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WO2015199141A1 - Composé à cycle condensé de coumaline présentant des propriétés de luminescence/semi-conducteur et son procédé de fabrication - Google Patents

Composé à cycle condensé de coumaline présentant des propriétés de luminescence/semi-conducteur et son procédé de fabrication Download PDF

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WO2015199141A1
WO2015199141A1 PCT/JP2015/068233 JP2015068233W WO2015199141A1 WO 2015199141 A1 WO2015199141 A1 WO 2015199141A1 JP 2015068233 W JP2015068233 W JP 2015068233W WO 2015199141 A1 WO2015199141 A1 WO 2015199141A1
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group
condensed ring
ring compound
coumarin
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稔 山路
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Gunma University NUC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

Definitions

  • the present invention relates to a novel luminescent organic material.
  • An organic compound used as a light emitting layer of an organic electroluminescence (EL) device is required to have fastness against an external environment such as high voltage, oxygen, light, moisture, and a large luminous efficiency at the same time. Therefore, the design and development of molecules having both robustness and high luminescence are desired.
  • coumarin is a molecule that does not emit fluorescence, it is known that fluorescence is observed by introducing substituents.
  • a molecule having a diethylamino group introduced at the 7-position of a coumarin skeleton (coumarin 466) and a coumarin derivative having a gelolidine skeleton (coumarin 102) are known as fluorescent probes and dyes.
  • Patent Document 1 coumarin compounds that emit red light with high brightness and coumarin-containing organic light-emitting materials obtained by chemically modifying known materials for the purpose of having high reliability have been reported (Patent Document 1, Patents). Reference 2).
  • 3-phenylcoumarin, 3-phenylisocoumarin, and the like are also known as fluorescent luminescent compounds, and a fluorescent substance of an isocoumarin-based compound has been reported (Patent Document 3).
  • an object of the present invention is to provide an organic compound that is resistant to an external environment such as high voltage and oxygen, and can be used as an electronic material or a blue light-emitting element, and a method for producing the same.
  • the present inventor has photocondensed a benzene ring at the C 3 -C 4 position and / or C 7 -C 8 position of the fluorescent coumarin skeleton or the isocoumarin skeleton.
  • a novel coumarin derivative or isocoumarin derivative that is expected to be fluorescent and to have high fastness to the external environment by arranging in zigzag.
  • a novel coumarin condensed ring compound and isocoumarin condensed compound are obtained.
  • R 1 to R 4 are each independently hydrogen, hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, trialkylamino group, trifluoromethyl group, nitro group or cyano group.
  • Ar represents an aromatic ring or a heteroaromatic ring which may have a substituent. However, when R 1 to R 4 are all hydrogen, Ar is not a benzene ring.
  • m is an integer of 1 to 7
  • n is an integer of 2 to 7.
  • n is an integer of 2 to 7.
  • R 1 to R 4 are each independently hydrogen, hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, trialkylamino group, trifluoromethyl group, nitro group or cyano group.
  • Ar represents an aromatic ring or a heteroaromatic ring which may have a substituent. However, when R 1 to R 4 are all hydrogen, Ar is not a benzene ring.
  • R 1 to R 4 are independently hydrogen, hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, trialkylamino group, trifluoromethyl group, nitro group or cyano group.
  • n is an integer from 2 to 7.
  • R 1 to R 4 are independently hydrogen, hydroxyl group, methoxy group, amino group, dimethylamino group, diethylamino group, trifluoromethyl group, nitro group.
  • R 1 to R 4 are independently hydrogen, hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, trialkylamino group, trifluoromethyl group, nitro group or cyano group.
  • n is an integer from 2 to 7.
  • R 3 is a hydroxyl group, a methoxy group, an amino group, a dimethylamino group, a diethylamino group, a trifluoromethyl group, a nitro group, or a cyano group.
  • a coumarin condensed ring compound an isocoumarin condensed ring compound exhibiting luminescent property and semiconductor performance, and a production method thereof.
  • FIG. 1 shows absorption / fluorescence spectra in acetonitrile of coumarin condensed ring compounds represented by formulas (7) to (10) and 7-methoxycoumarin.
  • FIG. 2 is an absorption / fluorescence spectrum in acetonitrile of a coumarin condensed ring compound represented by formula (8), formula (11), or formula (12).
  • FIG. 3 is an absorption / fluorescence spectrum in acetonitrile of a coumarin condensed ring compound represented by formula (15) or formula (16).
  • FIG. 4 shows the fluorescence yield ( ⁇ f ) and fluorescence lifetime ( ⁇ f ) of coumarin condensed ring compounds represented by formulas (7) to (12) and (15) to (16) and 7-methoxycoumarin. ) And the fluorescence speed (k f ).
  • FIG. 5 is a 400 MHz NMR spectrum in CDCl 3 of the coumarin condensed ring compound represented by the formula (7).
  • FIG. 6 is a 400 MHz NMR spectrum in CDCl 3 of the coumarin condensed ring compound represented by the formula (8).
  • FIG. 7 is a 400 MHz NMR spectrum in CDCl 3 of the coumarin condensed ring compound represented by the formula (9).
  • FIG. 8 is a 400 MHz NMR spectrum in CDCl 3 of the coumarin condensed ring compound represented by the formula (10).
  • FIG. 9 is a 400 MHz NMR spectrum in CDCl 3 of the coumarin condensed ring compound represented by the formula (11).
  • FIG. 10 is a 400 MHz NMR spectrum in CDCl 3 of the coumarin condensed ring compound represented by the formula (12).
  • FIG. 11 is a 400 MHz NMR spectrum in CDCl 3 of the coumarin condensed ring compound represented by the formula (15).
  • a coumarin condensed ring compound and an isocoumarin condensed ring compound may be described as a coumarin-type condensed ring compound.
  • the coumarin condensed ring compound according to the present invention is a compound represented by any one of the above general formulas (1) to (3).
  • R 1 to R 4 are independently hydrogen, hydroxyl, A group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, a trialkylamino group, a trifluoromethyl group, a nitro group or a cyano group
  • Ar is an aromatic ring or a heterocyclic group which may have a substituent. Represents an aromatic ring. However, when R 1 to R 4 are all hydrogen, Ar is not a benzene ring.
  • n is an integer from 2 to 7.
  • the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. It may be branched or cyclic.
  • the coumarin-based condensed ring compound represented by the above general formula (5) in which Ar in the general formula (1) has a phenacene structure is particularly preferable because of its high fastness.
  • n is 2 to 7.
  • R 1 to R 4 are a hydroxyl group, a methoxy group, an amino group, a dimethylamino group, a diethylamino group, a trifluoromethyl group, a nitro group, or It is preferably a cyano group, and in the formula (5), n is preferably 2 to 5.
  • a coumarin condensed ring compound which is a 7-methoxycoumarin derivative in which R 3 is a methoxy group and n is 2 to 5 is particularly preferable because high luminous efficiency can be obtained.
  • an electron-withdrawing substituent such as a halogen, a nitro group, a cyano group, a tosyl group, an acyl group, or a trifluoromethyl group into the condensed ring site represented by Ar in the formula (1)
  • an electron donating group such as a hydroxyl group, alkoxy group, amino group, alkylamino group, dialkylamino group or trialkylamino group into m stretched condensed ring sites may improve the fluorescence.
  • the physical properties of fluorescence are obtained, that is, fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) Can be changed.
  • fluorescence yield ⁇ f
  • fluorescence lifetime ⁇ f
  • fluorescence speed k f
  • the fluorescence yield is expected to increase due to charge transfer within the molecule, and control of electron mobility when used as an electronic device material can be expected.
  • Specific examples of the compound represented by the general formula (1) include compounds represented by the following structural formulas (7) to (16).
  • An aromatic compound having a phenacene skeleton in which benzene rings are arranged in a zigzag manner is known as a condensed ring compound resistant to high voltage and oxygen.
  • a molecule in which a condensed ring structure such as a phenacene skeleton is introduced into a coumarin compound has not been known so far.
  • the present inventor has found that a coumarin-based condensed ring compound having the above-described light-emitting properties and semiconductor performance can be produced by subjecting an existing fluorescent coumarin-based skeleton to a ring-condensation reaction using light.
  • the coumarin condensed ring compound according to the embodiment of the present invention can be easily obtained by a production method having a photocondensation process in which light is irradiated in the presence of an oxidizing agent.
  • a production method having a photocondensation process in which light is irradiated in the presence of an oxidizing agent With the manufacturing method according to the embodiment of the present invention, it is possible to manufacture an organic compound that can be used as an electronic material or a blue light-emitting element with a smaller number of steps than a general multi-step synthesis method.
  • the reaction since the reaction is completed in a short time in the photocondensation process, it is possible to manufacture the organic EL device in a short time by using this.
  • the coumarin condensed ring compound according to the embodiment of the present invention is produced by the following reaction formula.
  • the 4-position methyl group is brominated with N-bromosuccinimide (NBS).
  • N-bromosuccinimide N-bromosuccinimide
  • a phosphonium salt is formed with triphenylphosphine (PPh 3 ), and a Wittig reaction with 1-naphthaldehyde is performed to synthesize a photoreaction precursor.
  • PPh 3 triphenylphosphine
  • a Wittig reaction with 1-naphthaldehyde is performed to synthesize a photoreaction precursor.
  • O 2 and I 2 By irradiating with light, a coumarin condensed ring compound represented by the formula (8) is obtained.
  • the photoreaction precursor has a coumarin skeleton or an isocoumarin skeleton, and one carbon of a carbon-carbon double bond is bonded to the carbon at the 4-position and / or 8-position of the skeleton, A compound in which a benzene ring is photocondensed at the C 3 -C 4 position and / or the C 7 -C 8 position by irradiation with light in the presence of an oxidizing agent.
  • solvents that can be used in the above reaction include solvents that do not adversely affect the target photocondensation reaction, such as cyclohexene and toluene.
  • the photocondensation conditions are not particularly limited as long as they can be condensed without decomposing the coumarin skeleton.
  • the light to be irradiated preferably includes light having a wavelength of 220 nm or more and 400 nm or less. Long wavelength ultraviolet rays having a wavelength of about 400 to 320 nm and medium wavelength ultraviolet rays having a wavelength of about 320 to 280 nm are efficiently absorbed by the substrate, which is preferable. Irradiation light does not need to be a single light, and mercury lamps, black light lamps, sodium lamps, white lamps and the like including various wavelengths can be used.
  • the light to be irradiated may include both long wavelength ultraviolet rays and medium wavelength ultraviolet rays.
  • the irradiation time is about 10 to 40 hours.
  • oxidizing agent examples include O 2 and I 2 .
  • the oxidizing agent O 2 may be at a concentration (about 10 ⁇ 3 mol ⁇ dm ⁇ 3 ) that dissolves in the solvent at room temperature under atmospheric pressure, and I 2 may be added in a catalytic amount.
  • a sensitizer in the photocondensation process.
  • the sensitizer 9-fluorenone or the like can be used.
  • the sensitizer is preferably used in an equimolar amount or more with respect to the photoreaction precursor.
  • the sensitizer absorbs long-wavelength ultraviolet rays and / or medium-wavelength ultraviolet rays satisfactorily, thereby improving the reaction efficiency. Even if it uses a sensitizer, it can isolate
  • the purification method is not particularly limited, and examples include column chromatography and sublimation. Of these, purification by column chromatography is preferred. By purification, the purity is preferably 99.9% or more, and more preferably 99.99% or more.
  • a coumarin condensed ring compound having high purity can efficiently utilize light emission when it is used as an EL device. Purity can be determined by matching the fluorescence excitation spectrum with the absorption spectrum.
  • the isocoumarin condensed ring compound according to the present invention is a compound represented by the above general formula (4).
  • R 1 to R 4 are each independently hydrogen, hydroxyl group, alkoxy group, amino group, An alkylamino group, a dialkylamino group, a trialkylamino group, a trifluoromethyl group, a nitro group or a cyano group, and Ar represents an aromatic ring or a heteroaromatic ring which may have a substituent.
  • R 1 to R 4 are all hydrogen, Ar is not a benzene ring.
  • the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, which may be linear, branched or cyclic.
  • at least one of R 1 to R 4 is a hydroxyl group, a methoxy group, an amino group, a dimethylamino group, a diethylamino group, a trifluoromethyl group, a nitro group, or a cyano group.
  • n is 2-7.
  • n is an integer of 2 to 7, preferably 2 to 5.
  • the above-mentioned isocoumarin condensed ring compound having luminescent property and semiconductor performance can be produced by subjecting an existing isocoumarin skeleton to a condensation reaction using light. Specifically, it is produced by the following reaction formula.
  • an isocoumarin condensed ring compound represented by the formula (18) is obtained.
  • the raw material methylisocoumarin is, for example, Org. Lett. 8 (2006), pages 5829 to 5832, and can be synthesized by the following method.
  • Examples of the solvent that can be used in the photocondensation reaction include solvents such as toluene and cyclohexane that do not adversely affect the target photocondensation reaction.
  • the photocondensation conditions are not particularly limited as long as they can be condensed without decomposing the isocoumarin skeleton.
  • the light to be irradiated preferably includes light having a wavelength of 280 nm or more and 400 nm or less.
  • Long wavelength ultraviolet rays having a wavelength of about 400 to 320 nm and medium wavelength ultraviolet rays having a wavelength of about 320 to 280 nm are efficiently absorbed by the substrate, which is preferable.
  • Irradiation light does not need to be a single light, and mercury lamps, black light lamps, sodium lamps, white lamps and the like including various wavelengths can be used.
  • the light to be irradiated may include both long wavelength ultraviolet rays and medium wavelength ultraviolet rays.
  • the irradiation time is about 10 to 40 hours.
  • oxidizing agent examples include O 2 and I 2 .
  • the oxidizing agent O 2 may be at a concentration (about 10 ⁇ 3 mol ⁇ dm ⁇ 3 ) that is dissolved in the solvent at room temperature under atmospheric pressure, and I 2 may be added in a catalytic amount.
  • a sensitizer in the photocondensation process.
  • the sensitizer 9-fluorenone or the like can be used.
  • the sensitizer is preferably used in an equimolar amount or more with respect to the condensed ring reaction substrate.
  • the sensitizer absorbs long-wavelength ultraviolet rays and / or medium-wavelength ultraviolet rays satisfactorily, thereby improving the reaction efficiency. Even if it uses a sensitizer, it can isolate
  • the purification method is not particularly limited, and examples thereof include column chromatography, sublimation method, recrystallization and the like. Of these, purification by column chromatography is preferred.
  • the column chromatography developing solvent hexane and chloroform, a mixed solvent of hexane and ethyl acetate, or the like can be preferably used.
  • the recrystallization solvent chloroform or toluene can be preferably used.
  • a highly purified isocoumarin fused ring compound can efficiently utilize light emission when it is used as an organic EL device.
  • the isocoumarin condensed ring compound is preferably purified to a purity of 99.99% or higher.
  • the coumarin condensed ring compound and the isocoumarin condensed ring compound of the present invention emit light in a wavelength region of 380 to 460 nm and can be expected to have fastness, they can be suitably used as a blue organic EL material. In addition to the fluorescent property, it is expected to exhibit n-type semiconductor operation, and application to an electron transport layer of a field effect transistor can be expected.
  • the configuration of the organic EL device of the present invention is not particularly limited, and can be a normal configuration.
  • a substrate, an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are provided.
  • One layer may have two or more functions.
  • the organic layer containing the coumarin-based condensed ring compound of the present invention can be suitably used for a light emitting layer, an electron transport layer, and a layer having both of them.
  • the method for producing the organic layer of the organic EL device of the present invention is not particularly limited, but it can be produced by dissolving the coumarin-based condensed ring compound according to the present invention in, for example, a solvent and applying it onto a substrate.
  • the coating method include a casting method and a spin coating method.
  • Solvents include pentane, hexane, heptane, benzene, toluene, xylene, cyclohexane, methylcyclohexane, decalin, carbon tetrachloride, chloroform, 1,2-dichloroethane, ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran, acetone, methyl.
  • the solvent may be removed by drying after coating.
  • a material for forming a substrate an anode, a hole transport layer, an electron transport layer, a cathode and the like, a material generally used in an organic EL device can be used.
  • the organic EL device using the coumarin-based condensed ring compound of the present invention can be expected to withstand long-time use, it can be expected to have a flat light emitter such as an electrophotographic photosensitive member and a flat panel display, a copying machine, a printer, and a liquid crystal display. It can be used for backlights, light sources such as instruments, various light emitting elements, various display devices, various signs, various accessories, and the like.
  • the compound is MeOCM [4], the compound represented by Formula (16) is MeOCM [5], the compound represented by Formula (9) is MeOCM @ Phe, the compound represented by Formula (10) is MeOCM @ Py,
  • the compound represented by the formula (11) is also represented by CM [3], and the compound represented by the formula (12) which is a 7,8-benzocoumarin condensed ring is also represented by [1] CM [3].
  • Phe means Phenanthryl and Py means pyrenyl, and is a chromophore of a reaction precursor.
  • Example 1 Coumarin condensed ring compound represented by formula (7) (1) Step1. Synthesis of 4-Bromomethyl-7-methoxycoumarin phosphonium salt 4-Bromomethyl-7-methoxycoumarin (4-Bromomethyl-7-methoxycoumarin) 2.0 g (7.4 mmol), triphenylphosphine (triphenylphosphine) 1.95 g (7.4 mmol), xylene (75 mL) was added, The mixture was refluxed at 140 ° C. overnight under a nitrogen atmosphere.
  • the mixture was refluxed at 70 ° C. for 1 hour under a nitrogen atmosphere to synthesize Compound A.
  • the reaction solution was allowed to cool to room temperature and washed with water and saturated brine.
  • the target product was isolated as a mixture of EZ isomers by silica column chromatography using a mixed solvent of Hexane: ethyl acetate (78:22, v / v) as a developing solvent.
  • the product showed a spot with an Rf value of 0.14 on TLC (thin layer chromatography) using Hexane: ethyl acetate (4: 1, v / v) as the developing solvent.
  • the yield was 0.44 g, and the yield was 56%.
  • FIG. 1 shows the absorption / fluorescence spectrum of the coumarin condensed ring compound obtained at 10 ⁇ 4 mol / L in acetonitrile.
  • FIG. 1 also shows the absorption / fluorescence spectrum of 7-methoxycoumarin.
  • a JASCO V-550 spectrophotometer was used for the measurement of the absorption spectrum.
  • a Hitachi F-7000 fluorescence spectrophotometer was used for measurement of the fluorescence spectrum.
  • the excitation wavelength of the obtained coumarin condensed ring compound was 280 nm.
  • the excitation wavelength of 7-methoxycoumarin was 295 nm.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • the vertical axis in FIG. 4 represents the fluorescence yield ⁇ f in the upper stage, the fluorescence lifetime ⁇ f / ns in the middle stage, the fluorescence speed k f / 10 8 s ⁇ 1 in the lower stage, and the abscissa represents the condensed benzene ring. Represents the number [n].
  • an absolute PL photoquantum yield measuring apparatus (Hamamatsu Photonics C9920-02) was used, and in each Example, the absorbance at a wavelength longer than 300 nm of the obtained compound was maximum. Excitation was performed at the absorption maximum wavelength.
  • a single photon correlation measurement device (Hamamatsu Photonics Quantaurus-TAU System) is used to measure the fluorescence lifetime ⁇ f , and in each example, the wavelength that gives the maximum absorbance of the obtained compound at 310 nm, 340 nm, or 365 nm is selected. The excitation wavelength was used.
  • Example 2 Coumarin condensed ring compound represented by formula (8) 2-1. Synthesis of photoreaction precursor (compound B) by Wittig reaction 4-Bromomethyl-7-methoxycoumarin phosphonium salt 0.95 g (1.79 mmol) and 1-naphthaldehyde 0.26 ml (1.90 mmol) were added to chloroform 20 mL, and 10 mL of 50% KOH aqueous solution was added dropwise with stirring. . The mixture was refluxed at 70 ° C. for 3 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was washed with water and saturated brine. The product was isolated as a mixture of EZ isomers on a silica column chromatograph. The yield was 0.60 g, and the yield was 98%.
  • FIG. 1 and FIG. 2 show absorption and fluorescence spectra of the coumarin condensed ring compound at 10 ⁇ 4 mol / L in acetonitrile.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • Example 3 Coumarin condensed ring compound represented by formula (9) 3-1. Synthesis of photoreaction precursor (compound C) by Wittign reaction Add 4-Bromomethyl-7-methoxycoumarin phosphonium salt (1.6 g, 3.0 mmol), 9-phenanthrenecarbaldehyde (0.62 g, 3.0 mmol) and chloroform (30 mL), and stir with 10 mL of 50% KOH aqueous solution. It was dripped. The mixture was refluxed at 60 ° C. for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was washed with water and saturated brine. Isolation as a mixture of EZ isomers was performed on a silica column chromatograph.
  • the product showed a spot with an Rf value of 0.24 on TLC (Thin Layer Chromatography) using Hexane: ethyl acetate (4: 1, v / v) as the developing solvent.
  • the yield was 0.90 g, and the yield was 80%.
  • FIG. 1 shows the absorption / fluorescence spectrum of the coumarin condensed ring compound obtained at 10 ⁇ 4 mol / L in acetonitrile.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • Example 4 Coumarin condensed ring compound represented by formula (10) 4-1.
  • Synthesis of photoreaction precursor (compound D) by Wittig reaction Add 1.6 g (3.0 mmol) of 4-Bromomethyl-7-methoxycoumarin phosphonium salt, 0.76 g (3.3 mmol) of 1-pyrenecarboxaldehyde, 30 mL of dichloromethane, and add 50% KOH with stirring. 10 mL of aqueous solution was dripped. The mixture was refluxed at 45 ° C. for 1 hour under a nitrogen atmosphere. After allowing to cool to room temperature, the reaction solution was washed with water and saturated brine. Isolated as a mixture of EZ isomers by silica column chromatography. The product showed a spot with an Rf value of 0.24 on TLC using Hexane: ethyl acetate (4: 1, v / v) as the developing solvent. The yield was 0.15 g, and the yield was 12%.
  • FIG. 1 shows the absorption / fluorescence spectrum of the coumarin condensed ring compound obtained at 10 ⁇ 4 mol / L in acetonitrile.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • Example 5 Coumarin condensed ring compound represented by formula (11) (1) Step1. Synthesis of 4-Chloromethylcoumarin Add ethyl 4-chloroacetoacetate (Ethyl-4-chloroacetoacetate) 2.4mL (17.7mmol), phenol (5.0g (53.1mmol)), 6 drops of sulfuric acid (sulfuric acid), 120 ° C under nitrogen atmosphere And heated at reflux for 3 hours. After extraction with Ethyl acetate, the extract was washed twice with an aqueous sodium hydrogen carbonate solution, once with distilled water, and once with saturated saline. Isolation and purification were performed using a silica column chromatograph with a solvent of Hexane: ethyl acetate (4: 1, v / v). The yield was 330 mg, and the yield was 10%.
  • Step 3 Synthesis of photoreaction precursor (compound E) by Wittig reaction 4-Chloromethylcoumarin phosphonium salt 0.25 g (0.54 mmol), 1-naphthaldehyde 0.06 mL (0.59 mmol) 0.06 ml (0.59 mmol) and chloroform 10 mL were added, and 5 mL of 50% KOH aqueous solution was added dropwise with stirring. The mixture was refluxed at 60 ° C. for 1 hour under a nitrogen atmosphere. After allowing to cool to room temperature, the reaction solution was washed with water and saturated brine.
  • Hexane: ethyl acetate (4: 1, v / v) was isolated as a mixture of EZ isomers by silica column chromatography using a developing solvent. The yield was 0.15 g, and the yield was 92%.
  • the product showed a spot with an Rf value of 0.43 on TLC using Hexane: ethyl acetate (1: 5, v / v) as the developing solvent. Formation of the target product was confirmed by NMR measurement.
  • the NMR spectrum of the product is shown in FIG. The peak information of the NMR spectrum was as follows. The yield was 0.05 g, and the yield was 34%.
  • FIG. 2 shows an absorption / fluorescence spectrum of the obtained coumarin condensed ring compound at 10 ⁇ 4 mol / L in acetonitrile.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • Example 6 A coumarin condensed ring compound represented by the formula (12) which is a 7,8-benzocoumarin condensed ring (1) Step1. Synthesis of compound F Ethyl-4-chloroacetoacetate 2.4 mL (17.7 mmol), 1-naphthol 7.6 g (53.1 mmol), and 6 drops of sulfuric acid were added, and the mixture was heated to reflux at 120 ° C. for 3 hours in a nitrogen atmosphere. After extraction with Ethyl acetate, the extract was washed twice with an aqueous sodium hydrogen carbonate solution, once with distilled water, and once with saturated saline. The solvent was distilled off, and the precipitate was filtered with suction and washed with ethyl acetate. The yield was 1.62 g, and the yield was 37%. Compound F was used in the next reaction without purification.
  • the product showed a spot with an Rf value of 0.50 on TLC using Hexane: ethyl acetate (1: 5, v / v) as the developing solvent.
  • the target product was confirmed by NMR measurement.
  • the NMR spectrum of the product is shown in FIG.
  • the peak information of the NMR spectrum was as follows. The yield was 67 mg, and the yield was 42%.
  • FIG. 2 shows an absorption / fluorescence spectrum of the obtained coumarin condensed ring compound at 10 ⁇ 4 mol / L in acetonitrile.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • Example 7 Coumarin condensed ring compound represented by formula (15) 7-1.
  • Synthesis of photoreactive precursor (compound I) by Wittig reaction Add 1.6 g (3.0 mmol) of 4-Bromomethyl-7-methoxycoumarin phosphonium salt and 0.51 g (2.5 mmol) of phenanthrene-1-carbaldehyde to 30 mL of chloroform and stir 50% 10 mL of aqueous KOH solution was added dropwise. Subsequently, the mixture was refluxed at 65 ° C. for 1 hour in a nitrogen atmosphere. After cooling to room temperature, the mixture was washed with water and saturated brine.
  • the condensed ring product was purified by recrystallization using Ethyl acetate.
  • the obtained target product showed a spot having an Rf value of 0.19 on TLC using Hexane: chloroform (1: 5, v / v) as a developing solvent.
  • the yield was 15 mg and the yield was 21%.
  • the formation of the target product was confirmed by NMR.
  • the NMR of the product is shown in FIG.
  • the peak information of the NMR spectrum was as follows.
  • FIG. 3 shows the absorption / fluorescence spectrum of the obtained coumarin condensed ring compound at 10 ⁇ 4 mol / L in acetonitrile.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • Example 8 Coumarin condensed ring compound represented by formula (16) 8-1. Synthesis of photoreaction precursor (compound J) by Wittig reaction 4-Bromomethyl-7-methoxycoumarin phosphonium salt 0.37 g (0.70 mmol) and chrysene-1-carbaldehyde 0.08 g (0.30 mmol) were added to 10 mL of chloroform and stirred with 50% KOH. 5 mL of aqueous solution was dripped. The mixture was refluxed at 65 ° C. for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was washed with water and saturated brine.
  • the product after washing was isolated by silica column chromatography using a mixed solvent of Hexane: ethyl acetate (3: 1, v / v) as a developing solvent.
  • the product showed a spot with an Rf value of 0.28 on TLC using Hexane: ethyl acetate (3: 1, v / v) as the developing solvent.
  • the yield was 0.050 g, and the yield was 38%.
  • FIG. 3 shows the absorption / fluorescence spectrum of the obtained coumarin condensed ring compound at 10 ⁇ 4 mol / L in acetonitrile.
  • the fluorescence yield ( ⁇ f ), fluorescence lifetime ( ⁇ f ), and fluorescence speed (k f ) are shown in Table 1 and FIG.
  • the fluorescence yield of the compound represented by the formula (8) of Example 2 increases about 125 times as compared with 7-methoxycoumarin, and the fluorescence rate increases. Has also been shown to increase significantly. Further, the results of Examples 1, 2, 7 and Example 8 indicate that the fluorescence yield is further improved by increasing the number of benzene rings.
  • the compound of the embodiment of the present invention is expected to exhibit not only fluorescence but also an n-type semiconductor operation, and the application to the electron transport layer of the field effect transistor is expected. Application can be expected.
  • the organic EL device using the coumarin-based condensed ring compound of the present invention can be expected to be robust, it can be expected to be used in clothing tags and the like, and can complement the silicon semiconductor market. In addition, it can be produced from an existing coumarin by a photocondensation reaction, and since it has a high yield, it can be produced at low cost and is very useful industrially.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Pyrane Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne un composé organique résistant à des environnements extérieurs comme la haute tension ou taux d'oxygène élevé et pouvant être utilisé comme matériau électronique ou élément émettant de la lumière bleue. L'invention concerne un composé à cycle condensé de coumaline représenté par la formule générale (1). Dans la formule (1), R1-R4 représentent chacun indépendamment un atome d'hydrogène, un groupe hydroxyle, un groupe alcoxy, un groupe amino, un groupe alkylamino, un groupe dialkylamino, un groupe trialkylamino, un groupe trifluorométhyle, un groupe nitro, ou un groupe cyano, et Ar représente un cycle aromatique ou un cycle hétéroaromatique qui peut avoir un substituant. Lorsque R1-R4 sont tous des atomes d'hydrogène, Ar n'est pas un cycle benzénique.
PCT/JP2015/068233 2014-06-26 2015-06-24 Composé à cycle condensé de coumaline présentant des propriétés de luminescence/semi-conducteur et son procédé de fabrication Ceased WO2015199141A1 (fr)

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JP2018184393A (ja) * 2017-04-24 2018-11-22 東ソー株式会社 縮合環化合物及びその製造方法
CN111440137A (zh) * 2020-04-28 2020-07-24 华东理工大学 一种3,4-苯并香豆素衍生物及其制备方法与应用

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Publication number Priority date Publication date Assignee Title
JP2018184393A (ja) * 2017-04-24 2018-11-22 東ソー株式会社 縮合環化合物及びその製造方法
CN111440137A (zh) * 2020-04-28 2020-07-24 华东理工大学 一种3,4-苯并香豆素衍生物及其制备方法与应用
CN111440137B (zh) * 2020-04-28 2022-08-16 华东理工大学 一种3,4-苯并香豆素衍生物及其制备方法与应用

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