CN110078746B - 2-carbonyl thiazolothiophene compound with luminescent property and preparation method and application thereof - Google Patents
2-carbonyl thiazolothiophene compound with luminescent property and preparation method and application thereof Download PDFInfo
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- -1 2-carbonyl thiazolothiophene compound Chemical class 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000001308 synthesis method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000010189 synthetic method Methods 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 150
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 238000004440 column chromatography Methods 0.000 claims description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical class O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 238000004020 luminiscence type Methods 0.000 claims 1
- 150000002923 oximes Chemical class 0.000 abstract description 15
- 150000002576 ketones Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000000741 silica gel Substances 0.000 abstract 1
- 229910002027 silica gel Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 83
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 66
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 60
- 238000001228 spectrum Methods 0.000 description 36
- 239000003208 petroleum Substances 0.000 description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 30
- 229910052799 carbon Inorganic materials 0.000 description 30
- 230000002194 synthesizing effect Effects 0.000 description 21
- 239000003480 eluent Substances 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 description 4
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 4
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000010504 bond cleavage reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XXOHMWCSTKXDLH-JXMROGBWSA-N (ne)-n-[1-(4-methoxyphenyl)ethylidene]hydroxylamine Chemical compound COC1=CC=C(C(\C)=N\O)C=C1 XXOHMWCSTKXDLH-JXMROGBWSA-N 0.000 description 2
- XAAUYUMBCPRWED-CSKARUKUSA-N (ne)-n-[1-(4-methylphenyl)ethylidene]hydroxylamine Chemical compound O\N=C(/C)C1=CC=C(C)C=C1 XAAUYUMBCPRWED-CSKARUKUSA-N 0.000 description 2
- WPRAXAOJIODQJR-UHFFFAOYSA-N 1-(3,4-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C)C(C)=C1 WPRAXAOJIODQJR-UHFFFAOYSA-N 0.000 description 2
- BAYUSCHCCGXLAY-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanone Chemical compound COC1=CC=CC(C(C)=O)=C1 BAYUSCHCCGXLAY-UHFFFAOYSA-N 0.000 description 2
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 2
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 description 2
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 2
- PZOTXXRWCKDMBC-UHFFFAOYSA-N [3-(cyclohexylcarbamoyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC(C(=O)NC2CCCCC2)=C1 PZOTXXRWCKDMBC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 2
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YPFOSEYKSLTSSF-UXBLZVDNSA-N (ne)-n-[1-(4-fluorophenyl)ethylidene]hydroxylamine Chemical compound O\N=C(/C)C1=CC=C(F)C=C1 YPFOSEYKSLTSSF-UXBLZVDNSA-N 0.000 description 1
- BKIHFZLJJUNKMZ-UHFFFAOYSA-N 1-(3,5-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC(C)=CC(C)=C1 BKIHFZLJJUNKMZ-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- BMHMKWXYXFBWMI-UHFFFAOYSA-N 3,4-Methylenedioxyacetophenone Chemical compound CC(=O)C1=CC=C2OCOC2=C1 BMHMKWXYXFBWMI-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- MTIGMGPOXRUUMD-UHFFFAOYSA-N n-[1-(4-fluorophenyl)propan-2-ylidene]hydroxylamine Chemical compound ON=C(C)CC1=CC=C(F)C=C1 MTIGMGPOXRUUMD-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract
The invention discloses a 2-carbonyl thiazolothiophene compound with a luminescent property, and a preparation method and application thereof. The synthesis method comprises the following steps: adding oxime compounds, ketone, sulfur simple substance, alkali and solvent into a reactor, and heating and reacting under a stirring state; after the reaction is finished, separating and purifying the reaction liquid by a silica gel column to obtain the 2-carbonyl thiazolothiophene compound with the luminous performance. The synthetic method provided by the invention develops three-component serial cyclization reaction of oxime, ketone and sulfur simple substance, and constructs a series of highly functionalized 2-carbonyl thiazolothiophene compounds. In addition, the method provided by the invention has the advantages of simple and easily obtained raw materials, safe operation, good regioselectivity and wide substrate universality. In addition, the 2-carbonyl thiazolothiophene structure provided by the invention has certain application value in the field of organic light-emitting devices.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a 2-carbonyl thiazolothiophene compound with a luminescent property, and a preparation method and application thereof.
Background
The 2-carbonyl thiazole compound has good biological activity as a class of nitrogen-containing and sulfur-containing compounds. It has wide application in the medical field, and is used as antiviral drugs, anticancer drugs, enzyme inhibitors, etc. Therefore, the synthesis and modification of such heterocyclic compounds are of great importance in organic chemistry. However, the 2-carbonylthiazolothiophene molecular skeleton of its derivative still has many challenges in synthesis. In the reported method for synthesizing 2-carbonylthiazolothiophene compounds (V.N.Yarovenko, N.G.Smirnova, V.N.Bulgakova, I.V.Zavrin and M.M.Krayushkin. [ J ]. Russ.J.org.Chem.,2003,39,1161.), 2-bromothiophene is required as a starting material to obtain 2-carbonylthiazolothiophene compounds through a multi-step reaction. The traditional synthesis method has the disadvantages of multiple reaction steps, poor atom economy and extremely low required reaction temperature. Therefore, there is a need for a green, efficient and highly selective method for synthesizing 2-carbonylthiazolothiophene compounds.
The oxime is an important synthon in organic synthesis reaction and has the advantages of high reaction activity, mild storage condition, easy preparation and the like. Because the O-H bond energy is lower, the oxime compounds can participate in various reactions with O-H breakage to prepare organic nitrogen-oxygen bond-containing compounds such as oxime ether, nitrone, isoxazole and the like. N-OH bond cleavage is not common in reactions of oximes, compared to reactions involving O-H bond cleavage of oximes. To activate N-OH bonds, a common strategy (x.tang, w.wu, w.zeng and h.jiang, acc.chem.res.,2018,51, 1092; h.huang,; x.ji,; w.wu and h.jiang, chem.soc.rev.,2015,44,1155.) is to convert oximes (N-OH) into oxime esters (N-OR, R ═ Ac, Bz, Piv, etc.) by increasing the polarity of the N-OR bond, making it susceptible to a single electron transfer OR oxidative addition process with metals, thereby breaking the N-OR bond. Although this method is widely used, it still has certain disadvantages. The conversion of oximes to oxime esters results in a less economical reaction step, less economical atom, and requires storage conditions for oxime esters that require low temperatures (typically less than 10 ℃). There are still few reports of reactions in which oximes directly undergo N-OH bond cleavage to construct nitrogen-containing heterocyclic compounds, as compared to conversion of oximes into oxime esters to promote N-O bond cleavage thereof. Therefore, the method for preparing the nitrogen-containing compound by breaking the N-OH bond of the oxime in a green, efficient and high-selectivity manner has great significance.
With the rise of high-technology products such as large-screen televisions, smart phones, tablet computers, wearable smart mobile devices and the like, people increasingly demand increasingly thin and light display screens and low consumption. Compared with the traditional liquid crystal display material, the organic light-emitting material has the advantages of thinner thickness, higher flexibility, lower energy consumption, wider visual angle, rich color gamut and the like, and has attracted extensive attention in recent years. Although many organic light-emitting materials have been reported so far, most of them have disadvantages such as low light-emitting purity, low fluorescence quantum yield, and difficulty in preparation, and no light-emitting material having a molecular skeleton of 2-carbonylthiazolothiophene has been reported. Therefore, the development of the 2-carbonyl thiazolothiophene fluorescent material which is easy to prepare, high in luminous purity and high in brightness is significant.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a 2-carbonyl thiazolothiophene compound with a luminescent property, and a preparation method and application thereof.
The invention provides a synthetic method of a 2-carbonyl thiazolothiophene compound. The method takes simple and easily obtained oxime, ketone and sulfur simple substances as raw materials, efficiently constructs the 2-carbonyl thiazole thiophene compound, and has the advantages of high atom economy, single selectivity, simple and safe operation, wide substrate applicability and the like. The reaction product 2-carbonyl thiazole thiophene has good application prospect in the field of organic luminescent materials.
The synthesis method provided by the invention is a method for synthesizing 2-carbonyl thiazolothiophene with a luminescent property by using oxime, ketone and sulfur simple substance.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a 2-carbonyl thiazolothiophene compound with a luminescent property, which has the following structural formula:
wherein, R is1Is a substituent, R1Is hydrogen, 2At least one of methyl, 3-methyl, 4-fluoro, 4-chloro, 4-bromo, 4-iodo, 4-methoxy, 4-phenyl, 3-bromo, 2-bromo, 4-cyano, and 3, 4-dimethyl;
the R is2Is a substituent, R2Is one or more selected from hydrogen, 2-methyl, 3-methyl, 4-fluoro, 4-chloro, 4-bromo, 4-iodo, 4-methoxy, 4-phenyl, 3-bromo, 2-iodo, 2-phenyl, 4-cyano, 3, 4-methylenedioxy, 3, 4-dimethyl, 3, 5-dimethyl, etc.
The invention provides a method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property, wherein the chemical reaction equation in the synthesis process is as follows:
the invention provides a method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property, which comprises the following steps:
(1) synthesizing a product: adding substrates, namely acetophenone oxime compounds, ketone compounds, elemental sulfur, alkali and a solvent into a reactor, uniformly mixing, carrying out heating reaction under a stirring state, and then cooling to room temperature to obtain a mixture;
(2) separation and purification: and (2) extracting the mixture in the step (1) (multiple times of extraction can be carried out, then the organic phases are combined together to obtain an organic phase, drying, filtering to obtain a filtrate, removing the organic solvent to obtain a crude product, and then purifying by column chromatography to obtain the 2-carbonyl thiazolothiophene compound with the luminescent property.
Further, the ketone compound in the step (1) includes acetophenone, 3, 4-dimethylacetophenone, 3, 5-dimethylacetophenone, 3, 4-methylenedioxyacetophenone, 2-methoxyacetophenone, 3-methylacetophenone, 3-methoxyacetophenone, methyl 4-acetylbenzoate, 4-chloroacetophenone, 4-fluoroacetophenone, 4-phenylacetophenone, 4-methoxyacetophenone and 4-methylacetophenone.
Further, the acetophenone oxime compound as the substrate in the step (1) comprises acetophenone oxime, 4-fluoro acetophenone oxime, 4-phenyl acetophenone oxime, 4-methoxy acetophenone oxime and 4-methyl acetophenone oxime.
Further, the base in the step (1) is more than one of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1, 4-diazabicyclo [2.2.2] octane.
Further, the molar ratio of the base to the ketone compound in the step (1) is 0.5-1.5: 1.
further, the molar ratio of the substrate acetophenone oxime compound to the ketone compound in the step (1) is 1.0-3.0: 1.
Further, the molar ratio of the elemental sulfur to the ketone compound in the step (1) is 0.5-2: 1.
Further, the solvent is more than one of dimethyl sulfoxide, acetonitrile and toluene; the molar volume ratio of the ketone compound to the solvent is 0.01-0.5 mmol/ml.
Further, the stirring speed of the step (1) under the stirring state is 50-1000 rpm; the temperature of the heating reaction is 100-140 ℃, and the time of the heating reaction is 10-40 hours.
Further, the extraction of step (2) can be performed by extracting the mixture with ethyl acetate; the drying can be carried out using anhydrous magnesium sulfate to dry the organic phase; the manner of removing the organic solvent includes evaporation under reduced pressure.
Further, the eluent of the column chromatography in the step (2) is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 20-150:1, and preferably, the volume ratio of the petroleum ether to the ethyl acetate is 30-100: 1.
The 2-carbonyl thiazolothiophene compound with the light-emitting property can be applied to preparing a light-emitting layer of an organic light-emitting device.
The 2-carbonyl thiazole thiophene compound with the light-emitting property can be used as a guest material to prepare a light-emitting layer when being applied to the preparation of an organic light-emitting device.
The reaction principle of the synthesis method provided by the invention is as follows: under the promotion of alkali, the sulfur simple substance and oxime form a free radical intermediate, and then acetophenone and the oxime perform a serial cyclization reaction to obtain the 2-carbonyl thiazolothiophene compound.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the synthetic method provided by the invention is a synthetic method for constructing the 2-carbonyl thiazolothiophene compound which is difficult to synthesize by the traditional method through three-component serial cyclization, wherein the basic raw material oxime can be synthesized by cheap ketone, and the synthetic method has the characteristics of simple and easily obtained raw materials, safe and simple operation, mild conditions, high atom economy and wide substrate applicability;
(2) the synthesis method provided by the invention is convenient to operate, can use low-toxicity or non-toxic organic solvent as solvent, is green and environment-friendly, and has good tolerance to functional groups, so that the synthesis method is expected to be applied to actual industrial production and further derivatization;
(3) the 2-carbonyl thiazolothiophene compound with the luminescent property has obvious photoluminescence property and can be applied to the field of organic luminescent materials taking 2-carbonyl thiazolothiophene as a framework.
Drawings
FIGS. 1 and 2 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 1, respectively;
FIGS. 3 and 4 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 2, respectively;
FIGS. 5 and 6 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 3, respectively;
FIGS. 7 and 8 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 4;
FIGS. 9 and 10 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 5;
FIGS. 11 and 12 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 6;
FIGS. 13 and 14 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 7;
FIGS. 15 and 16 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 8;
FIGS. 17 and 18 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 9;
FIGS. 19 and 20 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 10;
FIGS. 21 and 22 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 11;
FIGS. 23 and 24 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 12;
FIGS. 25 and 26 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 13;
FIGS. 27 and 28 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 14;
FIGS. 29 and 30 are a hydrogen spectrum and a carbon spectrum, respectively, of the objective product obtained in example 15;
FIGS. 31 and 32 are an ultraviolet absorption spectrum and a fluorescence emission spectrum of the objective product obtained in example 1, respectively;
FIG. 33 and FIG. 34 are a UV absorption spectrum and a fluorescence emission spectrum of the objective product obtained in example 3, respectively;
FIG. 35 and FIG. 36 are a UV absorption spectrum and a fluorescence emission spectrum of the objective product obtained in example 13, respectively;
FIG. 37 and FIG. 38 are an ultraviolet absorption spectrum and a fluorescence emission spectrum of the objective product obtained in example 14, respectively.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.2 mmol of acetophenone oxime, 0.2 mmol of acetophenone, 0.05 mmol of elemental sulfur, 0.1 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 20 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 40 hours at the condition of 100 ℃ and the rotating speed of 50 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 150:1, so that the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 42%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 1 and fig. 2, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.63(d,J＝7.5Hz,2H),8.28(d,J＝7.6Hz,1H),7.83(d,J＝7.4Hz,1H),7.67(t,J＝7.3Hz,1H),7.61–7.54(m,2H),7.51(t,J＝7.5Hz,1H),7.44(t,J＝7.6Hz,1H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.5,169.5,156.9,143.1,138.8,134.9,133.7,131.1,130.4,128.4,126.1,125.5,123.4,122.1.
the structure of the target product is deduced from the above data as follows:
the ultraviolet absorption spectrum and the fluorescence emission spectrum of the obtained target product are shown in fig. 31 and fig. 32. The maximum absorption wavelength and the emission wavelength of the product are 372nm and 465nm respectively, the product can emit blue light in tetrahydrofuran solution, and the product has great potential in the application of blue light organic light-emitting devices. Other embodiments similar to embodiment 1, see fig. 31 and 32.
Example 2
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.6 mmol of acetophenone oxime, 0.2 mmol of 4-methylacetophenone, 0.4 mmol of elemental sulfur, 0.3 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 0.4 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 10 hours at 140 ℃ and the rotation speed of 1000 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 150:1, so that the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained, and the yield is 52%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 3 and 4, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):δ＝8.56(d,J＝8.2Hz,2H),8.30(d,J＝7.7Hz,1H),7.85(d,J＝8.0Hz,1H),7.53(t,J＝7.5Hz,1H),7.46(t,J＝7.2Hz,1H),7.37(d,J＝8.1Hz,2H),2.48(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.5,169.2,157.0,143.4,138.0,136.4,135.0,133.6,131.1,128.4,128.0,127.0,123.4,121.7,21.6.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 2 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 3
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of 4-methoxy acetophenone, 0.25 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 4.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 525 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 20:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 81%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 5 and 6, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):δ＝8.70(d,J＝8.5Hz,2H),8.26(d,J＝7.7Hz,1H),7.81(d,J＝8.0Hz,1H),7.50(t,J＝7.5Hz,1H),7.42(t,J＝7.6Hz,1H),7.03(d,J＝8.5Hz,2H),3.908(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝181.6,170.2,164.2,156.7,143.0,138.2,133.6,130.4,127.6,125.9,125.4,123.4,121.9,113.7,55.5.
the structure of the target product is deduced from the above data as follows:
the ultraviolet absorption spectrum and the fluorescence emission spectrum of the obtained target product are shown in fig. 33 and 34. The maximum absorption wavelength and the emission wavelength of the product are 367nm and 444nm respectively, the product can emit deep blue light in tetrahydrofuran solution, and the product has great potential in the application of deep blue light organic light-emitting devices.
Example 4
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of 4-phenylacetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 100:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 76%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 7 and fig. 8, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):δ＝8.73(d,J＝7.8Hz,2H),8.33(d,J＝7.7Hz,1H),7.87(d,J＝8.0Hz,1H),7.80(d,J＝7.8Hz,2H),7.70(d,J＝7.5Hz,2H),7.58–7.47(m,4H),7.47–7.40(m,1H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.1,169.7,157.0,146.4,143.2,139.9,138.8,133.7,131.8,130.5,129.0,128.3,127.3,127.1,126.1,125.5,123.5,122.2.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 4 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 5
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
adding 0.4 mmol of acetophenone oxime, 0.2 mmol of 4-fluoro acetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of acetonitrile (as a solvent) into a reaction tube, and stirring and reacting at 120 ℃ and 700rpm for 26 hours; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 100:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 62%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 9 and fig. 10, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):δ＝8.84–8.69(m,2H),8.33(d,J＝7.6Hz,1H),7.90(d,J＝7.9Hz,1H),7.57(t,J＝7.5Hz,1H),7.51(t,J＝7.5Hz,1H),7.28(t,J＝8.3Hz,2H).
13C NMR(100MHz,CDCl3,ppm):δ＝182.0,168.5(d,J＝178.3Hz),165.1,157.0,143.2,139.0,134.0(d,J＝9.4Hz),131.3(d,J＝3.0Hz),130.4,126.2,125.6,123.5,122.1,115.7(d,J＝21.8Hz).
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 5 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 6
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of 4-chloroacetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 100:1, so that the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained, and the yield is 70%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 11 and fig. 12, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.62(d,J＝8.1Hz,2H),8.30(d,J＝7.8Hz,1H),7.87(d,J＝7.9Hz,1H),7.55(d,J＝8.0Hz,3H),7.48(t,J＝7.1Hz,1H).
13C NMR(100MHz,CDCl3,ppm):δ＝182.4,169.1,157.1,143.2,140.4,139.7,133.3,132.6,130.3,128.8,126.3,125.6,123.6,122.2.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 6 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 7
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of methyl 4-acetylbenzoate, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 20:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained, and the yield is 56%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 13 and fig. 14, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.66(d,J＝8.1Hz,2H),8.29(d,J＝7.7Hz,1H),8.22(d,J＝8.1Hz,2H),7.86(d,J＝8.1Hz,1H),7.54(t,J＝7.5Hz,1H),7.48(t,J＝7.6Hz,1H),3.97(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.2,168.8,166.3,157.2,143.2,139.4,138.4,134.2,131.0,130.3,129.5,126.3,125.6,123.5,122.2,52.5.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 7 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 8
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of 3-methoxy acetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 30:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained, and the yield is 77%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 15 and fig. 16, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.35–8.23(m,2H),8.15(s,1H),7.84(d,J＝8.0Hz,1H),7.56–7.42(m,3H),7.22(d,J＝8.2Hz,1H),3.93(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.3,169.5,159.5,156.9,143.1,138.8,136.1,130.4,129.4,126.1,125.5,124.0,123.5,122.1,120.5,115.2,55.5.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 8 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 9
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of 3-methylacetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 100:1, so that the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 73%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 17 and fig. 18, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.48(d,J＝6.9Hz,1H),8.36(s,1H),8.29(d,J＝7.8Hz,1H),7.85(d,J＝8.0Hz,1H),7.53(t,J＝7.5Hz,1H),7.50–7.42(m,3H),2.496(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.9,169.7,157.0,143.2,138.7,138.2,135.0,134.5,131.4,130.5,128.6,128.3,126.1,125.5,123.5,122.1,21.4.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 9 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 10
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of 2-methoxy acetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 30:1, and a target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained, and the yield is 68%.
The hydrogen spectrogram and the carbon spectrogram of the obtained target product are respectively shown in fig. 19 and fig. 20, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.20(d,J＝7.3Hz,1H),7.83(t,J＝7.9Hz,2H),7.56(t,J＝7.9Hz,1H),7.51–7.40(m,2H),7.16–7.02(m,2H),3.841(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝186.4,169.6,158.7,156.9,143.1,138.6,133.3,131.2,130.4,126.3,126.0,125.4,123.4,122.2,120.2,112.1,56.0.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 10 is similar to that of embodiment 1, and reference is made to fig. 31 and 32.
Example 11
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
0.4 mmol of acetophenone oxime, 0.2 mmol of 3, 4-dimethylacetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) are added into a reaction tube, and the mixture is stirred and reacted for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 100:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 80%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 21 and 22, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.44(d,J＝7.8Hz,1H),8.34(s,1H),8.26(d,J＝7.8Hz,1H),7.81(d,J＝8.0Hz,1H),7.50(t,J＝7.4Hz,1H),7.460–7.382(m,1H),7.31(d,J＝7.9Hz,1H),2.384(s,3H),2.367(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.2,169.9,156.8,143.5,143.0,138.4,136.7,132.6,131.9,130.4,129.7,129.1,125.9,125.3,123.4,122.0,20.1,19.8.。
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 11 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
Example 12
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
adding 0.4 mmol of 4-methyl acetophenone oxime, 0.2 mmol of acetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) into a reaction tube, and stirring and reacting for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 100:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 81%.
The obtained hydrogen spectrogram and carbon spectrogram of the target product are respectively shown in fig. 23 and 24, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.63(d,J＝7.9Hz,2H),8.14(d,J＝8.0Hz,1H),7.67(t,J＝7.2Hz,1H),7.628–7.525(m,3H),7.31(d,J＝8.0Hz,1H),2.50(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.5,169.2,157.0,143.4,138.0,136.4,135.0,133.6,131.1,128.4,128.0,127.0,123.4,121.7,21.6.
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 12 is similar to that of embodiment 1, and reference is made to fig. 31 and 32.
Example 13
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
adding 0.4 mmol of 4-methoxy acetophenone oxime, 0.2 mmol of acetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) into a reaction tube, and stirring and reacting for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 30:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 83%.
The hydrogen spectrum and the carbon spectrum of the obtained target product are respectively shown in fig. 25 and 26, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.61(d,J＝7.5Hz,2H),8.12(d,J＝8.6Hz,1H),7.66(t,J＝7.3Hz,1H),7.56(t,J＝7.4Hz,2H),7.29(s,1H),7.09(d,J＝8.7Hz,1H),3.88(s,3H).
13C NMR(100MHz,CDCl3,ppm):δ＝183.5,169.2,158.6,156.8,144.7,136.6,135.0,133.6,131.1,128.4,124.0,122.6,114.4,106.7,55.6.
the structure of the target product is deduced from the above data as follows:
the ultraviolet absorption spectrum and the fluorescence emission spectrum of the obtained target product are shown in fig. 35 and fig. 36. The maximum absorption wavelength and the emission wavelength of the product are 393nm and 498nm respectively, the product can emit green light in tetrahydrofuran solution, and the product has great potential in the application of green organic light emitting devices.
Example 14
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
adding 0.4 mmol of 4-phenyl acetophenone oxime, 0.2 mmol of acetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1.0 ml of dimethyl sulfoxide (used as a solvent) into a reaction tube, and stirring and reacting for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 100:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 66%.
The hydrogen spectrum and the carbon spectrum of the obtained target product are respectively shown in fig. 27 and 28, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.65(d,J＝7.7Hz,2H),8.34(d,J＝8.1Hz,1H),8.05(s,1H),7.76(d,J＝8.2Hz,1H),7.68(d,J＝7.4Hz,3H),7.59(t,J＝7.5Hz,2H),7.49(t,J＝7.3Hz,2H),7.40(t,J＝7.3Hz,1H).；
13C NMR(100MHz,CDCl3,ppm):δ＝183.6,169.7,156.8,144.0,140.4,139.6,139.1,135.0,133.7,131.2,129.4,129.0,128.5,127.7,127.4,125.1,122.3,121.8。
the structure of the target product is deduced from the above data as follows:
the ultraviolet absorption spectrum and the fluorescence emission spectrum of the obtained target product are shown in fig. 37 and 38. The maximum absorption wavelength and the emission wavelength of the product are 383nm and 479nm respectively, the product can emit blue light in tetrahydrofuran solution, and the product has great potential in the application of blue light organic light-emitting devices.
Example 15
A method for synthesizing the 2-carbonyl thiazolothiophene compound with the luminescent property comprises the following steps:
adding 0.4 mmol of 4-fluorophenylacetoxime, 0.2 mmol of acetophenone, 0.2 mmol of elemental sulfur, 0.2 mmol of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene and 1.0 ml of dimethyl sulfoxide (as a solvent) into a reaction tube, and stirring and reacting for 26 hours at the temperature of 120 ℃ and the rotation speed of 700 rpm; stopping stirring, adding 5mL of water, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous magnesium sulfate, filtering, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, the volume ratio of the petroleum ether to the ethyl acetate is 100:1, and the target product (the 2-carbonyl thiazolothiophene compound with the luminous property) is obtained with the yield of 72%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 29 and fig. 30, and the structural characterization data are shown as follows:
1H NMR(400MHz,CDCl3,ppm):8.59(d,J＝7.5Hz,2H),8.25–8.10(m,1H),7.65(d,J＝7.0Hz,1H),7.61–7.42(m,8.6Hz,3H),7.28–7.15(m,1H).；
13C NMR(100MHz,CDCl3,ppm):δ＝183.4,169.9,161.2(d,J＝247.3Hz),156.1,144.05(d,J＝9.9Hz),137.9,134.8,133.7,131.1,128.4,126.9,123.0(d,J＝9.2Hz),114.1(d,J＝23.9Hz),110.1(d,J＝26.1Hz).
the structure of the target product is deduced from the above data as follows:
the light emitting effect of embodiment 15 is similar to that of embodiment 1, and reference can be made to fig. 31 and 32.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (5)
1. A synthetic method of a 2-carbonyl thiazolothiophene compound with a luminescent property is characterized in that a chemical reaction equation in the synthetic process is as follows:
wherein, R is1Is a substituent, R1Is one of hydrogen, 2-methyl, 3-methyl, 4-fluoro, 4-chloro, 4-bromo, 4-iodo, 4-methoxy, 4-phenyl, 3-bromo, 2-bromo, 4-cyano, 3, 4-methylenedioxy and 3, 4-dimethyl;
the R is2Is a substituent, R2Is one of hydrogen, 2-methyl, 3-methyl, 4-fluoro, 4-chloro, 4-bromo, 4-iodo, 4-methoxy, 4-phenyl, 3-bromo, 2-iodo, 2-phenyl, 4-cyano, 3, 4-methylenedioxy, 3, 4-dimethyl and 3, 5-dimethyl;
the method comprises the following steps:
(1) adding substrates, namely acetophenone oxime compounds, ketone compounds, elemental sulfur, alkali and a solvent into a reactor, uniformly mixing, carrying out heating reaction under a stirring state, and then cooling to room temperature to obtain a mixture;
(2) extracting the mixture obtained in the step (1) to obtain an organic phase, drying, filtering to obtain a filtrate, removing the organic solvent to obtain a crude product, and then purifying by column chromatography to obtain the 2-carbonyl thiazolothiophene compound with the luminescent property;
the structural formula of the ketone compound is as follows:
the structural formula of the acetophenone oxime compound is as follows:
the molar ratio of the acetophenone oxime compound to the ketone compound is 1.0-3.0: 1;
the alkali in the step (1) is more than one of 1,5, 7-triazabicyclo [4.4.0] -dec-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1, 4-diazabicyclo [2.2.2] octane; the molar ratio of the alkali to the ketone compound is 0.5-1.5: 1.
2. The method of claim 1, wherein the elemental sulfur of step (1) is S8The molar ratio of the sulfur simple substance to the ketone compound is 0.5-2: 1; the solvent is more than one of dimethyl sulfoxide, acetonitrile and toluene; the molar volume ratio of the ketone compound to the solvent is 0.01-0.5 mmol/mL.
3. The synthesis method according to claim 1, wherein the stirring speed in the stirring state in the step (1) is 50-1000 rpm; the temperature of the heating reaction is 100-140 ℃, and the time of the heating reaction is 10-40 hours.
4. The synthesis process according to claim 1, characterized in that in step (2), the mixture can be extracted with ethyl acetate; the organic phase can be dried using anhydrous magnesium sulfate; the manner of removing the organic solvent includes evaporation under reduced pressure.
5. 2-carbonyl thiazolothiophene compounds with luminescence property prepared by the synthesis method of any one of claims 1 to 4, wherein the structural formula is shown as follows:
wherein, R is1Is a substituent, R1Is one of hydrogen, 2-methyl, 3-methyl, 4-fluoro, 4-chloro, 4-bromo, 4-iodo, 4-methoxy, 4-phenyl, 3-bromo, 2-bromo, 4-cyano, 3, 4-methylenedioxy and 3, 4-dimethyl;
the R is2Is a substituent, R2Is one of hydrogen, 2-methyl, 3-methyl, 4-fluoro, 4-chloro, 4-bromo, 4-iodo, 4-methoxy, 4-phenyl, 3-bromo, 2-iodo, 2-phenyl, 4-cyano, 3, 4-methylenedioxy, 3, 4-dimethyl and 3, 5-dimethyl.
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| CN108822135A (en) * | 2018-08-25 | 2018-11-16 | 湘潭大学 | A kind of synthetic method of the cyclosubstituted thieno of azepine [3,2-d] thiazole and its derivative |
| CN109705146A (en) * | 2019-01-19 | 2019-05-03 | 湘潭大学 | 2- amino benzo [4,5] thieno [3,2-d] thiazole, derivative and its synthetic method |
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| CN108822135A (en) * | 2018-08-25 | 2018-11-16 | 湘潭大学 | A kind of synthetic method of the cyclosubstituted thieno of azepine [3,2-d] thiazole and its derivative |
| CN109705146A (en) * | 2019-01-19 | 2019-05-03 | 湘潭大学 | 2- amino benzo [4,5] thieno [3,2-d] thiazole, derivative and its synthetic method |
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