and Z907 serving as the dye sensitizer has good photoelectric conversion efficiency, the photoelectric conversion efficiency is 5.97-6.77%, most of the solar cells are higher than those of the solar cells sensitized by Z907 alone, and a new applicable substance is added for screening the co-sensitizer of Z907.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept, and the scope of protection of the present invention should not be construed as limited to the specific forms set forth in the examples, nor is it intended that the scope of protection of the present invention be limited to only equivalent technical means as would occur to those skilled in the art based on the inventive concept.
Claims (9)
- The N, N-diethylaminocoumarin compound is characterized in that the molecular structure is shown as a formula (C-4), a formula (C-5) or a formula (C-6);
- 2. a process for preparing N, N-diethylaminocoumarin compound according to claim 1, wherein the compound of formula (II-1), formula (II-2) or formula (II-3) and cyanoacetic acid are dissolved in solvent, alkaline substance is added, stirring is carried out under the protection of nitrogen atmosphere, heating reflux reaction is carried out, after the reaction is finished, the reaction solution is concentrated to remove solvent, the obtained concentrate is dissolved in eluent, then separation and purification are carried out through column chromatography silica gel, eluent is collected and the eluent is distilled off, thus obtaining the target product;the structural formulas of the compounds represented by the formula (II-1), the formula (II-2) and the formula (II-3) are as follows:
- 3. the method for preparing the N, N-diethylaminocoumarin compound according to claim 2, wherein the heating reflux reaction time is 8-12 hours.
- 4. The method for preparing the N, N-diethylaminocoumarin compound according to claim 2, wherein the solvent is a mixed solvent of chloroform and acetonitrile, and the volume ratio of chloroform to acetonitrile is 1:1-3, preferably 1:2.
- 5. The process for producing N, N-diethylaminocoumarin compound according to claim 2, wherein the molar ratio of the compound of formula (II-1), formula (II-2) or formula (II-3), cyanoacetic acid and basic substance is 1:2 to 4:8 to 12, preferably 1:3:10.
- 6. The method for producing an N, N-diethylaminocoumarin compound according to claim 2, wherein the alkaline substance is piperidine.
- 7. The method for producing an N, N-diethylaminocoumarin compound according to claim 2, wherein the ratio of the amount of the substance in mmol to the volume of the solvent in the compound of formula (II-1), formula (II-2) or formula (II-3) is 1:30-60, and the unit of the amount of the substance is mL.
- 8. The preparation method of the N, N-diethylaminocoumarin compound according to claim 2, wherein the eluent is a mixed solvent consisting of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is 10-30:1, preferably 20:1.
- 9. Use of an N, N-diethylaminocoumarin compound according to claim 1 as a dye sensitizer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087051A (en) * | 2013-01-17 | 2013-05-08 | 浙江工业大学 | Synthesis and application of coumarin type dye sensitizer |
| CN103709129A (en) * | 2013-12-11 | 2014-04-09 | 浙江工业大学 | Synthesis and application of diethylamino coumarin dye sensitizer |
| CN104610251A (en) * | 2015-01-29 | 2015-05-13 | 浙江工业大学 | Coumarin compound as well as preparation method and application thereof |
| EP3747957A1 (en) * | 2019-06-07 | 2020-12-09 | Universidade de Évora | Fluorescent vinyl tiophene and bitiophene coumarins dyes and method of synthesis thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087051A (en) * | 2013-01-17 | 2013-05-08 | 浙江工业大学 | Synthesis and application of coumarin type dye sensitizer |
| CN103709129A (en) * | 2013-12-11 | 2014-04-09 | 浙江工业大学 | Synthesis and application of diethylamino coumarin dye sensitizer |
| CN104610251A (en) * | 2015-01-29 | 2015-05-13 | 浙江工业大学 | Coumarin compound as well as preparation method and application thereof |
| EP3747957A1 (en) * | 2019-06-07 | 2020-12-09 | Universidade de Évora | Fluorescent vinyl tiophene and bitiophene coumarins dyes and method of synthesis thereof |
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